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Sample records for greater electrocatalytic activity

  1. Electrocatalytic Activity of Electropolymerized Cobalt ...

    African Journals Online (AJOL)

    Mercaptobenzimidazole (MBI) was studied. ... The poly-CoTAPc film exhibited efficiently electrocatalytic activity for 6MP and MBI with relatively high sensitivity, stability and long-life. ... HOW TO USE AJOL.

  2. Electrocatalytic Activity of Electropolymerized Cobalt ...

    African Journals Online (AJOL)

    NICO

    2010-09-20

    Sep 20, 2010 ... detection, HPLC coupled to electrochemical detector2–15 has been used. ... have been widely studied, in light of high stability and eletro- catalytic activity of .... relatively weak redox waves with a small ill-defined peak. However, the .... tative measure in terms of the role of signal to noise ratio of. 3:1(S/N = 3), ...

  3. Electrocatalytic activity of self-doped polyaniline

    International Nuclear Information System (INIS)

    Shieh, Yeong-Tarng; Jung, Jeng-Ji; Lin, Rong-Hsien; Yang, Chien-Hsin; Wang, Tzong-Liu

    2012-01-01

    Self-doped conducting polyaniline-modified indium tin oxide (ITO) electrodes were prepared by cyclic voltammetry on ITO substrates in aniline (AN) and o-aminobenzene sulfonic acid (OSA) mixed monomer solutions with AN/OSA mole ratios of 25/75, 50/50, and 75/25, followed by investigations on electrocatalytic activities of the copolymers to redox reactions of Fe(CN) 6 3−/4− as a probe in aqueous solutions of different pH using cyclic voltammetry. For a given pH, the P(25AN-co-75OSA)-modified ITO electrode demonstrated the highest current density, followed by the P(50AN-co-50OSA)- and by the P(75AN-co-25OSA)-modified ITO electrodes. It can be concluded that a higher content of OSA (sulfonate) in the copolymer exhibited a higher extent of self-doping in the copolymer, leading to a higher electrocatalytic activity to redox reactions of the probe. The electrocatalytic activities of the copolymers decreased with increasing pH. The P(25AN-co-75OSA)-modified ITO electrode was electroactive for sensing the redox reactions of the probe in aqueous solutions of up to pH 7, the P(50AN-co-50OSA)-modified ITO electrode was electroactive for up to only pH 5, but the P(75AN-co-25OSA)-modified ITO electrode was not electroactive in aqueous solution of pH even as low as 2.

  4. Electrocatalytic Activity and Selectivity - a Density Functional Theory Study

    DEFF Research Database (Denmark)

    Karamad, Mohammadreza

    -catalysts towards two appealing electrochemical reactions: 1)electroreduction of CO2 to hydrocarbons and alcohols, and 2) electrochemical production of hydrogen peroxide, i.e. H2O2, from its elements i.e. H2 and O2. The thesis is divided into three parts: In the first part, electro-catalytic activity of different...... metallic and functionalized graphene catalysts. Secondly, we considered CO2 reduction on RuO2, which has a distinctive catalytic activity and selectivity compared to Cu to get insight into mechanistic pathway of the CO2 reduction. Finally, in the last part, we have taken advantage of the isolated active...

  5. Electrocatalytic activity of bismuth doped silver electrodes

    CERN Document Server

    Amjad, M

    2002-01-01

    Investigation of redox reactions on silver, and bismuth doped silver electrodes in aqueous KOH solutions, by using potentiostatic steady-state polarization technique, has been carried out. The redox wave potential and current displacements along with multiplicity of the latter have been examined. These electrodes were employed for the oxidation of organic molecules such as ethylamine in alkaline media. Subsequently, these electrodes were ranked with respect to their activity for the redox reactions. (author)

  6. Enhancement of the Electrocatalytic Activity of Gold Nanoparticles via Anodic Treatment and the Decrease of the Enhanced Activity with Aging

    International Nuclear Information System (INIS)

    Jo, Kyung Min; Kang, Hyun Ju; Yang, Hae Sik

    2011-01-01

    We have recently shown that the electrocatalytic activity of Au nanoparticles (AuNPs) can be enhanced via NaBH 4 treatment and cathodic treatment and that the enhanced activity slowly decreases with aging. We have also demonstrated that the electrocatalytic activity of the AuNPs freshly prepared by electrochemical or chemical reduction slowly decreases with aging in both air and solution. Likewise, the electrocatalytic activity of anodically treated Au electrodes or AuNPs might change with aging. Herein, we report that the electrocatalytic activity of long-aged AuNPs can be enhanced via anodic treatment and that the enhanced electrocatalytic activity decreases with aging in air. The change in the electrocatalytic activity of AuNPs was evaluated by comparing cyclic voltammograms for the electrooxi-dation of hydrogen peroxide (H 2 O 2 ) and formic acid

  7. High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst

    KAUST Repository

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi Zhang

    2016-01-01

    Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

  8. High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.

    Science.gov (United States)

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi-Zhang

    2016-12-14

    Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

  9. High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst

    KAUST Repository

    Zheng, Yao

    2016-11-28

    Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

  10. Theory, Investigation and Stability of Cathode Electrocatalytic Activity

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Dong; Liu, Mingfei; Lai, Samson; Blinn, Kevin; Liu, Meilin

    2012-09-30

    The main objective of this project is to systematically characterize the surface composition, morphology, and electro-catalytic properties of catalysts coated on LSCF, aiming to establish the scientific basis for rational design of high-performance cathodes by combining a porous backbone (such as LSCF) with a thin catalyst coating. The understanding gained will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance. More specifically, the technical objectives include: (1) to characterize the surface composition, morphology, and electro-catalytic properties of catalysts coated on LSCF; (2) to characterize the microscopic details and stability of the LSCF-catalyst (e.g., LSM) interfaces; (3) to establish the scientific basis for rational design of high-performance cathodes by combining a porous backbone (such as LSCF) with a thin catalyst coating; and (4) to demonstrate that the performance and stability of porous LSCF cathodes can be enhanced by the application of a thin-film coating of LSM through a solution infiltration process in small homemade button cells and in commercially available cells of larger dimension. We have successfully developed dense, conformal LSM films with desired structure, composition, morphology, and thickness on the LSCF surfaces by two different infiltration processes: a non-aqueous and a water-based sol-gel process. It is demonstrated that the activity and stability of LSCF cathodes can be improved by the introduction of a thin-film LSM coating through an infiltration process. Surface and interface of the LSM-coated LSCF cathode were systematically characterized using advanced microscopy and spectroscopy techniques. TEM observation suggests that a layer of La and Sr oxide was formed on LSCF surfaces after annealing. With LSM infiltration, in contrast, we no longer observe such La/Sr oxide layer on the LSM-coated LSCF samples after annealing under similar

  11. Building up an electrocatalytic activity scale of cathode materials for organic halide reductions

    International Nuclear Information System (INIS)

    Bellomunno, C.; Bonanomi, D.; Falciola, L.; Longhi, M.; Mussini, P.R.; Doubova, L.M.; Di Silvestro, G.

    2005-01-01

    A wide investigation on the electrochemical activity of four model organic bromides has been carried out in acetonitrile on nine cathodes of widely different affinity for halide anions (Pt, Zn, Hg, Sn, Bi, Pb, Au, Cu, Ag), and the electrocatalytic activities of the latter have been evaluated with respect to three possible inert reference cathode materials, i.e. glassy carbon, boron-doped diamond, and fluorinated boron-doped diamond. A general electrocatalytic activity scale for the process is proposed, with a discussion on its modulation by the configuration of the reacting molecule, and its connection with thermodynamic parameters accounting for halide adsorption

  12. Investigation of the electrocatalytic activity for oxygen reduction of sputter deposited mixed metal films

    International Nuclear Information System (INIS)

    Schumacher, L.C.; Holzheuter, I.B.; Nucara, M.C.; Dignam, M.J.

    1989-01-01

    Sputter-deposited films of silver with lead, manganese and nickel have been studied as possible oxygen reduction electrocatalysts using cyclic voltammetry, rotating disc studies, steady-state polarization and Auger analysis. In general, the Ag-Pb and Ag-Mn films display superior electrocatalytic activity for O 2 reduction, while the Ag-Ni films' performance is inferior to that of pure Ag. For the Ag-Pb films, which show the highest electrocatalytic activity, the mixed metal films display oxidation-reduction behavior which is not simply a superposition of that of the separate metals, and suggests a mechanism for the improved behavior

  13. Selective Electrocatalytic Activity of Ligand Stabilized Copper Oxide Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Kauffman, Douglas R; Ohodnicki, Paul R; Kail, Brian W; Matranga, Christopher

    2011-01-01

    Ligand stabilization can influence the surface chemistry of Cu oxide nanoparticles (NPs) and provide unique product distributions for electrocatalytic methanol (MeOH) oxidation and CO{sub 2} reduction reactions. Oleic acid (OA) stabilized Cu{sub 2}O and CuO NPs promote the MeOH oxidation reaction with 88% and 99.97% selective HCOH formation, respectively. Alternatively, CO{sub 2} is the only reaction product detected for bulk Cu oxides and Cu oxide NPs with no ligands or weakly interacting ligands. We also demonstrate that OA stabilized Cu oxide NPs can reduce CO{sub 2} into CO with a {approx}1.7-fold increase in CO/H{sub 2} production ratios compared to bulk Cu oxides. The OA stabilized Cu oxide NPs also show 7.6 and 9.1-fold increases in CO/H{sub 2} production ratios compared to weakly stabilized and non-stabilized Cu oxide NPs, respectively. Our data illustrates that the presence and type of surface ligand can substantially influence the catalytic product selectivity of Cu oxide NPs.

  14. Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

    OpenAIRE

    Oyunbileg G; Batnyagt G; Enkhsaruul B; T Takeguchi

    2018-01-01

    The oxygen reduction reaction (ORR) is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs) and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM) and a transmission electron microscope (TEM) analyses confirm the ...

  15. Silver nanoparticles anchored reduced graphene oxide for enhanced electrocatalytic activity towards methanol oxidation

    Science.gov (United States)

    Kumar, Sanjeev; Mahajan, Mani; Singh, Rajinder; Mahajan, Aman

    2018-02-01

    In this report, silver nanoparticles (Ag NPs) anchored reduced graphene oxide (rGO) sheets (rGO/Ag) nanohybrid has been explored as anode material in direct methanol fuel cells (DMFCs). The synthesized rGO/Ag nanohybrid is characterized by XRD, XPS, FTIR spectroscopy and HRTEM techniques. Cyclic voltammograms demonstrate that the rGO/Ag nanohybrid exhibits higher electrocatalytic activity in comparison to rGO sheets for methanol oxidation reaction (MOR). This enhancement is attributed to the synergetic effect produced by the presence of more active sites provided by Ag NPs anchored on a conducting network of large surface area rGO sheets.

  16. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ju, Hua [School of Urban Rail Transportation, Soochow University, Suzhou 215006 (China); Li, Zhihu [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China); Xu, Yanhui, E-mail: xuyanhui@suda.edu.cn [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China)

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  17. Electrocatalytic activity of electropolymerized cobalt tetraaminophthalocyanine film modified electrode towards 6-mercaptopurine and 2-mercaptobenzimidazole

    OpenAIRE

    Fan, Jie-Ping; Zhang, Xiao-Min; Ying, Min

    2010-01-01

    The electrocatalytic activity of electropolymerized cobalt tetraaminophthalocyanine (poly-CoTAPc) film modified on the glassy carbon electrode (GCE) towards 6-mercaptopurine (6MP) and 2-Mercaptobenzimidazole (MBI) was studied. Comparing with the case at the unmodified GCE, the poly-CoTAPc film decreased the overpotential of oxidation of 6MP (1.0 x 10-3 mol L-1) and MBI (1.0 x 10-3 mol L-1) by 335 and 189 mV, respectively, and increased the peak current by about 3 and 2 times, respectively, wh...

  18. Interface architecture determined electrocatalytic activity of Pt on vertically oriented TiO(2) nanotubes.

    Science.gov (United States)

    Rettew, Robert E; Allam, Nageh K; Alamgir, Faisal M

    2011-02-01

    The surface atomic structure and chemical state of Pt is consequential in a variety of surface-intensive devices. Herein we present the direct interrelationship between the growth scheme of Pt films, the resulting atomic and electronic structure of Pt species, and the consequent activity for methanol electro-oxidation in Pt/TiO(2) nanotube hybrid electrodes. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements were performed to relate the observed electrocatalytic activity to the oxidation state and the atomic structure of the deposited Pt species. The atomic structure as well as the oxidation state of the deposited Pt was found to depend on the pretreatment of the TiO(2) nanotube surfaces with electrodeposited Cu. Pt growth through Cu replacement increases Pt dispersion, and a separation of surface Pt atoms beyond a threshold distance from the TiO(2) substrate renders them metallic, rather than cationic. The increased dispersion and the metallic character of Pt results in strongly enhanced electrocatalytic activity toward methanol oxidation. This study points to a general phenomenon whereby the growth scheme and the substrate-to-surface-Pt distance dictates the chemical state of the surface Pt atoms, and thereby, the performance of Pt-based surface-intensive devices.

  19. Facile synthesis of bacitracin-templated palladium nanoparticles with superior electrocatalytic activity

    Science.gov (United States)

    Li, Yanji; Wang, Zi; Li, Xiaoling; Yin, Tian; Bian, Kexin; Gao, Faming; Gao, Dawei

    2017-02-01

    Palladium nanomaterials have attracted great attention on the development of electrocatalysts for fuel cells. Herein, we depicted a novel strategy in the synthesis of palladium nanoparticles with superior electrocatalytic activity. The new approach, based on the self-assembly of bacitracin biotemplate and palladium salt for the preparation of bacitracin-palladium nanoparticles (Bac-PdNPs), was simple, low-cost, and green. The complex, composed by a series of spherical Bac-PdNPs with a diameter of 70 nm, exhibited a chain-liked morphology in TEM and a face-centered cubic crystal structure in X-Ray diffraction and selected area electron diffraction. The palladium nanoparticles were mono-dispersed and stable in aqueous solution as shown in TEM and zeta potential. Most importantly, compared to the commercial palladium on carbon (Pd/C) catalyst (8.02 m2 g-1), the Bac-PdNPs showed a larger electrochemically active surface area (47.57 m2 g-1), which endowed the products an excellent electrocatalytic activity for ethanol oxidation in alkaline medium. The strategy in synthesis of Bac-PdNPs via biotemplate approach might light up new ideas in anode catalysts for direct ethanol fuel cells.

  20. Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

    Directory of Open Access Journals (Sweden)

    Oyunbileg G

    2018-02-01

    Full Text Available The oxygen reduction reaction (ORR is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM and a transmission electron microscope (TEM analyses confirm the formation of the star-shaped nanoparticles. Among the investigated nanostar catalysts, an AuNS5 with smaller size and a few branches showed the higher electrocatalytic activity towards ORR than other catalysts with a bigger size. In addition, the electron numbers transferred for all the catalysts are approximately two. The present study results infer that the size of the Au-based nanostars may influence greatly on their catalytic activity. The present study results show that the further improvement is needed for Au-based nanostar catalysts towards the ORR reaction.

  1. Effective adsorption/electrocatalytic degradation of perchlorate using Pd/Pt supported on N-doped activated carbon fiber cathode

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Fubing; Zhong, Yu [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Yang, Qi, E-mail: yangqi@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Wang, Dongbo, E-mail: dongbowang@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Chen, Fei; Zhao, Jianwei; Xie, Ting; Jiang, Chen; An, Hongxue; Zeng, Guangming; Li, Xiaoming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China)

    2017-02-05

    Highlights: • Pd/Pt-NACF served as an adsorption/electrocatalysis electrode to reduce perchlorate. • The possible mechanisms involved in the reaction process were explained. • The reusability and stability of Pd/Pt-NACF bifunctional material was evaluated. - Abstract: In this work, Pd/Pt supported on N-doped activated carbon fiber (Pd/Pt-NACF) was employed as the electrode for electrocatalytic degradation of perchlorate through adsorption/electroreduction process. Perchlorate in solution was firstly adsorbed on Pd/Pt-NACF and then reduced to non-toxic chloride by the catalytic function of Pd/Pt at a constant current (20 mA). Compared with Pd/Pt-ACF, the adsorption capacity and electrocatalytic degradation efficiency of Pd/Pt-NACF for perchlorate increased 161% and 28%, respectively. Obviously, positively charged N-functional groups on NACF surface enhanced the adsorption capacity of Pd/Pt-NACF, and the dissociation of hydrogen to atomic H* by the Pd/Pt nanostructures on the cathode might drastically promote the electrocatalytic reduction of perchlorate. The role of atomic H* in the electroreduction process was identified by tertiary butanol inhibition test. Meanwhile, the perchlorate degradation performance was not substantially lower after three successive adsorption/electrocatalytic degradation experiments, demonstrating the electrochemical reusability and stability of the as-prepared electrode. These results showed that Pd/Pt-NACF was effective for electrocatalytic degradation of perchlorate and had great potential in perchlorate removal from water.

  2. High electro-catalytic activities of glucose oxidase embedded one-dimensional ZnO nanostructures

    International Nuclear Information System (INIS)

    Sarkar, Nirmal K; Bhattacharyya, Swapan K

    2013-01-01

    One-dimensional ZnO nanorods and nanowires are separately synthesized on Zn substrate by simple hydrothermal processes at low temperatures. Electro-catalytic responses of glucose oxidase/ZnO/Zn electrodes using these two synthesized nanostructures of ZnO are reported and compared with others available in literature. It is apparent the Michaelis–Menten constant, K M app , for the present ZnO nanowire, having a greater aspect ratio, is found to be the lowest when compared with others. This sensor shows lower oxidation peak potential with a long detection range of 6.6 μM–380 mM and the highest sensitivity of ∼35.1 μA cm −2 mM −1 , among the reported values in the literature. Enzyme catalytic efficiency and turnover numbers are also found to be remarkably high. (paper)

  3. Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction

    Science.gov (United States)

    Ge, Zhijun; Wang, Ling; He, Zhangxing; Li, Yuehua; Jiang, Yingqiao; Meng, Wei; Dai, Lei

    2018-04-01

    A novel strategy for improving the electro-catalytic properties of graphite felt (GF) electrode in vanadium redox flow battery (VRFB) is designed by depositing cobalt phosphide (CoP) onto GF surface. The CoP powder is synthesized by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Cyclic voltammetry results confirm that the CoP-modified graphite felt (GF-CoP) electrode has excellent reversibility and electro-catalytic activity to the VO2+/VO2+ cathodic reaction compared with the pristine GF electrode. The cell using GF-CoP electrode shows apparently higher discharge capacity over that based on GF electrode. The cell using GF-CoP electrode has the capacity of 67.2 mA h at 100 mA cm-2, 32.7 mA h larger than that using GF electrode. Compared with cell using GF electrode, the voltage efficiency of the cell based on GF-CoP electrode increases by 5.9% and energy efficiency by 5.4% at a current density of 100 mA cm-2. The cell using GF-CoP electrode can reach 94.31% capacity retention after 50 cycles at a current density of 30 mA cm-2. The results show that the CoP can effectively promote the VO2+/VO2+ redox reaction, implying that metal phosphides are a new kind of potential catalytic materials for VRFB.

  4. Fabrication of La-doped TiO2 Film Electrode and investigation of its electrocatalytic activity for furfural reduction

    International Nuclear Information System (INIS)

    Wang, Fengwu; Xu, Mai; Wei, Lin; Wei, Yijun; Hu, Yunhu; Fang, Wenyan; Zhu, Chuan Gao

    2015-01-01

    Lanthanum trivalent ions (La 3+ ) doped nano-TiO 2 film electrode was prepared by the sol–gel method. The prepared electrode was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). The electrocatalytic properties of the roughened TiO 2 film electrode towards the electrocatalytic reduction of furfural to furfural alcohol were evaluated by CV and preparative electrolysis experiments. The results of the optimum molar ratio of La: Ti was 0.005:1. Experimental evidence was presented that the La nano-TiO 2 electrode exhibited higher electrocatalytic activity for the reduction of furfural than the undoped nano-TiO 2 electrode in N,N-dimethylformamide medium. Bulk electrolysis studies were also carried out for the reduction of furfural and the product was confirmed by NMR

  5. Electrocatalytic activity mapping of model fuel cell catalyst films using scanning electrochemical microscopy

    International Nuclear Information System (INIS)

    Nicholson, P.G.; Zhou, S.; Hinds, G.; Wain, A.J.; Turnbull, A.

    2009-01-01

    Scanning electrochemical microscopy has been employed to spatially map the electrocatalytic activity of model proton exchange membrane fuel cell (PEMFC) catalyst films towards the hydrogen oxidation reaction (the PEMFC anode reaction). The catalyst films were composed of platinum-loaded carbon nanoparticles, similar to those typically used in PEMFCs. The electrochemical characterisation was correlated with a detailed physical characterisation using dynamic light scattering, transmission electron microscopy and field-emission scanning electron microscopy. The nanoparticles were found to be reasonably mono-dispersed, with a tendency to agglomerate into porous bead-type structures when spun-cast. The number of carbon nanoparticles with little or no platinum was surprisingly higher than would be expected based on the platinum-carbon mass ratio. Furthermore, the platinum-rich carbon particles tended to agglomerate and the clusters formed were non-uniformly distributed. This morphology was reflected in a high degree of heterogeneity in the film activity towards the hydrogen oxidation reaction.

  6. Comparative study on the electrocatalytic activities of ordered mesoporous carbons and graphene

    International Nuclear Information System (INIS)

    Wang Huan; Qi Bin; Lu Baoping; Bo Xiangjie; Guo Liping

    2011-01-01

    In this work, a comparative study on the electrocatalytic activities of ordered mesoporous carbons (OMCs) and graphene (GR) is presented. Using voltammetry and amperometry as detection methods, four DNA bases, double-stranded DNA (dsDNA), six important electroactive compounds and various biomolecules were employed to investigate their electrochemical responses on OMC and GR modified glassy carbon electrodes (OMC/GCE and GR/GCE). The results show that OMC/GCE enhances the electron transfer kinetics of these compounds compared to GR/GCE. The discrepancy in electrochemical activities can be attributed to the different microstructures of OMC and GR, which were examined by transmission electron microscopy, X-ray photoelectron spectra, X-ray diffraction, Raman spectra and nitrogen adsorption-desorption.

  7. Monodisperse, submicrometer-scale platinum colloidal spheres with high electrocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lixue; Wang, Liang; Guo, Shaojun; Zhai, Junfeng; Dong, Shaojun; Wang, Erkang [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Graduate School of the Chinese Academy of Sciences, 130022 Jilin, Changchun (China)

    2009-02-15

    Monodisperse, submicrometer-scale platinum (Pt) colloidal spheres were prepared through a simple direct chemical reduction of p-phenylenediamine (PPD)-chloroplatinic acid (H{sub 2}PtCl{sub 6}) coordination polymer colloids. It was found that the prepared Pt colloids had the similar size and morphology with their coordination polymer precursors, and the prepared Pt colloids with rough surfaces were three-dimensional (3D) structured assemblies of high-density small Pt nanoparticles. The electrochemical experiments confirmed that the prepared Pt colloids possessed a high electrocatalytic activity towards mainly four-electron reduction of dioxygen to water, making the prepared Pt colloids potential candidates for the efficient cathode material in fuel cells. (author)

  8. The electrochemical synthesis of polyaniline/polysulfone composite films and electrocatalytic activity for ascorbic acid oxidation

    International Nuclear Information System (INIS)

    Hu Zhongai; Shang Xiuli; Yang Yuying; Kong Chao; Wu Hongying

    2006-01-01

    Polyaniline (PANI)/polysulfone (PSF) composite films with asymmetric porous structure were successfully prepared by electropolymerization. The back face (in contact with the electrode) of the freestanding composite film is green while the outer face is white. The chemical component and the morphology of the surfaces were characterized by FTIR spectra and scanning electron microscopy, respectively. It was shown that replicate films gave reproducible voltammetry in 0.5 M H 2 SO 4 . The influence of the electrolyte and the acidic concentration on the redox peak currents of polyaniline were investigated in detail. The composite film electrode showed good electrocatalytic activity for ascorbic acid, which the anodic overpotential was evidently reduced compared with that obtained at bare Pt electrode. The diffusion coefficient of ascorbic acid was 1.38 x 10 -6 cm 2 s -1

  9. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

    Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo5+ and S2 2- species in the MoSx, especially with S2 2- serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g-1 cm-2 h-1 (286 mmol g-1 cm-2 h-1) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

  10. Urea assisted electrochemical synthesis of flower-like platinum arrays with high electrocatalytic activity

    International Nuclear Information System (INIS)

    Zhang, Ming; Lv, Jing-Jing; Li, Fang-Fang; Bao, Ning; Wang, Ai-Jun; Feng, Jiu-Ju; Zhou, Dan-Ling

    2014-01-01

    Graphical abstract: A simple, facile, and controllable method was developed for preparation of well-defined flower-like Pt arrays via one-step electrodeposition, assisted with urea as a growth directing agent. The as-prepared Pt nanocrystals have a larger electroactive surface area and higher electrocatalytic activity toward ethylene glycol and methanol oxidation in acid media, compared with Pt nanoparticles and commercial Pt black catalysts. - Highlights: • Well-defined flower-like Pt arrays were prepared via one-step electrodeposition, assisted with urea as a growth directing agent. • This method is simple, facile, and controllable, without using any template, seed or surfactant. • The Pt arrays show an enhanced electrocatalytic activity toward ethylene glycol and methanol oxidation. - Abstract: In this paper, well-defined flower-like Pt arrays were prepared on the glassy carbon electrode by one-step electrodeposition at–0.3 V for 600 s in 0.5 M H 2 SO 4 containing 5 mM H 2 PtCl 6 and 150 mM urea. This method is simple, facile, and controllable, without using any template, seed or surfactant. The experimental parameters were investigated and found urea acted as a growth directing agent. The as-prepared Pt nanocrystals were preferentially growing along the (111) directions, which were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy dispersive X-ray (EDX). Moreover, the flower-like Pt nanoarrays exhibited a large effective surface area (EASA) and enhanced performance toward the oxidation of ethylene glycol and methanol in acid media, compared with Pt nanoparticles and commercial Pt black catalysts. This strategy can be extended to prepare other noble metal nanostructures as good electrocatalysts in fuel cells

  11. Electrochemical properties and electrocatalytic activity of conducting polymer/copper nanoparticles supported on reduced graphene oxide composite

    Science.gov (United States)

    Ehsani, Ali; Jaleh, Babak; Nasrollahzadeh, Mahmoud

    2014-07-01

    Reduced graphene oxide (rGO) was used to support Cu nanoparticles. As electro-active electrodes for supercapacitors composites of reduced graphene oxide/Cu nanoparticles (rGO/CuNPs) and polytyramine (PT) with good uniformity are prepared by electropolymerization. Composite of rGO/CuNPs-PT was synthesized by cyclic voltammetry (CV) methods and electrochemical properties of film were investigated by using electrochemical techniques. The results show that, the rGO/CuNPs-PT/G has better capacitance performance. This is mainly because of the really large surface area and the better electronic and ionic conductivity of rGO/CuNPs-PT/G, which lead to greater double-layer capacitance and faradic pseudo capacitance. Modified graphite electrodes (rGO/CuNPs-PT/G) were examined for their redox process and electrocatalytic activities towards the oxidation of methanol in alkaline solutions. The methods of cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) were employed. In comparison with a Cu-PT/G (Graphite), rGO/CuNPs-PT/G modified electrode shows a significantly higher response for methanol oxidation. A mechanism based on the electro-chemical generation of Cu(III) active sites and their subsequent consumptions by methanol have been discussed.

  12. Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

    Science.gov (United States)

    Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

    2017-05-01

    Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH) 2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Understanding the electrocatalytic activity of Pt xSn y in direct ethanol fuel cells

    Science.gov (United States)

    Wang, Yi; Song, Shuqin; Andreadis, George; Liu, Hong; Tsiakaras, Panagiotis

    In the present work, the activity of Pt xSn y/C catalysts towards ethanol, acetaldehyde and acetic acid electrooxidation reactions is investigated for each one separately by means of cyclic voltammetry. To this purpose, a series of Pt xSn y/C catalysts with different atomic ratio (x: y = 2:1, 3:2, 1:1) and small particle size (∼3 nm) are fast synthesized by using the pulse microwave assisted polyol method. The catalysts are well dispersed over the carbon support based on the physicochemical characterization by means of XRD and TEM. Concerning the ethanol electrooxidation, it is found that the Sn addition strongly enhances Pt's electrocatalytic activity and the contributing effect of Sn depends on: (i) the Sn content and (ii) the operating temperature. More precisely, at lower temperatures, Sn-rich catalysts exhibit better ethanol electrooxidation performance while at higher temperatures Sn-poor catalysts give better performance. In the case of acetaldehyde electrooxidation, Pt 1Sn 1/C catalyst exhibits the highest activity at all the investigated temperatures; due to the role of Sn, which could effectively remove C 2 species and inhibit the poison formation by supplying oxygen-containing species. Finally, it is found that the Pt xSn y/C catalysts are almost inactive (little current was measured) towards the acetic acid electrooxidation. The above findings indicate that Sn cannot substantially promote the electrooxidation of acetic acid to C 1 species.

  14. Formation of Two-Dimensional Homologous Faults and Oxygen Electrocatalytic Activities in a Perovskite Nickelate.

    Science.gov (United States)

    Bak, Jumi; Bae, Hyung Bin; Kim, Jaehoon; Oh, Jihun; Chung, Sung-Yoon

    2017-05-10

    Atomic-scale direct probing of active sites and subsequent elucidation of the structure-activity relationship are important issues involving oxide-based electrocatalysts to achieve better electrochemical conversion efficiency. By generating Ruddlesden-Popper (RP) two-dimensional homologous faults via simple control of the cation nonstoichiometry in LaNiO 3 thin films, we demonstrate that strong tetragonal distortion of [NiO 6 ] octahedra is induced by more than 20% elongation of Ni-O bonds in the faults. In addition to direct visualization of the elongation by scanning transmission electron microscopy, we identify that the distorted [NiO 6 ] octahedra in the faults show considerably higher electrocatalytic activities than other surface sites during the electrochemical oxygen evolution reaction. This unequivocal evidence of the octahedral distortion and its impact on electrocatalysis in LaNiO 3 suggests that the formation of RP-type faults can provide an efficient way to control the octahedral geometry and thereby remarkably enhance the oxygen catalytic performance of perovskite oxides.

  15. Hollow raspberry-like PdAg alloy nanospheres: High electrocatalytic activity for ethanol oxidation in alkaline media

    Science.gov (United States)

    Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong

    2015-03-01

    Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).

  16. CORRELATION OF THE FERMI ENERGY OF Ni, Cr, Mn WITH THE ELECTROCATALYTIC ACTIVITY OF THE TRIPLE ALLOYS ON THE BASE OF THESE METALS

    Directory of Open Access Journals (Sweden)

    A. D. Andreyanov

    2016-04-01

    Full Text Available It was established the dependence of the electrocatalytic activity of alloys Ni-Cr-Mn at the variable contents of copper with values of Fermy energy of their components. Electrocatalytic activity of alloys was estimated by density of the current, determined by the method of suspended half-element. For Fermi energy calculation of various metals Sommerfeld model, in which distribution of electrons by speed is described by Fermi-Dirac statistic was used.

  17. Carbon Supported Engineering NiCo2O4 Hybrid Nanofibers with Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Diab Hassan

    2016-09-01

    Full Text Available The design of cheap and efficient oxygen reduction reaction (ORR electrocatalysts is of a significant importance in sustainable and renewable energy technologies. Therefore, ORR catalysts with superb electrocatalytic activity and durability are becoming a necessity but still remain challenging. Herein, we report C/NiCo2O4 nanocomposite fibers fabricated by a straightforward electrospinning technique followed by a simple sintering process as a promising ORR electrocatalyst in alkaline condition. The mixed-valence oxide can offer numerous accessible active sites. In addition, the as-obtained C/NiCo2O4 hybrid reveals significantly remarkable electrocatalytic performance with a highly positive onset potential of 0.65 V, which is only 50 mV lower than that of commercially available Pt/C catalysts. The analyses indicate that C/NiCo2O4 catalyst can catalyze O2-molecules via direct four electron pathway in a similar behavior as commercial Pt/C catalysts dose. Compared to single NiCo2O4 and carbon free NiCo2O4, the C/NiCo2O4 hybrid displays higher ORR current and more positive half-wave potential. The incorporated carbon matrices are beneficial for fast electron transfer and can significantly impose an outstanding contribution to the electrocatalytic activity. Results indicate that the synthetic strategy hold a potential as efficient route to fabricate highly active nanostructures for practical use in energy technologies.

  18. Size-selective electrocatalytic activity of (Pt)n/MoS2for oxygen reduction reaction

    DEFF Research Database (Denmark)

    Bothra, Pallavi; Pandey, Mohnish; Pati, Swapan K.

    2016-01-01

    In the present work, we have investigated the electrocatalytic activity of the oxygen reduction reaction (ORR), O2 + 4H+ + 4e− → 2H2O, for (Pt)n clusters (n = 1, 2, 3, 5, 7, 10 and 12) adsorbed on semiconducting (2H) and metallic (1T) MoS2 monolayers using first principles density functional theory....... We have considered four elementary reactions involved in ORR within a unified electrochemical thermodynamic framework and the corresponding Gibbs adsorption free energies of the key intermediates (*OOH, *O, *OH) associated with each step have been calculated. The results indicate that the reduction...... of adsorbed hydroxyl (*OH) to water (*OH + H+ + e− → H2O) is the bottleneck step in the ORR process. The adsorption free energy of *OH (ΔG*OH) is found to be the thermodynamic descriptor for the present systems. Eventually, the ORR activity has been described as a function of ΔG*OH and a volcano plot...

  19. Electrocatalytic activity of Pt nanoparticles on bamboo shaped carbon nanotubes for ethanol oxidation

    International Nuclear Information System (INIS)

    Zhu Zanzan; Wang Jianlong; Munir, Ahsan; Zhou, H. Susan

    2010-01-01

    Recently, bamboo shaped carbon nanotubes (BCNTs) have received increased attention for its bamboo shaped structure associated properties and its application in direct methanol/ethanol fuel cell. In this work, the potential to use BCNTs as the support material of high loaded Pt nanoparticles for improving the efficiency of ethanol/methanol fuel cell is explored. The structure and nature of the resulting Pt-BCNTS composite were characterized by transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) spectrum, it was found that Pt nanoparticles were homogeneously dispersed on the BCNTs surfaces with 23.5% by weight. Cyclic voltammogram (CV) indicated that the Pt-BCNTs catalyst displayed excellent electrocatalytic activity and long-term stability toward ethanol oxidation. The excellent performance may be attributed to the high dispersion of nanoscale Pt catalysts and the unique nature of BCNTs. The results imply that doping N atom introduces some defective sites and active sites onto the surface of CNTs. In general, this paper demonstrates that BCNTs are promising support material for Pt-nanoparticles catalyst and can be used to enhance the efficiency of fuel cell.

  20. Effect of iron on the production of high electrocatalytic activity carbons from ferrocene - PFA mixtures

    International Nuclear Information System (INIS)

    Cashion, J.D.; Brown, L.J.; Ozaki, J.; Yamada, K.; Nozawa, K.; Matsui, K.; Oya, A.

    1999-01-01

    Full text: We have previously studied the carbonisation of mixtures of ferrocene and poly(furfury 1 alcohol) (PFA) which, after heating at 700 deg C, produces electrodes with an electrocatalytic activity comparable to that of platinum. The carbons have a distinctive furry structure under the SEM and an XRD profile characteristic of turbostratic carbon. The iron had been converted to a mixture of α- and γiron and cementite, Fe 3 C and we conjectured that the furry carbon could be formed by the exsolution of carbon from the γ iron on cooling. The present experiments have shown that changing the cooling rate has only a small effect so exsolution is not the cause. However, the increased conductivity correlates well with the proportion of turbostratic carbon which, in turn, correlates with the percentage of cementite. The turbostratic carbon forms cages surrounding an iron phase, presumably the cementite. The conductivity data can be fitted well to either a power law or logarithmic behaviour above the percolation theory critical concentration. The normal percolation theory model for conductivity assumes a growing volume of good conductor in an insulating matrix. However, our system has a good conductor in a matrix of moderate conductor, the conductivity of which is not constant but is increasing under heat treatment at the same time as the good conductor volume is increasing. Some possible analyses will be given

  1. Direct Electrochemistry of Horseradish Peroxidase on NiO Nanoflower Modified Electrode and Its Electrocatalytic Activity

    Directory of Open Access Journals (Sweden)

    Lijun Yan

    2016-09-01

    Full Text Available In this paper nickel oxide (NiO nanoflower was synthesized and used for the realization of direct electrochemistry of horseradish peroxidase (HRP. By using carbon ionic liquid electrode (CILE as the substrate electrode, NiO-HRP composite was casted on the surface of CILE with chitosan (CTS as the film forming material and the modified electrode was denoted as CTS/NiO-HRP/CILE. UV-Vis absorption and FT-IR spectra confirmed that HRP retained its native structure after mixed with NiO nanoflower. Direct electron transfer of HRP on the modified electrode was investigated by cyclic voltammetry with a pair of quasi-reversible redox waves appeared, indicating that the presence of NiO nanoflower on the electrode surface could accelerate the electron transfer rate between the electroactive center of HRP and the substrate electrode. Electrochemical behaviors of HRP on the modified electrode were carefully investigated. The HRP modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid with wider linear range and lower detection limit. Therefore the presence of NiO nanoflower could provide a friendly biocompatible interface for immobilizing biomolecules and keeping their native structure. The fabricated electrochemical biosensor displayed the advantages such as high sensitivity, good reproducibility and long-term stability. This work is licensed under a Creative Commons Attribution 4.0 International License.

  2. High Electrocatalytic Activity of Vertically Aligned Single-Walled Carbon Nanotubes towards Sulfide Redox Shuttles.

    Science.gov (United States)

    Hao, Feng; Dong, Pei; Zhang, Jing; Zhang, Yongchang; Loya, Phillip E; Hauge, Robert H; Li, Jianbao; Lou, Jun; Lin, Hong

    2012-01-01

    Vertically aligned single-walled carbon nanotubes (VASWCNTs) have been successfully transferred onto transparent conducting oxide glass and implemented as efficient low-cost, platinum-free counter electrode in sulfide -mediated dye-sensitized solar cells (DSCs), featuring notably improved electrocatalytic activity toward thiolate/disulfide redox shuttle over conventional Pt counter electrodes. Impressively, device with VASWCNTs counter electrode demonstrates a high fill factor of 0.68 and power conversion efficiency up to 5.25%, which is significantly higher than 0.56 and 3.49% for that with a conventional Pt electrode. Moreover, VASWCNTs counter electrode produces a charge transfer resistance of only 21.22 Ω towards aqueous polysulfide electrolyte commonly applied in quantum dots-sensitized solar cells (QDSCs), which is several orders of magnitude lower than that of a typical Pt electrode. Therefore, VASWCNTs counter electrodes are believed to be a versatile candidate for further improvement of the power conversion efficiency of other iodine-free redox couple based DSCs and polysulfide electrolyte based QDSCs.

  3. Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

    International Nuclear Information System (INIS)

    Lohrasbi, Elaheh; Javanbakht, Mehran; Mozaffari, Sayed Ahmad

    2017-01-01

    Highlights: • SO_3H-graphene supported PtFeCo alloy nanoparticles were prepared. • Co:Fe atomic ratio plays important role in the electrocatalytic performance. • PtCoFe/SG with 7:3 Co:Fe atomic ratio is optimized for PEMFCs. • Power density of 530 mW cm"−"2 with 0.1 mg cm"−"2 Pt loading was obtained at 75 °C. - Abstract: The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO_3− groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm"−"2 Pt) reaches to a maximum of 530 mW cm"−"2 at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

  4. The electrocatalytic reduction of nitrate in water on Pd/Sn-modified activated carbon fiber electrode.

    Science.gov (United States)

    Wang, Ying; Qu, Jiuhui; Wu, Rongcheng; Lei, Pengju

    2006-03-01

    The Pd/Sn-modified activated carbon fiber (ACF) electrodes were successfully prepared by the impregnation of Pd2+ and Sn2+ ions onto ACF, and their electrocatalytic reduction capacity for nitrate ions in water was evaluated in a batch experiment. The electrode was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and temperature programmed reduction (TPR). The capacity for nitrate reduction depending on Sn content on the electrode and the pH of electrolyte was discussed at length. The results showed that at an applied current density of 1.11 mA cm(-2), nitrate ions in water (solution volume: 400 mL) were reduced from 110 to 3.4 mg L(-1) after 240 min with consecutive change of intermediate nitrite. Ammonium ions and nitrogen were formed as the main final products. The amount of other possible gaseous products (including NO and N2O) was trace. With the increase of Sn content on the Pd/Sn-modified ACF electrode, the activity for nitrate reduction went up to reach a maximum (at Pd/Sn = 4) and then decreased, while the selectivity to N2 was depressed. Higher pH value of electrolyte exhibited more suppression effect on the reduction of nitrite than that of nitrate. However, no significant influence on the final ammonia formation was observed. Additionally, Cu ion in water was found to cover the active sites of the electrode to make the electrode deactivated.

  5. Electrocatalytic activity of carbon-supported catalysts for direct ethanol fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez Varela, F.J. [CINVESTAV-Unidad Saltillo, Coahuila, (Mexico). Grupo de Investigacion en Energia; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

    2008-07-01

    Proton exchange membrane fuel cells (PEMFCs) can be fueled with hydrogen, alcohols, hydrocarbons and acetals. Ethanol is an important fuel candidate because it can be electro-oxidized to carbon dioxide on platinum (Pt)-based electrocatalysts in a direct ethanol fuel cell (DEFC) at relatively low temperatures. This study investigated the electrocatalytic activity of some carbon-supported electrocatalysts towards the ethanol oxidation (EOR) and the oxygen reduction reaction (ORR) in the presence of ethanol. Compared to other anode catalysts such as Pt, PtRu and Pt oxide, anodes based on PtSn alloys have a higher catalytic activity for the EOR. When tested in a DEFC, the current density at 0.4V and 90 degrees C based on a PtSn/C anode and a Pt/C cathode was 2 times higher than that of a cell based on a PtRu/C-Pt/C membrane electrode assembly (MEA) configuration. In addition, cathode catalysts based on Ru/C had good catalytic activity for the ORR and exhibited high selectivity for this reaction in the presence of ethanol. The results showed that in the presence of 0.125, 0.25 or 0.5 M ethanol concentrations, a decrease in onset potential of about 60, 62 and 68 mV emerged, respectively. These values were about 10 times lower than those measured for some Pt-based cathode catalysts tested in this study in the presence of 0.125 M EtOH. 20 refs., 5 figs.

  6. Co-N-macrocyclic modified graphene with excellent electrocatalytic activity for lithium-thionyl chloride batteries

    International Nuclear Information System (INIS)

    Li, Bimei; Yuan, Zhongzhi; Xu, Ying; Liu, Jincheng

    2016-01-01

    Highlights: • A Co-N-graphene catalyst composed of CoN 4 -macrocyclic-like (CoN x ) structure is synthesized. • Co-N x -Graphene has effective electrocatalytic activity for Li/SOCl 2 batteries. • The storage stability of the catalyst is attributed to its insolubility in electrolyte. - Abstract: A mixture of cobalt phthalocyanine (CoPc) and graphene is thermally decomposed at 800 °C to synthesize a novel catalyst. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) show that the catalyst retains the lamellar structure of graphene. X-ray diffraction (XRD) reveals that the catalyst is no longer composed of CoPc and high-resolution TEM (HRTEM), X-ray photoelectron spectra (XPS) prove that Co and N elements have entered the graphene molecular structure, thus forming a Co-N x -graphene (Co-N x -G) catalyst composed of a CoN 4 -macrocyclic-like structure. This catalyst serves as an excellent catalyst of thionyl chloride (SOCl 2 ) reduction. Cyclic voltammetry and battery discharge tests reveal that Co-N x -G-800 substantially increases the discharge voltage and capacity of a Li/SOCl 2 battery. Moreover, Co-N x -G-800 exhibits stable catalytic activity during battery storage. Ultraviolet–visible spectroscopy shows that CoPc is soluble in a SOCl 2 electrolyte solution, whereas Co-N x -G-800 is not, this characteristic contributes to the stable catalytic property of Co-N x -G.

  7. Durable electrocatalytic-activity of Pt-Au/C cathode in PEMFCs.

    Science.gov (United States)

    Selvaganesh, S Vinod; Selvarani, G; Sridhar, P; Pitchumani, S; Shukla, A K

    2011-07-21

    Longevity remains as one of the central issues in the successful commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and primarily hinges on the durability of the cathode. Incorporation of gold (Au) to platinum (Pt) is known to ameliorate both the electrocatalytic activity and stability of cathode in relation to pristine Pt-cathodes that are currently being used in PEMFCs. In this study, an accelerated stress test (AST) is conducted to simulate prolonged fuel-cell operating conditions by potential cycling the carbon-supported Pt-Au (Pt-Au/C) cathode. The loss in performance of PEMFC with Pt-Au/C cathode is found to be ∼10% after 7000 accelerated potential-cycles as against ∼60% for Pt/C cathode under similar conditions. These data are in conformity with the electrochemical surface-area values. PEMFC with Pt-Au/C cathode can withstand >10,000 potential cycles with very little effect on its performance. X-ray diffraction and transmission electron microscopy studies on the catalyst before and after AST suggest that incorporating Au with Pt helps mitigate aggregation of Pt particles during prolonged fuel-cell operations while X-ray photoelectron spectroscopy reflects that the metallic nature of Pt is retained in the Pt-Au catalyst during AST in comparison to Pt/C that shows a major portion of Pt to be present as oxidic platinum. Field-emission scanning electron microscopy conducted on the membrane electrode assembly before and after AST suggests that incorporating Au with Pt helps mitigating deformations in the catalyst layer. This journal is © the Owner Societies 2011

  8. Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability.

    Science.gov (United States)

    Li, Yifeng; Zhang, Wenqiang; Zheng, Yun; Chen, Jing; Yu, Bo; Chen, Yan; Liu, Meilin

    2017-10-16

    Solid oxide cell (SOC) based energy conversion systems have the potential to become the cleanest and most efficient systems for reversible conversion between electricity and chemical fuels due to their high efficiency, low emission, and excellent fuel flexibility. Broad implementation of this technology is however hindered by the lack of high-performance electrode materials. While many perovskite-based materials have shown remarkable promise as electrodes for SOCs, cation enrichment or segregation near the surface or interfaces is often observed, which greatly impacts not only electrode kinetics but also their durability and operational lifespan. Since the chemical and structural variations associated with surface enrichment or segregation are typically confined to the nanoscale, advanced experimental and computational tools are required to probe the detailed composition, structure, and nanostructure of these near-surface regions in real time with high spatial and temporal resolutions. In this review article, an overview of the recent progress made in this area is presented, highlighting the thermodynamic driving forces, kinetics, and various configurations of surface enrichment and segregation in several widely studied perovskite-based material systems. A profound understanding of the correlation between the surface nanostructure and the electro-catalytic activity and stability of the electrodes is then emphasized, which is vital to achieving the rational design of more efficient SOC electrode materials with excellent durability. Furthermore, the methodology and mechanistic understanding of the surface processes are applicable to other materials systems in a wide range of applications, including thermo-chemical photo-assisted splitting of H 2 O/CO 2 and metal-air batteries.

  9. Electrocatalytic Activity of Carbonized Nanostructured Polyanilines for Oxidation Reactions: Sensing of Nitrite Ions and Ascorbic Acid

    International Nuclear Information System (INIS)

    Micić, Darko; Šljukić, Biljana; Zujovic, Zoran; Travas-Sejdic, Jadranka; Ćirić-Marjanović, Gordana

    2014-01-01

    Highlights: • Carbonized PANIs prepared from various nanostructured PANI precursors • Electroanalytical performances of carbonized PANIs evaluated using voltammetry • Study of carbonized PANIs physico-chemical properties related to electroactivity • The lowest over-potential for NO 2 − oxidation at c-PANI (+0.87 V vs. SCE) • The lowest over-potential for ascorbic acid oxidation at both c-PANI and c-PANI-SSA - Abstract: A comparative study of the electrocatalytic activity of nitrogen-containing carbon nanomaterials, prepared by the carbonization of nanostructured polyaniline (PANI) salts, for the electrooxidation reactions is presented. Nanostructured PANI salts were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous solution in the presence of 5-sulfosalicylic acid (PANI-SSA), 3,5-dinitrosalicylic acid (PANI-DNSA) as well as without added acid (PANI), and subsequently carbonized to c-PANI-SSA, c-PANI-DNSA and c-PANI, respectively. Glassy carbon tip was modified with nanostructured c-PANIs and used for the investigation of sensing of nitrite and ascorbic acid in aqueous solutions as model analytes by linear sweep voltammetry. All three types of the investigated c-PANIs gave excellent response to the nitrite ions and ascorbic acid electrooxidation. The lowest peak potential for nitrite ion oxidation exhibited c-PANI (+0.87 V vs. SCE), and for ascorbic acid oxidation both c-PANI and c-PANI-SSA (ca. + 0.13 V vs. SCE). Electrochemical data were correlated with structural and textural data obtained by Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, elemental and nitrogen sorption analysis

  10. The Synthesis and Electrocatalytic Activities of Molybdenum Sulfide for Hydrogen Evolution Reaction

    KAUST Repository

    Li, Zhengxing

    2014-07-01

    In the context of the future hydrogen economy, effective production of hydrogen (H2) from readily available and sustainable resources is of crucial importance. Hydrogen generation via water splitting by solar energy or electricity has attracted great attention in recent years. In comparison with photocatalytic water-splitting directly using solar light, which is ideal but the relevant technologies are not yet mature, electrolysis of water with catalyst is more practical at the current stage. The Pt-group noble metals are the most effective electrocatalysts for hydrogen evolution reaction (HER) from water, but their high costs limit their applications. Due to the earth-abundance and low price, MoS2 is expected to be a good alternative of the Pt-group metals for HER. Plenty of researches have been conducted for improving the HER activities of MoS2 by optimizing its synthesis method. However, it remains challenging to prepare MoS2 catalysts with high and controllable activity, and more investigations are still needed to better understand the structure-performance correlation in this system. In this thesis, we report a new strategy for fabricating MoS2 eletrocatalysts which gives rise to much improved HER performance and allows us to tune the electrocatalytic activity by varying the preparation conditions. Specifically, we sulfurized molybdenum oxide on the surface of a Ti foil electrode via a facile chemical vapor deposition (CVD) method, and directly used the electrode for HER testing. Depending on the CVD temperature, the MoO2-MoS2 nanocomposites show different HER activities. Under the optimal synthesis condition (400ºC), the resulting catalyst exhibited excellent HER activity: an onset potential (overpotential) of 0.095 V versus RHE and the Tafel slope of 40 mv/dec. Such a performance exceeds those of most reported MoS2 based HER electrocatalysts. We demonstrated that the CVD temperature has significant influence on the catalysts in crystallinity degree, particle

  11. Polymer-mediated synthesis of a nitrogen-doped carbon aerogel with highly dispersed Pt nanoparticles for enhanced electrocatalytic activity

    International Nuclear Information System (INIS)

    2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" data-affiliation=" (World Class University (WCU) Program of Chemical Convergence for Energy & Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" >Kim, Gil-Pyo; 2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" data-affiliation=" (World Class University (WCU) Program of Chemical Convergence for Energy & Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" >Lee, Minzae; Lee, Yoon Jae; 2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" data-affiliation=" (World Class University (WCU) Program of Chemical Convergence for Energy & Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" >Bae, Seongjun; 2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" data-affiliation=" (World Class University (WCU) Program of Chemical Convergence for Energy & Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" >Song, Hyeon Dong; Song, In Kyu; 2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" data-affiliation=" (World Class University (WCU) Program of Chemical Convergence for Energy & Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), Seoul 151-742 (Korea, Republic of))" >Yi, Jongheop

    2016-01-01

    Highlights: • Highly dispersed Pt nanoparticles on N-doped carbon aerogel were synthesized for ORR. • Poly(ethyleneimine) was used as nitrogen source and as nucleation sites for Pt. • Precise discussion were conducted to clarify the effect of poly(ethyleneimine). • High Pt dispersion and N-doping results in superior electrocatalytic activity. - Abstract: A simple chemical process for the direct synthesis of a nitrogen (N)-doped carbon aerogel (NCA) with highly dispersed Pt nanoparticles via a poly(ethyleneimine) (PEI)-assisted strategy is described. A resorcinol-formaldehyde (RF) gel was treated with water soluble cationic PEI, which mainly functions as an anchoring site for metal ions. The functionalized PEI chains on the surface of the RF gel resulted in the unique formation of chemical complexes, with PtCl 6 2− anchored to the RF gel, and subsequent homogeneous metal nanoparticle growth. The abundant amino groups containing PEI grafted to the RF gel also allowed the nitrogen atoms to be incorporated into the carbon framework, which can directly be converted into a NCA. The spherical Pt nanoparticles in the resulting material (Pt/NCA) were highly dispersed on the surface of the NCA without any evidenced of agglomeration, even after a thermal annealing at 900 °C. Compared with a Pt/CA synthesized by a conventional reduction method, the Pt/NCA showed enhanced electrochemical performance with a high electrochemically active surface area (191.1 cm 2 g −1 ) and electrocatalytic activity (V onset = 0.95 V vs. RHE) with respect to oxygen reduction. The superior electrocatalytic activities of the Pt/NCA can be attributed to the synergistic effect of the highly dispersed Pt nanoparticles and the N-doped carbon supports that were prepared using the PEI-assisted strategy. The findings reported herein suggest that the use of PEI can be effectively extended to broad applications that require the homogeneous deposition of metal nanoparticles.

  12. PdM (M = Pt, Au) bimetallic alloy nanowires with enhanced electrocatalytic activity for electro-oxidation of small molecules.

    Science.gov (United States)

    Zhu, Chengzhou; Guo, Shaojun; Dong, Shaojun

    2012-05-02

    A facile and general method has been developed to synthesize well-defined PdPt and PdAu alloy nanowires, which exhibit significantly enhanced activity towards small molecules, such as ethanol, methanol, and glucose electro-oxidation in an alkaline medium. Considering the important role of one-dimensional alloy nanowires in electrocatalytic systems, the present Pd-based alloy nanostructures could offer a promising new class of advanced electrocatalysts for direct alcohol fuel cells and electrochemical sensors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    International Nuclear Information System (INIS)

    Abdel Hameed, R.M.; Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M.

    2015-01-01

    Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO_2/C-1 and Pt–MnO_2/C-2 electrocatalysts. - Highlights: • Adding MnO_2 to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO_2 improved the kinetics of methanol oxidation reaction. • R_c_t value of Pt–MnO_2/C was about 10 times as low as that at Pt/C. • The removal of CO_a_d_s poisoning species was facilitated at Pt–MnO_2/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO_2/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO_2 improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO_2/C towards methanol oxidation in H_2SO_4 solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO_2 is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO_2/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO_2/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  14. {331}-Faceted trisoctahedral gold nanocrystals: synthesis, superior electrocatalytic performance and highly efficient SERS activity

    Science.gov (United States)

    Song, Yahui; Miao, Tingting; Zhang, Peina; Bi, Cuixia; Xia, Haibing; Wang, Dayang; Tao, Xutang

    2015-04-01

    We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by using 3.0 nm CTAC-Au seeds or as-prepared 70 nm TOH Au NCs as seeds. We find that the electrocatalytic performance on methanol oxidation and surface enhancement Raman spectroscopy (SERS) activity of {331}-faceted TOH Au NCs is size-dependent. In comparison with well-known nanoporous gold (0.088 mA cm-2), {331}-faceted TOH Au NCs with sizes of 110 nm exhibit fairly high catalytic activity (0.178 mA cm-2) on methanol oxidation (1.0 M) in alkaline media due to the presence of increasing density of atomic steps, ledges, and kinks on the NC surfaces. Their current density is reduced by less than 7% after 500 cycling tests. {331}-Faceted TOH Au NCs with sizes of 175 nm exhibit the highest SERS activity for 4-aminothiophenol (4-ATP) molecules. The enhancement factors of a1 modes of 4-ATP molecules can reach the order of 109 when the 4-ATP concentration is 3 × 10-6 M. Moreover, Raman signals (ag modes) of 4,4'-dimercaptoazobenzene (DMAB) molecules on TOH Au NCs are stronger than those on spherical Au NCs of comparable size due to the enhanced laser-induced transformation of 4-ATP molecules by high-index {331}-facets during SERS measurement. Furthermore, the SERS intensities of 4-methylbenzenethiol (4-MTP) molecules on TOH Au NCs are also higher than those on spherical Au NCs of comparable size due to sharp extremities.We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by

  15. Two Water Stable Copper Metal-Organic Frameworks with Performance in the Electrocatalytic Activity for Water Oxidation

    Directory of Open Access Journals (Sweden)

    Liu Xiuping

    2018-01-01

    Full Text Available Two novel water stable metal-organic frameworks, [Cu(L·(4,4′-bipy·(ClO4]n (1, [Cu(L·(phen·(ClO4·(H2O]2 (2, have been constructed by HL=[5-Mercapto-1-methyl] tetrazole acetic acid and Cu (II salt in the presence of assistant N-containing ligands. MOF 1 and MOF 2 with open CuII sites, resulting the framework 1 and 2 show electrocatalytic activity for water oxidation in alkaline solution. The electrochemical properties of complex for oxygen evolution reaction (OER were evaluated by linear sweep voltammetry (LSV and the Tafel slopes. Complex 1 has a higher LSV activity with a lower over potential of 1.54 V and a much higher increase in current density. Meanwhile, the Tafel slope of complex 1 (122.0 mV dec-1 is much lower than complex 2 (243.5 mV dec-1. This phenomenon makes complex 1 a promising porous material for electrocatalytic activity.

  16. Synthesis and Electrocatalytic Activity of Ammonium Nickel Phosphate, [NH4]NiPO4·6H2O, and β-Nickel Pyrophosphate, β-Ni2P2O7: Catalysts for Electrocatalytic Decomposition of Urea.

    Science.gov (United States)

    Meguerdichian, Andrew G; Jafari, Tahereh; Shakil, Md R; Miao, Ran; Achola, Laura A; Macharia, John; Shirazi-Amin, Alireza; Suib, Steven L

    2018-02-19

    Electrocatalytic decomposition of urea for the production of hydrogen, H 2, for clean energy applications, such as in fuel cells, has several potential advantages such as reducing carbon emissions in the energy sector and environmental applications to remove urea from animal and human waste facilities. The study and development of new catalyst materials containing nickel metal, the active site for urea decomposition, is a critical aspect of research in inorganic and materials chemistry. We report the synthesis and application of [NH 4 ]NiPO 4 ·6H 2 O and β-Ni 2 P 2 O 7 using in situ prepared [NH 4 ] 2 HPO 4 . The [NH 4 ]NiPO 4 ·6H 2 O is calcined at varying temperatures and tested for electrocatalytic decomposition of urea. Our results indicate that [NH 4 ]NiPO 4 ·6H 2 O calcined at 300 °C with an amorphous crystal structure and, for the first time applied for urea electrocatalytic decomposition, had the greatest reported electroactive surface area (ESA) of 142 cm 2 /mg and an onset potential of 0.33 V (SCE) and was stable over a 24-h test period.

  17. Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

    Energy Technology Data Exchange (ETDEWEB)

    Lohrasbi, Elaheh [Department of Chemistry, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Javanbakht, Mehran, E-mail: mehranjavanbakht@gmail.com [Department of Chemistry, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Fuel and Solar Cell Lab, Renewable Energy Research Center, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Mozaffari, Sayed Ahmad [Fuel and Solar Cell Lab, Renewable Energy Research Center, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Thin Layer and Nanotechnology Laboratory, Department of Chemical Technology, Iranian Research Organization for Science and Technology (IROST), Tehran (Iran, Islamic Republic of)

    2017-06-15

    Highlights: • SO{sub 3}H-graphene supported PtFeCo alloy nanoparticles were prepared. • Co:Fe atomic ratio plays important role in the electrocatalytic performance. • PtCoFe/SG with 7:3 Co:Fe atomic ratio is optimized for PEMFCs. • Power density of 530 mW cm{sup −2} with 0.1 mg cm{sup −2} Pt loading was obtained at 75 °C. - Abstract: The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO{sub 3}− groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm{sup −2} Pt) reaches to a maximum of 530 mW cm{sup −2} at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

  18. Immobilization of platinum nanoparticles on 3,4-diaminobenzoyl-functionalized multi-walled carbon nanotube and its electrocatalytic activity

    International Nuclear Information System (INIS)

    Choi, Hyun-Jung; Kang, Ji-Ye; Jeon, In-Yup; Eo, Soo-Mi; Tan, Loon-Seng; Baek, Jong-Beom

    2012-01-01

    Multi-walled carbon nanotubes (MWCNTs) are functionalized at the sp 2 C–H defect sites with 3,4-diaminobenzoic acid by a “direct” Friedel–Crafts acylation reaction in a mild polyphosphoric acid/phosphorous pentoxide medium. Owing to enhanced surface polarity, the resulting 3,4-diaminobenzoyl-functionalized MWCNTs (DAB-MWCNT) are highly dispersible in polar solvents, such as ethanol, N-methyl-2-pyrrolidone, and methanesulfonic acid. The absorption and emission properties of DAB-MWCNT in solution state are qualitatively shown to be sensitive to the pH in the environment. The DAB-MWCNT is used as a stable platform on which to deposit platinum nanoparticles (PNP). The PNP/DAB-MWCNT hybrid displays high electrocatalytic activity with good electrochemical stability for an oxygen reduction reaction under an alkaline condition.Graphical AbstractMulti-walled carbon nanotubes (MWCNTs) were functionalized with 3,4-diaminobenzoic acid to produce 3,4-diaminobenzoyl-functionalized MWCNT (DAB-MWCNT). Platinum nanoparticles (PNP) were deposited to DAB-MWCNT. The resulting PNP/DAB-MWCNT hybrid displayed high electrocatalytic activity.

  19. Significant promotion effect of carbon nanotubes on the electrocatalytic activity of supported Pd NPs for ethanol oxidation reaction of fuel cells: the role of inner tubes.

    Science.gov (United States)

    Zhang, Jin; Cheng, Yi; Lu, Shanfu; Jia, Lichao; Shen, Pei Kang; Jiang, San Ping

    2014-11-18

    The inner tubes of carbon nanotubes (CNTs) have a significant promotion effect on the electrocatalytic activity of Pd nanoparticles (NPs) for the ethanol oxidation of direct alcohol fuel cells (DAFCs) and Pd NPs supported on CNTs with 3-7 walls show a much higher activity as compared to that supported on typical single-walled and multi-walled CNTs.

  20. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    Energy Technology Data Exchange (ETDEWEB)

    Abdel Hameed, R.M., E-mail: randa311eg@yahoo.com [Chemistry Department, Faculty of Science, Cairo University, Giza (Egypt); Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M. [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt)

    2015-12-30

    Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO{sub 2}/C-1 and Pt–MnO{sub 2}/C-2 electrocatalysts. - Highlights: • Adding MnO{sub 2} to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO{sub 2} improved the kinetics of methanol oxidation reaction. • R{sub ct} value of Pt–MnO{sub 2}/C was about 10 times as low as that at Pt/C. • The removal of CO{sub ads} poisoning species was facilitated at Pt–MnO{sub 2}/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO{sub 2}/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO{sub 2} improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO{sub 2}/C towards methanol oxidation in H{sub 2}SO{sub 4} solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO{sub 2} is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO{sub 2}/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO{sub 2}/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  1. Radiolytic synthesis and electrocatalytic activity of bimetallic nanoaggregates grafted upon various electrodes

    International Nuclear Information System (INIS)

    Amblard, J.; Belloni, J.; Platzer, O.

    1991-01-01

    We show how to utilize the radiolytic pathway for grafting metal nanoaggregates upon anodes or cathodes involved in the chlorine-soda process, thus enhancing their electrochemical behaviour. In both cases important overpotentials are usually measured on unmodified electrodes. The electrocatalytic efficiency of bimetallic nanoparticles (such as Pt-Ru and Ni-Ru), once grafted onto bulk metal electrodes (Ti or Ni), has been investigated by measuring the overpotential for chlorine or hydrogen evolution, respectively. Experimental conditions are similar to those of the industrial process. A synergistic effect is shown when Pt and Ru are alloyed in a 2: 1 atomic ratio. Then the chlorine overpotential is minimum. Conversely, there is no synergy between Ni and Ru, although a minimum amount of Ru in Ru-Ni (50% atomic) ensures a very low hydrogen overpotential [fr

  2. Ultrafast synthesis of flower-like ordered Pd3Pb nanocrystals with superior electrocatalytic activities towards oxidation of formic acid and ethanol

    Science.gov (United States)

    Jana, Rajkumar; Subbarao, Udumula; Peter, Sebastian C.

    2016-01-01

    Ordered intermetallic nanocrystals with high surface area are highly promising as efficient catalysts for fuel cell applications because of their unique electrocatalytic properties. The present work discusses about the controlled synthesis of ordered intermetallic Pd3Pb nanocrystals in different morphologies at relatively low temperature for the first time by polyol and hydrothermal methods both in presence and absence of surfactant. Here for the first time we report surfactant free synthesis of ordered flower-like intermetallic Pd3Pb nanocrystals in 10 s. The structural characteristics of the nanocrystals are confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. The as synthesized ordered Pd3Pb nanocrystals exhibit far superior electrocatalytic activity and durability towards formic acid and ethanol oxidation over commercially available Pd black (Pd/C). The morphological variation of nanocrystals plays a crucial role in the electrocatalytic oxidation of formic acid and ethanol. Among the catalysts, the flower-like Pd3Pb shows enhanced activity and stability in electrocatalytic formic acid and ethanol oxidation. The current density and mass activity of flower-like Pd3Pb catalyst are higher by 2.5 and 2.4 times than that of Pd/C for the formic acid oxidation and 1.5 times each for ethanol oxidation.

  3. Facile Electrodeposition of Flower-Like PMo12-Pt/rGO Composite with Enhanced Electrocatalytic Activity towards Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Xiaoying Wang

    2015-07-01

    Full Text Available A facile, rapid and green method based on potentiostatic electrodeposition is developed to synthesize a novel H3PMo12O40-Pt/reduced graphene oxide (denoted as PMo12-Pt/rGO composite. The as-prepared PMo12-Pt/rGO is characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM and X-ray photoelectron spectroscopy (XPS. The results reveal that graphene oxide (GO is reduced to the rGO by electrochemical method and POMs clusters are successfully located on the rGO as the modifier. Furthermore, the PMo12-Pt/rGO composite shows higher electrocatalytic activity, better tolerance towards CO and better stability than the conventional pure Pt catalyst.

  4. Pd/Co bimetallic nanoparticles: coelectrodeposition under protection of PVP and enhanced electrocatalytic activity for ethanol electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Z.S.; Wu, J.J. [College of Chemistry and Materials Science, Anhui Key Laboratory of Chemo-Biosensing, Anhui Normal University, Wuhu 241000 (China)

    2012-06-15

    A series of Pd-Co bimetallic nanostructures with Co compositions ranging from 0 to 13 at.% were fabricated on glassy carbon electrode by one step electrodeposition in the presence of polyvinylpyrrolidone (PVP). The roles of PVP and Co have been systematically investigated by using combined techniques such as scanning electron microscopy, energy dispersive spectrometry, cyclic voltammetry, X-ray diffraction, and chronoamperograms. PVP was used as an additive to stabilize the Pd nanoparticles and inhibit agglomeration during their formation. The prepared Pd{sub 100}Co{sub 10} bimetallic nanostructures exhibited great catalytic activity towards ethanol oxidation in alkaline, which implies that low Co doping can be a convenient way to enhance the electrocatalytic property of Pd. The present study shows that the Pd/Co bimetallic nanoparticulate can be a promising catalyst for portable applications in direct ethanol fuel cell in alkaline solution. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Enhanced electrocatalytic activity of graphene-gold nanoparticles hybrids for peroxynitrite electrochemical detection on hemin-based electrode.

    Science.gov (United States)

    Wang, Beibei; Ji, Xueping; Ren, Jujie; Ni, Ruixing; Wang, Lin

    2017-12-01

    A simple, ultrasensitive peroxynitrite anion (ONOO - ) electrochemical sensing platform was developed by immobilizing hemin on a density controllable electrochemically reduced graphene oxide-Au nanoparticles (ERGO-AuNPs) nanohybrids. The ERGO-AuNPs in situ nanohybrids were produced onto a glass carbon electrode (GCE) by one-step electrodeposition, the density of which could be easily controlled by electrodeposited time. The morphology of ERGO-AuNPs nanohybrids was characterized by a scanning electron microscope (SEM). The ERGO-AuNPs nanohybrids showed a high electrocatalytic activity for immobilized-hemin, because the nanostructures hybrids could effectively promote electron transfer rate between hemin and the electrode. Due to nanohybrids-enhanced catalytic effect for hemin, they were firstly selected for use as a highly sensitive electrochemical platform for ONOO - detection. The resulted sensor showed a high electrocatalytic activity toward ONOO - oxidation, being free from the electroactive interferents, including nitrite, nitrate, dopamine and uric acid at an applied potential of 0.7V. The sensor exhibited a high sensitivity of 123.1nAμM -1 and a lower detection limit of 0.1μM, and a wide linear range of 2.4×10 -6 to 5.5×10 -5 M, which could be attributed to the synergy between ERGO and AuNPs in hybrids. The nanohybrids in situ preparation and ONOO - detection methods would be beneficial to developing other sensing interface and have promising applications in biological molecules analysis and clinical diagnostic. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Incorporation of tantalum ions enhances the electrocatalytic activity of hexagonal WO3 nanowires for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Xie, Xiang; Mu, Wanjun; Li, Xingliang; Wei, Hongyuan; Jian, Yuan; Yu, Qianhong; Zhang, Rui; Lv, Kai; Tang, Hui; Luo, Shunzhong

    2014-01-01

    WO 3 has been identified as a promising candidate electrocatalyst for hydrogen evolution reaction (HER), because it can form a tungsten bronze (HxWO 3 ) which is highly electron and proton conducting. In this paper, we report that the electrocatalytic activity of WO 3 for HER can be enhanced by incorporation of tantalum ions (Ta 5+ ) into the lattice of WO 3 . The most active performance is achieved with the molar ratio of Ta/W being 0.01, which is two times more active than that of undoped WO 3 at an overpotential of -0.52 V. It is shown that incorporation of proper Ta 5+ into WO 3 can induce moderate defects and oxygen vacancies, as well as intercalate a higher amount of protons, which enhance the electron transfer and short the protons diffusion paths. These changes correlated positively with the enhanced catalytic HER activity. This study demonstrates, for the first time, that metal ions-doped WO 3 nanowires are promising electrocatalysts for HER

  7. Improving the electrocatalytic performance of carbon nanotubes for VO"2"+/VO_2"+ redox reaction by KOH activation

    International Nuclear Information System (INIS)

    Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

    2017-01-01

    Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO"2"+/VO_2"+ redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO"2"+/VO_2"+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO"2"+/VO_2"+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO"2"+/VO_2"+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO"2"+/VO_2"+ redox reaction for VRFB system.

  8. The self-activation and synergy of amorphous Re nanoparticle – Si nanowire composites for the electrocatalytic hydrogen evolution

    International Nuclear Information System (INIS)

    Yang, Lulu; Lu, Shunkai; Wang, Hui; Shao, Qi; Liao, Fan; Shao, Mingwang

    2017-01-01

    Highlights: • Amorphous Re nanoparticle modified Si nanowire nanocomposites were prepared. • An interesting self-activation phenomenon was observed in HER process. • Re/SiNW showed synergy in HER process. • The optimal mass ratio of Re: Si was determined to be 31.1: 68.9. - Abstract: Amorphous rhenium nanoparticles modified silicon nanowires were prepared via reducing Re ion by Si−H bonds, which were employed to electrocatalysize the hydrogen evolution reaction because amorphous structure may have excellent catalytic activity. It is interesting that an obvious self-activation for Re/Si catalysts was observed with the current density enhanced by 2.2 times its previous value at 400 mV after a 3,000 s of continuous cyclic voltammetry scanning, and the catalytic performance remained steady thereafter. The optimal electrocatalytic performance was found with the Re: Si mass ratio of 31.1: 68.9, resulting in a Tafel slope of 81 mV·dec −1 and overpotential of 100 mV at current density of 10 mA·cm −2 .

  9. Facile Synthesis of Pt Nanoparticle and Graphene Composite Materials: Comparison of Electrocatalytic Activity with Analogous CNT Composite

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jihye; Jang, Ho Young; Jung, Insub; Yoon, Yeoheung; Jang, Heejeong; Lee, Hyoyoung; Park, Sungho [Sungkyunkwan Univ., Suwon (Korea, Republic of)

    2014-07-15

    Here, we present a facile method to synthesize Pt nanoparticles (NPs) and graphene composite materials (Pt/G) via vacuum filtration. Anodic aluminum oxide (AAO) templates were used to separate Pt/G composite and liquid phase. This method can be used to easily tune the mass ratio of Pt NPs and graphene. Pt NPs, graphene, and carbon nanotubes (CNTs) as building blocks were characterized by a variety of techniques such as scanning electron microscopy, UV-Vis spectroscopy, and Raman spectroscopy. We compared the electrocatalytic activities of Pt/G with Pt NP and CNT films (Pt/CNT) by cyclic voltammetry (CV), CO oxidation, and methanol oxidation. Pt/G was much more stable than pure Pt films. Also, Pt/G had better electrochemical activity, CO tolerance and methanol oxidation than Pt/CNT loaded with the same amount of Pt NPs due to the better dispersion of Pt NPs on graphene flakes without aggregation. We further synthesized Au Pt disk/G and Pt nanorods/G to determine if our synthetic method can be applied to other NP shapes such as nanodisks and nanorods, for further electrocatalysis studies.

  10. Co/N–C nanotubes with increased coupling sites by space-confined pyrolysis for high electrocatalytic activity

    Directory of Open Access Journals (Sweden)

    Jun Yang

    2017-01-01

    Full Text Available Searching low cost and non-precious metal catalysts for high-performance oxygen reduction reaction is highly desired. Herein, Co nanoparticles embedded in nitrogen-doped carbon (Co/N–C nanotubes with internal void space are successfully synthesized by space-confined pyrolysis, which effectively improve the cobalt loading content and restrict the encapsulated particles down to nanometer. Different from the typical conformal carbon encapsulation, the resulting Co/N–C nanotubes possess more cobalt nanoparticles embedded in the nanotubes, which can provide more coupling sites and active sites in the oxygen reduction reaction (ORR. Moreover, the one-dimensional and porous structure provides a high surface area and a fast electron transfer pathway for the ORR. And the Co/N–C electrode presents excellent electrocatalytic ORR activity in terms of low onset potential (30 mV lower than that of Pt/C, small Tafel slop (45.5 mV dec−1 and good durability (88.5% retention after 10,000 s. Keywords: Co nanoparticles, Nitrogen-doped carbon nanotubes, Oxygen reduction reaction

  11. Indented Cu2MoS4 nanosheets with enhanced electrocatalytic and photocatalytic activities realized through edge engineering.

    Science.gov (United States)

    Chen, Bang-Bao; Ma, De-Kun; Ke, Qing-Ping; Chen, Wei; Huang, Shao-Ming

    2016-03-07

    Edges often play a role as active centers for catalytic reactions in some nanomaterials. Therefore it is highly desirable to enhance catalytic activity of a material through modulating the microstructure of the edges. However, the study associated with edge engineering is less investigated and still at its preliminary stage. Here we report that Cu2MoS4 nanosheets with indented edges can be fabricated through a simple chemical etching route at room temperature, using Cu2MoS4 nanosheets with flat ones as sacrifice templates. Taking the electrocatalytic hydrogen evolution reaction (HER), photocatalytic degradation of rhodamine B (RhB) and conversion of benzyl alcohol as examples, the catalytic activity of Cu2MoS4 indented nanosheets (INSs) obtained through edge engineering was comparatively studied with those of Cu2MoS4 flat nanosheets (FNSs) without any modification. The photocatalytic tests revealed that the catalytic active sites of Cu2MoS4 nanosheets were associated with their edges rather than basal planes. Cu2MoS4 INSs were endowed with larger electrochemically active surface area (ECSA), more active edges and better hydrophilicity through the edge engineering. As a result, the as-fabricated Cu2MoS4 INSs exhibited an excellent HER activity with a small Tafel slope of 77 mV dec(-1), which is among the best records for Cu2MoS4 catalysts. The present work demonstrated the validity of adjusting catalytic activity of the material through edge engineering and provided a new strategy for designing and developing highly efficient catalysts.

  12. One-pot synthesis of Pd-Pt@Pd core-shell nanocrystals with enhanced electrocatalytic activity for formic acid oxidation

    KAUST Repository

    Yuan, Qiang

    2014-01-01

    Well-defined Pd-Pt@Pd core-shell nanocrystals with a Pd-Pt alloy core and a conformal Pd shell of ~2-3 nm were directly synthesized through a one-pot, aqueous solution approach without any preformed Pd or Pt seeds. These Pd-Pt@Pd core-shell nanocrystals show an enhanced electrocatalytic activity for formic acid oxidation compared with commercial Pd black. This journal is © 2014 The Royal Society of Chemistry.

  13. Dual-functional Pt-on-Pd supported on reduced graphene oxide hybrids: peroxidase-mimic activity and an enhanced electrocatalytic oxidation characteristic.

    Science.gov (United States)

    Zhang, Xiahong; Wu, Genghuang; Cai, Zhixiong; Chen, Xi

    2015-03-01

    In this study, a facile hydrothermal method was developed to synthesize Pt-on-Pd supported on reduced graphene oxide (Pt-on-Pd/RGO) hybrids. Because of the synergistic effect between Pt-on-Pd and RGO, the obtained Pt-on-Pd/RGO had superior peroxidase-mimic activities in H2O2 reduction and TMB oxidation. The reaction medium was optimized and a sensing approach for H2O2 was developed with a linear range from 0.98 to 130.7 μM of H2O2. In addition, the characteristic of electrocatalytic oxidation of methanol was investigated. The peak current density value, j(f), for the Pt-on-Pd/RGO hybrid (328 mA mg(Pt)(-1)) was about 1.85 fold higher than that of commercial Pt black (177 mA mg(Pt)(-1)) and, also, more durable electrocatalytic activity could be obtained. For the first time, the dual-functional Pt-on-Pd/RGO with peroxidase-mimic activity and an enhanced electrocatalytic oxidation characteristic was reported. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Synthesis of flower-like gold nanoparticles and their electrocatalytic activity towards the oxidation of methanol and the reduction of oxygen.

    Science.gov (United States)

    Jena, Bikash Kumar; Raj, C Retna

    2007-03-27

    This article describes the synthesis of branched flower-like gold (Au) nanocrystals and their electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Gold nanoflowers (GNFs) were obtained by a one-pot synthesis using N-2-hydroxyethylpiperazine-N-2-ethanesulphonic acid (HEPES) as a reducing/stabilizing agent. The GNFs have been characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical measurements. The UV-visible spectra show two bands corresponding to the transverse and longitudinal surface plasmon (SP) absorption at 532 and 720 nm, respectively, for the colloidal GNFs. The GNFs were self-assembled on a sol-gel-derived silicate network, which was preassembled on a polycrystalline Au electrode and used for electrocatalytic applications. The GNFs retain their morphology on the silicate network; the UV-visible diffuse reflectance spectra (DRS) of GNFs on the silicate network show longitudinal and transverse bands as in the case of colloidal GNFs. The GNFs show excellent electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Oxidation of methanol in alkaline solution was observed at approximately 0.245 V, which is much less positive than that on an unmodified polycrystalline gold electrode. Reduction of oxygen to H2O2 and the further reduction of H2O2 to water in neutral pH were observed at less negative potentials on the GNFs electrode. The electrocatalytic activity of GNFs is significantly higher than that of the spherically shaped citrate-stabilized Au nanoparticles (SGNs).

  15. Visible-light-assisted SLCs template synthesis of sea anemone-like Pd/PANI nanocomposites with high electrocatalytic activity for methane oxidation in acidic medium

    Science.gov (United States)

    Tan, De-Xin; Wang, Yan-Li

    2018-03-01

    Sea anemone-like palladium (Pd)/polyaniline (PANI) nanocomposites were synthesized via visible-light-assisted swollen liquid crystals (SLCs) template method. The resulting samples were characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive spectrometer (EDS), x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet-visible (UV–vis) absorption spectroscopy and Fourier transform infrared (FT-IR) spectroscopy, respectively. The electrocatalytic properties of Pd/PANI nanocomposites modified glass carbon electrode (GCE) for methane oxidation were investigated by cycle voltammetry (CV) and chronoamperometry. Those dispersed sea anemone-like Pd/PANI nanocomposites had an average diameter of 320 nm. The obtained Pd nanoparticles with an average diameter of about 45 nm were uniformly distributed in PANI matrix. Sea anemone-like Pd/PANI nanocomposites exhibited excellent electrocatalytic activity and stability for oxidation of methane (CH4).

  16. Preparation, electrochemical behavior and electrocatalytic activity of chlorogenic acid multi-wall carbon nanotubes as a hydroxylamine sensor

    Energy Technology Data Exchange (ETDEWEB)

    Zare, Hamid R., E-mail: hrzare@yazduni.ac.ir; Nasirizadeh, Navid; Ajamain, Hamideh; Sahragard, Ali

    2011-07-20

    Electrochemical characteristics of an electrodeposited chlorogenic acid film on multi-wall carbon nanotubes glassy carbon electrode (CGA-MWCNT-GCE) and its role as a sensor for electrocatalytic oxidation of hydroxylamine are described. Cyclic voltammograms of the CGA-MWCNT-GCE indicate a pair of well-defined and nearly reversible redox couple with the surface confined characteristics at a wide pH range of 2.0-12.0. The charge transfer coefficient, {alpha}, and the charge transfer rate constant, k{sub s}, of CGA adsorbed on MWCNT were calculated 0.48 and 44 {+-} 2 s{sup -1} respectively. The CGA-MWCNT-GCE shows a dramatic increase in the peak current and/or a decrease in the overvoltage of hydroxylamine electrooxidation in comparison with that seen at a CGA modified GCE, MWCNT modified GCE and activated GCE. The kinetic parameters of electron transfer coefficient, {alpha}, the heterogeneous electron transfer rate constant, k', and exchange current, i{sub 0}, for oxidation of hydroxylamine at the modified electrode surface were determined using cyclic voltammetry. Four linear calibration ranges and high repeatability with relative standard deviation of 4.6%, for a series of four successive measurements in 17.7 {mu}M hydroxylamine, are obtained at the CGA-MWCNT-GCE using an amperometric method. Finally, the modified electrode was successfully used for determination of spiked hydroxylamine in two water samples.

  17. Engineering phase transformation of cobalt selenide in carbon cages and the phases’ bifunctional electrocatalytic activity for water splitting

    Science.gov (United States)

    Gao, Jiaojiao; Liu, Li; Qiu, Hua-Jun; Wang, Yu

    2017-08-01

    Using Co-based metal-organic frameworks as the precursor, we synthesized cobalt selenide (CoSe2) nanoparticles imbedded in carbon cages. By simply controlling the annealing conditions, phase transformation of CoSe2 from the orthorhombic phase to the cubic phase has been realized. Benefitting from the metallic character, the cubic phase CoSe2 shows greatly enhanced electrocatalytic activity for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). The as-prepared cubic phase CoSe2 electrode possesses onset overpotentials of 43 and 200 mV, and Tafel slopes of 51 and 83 mV dec-1 for HER and OER, respectively, which are remarkably superior to that of the orthorhombic phase CoSe2 catalyst and comparable to those of commercial noble-metal catalysts. In addition, the cubic phase CoSe2 electrode also demonstrates excellent stability after long-term operations. Our work not only provides a high performance catalyst for water splitting, but also introduces a new route to the design of a highly efficient catalyst by phase transformation.

  18. Enhanced electrocatalytic activity of reduced graphene oxide-Os nanoparticle hybrid films obtained at a liquid/liquid interface

    Science.gov (United States)

    Bramhaiah, K.; Pandey, Indu; Singh, Vidya N.; Kavitha, C.; John, Neena S.

    2018-03-01

    Hybrid films of reduced graphene oxide-osmium nanoparticles (rGO-Os NPs) synthesized at a liquid/liquid interface are explored for their electrocatalytic activity towards the oxidation of rhodamine B (RhB), a popular colourant found in textile industry effluents and a non-permitted food colour. The free-standing nature of the films enables them to be lifted directly on to electrodes without the aid of any binders. The films consist of aggregates of ultra-small Os NPs interspersed with rGO layers. The hybrid film exhibits enhanced RhB oxidation when compared to its constituents arising from the synergic effect between rGO and Os NPs, Os contributing to electrocatalysis and rGO contributing to high surface area and conductance as well as stabilization of Os nanoparticles. The electrochemical sensor based on rGO-Os NP hybrid film on pencil graphite electrode shows a remarkable performance for the quantitative detection of RhB with a linear variation in a wide range of concentrations, 4-1300 ppb (8.3 nM-2.71 μM). The modified electrode presents good stability over more than 6 months, reproducibility and anti-interference capability. The use of developed sensor for adequate detection of RhB in real samples such as food samples and pen markers is also demonstrated.

  19. Preparation, electrochemical behavior and electrocatalytic activity of chlorogenic acid multi-wall carbon nanotubes as a hydroxylamine sensor

    International Nuclear Information System (INIS)

    Zare, Hamid R.; Nasirizadeh, Navid; Ajamain, Hamideh; Sahragard, Ali

    2011-01-01

    Electrochemical characteristics of an electrodeposited chlorogenic acid film on multi-wall carbon nanotubes glassy carbon electrode (CGA-MWCNT-GCE) and its role as a sensor for electrocatalytic oxidation of hydroxylamine are described. Cyclic voltammograms of the CGA-MWCNT-GCE indicate a pair of well-defined and nearly reversible redox couple with the surface confined characteristics at a wide pH range of 2.0-12.0. The charge transfer coefficient, α, and the charge transfer rate constant, k s , of CGA adsorbed on MWCNT were calculated 0.48 and 44 ± 2 s -1 respectively. The CGA-MWCNT-GCE shows a dramatic increase in the peak current and/or a decrease in the overvoltage of hydroxylamine electrooxidation in comparison with that seen at a CGA modified GCE, MWCNT modified GCE and activated GCE. The kinetic parameters of electron transfer coefficient, α, the heterogeneous electron transfer rate constant, k', and exchange current, i 0 , for oxidation of hydroxylamine at the modified electrode surface were determined using cyclic voltammetry. Four linear calibration ranges and high repeatability with relative standard deviation of 4.6%, for a series of four successive measurements in 17.7 μM hydroxylamine, are obtained at the CGA-MWCNT-GCE using an amperometric method. Finally, the modified electrode was successfully used for determination of spiked hydroxylamine in two water samples.

  20. Electrocatalytic Activity for CO, MeOH, and EtOH Oxidation on the Surface of Pt-Ru Nanoparticles Supported by Metal Oxide

    Directory of Open Access Journals (Sweden)

    Kwang-Sik Sim

    2011-01-01

    Full Text Available This paper describes the electrocatalytic activity for CO, MeOH, and EtOH oxidation on the surface of Pt-Ru nanoparticles supported by metal oxide (Nb-TiO2-H prepared for use in a fuel cell. To prepare Nb-TiO2-supported Pt-Ru nanoparticles, first, the Nb-TiO2 supports were prepared by sol-gel reaction of titanium tetraisopropoxide with a small amount of the niobium ethoxide in polystyrene (PS colloids. Second, Pt-Ru nanoparticles were then deposited by chemical reduction of the Pt4+ and Ru3+ ions onto Nb-TiO2 supports (Pt-Ru@Nb-TiO2-CS. Nb element was used to reduce electrical resistance to facilitate electron transport during the electrochemical reactions on a fuel cell electrode. Finally, the Pt-Ru@Nb-TiO2-H catalysts were formed by the removal of core-polystyrene ball from Pt-Ru@TiO2-CS at 500∘C. The successfully prepared Pt-Ru electrocatalysts were confirmed via TEM, XPS, and ICP analysis. The electrocatalytic efficiency of Pt-Ru nanoparticles was evaluated via CO, MeOH, and EtOH oxidation for use in a direct methanol fuel cell (DMFC. As a result, the Pt-Ru@Nb-TiO2-H electrodes showed high electrocatalytic activity for the electrooxidation of CO, MeOH, and EtOH.

  1. Green synthesis of Pt-on-Pd bimetallic nanodendrites on graphene via in situ reduction, and their enhanced electrocatalytic activity for methanol oxidation

    International Nuclear Information System (INIS)

    Cai, Zhi-xiong; Liu, Cong-cong; Wu, Geng-huang; Chen, Xiao-mei; Chen, Xi

    2014-01-01

    Graphical abstract: - Highlights: • Porous 3D dendrite-like structure of Pt-on-Pd bimetallic nanostructures supported on graphene were prepared. • The surface of nanostructures was very “clean” because of the surfactant-free formation process and the use of green reagent. • The hetero-nanostructures showed excellent electrocatalytic performance in methanol oxidation. - Abstract: A green synthesis of Pt-on-Pd bimetallic nanodendrites supported on graphene (GPtPdNDs) with a Pd interior and a dendrite-like Pt exterior was achieved using a two-step preparation, mixing graphene and PdCl 4 2− first, then adding PtCl 4 2− and ethanol without any other solvent. The morphology, structure and composition of the thus-prepared GPtPdNDs were characterized by transmission electron microscopy (TEM), high resolution TEM, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Because no halide ions (refer in particular to Br - , I − ) or surfactant was involved in the synthesis, the prepared GPtPdNDs were directly modified onto a glassy carbon electrode and showed excellent electrocatalytic performance in methanol oxidation without any pretreatments. Moreover, with the special structure of PtPdNDs and the synergetic effects of Pt and Pd and the enhanced electron transfer by graphene, the GPtPdNDs composites exhibited higher electrocatalytic activity and better tolerance to Pt nanoparticles supported on graphene (GPtNPs) and Pt/C for methanol oxidation

  2. 2,3-diaminopyridine functionalized reduced graphene oxide-supported palladium nanoparticles with high activity for electrocatalytic oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon, E-mail: swjeon3380@naver.com

    2017-06-01

    Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H{sub 2}O{sub 2}. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H{sub 2}O{sub 2} yield.

  3. 2,3-diaminopyridine functionalized reduced graphene oxide-supported palladium nanoparticles with high activity for electrocatalytic oxygen reduction reaction

    International Nuclear Information System (INIS)

    Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon

    2017-01-01

    Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H_2O_2. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H_2O_2 yield.

  4. The Active Structure of the Greater Dead Sea Basin

    Science.gov (United States)

    Shamir, G.

    2002-12-01

    The Greater Dead Sea Basin (GDSB) is a 220km long depression situated along the southern section of the Dead Sea Transform (DST), between two structurally and gravitationally elevated points, Wadi Malih in the north and Paran fault zone in the south. In its center is the Dead Sea basin 'sensu strictu' (DSB), which has been described since the 1970s as a pull-apart basin at a left step-over along the DST. However, several observations, or their lack thereof, contradict this scheme, e.g. (i) It is not supported by recent seismological and geomorphic data; (ii) It does not explain the fault pattern and mixed sinistral and dextral offset along the DSB western boundary; (iii) It does not simply explain the presence of intense deformation outside the presumed fault step zone; (iv) It is inconsistent with the orientation of seismically active faults within the Dead Sea and Jericho Valley; (v) The length of the DSB exceeds the total offset along the Dead Sea Transform, while its subsidence is about the age of the DST. In this study, newly acquired and analyzed data (high resolution seismic reflection and earthquake relocation and fault plane solutions) has been integrated with previously published data (structural mapping, fracture orientation distribution, Bouguer anomaly maps, sinkhole distribution, geomorphic lineaments). The results show that the GDSB is dominated by two active fault systems, one trending NNE and showing normal-dextral motion, the other trending NW. These systems are identified by earthquake activity, seismic reflection observations, alignment of recent sinkholes, and distribution of Bouguer anomaly gradients. As a result, the intra-basin structure is of a series of rectangular blocks. The dextral slip component along NNE trending faults, the mixed sense of lateral offset along the western boundary of the DSB and temporal change in fracture orientation in the Jericho Valley suggest that the intra-basin blocks have rotated counterclockwise since the

  5. N-Doped graphene/PEDOT composite films as counter electrodes in DSSCs: Unveiling the mechanism of electrocatalytic activity enhancement

    Science.gov (United States)

    Paterakis, Georgios; Raptis, Dimitrios; Ploumistos, Alexandros; Belekoukia, Meltiani; Sygellou, Lamprini; Ramasamy, Madeshwaran Sekkarapatti; Lianos, Panagiotis; Tasis, Dimitrios

    2017-11-01

    A composite film was obtained by layer deposition of N-doped graphene and poly(3,4-ethylenedioxythiophene) (PEDOT) and was used as Pt-free counter electrode for dye-sensitized solar cells. N-doping of graphene was achieved by annealing mixtures of graphene oxide with urea. Various parameters concerning the treatment of graphene oxide-urea mixtures were monitored in order to optimize the electrocatalytic activity in the final solar cell device. These include the mass ratio of components, the annealing temperature, the starting concentration of the mixture in aqueous solution and the spinning rate for film formation. PEDOT was applied by electrodeposition. The homogeneity of PEDOT coverage onto either untreated or thermally annealed graphene oxide-urea film was assessed by imaging (AFM/SEM) and surface techniques (XPS). It was found that PEDOT was deposited in the form of island structures onto untreated graphene oxide-urea film. On the contrary, the annealed film was homogeneously covered by the polymer, acquiring morphology of decreased roughness. An apparent chemical interaction between PEDOT and N-doped graphene flakes was revealed by XPS data, involving potential grafting of PEDOT chains onto graphitic lattice through Csbnd C bonding. In addition, diffusion of nitrogen-containing fragments within the PEDOT layer was found to take place during electrodeposition process, resulting in enhanced interfacial interactions between components. The solar cell with the optimized N-doped graphene/PEDOT composite counter electrode exhibited a power conversion efficiency (η) of 7.1%, comparable within experimental error to that obtained by using a reference Pt counter electrode, which showed a value of 7.0%.

  6. An amperometric bienzymatic cholesterol biosensor based on functionalized graphene modified electrode and its electrocatalytic activity towards total cholesterol determination.

    Science.gov (United States)

    Manjunatha, Revanasiddappa; Shivappa Suresh, Gurukar; Melo, Jose Savio; D'Souza, Stanislaus F; Venkatesha, Thimmappa Venkatarangaiah

    2012-09-15

    Cholesterol oxidase (ChOx) and cholesterol esterase (ChEt) have been covalently immobilized onto functionalized graphene (FG) modified graphite electrode. Enzymes modified electrodes were characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). FG accelerates the electron transfer from electrode surface to the immobilized ChOx, achieving the direct electrochemistry of ChOx. A well defined redox peak was observed, corresponding to the direct electron transfer of the FAD/FADH(2) of ChOx. The electron transfer coefficient (α) and electron transfer rate constant (K(s)) were calculated and their values are found to be 0.31 and 0.78 s(-1), respectively. For the free cholesterol determination, ChOx-FG/Gr electrode exhibits a sensitive response from 50 to 350 μM (R=-0.9972) with a detection limit of 5 μM. For total cholesterol determination, co-immobilization of ChEt and ChOx on modified electrode, i.e. (ChEt/ChOx)-FG/Gr electrode showed linear range from 50 to 300 μM (R=-0.9982) with a detection limit of 15 μM. Some common interferents like glucose, ascorbic acid and uric acid did not cause any interference, due to the use of a low operating potential. The FG/Gr electrode exhibits good electrocatalytic activity towards hydrogen peroxide (H(2)O(2)). A wide linear response to H(2)O(2) ranging from 0.5 to 7 mM (R=-0.9967) with a sensitivity of 443.25 μA mM(-1) cm(-2) has been obtained. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. Progress in the understanding of surface structure and surfactant influence on the electrocatalytic activity of gold nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, V.C. [CQB, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal); CIQ-UP, Linha 4, Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Solla-Gullon, J.; Aldaz, A. [Instituto Universitario de Electroquimica, Universidad de Alicante, Apartado 99, 03080 Alicante (Spain); Silva, F. [CIQ-UP, Linha 4, Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Abrantes, L.M., E-mail: luisa.abrantes@fc.ul.pt [CQB, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal)

    2011-11-01

    Research highlights: > Electrochemical behaviour of AuNPs depends on the facets present in their surface. > Cubic and rod shaped nanoparticles comprise distinct crystallographic orientation. > Key rule of surfactant on the selective availability of specific surface domains. > AA oxidation at less stabilised (1 1 1) rod facets displays single-crystal response. - Abstract: The preparation of gold nanoparticles (Au-NPs) displaying specific shape, size and surface crystallographic domains has been investigated aiming to clarify the effect of the surface crystallographic orientation, of the synthesised nanoparticles, and surfactant influence on the electrochemical response of the ITO/Au-NPs modified electrodes. Polymorphic and nanorod-shaped Au-NPs have been obtained using distinct synthetic procedures in the presence of cetyltrimethylammonium bromide (CTAB), through seed-mediated growth methods, displaying distinct surface crystallographic domains confirmed by transmission electron microscopy, X-ray diffraction analysis and under potential deposition (UPD) of lead. The nanoparticles have been physically immobilised by casting on indium tin oxide (ITO) surfaces and the electrocatalytic activity of the Au-NPs evaluated using the ascorbic acid (AA) oxidation reaction, by cyclic voltammetry. The polymorphic and distinct surface crystallographic orientations of the Au-NPs were reflected in an irreproducible electrochemical response. Using gold nanorods comprising (1 1 1) and (1 1 0) facets and gold nanocubes consisting of faces displaying (1 0 0) surface domains, by contrasting the behaviour of CTAB-stabilised and clean particles, it has been possible to verify that the distinct voltammetric results are due to the exposure of specific crystallographic orientations owing to dissimilar interaction strength of CTAB with those facets.

  8. Microwave activation of palladium nanoparticles for enhanced ethanol electrocatalytic oxidation reaction in alkaline medium

    CSIR Research Space (South Africa)

    Rohwer, MB

    2015-02-01

    Full Text Available in alkaline medium (in terms of high mass activity stability and fast reaction kinetics). The remarkable microwave-induced properties on the Pd catalyst promise to revolutionize the use of microwave for catalyst activation for enhanced heterogeneous catalysis...

  9. The Synthesis and Electrocatalytic Activities of Molybdenum Sulfide for Hydrogen Evolution Reaction

    KAUST Repository

    Li, Zhengxing

    2014-01-01

    of the Pt-group metals for HER. Plenty of researches have been conducted for improving the HER activities of MoS2 by optimizing its synthesis method. However, it remains challenging to prepare MoS2 catalysts with high and controllable activity, and more

  10. ELECTROCATALYTIC ACTIVITY FOR O2 REDUCTION OF UNSUBSTITUTED AND PERCHLORINATED IRON PHTHALOCYANINES ADSORBED ON AMINO-TERMINATED MULTIWALLED CARBON NANOTUBES DEPOSITED ON GLASSY CARBON ELECTRODES

    OpenAIRE

    CAÑETE, PAULINA; SILVA, J. FRANCISCO; ZAGAL, JOSÉ H

    2014-01-01

    Amino-functionalized multiwalled carbon nanotubes (MWCNT-NH2) were modified with Fe phthalocyanine (FePc) and perchlorinated Fe phthalocyanine (16(Cl)FePc) and deposited on glassy carbon electrodes (GCE). The electrocatalytic activity of these hybrid electrodes was examined for the reduction of molecular oxygen in alkaline media (0.2 M NaOH) using stationary and rotating disk electrodes. Electrodes containing 16(Cl)FePc are more active than those containing FePc. Electrodes containing CNTs ar...

  11. Improvements of electrocatalytic activity of PtRu nanoparticles on multi-walled carbon nanotubes by a H2 plasma treatment in methanol and formic acid oxidation

    International Nuclear Information System (INIS)

    Jiang Zhongqing; Jiang Zhongjie

    2011-01-01

    Graphical abstract: A H 2 plasma, that aims at reducing the fraction of the oxidized species at the outermost perimeter of metal particles, has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, reduced charge transfer resistance, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. Highlights: → A H 2 plasma technique is used to treat the PtRu nanoparticles. → The H 2 plasma treated PtRu/PS-MWCNTs exhibit improved electrocatalytic activity. → The H 2 plasma treated PtRu/PS-MWCNTs have significantly reduced charge transfer resistance. → The H 2 plasma treated PtRu/PS-MWCNTs show the increased stability. → The Pt:Ru atomic ratio of PtRu nanoparticles has a significant effect on the electrochemical activity. - Abstract: A H 2 plasma has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treatment does not change the size and crystalline structure of PtRu nanoparticles, but reduces the fraction of the oxidized species at the outermost perimeter of particles. The electrochemical results show that these plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. The electrocatalytic activities of the plasma treated PtRu/PS-MWCNTs are found to be dependent upon the Pt:Ru atomic ratios of PtRu nanoparticles. The catalysts with a Pt:Ru atomic ratio close to 1:1 show superior properties in the electrooxidation of methanol and formic acid

  12. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  13. Hydrogen adsorption-mediated synthesis of concave Pt nanocubes and their enhanced electrocatalytic activity

    Science.gov (United States)

    Lu, Bang-An; Du, Jia-Huan; Sheng, Tian; Tian, Na; Xiao, Jing; Liu, Li; Xu, Bin-Bin; Zhou, Zhi-You; Sun, Shi-Gang

    2016-06-01

    Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts.Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts. Electronic supplementary information (ESI) available: Details of DFT calculation, SEM images of concave Pt nanocubes, mass activity and stability characterization of the catalysts. See DOI: 10.1039/c6nr02349e

  14. Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide

    DEFF Research Database (Denmark)

    Xu, Junyuan; Kan, Yuhe; Huang, Rui

    2016-01-01

    Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2). The investigation explores the origin of the catalyst’s activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90% current efficiency...... for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2, which leads to the formation of carbon dioxide radical anion (CO2C). The initial...

  15. Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Kou, Rong; Shao, Yuyan; Wang, Donghai; Engelhard, Mark H.; Kwak, Ja Hun; Wang, Jun; Viswanathan, Vilayanur V.; Wang, Chongmin; Lin, Yuehe; Wang, Yong; Liu, Jun [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Aksay, Ilhan A. [Department of Chemical Engineering, Princeton University, Princeton, NJ 08544 (United States)

    2009-05-15

    Electrocatalysis of oxygen reduction using Pt nanoparticles supported on functionalized graphene sheets (FGSs) was studied. FGSs were prepared by thermal expansion of graphite oxide. Pt nanoparticles with average diameter of 2 nm were uniformly loaded on FGSs by impregnation methods. Pt-FGS showed a higher electrochemical surface area and oxygen reduction activity with improved stability as compared with the commercial catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization suggest that the improved performance of Pt-FGS can be attributed to smaller particle size and less aggregation of Pt nanoparticles on the functionalized graphene sheets. (author)

  16. One-Step Preparation of Large Area Films of Oriented MoS2 Nanoparticles on Multilayer Graphene and Its Electrocatalytic Activity for Hydrogen Evolution

    Directory of Open Access Journals (Sweden)

    Jinbao He

    2018-01-01

    Full Text Available MoS2 is a promising material to replace Pt-based catalysts for the hydrogen evolution reaction (HER, due to its excellent stability and high activity. In this work, MoS2 nanoparticles supported on graphitic carbon (about 20 nm with a preferential 002 facet orientation have been prepared by pyrolysis of alginic acid films on quartz containing adsorbed (NH42MoS4 at 900 °C under Ar atmosphere. Although some variation of the electrocatalytic activity has been observed from batch to batch, the MoS2 sample exhibited activity for HER (a potential onset between 0.2 and 0.3 V vs. SCE, depending on the concentrations of (NH42MoS4 precursor used in the preparation process. The loading and particle size of MoS2, which correlate with the amount of exposed active sites in the sample, are the main factors influencing the electrocatalytic activity.

  17. Facile synthesis of PdAgTe nanowires with superior electrocatalytic activity

    Science.gov (United States)

    Hong, Wei; Wang, Jin; Wang, Erkang

    2014-12-01

    In this work, ultrathin Te nanowires (NWs) with high-aspect-ratio are prepared by a simple hydrothermal method. By using Te NWs as the sacrificial template, we demonstrate a facile and efficient method for the synthesis of PdAgTe NWs with high-quality through the partly galvanic replacement between Te NWs and the corresponding noble metal salts precursors in an aqueous solution. The compositions of PdAgTe NWs can be tuned by simply altering the concentration of the precursors. After cyclic voltammetry treatment, multi-component PdAgTe NW with a highly active and stable surface can be obtained. The structure and composition of the as-prepared nanomaterials are analyzed by transmission electron microscope, X-ray diffraction, energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy and X-ray photoelectron spectroscopy. Electrochemical catalytic measurement results prove that the as synthesized PdAgTe NWs present superior catalytic activity toward ethanol electrooxidation in alkaline solution than the commercial Pd/C catalyst, which making them can be used as effective catalysts for the direct ethanol fuel cells.

  18. Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.

    Science.gov (United States)

    Xu, Junyuan; Kan, Yuhe; Huang, Rui; Zhang, Bingsen; Wang, Bolun; Wu, Kuang-Hsu; Lin, Yangming; Sun, Xiaoyan; Li, Qingfeng; Centi, Gabriele; Su, Dangsheng

    2016-05-23

    Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Preparation and Electrocatalytic Activity of Gold Nanoparticles Immobilized on the Surface of 4-Mercaptobenzoyl-Functionalized Multiwalled Carbon Nanotubes

    Science.gov (United States)

    2010-12-20

    thiolate -Au bonds,30 and so GNP/MB-MWCNT hybrids were synthesized using a modified literature procedure.31 The SEM images show sequential...4 The electrocatalytic stability of GNP/MB-MWCNT supposes to be originated from the formation of stable thiolate -Au bonds that prevent aggregation of...Moon, K.-S.; Wong, C. P. Carbon 2007, 45, 655–661. (19) Sandler, J.; Shaffer, M. S. P.; Prasse, T.; Bauhofer, W.; Schulte, K.; Windle, A. H. Polymer

  20. Efficient Synthesis of MCu (M = Pd, Pt, and Au) Aerogels with Accelerated Gelation Kinetics and their High Electrocatalytic Activity.

    Science.gov (United States)

    Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang; Song, Junhua; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-10-01

    To accelerate hydrogel formation and further simplify the synthetic procedure, a series of MCu (M = Pd, Pt, and Au) bimetallic aerogels is synthesized from the in situ reduction of metal precursors through enhancement of the gelation kinetics at elevated temperature. Moreover, the resultant PdCu aerogel with ultrathin nanowire networks exhibits excellent electrocatalytic performance toward ethanol oxidation, holding promise in fuel-cell applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Electrocatalytic activity of ZnS nanoparticles in direct ethanol fuel cells

    Science.gov (United States)

    Bredol, Michael; Kaczmarek, Michał; Wiemhöfer, Hans-Dieter

    2014-06-01

    Low temperature fuel cells consuming ethanol without reformation would be a major step toward the use of renewable energy sources from biomass. However, the necessary electrodes and electrocatalysts still are far from being perfect and suffer from various poisoning and deactivation processes. This work describes investigations on systems using carbon/ZnS-based electrocatalysts for ethanol oxidation in complete membrane electrode assemblies (MEAs). MEAs were built on Nafion membranes with active masses prepared from ZnS nanoparticles and Vulcan carbon support. Under operation, acetic acid and acetaldehyde were identified and quantified as soluble oxidation products, whereas the amount of CO2 generated could not be quantified directly. Overall conversion efficiencies of up to 25% were estimated from cells operated over prolonged time. From polarization curves, interrupt experiments and analysis of reaction products, mass transport problems (concentration polarization) and breakthrough losses were found to be the main deficiencies of the ethanol oxidation electrodes fabricated so far.

  2. Electrocatalytic activity of Pt grown by ALD on carbon nanotubes for Si-based DMFC applications

    DEFF Research Database (Denmark)

    Johansson, Alicia Charlotte; Dalslet, Bjarke Thomas; Yang, R.B.

    2012-01-01

    in a top-flow ALD reactor at 250°C, using MeCpPtMe3 and O2 as precursors. The anode was tested for the methanol oxidation reaction (MOR) in a three-electrode electrochemical set-up and it showed improved catalytic activity compared to a reference sample of Pt deposited on flat Si. It is demonstrated......We present an anode design for silicon-based direct methanol fuel cell (DMFC) applications. Platinum was deposited conformally by atomic layer deposition (ALD) onto vertically aligned, nitrogendoped multi-walled carbon nanotubes (MWCNTs) grown on porous silicon. The deposition was carried out...... that ALD could be a MEMS compatible deposition technique for Si-based fuel cell applications. © The Electrochemical Society....

  3. Facile synthesis of dendritic gold nanostructures with hyperbranched architectures and their electrocatalytic activity toward ethanol oxidation.

    Science.gov (United States)

    Huang, Jianshe; Han, Xinyi; Wang, Dawei; Liu, Dong; You, Tianyan

    2013-09-25

    Gold dendritic nanostructures with hyperbranched architectures were synthesized by the galvanic replacement reaction between nickel wire and HAuCl4 in aqueous solution. The study revealed that the morphology of the obtained nanostructures strongly depended on experimental parameters such as the HAuCl4 solution concentration, reaction temperature, and time, as well as stirring or not. According to the investigation of the growth process, it was proposed that gold nanoparticles with rough surfaces were first deposited on the nickel substrate and that subsequent growth preferentially occurred on the preformed gold nanoparticles, finally leading to the formation of hyperbranched gold dendrites via a self-organization process under nonequilibrium conditions. The electrochemical experiment results demonstrated that the as-obtained gold dendrites exhibited high catalytic activity toward ethanol electrooxidation in alkaline solution, indicating that this nanomaterial may be a potential catalyst for direct ethanol fuel cells.

  4. Enhanced Electrocatalytic Activity for Water Splitting on NiO/Ni/Carbon Fiber Paper

    Directory of Open Access Journals (Sweden)

    Ruoyu Zhang

    2016-12-01

    Full Text Available Large-scale growth of low-cost, efficient, and durable non-noble metal-based electrocatalysts for water splitting is crucial for future renewable energy systems. Atomic layer deposition (ALD provides a promising route for depositing uniform thin coatings of electrocatalysts, which are useful in many technologies, including the splitting of water. In this communication, we report the growth of a NiO/Ni catalyst directly on carbon fiber paper by atomic layer deposition and report subsequent reduction and oxidation annealing treatments. The 10–20 nm NiO/Ni nanoparticle catalysts can reach a current density of 10 mA·cm−2 at an overpotential of 189 mV for hydrogen evolution reactions and 257 mV for oxygen evolution reactions with high stability. We further successfully achieved a water splitting current density of 10 mA·cm−2 at 1.78 V using a typical NiO/Ni coated carbon fiber paper two-electrode setup. The results suggest that nanoparticulate NiO/Ni is an active, stable, and noble-metal-free electrocatalyst, which facilitates a method for future water splitting applications.

  5. Electrocatalytic activity of Pt and PtCo deposited on Ebonex by BH reduction

    International Nuclear Information System (INIS)

    Slavcheva, E.; Nikolova, V.; Petkova, T.; Lefterova, E.; Dragieva, I.; Vitanov, T.; Budevski, E.

    2005-01-01

    The method of borohydride reduction (BH) has been applied to synthesize Pt and PtCo nanoparticles supported on Magneli phase titanium oxides, using Pt and Co ethylenediamine complexes as metal precursors. The phase composition of the synthesized catalysts, their morphology and surface structure were studied by physical methods for bulk and surface analysis, such as electron microprobe analysis (EMPA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and BET technique. The catalytic activity towards oxygen evolution reaction in alkaline aqueous solution was investigated using the common electrochemical techniques. It was found that PtCo/Ebonex facilitates essentially the oxygen evolution which starts at lower overpotentials and proceeds with higher rate compared to both the supported Pt and unsupported PtCo catalysts. The observed effect is prescribed to metal-metal and metal-support interactions. The Ebonex possesses a good electrical conductivity and corrosion resistance at high anodic potentials and despite its low surface area is considered as a potential catalyst carrier for the oxygen evolution reaction

  6. One-pot synthesis of reduced graphene oxide supported PtCuy catalysts with enhanced electro-catalytic activity for the methanol oxidation reaction

    International Nuclear Information System (INIS)

    Peng, Xinglan; Zhao, Yanchun; Chen, Duhong; Fan, Yanfang; Wang, Xiao; Wang, Weili; Tian, Jianniao

    2014-01-01

    The outstanding performance PtCu y (y = 1,2,3) alloy nanoparticles supported on reduced graphene oxide (rGO) have been synthesized by a facile, efficient, one-pot hydrothermal synthesis approach. The as-prepared PtCu y /rGO catalysts are comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy. Cyclic voltammetry, CO-stripping voltammetry and chronoamperometry results reveal that the PtCu y /rGO catalysts have higher electro-catalytic activity, more negative onset oxidative potential, more excellent tolerance ability for CO poisoning and enhanced stability for the electro-oxidation of methanol compared to pure Pt/rGO. As far as the as-made PtCu y /rGO catalysts are concerned, the PtCu 2 /rGO exhibits the highest electro-catalytic activity. The mechanism of the promoting effect of Cu on Pt is explained based on the electronic modification effect. The nature of interfacial interactions between the Pt-Cu active metal phase and the rGO supporting materials is crucial to achieving high performance

  7. Accurate Assessment of the Oxygen Reduction Electrocatalytic Activity of Mn/Polypyrrole Nanocomposites Based on Rotating Disk Electrode Measurements, Complemented with Multitechnique Structural Characterizations

    Science.gov (United States)

    Sánchez, Carolina Ramírez; Taurino, Antonietta; Bozzini, Benedetto

    2016-01-01

    This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR) electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy) nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE) method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i) morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM) and Atomic Force Microscope (AFM); (ii) local electrical conductivity, as measured by Scanning Probe Microscopy (SPM); and (iii) molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt). Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement. PMID:28042491

  8. Accurate Assessment of the Oxygen Reduction Electrocatalytic Activity of Mn/Polypyrrole Nanocomposites Based on Rotating Disk Electrode Measurements, Complemented with Multitechnique Structural Characterizations

    Directory of Open Access Journals (Sweden)

    Patrizia Bocchetta

    2016-01-01

    Full Text Available This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM and Atomic Force Microscope (AFM; (ii local electrical conductivity, as measured by Scanning Probe Microscopy (SPM; and (iii molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt. Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement.

  9. Scanning electrochemical microscopy. 47. Imaging electrocatalytic activity for oxygen reduction in an acidic medium by the tip generation-substrate collection mode.

    Science.gov (United States)

    Fernández, José L; Bard, Allen J

    2003-07-01

    The oxygen reduction reaction (ORR) in acidic medium was studied on different electrode materials by scanning electrochemical microscopy (SECM) operating in a new variation of the tip generation-substrate collection mode. An ultramicroelectrode tip placed close to the substrate electrode oxidizes water to oxygen at a constant current. The substrate is held at a potential where the tip-generated oxygen is reduced and the resulting substrate current is measured. By changing the substrate potential, it is possible to obtain a polarization (current-potential) curve, which depends on the electrocatalytic activity of the substrate material. The main difference between this mode and the classical feedback SECM mode of operation is that the feedback diffusion process is not required for the measurement, allowing its application for studying the ORR in acidic solutions. Activity-sensitive images of heterogeneous surfaces, e.g., with Pt and Au electrodes, were obtained from the substrate current when the x-y plane was scanned with the tip. The usefulness of this technique for imaging electrocatalytic activity of smooth metallic electrodes and of highly dispersed fuel cell-type electrocatalysts was demonstrated. The application of this method to the combinatorial chemical analysis of electrode materials and electrocatalysts is discussed.

  10. Enhanced Electrocatalytic Activity of Pt Particles Supported on Reduced Graphene Oxide/Poly(3,4-ethylenedioxythiophene RGO/PEDOT Composite towards Ethanol Oxidation

    Directory of Open Access Journals (Sweden)

    Juanito Raphael F. Foronda

    2013-01-01

    Full Text Available Catalysts in fuel cells are normally platinum based because platinum exhibits high electrocatalytic activity towards ethanol oxidation in acidic medium. However, bulk Pt is expensive and rare in nature. To reduce the consumption of Pt, a support material or matrix is needed to disperse Pt on its surface as micro- or nanoparticles with potential application as anode material in direct ethanol fuel cells (DEFCs. In this study, a composite material consisting of platinum particles dispersed on reduced graphene oxide/poly(3,4-ethylenedioxythiophene (RGO/PEDOT support was electrochemically prepared for ethanol oxidation in sulfuric acid electrolyte. PEDOT, a conductive polymer, was potentiodynamically polymerized from the corresponding monomer, 0.10 M EDOT in 0.10 M HClO4 electrolyte. The PEDOT-modified electrode was used as a substrate for exfoliated graphene oxide (EGO which was prepared by electrochemical exfoliation of graphite from carbon rod of spent batteries and subsequently reduced to form RGO. The Pt/RGO/PEDOT composite gave the highest electrocatalytic activity with an anodic current density of 2688.7 mA·cm−2 at E = 0.70 V (versus Ag/AgCl towards ethanol oxidation compared to bare Pt electrode and other composites. Scanning electron microscopy (SEM revealed the surface morphology of the hybrid composites while energy dispersive X-ray (EDX confirmed the presence of all the elements for the Pt/RGO/PEDOT composite.

  11. Activity of the greater padloper, Homopus femoralis (Testudinidae ...

    African Journals Online (AJOL)

    ... or imminent rain, perhaps to avoid avian predators or physiological costs of water and food shortages. Future studies might locate active tortoises in the highest rainfall months, and use telemetry to identify activity patterns throughout the year. Key words: behaviour, ecology, Karoo, morphology, predation, reptile, tortoise.

  12. Cobalt selenide hollow nanorods array with exceptionally high electrocatalytic activity for high-efficiency quasi-solid-state dye-sensitized solar cells

    Science.gov (United States)

    Jin, Zhitong; Zhang, Meirong; Wang, Min; Feng, Chuanqi; Wang, Zhong-Sheng

    2018-02-01

    In quasi-solid-state dye-sensitized solar cells (QSDSSCs), electron transport through a random network of catalyst in the counter electrode (CE) and electrolyte diffusion therein are limited by the grain boundaries of catalyst particles, thus diminishing the electrocatalytic performance of CE and the corresponding photovoltaic performance of QSDSSCs. We demonstrate herein an ordered Co0.85Se hollow nanorods array film as the Pt-free CE of QSDSSCs. The Co0.85Se hollow nanorods array displays excellent electrocatalytic activity for the reduction of I3- in the quasi-solid-state electrolyte with extremely low charge transfer resistance at the CE/electrolyte interface, and the diffusion of redox species within the Co0.85Se hollow nanorods array CE is pretty fast. The QSDSSC device with the Co0.85Se hollow nanorods array CE produces much higher photovoltaic conversion efficiency (8.35%) than that (4.94%) with the Co0.85Se randomly packed nanorods CE, against the control device with the Pt CE (7.75%). Moreover, the QSDSSC device based on the Co0.85Se hollow nanorods array CE presents good long-term stability with only 4% drop of power conversion efficiency after 1086 h one-sun soaking.

  13. Characterization and electrocatalytic activity of Pt–M (M=Cu, Ag, and Pd) bimetallic nanoparticles synthesized by pulsed plasma discharge in water

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung-Min; Cho, Ah-Rong; Lee, Sang-Yul, E-mail: sylee@kau.ac.kr [Korea Aerospace University, Department of Materials Engineering, Center for Surface Technology and Applications (Korea, Republic of)

    2015-07-15

    The synthetic approach for electrocatalysts is one of the most important methods of determining electrocatalytic performance. In this work, we synthesized Pt and Pt–M (M=Cu, Ag, and Pd) bimetallic nanoparticles using a pulsed plasma discharge in water. A morphological investigation revealed that the as-synthesized Pt and Pt–M bimetallic nanoparticles constituted a nanochain network structure interconnected with primary nanoparticles of 4–6 nm in size, and the nanochains grew from the primary nanoparticles via the oriented attachment. The Z-contrast, EDX line scanning, and XRD analysis confirmed that the Pt was alloyed with M without elemental segregation or phase segregation. Furthermore, it was found that the composition difference was dependent on the electrode temperature determined by the power density and thermal parameters. The electrochemical results revealed that the electrocatalytic activity, stability, and durability of the Pt–Ag bimetallic nanoparticles were superior with respect to the methanol oxidation reaction, which could be attributed to the downshift of the d-band center via electronic modification.

  14. Influence of the nature of conductive support on the electrocatalytic activity of electrodeposited Ni films towards methanol oxidation in 1 M KOH

    Energy Technology Data Exchange (ETDEWEB)

    Singh, R.N.; Singh, A.; Anindita; Mishra, D. [Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005 (India)

    2008-12-15

    The study of electrochemical behaviour of dispersed Ni on graphite, glassy carbon, and Ti electrodes, obtained by an electro-deposition method, is carried out in 1 M KOH + 1 M CH{sub 3}OH at 25 C. Results show that the nature of substrate influences the apparent electrocatalytic activities of the Ni over layer greatly. It is observed that at E = 0.50 V vs. Hg/HgO (25 C), the dispersed Ni on graphite is approx. 300 times more active than that dispersed on Ti and is approx. 260 times more active than that dispersed on glassy carbon. Further, these electrodes show quite good resistance against electrode poisoning by the methanol oxidation intermediates/products. (author)

  15. Electrocatalytic glucose sensor

    Energy Technology Data Exchange (ETDEWEB)

    Gebhardt, U; Luft, G; Mund, K; Preidel, W; Richter, G J

    1983-01-01

    An artificial pancreas consists of an insulin depot, a dosage unit and a glucose sensor. The measurement of the actual glucose concentration in blood is still an unsolved problem. Two methods are described for an electrocatalytic glucose sensor. Under the interfering action of amino acids and urea in-vitro measurements show an error of between 10% and 20%.

  16. Influence of Sn content on PtSn/C catalysts for electrooxidation of C{sub 1}-C{sub 3} alcohols: Synthesis, characterization, and electrocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jae Hong; Choi, Sung Mook; Nam, Sang Hoon; Seo, Min Ho; Kim, Won Bae [Department of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), 261 Cheomdan-gwagiro, Buk-gu, Gwangju 500-712 (Korea); Choi, Sun Hee [Pohang Accelerator Laboratory, San-31 Hyoja-dong, Pohang, Kyungbuk 790-984 (Korea)

    2008-07-16

    A series of carbon-supported bimetallic PtSn catalysts for the electrooxidation of C{sub 1}-C{sub 3} alcohols (i.e., methanol (C{sub 1}), ethanol (C{sub 2}), and 1-propanol (C{sub 3})) were prepared with different Pt:Sn atomic ratios using borohydride reduction method combined with freeze-drying procedure at room temperature. The catalysts were investigated by employing various physicochemical analyses: X-ray diffraction (XRD), transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS) to investigate the structural modification, and X-ray photoelectron spectroscopy (XPS) and X-ray absorption-near-edge spectroscopy (XANES) to characterize the change in electronic features. The variation of Sn content by forming PtSn alloys causes significant structural and electronic modifications of Pt crystallites, resulting in increases of lattice parameter and decreases of the Pt 5d band vacancies with Sn content. Cyclic voltammetry (CV) measurements showed that the addition of Sn into the Pt catalyst promotes the electro-catalytic activities for the electrooxidations of C{sub 1}, C{sub 2}, and C{sub 3} alcohols, in which the maximum activities appeared at different Sn contents for the C{sub 1}-C{sub 3} alcohols. In particular, a shift in optimum Pt:Sn composition was observed in that the Sn content required to reach the maximum peak current density was increased with the increasing number of carbon atoms in the C{sub 1}-C{sub 3} alcohols. Both the geometric and electronic effects with variation of Sn content are in close relationship in the bimetallic PtSn catalysts, consequently affecting the electrocatalytic activities by showing volcano-type behaviors over the electrooxidation of the individual alcohol. (author)

  17. Electrocatalytic cermet gas detector/sensor

    Science.gov (United States)

    Vogt, Michael C.; Shoemarker, Erika L.; Fraioli, deceased, Anthony V.

    1995-01-01

    An electrocatalytic device for sensing gases. The gas sensing device includes a substrate layer, a reference electrode disposed on the substrate layer comprised of a nonstoichiometric chemical compound enabling oxygen diffusion therethrough, a lower reference electrode coupled to the reference electrode, a solid electrolyte coupled to the lower reference electrode and an upper catalytically active electrode coupled to the solid electrolyte.

  18. Nanostructured 3D-porous graphene hydrogel based Ti/Sb-SnO2-Gr electrode with enhanced electrocatalytic activity.

    Science.gov (United States)

    Asim, Sumreen; Zhu, Yunqing; Rana, Masud; Yin, Jiao; Shah, Muhammad Wajid; Li, Yingxuan; Wang, Chuanyi

    2017-02-01

    Nanostructured highly porous 3D-Ti/Sb-SnO 2 -Gr electrode, based on 3D porous graphene hydrogel was fabricated via a fast-evaporation technique through layer by layer (LBL) deposition. The 3D pores are uniformly distributed on the high fidelity of substrate with pore sizes of 7-12 nm, as confirmed by SEM analysis. Compared to Ti/Sb-SnO 2 electrode, the fabricated 3D porous electrode possesses high oxygen evolution potential (2.40 V), smaller charge transfer resistance (29.40 Ω cm -2 ), higher porosity (0.90), enhanced roughness factor (181), and larger voltammetric charge value (57.4 mC cm -2 ). Electrocatalytic oxidation of Rhodamine B (RhB) was employed to evaluate the efficiency of the fabricated 3D-Ti/Sb-SnO 2 -Gr anode. The results show that the electrochemical reaction follows pseudo first order kinetics with rate constant (k) value of 4.93 × 10 -2 min -1 , which is about 3.91 times higher compared to flat Ti/Sb-SnO 2 . The fabricated electrode demonstrates better stability and low specific energy consumption signifying its potential usage in electrocatalysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Electrocatalytic activity of Pd-loaded Ti/TiO2 nanotubes cathode for TCE reduction in groundwater.

    Science.gov (United States)

    Xie, Wenjing; Yuan, Songhu; Mao, Xuhui; Hu, Wei; Liao, Peng; Tong, Man; Alshawabkeh, Akram N

    2013-07-01

    A novel cathode, Pd loaded Ti/TiO2 nanotubes (Pd-Ti/TiO2NTs), is synthesized for the electrocatalytic reduction of trichloroethylene (TCE) in groundwater. Pd nanoparticles are successfully loaded on TiO2 nanotubes which grow on Ti plate via anodization. Using Pd-Ti/TiO2NTs as the cathode in an undivided electrolytic cell, TCE is efficiently and quantitatively transformed to ethane. Under conditions of 100 mA and pH 7, the removal efficiency of TCE (21 mg/L) is up to 91% within 120 min, following pseudo-first-order kinetics with the rate constant of 0.019 min(-1). Reduction rates increase from 0.007 to 0.019 min(-1) with increasing the current from 20 to 100 mA, slightly decrease in the presence of 10 mM chloride or bicarbonate, and decline with increasing the concentrations of sulfite or sulfide. O2 generated at the anode slightly influences TCE reduction. At low currents, TCE is mainly reduced by direct electron transfer on the Pd-Ti/TiO2NT cathode. However, the contribution of Pd-catalytic hydrodechlorination, an indirect reduction mechanism, becomes significant with increasing the current. Compared with other common cathodes, i.e., Ti-based mixed metal oxides, graphite and Pd/Ti, Pd-Ti/TiO2NTs cathode shows superior performance for TCE reduction. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Nanorods of a new metal-biomolecule coordination polymer showing novel bidirectional electrocatalytic activity and excellent performance in electrochemical sensing.

    Science.gov (United States)

    Yang, Jiao; Zhou, Bo; Yao, Jie; Jiang, Xiao-Qing

    2015-05-15

    Metal organic coordination polymers (CPs), as most attractive multifunctional materials, have been studied extensively in many fields. However, metal-biomolecule CPs and CPs' electrochemical properties and applications were studied much less. We focus on this topic aiming at electrochemical biosensors with excellent performance and high biocompatibility. A new nanoscaled metal-biomolecule CP, Mn-tyr, containing manganese and tyrosine, was synthesized hydrothermally and characterized by various techniques, including XRD, TEM, EDS, EDX mapping, elemental analysis, XPS, and IR. Electrode modified with Mn-tyr showed novel bidirectional electrocatalytic ability toward both reduction and oxidation of H2O2, which might be due to Mn. With the assistance of CNTs, the sensing performance of Mn-tyr/CNTs/GCE was improved to a much higher level, with high sensitivity of 543 mA mol(-1) L cm(-2) in linear range of 1.00×10(-6)-1.02×10(-4) mol L(-1), and detection limit of 3.8×10(-7) mol L(-1). Mn-tyr/CNTs/GCE also showed fast response, high selectivity, high steadiness and reproducibility. The excellent performance implies that the metal-biomolecule CPs are promising candidates for using in enzyme-free electrochemical biosensing. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Improving the electrocatalytic performance of carbon nanotubes for VO{sup 2+}/VO{sub 2}{sup +} redox reaction by KOH activation

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); Wang, Ling, E-mail: tswling@126.com [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); He, Zhangxing, E-mail: zxhe@ncst.edu.cn [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Nanchang 330013 (China)

    2017-04-15

    Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO{sup 2+}/VO{sub 2}{sup +} redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO{sup 2+}/VO{sub 2}{sup +} redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for VRFB system.

  2. Electrocatalytical activity of Pt, SnO2 and RuO2 mixed electrodes for the electrooxidation of formic acid and formaldehyde

    International Nuclear Information System (INIS)

    Profeti, L.P.R.; Profeti, D.; Olivi, P.

    2005-01-01

    The electrocatalytical activity of binary electrodes of Pt and SnO 2 and ternary electrodes of Pt and SnO 2 and RuO 2 for the electrooxidation of formic acid and formaldehyde was investigated by cyclic voltammetry and chronoamperometry techniques. The electrode materials were prepared by the thermal decomposition of polymeric precursors at 400 deg C. The cyclic voltammetry results showed that the methanol electrooxidation process presents peak potentials for those electrodes approximately 100 mV lower than the values obtained for metallic platinum electrodes. The Pt 0.6 Ru 0.2 Sn 0.2 O y electrodes presented the highest current density values for potentials lower than the peak potential values. The chronoamperometric experiments also showed that the addition of SnO 2 and RuO 2 contributed for the enhancement of the electrode activity in low potential values. The preparation method was found to be useful to obtain high active materials. (author)

  3. Redox-active porous coordination polymers prepared by trinuclear heterometallic pivalate linking with the redox-active nickel(II) complex: synthesis, structure, magnetic and redox properties, and electrocatalytic activity in organic compound dehalogenation in heterogeneous medium.

    Science.gov (United States)

    Lytvynenko, A S; Kolotilov, S V; Kiskin, M A; Cador, O; Golhen, S; Aleksandrov, G G; Mishura, A M; Titov, V E; Ouahab, L; Eremenko, I L; Novotortsev, V M

    2014-05-19

    Linking of the trinuclear pivalate fragment Fe2CoO(Piv)6 by the redox-active bridge Ni(L)2 (compound 1; LH is Schiff base from hydrazide of 4-pyridinecarboxylic acid and 2-pyridinecarbaldehyde, Piv(-) = pivalate) led to formation of a new porous coordination polymer (PCP) {Fe2CoO(Piv)6}{Ni(L)2}1.5 (2). X-ray structures of 1 and 2 were determined. A crystal lattice of compound 2 is built from stacked 2D layers; the Ni(L)2 units can be considered as bridges, which bind two Fe2CoO(Piv)6 units. In desolvated form, 2 possesses a porous crystal lattice (SBET = 50 m(2) g(-1), VDR = 0.017 cm(3) g(-1) estimated from N2 sorption at 78 K). At 298 K, 2 absorbed a significant quantity of methanol (up to 0.3 cm(3) g(-1)) and chloroform. Temperature dependence of molar magnetic susceptibility of 2 could be fitted as superposition of χMT of Fe2CoO(Piv)6 and Ni(L)2 units, possible interactions between them were taken into account using molecular field model. In turn, magnetic properties of the Fe2CoO(Piv)6 unit were fitted using two models, one of which directly took into account a spin-orbit coupling of Co(II), and in the second model the spin-orbit coupling of Co(II) was approximated as zero-field splitting. Electrochemical and electrocatalytic properties of 2 were studied by cyclic voltammetry in suspension and compared with electrochemical and electrocatalytic properties of a soluble analogue 1. A catalytic effect was determined by analysis of the catalytic current dependency on concentrations of the substrate. Compound 1 possessed electrocatalytic activity in organic halide dehalogenation, and such activity was preserved for the Ni(L)2 units, incorporated into the framework of 2. In addition, a new property occurred in the case of 2: the catalytic activity of PCP depended on its sorption capacity with respect to the substrate. In contrast to homogeneous catalysts, usage of solid PCPs may allow selectivity due to porous structure and simplify separation of product.

  4. Crystal-defect-induced facet-dependent electrocatalytic activity of 3D gold nanoflowers for the selective nanomolar detection of ascorbic acid.

    Science.gov (United States)

    De, Sandip Kumar; Mondal, Subrata; Sen, Pintu; Pal, Uttam; Pathak, Biswarup; Rawat, Kuber Singh; Bardhan, Munmun; Bhattacharya, Maireyee; Satpati, Biswarup; De, Amitabha; Senapati, Dulal

    2018-06-14

    Understanding and exploring the decisive factors responsible for superlative catalytic efficiency is necessary to formulate active electrode materials for improved electrocatalysis and high-throughput sensing. This research demonstrates the ability of bud-shaped gold nanoflowers (AuNFs), intermediates in the bud-to-blossom gold nanoflower synthesis, to offer remarkable electrocatalytic efficiency in the oxidation of ascorbic acid (AA) at nanomolar concentrations. Multicomponent sensing in a single potential sweep is measured using differential pulse voltammetry while the kinetic parameters are estimated using electrochemical impedance spectroscopy. The outstanding catalytic activity of bud-structured AuNF [iAuNFp(Bud)/iGCp ≅ 100] compared with other bud-to-blossom intermediate nanostructures is explained by studying their structural transitions, charge distributions, crystalline patterns, and intrinsic irregularities/defects. Detailed microscopic analysis shows that density of crystal defects, such as edges, terraces, steps, ledges, kinks, and dislocation, plays a major role in producing the high catalytic efficiency. An associated ab initio simulation provides necessary support for the projected role of different crystal facets as selective catalytic sites. Density functional theory corroborates the appearance of inter- and intra-molecular hydrogen bonding within AA molecules to control the resultant fingerprint peak potentials at variable concentrations. Bud-structured AuNF facilitates AA detection at nanomolar levels in a multicomponent pathological sample.

  5. Enhanced electrocatalytic activity of PANI and CoFe2O4/PANI composite supported on graphene for fuel cell applications

    Science.gov (United States)

    Mohanraju, Karuppannan; Sreejith, Vasudevan; Ananth, Ramaiyan; Cindrella, Louis

    2015-06-01

    New catalysts of reduced graphene oxide (rGO) with poly aniline (PANI) and cobalt ferrite (CF) have been successfully prepared by simple chemical reduction method. Their electrocatalytic activity for oxygen reduction reaction (ORR) was evaluated. Semi-crystalline nature of CF was analyzed by X-ray diffraction (XRD) study. Surface morphology by HR-SEM showed features of CF particles and PANI film on graphene sheets. FT-IR studies revealed changes in C-N and Cdbnd N stretching vibrations of PANI confirming bonding of PANI to graphene sheets. Raman spectrum showed presence of PANI on distorted graphene layers. TG/DTA revealed thermal stability and extent of loading of CF in composite. ORR performance was studied using catalyst modified rotating disc electrode (RDE). A maximum kinetic current density of -3.46 mA cm-2 at -0.2 V was obtained for CF/PANI/rGO. Tafel slope, onset and half wave potentials for the catalyst were obtained from ORR response. Durability studies showed that synthesized electrocatalyst has better stability and methanol tolerance than commercial Pt/C catalyst. To the best of our knowledge, this is the first study aiming enhancement of ORR activity using PANI and CoFe2O4 on graphene support. A trace amount of Pt in the composite boosted the performance of single PEM fuel cell.

  6. Statistical analysis of the electrocatalytic activity of Pt nanoparticles supported on novel functionalized reduced graphene oxide-chitosan for methanol electrooxidation

    Science.gov (United States)

    Ekrami-Kakhki, Mehri-Saddat; Abbasi, Sedigheh; Farzaneh, Nahid

    2018-01-01

    The purpose of this study is to statistically analyze the anodic current density and peak potential of methanol oxidation at Pt nanoparticles supported on functionalized reduced graphene oxide (RGO), using design of experiments methodology. RGO is functionalized with methyl viologen (MV) and chitosan (CH). The novel Pt/MV-RGO-CH catalyst is successfully prepared and characterized with transmission electron microscopy (TEM) image. The electrocatalytic activity of Pt/MV-RGOCH catalyst is experimentally evaluated for methanol oxidation. The effects of methanol concentration and scan rate factors are also investigated experimentally and statistically. The effects of these two main factors and their interactions are investigated, using analysis of variance test, Duncan's multiple range test and response surface method. The results of the analysis of variance show that all the main factors and their interactions have a significant effect on anodic current density and peak potential of methanol oxidation at α = 0.05. The suggested models which encompass significant factors can predict the variation of the anodic current density and peak potential of methanol oxidation. The results of Duncan's multiple range test confirmed that there is a significant difference between the studied levels of the main factors. [Figure not available: see fulltext.

  7. Differences in the electrochemical behavior of ruthenium and iridium oxide in electrocatalytic coatings of activated titanium anodes prepared by the sol–gel procedure

    Directory of Open Access Journals (Sweden)

    VLADIMIR V. PANIĆ

    2010-10-01

    Full Text Available The electrochemical characteristics of Ti0.6Ir0.4O2/Ti and Ti0.6Ru0.4O2/Ti anodes prepared by the sol–gel procedure from the corresponding oxide sols, obtained by force hydrolysis of the corresponding metal chlorides, were compared. The voltammetric properties in H2SO4 solution indicate that Ti0.6Ir0.4O2/Ti has more pronounced pseudocapacitive characteristics, caused by proton-assisted, solid state surface redox transitions of the oxide. At potentials negative to 0.0 VSCE, this electrode is of poor conductivity and activity, while the voltammetric behavior of the Ti0.6Ru0.4O2/Ti electrode is governed by proton injection/ejection into the oxide structure. The Ti0.6Ir0.4O2/Ti electrode had a higher electrocatalytical activity for oxygen evolution, while the investigated anodes were of similar activity for chlorine evolution. The potential dependence of the impedance characteristics showed that the Ti0.6Ru0.4O2/Ti electrode behaved like a capacitor over a wider potential range than the Ti0.6Ir0.4O2/Ti electrode, with fully-developed pseudocapacitive properties at potentials positive to 0.60 VSCE. However, the impedance characteristics of the Ti0.6Ir0.4O2/Ti electrode changed with increasing potential from resistor-like to capacitor-like behavior.

  8. Solvothermal synthesis of size-tunable ZnFe{sub 2}O{sub 4} colloidal nanocrystal assemblies and their electrocatalytic activity towards hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ruirui, E-mail: liurui1114@outlook.com; Lv, Meng, E-mail: lm199133@126.com; Wang, Qianbin, E-mail: material_wqb@163.com; Li, Hongliang, E-mail: lhl@qdu.edu.cn; Guo, Peizhi, E-mail: pzguo@qdu.edu.cn; Zhao, X.S., E-mail: chezxs@qdu.edu.cn

    2017-02-15

    Three ZnFe{sub 2}O{sub 4} colloidal nanocrystal assemblies (CNAs), namely CNA1, CNA2 and CNA3, have been synthesized solvothermally with the size of 560 nm, 460 nm and 330 nm and are formed by the self-assembly of primary nanocrystals with the crystallite sizes of 19.2 nm, 15.5 nm and 21.8 nm, respectively. It was found that CNA2 performed superparamagnetic behavior with a saturation magnetization value of 36.9 emu g{sup −1} while either CNA1 or CNA3 exhibited weak ferromagnetic with a small hysteresis loop and large saturation magnetization. Electrochemical sensing measurements toward the reduction of hydrogen peroxide showed that the peak currents of the CNAs in cyclic voltammograms showed a linear relationship with the concentration of hydrogen peroxide in the experimental conditions and the peak potentials were increased with the order of CNA3, CNA2 and CNA1. The formation mechanism of ZnFe{sub 2}O{sub 4} CNAs had been discussed based on the experimental data. The magnetism and electrocatalysis of the ZnFe{sub 2}O{sub 4} CNAs were supposed to be dependent on the size of primary nanoparticles and the structure of the CNAs. - Highlights: • Size-tunable ZnFe{sub 2}O{sub 4} colloidal nanocrystal assemblies were synthesized solvothermally. • Magnetic properties of ZnFe{sub 2}O{sub 4} assemblies are depended on the size and self-assembly of primary nanoparticles. • Electrocatalytic activity of ZnFe{sub 2}O{sub 4} assemblies is determined by their structure.

  9. Facile solvothermal synthesis of monodisperse Pt2.6Co1 nanoflowers with enhanced electrocatalytic activity towards oxygen reduction and hydrogen evolution reactions

    International Nuclear Information System (INIS)

    Jiang, Liu-Ying; Lin, Xiao-Xiao; Wang, Ai-Jun; Yuan, Junhua; Feng, Jiu-Ju; Li, Xin-Sheng

    2017-01-01

    Highlights: • Uniform Pt 2.6 Co 1 nanoflowers were prepared by a simple solvothermal method. • Glucose and CTAC were used as the green reductant and structure director, respectively. • The architectures had the enlarged ECSA. • The architectures exhibited excellent catalytic performances for HER in acid and alkaline media. • The architectures showed highly catalytic performances for ORR in acid media. - Abstract: Herein, uniform Pt 2.6 Co 1 nanoflowers (NFs) were synthesized in oleylamine by a one-pot solvothermal method, using cetyltrimethylammonium chloride (CTAC) and glucose as the capping agent and green reducing agent. The samples were mainly characterized by transmission electron microscopy (TEM), high angle annular dark-field scanning TEM (HAADF-STEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The architectures had larger electrochemically active surface area (ECSA) of 23.84 m 2 g −1 Pt than Pt 1.2 Co 1 nanocrystals (NCs, 14.96 m 2 g −1 Pt ), Pt 3.7 Co 1 NCs (16.96 m 2 g −1 Pt ) and commercial Pt black (20.35 m 2 g −1 Pt ). And the as-obtained Pt 2.6 Co 1 catalyst displayed superior catalytic performance and better durability for hydrogen evolution reaction (HER) as compared to Pt 1.2 Co 1 NCs, Pt 3.7 Co 1 NCs, commercial 50% Pt/C and Pt black catalysts in acid and alkaline media. Meanwhile, the electrocatalytic performance of Pt 2.6 Co 1 NFs for oxygen reduction reaction (ORR) is better in acid media as compared with that in alkaline media. It indicates the great potential applications of the as-prepared catalyst in fuel cells.

  10. [Treatment of acrylate wastewater by electrocatalytic reduction process].

    Science.gov (United States)

    Yu, Li-Na; Song, Yu-Dong; Zhou, Yue-Xi; Zhu, Shu-Quan; Zheng, Sheng-Zhi; Ll, Si-Min

    2011-10-01

    High-concentration acrylate wastewater was treated by an electrocatalytic reduction process. The effects of the cation exchange membrane (CEM) and cathode materials on acrylate reduction were investigated. It indicated that the acrylate could be reduced to propionate acid efficiently by the electrocatalytic reduction process. The addition of CEM to separator with the cathode and anode could significantly improve current efficiency. The cathode materials had significant effect on the reduction of acrylate. The current efficiency by Pd/Nickel foam, was greater than 90%, while those by nickel foam, the carbon fibers and the stainless steel decreased successively. Toxicity of the wastewater decreased considerably and methane production rate in the biochemical methane potential (BMP) test increased greatly after the electrocatalytic reduction process.

  11. Unlocking the Electrocatalytic Activity of Antimony for CO2 Reduction by Two-Dimensional Engineering of the Bulk Material.

    Science.gov (United States)

    Li, Fengwang; Xue, Mianqi; Li, Jiezhen; Ma, Xinlei; Chen, Lu; Zhang, Xueji; MacFarlane, Douglas R; Zhang, Jie

    2017-11-13

    Two-dimensional (2D) materials are known to be useful in catalysis. Engineering 3D bulk materials into the 2D form can enhance the exposure of the active edge sites, which are believed to be the origin of the high catalytic activity. Reported herein is the production of 2D "few-layer" antimony (Sb) nanosheets by cathodic exfoliation. Application of this 2D engineering method turns Sb, an inactive material for CO 2 reduction in its bulk form, into an active 2D electrocatalyst for reduction of CO 2 to formate with high efficiency. The high activity is attributed to the exposure of a large number of catalytically active edge sites. Moreover, this cathodic exfoliation process can be coupled with the anodic exfoliation of graphite in a single-compartment cell for in situ production of a few-layer Sb nanosheets and graphene composite. The observed increased activity of this composite is attributed to the strong electronic interaction between graphene and Sb. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Unlocking the Electrocatalytic Activity of Chemically Inert Amorphous Carbon-Nitrogen for Oxygen Reduction: Discerning and Refactoring Chaotic Bonds

    DEFF Research Database (Denmark)

    Zhang, Caihong; Zhang, Wei; Wang, Dong

    2017-01-01

    Mild annealing enables inactive nitrogen (N)-doped amorphous carbon (a-C) films abundant with chaotic bonds prepared by magnetron sputtering to become effective for the oxygen reduction reaction (ORR) by virtue of generating pyridinic N. The rhythmic variation of ORR activity elaborates well...... on the subtle evolution of the amorphous C−N bonds conferred by spectroscopic analysis....

  13. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    Science.gov (United States)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  14. Electro-catalytic degradation of sulfisoxazole by using graphene anode.

    Science.gov (United States)

    Wang, Yanyan; Liu, Shuan; Li, Ruiping; Huang, Yingping; Chen, Chuncheng

    2016-05-01

    Graphite and graphene electrodes were prepared by using pure graphite as precursor. The electrode materials were characterized by a scanning electron microscope (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV) measurements. The electro-catalytic activity for degradation of sulfisoxazole (SIZ) was investigated by using prepared graphene or graphite anode. The results showed that the degradation of SIZ was much more rapid on the graphene than that on the graphite electrode. Moreover, the graphene electrode exhibited good stability and recyclability. The analysis on the intermediate products and the measurement of active species during the SIZ degradation demonstrated that indirect oxidation is the dominant mechanism, involving the electro-catalytic generation of OH and O2(-) as the main active oxygen species. This study implies that graphene is a promising potential electrode material for long-term application to electro-catalytic degradation of organic pollutants. Copyright © 2015. Published by Elsevier B.V.

  15. Application of Polarization Modulated Infrared Reflection Absorption Spectroscopy for electrocatalytic activity studies of laccase adsorbed on modified gold electrodes

    International Nuclear Information System (INIS)

    Olejnik, Piotr; Pawłowska, Aleksandra; Pałys, Barbara

    2013-01-01

    Orientation of the enzyme macromolecule on the electrode surface is crucially important for the efficiency of the electron transport between the active site and electrode surface. The orientation can be controlled by affecting the surface charge and the pH of the buffer solution. In this contribution we study laccase physically adsorbed on gold surface modified by mercapto-ethanol, lipid and variously charged diazonium salts. Polarization Modulated Infrared Reflection Absorption Spectroscopy (PMIRRAS) enables the molecular orientation study of the protein molecule by comparison of the amide I to amide II band intensity ratios assuming that the protein secondary structure does not change. We observe significant differences in the intensity ratios depending on the kind of support and the enzyme deposition. The comparison of infrared spectra and cyclic voltammetry responses of variously prepared laccase layers reveals that the parallel orientation of beta-sheet moieties results in high enzyme activity

  16. Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

    Science.gov (United States)

    Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

    2014-01-01

    Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

  17. Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Vladimir Linkov

    2013-07-01

    Full Text Available Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C, were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM, X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS, and methanol oxidation activity compared using CV and chronoamperometry (CA. While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells.

  18. Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

    KAUST Repository

    Ou, Yiwei

    2011-11-01

    The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

  19. Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

    KAUST Repository

    Ou, Yiwei; Kumagai, Hiromu; Yin, Fengxiang; Okada, Saori; Hatasawa, Haruna; Morioka, Hiroyuki; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2011-01-01

    The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

  20. Effect of Mo addition on the electrocatalytic activity of Pt-Sn-Mo/C for direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Lee, Eungje; Murthy, Arun; Manthiram, Arumugam

    2011-01-01

    Carbon-supported Pt-Sn-Mo electrocatalysts have been synthesized by a polyol reduction method and characterized for ethanol electro-oxidation reaction (EOR). While the percent loading of the synthesized nanoparticles on the carbon support is higher than 35%, energy dispersive spectroscopy (EDS) reveals that the Mo contents in the nanoparticle catalysts are lower than the nominal value, indicating incomplete reduction of the Mo precursor. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses reveal that the Sn and Mo exist as oxide phases at the surface layers of the nanoparticles and the degree of alloying is very low. The electrochemical properties of the electrocatalysts have been evaluated by cyclic voltammetry (CV) and chronoamperometry. The catalytic activity for EOR decreases in the order PtSnMo 0.6 /C > PtSnMo 0.4 /C > PtSn/C. Single cell direct ethanol fuel cell (DEFC) tests also confirm that the PtSnMo 0.6 /C anode catalyst exhibit better performance than the PtSn/C anode catalyst. An analysis of the electrochemical data suggests that the incorporation of Mo to Pt-Sn enhances further the catalytic activity for EOR.

  1. Electrocatalytic activity and stability of Ag-MnOx/C composites toward oxygen reduction reaction in alkaline solution

    International Nuclear Information System (INIS)

    Wu, Qiumei; Jiang, Luhua; Qi, Luting; Yuan, Lizhi; Wang, Erdong; Sun, Gongquan

    2014-01-01

    Ag-MnO x /C composites were prepared using AgNO 3 and KMnO 4 as the precursors and Vulcan XC-72 as the support. The physical properties of the Ag-MnO x /C composites were investigated via X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The activity and the stability of the series of Ag-MnO x /C composites toward the oxygen reduction reaction (ORR) in alkaline media were investigated through the electrochemical techniques. The results show that the main species MnO 2 and Ag 2 O in the fresh sample convert into Mn 3 O 4 and Ag(0), respectively, after the heat treatment in N 2 at 300 °C (Ag-MnO x /C-300). The Ag-MnO x /C-300 sample shows the highest activity toward the ORR, with the half-wave potential of the ORR shifting negatively only 0.035 V compared to that on the commercial 40 wt. % Pt/C (JM). The electron transfer number during the ORR on the Ag-MnO x /C composite increases with the value close to four after the heat treatment at 300 °C, which is mainly attributed to the formation of Ag(0), rather than Mn 3 O 4 . The heat treatment brings about a better catalytic stability of the composite, and no obviously negative shift takes place for the half-wave potential of the ORR on the Ag-MnO x /C-300 composite after 1000 cycles accelerated aging test. The maximum power density of the zinc-air battery with the Ag-MnO x /C-300 air electrode reaches up to 130 mW cm −2 , higher than those based on the Pd/C and Pt/C cathode catalysts, which shows that the Ag-MnO x /C-300 composite is a promising candidate as the catalyst for the air electrode

  2. Synthesis of bimetallic Pt-Pd core-shell nanocrystals and their high electrocatalytic activity modulated by Pd shell thickness

    Science.gov (United States)

    Li, Yujing; Wang, Zhi Wei; Chiu, Chin-Yi; Ruan, Lingyan; Yang, Wenbing; Yang, Yang; Palmer, Richard E.; Huang, Yu

    2012-01-01

    Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more resistant to the CO poisoning than Pt NCs and Pt black. It is also demonstrated that the bimetallic Pt-Pd core-shell NCs can enhance the current density of the methanol oxidation reaction, lowering the over-potential by 35 mV with respect to the Pt core NCs. Further investigation reveals that the Pd/Pt ratio of 1/3, which corresponds to nearly monolayer Pd deposition on Pt core NCs, gives the highest oxidation current density and lowest over-potential. This study shows for the first time the systematic investigation of effects of Pd atomic shells on Pt-Pd bimetallic nanocatalysts, providing valuable guidelines for designing high-performance catalysts for fuel cell applications.Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more

  3. α-MnO2 Nanowires/Graphene Composites with High Electrocatalytic Activity for Mg-Air Fuel Cell

    International Nuclear Information System (INIS)

    Jiang, Min; He, Hao; Huang, Chen; Liu, Bo; Yi, Wen-Jun; Chao, Zi-Sheng

    2016-01-01

    Highlights: • α-MnO 2 NWs/graphene was synthesized and studied in Mg-air fuel cell. • The performance of α-MnO 2 NWs/graphene is close to the Pt/C. • The ORR mechanism involves a one-step, quasi-4-electron pathway. • A large area (5 cm*5 cm) cathode was prepared and tested in a full cell. - Abstract: This paper reports the preparation of α-MnO 2 NWs/graphene composites as the cathode catalyst for magnesium-air fuel cell and its excellent electrochemistry performance. The composites are synthesized by self-assembly of α-MnO 2 nan α-MnO 2 NWs/graphene was synthesized and studied in Mg-air fuel cell. α-MnO 2 NWs/graphene was synthesized and studied in Mg-air fuel cell. owires (NWs) on the surface of graphene via a simple hydrothermal method. The α-MnO 2 NWs/graphene composites showed a higher electrochemical activity than the commercial MnO 2 . The oxygen reduction peak of the α-MnO 2 NWs/graphene composites catalyst is tested in a 0.1 M KOH solution at −0.252 V, which is more positive than the commercial MnO 2 (−0.287 V). The ORR limit current density for 28% α-MnO2 NWs/graphene composite is approximately 2.74 mA/cm 2 , which is similar to that of the 20% Pt/C(2.79 mA/cm 2 ) in the same conditions. Based on the Koutecky–Levich plot, the ORR mechanism of the composite involves a one-step, quasi-4-electron pathway. In addition, magnesium-air fuel cell with α-MnO 2 NWs/graphene as catalyst possesses higher current density (140 mA/cm 2 ) and power density (96 mW/cm 2 ) compared to the commercial MnO 2 . This study proves that the cost-effective α-MnO 2 NWs/graphene with higher power generation ability make it possible for the substitute of the noble metals catalyst in the Mg-air fuel cell.

  4. Electrocatalytic hydrogenation of organic molecules on conductive new catalytic material

    Energy Technology Data Exchange (ETDEWEB)

    Tountian, D. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide; Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Brisach-Wittmeyer, A.; Menard, H. [Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Nkeng, P.; Poillerat, G. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide

    2008-07-01

    Electrocatalytic hydrogenation (ECH) of organic molecules is a process where chemisorbed hydrogen is produced by electroreduction of water which reacts with the species in bulk. Greater emphasis is being placed on improving the nature of the building material of the electrodes in order to increase ECH efficiency. The effectiveness of the ECH is known to be linked to the nature of electrode materials used and their adsorption properties. This work presented the effect of conductive support material on ECH. The conductive catalysts were obtained from tin dioxide which is chemically stable. Palladium was the catalytic metal used in this study. The production of chemisorbed hydrogen was shown to depend on the quantity of metallic nanoaggregates in electrical contact with the reticulated vitreous carbon use as electrode. The conductive support, F-doped tin dioxide, was obtained by the sol-gel method. The electrocatalysts were characterized by different methods as resistivity measurements, linear sweep voltammetry, XRD, SEM, TGA/DSC, and FTIR analysis. The effects of temperature and time of calcination were also investigated. The study showed that the F-doped SnO2 electrocatalyst appeared to increase the rate of phenol electrohydrogenation. It was concluded that the improved electrocatalytic activity of Pd/F-doped SnO2 can be attributed to the simultaneous polarization of all the metallic Pd nanoaggregates present on the surface as well as in the pores of the matrix by contact with RVC. This results in a better production of chemisorbed atomic hydrogen with a large number of adlienation points. 9 refs., 3 figs.

  5. The electrocatalytic activity of a supramolecular assembly of CoTsPc/FeT4MPyP on multi-walled carbon nanotubes towards L-glutathione, and its determination in human erythrocytes

    International Nuclear Information System (INIS)

    Luz, R.C.S.; Maroneze, C.M.; Tanaka, A.A.; Kubota, L.T.; Gushikem, Y.; Damos, F.S.

    2010-01-01

    The electrocatalytic activity of a supramolecular complex based on cobalt(II) phthalocyanine tetrasulfonate and iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin adsorbed on multi-walled carbon nanotubes for the oxidation of L-glutathione (GSH) was investigated at pH 7.4. Scanning electron microscopy and energy dispersive X-ray spectrometry were used to characterize the morphologies and composition of the materials. The modified electrode displayed efficient electrocatalytic activity in terms of oxidation of GSH at an oxidation potential of 0 V (versus Ag/AgCl). Cyclic voltammetry and amperometry indicated that the oxidation involves 2-electrons, with a heterogeneous rate constant of 4.9 x 10 5 mol -1 L s -1 . The response is linear from 2 to 210 μmol L -1 , the sensitivity is 1570 μA L mmol -1 , the detection limit is 0.03 μmol L -1 , and the relative standard deviation of 110 μmol L -1 GSH was 2.6% (n=10). The modified electrode was applied to the determination of GSH in erythrocytes and the results were in agreement with those obtained by a method reported in the literature. (author)

  6. The shaking signal of the honey bee informs workers to prepare for greater activity

    OpenAIRE

    Seeley, Thomas D.; Weidenmüller, Anja; Kühnholz, Susanne

    2010-01-01

    One of the most conspicuous activities o f worker bees inside a hive is the shaking of other wc~rliersT. his shaking has long been suspected to be a communication behavior, but its information content and function have until recently remained mysterious. Prior studies of the colony-level patterns of the production of ihc shaking signal supgest strongly that this signal semes to arouse workers to greater activity, such as at times of good foraging. Data from our obsenrauons of mdividual bees h...

  7. Cognitively Engaging Activity is Associated with Greater Cortical and Subcortical Volumes

    Directory of Open Access Journals (Sweden)

    Talia R. Seider

    2016-05-01

    Full Text Available As the population ages and dementia becomes a growing healthcare concern, it is increasingly important to identify targets for intervention to delay or attenuate cognitive decline. Research has shown that the most successful interventions aim at altering lifestyle factors. Thus, this study examined how involvement in physical, cognitive, and social activity is related to brain structure in older adults. Sixty-five adults (mean age = 71.4 years, standard deviation = 8.9 received the Community Healthy Activities Model Program for Seniors (CHAMPS, a questionnaire that polls everyday activities in which older adults may be involved, and also underwent structural magnetic resonance imaging. Stepwise regression with backwards selection was used to predict weekly time spent in either social, cognitive, light physical, or heavy physical activity from the volume of one of the cortical or subcortical regions of interest (corrected by intracranial volume as well as age, education, and gender as control variables. Regressions revealed that more time spent in cognitive activity was associated with greater volumes of all brain regions studied: total cortex (β = .289, p = .014, frontal (β = .276, p = .019, parietal (β = .305, p = .009, temporal (β = .275, p = .020, and occipital (β = .256, p = .030 lobes, and thalamus (β = .310, p = .010, caudate (β = .233, p = .049, hippocampus (β = .286, p = .017, and amygdala (β = .336, p = .004. These effects remained even after accounting for the positive association between cognitive activity and education. No other activity variable was associated with brain volumes. Results indicate that time spent in cognitively engaging activity is associated with greater cortical and subcortical brain volume. Findings suggest that interventions aimed at increasing levels of cognitive activity may delay cognitive consequences of aging and decrease the risk of developing dementia.

  8. Active convergence between the Lesser and Greater Caucasus in Georgia: Constraints on the tectonic evolution of the Lesser-Greater Caucasus continental collision

    Science.gov (United States)

    Sokhadze, G.; Floyd, M.; Godoladze, T.; King, R.; Cowgill, E. S.; Javakhishvili, Z.; Hahubia, G.; Reilinger, R.

    2018-01-01

    We present and interpret newly determined site motions derived from GPS observations made from 2008 through 2016 in the Republic of Georgia, which constrain the rate and locus of active shortening in the Lesser-Greater Caucasus continental collision zone. Observation sites are located along two ∼160 km-long profiles crossing the Lesser-Greater Caucasus boundary zone: one crossing the Rioni Basin in western Georgia and the other crossing further east near the longitude of Tbilisi. Convergence across the Rioni Basin Profile occurs along the southern margin of the Greater Caucasus, near the surface trace of the north-dipping Main Caucasus Thrust Fault (MCTF) system, and is consistent with strain accumulation on the fault that generated the 1991 MW6.9 Racha earthquake. In contrast, convergence along the Tbilisi Profile occurs near Tbilisi and the northern boundary of the Lesser Caucasus (near the south-dipping Lesser Caucasus Thrust Fault), approximately 50-70 km south of the MCTF, which is inactive within the resolution of geodetic observations (< ± 0.5 mm/yr) at the location of the Tbilisi Profile. We suggest that the southward offset of convergence along strike of the range is related to the incipient collision of the Lesser-Greater Caucasus, and closing of the intervening Kura Basin, which is most advanced along this segment of the collision zone. The identification of active shortening near Tbilisi requires a reevaluation of seismic hazards in this area.

  9. Preparation and electrocatalytic property of WC/carbon nanotube composite

    International Nuclear Information System (INIS)

    Li Guohua; Ma Chunan; Tang Junyan; Sheng Jiangfeng

    2007-01-01

    Tungsten carbide/carbon nanotube composite was prepared by surface decoration and in situ reduction-carbonization. The samples were characterized by XRD, SEM, EDS, TEM, HRTEM and BET, respectively. The XRD results show that the sample is composed of carbon nanotube, tungsten carbide and tungsten oxide. The EDS results show that the distribution of tungsten oxide is consistent with that of tungsten carbide. SEM, TEM and HRTEM results show that the tungsten carbide nanoparticle with irregular granule grows on the outside surface of carbon nanotube homogenously. The electrocatalytic activity of the sample for p-nitrophenol reduction was tested by a powder microelectrode in a basic solution. The results show that the electrocatalytic activity of the sample is higher than that of granular tungsten carbide, hollow globe tungsten carbide with mesoporosity and carbon nanotube purified. The improvement of the electrocatalytic activity of the sample can be attributed to its components and composite structure. These results indicate that tungsten carbide/carbon nanotube composite is one of the effective ways to improve the electrocatalytic activity of tungsten carbide

  10. Major depressive disorder is characterized by greater reward network activation to monetary than pleasant image rewards.

    Science.gov (United States)

    Smoski, Moria J; Rittenberg, Alison; Dichter, Gabriel S

    2011-12-30

    Anhedonia, the loss of interest or pleasure in normally rewarding activities, is a hallmark feature of unipolar Major Depressive Disorder (MDD). A growing body of literature has identified frontostriatal dysfunction during reward anticipation and outcomes in MDD. However, no study to date has directly compared responses to different types of rewards such as pleasant images and monetary rewards in MDD. To investigate the neural responses to monetary and pleasant image rewards in MDD, a modified Monetary Incentive Delay task was used during functional magnetic resonance imaging to assess neural responses during anticipation and receipt of monetary and pleasant image rewards. Participants included nine adults with MDD and 13 affectively healthy controls. The MDD group showed lower activation than controls when anticipating monetary rewards in right orbitofrontal cortex and subcallosal cortex, and when anticipating pleasant image rewards in paracingulate and supplementary motor cortex. The MDD group had relatively greater activation in right putamen when anticipating monetary versus pleasant image rewards, relative to the control group. Results suggest reduced reward network activation in MDD when anticipating rewards, as well as relatively greater hypoactivation to pleasant image than monetary rewards. 2011 Elsevier Ireland Ltd. All rights reserved.

  11. Electrocatalytic Reduction-oxidation of Chlorinated Phenols using a Nanostructured Pd-Fe Modified Graphene Catalyst

    International Nuclear Information System (INIS)

    Shi, Qin; Wang, Hui; Liu, Shaolei; Pang, Lei; Bian, Zhaoyong

    2015-01-01

    A Pd-Fe modified graphene (Pd-Fe/G) catalyst was prepared by the Hummers oxidation method and bimetallic co-deposition method. The catalyst was then characterized by various characterization techniques and its electrochemical property toward the electrocatalytic reduction-oxidation of chlorinated phenols was investigated by using cyclic voltammetry and differential pulse voltammetry. The results of the characterization show that the Pd-Fe/G catalyst in which the weight proportion of Pd and Fe is 1:1 has an optimal surface performance. The diameter of the Pd-Fe particles is approximately 5.2 ± 0.3 nm, with a uniform distribution on the supporting graphene. This is smaller than the Pd particles of a Pd-modified graphene (Pd/G) catalyst. The Pd-Fe/G catalyst shows a higher electrocatalytic activity than the Pd/G catalyst for reductive dechlorination when feeding with hydrogen gas. The reductive peak potentials of −0.188 V, −0.836 V and −0.956 V in the DPV curves are attributed to the dechlorination of ortho-Cl, meta-Cl, and para-Cl in 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, respectively. In accordance with an analysis of the frontier orbital theory, the order of ease of dechlorination with Pd-Fe/G catalyst is 2-chlorophenol > 3-chlorophenol > 4-chlorophenol. The Pd-Fe/G catalyst has a greater activity than the Pd/G catalyst in accelerating the two-electron reduction of O_2 to H_2O_2, which is attributed to the higher current of the reduction peak at approximately −0.40 V when feeding with oxygen gas. Therefore, the Pd-Fe/G catalyst exhibits a higher electrocatalytic activity than the Pd/G catalyst for the reductive dechlorination and acceleration of the two-electron reduction of O_2 to H_2O_2.

  12. Effect of exposure to greater active videogame variety on time spent in moderate- to vigorous-intensity physical activity.

    Science.gov (United States)

    Raynor, Hollie A; Cardoso, Chelsi; Bond, Dale S

    2016-07-01

    This investigation examined whether exposure to greater active videogame variety increases moderate- to vigorous-intensity physical activity (MVPA). Twenty-three participants (age=22.7±4.2yrs; body mass index=23.5±3.0kg/m(2); self-reported MVPA=298.7±116.7min/wk; 62.2% female; 73.9% Caucasian) participated in VARIETY (4 different active videogames during 4, 15-min bouts) and NON-VARIETY (only 1 active videogame during 4, 15-min bouts) counterbalanced sessions. VARIETY provided a different active videogame in each bout. NON-VARIETY provided participants their most highly liked active videogame in each bout. The Sensewear Mini Armband objectively assessed MVPA. For MVPA minutes, a session×bout (p<0.05) interaction occurred. In NON-VARIETY, bouts 2, 3, and 4 had significantly (p<0.05) fewer minutes than bout 1, with no decrease occurring in VARIETY. In bout 4, VARIETY had significantly (p<0.05) more minutes than NON-VARIETY. A main effect of session (p<0.05) occurred for MVPA minutes and energy expenditure, with VARIETY achieving greater amounts (31.8±14.3min vs. 27.6±16.9min; 186.1±96.8kcal vs. 171.2±102.8kcal). Exposure to greater activity variety within a session increased MVPA. Future research should examine exposure to a variety of activities over a longer time frame with participants of differing lifestyles in free-living environments. Copyright © 2016. Published by Elsevier Inc.

  13. Electrocatalytic cermet sensor

    Science.gov (United States)

    Shoemaker, Erika L.; Vogt, Michael C.

    1998-01-01

    A sensor for O.sub.2 and CO.sub.2 gases. The gas sensor includes a plurality of layers driven by a cyclic voltage to generate a unique plot characteristic of the gas in contact with the sensor. The plurality of layers includes an alumina substrate, a reference electrode source of anions, a lower electrical reference electrode of Pt coupled to the reference source of anions, a solid electrolyte containing tungsten and coupled to the lower reference electrode, a buffer layer for preventing flow of Pt ions into the solid electrolyte and an upper catalytically active Pt electrode coupled to the buffer layer.

  14. Lizard activity and abundance greater in burned habitat of a xeric montane forest

    Science.gov (United States)

    Fouts, Kevin L.; Moore, Clinton; Johnson, Kristine D.; Maerz, John C.

    2017-01-01

    Restoring the natural or historical state of ecosystems is a common objective among resource managers, but determining whether desired system responses to management actions are occurring is often protracted and challenging. For wildlife, the integration of mechanistic habitat modeling with population monitoring may provide expedited measures of management effectiveness and improve understanding of how management actions succeed or fail to recover populations. Southern Appalachia is a region of high biodiversity that has undergone dramatic change as a result of human activities such as historic logging, exotic invasions, and alteration of disturbance regimes—including reduction in application of fire. Contemporary efforts to restore fire-maintained ecosystems within southern Appalachian forests require tools to assess the effects of fire management practices on individual animal fitness and relate them to corresponding influences on species abundance. Using automated sensing equipment, we investigated the effects of burned forests on reptile habitat suitability within the western portion of Great Smoky Mountains National Park, Tennessee. Specifically, we used microclimate measurements to model northern fence lizard Sceloporus undulatus hyacinthinus diurnal activity budgets in unburned and variable burn age (3–27-y) forest stands. We estimated northern fence lizard occurrence and abundance along transects through burned and unburned forests. Burned forest stands had microclimates that resulted in longer modeled daily activity periods under most conditions during summer. S. undulatus abundance was 4.75 times greater on burned stands compared to paired unburned stands, although the relationship between burn age and abundance was not well determined. Results suggest the more open habitat structure of burned areas within these xeric pine–oak forests may benefit S. undulatus.

  15. Versatility of cooperative transcriptional activation: a thermodynamical modeling analysis for greater-than-additive and less-than-additive effects.

    Directory of Open Access Journals (Sweden)

    Till D Frank

    Full Text Available We derive a statistical model of transcriptional activation using equilibrium thermodynamics of chemical reactions. We examine to what extent this statistical model predicts synergy effects of cooperative activation of gene expression. We determine parameter domains in which greater-than-additive and less-than-additive effects are predicted for cooperative regulation by two activators. We show that the statistical approach can be used to identify different causes of synergistic greater-than-additive effects: nonlinearities of the thermostatistical transcriptional machinery and three-body interactions between RNA polymerase and two activators. In particular, our model-based analysis suggests that at low transcription factor concentrations cooperative activation cannot yield synergistic greater-than-additive effects, i.e., DNA transcription can only exhibit less-than-additive effects. Accordingly, transcriptional activity turns from synergistic greater-than-additive responses at relatively high transcription factor concentrations into less-than-additive responses at relatively low concentrations. In addition, two types of re-entrant phenomena are predicted. First, our analysis predicts that under particular circumstances transcriptional activity will feature a sequence of less-than-additive, greater-than-additive, and eventually less-than-additive effects when for fixed activator concentrations the regulatory impact of activators on the binding of RNA polymerase to the promoter increases from weak, to moderate, to strong. Second, for appropriate promoter conditions when activator concentrations are increased then the aforementioned re-entrant sequence of less-than-additive, greater-than-additive, and less-than-additive effects is predicted as well. Finally, our model-based analysis suggests that even for weak activators that individually induce only negligible increases in promoter activity, promoter activity can exhibit greater

  16. Beaver Activity, Holocene Climate and Riparian Landscape Change Across Stream Scales in the Greater Yellowstone Ecosystem

    Science.gov (United States)

    Levine, R.; Meyer, G. A.

    2013-12-01

    Beaver (Castor canadensis) have been part of the fluvial and riparian landscape across much of North America since the Pleistocene, increasing channel habitat complexity and expanding riparian landscapes. The fur trade, however, decimated beaver populations by the 1840s, and other human activities have limited beaver in many areas, including parts of the Greater Yellowstone Ecosystem (GYE). Understanding fluctuations in beaver occupation through the Holocene will aid in understanding the natural range of variability in beaver activity as well as climatic and anthropogenic impacts to fluvial systems. We are developing a detailed chronology of beaver-assisted sedimentation and overall fluvial activity for Odell and Red Rock Creeks (basin areas 83 and 99 km2) in Centennial Valley (CV), Montana, to augment related studies on the long-term effects of beaver on smaller GYE fluvial systems (basin areas 0.1-50 km2). In developing the CV chronology, we use the presence of concentrations of beaver-chewed sticks as a proxy for beaver occupancy. Beaver-stick deposits are found in paleochannel and fluvial terrace exposures. The relative ages of exposures were determined by elevation data from airborne LiDAR and ground surveys. Numerical ages were obtained from 36 14C ages (~30 more are pending) of beaver-stick wood collected during investigation of the stratigraphy. Most beaver-stick deposits are associated with ~ 1 meter of fine-grained sediment, interpreted as overbank deposits, commonly overlying gravelly sand or pebble gravel channel deposits which is consistent with enhanced overbank sedimentation associated with active beaver dams in CV streams. The CV deposits differ from those on smaller GYE streams where beaver-stick deposits are associated with abandoned dams (berms), infilled ponds and laminated sediments. The lack of pond-related deposition associated with CV beaver-stick deposits is consistent with frequent dam breaching (≤ 5 years) in the modern channel of Odell

  17. Direct electrochemistry with enhanced electrocatalytic activity of hemoglobin in hybrid modified electrodes composed of graphene and multi-walled carbon nanotubes.

    Science.gov (United States)

    Sun, Wei; Cao, Lili; Deng, Ying; Gong, Shixing; Shi, Fan; Li, Gaonan; Sun, Zhenfan

    2013-06-05

    A graphene (GR) and multi-walled carbon nanotubes (MWCNT) hybrid was prepared and modified on a 1-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE). Hemoglobin (Hb) was immobilized on GR-MWCNT/CILE surface with Nafion as the film forming material and the modified electrode was denoted as Nafion/Hb-GR-MWCNT/CILE. Spectroscopic results revealed that Hb molecules retained its native structure in the GR-MWCNT hybird. Electrochemical behaviors of Hb were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks obtained, which indicated that direct electron transfer of Hb was realized in the hybrid modified electrode. The result could be attributed to the synergistic effects of GR-MWCNT hybrid with enlarged surface area and improved conductivity through the formation of a three-dimensional network. Electrochemical parameters of the immobilized Hb on the electrode surface were further calculated with the results of the electron transfer number (n) as 1.03, the charge transfer coefficient (a) as 0.58 and the electron-transfer rate constant (ks) as 0.97 s(-1). The Hb modified electrode showed good electrocatalytic ability toward the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.05 to 38.0 mmol L(-1) with a detection limit of 0.0153 mmol L(-1) (3σ), H2O2 in the concentration range from 0.1 to 516.0 mmol L(-1) with a detection limit of 34.9 nmol/L (3σ) and NaNO2 in the concentration range from 0.5 to 650.0 mmol L(-1) with a detection limit of 0.282 μmol L(-1) (3σ). So the proposed electrode had the potential application in the third-generation electrochemical biosensors without mediator. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Elk migration patterns and human activity influence wolf habitat use in the Greater Yellowstone Ecosystem.

    Science.gov (United States)

    Nelson, Abigail A; Kauffman, Matthew J; Middleton, Arthur D; Jimenez, Michael D; McWhirter, Douglas E; Barber, Jarrett; Gerow, Kenneth

    2012-12-01

    Identifying the ecological dynamics underlying human-wildlife conflicts is important for the management and conservation of wildlife populations. In landscapes still occupied by large carnivores, many ungulate prey species migrate seasonally, yet little empirical research has explored the relationship between carnivore distribution and ungulate migration strategy. In this study, we evaluate the influence of elk (Cervus elaphus) distribution and other landscape features on wolf (Canis lupus) habitat use in an area of chronic wolf-livestock conflict in the Greater Yellowstone Ecosystem, USA. Using three years of fine-scale wolf (n = 14) and elk (n = 81) movement data, we compared the seasonal habitat use of wolves in an area dominated by migratory elk with that of wolves in an adjacent area dominated by resident elk. Most migratory elk vacate the associated winter wolf territories each summer via a 40-60 km migration, whereas resident elk remain accessible to wolves year-round. We used a generalized linear model to compare the relative probability of wolf use as a function of GIS-based habitat covariates in the migratory and resident elk areas. Although wolves in both areas used elk-rich habitat all year, elk density in summer had a weaker influence on the habitat use of wolves in the migratory elk area than the resident elk area. Wolves employed a number of alternative strategies to cope with the departure of migratory elk. Wolves in the two areas also differed in their disposition toward roads. In winter, wolves in the migratory elk area used habitat close to roads, while wolves in the resident elk area avoided roads. In summer, wolves in the migratory elk area were indifferent to roads, while wolves in resident elk areas strongly avoided roads, presumably due to the location of dens and summering elk combined with different traffic levels. Study results can help wildlife managers to anticipate the movements and establishment of wolf packs as they expand into areas

  19. Elk migration patterns and human activity influence wolf habitat use in the Greater Yellowstone Ecosystem

    Science.gov (United States)

    Nelson, Abigail; Kauffman, Matthew J.; Middleton, Arthur D.; Jimenez, Mike; McWhirter, Douglas; Barber, Jarrett; Gerow, Ken

    2012-01-01

    Identifying the ecological dynamics underlying human–wildlife conflicts is important for the management and conservation of wildlife populations. In landscapes still occupied by large carnivores, many ungulate prey species migrate seasonally, yet little empirical research has explored the relationship between carnivore distribution and ungulate migration strategy. In this study, we evaluate the influence of elk (Cervus elaphus) distribution and other landscape features on wolf (Canis lupus) habitat use in an area of chronic wolf–livestock conflict in the Greater Yellowstone Ecosystem, USA. Using three years of fine-scale wolf (n = 14) and elk (n = 81) movement data, we compared the seasonal habitat use of wolves in an area dominated by migratory elk with that of wolves in an adjacent area dominated by resident elk. Most migratory elk vacate the associated winter wolf territories each summer via a 40–60 km migration, whereas resident elk remain accessible to wolves year-round. We used a generalized linear model to compare the relative probability of wolf use as a function of GIS-based habitat covariates in the migratory and resident elk areas. Although wolves in both areas used elk-rich habitat all year, elk density in summer had a weaker influence on the habitat use of wolves in the migratory elk area than the resident elk area. Wolves employed a number of alternative strategies to cope with the departure of migratory elk. Wolves in the two areas also differed in their disposition toward roads. In winter, wolves in the migratory elk area used habitat close to roads, while wolves in the resident elk area avoided roads. In summer, wolves in the migratory elk area were indifferent to roads, while wolves in resident elk areas strongly avoided roads, presumably due to the location of dens and summering elk combined with different traffic levels. Study results can help wildlife managers to anticipate the movements and establishment of wolf packs as they expand into

  20. Overview of Milestone E activities, greater confinement than shallow land burial

    International Nuclear Information System (INIS)

    Mezga, L.J.

    1981-01-01

    In summary, the objective of Milestone E is to provide the technology and documentation needed to open a site providing greater confinement than shallow land burial. To that end, ORNL has prepared a technical position paper defining greater confinement disposal, options for achieving it, and the need for this disposal technology. In order to meet the objective of the milestones, the LLWMP evaluated the full range of options to shallow land burial and decided to focus on a combination of greater depth solidification containment and engineered barriers. The program identified a series of research needs and then focused program efforts on resolving those needs. These tasks are proceeding on schedule at this time but budget reductions may have an impact on our ability to maintain the schedule

  1. Electrocatalytic activity of a mononuclear yttrium(III)–methyl orange complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles for adsorption/desorption of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Shafaie, Fahimeh [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Hadadzadeh, Hassan, E-mail: hadad@cc.iut.ac.ir [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Behnamfar, Mohammad Taghi [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Rudbari, Hadi Amiri [Faculty of Chemistry, University of Isfahan, Isfahan, 81746-73441 (Iran, Islamic Republic of)

    2016-12-01

    A new mononuclear yttrium(III) complex, [Y(MO){sub 3}(DMF){sub 3}(H{sub 2}O){sub 2}] (where MO{sup –} is methyl orange anion (4-[(4-dimethylamino)phenyldiazenyl]benzenesulfonate)), was synthesized in an aqueous solution. The complex was characterized by elemental analysis, UV/Vis, FT-IR, and single-crystal X-ray crystallography. The yttrium oxysulfate nanoparticles (Y{sub 2}O{sub 2}SO{sub 4}) were then prepared by calcination of [Y(MO){sub 3}(DMF){sub 3}(H{sub 2}O){sub 2}]. The obtained nanoparticles were characterized by FT-IR, X-ray diffraction analysis (XRD), and field-emission scanning electron microscopy (FE-SEM). The hydrogen adsorption/desorption (H{sub ads}/H{sub des}) behavior of the Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles was studied at a carbon paste electrode (CPE) in H{sub 2}SO{sub 4} by cyclic voltammetry (CV). The recorded voltammograms exhibited a pair of peaks corresponding to the adsorption/desorption of hydrogen for the Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles. The results show a reversible hydrogen adsorption/desorption reaction for both compounds. The voltammograms of the nanoparticles indicate an excellent cycling stability for the adsorption/desorption of hydrogen. In addition, the linear sweep voltammetry (LSV) technique was used to investigate the electrocatalytic activity of both compounds for the hydrogen adsorption reaction. The linear voltammograms of both compounds demonstrate the excellent electrocatalytic activity for the hydrogen adsorption reaction. - Highlights: • Preparation of a new Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles. • Investigation of the H{sub ads}/H{sub des} reaction for both compounds by voltammetry. • Observation of two peaks corresponding to the H{sub ads}/H{sub des} in both compounds. • An excellent cycling stability for the nanoparticles in H{sub 2}SO{sub 4}.

  2. Direct electrochemistry with enhanced electrocatalytic activity of hemoglobin in hybrid modified electrodes composed of graphene and multi-walled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wei, E-mail: swyy26@hotmail.com [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 China (China); College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Cao, Lili; Deng, Ying; Gong, Shixing [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Shi, Fan; Li, Gaonan; Sun, Zhenfan [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 China (China)

    2013-06-05

    Graphical abstract: -- Highlights: •A graphene and multi-walled carbon nanotubes nanocomposite was prepared. •Hemoglobin and nanocomposite modified carbon ionic liquid electrode was fabricated. •Direct electrochemistry of hemoglobin was realized on the modified electrode. •Bioelectrocatalysis towards the reduction of different substrates was enhanced. -- Abstract: A graphene (GR) and multi-walled carbon nanotubes (MWCNT) hybrid was prepared and modified on a 1-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE). Hemoglobin (Hb) was immobilized on GR-MWCNT/CILE surface with Nafion as the film forming material and the modified electrode was denoted as Nafion/Hb-GR-MWCNT/CILE. Spectroscopic results revealed that Hb molecules retained its native structure in the GR-MWCNT hybird. Electrochemical behaviors of Hb were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks obtained, which indicated that direct electron transfer of Hb was realized in the hybrid modified electrode. The result could be attributed to the synergistic effects of GR-MWCNT hybrid with enlarged surface area and improved conductivity through the formation of a three-dimensional network. Electrochemical parameters of the immobilized Hb on the electrode surface were further calculated with the results of the electron transfer number (n) as 1.03, the charge transfer coefficient (a) as 0.58 and the electron-transfer rate constant (k{sub s}) as 0.97 s{sup −1}. The Hb modified electrode showed good electrocatalytic ability toward the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.05 to 38.0 mmol L{sup −1} with a detection limit of 0.0153 mmol L{sup −1} (3σ), H{sub 2}O{sub 2} in the concentration range from 0.1 to 516.0 mmol L{sup −1} with a detection limit of 34.9 nmol/L (3σ) and NaNO{sub 2} in the concentration range from 0.5 to 650.0 mmol L{sup −1} with a detection limit of 0

  3. Direct electrochemistry with enhanced electrocatalytic activity of hemoglobin in hybrid modified electrodes composed of graphene and multi-walled carbon nanotubes

    International Nuclear Information System (INIS)

    Sun, Wei; Cao, Lili; Deng, Ying; Gong, Shixing; Shi, Fan; Li, Gaonan; Sun, Zhenfan

    2013-01-01

    Graphical abstract: -- Highlights: •A graphene and multi-walled carbon nanotubes nanocomposite was prepared. •Hemoglobin and nanocomposite modified carbon ionic liquid electrode was fabricated. •Direct electrochemistry of hemoglobin was realized on the modified electrode. •Bioelectrocatalysis towards the reduction of different substrates was enhanced. -- Abstract: A graphene (GR) and multi-walled carbon nanotubes (MWCNT) hybrid was prepared and modified on a 1-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE). Hemoglobin (Hb) was immobilized on GR-MWCNT/CILE surface with Nafion as the film forming material and the modified electrode was denoted as Nafion/Hb-GR-MWCNT/CILE. Spectroscopic results revealed that Hb molecules retained its native structure in the GR-MWCNT hybird. Electrochemical behaviors of Hb were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks obtained, which indicated that direct electron transfer of Hb was realized in the hybrid modified electrode. The result could be attributed to the synergistic effects of GR-MWCNT hybrid with enlarged surface area and improved conductivity through the formation of a three-dimensional network. Electrochemical parameters of the immobilized Hb on the electrode surface were further calculated with the results of the electron transfer number (n) as 1.03, the charge transfer coefficient (a) as 0.58 and the electron-transfer rate constant (k s ) as 0.97 s −1 . The Hb modified electrode showed good electrocatalytic ability toward the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.05 to 38.0 mmol L −1 with a detection limit of 0.0153 mmol L −1 (3σ), H 2 O 2 in the concentration range from 0.1 to 516.0 mmol L −1 with a detection limit of 34.9 nmol/L (3σ) and NaNO 2 in the concentration range from 0.5 to 650.0 mmol L −1 with a detection limit of 0.282 μmol L −1 (3σ). So the proposed

  4. Facile synthesis of Pt–Pd bimetallic nanoparticles by plasma discharge in liquid and their electrocatalytic activity toward methanol oxidation in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung-Min; Lee, Yu-Jin [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Department of Materials Engineering, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Kim, Jung-Wan [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Division of Bioengineering, InCheon National University, Incheon, 406-772 (Korea, Republic of); Lee, Sang-Yul, E-mail: sylee@kau.ac.kr [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Department of Materials Engineering, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of)

    2014-12-01

    The Pt–Pd bimetallic nanoparticles for direct methanol fuel cell applications were successfully prepared by plasma discharge in aqueous solution. The obtained nanoparticles were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, and transmission electron microscopy. During plasma discharge, the nanoparticles were produced from the erosion of electrodes. It was noted that the erosion amount of anode electrodes was much greater than that of cathode electrodes so that the composition of Pt–Pd bimetallic nanoparticles could be changed with different power types and electrode configurations. Diffraction patterns fitted from Gaussian devolution indicated that the crystalline phase of Pt{sub 40}Pd{sub 60} products was composed of pure Pt, pure Pd and Pt–Pd alloy phases. The morphology of synthesized nanoparticles showed that nanowires connected with quasi-spherical nanoparticles with 2–3 nm in diameter were observed and large spherical particles with > 50 nm in diameter were also detected intermittently. The cyclic voltammetric measurement and continuous potential scan demonstrated that Pt{sub 40}Pd{sub 60} had much higher catalytic activity and better resistance to CO poisoning than Pt{sub 94}Pd{sub 6} and Pt{sub 1}Pd{sub 99} for methanol oxidation. These results indicate that the Pt{sub 40}Pd{sub 60} could be an excellent candidate for the direct methanol fuel cell applications.

  5. Study of the Electrocatalytic Activity of Cerium Oxide and Gold-Studded Cerium Oxide Nanoparticles Using a Sonogel-Carbon Material as Supporting Electrode: Electroanalytical Study in Apple Juice for Babies

    Science.gov (United States)

    Abdelrahim, M. Yahia M.; Benjamin, Stephen R.; Cubillana-Aguilera, Laura Ma; Naranjo-Rodríguez, Ignacio; Hidalgo-Hidalgo de Cisneros, Josè L.; Delgado, Juan Josè; Palacios-Santander, Josè Ma

    2013-01-01

    The present work reports a study of the electrocatalytic activity of CeO2 nanoparticles and gold sononanoparticles (AuSNPs)/CeO2 nanocomposite, deposited on the surface of a Sonogel-Carbon (SNGC) matrix used as supporting electrode and the application of the sensing devices built with them to the determination of ascorbic acid (AA) used as a benchmark analyte. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to investigate the electrocatalytic behavior of CeO2- and AuSNPs/CeO2-modified SNGC electrodes, utilizing different concentrations of CeO2 nanoparticles and different AuSNPs:CeO2 w/w ratios. The best detection and quantification limits, obtained for CeO2 (10.0 mg·mL−1)- and AuSNPs/CeO2 (3.25% w/w)-modified SNGC electrodes, were 1.59 × 10−6 and 5.32 × 10−6 M, and 2.93 × 10−6 and 9.77 × 10−6 M, respectively, with reproducibility values of 5.78% and 6.24%, respectively, for a linear concentration range from 1.5 μM to 4.0 mM of AA. The electrochemical devices were tested for the determination of AA in commercial apple juice for babies. The results were compared with those obtained by applying high performance liquid chromatography (HPLC) as a reference method. Recovery errors below 5% were obtained in most cases, with standard deviations lower than 3% for all the modified SNGC electrodes. Bare, CeO2- and AuSNPs/CeO2-modified SNGC electrodes were structurally characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). AuSNPs and AuSNPs/CeO2 nanocomposite were characterized by UV-vis spectroscopy and X-ray diffraction (XRD), and information about their size distribution and shape was obtained by transmission electron microscopy (TEM;. The advantages of employing CeO2 nanoparticles and AuSNPs/CeO2 nanocomposite in SNGC supporting material are also described. This research suggests that the modified electrode can be a very promising voltammetric sensor for the determination of

  6. A facile one-pot preparation of Co3O4/g-C3N4 heterojunctions with excellent electrocatalytic activity for the detection of environmental phenolic hormones

    Science.gov (United States)

    Sun, Yanjuan; Jiang, Jizhou; Liu, Yi; Wu, Shengli; Zou, Jing

    2018-02-01

    The Co3O4/g-C3N4 heterojunctions were prepared by a facile one-pot thermal decomposition technique. Compared with g-C3N4, it was found that Co3O4/g-C3N4 heterojunctions possessed a higher Brunner-Emmet-Teller (BET) surface area, which was beneficial to the diffusion of aim molecules on the electrode surfaces. And the optimal Co3O4/g-C3N4 heterojunctions exhibited a narrower band gap and a higher donor density, resulting in an excellent electrocatalytic activity for environmental phenolic hormones. Moreover, the Co3O4/g-C3N4 heterojunctions were used for the electrochemical sensing of environmental phenolic hormones such as bisphenol A, pentachlorophenol, p-nitrophenol and octylphenol. All detection ranges reached three orders of magnitude, showing a lower limit of detection of 10-9 mol L-1. So, sensitivity and accurate determination of environmental phenolic hormones in real water samples may use this Co3O4/g-C3N4 heterojunctions modified electrode.

  7. Synthesis and characterization of polyhedral and quasi-sphere non-polyhedral Pt nanoparticles: effects of their various surface morphologies and sizes on electrocatalytic activity for fuel cell applications

    International Nuclear Information System (INIS)

    Long, Nguyen Viet; Ohtaki, Michitaka; Hien, Tong Duy; Jalem, Randy; Nogami, Masayuki

    2011-01-01

    In this article, polyhedral and non-polyhedral Pt nanoparticles were prepared by modified polyol method using AgNO 3 as a good structure-modifying agent. Their TEM and HRTEM images showed the particle size in the range of 8–16 nm for both the above cases. The structures and properties of the surfaces of Pt nanoparticles were investigated through cyclic voltammetry in dilute perchloric acid (HClO 4 ) electrolyte solution. A comparison of the electrocatalytic property in methanol electrooxidation was made. Here, the effects of polyhedral and non-polyhedral morphologies on their catalytic properties were studied. The results revealed that the special catalytic activity of quasi-sphere non-polyhedral Pt nanoparticles is higher than that of polyhedral Pt nanoparticles. In addition, Pt nanoparticles of un-sharp and quasi-sphere morphologies exhibit the tolerance to poisoning species better than that of Pt nanoparticles of sharp and polyhedral morphologies due to the various morphologies of the catalyst surfaces in the chronoamperometric plots. Therefore, these experimental evidences showed the morphology-dependent catalytic property according to the various morphologies and complexity of their catalyst surfaces.

  8. Impact Of anthropogenic activities on the water quality of Songor Lagoon, Ada, Greater Accra Region

    International Nuclear Information System (INIS)

    Sackey, Justice

    2014-06-01

    Wetlands are vital ecosystems with important social, economic and environmental functions. The Ada Songor lagoon (located in the Dangbe East district, Greater Accra Region), is an internationally designated wetland (Ramsar site). Intense anthropogenic activities have impacted negatively on the quality of water and sediment in the lagoon. The study assessed the extent of heavy metal, pesticide residues and nutrients contamination of surface water and sediment in the Ada Songor Lagoon. The objective of the study was achieved through the determination of physico-chemical parameters [pH, temperature, electrical conductivity (EC), salinity, total dissolved solids (TDS), alkalinity, turbidity, biological oxygen demand (BOD), total hardness)]; the nutrients load (SO_4"2"- , PO_4"3"- , NO_3"- ) using UV-Visible Spectrophotometry; major ions (Na"+, K"+, Ca"2"+, HCO_3 "-); trace metals (Cd, Cr, Ni, Pb, Co, Zn, Cu, As and Hg) using Atomic Absorption Spectrometry (AAS); and pesticides residues [organochlorines (OC’s), and synthetic pyrethroids by gas chromatography-electron capture detection (GC-ECD) and organophosphorus (OP’s) by gas chromatography-pulse flame photometric detection (G C-PFPD)]. Na and K contents were determined by Flame Emission Photometry. The water temperature (25.7 to 26.6 "oC), fall in the range of 25 to 30 "oC suitable for sustainability fish and aquatic organisms. The pH range (8.18 to 9.70) which is typical of coastal waters in Ghana is ideal for aquatic organisms. The TDS range (591 to 1,046 mg/L) is not ideal for water birds spawning since it makes it harder for them to find food. BOD ranges from 1.19 to 5.35 mg/L. The pattern of ionic dominance in the lagoon during the present study was K"+ > Na"+ > Ca"2"+ > Mg"2"+. The cationic dominance pattern was similar to that of seawater as observed by other works. Nitrate levels ranges from 0.83 to 0.92 mg/L. PO_4"3"- in this study varied from 0.05 to 2.92 mg/L which exceeds the levels in most natural

  9. Electrocatalytic process for carbon dioxide conversion

    Science.gov (United States)

    Masel, Richard I.; Salehi-Khojin, Amin; Kutz, Robert

    2017-11-14

    An electrocatalytic process for carbon dioxide conversion includes combining a Catalytically Active Element and a Helper Polymer in the presence of carbon dioxide, allowing a reaction to proceed to produce a reaction product, and applying electrical energy to said reaction to achieve electrochemical conversion of said carbon dioxide reactant to said reaction product. The Catalytically Active Element can be a metal in the form of supported or unsupported particles or flakes with an average size between 0.6 nm and 100 nm. The reaction products comprise at least one of CO, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, (COOH).sub.2, (COO.sup.-).sub.2, and CF.sub.3COOH.

  10. A survey of joint activities and travel of household members in the Greater Copenhagen Metropolitan Region

    DEFF Research Database (Denmark)

    Thorhauge, Mikkel; Vuk, Goran; Kaplan, Sigal

    2012-01-01

    and family quality time, within a daily schedule. The current study unveils the joint activity and travel patterns of household members in the Copenhagen area, as part of the ACTUM research project, funded by the Danish Strategic Research Council, for the development of a new generation of activity......The traditional approach for modeling transport-related choices in Denmark refers to individual decision makers. However, in daily activities and travel choices individuals function according to the commitments as family members, and thus their choices derive from the welfare needs of other family...... members. A family-based approach enables to capture intra-household interactions and the priorities of household members in scheduling their daily activities, thus adding to the realism and the predictive strength of transport models. Joint activities and travel occur in order to maximize efficiency...

  11. Superior photocatalytic, electrocatalytic, and self-cleaning applications of Fly ash supported ZnO nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Thirumalai, Kuppulingam; Balachandran, Subramanian [Department of Chemistry, Annamalai University, Annamalainagar, 608 002, Tamil Nadu (India); Swaminathan, Meenakshisundaram, E-mail: chemres50@gmail.com [Department of Chemistry, Annamalai University, Annamalainagar, 608 002, Tamil Nadu (India); Nanomaterials Laboratory, International Research Centre, Kalasalingam Universty, Krihnankoil, 626126 (India)

    2016-11-01

    Ever growing research on modified semiconductor oxides made a significant progress in catalytic functional materials. In this article, we report the modification of ZnO photocatalyst by a simple hydrothermal decomposition method utilizing the cheaply available industrial waste fly ash. This modified Fly ash-ZnO photocatalyst was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), high resolution transmission electron microscopy (HR-TEM), Atomic force microscopy (AFM), photoluminescence spectroscopy (PL) and diffuse reflectance spectroscopy (DRS). The XRD pattern indicates the presence of fly ash components and the hexagonal wurtzite structured ZnO. TEM images reveal well defined nanorod like structure. Reduction of photoluminescence intensity of Fly ash-ZnO at 418 nm, when compared to, prepared ZnO, indicates the suppression of recombination of the photogenerated electron–hole pair by loaded Fly ash on ZnO. Fly ash-ZnO exhibits enhanced photocatalytic activity for the degradation of azo dyes Reactive Orange 4, Rhodamine-B and Trypan Blue. This catalyst shows higher electrocatalytic activity than ZnO in the oxidation of methanol. Significant hydrophobicity of Fly ash-ZnO reveals its self cleaning property. - Highlights: • The degradation efficiency of Fly ash-ZnO under UV and Solar irradiation is greater than prepared ZnO and TiO{sub 2}‒P25. • Electrocatalytic activity of Fly ash-ZnO exhibits enhanced current production by methanol oxidation. • Fly ash-ZnO shows the high hydrophobicity than ZnO, it can be used as a self cleaning material for industrial applications.

  12. Motor competence and cardiorespiratory fitness have greater influence on body fatness than physical activity across time

    DEFF Research Database (Denmark)

    Lima, R A; Pfeiffer, K A; Bugge, A

    2017-01-01

    We investigated the longitudinal associations among physical activity (PA), motor competence (MC), cardiorespiratory fitness (VO2peak ), and body fatness across 7 years, and also analyzed the possible mediation effects of PA, MC, and VO2peak on the relationships with body fatness. This was a seven...

  13. Comparative electrocatalytic oxidation of ethanol, ethylene glycol and glycerol in alkaline medium at Pd-decorated FeCo@Fe/C core-shell nanocatalysts

    CSIR Research Space (South Africa)

    Fashedemi, OO

    2014-05-01

    Full Text Available ) were explored, and compared with those of the Pd/C alone. FeCo@Fe@Pd/C exhibited a remarkable performance in all three alcohols but its best electrocatalytic activity was found in the oxidation of EG where the electrocatalytic rate constant (K...

  14. Microenvironment effects in electrocatalysis: ionic-liquid-like coating on carbon nanotubes enhances the Pd-electrocatalytic alcohol oxidation.

    Science.gov (United States)

    Li, Shuwen; Dong, Zhengping; Yang, Honglei; Guo, Shujing; Gou, Galian; Ren, Ren; Zhu, Zhejun; Jin, Jun; Ma, Jiantai

    2013-02-11

    A new catalyst consisting of ionic liquid (IL)-functionalized carbon nanotubes (CNTs) obtained through 1,3-dipolar cycloaddition support-enhanced electrocatalytic Pd nanoparticles (Pd@IL(Cl(-))-CNTs) was successfully fabricated and applied in direct ethanol alkaline fuel cells. The morphology, structure, component and stability of Pd@IL(Cl(-))-CNTs were systematic characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Raman spectra, thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The new catalyst exhibited higher electrocatalytic activity, better tolerance and electrochemical stability than the Pd nanoparticles (NPs) immobilized on CNTs (Pd@CNTs), which was ascribed to the effects of the IL, larger electrochemically active surface area (ECSA), and greater processing performance. Cyclic voltammograms (CVs) at various scan rates illustrated that the oxidation behaviors of ethanol at all electrodes were controlled by diffusion processes. The investigation of the different counteranions demonstrated that the performance of the IL-CNTs hybrid material was profoundly influenced by the subtly varied structures of the IL moiety. All the results indicated that the Pd@IL(Cl(-))-CNTs catalyst is an efficient anode catalyst, which has potential applications in direct ethanol fuel cells and the strategy of IL functionalization of CNTs could be available to prepare other carbonaceous carrier supports to enhance the dispersivity, stability, and catalytic performance of metal NPs as well. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Fostering Culture Change in an Undergraduate Business Program: "Nudging" Students towards Greater Involvement in Extra-Curricular Activities

    Science.gov (United States)

    Martin, Elizabeth M.

    2013-01-01

    A report on a successfully implemented program to increase student participation in extra-curricular activities in an undergraduate business program with a high percentage of first-generation college students. A market-research study offered insight as to why students were not participating before the program was launched. Greater participation in…

  16. Active unicameral bone cysts in the upper limb are at greater risk of fracture.

    Science.gov (United States)

    Tey, Inn Kuang; Mahadev, Arjandas; Lim, Kevin Boon Leong; Lee, Eng Hin; Nathan, Saminathan Suresh

    2009-08-01

    To elucidate the natural history of unicameral bone cyst (UBC) and risk factors for pathological fracture. 14 males and 8 females (mean age, 9 years) diagnosed with UBC were reviewed. Cyst location, symptoms, and whether there was any fracture or surgery were recorded. Cyst parameters were measured on radiographs, and included (1) the cyst index, (2) the ratio of the widest cyst diameter to the growth plate diameter, and (3) the adjusted distance of the cyst border from the growth plate. There were 11 upper- and 11 lower-limb cysts. 13 patients had pathological fractures and 9 did not. 20 patients were treated conservatively with limb immobilisation; 2 underwent curettage and bone grafting (one resolved and one did not). Seven cysts resolved (5 had fractures and 2 did not). The risk of fracture was higher in the upper than lower limbs (100% vs 18%, pFractured cysts were larger than unfractured cysts (mean cyst index, 4.5 vs. 2.2, p=0.07). Active cysts were more likely to fracture. Conservative management had a 30% resolution rate. Surgery should be considered for large active cysts in the upper limbs in order to minimise the fracture risk.

  17. Motor competence and cardiorespiratory fitness have greater influence on body fatness than physical activity across time.

    Science.gov (United States)

    Lima, R A; Pfeiffer, K A; Bugge, A; Møller, N C; Andersen, L B; Stodden, D F

    2017-12-01

    We investigated the longitudinal associations among physical activity (PA), motor competence (MC), cardiorespiratory fitness (VO 2peak ), and body fatness across 7 years, and also analyzed the possible mediation effects of PA, MC, and VO 2peak on the relationships with body fatness. This was a seven-year longitudinal study with three measuring points (mean ages [in years] and respective sample size: 6.75±0.37, n=696; 9.59±1.07, n=617; 13.35±0.34, n=513). PA (moderate-to-vigorous PA-MVPA and vigorous PA-VPA) was monitored using accelerometers. MC was assessed by the "Körperkoordinationstest für Kinder-KTK" test battery. VO 2peak was evaluated using a continuous running protocol until exhaustion. Body fatness was determined by the sum of four skinfolds. Structural equation modeling was performed to evaluate the longitudinal associations among PA, MC, VO 2peak, and body fatness and the potential mediation effects of PA, MC, and VO 2peak . All coefficients presented were standardized (z-scores). MC and VO 2peak directly influenced the development of body fatness, and VO 2peak mediated the associations between MVPA, VPA, MC, and body fatness. MC also mediated the associations between MVPA, VPA, and body fatness. In addition, VO 2peak had the largest total association with body fatness (β=-0.431; Pfitness and MC through developmentally appropriate physical activities, as the synergistic interactions of all three variables impacted body fatness. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  18. Poly-Alizarin red S/multiwalled carbon nanotube modified glassy carbon electrode for the boost up of electrocatalytic activity towards the investigation of dopamine and simultaneous resolution in the presence of 5-HT: A voltammetric study

    International Nuclear Information System (INIS)

    Reddaiah, K.; Madhusudana Reddy, T.; Venkata Ramana, D.K.; Subba Rao, Y.

    2016-01-01

    Poly-Alizarin red S/multiwalled carbon nanotube film on the surface of glassy carbon electrode (poly-AzrS/MWCNT/GCE) was synthesized by electrochemical process and was used for the sensitive and selective determination of dopamine (DA) by employing voltammetric techniques. The electrocatalytic response of the modified electrode was found to exhibit admirable activity. The simultaneous determination of dopamine in the presence of serotonin (5-HT) was found to exhibit very good response at poly-AzrS/MWCNTs/GCE. The effect of pH, scan rate, accumulation time and concentration of dopamine was studied at the developed poly-AzrS/MWCNTs/GCE. The poly-AzrS/MWCNTs/GCE exhibited an efficient electron mediating behavior together with well resolved peaks for dopamine, in 0.1 mol/dm"3 phosphate buffer (PBS) solution of pH 7.0. The limit of detection (LOD) and limit of quantification (LOQ) were found to be as 1.89 × 10"−"7 mol/dm"3 and 6.312 × 10"−"7 mol/dm"3 respectively with a dynamic range from 1 × 10"−"6 to 1.8 × 10"−"5 mol/dm"3. The interfacial electron transfer behavior of DA was studied by electrochemical impedance spectroscopy (EIS); the studies showed that the charge transfer rate was enhanced at poly-AzrS/MWCNTs/GCE when compared with bare GCE and poly-AzrS/GCE. - Highlights: • The poly-AzrS/MWCNTs/GCE showed good sensitivity towards DA sensing. • The sensor reduced the overoxidation potentials for DA. • This electrode was successfully used for simultaneous sensing of DA and 5-HT. • The electrode was effectively used for the determination of DA in pharmaceutical formulations.

  19. Poly-Alizarin red S/multiwalled carbon nanotube modified glassy carbon electrode for the boost up of electrocatalytic activity towards the investigation of dopamine and simultaneous resolution in the presence of 5-HT: A voltammetric study

    Energy Technology Data Exchange (ETDEWEB)

    Reddaiah, K. [Electrochemical Research Laboratory, Department of Chemistry, S.V.U. College of Sciences, Sri Venkateswara University, Tirupati 517 502, Andhra Pradesh (India); Madhusudana Reddy, T., E-mail: tmsreddysvu@gmail.com [Electrochemical Research Laboratory, Department of Chemistry, S.V.U. College of Sciences, Sri Venkateswara University, Tirupati 517 502, Andhra Pradesh (India); Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455 (United States); Venkata Ramana, D.K. [Department of Safety Engineering, Dongguk University, 123 Dongdae-ro, Gyeongju, Gyeongbuk 780 714 (Korea, Republic of); Subba Rao, Y. [DST-PURSE Centre, Sri Venkateswara University, Tirupati 517502, Andhra Pradesh (India)

    2016-05-01

    Poly-Alizarin red S/multiwalled carbon nanotube film on the surface of glassy carbon electrode (poly-AzrS/MWCNT/GCE) was synthesized by electrochemical process and was used for the sensitive and selective determination of dopamine (DA) by employing voltammetric techniques. The electrocatalytic response of the modified electrode was found to exhibit admirable activity. The simultaneous determination of dopamine in the presence of serotonin (5-HT) was found to exhibit very good response at poly-AzrS/MWCNTs/GCE. The effect of pH, scan rate, accumulation time and concentration of dopamine was studied at the developed poly-AzrS/MWCNTs/GCE. The poly-AzrS/MWCNTs/GCE exhibited an efficient electron mediating behavior together with well resolved peaks for dopamine, in 0.1 mol/dm{sup 3} phosphate buffer (PBS) solution of pH 7.0. The limit of detection (LOD) and limit of quantification (LOQ) were found to be as 1.89 × 10{sup −7} mol/dm{sup 3} and 6.312 × 10{sup −7} mol/dm{sup 3} respectively with a dynamic range from 1 × 10{sup −6} to 1.8 × 10{sup −5} mol/dm{sup 3}. The interfacial electron transfer behavior of DA was studied by electrochemical impedance spectroscopy (EIS); the studies showed that the charge transfer rate was enhanced at poly-AzrS/MWCNTs/GCE when compared with bare GCE and poly-AzrS/GCE. - Highlights: • The poly-AzrS/MWCNTs/GCE showed good sensitivity towards DA sensing. • The sensor reduced the overoxidation potentials for DA. • This electrode was successfully used for simultaneous sensing of DA and 5-HT. • The electrode was effectively used for the determination of DA in pharmaceutical formulations.

  20. An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

    Science.gov (United States)

    Almeida, T. S.; Palma, L. M.; Leonello, P. H.; Morais, C.; Kokoh, K. B.; De Andrade, A. R.

    2012-10-01

    The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved.

  1. A two step method to synthesize palladium-copper nanoparticles on reduced graphene oxide and their extremely high electrocatalytic activity for the electrooxidation of methanol and ethanol

    Science.gov (United States)

    Na, HeYa; Zhang, Lei; Qiu, HaiXia; Wu, Tao; Chen, MingXi; Yang, Nian; Li, LingZhi; Xing, FuBao; Gao, JianPing

    2015-08-01

    Palladium-copper nanoparticles (Pd-Cu NPs) supported on reduced graphene oxide (RGO) with different Pd/Cu ratios (Pd-Cu/RGO) were prepared by a two step method. The Pd-Cu/RGO hybrids were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and thermogravimetric analyses. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of the Pd-Cu/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. The Pd-Cu/RGO catalysts exhibited high catalytic activities and good stabilities. This is because the catalysts have a bimetallic structure consisting of a small Pd-Cu core surrounded by a thin Pd-rich shell which improves the catalytic activities of the Pd-Cu/RGO hybrids. Thus they should be useful in direct methanol and ethanol fuel cells.

  2. Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells.

    Science.gov (United States)

    V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V; Mitra, Somenath

    2012-11-30

    Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol(-1) which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel.

  3. Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells

    Science.gov (United States)

    V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V.; Mitra, Somenath

    2012-01-01

    Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol−1 which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel. PMID:23118490

  4. The impact of electrochemical reduction potentials on the electrocatalytic activity of graphene oxide toward the oxygen reduction reaction in an alkaline medium

    International Nuclear Information System (INIS)

    Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom; Daud, Wan Ramli Wan

    2016-01-01

    We report the synthesis of graphene via the electrochemical reduction of graphene oxide (GO). In this study, GO nanosheets from aqueous dispersion were pre-assembled on a glassy carbon (GC) electrode and then electrochemically reduced in 1 M KOH under various constant reduction potentials in the range of −0.6 V to −1.5 V (vs. Ag/AgCl). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses revealed that the graphitic structure was substantially restored in the resulting electrochemically reduced graphene oxide (ERGO). The ERGO electrodes exhibited significantly enhanced catalytic activity toward the oxygen reduction reaction (ORR) in an alkaline medium compared with the initial GO electrode. Of the ERGO electrodes produced at various cathodic potentials, the ERGO-1.2 V electrode, which was produced at a reduction potential of −1.2 V, demonstrated the best catalytic activity toward the ORR in an alkaline medium. The ORR on GO and ERGO electrodes was shown to proceed via a two-electron mechanism at low overpotentials. The agreement between the spectroscopy results and electrochemical measurements provide strong evidence that the enhanced ORR catalytic activity is mainly attributed to the restoration of GO’s graphitic structure. Furthermore, the ERGO-1.2 V electrode showed excellent tolerance to the methanol poisoning effect compared with a Pt/C catalyst electrode.

  5. Direct electrocatalytic reduction of coenzyme NAD{sup +} to enzymatically-active 1,4-NADH employing an iridium/ruthenium-oxide electrode

    Energy Technology Data Exchange (ETDEWEB)

    Ullah, Nehar, E-mail: nehar.ullah@mail.mcgill.ca; Ali, Irshad; Omanovic, Sasha

    2015-01-15

    A thermally prepared iridium/ruthenium-oxide coating (Ir{sub 0.8}Ru{sub 0.2}-oxide) formed on a titanium substrate was investigated as a possible electrode for direct electrochemical regeneration of enzymatically-active 1,4-NADH from its oxidized form NAD{sup +}, at various electrode potentials, in a batch electrochemical reactor. The coating surface was characterized by ‘cracked mud’ morphology, yielding a high surface roughness. The NADH regeneration results showed that the percentage of enzymatically-active 1,4-NADH present in the product mixture (i.e. recovery) is strongly dependent on the electrode potential, reaching a maximum (88%) at −1.70 V vs. MSE. The relatively high recovery was explained on the basis of availability of adsorbed ‘active’ hydrogen (H{sub ads}) on the Ir/Ru-oxide surface, i.e. on the basis of electrochemical hydrogenation. - Highlights: • Ir{sub 0.8}Ru{sub 0.2}-oxide coating was formed thermally on a Ti substrate. • Electrochemical regeneration of enzymatically-active 1,4-NADH was investigated. • The 1,4-NADH recovery percentage is strongly dependent on the electrode potential. • A highest recovery, 88%, was obtained at −1.70 V vs. MSE. • The NADH regeneration process involved electrochemical hydrogenation.

  6. Photo-electrocatalytic activity of TiO2 nanotubes prepared with two-step anodization and treated under UV light irradiation

    Directory of Open Access Journals (Sweden)

    Mohamad Mohsen Momeni

    2016-01-01

    Full Text Available To improve the photo-catalytic degradation of salicylic acid, we reported the fabrication of ordered TiO2 nanotube arrays by a simple and effective two-step anodization method and then these TiO2 nanotubes treated in a methanol solution under UV light irradiation. The TiO2 nanotubes prepared in the two-step anodization process showed better photo-catalytic activity than TiO2 nanotubes prepared in one-step anodization process. Also, compared with TiO2 nanotubes without the UV pretreatment, the TiO2 nanotubes pretreated in a methanol solution under UV light irradiation exhibited significant enhancements in both photocurrent and activity. The treated TiO2 nanotubes exhibited a 5-fold enhancement in photocurrent and a 2.5-fold increase in the photo-catalytic degradation of salicylic acid. Also the effect of addition of persulfate and periodate on the photo-catalytic degradation of salicylic acid were investigated. The results showed that the degradation efficiency of salicylic acid increased with increasing persulfate and periodate concentrations. These treated TiO2 nanotubes are promising candidates for practical photochemical reactors.

  7. Preparation and characterization of micro-arc-induced Pd/TM(TM = Ni, Co and Ti) catalysts and comparison of their electrocatalytic activities toward ethanol oxidation

    International Nuclear Information System (INIS)

    Wang, Xiaoguang; Ma, Guanshui; Zhu, Fuchun; Lin, Naiming; Tang, Bin; Zhang, Zhonghua

    2013-01-01

    Using the electro-spark deposition technique, a novel kind of Pd/TM (TM = Ni, Co and Ti) electrode was successfully prepared by arc-depositing Pd on the transition metal substrates. The structure, morphology and chemical composition of the arc-deposited films were investigated using thin-film X-ray diffraction (TF-XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The results show that, a coarsening topographical morphology can be obtained, being composed of numerous craters/spots with sizes ranging from nano-scales to several microns. The electrochemical measurements indicate that the arc-deposited Pd/TM electrodes exhibit distinct electrochemical behaviors and the catalytic activity toward ethanol electro-oxidation reaction (EOR) is highly dependent upon the nature of substrate. Among the Pd/TM electrodes investigated, the arc-deposited Pd/Co reveals the best activity and superior poisoning tolerance towards ethanol oxidation and will find promising applications as a candidate for the anode catalyst of direct ethanol fuel cells (DEFCs)

  8. Electrocatalytic Metal-Organic Frameworks for Energy Applications.

    Science.gov (United States)

    Downes, Courtney A; Marinescu, Smaranda C

    2017-11-23

    With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal-organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best-performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble-metal-based catalysts in commercial energy-converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy-related reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, H.; Habas, S.E.; Somorjai, G.A.; Yang, P.

    2008-03-20

    Binary Pt/Pd nanoparticles were synthesized by localized overgrowth of Pd on cubic Pt seeds for the investigation of electrocatalytic formic acid oxidation. The binary particles exhibited much less self-poisoning and a lower activation energy relative to Pt nanocubes, consistent with the single crystal study.

  10. Greater confinement disposal of high activity and special case wastes at the Nevada Test Site: A unified migration assessment approach

    International Nuclear Information System (INIS)

    Davis, P.A.; Olague, N.E.; Johnson, V.L.; Dickman, P.T.; O'Neill, L.J.

    1993-01-01

    The Department of Energy's Nevada Field Office has disposed of a small quantity of high activity and special case wastes using Greater Confinement Disposal facilities in Area 5 of the Nevada Test Site. Because some of these wastes are transuranic radioactive wastes, the Environmental Protection Agency standards for their disposal under 40 CFR Part 191 which requires a compliance assessment. In conducting the 40 CFR Part 191 compliance assessment, review of the Greater Confinement Disposal inventory revealed potentially land disposal restricted hazardous wastes. The regulatory options for disposing of land disposal restricted wastes consist of (1) treatment and monitoring, or (2) developing a no-migration petition. Given that the waste is already buried without treatment, a no-migration petition becomes the primary option. Based on a desire to minimize costs associated with site characterization and performance assessment, a single approach has been developed for assessing compliance with 40 CFR Part 191, DOE Order 5820.2A (which regulates low-level radioactive wastes contained in Greater Confinement Disposal facilities) and developing a no-migration petition. The approach consists of common points of compliance, common time frame for analysis, and common treatment of uncertainty. The procedure calls for conservative bias of modeling assumptions, including model input parameter distributions and adverse processes and events that can occur over the regulatory time frame, coupled with a quantitative treatment of data and parameter uncertainty. This approach provides a basis for a defensible regulatory decision. In addition, the process is iterative between modeling and site characterization activities, where the need for site characterization activities is based on a quantitative definition of the most important and uncertain parameters or assumptions

  11. Fabrication of miniaturised Si-based electrocatalytic membranes

    International Nuclear Information System (INIS)

    D'Arrigo, G.; Spinella, C.; Arena, G.; Lorenti, S.

    2003-01-01

    The increasing interest for light and movable electronic systems, cell phones and small digital devices, drives the technological research toward integrated regenerating power sources with small dimensions and great autonomy. Conventional batteries are already unable to deliver power in more and more shrunk volumes maintaining the requirements of long duration and light weight. A possible solution to overcome these limits is the use of miniaturised fuel cell. The fuel cell offers a greater gravimetric energy density compared to conventional batteries. The micromachining technology of silicon is an important tool to reduce the fuel cell structure to micrometer sizes. The use of silicon also gives the opportunity to integrate the power source and the electronic circuits controlling the fuel cell on the same structure. This paper reports preliminary results concerning the micromachining procedure for fabricating a Si-based electrocatalytic membrane for miniaturised Si-based proton exchange membrane fuel cells (PEMFC)

  12. Materials design for electrocatalytic carbon capture

    Directory of Open Access Journals (Sweden)

    Xin Tan

    2016-05-01

    Full Text Available We discuss our philosophy for implementation of the Materials Genome Initiative through an integrated materials design strategy, exemplified here in the context of electrocatalytic capture and separation of CO2 gas. We identify for a group of 1:1 X–N graphene analogue materials that electro-responsive switchable CO2 binding behavior correlates with a change in the preferred binding site from N to the adjacent X atom as negative charge is introduced into the system. A reconsideration of conductive N-doped graphene yields the discovery that the N-dopant is able to induce electrocatalytic binding of multiple CO2 molecules at the adjacent carbon sites.

  13. The contribution of human agricultural activities to increasing evapotranspiration is significantly greater than climate change effect over Heihe agricultural region.

    Science.gov (United States)

    Zou, Minzhong; Niu, Jun; Kang, Shaozhong; Li, Xiaolin; Lu, Hongna

    2017-08-18

    Evapotranspiration (ET) is a major component linking the water, energy, and carbon cycles. Understanding changes in ET and the relative contribution rates of human activity and of climate change at the basin scale is important for sound water resources management. In this study, changes in ET in the Heihe agricultural region in northwest China during 1984-2014 were examined using remotely-sensed ET data with the Soil and Water Assessment Tool (SWAT). Correlation analysis identified the dominant factors that influence change in ET per unit area and those that influence change in total ET. Factor analysis identified the relative contribution rates of the dominant factors in each case. The results show that human activity, which includes factors for agronomy and irrigation, and climate change, including factors for precipitation and relative humidity, both contribute to increases in ET per unit area at rates of 60.93% and 28.01%, respectively. Human activity, including the same factors, and climate change, including factors for relative humidity and wind speed, contribute to increases in total ET at rates of 53.86% and 35.68%, respectively. Overall, in the Heihe agricultural region, the contribution of human agricultural activities to increased ET was significantly greater than that of climate change.

  14. Controlling of morphology and electrocatalytic properties of cobalt oxide nanostructures prepared by potentiodynamic deposition method

    Energy Technology Data Exchange (ETDEWEB)

    Hallaj, Rahman [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Akhtari, Keivan [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O.Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah, E-mail: absalimi@uok.ac.ir [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O.Box 416, Sanandaj (Iran, Islamic Republic of); Soltanian, Saied [Department of Physics, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2013-07-01

    Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO{sub 3}){sub 2}, (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H{sub 2}O{sub 2} and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic

  15. Controlling of morphology and electrocatalytic properties of cobalt oxide nanostructures prepared by potentiodynamic deposition method

    International Nuclear Information System (INIS)

    Hallaj, Rahman; Akhtari, Keivan; Salimi, Abdollah; Soltanian, Saied

    2013-01-01

    Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO 3 ) 2 , (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H 2 O 2 and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic activity decreased

  16. Synthesis, characterization and electrocatalytic properties of delafossite CuGaO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Jahangeer [Department of Chemistry, University of Texas Rio Grande Valley, 1201 West University Drive, Edinburg, TX 78539 (United States); Department of Chemistry, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Mao, Yuanbing, E-mail: yuanbing.mao@utrgv.edu [Department of Chemistry, University of Texas Rio Grande Valley, 1201 West University Drive, Edinburg, TX 78539 (United States)

    2016-10-15

    Delafossite CuGaO{sub 2} has been employed as photocatalysts for solar cells, but their electrocatalytic properties have not been extensively studied, especially no comparison among samples made by different synthesis routes. Herein, we first reported the successful synthesis of delafossite CuGaO{sub 2} particles with three different morphologies, i.e. nanocrystalline hexagons, sub-micron sized plates and micron–sized particles by a modified hydrothermal method at 190 °C for 60 h [1–3], a sono-chemical method followed by firing at 850 °C for 48 h, and a solid state route at 1150 °C, respectively. Morphology, composition and phase purity of the synthesized samples was confirmed by powder X-ray diffraction and Raman spectroscopic studies, and then their electrocatalytic performance as active and cost effective electrode materials to the oxygen and hydrogen evolution reactions in 0.5 M KOH electrolyte versus Ag/AgCl was investigated and compared under the same conditions for the first time. The nanocrystalline CuGaO{sub 2} hexagons show enhanced electrocatalytic activity than the counterpart sub-micron sized plates and micron-sized particles. - Graphical abstract: Representative delafossite CuGaO2 samples with sub-micron sized plate and nanocrystalline hexagon morphologies accompanying with chronoamperometric voltammograms for oxygen evolution reaction and hydrogen evolution reaction in 0.5 M KOH electrolyte after purged with N{sub 2} gas. - Highlights: • Delafossite CuGaO{sub 2} with three morphologies has been synthesized. • Phase purity of the synthesized samples was confirmed. • Comparison on their electrocatalytic properties was made for the first time. • Their use as electrodes for oxygen and hydrogen evolution reactions was evaluated. • Nanocrystalline CuGaO{sub 2} hexagons show highest electrocatalytic activity.

  17. Lowland tapir (Tapirus terrestris) distribution, activity patterns and relative abundance in the Greater Madidi-Tambopata Landscape.

    Science.gov (United States)

    Wallace, Robert; Ayala, Guido; Viscarra, Maria

    2012-12-01

    Lowland tapir distribution is described in northwestern Bolivia and southeastern Peru within the Greater Madidi-Tambopata Landscape, a priority Tapir Conservation Unit, using 1255 distribution points derived from camera trapping efforts, field research and interviews with park guards from 5 national protected areas and hunters from 19 local communities. A total of 392 independent camera trapping events from 14 camera trap surveys at 11 sites demonstrated the nocturnal and crepuscular activity patterns (86%) of the lowland tapir and provide 3 indices of relative abundance for spatial and temporal comparison. Capture rates for lowland tapirs were not significantly different between camera trapping stations placed on river beaches versus those placed in the forest. Lowland tapir capture rates were significantly higher in the national protected areas of the region versus indigenous territories and unprotected portions of the landscape. Capture rates through time suggested that lowland tapir populations are recovering within the Tuichi Valley, an area currently dedicated towards ecotourism activities, following the creation (1995) and subsequent implementation (1997) of the Madidi National Park in Bolivia. Based on our distributional data and published conservative estimates of population density, we calculated that this transboundary landscape holds an overall lowland tapir population of between 14 540 and 36 351 individuals, of which at least 24.3% are under protection from national and municipal parks. As such, the Greater Madidi-Tambopata Landscape should be considered a lowland tapir population stronghold and priority conservation efforts are discussed in order to maintain this population. © 2012 Wiley Publishing Asia Pty Ltd, ISZS and IOZ/CAS.

  18. Electrodeposited nanostructured raspberry-like gold-modified electrodes for electrocatalytic applications

    Energy Technology Data Exchange (ETDEWEB)

    Manivannan, Shanmugam; Ramaraj, Ramasamy, E-mail: ramarajr@yahoo.com [Madurai Kamaraj University, Centre for Photoelectrochemistry, School of Chemistry (India)

    2013-10-15

    A facile method for fabrication of raspberry-like Au nanostructures (Au NRBs)-modified electrode by electrodeposition and its applications toward the electrocatalytic oxidation of methanol (MOR) in alkaline medium and oxygen reduction reaction (ORR) in both alkaline and acidic media are demonstrated. The Au NRBs are characterized by UV-Vis absorption spectra, SEM, X-ray diffraction, and electrochemical measurements. The growth of Au NRBs was monitored by recording the in-situ absorption spectral changes during electrodeposition using spectroelectrochemical technique. Here we systematically studied the MOR by varying several reaction parameters such as potential scan rate and methanol concentration. The electrocatalytic poisoning effect due to the MOR products are not observed at the Au NRBs-modified electrode. At the alkaline medium the Au NRBs-modified electrode shows the better catalytic activities toward the MOR and ORR when compared to the poly crystalline gold and bare glassy carbon electrodes. The Au NRBs-modified electrode is a promising and inexpensive electrode material for other electrocatalytic applications.Graphical AbstractRaspberry-like Au nanostructures modified electrode is prepared and used for electrocatalytic applications.

  19. Greater-than-Class C low-level radioactive waste characterization: Estimated volumes, radionuclide activities, and other characteristics

    International Nuclear Information System (INIS)

    Hulse, R.A.

    1991-08-01

    Planning for storage or disposal of greater-than-Class C low-level radioactive waste (GTCC LLW) requires characterization of that waste to estimate volumes, radionuclide activities, and waste forms. Data from existing literature, disposal records, and original research were used to estimate the characteristics and project volumes and radionuclide activities to the year 2035. GTCC LLW is categorized as: nuclear utilities waste, sealed sources waste, DOE-held potential GTCC LLW; and, other generator waste. It has been determined that the largest volume of those wastes, approximately 57%, is generated by nuclear power plants. The Other Generator waste category contributes approximately 10% of the total GTCC LLW volume projected to the year 2035. Waste held by the Department of Energy, which is potential GTCC LLW, accounts for nearly 33% of all waste projected to the year 2035; however, no disposal determination has been made for that waste. Sealed sources are less than 0.2% of the total projected volume of GTCC LLW

  20. Greater anterior insula activation during anticipation of food images in women recovered from anorexia nervosa versus controls

    Science.gov (United States)

    Oberndorfer, Tyson; Simmons, Alan; McCurdy, Danyale; Strigo, Irina; Matthews, Scott; Yang, Tony; Irvine, Zoe; Kaye, Walter

    2013-01-01

    Individuals with anorexia nervosa (AN) restrict food consumption and become severely emaciated. Eating food, even thinking of eating food, is often associated with heightened anxiety. However, food cue anticipation in AN is poorly understood. Fourteen women recovered from AN and 12 matched healthy control women performed an anticipation task viewing images of food and object images during functional magnetic resonance imaging. Comparing anticipation of food versus object images between control women and recovered AN groups showed significant interaction only in the right ventral anterior insula, with greater activation in recovered AN anticipating food images. These data support the hypothesis of a disconnect between anticipating and experiencing food stimuli in recovered AN. Insula activation positively correlated with pleasantness ratings of palatable foods in control women, while no such relationship existed in recovered AN, which is further evidence of altered interoceptive function. Finally, these findings raise the possibility that enhanced anterior insula anticipatory response to food cues in recovered AN could contribute to exaggerated sensitivity and anxiety related to food and eating. PMID:23993362

  1. Greater-than-Class C low-level radioactive waste characterization: Estimated volumes, radionuclide activities, and other characteristics. Revision 1

    Energy Technology Data Exchange (ETDEWEB)

    1994-09-01

    The Department of Energy`s (DOE`s) planning for the disposal of greater-than-Class C low-level radioactive waste (GTCC LLW) requires characterization of the waste. This report estimates volumes, radionuclide activities, and waste forms of GTCC LLW to the year 2035. It groups the waste into four categories, representative of the type of generator or holder of the waste: Nuclear Utilities, Sealed Sources, DOE-Held, and Other Generator. GTCC LLW includes activated metals (activation hardware from reactor operation and decommissioning), process wastes (i.e., resins, filters, etc.), sealed sources, and other wastes routinely generated by users of radioactive material. Estimates reflect the possible effect that packaging and concentration averaging may have on the total volume of GTCC LLW. Possible GTCC mixed LLW is also addressed. Nuclear utilities will probably generate the largest future volume of GTCC LLW with 65--83% of the total volume. The other generators will generate 17--23% of the waste volume, while GTCC sealed sources are expected to contribute 1--12%. A legal review of DOE`s obligations indicates that the current DOE-Held wastes described in this report will not require management as GTCC LLW because of the contractual circumstances under which they were accepted for storage. This report concludes that the volume of GTCC LLW should not pose a significant management problem from a scientific or technical standpoint. The projected volume is small enough to indicate that a dedicated GTCC LLW disposal facility may not be justified. Instead, co-disposal with other waste types is being considered as an option.

  2. Greater-than-Class C low-level radioactive waste characterization: Estimated volumes, radionuclide activities, and other characteristics. Revision 1

    International Nuclear Information System (INIS)

    1994-09-01

    The Department of Energy's (DOE's) planning for the disposal of greater-than-Class C low-level radioactive waste (GTCC LLW) requires characterization of the waste. This report estimates volumes, radionuclide activities, and waste forms of GTCC LLW to the year 2035. It groups the waste into four categories, representative of the type of generator or holder of the waste: Nuclear Utilities, Sealed Sources, DOE-Held, and Other Generator. GTCC LLW includes activated metals (activation hardware from reactor operation and decommissioning), process wastes (i.e., resins, filters, etc.), sealed sources, and other wastes routinely generated by users of radioactive material. Estimates reflect the possible effect that packaging and concentration averaging may have on the total volume of GTCC LLW. Possible GTCC mixed LLW is also addressed. Nuclear utilities will probably generate the largest future volume of GTCC LLW with 65--83% of the total volume. The other generators will generate 17--23% of the waste volume, while GTCC sealed sources are expected to contribute 1--12%. A legal review of DOE's obligations indicates that the current DOE-Held wastes described in this report will not require management as GTCC LLW because of the contractual circumstances under which they were accepted for storage. This report concludes that the volume of GTCC LLW should not pose a significant management problem from a scientific or technical standpoint. The projected volume is small enough to indicate that a dedicated GTCC LLW disposal facility may not be justified. Instead, co-disposal with other waste types is being considered as an option

  3. Greater Glycaemic Response to an Oral Glucose Load in Healthy, Lean, Active and Young Chinese Adults Compared to Matched Caucasians

    Directory of Open Access Journals (Sweden)

    Trevor Simper

    2018-04-01

    Full Text Available There are ethnic differences recorded in glycaemic response and rates of type 2 diabetes mellitus (DM between Chinese and Caucasian populations. Whether these differences are evident in matched healthy, lean, active, young adults is unclear. This study compares the postprandial glycaemic response of a group of Chinese participants (n = 49 with a group of similar Caucasians, (n = 48 aged 23.8 (±4.35 years, body mass index (BMI 22.7 (±2.6 kg/m2, healthy (free from non-communicable disease, and lean (body fat % 23.28% (±5.04. Participants undertook an oral glucose tolerance test to identify any significant differences in postprandial blood glucose response. Body fat percentage, body mass, age, physical activity, baseline glucose and HbA1c did not significantly differ between groups. Data from food frequency questionnaires indicated that the Chinese participants consumed less starchy foods, candy and “other” sweets and sugary drinks, and more rice than the Caucasians (all p ≤ 0.001, but not a greater overall intake of carbohydrates or any other macronutrient (all p > 0.05. The two groups’ postprandial blood glucose responses and 2-h incremental area under the curve values (iAUC—156.67 (74.12 mmol/L 120 min for Caucasians versus 214.03 (77.49 mmol/L 120 min for Chinese—indicate significant differences (p = 0.003 and p < 0.001 respectively between groups. Findings suggest that the difference between the two groups’ iAUC values do not relate to obvious lifestyle factors. The Chinese group were eating the least sugary and starchy food but had the highest iAUC. It is argued that the Chinese group in this investigation have the most favourable BMI, body fat percentage, and body mass, yet “poorest” glycaemic response.

  4. Microwave-polyol synthesis and electrocatalytic performance of Pt/graphene nanocomposites

    International Nuclear Information System (INIS)

    Liao, Chien-Shiun; Liao, Chien-Tsao; Tso, Ching-Yu; Shy, Hsiou-Jeng

    2011-01-01

    Highlights: · One-pot microwave-polyol synthesis of Pt/graphene electrocatalyst. · Simultaneous formation of Pt nanoparticles and reduction of graphene oxide. · Electrocatalytic activities depend on the morphology of the deposited Pt particles. · Dense dispersion of isolated Pt particles with high electrochemical active surface. · Few particle clusters of Pt have large number of active sites for methanol oxidation. - Abstract: Graphene oxide (GO) prepared by the modified Hummers method is used as a support in the formation of a Pt/GO nanocomposite electrocatalyst by microwave-polyol synthesis. The effects of microwave reaction times on particle size, dispersion, and electrocatalytic performance of Pt nanoparticles are studied using wide-angle X-ray diffractometery, Raman spectroscopy, transmission electron microscopy and three-electrode electrochemical measurements. The results indicate that Pt nanoparticles nucleation and growth occur, and the particles are uniformly deposited on the GO nanosheets within a short time. The maximum electrochemical active surface area 85.71 m 2 g -1 for a Pt/GO reaction time of 5 min, is a result of the deposition of a dense dispersion of small Pt particles. The highest methanol oxidation peak current density, I f , of 0.59 A mg -1 occurs for a Pt/GO reaction time of 10 min and is due to the formation of interconnecting Pt particles clusters. This novel Pt/GO nanocomposite electrocatalyst with high electrocatalytic activities has the potential for use as an anode material in fuel cells.

  5. Biopolymer protected silver nanoparticles on the support of carbon nanotube as interface for electrocatalytic applications

    Energy Technology Data Exchange (ETDEWEB)

    Satyanarayana, M.; Kumar, V. Sunil; Gobi, K. Vengatajalabathy, E-mail: drkvgobi@gmail.com, E-mail: satyam.nitw@gmail.com [Department of Chemistry, National Institute of Technology, Warangal - 506004, Telangana (India)

    2016-04-13

    In this research, silver nanoparticles (SNPs) are prepared on the surface of carbon nanotubes via chitosan, a biopolymer linkage. Here chitosan act as stabilizing agent for nanoparticles and forms a network on the surface of carbon nanotubes. Synthesized silver nanoparticles-MWCNT hybrid composite is characterized by UV-Visible spectroscopy, XRD analysis, and FESEM with EDS to evaluate the structural and chemical properties of the nanocomposite. The electrocatalytic activity of the fabricated SNP-MWCNT hybrid modified glassy carbon electrode has been evaluated by cyclic voltammetry and electrochemical impedance analysis. The silver nanoparticles are of size ∼35 nm and are well distributed on the surface of carbon nanotubes with chitosan linkage. The prepared nanocomposite shows efficient electrocatalytic properties with high active surface area and excellent electron transfer behaviour.

  6. Electrocatalytic behavior of carbon paste electrode modified with metal phthalocyanines nanoparticles toward the hydrogen evolution

    International Nuclear Information System (INIS)

    Abbaspour, Abdolkarim; Norouz-sarvestani, Fatemeh; Mirahmadi, Ehsan

    2012-01-01

    Highlights: ► The new construction of a carbon paste electrode impregnated with nanoparticles of Zn and Ni phthalocyanine (nano ZnPc and nano NiPc). ► The decrease overpotential and higher current value obtained in nano ZnPc and nano NiPc compared to bulky ZnPc and bulky NiPc, respectively. ► Types of the catalyst and pH of the solution affect the electro catalytic proton reduction reaction considerably. - Abstract: This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of Zn and Ni phthalocyanine (nano ZnPc and nano NiPc). These new electrodes (nano ZnPc-CPE and nano NiPc-CPE) reveal interesting electrocatalytic behavior toward hydrogen evolution reaction (HER). Voltammetric characteristics indicated that the proposed electrodes display better electrocatalytic activity compared to their corresponding bulky modified metal phthalocyanines (MPcs) in minimizing overpotential and increasing the reduction current of HER. Electrocatalytic activities irregularly change with the pH of the solution. However by increasing the pH while nano MPcs are still active, bulky MPcs are almost inactive, and their corresponding ΔE increase by increasing the pH.

  7. Formic acid-assisted synthesis of palladium nanocrystals and their electrocatalytic properties.

    Science.gov (United States)

    Wang, Qinchao; Wang, Yiqian; Guo, Peizhi; Li, Qun; Ding, Ruixue; Wang, Baoyan; Li, Hongliang; Liu, Jingquan; Zhao, X S

    2014-01-14

    Palladium (Pd) nanocrystals have been synthesized by using formic acid as the reducing agent at room temperature. When the concentration of formic acid was increased continuously, the size of Pd nanocrystals first decreased to a minimum and then increased slightly again. The products have been investigated by a series of techniques, including X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), UV-vis absorption, and electrochemical measurements. The formation of Pd nanocrystals is proposed to be closely related to the dynamical imbalance of the growth and dissolution rate of Pd nanocrystals associated with the adsorption of formate ions onto the surface of the intermediates. It is found that small Pd nanocrystals showed blue-shifted adsorption peaks compared with large ones. Pd nanocrystals with the smallest size display the highest electrocatalytic activity for the electrooxidation of formic acid and ethanol on the basis of cyclic voltammetry and chronoamperometric data. It is suggested that both the electrochemical active surface area and the small size effect are the key roles in determining the electrocatalytic performances of Pd nanocrystals. A "dissolution-deposition-aggregation" process is proposed to explain the variation of the electrocatalytic activity during the electrocatalysis according to the HRTEM characterization.

  8. Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

    Directory of Open Access Journals (Sweden)

    Da-Ming Feng

    2017-12-01

    Full Text Available Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO2 to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.

  9. Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

    KAUST Repository

    Feng, Da-Ming

    2017-12-01

    Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO2) to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.

  10. Electrocatalytic carboxylation of chloroacetonitrile at a silver cathode for the synthesis of cyanoacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Scialdone, Onofrio [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy)], E-mail: scialdone@dicpm.unipa.it; Galia, Alessandro; Filardo, Giuseppe [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy); Isse, Abdirisak Ahmed [Dipartimento di Scienze Chimiche, Universita di Padova, Via Marzolo 1, 35131 Padova (Italy)], E-mail: Abdirisak.ahmedisse@unipd.it; Gennaro, Armando [Dipartimento di Scienze Chimiche, Universita di Padova, Via Marzolo 1, 35131 Padova (Italy)

    2008-12-30

    The electrocatalytic carboxylation of chloroacetonitrile to cyanoacetic acid performed at silver cathodes was investigated both theoretically and experimentally. Silver exhibits powerful electrocatalytic activities towards the reduction of chloroacetonitrile. In CO{sub 2}-saturated CH{sub 3}CN, reduction of NCCH{sub 2}Cl occurs at potentials that are about 0.7 V more positive than those observed at glassy carbon and gives cyanoacetic acid in good yields. Theoretical considerations on the effect of operative parameters on the performances of the process were confirmed by electrocarboxylation experiments performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivities and Faradic efficiencies higher than 80% were obtained by working under anhydrous conditions both under amperostatic and potentiostatic alimentation at proper values of either current density or applied potential.

  11. Impact of the spatial distribution of morphological pattern on the efficiency of electrocatalytic gas evolving reactions

    Directory of Open Access Journals (Sweden)

    Žerađanin Aleksandar R.

    2014-01-01

    Full Text Available The efficiency of electrocatalytic gas evolving reactions (hydrogen, chlorine and oxygen evolution is a key challenge for the important industrial processes, such as chlor-alkali electrolysis or water electrolysis. Central issue for the aforementioned electrocatalytic processes is huge power consumption. Experimental results accumulated in the past, as well as some predictive models ("volcano" plots indicate that altering the nature of the electrode material cannot significantly increase the activity of mentioned reactions. Consequently, it is necessary to find a qualitatively different strategy for improving the energy efficiency of electrocatalytic gas evolving reactions. Usually disregarded fact is that the gas evolution is an oscillatory phenomenon. Given the oscillatory behavior, a key parameter of macrokinetics of gas electrode is the frequency of gas-bubble detachment. Bearing in mind that the gas evolution greatly depends on the surface morphology, a methodology is proposed that establishes a rational link between the morphological pattern of electrode with electrode activity and stability. Characterization was performed using advanced analytical tools. Frequency of gas-bubble detachment is obtained in the configuration of scanning electrochemical microscopy (SECM while the corrosion stability is analyzed using miniaturized scanning flow electrochemical cell connected to the mass spectrometer (SFC-ICPMS.

  12. Shape-Dependent Electrocatalytic Reduction of CO2 to CO on Triangular Silver Nanoplates.

    Science.gov (United States)

    Liu, Subiao; Tao, Hongbiao; Zeng, Li; Liu, Qi; Xu, Zhenghe; Liu, Qingxia; Luo, Jing-Li

    2017-02-15

    Electrochemical reduction of CO 2 (CO 2 RR) provides great potential for intermittent renewable energy storage. This study demonstrates a predominant shape-dependent electrocatalytic reduction of CO 2 to CO on triangular silver nanoplates (Tri-Ag-NPs) in 0.1 M KHCO 3 . Compared with similarly sized Ag nanoparticles (SS-Ag-NPs) and bulk Ag, Tri-Ag-NPs exhibited an enhanced current density and significantly improved Faradaic efficiency (96.8%) and energy efficiency (61.7%), together with a considerable durability (7 days). Additionally, CO starts to be observed at an ultralow overpotential of 96 mV, further confirming the superiority of Tri-Ag-NPs as a catalyst for CO 2 RR toward CO formation. Density functional theory calculations reveal that the significantly enhanced electrocatalytic activity and selectivity at lowered overpotential originate from the shape-controlled structure. This not only provides the optimum edge-to-corner ratio but also dominates at the facet of Ag(100) where it requires lower energy to initiate the rate-determining step. This study demonstrates a promising approach to tune electrocatalytic activity and selectivity of metal catalysts for CO 2 RR by creating optimal facet and edge site through shape-control synthesis.

  13. Electrocatalytic approach for the efficiency increase of electrolytic hydrogen production: Proof-of-concept using platinum-dysprosium alloys

    International Nuclear Information System (INIS)

    Santos, D.M.F.; Šljukić, B.; Sequeira, C.A.C.; Macciò, D.; Saccone, A.; Figueiredo, J.L.

    2013-01-01

    Development of electrocatalytic materials for the hydrogen evolution reaction (HER) is attempted with the aim of reducing the water electrolysis overpotential and increasing its efficiency. Using linear scan voltammetry measurements of the hydrogen discharge enables evaluation of the electrocatalytic activity for the HER of platinum–dysprosium (Pt–Dy) intermetallic alloy electrodes of different compositions. Understanding of materials electrocatalytic performance is based on determination of several crucial kinetic parameters, including the Tafel coefficients, b, charge transfer coefficients, α, exchange current densities, j 0 , and activation energies, E a . Influence of temperature on HER is investigated by performing studies at temperatures ranging from 25 °C to 85 °C. The effect of the Dy amount in the efficiency of the HER on the Pt–Dy alloys is analysed. Results demonstrate that Dy can substantially increase the electrocatalytic activity of the Pt alloys, in comparison to the single Pt electrode. Efforts are made to correlate the microstructure of the alloys with their performance towards the HER. - Highlights: ► Development of electrocatalysts to increase efficiency of electrolytic hydrogen production. ► Synthesis and evaluation of composition and morphology of platinum–dysprosium (Pt–Dy) alloys. ► Hydrogen evolution reaction on Pt–Dy alloys electrodes studied using linear scan voltammetry in alkaline medium. ► Pt–Dy alloy with equiatomic composition enhances kinetics of hydrogen discharge compared to single Pt

  14. Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S.

    2016-07-01

    The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1-2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2‧-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2‧-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how

  15. Summary of science, activities, programs, and policies that influence the rangewide conservation of Greater Sage-Grouse (Centrocercus urophasianus)

    Science.gov (United States)

    Manier, D.J.; Wood, David J.A.; Bowen, Z.H.; Donovan, R.M.; Holloran, M.J.; Juliusson, L.M.; Mayne, K.S.; Oyler-McCance, S.J.; Quamen, F.R.; Saher, D.J.; Titolo, A.J.

    2013-01-01

    The Greater Sage-Grouse, has been observed, hunted, and counted for decades. The sagebrush biome, home to the Greater Sage-Grouse, includes sagebrush-steppe and Great Basin sagebrush communities, interspersed with grasslands, salt flats, badlands, mountain ranges, springs, intermittent creeks and washes, and major river systems, and is one of the most widespread and enigmatic components of Western U.S. landscapes. Over time, habitat conversion, degradation, and fragmentation have accumulated across the entire range such that local conditions as well as habitat distributions at local and regional scales are negatively affecting the long-term persistence of this species. Historic patterns of human use and settlement of the sagebrush ecosystem have contributed to the current condition and status of sage-grouse populations. The accumulation of habitat loss, persistent habitat degradation, and fragmentation by industry and urban infrastructure, as indicated by U.S. Fish and Wildlife Service (USFWS) findings, presents a significant challenge for conservation of this species and sustainable management of the sagebrush ecosystem. Because of the wide variations in natural and human history across these landscapes, no single prescription for management of sagebrush ecosystems (including sage-grouse habitats) will suffice to guide the collective efforts of public and private entities to conserve the species and its habitat. This report documents and summarizes several decades of work on sage-grouse populations, sagebrush as habitat, and sagebrush community and ecosystem functions based on the recent assessment and findings of the USFWS under consideration of the Endangered Species Act. As reflected here, some of these topics receive a greater depth of discussion because of the perceived importance of the issue for sagebrush ecosystems and sage-grouse populations. Drawing connections between the direct effects on sagebrush ecosystems and the effect of ecosystem condition on

  16. Nanocrystalline Mn-Mo-Ce Oxide Anode Doped Rare Earth Ce and Its Selective Electro-catalytic Performance

    Directory of Open Access Journals (Sweden)

    SHI Yan-hua

    2017-09-01

    Full Text Available The anode oxide of nanocrystalline Mn-Mo-Ce was prepared by anode electro-deposition technology, and its nanostructure and selective electro-catalytic performance were investigated using the SEM, EDS, XRD, HRTEM, electrochemical technology and oxygen evolution efficiency testing. Furthermore, the selective electro-catalytic mechanism of oxygen evolution and chlorine depression was discussed. The results show that the mesh-like nanostructure Mn-Mo-Ce oxide anode with little cerium doped is obtained, and the oxygen evolution efficiency for the anode in the seawater is 99.51%, which means a high efficiency for the selective electro-catalytic for the oxygen evolution. Due to the structural characteristics of γ-MnO2, the OH- ion is preferentially absorbed, while Cl- absorption is depressed. OH- accomplishes the oxygen evolution process during the valence transition electrocatalysis of Mn4+/Mn3+, completing the selective electro-catalysis process. Ce doping greatly increases the reaction activity, and promotes the absorption and discharge; the rising interplanar spacing between active (100 crystalline plane promotes OH- motion and the escape of newborn O2, so that the selective electro-catalytic property with high efficient oxygen evolution and chlorine depression is achieved from the nano morphology effect.

  17. Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

    2011-06-30

    Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

  18. GREATER HEMOCYTE BACTERICIDAL ACTIVITY IN OYSTERS (CRASSOSTREA VIRGINICA) FROM A RELATIVELY CONTAMINATED SITE IN PENSACOLA BAY, FLORIDA.

    Science.gov (United States)

    Bivalve mollusks such as Crassostrea virginica inhabiting polluted estuaries and coastal areas may bioaccumulate high concentrations of contaminants without apparent ill effects. However, changes in putative internal defense activities have been associated with contaminant accumu...

  19. Higher percent body fat in young women with lower physical activity level and greater proportion Pacific Islander ancestry.

    Science.gov (United States)

    Black, Nate; Nabokov, Vanessa; Vijayadeva, Vinutha; Novotny, Rachel

    2011-11-01

    Samoan women exhibit high rates of obesity, which can possibly be attenuated through diet and physical activity. Obesity, and body fatness in particular, is associated with increased risk for chronic diseases. Ancestry, physical activity, and dietary patterns have been associated with body composition. Using a cross-sectional design, the relative importance of proportion of Pacific Islander (PI) ancestry, level of physical activity, and macronutrients among healthy women in Honolulu, Hawai'i, ages 18 to 28 years was examined. All data were collected between January 2003 and December 2004. Percent body fat (%BF) was determined by whole body dual energy x-ray absorptiometry (DXA). Nutrient data were derived from a three-day food record. Means and standard deviations were computed for all variables of interest. Bivariate correlation analysis was used to determine correlates of %BF. Multiple regression analysis was used to determine relative contribution of variables significantly associated with %BF. Proportion of PI ancestry was significantly positively associated with %BF (P=0.0001). Physical activity level was significantly negatively associated with %BF (P=0.0006). Intervention to increase physical activity level of young Samoan women may be effective to decrease body fat and improve health. CRC-NIH grant: 0216.

  20. Electrocatalytic reduction of oxygen at glassy carbon electrode modified by polypyrrole/anthraquinones composite film in various pH media

    International Nuclear Information System (INIS)

    Valarselvan, S.; Manisankar, P.

    2011-01-01

    Graphical abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . Highlights: → Hydroxyl derivatives of anthraquinones as electrocatalysts for dioxygen reduction. → AQ/PPy composite film on GC electrode exhibits potent electrocatalytic activity. → Substituent groups influence electrocatalytic dioxygen reduction. → Surface coverage varies the rate of electrocatalytic dioxygen reduction. - Abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. The electrochemical behaviour of the modified electrodes was examined in various pH media and both the formal potential of anthraquinones and reduction potential of dioxygen exhibited pH dependence. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . pH 6.0 was chosen as the most suitable medium to study the electrocatalysis by comparing the peak potential of oxygen reduction and enhancement in peak current for oxygen reduction. The diffusion coefficient values of AQ at the modified electrodes and the number of electrons involved in AQ reduction were evaluated by chronoamperometric and chronocoulometric techniques, respectively. In addition, hydrodynamic voltammetric studies showed the involvement of two electrons in O 2 reduction. The mass specific activity of AQ used, the diffusion coefficient of oxygen and the heterogeneous rate constants for the oxygen reduction at the surface of modified electrodes were also determined by rotating disk voltammetry.

  1. Electrocatalytic properties of graphite nanofibers-supported platinum catalysts for direct methanol fuel cells.

    Science.gov (United States)

    Park, Soo-Jin; Park, Jeong-Min; Seo, Min-Kang

    2009-09-01

    Graphite nanofibers (GNFs) treated at various temperatures were used as carbon supports to improve the efficiency of PtRu catalysts. The electrochemical properties of the PtRu/GNFs catalysts were then investigated to evaluate their potential for application in DMFCs. The results indicated that the particle size and dispersibility of PtRu in the catalysts were changed by heat treatment, and the electrochemical activity of the catalysts was improved. Consequently, it was found that heat treatments could have an influence on the surface and structural properties of GNFs, resulting in enhancing an electrocatalytic activity of the catalysts for DMFCs.

  2. Highly-sensitive electrocatalytic determination for toxic phenols based on coupled cMWCNT/cyclodextrin edge-functionalized graphene composite

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Juanjuan; Liu, Maoxiang [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Song, Haiou, E-mail: songhaiou2011@126.com [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Zhang, Shupeng, E-mail: shupeng_2006@126.com [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Qian, Yueyue [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Li, Aimin, E-mail: liaimin@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-11-15

    Highlights: • Phenol detection based on coupled cMWCNT/CD edge-functionalized graphene composite. • Increased conductivity can inspire enhancement of electrocatalytic performance. • The synergistic combination of the trace amounts of CDs and cMWCNT is a pivotal. • GN-CD-cMWCNT shows an excellent electrocatalytic and anti-interference ability. - Abstract: Highly-sensitive electrocatalytic determination of toxic phenol compounds is of significance in environmental monitoring due to their low degradation and high toxicity to the environment and humans. In this paper, a rapid and sensitive electrochemical sensor based on coupled carboxyl-multi-walled carbon nanotube (cMWCNT) and cyclodextrin (CD) edge-functionalized graphene composite was successfully employed towards trace detection of three typical phenols (4-aminophenol, 4-AP; 4-chlorophenol, 4-CP; 4-nitrophenol, 4-NP). The morphology studies from scanning electron microscope and transmission electron microscope analysis revealed that cMWCNTs as conductive bridges were successfully incorporated into CD edge-functionalized graphene layers. Further, The electrocatalytic detection performance of the 3D simultaneously reduced and self-assembled sensing architecture (GN-CD-cMWCNT) with trace amounts of CDs was evaluated. The electrochemical studies demonstrated that GN-CD-cMWCNT displays excellent electrocatalytic activity, high sensitivity and stability. Under optimal conditions, the current responses of 4-AP, 4-CP and 4-NP are linear to concentrations over two different ranges, with low detection limit of 0.019, 0.017 and 0.027 μM (S/N = 3), respectively. And, GN-CD-cMWCNT shows an excellent anti-interference ability against electroactive species and metal ions. In addition, validation of the applicability of the presented sensor was also performed for the determination of three phenols in tap water sample with satisfactory results.

  3. Highly-sensitive electrocatalytic determination for toxic phenols based on coupled cMWCNT/cyclodextrin edge-functionalized graphene composite

    International Nuclear Information System (INIS)

    Gao, Juanjuan; Liu, Maoxiang; Song, Haiou; Zhang, Shupeng; Qian, Yueyue; Li, Aimin

    2016-01-01

    Highlights: • Phenol detection based on coupled cMWCNT/CD edge-functionalized graphene composite. • Increased conductivity can inspire enhancement of electrocatalytic performance. • The synergistic combination of the trace amounts of CDs and cMWCNT is a pivotal. • GN-CD-cMWCNT shows an excellent electrocatalytic and anti-interference ability. - Abstract: Highly-sensitive electrocatalytic determination of toxic phenol compounds is of significance in environmental monitoring due to their low degradation and high toxicity to the environment and humans. In this paper, a rapid and sensitive electrochemical sensor based on coupled carboxyl-multi-walled carbon nanotube (cMWCNT) and cyclodextrin (CD) edge-functionalized graphene composite was successfully employed towards trace detection of three typical phenols (4-aminophenol, 4-AP; 4-chlorophenol, 4-CP; 4-nitrophenol, 4-NP). The morphology studies from scanning electron microscope and transmission electron microscope analysis revealed that cMWCNTs as conductive bridges were successfully incorporated into CD edge-functionalized graphene layers. Further, The electrocatalytic detection performance of the 3D simultaneously reduced and self-assembled sensing architecture (GN-CD-cMWCNT) with trace amounts of CDs was evaluated. The electrochemical studies demonstrated that GN-CD-cMWCNT displays excellent electrocatalytic activity, high sensitivity and stability. Under optimal conditions, the current responses of 4-AP, 4-CP and 4-NP are linear to concentrations over two different ranges, with low detection limit of 0.019, 0.017 and 0.027 μM (S/N = 3), respectively. And, GN-CD-cMWCNT shows an excellent anti-interference ability against electroactive species and metal ions. In addition, validation of the applicability of the presented sensor was also performed for the determination of three phenols in tap water sample with satisfactory results.

  4. Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

    KAUST Repository

    Nurlaela, Ela

    2016-01-25

    The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.

  5. Co-sputter deposited nickel-copper bimetallic nanoalloy embedded carbon films for electrocatalytic biomarker detection

    Science.gov (United States)

    Shiba, Shunsuke; Kato, Dai; Kamata, Tomoyuki; Niwa, Osamu

    2016-06-01

    We report the fabrication of a nickel (Ni)-copper (Cu) bimetallic nanoalloy (~3 nm) embedded carbon film electrode with the unbalanced magnetron (UBM) co-sputtering technique, which requires only a one-step process at room temperature. Most of each nanoalloy body was firmly embedded in a chemically stable carbon matrix with an atomically flat surface (Ra: 0.21 nm), suppressing the aggregation and/or detachment of the nanoalloy from the electrode surface. The nanoalloy size and composition can be controlled simply by individually controlling the target powers of carbon, Ni and Cu, which also makes it possible to localize the nanoalloys near the electrode surface. This electrode exhibited excellent electrocatalytic activity for d-mannitol, which should be detected with a low detection limit in urine samples for the diagnosis of severe intestinal diseases. With a Ni/Cu ratio of around 64/36, the electrocatalytic current per metal area was 3.4 times larger than that of an alloy film electrode with a similar composition (~70/30). This improved electrocatalytic activity realized higher stability (n = 60, relative standard deviation (RSD): 4.6%) than the alloy film (RSD: 32.2%) as demonstrated by continuous measurements of d-mannitol.We report the fabrication of a nickel (Ni)-copper (Cu) bimetallic nanoalloy (~3 nm) embedded carbon film electrode with the unbalanced magnetron (UBM) co-sputtering technique, which requires only a one-step process at room temperature. Most of each nanoalloy body was firmly embedded in a chemically stable carbon matrix with an atomically flat surface (Ra: 0.21 nm), suppressing the aggregation and/or detachment of the nanoalloy from the electrode surface. The nanoalloy size and composition can be controlled simply by individually controlling the target powers of carbon, Ni and Cu, which also makes it possible to localize the nanoalloys near the electrode surface. This electrode exhibited excellent electrocatalytic activity for d

  6. Poly(anthranilic acid) Microspheres: Synthesis, Characterization and their Electrocatalytic Properties

    Energy Technology Data Exchange (ETDEWEB)

    Ranganathan, Suresh; Raju, Prabu; Arunachalam, Vijayaraj; Krishnamoorty, Giribabu; Ramadoss, Manigandan; Arumainathan, Stephen; Vengidusamy, Narayanan [University of Madras, Guindy Maraimalai Campus, Chennai (India)

    2012-06-15

    Poly(anthranilic acid) was synthesized by rapid mixing method using 5-sulphosalicylic acid as a dopant. The synthesized polymer was characterized by various techniques like FT-IR, UV-Visible, and X-ray diffraction etc., The FT-IR studies reveal that the 5-sulphosalicylic acid is well doped within the polymer. The morphological property was characterized by field emission scanning electron microscopic technique. The electrochemical properties of the polymer were studied by cyclic voltammetric method. The synthesized polymer was used to modify glassy carbon electrode (GCE) and the modified electrode was found to exhibit electrocatalytic activity for the oxidation of uric acid (UA)

  7. Poly(anthranilic acid) Microspheres: Synthesis, Characterization and their Electrocatalytic Properties

    International Nuclear Information System (INIS)

    Ranganathan, Suresh; Raju, Prabu; Arunachalam, Vijayaraj; Krishnamoorty, Giribabu; Ramadoss, Manigandan; Arumainathan, Stephen; Vengidusamy, Narayanan

    2012-01-01

    Poly(anthranilic acid) was synthesized by rapid mixing method using 5-sulphosalicylic acid as a dopant. The synthesized polymer was characterized by various techniques like FT-IR, UV-Visible, and X-ray diffraction etc., The FT-IR studies reveal that the 5-sulphosalicylic acid is well doped within the polymer. The morphological property was characterized by field emission scanning electron microscopic technique. The electrochemical properties of the polymer were studied by cyclic voltammetric method. The synthesized polymer was used to modify glassy carbon electrode (GCE) and the modified electrode was found to exhibit electrocatalytic activity for the oxidation of uric acid (UA)

  8. Controllable synthesis of palladium nanocubes/reduced graphene oxide composites and their enhanced electrocatalytic performance

    Science.gov (United States)

    Zhang, Yuting; Huang, Qiwei; Chang, Gang; Zhang, Zaoli; Xia, Tiantian; Shu, Honghui; He, Yunbin

    2015-04-01

    Homogeneous distribution of cube-shaped Pd nanocrystals on the surface of reduced graphene oxide is obtained via a facile one-step method by employing AA and KBr as the reductant and capping agent, respectively. The experimental factors affecting the morphology and structure of Pd nanoparticles have been systematically investigated to explore the formation mechanism of Pd nanocubes (PdNCs). It is revealed that PdNCs enclosed by active {100} facets with an average side length of 15 nm were successfully synthesized on the surface of reduced graphene oxide. KBr plays the role for facet selection by surface passivation and AA controls the reduction speed of Pd precursors, both of which govern the morphology changes of palladium nanoparticles. In the further electrochemical evaluations, the Pd nanocubes/reduced graphene oxide composites show better electrocatalytic activity and stability towards the electro-oxidation of ethanol than both reduced graphene oxide supported Pd nanoparticles and free-standing PdNCs. It could be attributed to the high electrocatalytic activity of the dominated active {100} crystal facets of Pd nanocubes and the enhanced electron transfer of graphene. The developed approach provide a versatile way for shape-controlled preparation of noble metal nanoparticles, which can work as novel electrocatalysts in the application of direct alcohols fuel cells.

  9. Efficient electrocatalytic performance of thermally exfoliated reduced graphene oxide-Pt hybrid

    Energy Technology Data Exchange (ETDEWEB)

    Antony, Rajini P., E-mail: raji.anna@gmail.com; Preethi, L.K.; Gupta, Bhavana; Mathews, Tom, E-mail: tom@igcar.gov.in; Dash, S.; Tyagi, A.K.

    2015-10-15

    Highlights: • Synthesis of Pt–RGO nanohybrids of very high electrochemically active surface area. • Electrocatalytic activity-cum-stability: ∼10 times that of commercial Pt-C catalyst. • TEM confirms narrow size distribution and excellent dispersion of Pt nanoparticles. • SAED and XRD indicate (1 1 1) orientation of Pt nanoparticles. • Methanol oxidation EIS reveal decrease in charge transfer resistance with potential - Abstract: High quality thermally exfoliated reduced graphene oxide (RGO) nanosheets decorated with platinum nanocrystals have been synthesized using a simple environmentally benign process. The electrocatalytic behaviour of the Pt–RGO nanohybrid for methanol oxidation was studied using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. High resolution transmission electron microscopy shows uniform dispersion of Pt nanoparticles of ∼2–4 nm size. X-ray diffraction and selected area diffraction studies reveal (1 1 1) orientation of the platinum nanoparticles. The cyclic voltammetry and chronoamperometry results indicate higher catalytic activity and stability for Pt–RGO compared to commercial Pt-C. The electrochemical active surface area of Pt–RGO (52.16 m{sup 2}/g) is found to be 1.5 times that of commercial Pt-C. Impedance spectroscopy shows different impedance behaviour at different potential regions, indicating change in methanol oxidation reaction mechanism with potential. The reversal of impedance pattern to the second quadrant, at potentials higher than ∼0.40 V, indicates change in the rate determining reaction.

  10. Uranium-mediated electrocatalytic dihydrogen production from water

    Science.gov (United States)

    Halter, Dominik P.; Heinemann, Frank W.; Bachmann, Julien; Meyer, Karsten

    2016-02-01

    Depleted uranium is a mildly radioactive waste product that is stockpiled worldwide. The chemical reactivity of uranium complexes is well documented, including the stoichiometric activation of small molecules of biological and industrial interest such as H2O, CO2, CO, or N2 (refs 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11), but catalytic transformations with actinides remain underexplored in comparison to transition-metal catalysis. For reduction of water to H2, complexes of low-valent uranium show the highest potential, but are known to react violently and uncontrollably forming stable bridging oxo or uranyl species. As a result, only a few oxidations of uranium with water have been reported so far; all stoichiometric. Catalytic H2 production, however, requires the reductive recovery of the catalyst via a challenging cleavage of the uranium-bound oxygen-containing ligand. Here we report the electrocatalytic water reduction observed with a trisaryloxide U(III) complex [((Ad,MeArO)3mes)U] (refs 18 and 19)—the first homogeneous uranium catalyst for H2 production from H2O. The catalytic cycle involves rare terminal U(IV)-OH and U(V)=O complexes, which have been isolated, characterized, and proven to be integral parts of the catalytic mechanism. The recognition of uranium compounds as potentially useful catalysts suggests new applications for such light actinides. The development of uranium-based catalysts provides new perspectives on nuclear waste management strategies, by suggesting that mildly radioactive depleted uranium—an abundant waste product of the nuclear power industry—could be a valuable resource.

  11. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun; Zhang, Chenhui; Wang, Zhenyu; Zhu, Jian; Wen, Zhiwei; Zhao, Xingzhong; Zhang, Xixiang; Xu, Jun; Lu, Zhouguang

    2017-01-01

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  12. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun

    2017-12-27

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  13. Biomolecule-assisted synthesis of Ag/reduced graphene oxide nanocomposite with excellent electrocatalytic and antibacterial performance

    Energy Technology Data Exchange (ETDEWEB)

    Fathalipour, Soghra, E-mail: fathalipour@pnu.ac.ir [Department of Chemistry, Payame Noor University, PO Box: 19395-3697, Tehran (Iran, Islamic Republic of); Pourbeyram, Sima; Sharafian, Aziaeh [Department of Chemistry, Payame Noor University, PO Box: 19395-3697, Tehran (Iran, Islamic Republic of); Tanomand, Asghar [Department of Basic Sciences, Faculty Of Medicine, Maragheh University of Medical Sciences, PO Box: 78151-55158 (Iran, Islamic Republic of); Azam, Parisa [Department of Chemistry, Payame Noor University, PO Box: 19395-3697, Tehran (Iran, Islamic Republic of)

    2017-06-01

    In this work, an environmentally friendly method was applied for the synthesis of aqueous suspension of L-cysteine modified Ag nanoparticles (NPs)-decorated reduced graphene oxide (rGO) nanocomposite. L-cysteine played a triple role as reducing agent, stabilizer and linker of Ag NPs onto the surface of rGO. The resultant nanocomposite was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction studies (XRD), zeta potential, Raman spectroscopy, scanning electron microscopy (SEM) and energy dispersive analysis of X-ray (EDX). Meanwhile, minimum inhibitory concentration (MIC), minimum bacterial concentration (MBC), agar well diffusion and cyclic voltammetry (CV) techniques were used for the investigation of antibacterial and electrocatalytic behaviors of the nanocomposite, respectively. The obtained nanocomposite showed not only enhanced electrocatalytic activity for glucose but also excellent antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). - Highlights: • Biocompatible reduced graphene oxide/ Ag nanocomposite was synthesized based on cysteine- Ag nanoparticles. • The reaction was carried out at room temperature without any further reducer. • The nanocomposite displayed excellent antibacterial and electrocatalytic activity against glucose.

  14. Comparison of electrocatalytic characterization of boron-doped diamond and SnO2 electrodes

    International Nuclear Information System (INIS)

    Lv, Jiangwei; Feng, Yujie; Liu, Junfeng; Qu, Youpeng; Cui, Fuyi

    2013-01-01

    Boron-doped diamond (BDD) and SnO 2 electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) and sol–gel method, respectively. Electrochemical characterization of the two electrodes were investigated by phenol electrochemical degradation, accelerated service life test, cyclic voltammetry (CV) in phenol solution, polarization curves in H 2 SO 4 . The surface morphology and crystal structure of two electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. The results showed a considerable difference between the two electrodes in their electrocatalytic activity, electrochemical stability and surface properties. Phenol was readily mineralized to CO 2 at BDD electrode, favoring electrochemical combustion, but its degradation was much slower at SnO 2 electrode. The service life of BDD electrode was 10 times longer than that of SnO 2 . Higher electrocatalytic activity and electrochemical stability of BDD electrode arise from its high oxygen evolution potential and the physically absorbed hydroxyl radicals (·OH) on electrode surface.

  15. Gold nanoparticles-decorated fluoroalkylsilane nano-assemblies for electrocatalytic applications

    Energy Technology Data Exchange (ETDEWEB)

    Ballarin, Barbara, E-mail: barbara.ballarin@unibo.it [Department of Industrial Chemistry “Toso Montanari”, UdR INSTM of Bologna and CIRI MAM, Alma Mater Studiorum – University of Bologna, Viale del Risorgimento 4, 40136 Bologna (Italy); Barreca, Davide [CNR-IENI and INSTM, Department of Chemistry, Padova University, Via Marzolo 1, 35131 Padova (Italy); Cassani, Maria Cristina, E-mail: maria.cassani@unibo.it [Department of Industrial Chemistry “Toso Montanari”, UdR INSTM of Bologna and CIRI MAM, Alma Mater Studiorum – University of Bologna, Viale del Risorgimento 4, 40136 Bologna (Italy); Carraro, Giorgio; Maccato, Chiara [Department of Chemistry, Padova University and INSTM, Via Marzolo 1, 35131 Padova (Italy); Mignani, Adriana [Center for Industrial Research – Advanced Applications in Mechanical Engineering and Materials Technology (CIRI-MAM), University of Bologna, Viale del Risorgimento 2, 40136 Bologna (Italy); Lazzari, Dario; Bertola, Maurizio [Miteni S.p.A., Località Colombara 91, 36070 Trissino, VI (Italy)

    2016-01-30

    Graphical abstract: - Highlights: • Au{sub NPs}/short-chain fluoroalkylsilane (FAS) layers/indium tin oxide (ITO) sandwich structures were prepared by a two-step method. • The FAS-embedded amide functional group enhances the Au{sub NPs} surface coverage. • The Au{sub NPs}/FAS/ITO systems are electrocatalytically active toward methanol oxidation. - Abstract: Metal/organosilane/oxide sandwich structures were prepared via a two-step self-assembly method. First, indium tin oxide (ITO) substrates were functionalized with the following fluoroalkylsilanes (FAS): R{sub F}C(O)N(H)(CH{sub 2}){sub 3}Si(OMe){sub 3} (1, R{sub F} = C{sub 5}F{sub 11}), containing an embedded amide between the perfluoroalkyl chain and the syloxanic moiety, and R{sub F}(CH{sub 2}){sub 2}Si(OEt){sub 3} (2, R{sub F} = C{sub 6}F{sub 13}). Subsequently, Au nanoparticles (Au{sub NPs}) introduction in the obtained systems was carried out by controlled immersion into a solution of citrate-stabilized Au{sub NPs}. The physico-chemical properties of the target materials were thoroughly investigated by using various complementary techniques. Finally, the application of such systems as catalysts for methanol electro-oxidation under alkaline conditions was investigated, revealing the synergistical role played by FAS and Au{sub NPs} in promoting a remarkable electrocatalytic activity.

  16. Enhancement of electrocatalytic properties of carbonized polyaniline nanoparticles upon a hydrothermal treatment in alkaline medium

    International Nuclear Information System (INIS)

    Gavrilov, Nemanja; Vujkovic, Milica; Pasti, Igor A.; Ciric-Marjanovic, Gordana; Mentus, Slavko V.

    2011-01-01

    Highlights: → Carbonized polyaniline nanoparticles were treated hydrothermally in 1 M KOH. → Hydrothermal treatment improved the electrocatalytic activity towards ORR. → Significant effect of catalyst loading was evidenced too. → At the loading 0.5 mg cm -2 the 4e - reaction path was achieved. - Abstract: The electrocatalytic activity of carbonized polyaniline nanostructures (Carb-nanoPANI) towards oxygen reduction reaction (ORR), estimated in 0.1 mol dm -3 KOH solution, was significantly improved upon a hydrothermal treatment in 1 mol dm -3 KOH solution. Namely, the onset of ORR was shifted by ∼70 mV to more positive potentials, and the number of electrons consumed per O 2 molecule was enhanced in comparison to the original material. The number of electrons involved in ORR depended on loading, and with a loading of 0.5 mg cm -2 , for the potentials lower than -0.5 V vs SCE, the number of electrons approached 4. For this material, high stability of electrochemical behavior and resistance to the poisoning by ethanol was evidenced by potentiodynamic cycling.

  17. Enhancement of electrocatalytic properties of carbonized polyaniline nanoparticles upon a hydrothermal treatment in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Gavrilov, Nemanja; Vujkovic, Milica; Pasti, Igor A.; Ciric-Marjanovic, Gordana [University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12-16, 11158 Belgrade (Serbia); Mentus, Slavko V., E-mail: slavko@ffh.bg.ac.rs [University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12-16, 11158 Belgrade (Serbia); Serbian Academy of Sciences and Arts, Knez Mihajlova 35, 11158 Belgrade (Serbia)

    2011-10-30

    Highlights: > Carbonized polyaniline nanoparticles were treated hydrothermally in 1 M KOH. > Hydrothermal treatment improved the electrocatalytic activity towards ORR. > Significant effect of catalyst loading was evidenced too. > At the loading 0.5 mg cm{sup -2} the 4e{sup -} reaction path was achieved. - Abstract: The electrocatalytic activity of carbonized polyaniline nanostructures (Carb-nanoPANI) towards oxygen reduction reaction (ORR), estimated in 0.1 mol dm{sup -3} KOH solution, was significantly improved upon a hydrothermal treatment in 1 mol dm{sup -3} KOH solution. Namely, the onset of ORR was shifted by {approx}70 mV to more positive potentials, and the number of electrons consumed per O{sub 2} molecule was enhanced in comparison to the original material. The number of electrons involved in ORR depended on loading, and with a loading of 0.5 mg cm{sup -2}, for the potentials lower than -0.5 V vs SCE, the number of electrons approached 4. For this material, high stability of electrochemical behavior and resistance to the poisoning by ethanol was evidenced by potentiodynamic cycling.

  18. Gold electrodes modified with 16H, 18H-dibenzo[c,l]-7,9-dithia-16,18-diazapentacene for electrocatalytic oxidation of NADH

    NARCIS (Netherlands)

    Rosca, V.; Muresan, L.; Popescu, I.C.; Cristea, C.; Silberg, I.A.

    2001-01-01

    16H,18H-Dibenzo[c,l]-7,9-dithia-16,18-diazapentacene (DDDP), a new phenothiazine derivative containing two linearly condensed phenothiazine rings, strongly adsorbs on polyoriented gold resulting in a modified electrode with electrocatalytic activity for ß-nicotinamide adenine dinucleotide (NADH)

  19. Preparation of SnO{sub 2}-CNTs supported Pt catalysts and their electrocatalytic properties for ethanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Pang, H.L.; Lu, J.P. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Chen, J.H. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)], E-mail: chenjinhua@hnu.cn; Huang, C.T.; Liu, B.; Zhang, X.H. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)

    2009-03-30

    SnO{sub 2}-carbon nanotubes (CNTs) composites were prepared by sol-gel method, and characterized by scanning electron microscopy and X-ray diffraction. Due to high stability in diluted acidic solution, SnO{sub 2}-CNTs composites were selected as the catalyst support and second catalyst for ethanol electrooxidation. The electrocatalytic properties of the SnO{sub 2}-CNTs supported platinum (Pt) catalyst (Pt/SnO{sub 2}-CNTs) for ethanol oxidation have been investigated by typical electrochemical methods. Under the same mass loading of Pt, the Pt/SnO{sub 2}-CNTs catalyst shows higher electrocatalytic activity and better long-term cycle stability than Pt/SnO{sub 2} catalyst. Additionally, the effect of the mass ratio of CNTs to SnO{sub 2} on the electrocatalytic activity of the electrode for ethanol oxidation was investigated, and the optimum mass ratio of CNTs to SnO{sub 2} in the Pt/SnO{sub 2}-CNTs catalyst is 1/6.3.

  20. Adjustment of Daily Activities: the Influence of Smartphone Adoption on the Travel Pattern of Mobile Professionals in the Greater Jakarta Area

    Directory of Open Access Journals (Sweden)

    Gloriani Novita Christin

    2014-12-01

    Full Text Available The swift augmentation in the adoption of smartphones, the gadget that resulted from the convergence of Information and Communication Technology (ICT, potentially transforms people's life in myriad dimensions. One potential change induced by smartphones, is how people restructure their daily agenda and consecutively influence their travel pattern. To understand it, this study theoretically reviews mobile professional work, smartphone adoption, and how people conduct their mobile interaction, planning and execution of daily activities. Mobile professionals, the cohort of professionals that spend more than 20% of their total working time moving around out of their work environment; they are important beneficiaries of smartphones and have been chosen as the target of this study. Empirical results of mobile professionals´ experiences in the Greater Jakarta Area are presented at this juncture. Furthermore, their adjustment of activities as a dynamic response to receiving extensive information via smartphones is also analysed. The results indicate that there is a strong adjustment of daily activities by mobile professionals. Through those changes, the transformation of daily travel patterns related to the activity is also brought about by the use of this high-end ICT contrivance.

  1. Memory retrieval of smoking-related images induce greater insula activation as revealed by an fMRI-based delayed matching to sample task.

    Science.gov (United States)

    Janes, Amy C; Ross, Robert S; Farmer, Stacey; Frederick, Blaise B; Nickerson, Lisa D; Lukas, Scott E; Stern, Chantal E

    2015-03-01

    Nicotine dependence is a chronic and difficult to treat disorder. While environmental stimuli associated with smoking precipitate craving and relapse, it is unknown whether smoking cues are cognitively processed differently than neutral stimuli. To evaluate working memory differences between smoking-related and neutral stimuli, we conducted a delay-match-to-sample (DMS) task concurrently with functional magnetic resonance imaging (fMRI) in nicotine-dependent participants. The DMS task evaluates brain activation during the encoding, maintenance and retrieval phases of working memory. Smoking images induced significantly more subjective craving, and greater midline cortical activation during encoding in comparison to neutral stimuli that were similar in content yet lacked a smoking component. The insula, which is involved in maintaining nicotine dependence, was active during the successful retrieval of previously viewed smoking versus neutral images. In contrast, neutral images required more prefrontal cortex-mediated active maintenance during the maintenance period. These findings indicate that distinct brain regions are involved in the different phases of working memory for smoking-related versus neutral images. Importantly, the results implicate the insula in the retrieval of smoking-related stimuli, which is relevant given the insula's emerging role in addiction. © 2013 Society for the Study of Addiction.

  2. Current Population Status and Activity Pattern of Lesser Flamingos (Phoeniconaias minor and Greater Flamingo (Phoenicopterus roseus in Abijata-Shalla Lakes National Park (ASLNP, Ethiopia

    Directory of Open Access Journals (Sweden)

    Tewodros Kumssa

    2014-01-01

    Full Text Available A study of the population status, habitat preference, and activity pattern of nonbreeding flamingos was carried out in Lakes Abijata, Shalla, and Chitu, part of the Great Rift Valley, Ethiopia, from 2011 to 2013. The current population status and habitat preference of flamingos in the area are still poorly known. Likewise, data on diurnal and seasonal activity pattern of the species are scarce and this leads to the misunderstanding of how Flamingos use local wetlands throughout the different seasons. Data regarding population size and activity pattern were gathered during the wet and dry seasons. Point-count method was used to estimate the population size. Behaviors were recorded using scan sampling techniques. A total of 53671 individuals representing two species of flamingo were counted during both wet and dry seasons from the three lakes. There were more flamingos during the dry season than the wet season in Lake Abijata contrary to Lakes Shalla and Chitu during the wet season. Lesser flamingos (Phoeniconaias minor were the most abundant species comprising 95.39%, while Greater Flamingos (Phoenicopterus roseus accounted for 4.61% of the total population. Lake Abijata is the major stronghold of Lesser Flamingos in the area. There was significant variation in the mean number of both species during the wet and dry season in the different study sites of the lake, respectively. The species were known to use varied habitats within the lakes. The Lesser Flamingo mainly preferred the shoreline and mudflat areas of the lakes. However, Greater Flamingo on several occasions showed preference to offshore area of the lakes. Seasonal average flock sizes were not similar between the species. There was a strong relationship between time allocated to each activity and time of day. Feeding activity varied among daylight hours and was higher in the evening (76.5% and late morning (74.56% and least during midday (54%. Some variations in activity breakdown were

  3. Electrocatalytic glucose oxidation at gold and gold-carbon nanoparticulate film prepared from oppositely charged nanoparticles

    International Nuclear Information System (INIS)

    Karczmarczyk, Aleksandra; Celebanska, Anna; Nogala, Wojciech; Sashuk, Volodymyr; Chernyaeva, Olga; Opallo, Marcin

    2014-01-01

    Graphical abstract: - Highlights: • Gold nanoparticulate film electrodes were prepared by layer-by-layer method from oppositely charged nanoparticles. • Positively charged nanoparticles play dominant role in glucose oxidation in alkaline solution. • Gold and gold-carbon nanoparticulate film electrodes exhibit similar glucose oxidation current and onset potential. - Abstract: Electrocatalytic oxidation of glucose was studied at nanoparticulate gold and gold-carbon film electrodes. These electrodes were prepared by a layer-by-layer method without application of any linker molecules. Gold nanoparticles were stabilized by undecane thiols functionalized by trimethyl ammonium or carboxylate groups, whereas the carbon nanoparticles were covered by phenylsulfonate functionalities. The gold nanoparticulate electrodes were characterized by UV-vis and XPS spectroscopy, atomic force microscopy and voltammetry, before and after heat-treatment. Heat-treatment facilitates the aggregation of the nanoparticles and affects the structure of the film. The comparison of the results obtained with film electrodes prepared from gold nanoparticles with the same charge and with gold-carbon nanoparticulate electrodes, proved that positively charged nanoparticles are responsible for the high electrocatalytic activity, whereas negatively charged ones act rather as a linker of the film

  4. Electrocatalytic oxidation of some anti-inflammatory drugs on a nickel hydroxide-modified nickel electrode

    Energy Technology Data Exchange (ETDEWEB)

    Hajjizadeh, M. [Department of Chemistry, Faculty of Science, K. N. Toosi University of Technology, P.O. Box 16315-1618, Tehran (Iran, Islamic Republic of); Jabbari, A. [Department of Chemistry, Faculty of Science, K. N. Toosi University of Technology, P.O. Box 16315-1618, Tehran (Iran, Islamic Republic of)], E-mail: jabbari@kntu.ac.ir; Heli, H.; Moosavi-Movahedi, A.A. [Institute of Biochemistry and Biophysics, University of Tehran, Tehran (Iran, Islamic Republic of); Haghgoo, S. [Center of Quality Control of Drug, Tehran (Iran, Islamic Republic of)

    2007-12-31

    The electrocatalytic oxidation of several anti-inflammatory drugs (mefenamic acid, diclofenac and indomethacin) was investigated on a nickel hydroxide-modified nickel (NHMN) electrode in alkaline solution. This oxidation process and its kinetics were studied using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy techniques. Voltammetric studies indicated that in the presence of drugs, the anodic peak current of low-valence nickel species increases, followed by a decrease in the corresponding cathodic current. This pattern indicates that drugs were oxidized on the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. A mechanism based on the electrochemical generation of Ni(III) active sites and their subsequent consumption by drugs was also investigated. The corresponding rate law under the control of charge transfer was developed and kinetic parameters were derived. In this context, the charge-transfer resistance accessible both theoretically and through impedancemetry was used as a criterion. The rate constants of the catalytic oxidation of drugs and the electron-transfer coefficients are reported. A sensitive, simple and time-saving amperometric procedure was developed for the analysis of these drugs in bulk form and for the direct assay of tablets, using the NHMN electrode.

  5. Electrocatalytic oxidation of some anti-inflammatory drugs on a nickel hydroxide-modified nickel electrode

    International Nuclear Information System (INIS)

    Hajjizadeh, M.; Jabbari, A.; Heli, H.; Moosavi-Movahedi, A.A.; Haghgoo, S.

    2007-01-01

    The electrocatalytic oxidation of several anti-inflammatory drugs (mefenamic acid, diclofenac and indomethacin) was investigated on a nickel hydroxide-modified nickel (NHMN) electrode in alkaline solution. This oxidation process and its kinetics were studied using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy techniques. Voltammetric studies indicated that in the presence of drugs, the anodic peak current of low-valence nickel species increases, followed by a decrease in the corresponding cathodic current. This pattern indicates that drugs were oxidized on the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. A mechanism based on the electrochemical generation of Ni(III) active sites and their subsequent consumption by drugs was also investigated. The corresponding rate law under the control of charge transfer was developed and kinetic parameters were derived. In this context, the charge-transfer resistance accessible both theoretically and through impedancemetry was used as a criterion. The rate constants of the catalytic oxidation of drugs and the electron-transfer coefficients are reported. A sensitive, simple and time-saving amperometric procedure was developed for the analysis of these drugs in bulk form and for the direct assay of tablets, using the NHMN electrode

  6. Rise of nano effects in electrode during electrocatalytic CO2 conversion

    Science.gov (United States)

    Yang, Ki Dong; Lee, Chan Woo; Jang, Jun Ho; Ha, Tak Rae; Nam, Ki Tae

    2017-09-01

    The electrocatalytic conversion of CO2 into value-added fuels has received increasing attention as a promising way to mitigate the atmospheric CO2 concentration and close the broken carbon-cycle. Early studies, focused on polycrystalline metal electrodes, outlined in detail the overall trends in the catalytic activity and product selectivity of pure metals; however, several inherent limitations were found, such as low current density and high overpotential, which hindered electrocatalytic CO2 reduction from practical application. Fortunately, the recent development of precisely synthesized nanocatalysts has led to several breakthroughs in catalytic CO2 conversion. By carefully controlling the thermodynamic adsorption energies and flow dynamics of reaction intermediates, nanosized electrocatalysts afford more versatile and energetically efficient routes to convert CO2 into desired chemicals. In this article, we review the state-of-the-art nanocatalysts applied for CO2 conversion and discuss newly found phenomena at the local environment near the catalyst surface. The mechanistic understanding of these findings can provide insight into the future design of catalysts for the efficient and selective reduction of CO2.

  7. A DNA biosensor based on the electrocatalytic oxidation of amine by a threading intercalator

    International Nuclear Information System (INIS)

    Gao Zhiqiang; Tansil, Natalia

    2009-01-01

    An electrochemical biosensor for the detection of DNA based a peptide nucleic acid (PNA) capture probe (CP) modified indium tin oxide electrode (ITO) is described in this report. After hybridization, a threading intercalator, N,N'-bis[(3-propyl)-imidazole]-1,4,5,8-naphthalene diimide (PIND) imidazole complexed with Ru(bpy) 2 Cl (PIND-Ru, bpy = 2,2'-bipyridine), was introduced to the biosensor. PIND-Ru selectively intercalated to double-stranded DNA (ds-DNA) and became immobilized on the biosensor surface. Voltammetric tests showed highly stable and reversible electrochemical oxidation/reduction processes and the peak currents can directly be utilized for DNA quantification. When the tests were conducted in an amine-containing medium, Tris-HCl buffer for example, a remarkable improvement in the voltammetric response and noticeable enhancements of voltammetric and amperometric sensitivities were observed due to the electrocatalytic activity of the [Ru(bpy) 2 Cl] redox moieties. Electrocatalytic current was observed when as little as 3.0 attomoles of DNA was present in the sample solution

  8. Selective electrocatalytic oxidation of sorbitol to fructose and sorbose.

    Science.gov (United States)

    Kwon, Youngkook; de Jong, Ed; van der Waal, Jan Kees; Koper, Marc T M

    2015-03-01

    A new electrocatalytic method for the selective electrochemical oxidation of sorbitol to fructose and sorbose is demonstrated by using a platinum electrode promoted by p-block metal atoms. By the studying a range of C4, C5 and C6 polyols, it is found that the promoter interferes with the stereochemistry of the polyol and thereby modifies its reactivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electro-catalytic degradation of bisphenol A with modified Co3O4/β-PbO2/Ti electrode

    International Nuclear Information System (INIS)

    Zhao, Jun; Zhu, Chengzhu; Lu, Jun; Hu, Caiju; Peng, Shuchuan; Chen, Tianhu

    2014-01-01

    Graphical abstract: - Highlights: • Co 3 O 4 /β-PbO 2 electrode was prepared and an excellent electrocatalytic property. • Co 3 O 4 /β-PbO 2 electrode had good corrosion resistance characterization and lifetime. • BPA electrocatalytic degradation followed pseudo-first-order reaction process. - Abstract: Ti-base Co 3 O 4 /β-PbO 2 composite electrodes were prepared using electro-deposition and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry and the accelerated life testing, it indicated that the self-made electrode had high activity in electrolysis as well as excellent corrosion resistance and excellent catalytic performance. The results showed that the removal efficiency of COD Cr could be reached up to 92.2% after 1.5 h electrolysis at NaCl concentration of 0.020 mol·L −1 , bisphenol A initial concentration of 20 mg·L −1 , applied voltage of 20 V, electrode spacing of 7 cm and electrolyte pH of 5. The reaction mechanism and kinetics of Co 3 O 4 /β-PbO 2 /Ti composite electrodes electro-catalytic degradation bisphenol A mainly caused by the OH radical attacking parent molecules and the degradation followed pseudo-first-order kinetics

  10. Hierarchical porous microspheres of the Co3O4@graphene with enhanced electrocatalytic performance for electrochemical biosensors.

    Science.gov (United States)

    Yang, MinHo; Jeong, Jae-Min; Lee, Kyoung G; Kim, Do Hyun; Lee, Seok Jae; Choi, Bong Gill

    2017-03-15

    The integration of organic and inorganic building blocks into hierarchical porous architectures makes potentially desirable electrocatalytic materials in many electrochemical applications due to their combination of attractive qualities of dissimilar components and well-constructed charge transfer pathways. Herein, we demonstrate the preparation of the hierarchical porous Co 3 O 4 @graphene (Co 3 O 4 @G) microspheres by one-step hydrothermal method to achieve high electrocatalytic performance for enzyme-free biosensor applications. The obtained Co 3 O 4 @G microspheres are consisted of the interconnected networks of Co 3 O 4 and graphene sheets, and thus provide large accessible active sites through porous structure, while graphene sheets offer continuous electron pathways for efficient electrocatalytic reaction of Co 3 O 4 . These structural merits with synergy effect of Co 3 O 4 and graphene lead to a high performance of enzyme-free detection for glucose: high sensitivity, good selectivity, and remarkable stability. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. A novel electrochemical sensor based on metal-organic framework for electro-catalytic oxidation of L-cysteine.

    Science.gov (United States)

    Hosseini, Hadi; Ahmar, Hamid; Dehghani, Ali; Bagheri, Akbar; Tadjarodi, Azadeh; Fakhari, Ali Reza

    2013-04-15

    A novel electrochemical sensor based on Au-SH-SiO₂ nanoparticles supported on metal-organic framework (Au-SH-SiO₂@Cu-MOF) has been developed for electrocatalytic oxidation and determination of L-cysteine. The Au-SH-SiO₂@Cu-MOF was characterized by scanning electron microscopy, transmission electron microscopy, x-ray diffraction and cyclic voltammetry. The electrochemical behavior of L-cysteine at the Au-SH-SiO₂@Cu-MOF was investigated by cyclic voltammetry. The Au-SH-SiO₂@Cu-MOF showed a very efficient electrocatalytic activity for the oxidation of L-cysteine in 0.1 M phosphate buffer solution (pH 5.0). The oxidation overpotentials of L-cysteine decreased significantly and their oxidation peak currents increased dramatically at Au-SH-SiO₂@Cu-MOF. The potential utility of the sensor was demonstrated by applying it to the analytical determination of L-cysteine concentration. The results showed that the electrocatalytic current increased linearly with the L-cysteine concentration in the range of 0.02-300 μM and the detection limit was 0.008 μM. Finally, the sensor was applied to determine L-cysteine in water and biological samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Environmental damage costs from airborne pollution of industrial activities in the greater Athens, Greece area and the resulting benefits from the introduction of BAT

    International Nuclear Information System (INIS)

    Mirasgedis, S.; Hontou, V.; Georgopoulou, E.; Sarafidis, Y.; Gakis, N.; Lalas, D.P.; Loukatos, A.; Gargoulas, N.; Mentzis, A.; Economidis, D.; Triantafilopoulos, T.; Korizi, K.; Mavrotas, G.

    2008-01-01

    Attributing costs to the environmental impacts associated with industrial activities can greatly assist in protecting human health and the natural environment as monetary values are capable of directly influencing technological and policy decisions without changing the rules of the market. This paper attempts to estimate the external cost attributable to the atmospheric pollution from 'medium and high environmental burden' industrial activities located in the greater Athens area and the benefits from Best Available Techniques (BAT) introduction. To this end a number of typical installations were defined to be used in conjunction with the Impact Pathway Approach developed in the context of the ExternE project to model all industrial sectors/sub-sectors located in the area of interest. Total environmental externalities due to air pollutants emitted by these industrial activities were found to reach 211 M Euro per year, associated mainly with human mortality and morbidity due to PM 10 emissions, as well as with climate change impacts due to CO 2 emissions for which non-metallic minerals and oil processing industries are the main sources. The results obtained can be used as the basis for an integrated evaluation of potential BAT, taking into account not only private costs and benefits but also the environmental externalities, thus leading to policy decisions that maximize social welfare in each industrial sector/sub-sector

  13. Greater Activity in the Frontal Cortex on Left Curves: A Vector-Based fNIRS Study of Left and Right Curve Driving.

    Directory of Open Access Journals (Sweden)

    Noriyuki Oka

    Full Text Available In the brain, the mechanisms of attention to the left and the right are known to be different. It is possible that brain activity when driving also differs with different horizontal road alignments (left or right curves, but little is known about this. We found driver brain activity to be different when driving on left and right curves, in an experiment using a large-scale driving simulator and functional near-infrared spectroscopy (fNIRS.The participants were fifteen healthy adults. We created a course simulating an expressway, comprising straight line driving and gentle left and right curves, and monitored the participants under driving conditions, in which they drove at a constant speed of 100 km/h, and under non-driving conditions, in which they simply watched the screen (visual task. Changes in hemoglobin concentrations were monitored at 48 channels including the prefrontal cortex, the premotor cortex, the primary motor cortex and the parietal cortex. From orthogonal vectors of changes in deoxyhemoglobin and changes in oxyhemoglobin, we calculated changes in cerebral oxygen exchange, reflecting neural activity, and statistically compared the resulting values from the right and left curve sections.Under driving conditions, there were no sites where cerebral oxygen exchange increased significantly more during right curves than during left curves (p > 0.05, but cerebral oxygen exchange increased significantly more during left curves (p < 0.05 in the right premotor cortex, the right frontal eye field and the bilateral prefrontal cortex. Under non-driving conditions, increases were significantly greater during left curves (p < 0.05 only in the right frontal eye field.Left curve driving was thus found to require more brain activity at multiple sites, suggesting that left curve driving may require more visual attention than right curve driving. The right frontal eye field was activated under both driving and non-driving conditions.

  14. A feasibility study of a culturally and gender-specific dance to promote physical activity for South Asian immigrant women in the greater Toronto area.

    Science.gov (United States)

    Vahabi, Mandana; Damba, Cynthia

    2015-01-01

    Despite ample evidence demonstrating the protective effect of physical activity, the uptake of regular physical activity among South Asian (SA) women remains relatively low. The purpose of this study was to explore the feasibility and health impacts of implementing a culture- and gender-specific physical activity among SA immigrant women residing in Greater Toronto Area (GTA) in Ontario, Canada. A community-based mixed methods approach combining cohort pretest and posttest design and qualitative methods employing in depth interviews was used. Twenty-seven SA women from the GTA participated in a 6-week, 2 days per week, Bollywood Dance exercise program led by a female SA instructor. The participation rate was considerably high (85%) and approximately 82% of the participants attended 10 or more of the classes offered. The participants' physical measurements (weight, waist and hip, and body mass index) decreased, although not significantly, over the 6-week period and there was an improvement in their physical, mental, and social health. During the face-to-face interviews, participants reported feeling less stressed and tired, being more mentally and physically robust, and having a sense of fulfillment and self-satisfaction. The only common criticism expressed was that the 6-week duration of the intervention was too short. The results showed that the Bollywood Dance was a feasible strategy in engaging SA immigrant women in physical activity. The key aspects when designing culture- and gender-specific dance interventions include community participation and active engagement in planning and implementation of the program, a supportive environment, same gender and culturally attuned dance instructor, easy access, and minimal to no cost. Copyright © 2015 Jacobs Institute of Women's Health. Published by Elsevier Inc. All rights reserved.

  15. Greater Activity in the Frontal Cortex on Left Curves: A Vector-Based fNIRS Study of Left and Right Curve Driving

    Science.gov (United States)

    Oka, Noriyuki; Yoshino, Kayoko; Yamamoto, Kouji; Takahashi, Hideki; Li, Shuguang; Sugimachi, Toshiyuki; Nakano, Kimihiko; Suda, Yoshihiro; Kato, Toshinori

    2015-01-01

    Objectives In the brain, the mechanisms of attention to the left and the right are known to be different. It is possible that brain activity when driving also differs with different horizontal road alignments (left or right curves), but little is known about this. We found driver brain activity to be different when driving on left and right curves, in an experiment using a large-scale driving simulator and functional near-infrared spectroscopy (fNIRS). Research Design and Methods The participants were fifteen healthy adults. We created a course simulating an expressway, comprising straight line driving and gentle left and right curves, and monitored the participants under driving conditions, in which they drove at a constant speed of 100 km/h, and under non-driving conditions, in which they simply watched the screen (visual task). Changes in hemoglobin concentrations were monitored at 48 channels including the prefrontal cortex, the premotor cortex, the primary motor cortex and the parietal cortex. From orthogonal vectors of changes in deoxyhemoglobin and changes in oxyhemoglobin, we calculated changes in cerebral oxygen exchange, reflecting neural activity, and statistically compared the resulting values from the right and left curve sections. Results Under driving conditions, there were no sites where cerebral oxygen exchange increased significantly more during right curves than during left curves (p > 0.05), but cerebral oxygen exchange increased significantly more during left curves (p right premotor cortex, the right frontal eye field and the bilateral prefrontal cortex. Under non-driving conditions, increases were significantly greater during left curves (p right frontal eye field. Conclusions Left curve driving was thus found to require more brain activity at multiple sites, suggesting that left curve driving may require more visual attention than right curve driving. The right frontal eye field was activated under both driving and non-driving conditions

  16. Is the intention-behaviour gap greater amongst the more deprived? A meta-analysis of five studies on physical activity, diet, and medication adherence in smoking cessation.

    Science.gov (United States)

    Vasiljevic, Milica; Ng, Yin-Lam; Griffin, Simon J; Sutton, Stephen; Marteau, Theresa M

    2016-02-01

    Unhealthy behaviour is more common amongst the deprived, thereby contributing to health inequalities. The evidence that the gap between intention and behaviour is greater amongst the more deprived is limited and inconsistent. We tested this hypothesis using objective and self-report measures of three behaviours, both individual- and area-level indices of socio-economic status, and pooling data from five studies. Secondary data analysis. Multiple linear regressions and meta-analyses of data on physical activity, diet, and medication adherence in smoking cessation from 2,511 participants. Across five studies, we found no evidence for an interaction between deprivation and intention in predicting objective or self-report measures of behaviour. Using objectively measured behaviour and area-level deprivation, meta-analyses suggested that the gap between self-efficacy and behaviour was greater amongst the more deprived (B = .17 [95% CI = 0.02, 0.31]). We find no compelling evidence to support the hypothesis that the intention-behaviour gap is greater amongst the more deprived. What is already known on this subject? Unhealthy behaviour is more common in those who are more deprived. This may reflect a larger gap between intentions and behaviour amongst the more deprived. The limited evidence to date testing this hypothesis is mixed. What does this study add? In the most robust study to date, combining results from five trials, we found no evidence for this explanation. The gap between intentions and behaviour did not vary with deprivation for the following: diet, physical activity, or medication adherence in smoking cessation. We did, however, find a larger gap between perceived control over behaviour (self-efficacy) and behaviour in those more deprived. These findings add to existing evidence to suggest that higher rates of unhealthier behaviour in more deprived groups may be reduced by the following: ◦ Strengthening behavioural control mechanisms (such as executive

  17. Preparation and electrocatalytic activity of platinum nano-particles in electrodes of proton exchange membrane fuel cell; Preparation et activite electrocatalytique des nano-particules de platine dans les electrodes de piles a combustible a membrane echangeuse de protons

    Energy Technology Data Exchange (ETDEWEB)

    Antoine, Olivier

    1998-07-01

    This work treats of the basic study of the reactions taking place on platinum nano-particles inside the active layers of proton exchange membrane fuel cells (PEMFC): oxygen reduction and hydrogen oxidation, and of the applied study of a method for the in-situ preparation of these particles. The study of oxygen reduction completes the previous works by confirming the effect of the particles size on the reaction kinetics (optimum of mass activity towards 3 nm of diameter), by considering the effect of the temperature and of the substrate, and also by the study of H{sub 2}O{sub 2} production at the disc-ring electrode and the reaction mechanism using impedance spectroscopy measurements: like with massive platinum in acid environment, the Damjanovic mechanism is retained for the platinum nano-particles. Hydrogen oxidation is much faster and limited by gas diffusion, and thus is more difficult to study. This work required the use of sophisticated correction programs and of an original geometry (very thin active layer: L < 1 {mu}m) to show a clear effect of the particle size on the kinetics: the catalytic activity increases with the smallest particles. This study has also tried to precise the poorly known reaction mechanism: the Heyrovsky-Volmer mechanism has been retained but it needs to be confirmed. The optimization of the catalyst used requires 3 nm particles for a maximum oxygen reduction mass activity and mass percentages Pt/(Pt+C)30% in order to minimize the thickness of the active layer and the diffusion limitations. An original in-situ electrochemical method respecting these conditions has been developed. Starting from carbon impregnated with platinum salts, it allows the deposition of catalyst nano-particles on the carbon in Nafion. (J.S.)

  18. Distress calls of the greater short-nosed fruit bat Cynopterus sphinx activate hypothalamic-pituitary-adrenal (HPA) axis in conspecifics.

    Science.gov (United States)

    Mariappan, Subramanian; Bogdanowicz, Wieslaw; Marimuthu, Ganapathy; Rajan, Koilmani Emmanuvel

    2013-09-01

    In a stressful situation, greater short-nosed fruit bats (Cynopterus sphinx) emit audible vocalization either to warn or to inform conspecifics. We examined the effect of distress calls on bats emitting the call as well as the bats receiving the distress signal through analysis of the hypothalamic-pituitary-adrenal axis and catacholaminargic systems. We measured the levels of neurotransmitters [serotonin (5-HT), dopamine (DA), norepinephrine (NE)] and stress hormones [(adrenocorticotropic hormone (ACTH) and corticosterone (CORT)]. Our results showed that distress call emission elevated the level of ACTH and CORT, as well as 5-HT, DA and NE in the amygdala, for both the call emitting bat and the responding bat. Subsequently, we observed increased activity of glucocorticoid receptor and its steroid receptor co-activator (SRC-1). An expression of SRC-1 was up-regulated in the distress call emitter only, whereas it was at a similar level in both the call responder and silent bats. These findings suggest that bats emitting distress calls and also bats responding to such calls have similar neurotransmitter expression patterns, and may react similarly in response to stress.

  19. Fabrication, characterization and electrocatalytic application of a lead dioxide electrode with porous titanium substrate

    International Nuclear Information System (INIS)

    Zhang, Wenli; Kong, Haishen; Lin, Haibo; Lu, Haiyan; Huang, Weimin; Yin, Jian; Lin, Zheqi; Bao, Jinpeng

    2015-01-01

    In this study, PbO 2 electrode was prepared on porous Ti/SnO 2 –Sb 2 O 5 substrate (denoted as 3D-Ti/PbO 2 electrode), and its electrochemical properties were investigated in detail. The electrodeposition mechanism of 3D-Ti/PbO 2 electrode was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Scanning electron microscope (SEM) result showed that the 3D-Ti/PbO 2 electrode possessed porous structure when it was electrodeposited for time less than 30 min. The 3D-Ti/PbO 2 electrode prepared for 10 min had more active sites than the lead dioxide electrode electrodeposited on planar titanium substrate (denoted as 2D-Ti/PbO 2 electrode) and its electrochemical porosity is about 54%. The embedded structure between porous Ti/SnO 2 –Sb 2 O 5 substrate and PbO 2 coating increased the stability of 3D-Ti/PbO 2 electrode. The service life of 3D-Ti/PbO 2 electrode was about 350 h which was much longer than 2D-Ti/PbO 2 electrode. What's more, 3D-Ti/PbO 2 electrode had better electrocatalytic activity towards phenol degradation than 2D-Ti/PbO 2 electrode. - Highlights: • 3D-Ti/PbO 2 electrode was prepared on a porous titanium substrate. • The electrochemical active surface area was investigated. • The activity of 3D-Ti/PbO 2 electrode towards phenol oxidation was investigated. • 3D-Ti/PbO 2 electrode shows superior electrocatalytic activity.

  20. Effect of Co3O4 and Co3O4/CeO2 infiltration on the catalytic and electro-catalytic activity of LSM15/CGO10 porous cells stacks for oxidation of propene

    DEFF Research Database (Denmark)

    Ippolito, Davide; Kammer Hansen, Kent

    2015-01-01

    The objective of this work was to study the effect of Co3O4 and Co3O4/CeO2 infiltration on the propene oxidation catalytic activity of a La0.85Sr0.15MnO3/Ce0.9Gd0.1O1.95 electrochemical porous cell stack (11 layers, 5 single cells in series). The effect of the infiltration of Co3O4 and Co3O4/CeO2...... on the electrochemical properties of the porous cell stack was also investigated by electrochemical impedance spectroscopy (EIS). Co3O4 and Co3O4/CeO2 exhibited high catalytic activity for propene oxidation. The increase of propene oxidation rate with +4 V (0.8 V/cell) polarization reached 10% for the Co3O4 infiltrated...... reactor and 48% of efficiency at 300 °C. The Co3O4/CeO2 co-infiltration decreased the reactor polarization resistance, while Co3O4 infiltration had negligible effect on reactor electrochemical performance. The beneficial effect of CeO2 on the electrode activity was attributed to the increased...

  1. Study of the electrocatalytic oxidation of Ethanol over platinum in medium acid

    International Nuclear Information System (INIS)

    Hoyos, Bibian; Gonzalez, Javier; Sanchez, Carlos

    2002-01-01

    Electro-catalytic oxidation of ethanol on platinum surfaces in sulfuric acid solutions at different temperatures and concentrations was studied by cyclic voltammetry. The results shown that there is ethanol adsorption at potentials below 0.4V (vs. RHE) with electrode coverage fraction for residues of 0.3 or less. There are also, two irreversible oxidation reactions. Former reaction seems be catalyzed by Pt(OH) species with electronic charge transfer control and the second reaction seems be catalyzed by Pt(OH) 4 with diffusion control while Pt(OH) 2 does not have catalytic activity. The activity and selectivity for total oxidation increases with ethanol concentration and temperature. Finally, a reaction mechanism, which explains the obtained data, is proposed

  2. Preparation and elementary research on electrocatalytic hydrogen evolution of highly ordered titanium dioxide nanotube arrays

    International Nuclear Information System (INIS)

    Wu Qinglong; Liao Junsheng; Bai Yun

    2010-01-01

    Well ordered and uniform titanium dioxide nanotube arrays were fabricated by anodiaing process from a bath containing 1% NaF, 1mol/L Na 2 SO 4 , 0.5 mol/L H 2 SO 4 at room temperature. Surface morphology of titanium dioxide nanotube arrays were observed with SEM. The formation process of titanium dioxide nanotube arrays was suggested by current-time transient. Its catalytic hydrogen evolution behavior was studied by electrochemical measurements in a 5%(mass fraction) H 2 SO 4 solution. The results showed that the titanium dioxide nanotube arrays on titanium had better hydrogen evolution activity and trace palladium lead to the maximum electrocatalytic activity of hydrogen production. (authors)

  3. Hybrid methyl green/cobalt-polyoxotungstate nanostructured films: Self-assembly, electrochemical and electrocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Novais, Hugo C.; Fernandes, Diana M., E-mail: diana.fernandes@fc.up.pt; Freire, Cristina, E-mail: acfreire@fc.up.pt

    2015-08-30

    Graphical abstract: Hybrid {MG/Co(PW9)2}{sub n} multilayer films were successfully prepared and exhibit W-based electrocatalytic activity towards reduction of nitrite and iodate anions. - Highlights: • Layer-by-layer hybrid films {MG/Co(PW_9)_2}{sub n} were sucessfully prepared. • UV–vis was used to monitor film build-up and showed regular stepwise film growth. • XPS confirmed sucessfull {MG/Co(PW_9)_2}{sub n} film fabrication. • Films showed excellent electrocatalytic activity towards nitrite and iodate reduction. - Abstract: Hybrid multilayer films were prepared by alternately depositing cationic dye methyl green (MG) and anionic sandwich-type polyoxometalate K{sub 10}[Co{sub 4}(H{sub 2}O){sub 2}(PW{sub 9}O{sub 34}){sub 2}] (Co(PW{sub 9}){sub 2}) via electrostatic layer-by-layer (LbL) self-assembly method. Film build-up was monitored by UV–vis spectroscopy which showed a regular stepwise growth. X-ray photoelectron spectroscopy data confirmed the successful fabrication of the hybrid films with MG-Co(PW{sub 9}){sub 2} composition and scanning electron microscopy images revealed a completely covered surface with a non-uniform distribution of the molecular species. Electrochemical characterization of films by cyclic voltammetry revealed two tungsten-based reduction processes in the potential range between −0.9 and −0.5 V due to W{sup VI} → W{sup V} in Co(PW{sub 9}){sub 2}. Studies with the redox probes, [Fe(CN){sub 6}]{sup 3−/4−} and [Ru(NH{sub 3}){sub 6}]{sup 3+/2+}, revealed that not only the electrostatic attractions or repulsions have effects on the kinetics of the probe reactions, but also the film thickness. Additionally, the {MG/Co(PW_9)_2}{sub n} multilayer films exhibit efficient W-based electrocatalytic activity towards reduction of nitrite and iodate.

  4. Influence of boron concentration on growth characteristic and electro-catalytic performance of boron-doped diamond electrodes prepared by direct current plasma chemical vapor deposition

    International Nuclear Information System (INIS)

    Feng Yujie; Lv Jiangwei; Liu Junfeng; Gao Na; Peng Hongyan; Chen Yuqiang

    2011-01-01

    A series of boron-doped diamond (BDD) electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) with different compositions of CH 4 /H 2 /B(OCH 3 ) 3 gas mixture. A maximum growth rate of 0.65 mg cm -2 h -1 was obtained with CH 4 /H 2 /B(OCH 3 ) 3 radio of 4/190/10 and this growth condition was also a turning point for discharge plasma stability which arose from the addition of B(OCH 3 ) 3 that changed electron energy distribution and influenced the plasma reaction. The surface coating structure and electro-catalytic performance of the BDD electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Hall test, and electrochemical measurement and electro-catalytic oxidation in phenol solution. It is suggested that the boron doping level and the thermal stress in the films are the main factors affecting the electro-catalytic characteristics of the electrodes. Low boron doping level with CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/199/1 decreased the films electrical conductivity and its electro-catalytic activity. When the carrier concentration in the films reached around 10 20 cm -3 with CH 4 /H 2 /B(OCH 3 ) 3 ratio over a range of 4/195/5-4/185/15, the thermal stress in the films was the key reason that influenced the electro-catalytic activity of the electrodes for its effect on diamond lattice expansion. Therefore, the BDD electrode with modest CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/190/10 possessed the best phenol removal efficiency.

  5. Synthesis of Silver Nanowires and Studies on its Electrocatalytic Activity of Oxygen Electroreduction%银纳米线的制备及电催化还原氧性能研究

    Institute of Scientific and Technical Information of China (English)

    倪昆; 吕功煊

    2011-01-01

    The paper focuses on the easy and fast synthesis of silver nanowires, and the catalysis activity of for oxygen electroreduction reaction. AgCI, PVP, and ethylene glycol (EG) were used as soft - template, and reducing agent, respectively. And different aspect ratios of silver nanowires were synthesized with different seeds ( AgCI and Ag). By the characterization of SEM, TEM and others, a large quantity of nanowire with a little of nanoparticles was achieved . It was found the aspect ratios of silver nanowires were about 200 (SNWH) with AgCI, and the others were 30 (SNWL) with Ag. It was found the catalysis activity of silver nanowires was obviously and the onset reduction potentials at about -0.17 V and the reduction peaks at about -0.45 V were observed from cyclic voltammetry curves. The current values of reduction peaks on SNWH and SNWL were 3.01 × 10 -5A and 2.42 × 10 -5A, and the slope data of Tafel curves were 94 and 96 mV/dec respectively. Those above results implied that the activity of SNWH was better than that of SNWL for ORR. The difference of the activity might be due to the different specific surface area of both silver nanowires. The result indicated that both silver nanowires were alcohol-tolerant for ORR. The effects of alcohol on the loss of ORR activity for silver nanowires follow the order: iso-propanol > ethanol > methanol.%分别以聚乙烯基吡咯烷酮(PVP),乙二醇作为软模板和还原剂,采用不同晶种(AgCl、Ag)快速合成了银纳米线.通过SEM和TEM表征,证明合成银纳米线材料形貌均一,颗粒含量很少.并且发现以AgCl为晶种合成的银纳米线长径比为200左右(SNWH),而以Ag为晶种合成的长径比为30左右(SNWL).以银纳米线作为电催化氧气还原反应(ORR)的催化剂.通过循环伏安法测定,发现银纳米线对氧还原具有显著的活性,反应起始还原电压为-0.17V左右,还原峰电压为-0.45V左右,并且反应受O2扩散的控制.研究表明两种长径比

  6. Past climate change and recent anthropogenic activities affect genetic structure and population demography of the greater long-tailed hamster in northern China.

    Science.gov (United States)

    Ye, Junbin; Xiao, Zhenlong; Li, Chuanhai; Wang, Fusheng; Liao, Jicheng; Fu, Jinzhong; Zhang, Zhibin

    2015-09-01

    The genetic diversity and the spatial structure of a species are likely consequences of both past and recent evolutionary processes, but relevant studies are still rare in East Asia where the Pleistocene climate has unique influences. In this study, we examined the impact of past climate change and recent anthropogenic activities on the genetic structure and population size of the greater long-tailed hamster (Tscherskia triton), an agricultural rodent pest species in northern China. DNA sequence data of 2 mitochondrial genes and genotypic data of 11 microsatellite DNA loci from 41 populations (545 individuals) were gathered. Phylogenetic and population genetic analyses, as well as species distribution modeling and coalescent simulations, were conducted to infer its historical and demographic patterns and processes. Two deeply diverged mitochondrial clades were recovered. A small one was restricted to the Shandong Peninsula while the main clade was further divided into 3 geographic clusters by their microsatellite DNA genotypes: Northwest, North-center and Northeast. Divergence dating indicated a Middle-to-Late Pleistocene divergence between the 2 clades. Demographic analysis indicated that all 3 and pooled populations showed consistent long-period expansions during last glacial period; but not during the Holocene, probably due to the impact of climate warming and human disturbances. Conflicting patterns between mtDNA and microsatellite markers imply an anthropogenic impact on North-center populations due to intensified agricultural cultivation in this region. Our study demonstrated that the impact of past glaciation on organisms in East Asia significantly differs from that of Europe and North America, and human activity is an important factor in determining the genetic diversity of a species, as well as its spatial structure. © 2015 International Society of Zoological Sciences, Institute of Zoology/Chinese Academy of Sciences and Wiley Publishing Asia Pty Ltd.

  7. Fabrication and electrocatalytic application of functionalized nanoporous carbon material with different transition metal oxides

    International Nuclear Information System (INIS)

    Samiee, L.; Shoghi, F.; Vinu, A.

    2013-01-01

    Highlights: ► Fabrication of highly ordered functionalized nanoporous carbon material with different types of transition metal oxides. ► Novel electrocatalytic activity of functionalized nanoporous carbon material. ► Simultaneous effect of surface area and surface reactivity parameters on electrocatalytic activity. - Abstract: In the work presented here, an attempt is made to study the effect of functionalization with different transition metal oxides on the mesostructural properties as well as electrochemical behavior of Pt/nanoporous carbon supports. In this respect, the functionalized samples have been synthesized by using CMK-3 and metallocene as transition metal sources. The platinum catalysts (5 wt% Pt) obtained through a conventional wet impregnation method. All the materials have been characterized by XRD (low and high), N 2 adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron, EDX mapping images and cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results showed that the mesostructural order has been destroyed by functionalization of CMK-3 with CoO, whereas it is not that much affected in NiO and CuO functionalized samples. EDX image mapping exhibited the good and uniform dispersion of functionalizing elements (Ni, Cu, Fe and Co), Pt in the carbon supports. Moreover, XRD studies revealed the formation of smaller platinum crystallite sizes in NiO and CuO functionalized samples in relative to other functionalized supports. Electrochemical measurements were performed using CV and RDE method. Kinetic analysis revealed an activity increases in the following order: CMK-3-NiO-Pt > CMK-3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe 2 O 3 -Pt which is showing of simultaneous effect of surface area and surface reactivity parameters.

  8. Fabrication and electrocatalytic application of functionalized nanoporous carbon material with different transition metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Samiee, L., E-mail: Leila.Samiee83@gmail.com [Development and Optimization of Energy Technologies Research Division, Research Institute of Petroleum Industry (RIPI), West Boulevard, Near Azadi Sports Complex, Tehran (Iran, Islamic Republic of); Shoghi, F. [Development and Optimization of Energy Technologies Research Division, Research Institute of Petroleum Industry (RIPI), West Boulevard, Near Azadi Sports Complex, Tehran (Iran, Islamic Republic of); Vinu, A., E-mail: a.vinu@uq.edu.au [Australian Institute for Bioengineering and Nanotechnology(AIBN), University of Queensland, Corner College and Cooper Roads (Bld75), Brisbane, Qld 4072 (Australia)

    2013-01-15

    Highlights: Black-Right-Pointing-Pointer Fabrication of highly ordered functionalized nanoporous carbon material with different types of transition metal oxides. Black-Right-Pointing-Pointer Novel electrocatalytic activity of functionalized nanoporous carbon material. Black-Right-Pointing-Pointer Simultaneous effect of surface area and surface reactivity parameters on electrocatalytic activity. - Abstract: In the work presented here, an attempt is made to study the effect of functionalization with different transition metal oxides on the mesostructural properties as well as electrochemical behavior of Pt/nanoporous carbon supports. In this respect, the functionalized samples have been synthesized by using CMK-3 and metallocene as transition metal sources. The platinum catalysts (5 wt% Pt) obtained through a conventional wet impregnation method. All the materials have been characterized by XRD (low and high), N{sub 2} adsorption-desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron, EDX mapping images and cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results showed that the mesostructural order has been destroyed by functionalization of CMK-3 with CoO, whereas it is not that much affected in NiO and CuO functionalized samples. EDX image mapping exhibited the good and uniform dispersion of functionalizing elements (Ni, Cu, Fe and Co), Pt in the carbon supports. Moreover, XRD studies revealed the formation of smaller platinum crystallite sizes in NiO and CuO functionalized samples in relative to other functionalized supports. Electrochemical measurements were performed using CV and RDE method. Kinetic analysis revealed an activity increases in the following order: CMK-3-NiO-Pt > CMK-3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe{sub 2}O{sub 3}-Pt which is showing of simultaneous effect of surface area and surface reactivity parameters.

  9. Charge transfer mediator based systems for electrocatalytic oxygen reduction

    Science.gov (United States)

    Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

    2017-07-18

    Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

  10. Charge transfer mediator based systems for electrocatalytic oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

    2017-11-07

    Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

  11. Greater autonomy at work

    NARCIS (Netherlands)

    Houtman, I.L.D.

    2004-01-01

    In the past 10 years, workers in the Netherlands increasingly report more decision-making power in their work. This is important for an economy in recession and where workers face greater work demands. It makes work more interesting, creates a healthier work environment, and provides opportunities

  12. Gold nanoparticles-decorated fluoroalkylsilane nano-assemblies for electrocatalytic applications

    Science.gov (United States)

    Ballarin, Barbara; Barreca, Davide; Cassani, Maria Cristina; Carraro, Giorgio; Maccato, Chiara; Mignani, Adriana; Lazzari, Dario; Bertola, Maurizio

    2016-01-01

    Metal/organosilane/oxide sandwich structures were prepared via a two-step self-assembly method. First, indium tin oxide (ITO) substrates were functionalized with the following fluoroalkylsilanes (FAS): RFC(O)N(H)(CH2)3Si(OMe)3 (1, RF = C5F11), containing an embedded amide between the perfluoroalkyl chain and the syloxanic moiety, and RF(CH2)2Si(OEt)3 (2, RF = C6F13). Subsequently, Au nanoparticles (AuNPs) introduction in the obtained systems was carried out by controlled immersion into a solution of citrate-stabilized AuNPs. The physico-chemical properties of the target materials were thoroughly investigated by using various complementary techniques. Finally, the application of such systems as catalysts for methanol electro-oxidation under alkaline conditions was investigated, revealing the synergistical role played by FAS and AuNPs in promoting a remarkable electrocatalytic activity.

  13. Charge transfer effects in electrocatalytic Ni-C revealed by x-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Haslam, G. E.; Chin, X.-Y.; Burstein, G. T. [Department of Materials Science and Metallurgy, University of Cambridge, Pembroke St., Cambridge CB2 3QZ (United Kingdom); Sato, K.; Mizokawa, T. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Chiba 277-8651 (Japan)

    2012-06-04

    Binary Ni-C thin-film alloys, which have been shown to be passive against corrosion in hot sulphuric acid solution whilst also being electrocatalytically active, were investigated by XPS to determine the oxidation state of the metal and carbon components. The Ni component produces a Ni 2p spectrum similar to that of metallic nickel (i.e., no oxidation occurs) but with a 0.3 eV shift to higher binding energy (BE) due to electron donation to the carbon matrix. The C 1s peak shows a shift to lower BE by accepting electrons from the Ni nanocrystals. A cluster-model analysis of the observed Ni 2p spectrum is consistent with the electron transfer from the nickel to the carbon.

  14. Preparation and electrocatalytic properties of Pt-SiO2 nanocatalysts for ethanol electrooxidation.

    Science.gov (United States)

    Liu, B; Chen, J H; Zhong, X X; Cui, K Z; Zhou, H H; Kuang, Y F

    2007-03-01

    Due to their high stability in general acidic solutions, SiO(2) nanoparticles were selected as the second catalyst for ethanol oxidation in sulfuric acid aqueous solution. Pt-SiO(2) nanocatalysts were prepared in this paper. The micrography and elemental composition of Pt-SiO(2) nanoparticles were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy, respectively. The electrocatalytic properties of Pt-SiO(2) nanocatalysts for ethanol oxidation were investigated by cyclic voltammetry. Under the same Pt loading mass and experimental conditions for ethanol oxidation, Pt-SiO(2) nanocatalysts show higher activity than PtRu/C (E-Tek), Pt/C (E-Tek), and Pt catalysts. Additionally, Pt-SiO(2) nanocatalysts possess good anti-poisoning ability. The results indicate that Pt-SiO(2) nanocatalysts may have good potential applications in direct ethanol fuel cells.

  15. Electrocatalytic reduction of carbon dioxide on electrodeposited tin-based surfaces

    Science.gov (United States)

    Alba, Bianca Christina S.; Camayang, John Carl A.; Mopon, Marlon L.; del Rosario, Julie Anne D.

    2017-08-01

    The electrocatalytic reduction of carbon dioxide to small organic molecular compounds provides a means of generating alternative fuel source while suppressing climate change. Suitable catalysts, however, are necessary to optimize its reaction kinetics towards more valuable products. Consequently, in this study, electrodeposited Sn electrodes have been developed as catalysts for CO2 electroreduction. Deposition potential was varied to produce different Sn catalysts. SEM showed varying morphologies and increasing amount as the applied potential becomes more negative. Cyclic voltammetry and chronoamperometry showed that the activity and stability of the catalysts towards CO2 reduction depend on the morphology and presence of tin oxides. These results provide a better understanding on the performance of electrodeposited Sn-based surfaces as catalysts for CO2 reduction.

  16. Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon

    International Nuclear Information System (INIS)

    Rodriguez, Henry; Hoyos Bibian

    2004-01-01

    Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon was studied, in acid media at different temperatures and concentrations. During the maturation time of deposited iridium, the surface is covered by an irreversible oxide formation, which affects the behavior of the catalytic mixture. The Pt 7 0 Ir 3 0 and Pt 9 0 Ir 1 0 mixtures seem to be a little more active than the Pt/C electrode at potentials below 800 mV (vs. HRE). In all electrodes appears two reactions: partial ethanol oxidation to produce acetaldehyde (main path of reaction at low temperatures and high electrode coverage with ethanol adsorption residues) and the total oxidation to carbon dioxide which is considerable at potential above 800 mV and it is increased with increasing temperature

  17. Electrochemical fabrication of clean dendritic Au supported Pt clusters for electrocatalytic oxidation of formic acid

    International Nuclear Information System (INIS)

    Xia Yue; Liu Jun; Huang Wei; Li Zelin

    2012-01-01

    Highlights: ► A smooth Au surface was rebuilt into clean dendrite via square wave potential pulses. ► It was performed in blank H 2 SO 4 solution without Au(III) species and other additives. ► Dendritic Au provided certain advantage for dispersing Pt due to its unique structure. ► Pt-decorated dendritic Au demonstrated high activity for the HCOOH electrooxidation. - Abstract: We report here the fabrication of clean dendritic gold (DG) directly on a smooth Au electrode via square wave potential pulses (SWPPs) in a blank H 2 SO 4 solution containing no Au(III) species and additives. The effects of potential range, frequency and duration time of SWPPs and H 2 SO 4 concentration on the construction of DG were systematically investigated. A possible mechanism was proposed to explain the growth of DG. The whole process was templateless and surfactantless, and therefore effectively avoided possible contaminations that occurred in other synthetic routes. Further, the prepared DG electrode functioned as a scaffold to support electrodeposited Pt clusters, producing Pt-decorated DG (Pt-DG) electrodes. The electrocatalytic properties of Pt-DG electrodes with various Pt loadings were examined for the oxidation of formic acid. The low Pt loading Pt-DG demonstrated different electrochemical behavior from that on Pt-decorated smooth gold (Pt-SG) and on Pt-decorated gold nanoparticles because there were more defect sites like steps and edges on the DG surface. Ensemble effect, as well as electronic effect, accounts for the improved electrocatalytic activity of low Pt loading Pt-DG.

  18. Electrocatalytic Alloys for CO2 Reduction.

    Science.gov (United States)

    He, Jingfu; Johnson, Noah J J; Huang, Aoxue; Berlinguette, Curtis P

    2018-01-10

    Electrochemically reducing CO 2 using renewable energy is a contemporary global challenge that will only be met with electrocatalysts capable of efficiently converting CO 2 into fuels and chemicals with high selectivity. Although many different metals and morphologies have been tested for CO 2 electrocatalysis over the last several decades, relatively limited attention has been committed to the study of alloys for this application. Alloying is a promising method to tailor the geometric and electric environments of active sites. The parameter space for discovering new alloys for CO 2 electrocatalysis is particularly large because of the myriad products that can be formed during CO 2 reduction. In this Minireview, mixed-metal electrocatalyst compositions that have been evaluated for CO 2 reduction are summarized. A distillation of the structure-property relationships gleaned from this survey are intended to help in the construction of guidelines for discovering new classes of alloys for the CO 2 reduction reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Enhancing electrocatalytic performance of Sb-doped SnO ₂ electrode by compositing nitrogen-doped graphene nanosheets.

    Science.gov (United States)

    Duan, Tigang; Wen, Qing; Chen, Ye; Zhou, Yiding; Duan, Ying

    2014-09-15

    An efficient Ti/Sb-SnO2 electrode modified with nitrogen-doped graphene nanosheets (NGNS) was successfully fabricated by the sol-gel and dip coating method. Compared with Ti/Sb-SnO2 electrode, the NGNS-modified electrode possesses smaller unite crystalline volume (71.11Å(3) vs. 71.32Å(3)), smaller electrical resistivity (13Ωm vs. 34Ωm), and lower charge transfer resistance (10.91Ω vs. 21.01Ω). The accelerated lifetime of Ti/Sb-SnO2-NGNS electrode is prolonged significantly, which is 4.45 times as long as that of Ti/Sb-SnO2 electrode. The results of X-ray photoelectron spectroscopy measurement and voltammetric charge analysis indicate that introducing NGNS into the active coating can increase more reaction active sites to enhance the electrocatalytic efficiency. The electrochemical dye decolorization analysis demonstrates that Ti/Sb-SnO2-NGNS presents efficient electrocatalytic performance for methylene blue and orange II decolorization. And its pseudo-first order kinetic rate constants for methylene blue and orange II decolorization are 36.6 and 44.0 min(-1), respectively, which are 6.0 and 7.1 times as efficient as those of Ti/Sb-SnO2, respectively. Considering the significant electrocatalytic activity and low resistivity of Ti/Sb-SnO2-NGNS electrode, the cost of wastewater treatment can be expected to be reduced obviously and the application prospect is broad. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. High Electrocatalytic Performance of CuCoNi@CNTs Modified Glassy Carbon Electrode towards Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Amina A. Hamza

    2017-01-01

    Full Text Available A novel non-precious multiwalled carbon nanotubes (CNTs—supported metal oxide electrocatalyst was developed for methanol electrooxidation in alkaline medium. The catalyst was fabricated by simultaneous electrodeposition of copper-cobalt-nickel ternary nanostructures (CuCoNi on a glassy carbon electrode (GCE modified with CNTs. The proposed electrode was characterized using X-ray diffraction (XRD, energy dispersive X-ray (EDX, and scanning electron microscopy (SEM. The electrochemical behavior and the electrocatalytic performance of the suggested electrode towards the oxidation of methanol were evaluated by cyclic voltammetry (CV, linear sweep voltammetry (LSV, and chronoamperometry (CA in alkaline medium. Several parameters were investigated, e.g., deposition time, potential scan rate, etc. Compared to Cu, Co, or Ni mono electrocatalysts, the electrode based on ternary-metals exhibited superior electrocatalytic activity and stability towards methanol electrooxidation. For instance, CuCoNi@CNTs/GCE has shown at least 2.5 times electrocatalytic activity and stability compared to the mono eletrocatalysts. Moreover, the present study found that the optimized loading level is 1500 s of simultaneous electrodeposition. At this loading level, it was found that the relation between the Ip/ν1/2 function and scan rate gives the characteristic features of a catalytic process. The enhanced activity and stability of CuCoNi@CNTs/GCE was attributed to (i a synergism between three metal oxides coexisting in the same structure; (ii the presence of CNTs as a support for the metal oxides, that offers high surface area for the deposited tertiary alloy and suppresses the aggregation and sintering of the metals oxide with time; as well as (iii the increase of the conductivity of the deposited semiconducting metal oxides.

  1. On the electrocatalytic activity of nitrogen-doped reduced graphene ...

    Indian Academy of Sciences (India)

    ... battery applications. The heteroatom-doped graphene/reduced graphene oxide (rGO) ... over, in the membrane electrode assembly of fuel cell, the carbon supported ..... Wang Y, Shao Y, Matson D W, Li J and Lin Y 2010. ACS Nano 4 1790.

  2. On the electrocatalytic activity of nitrogen-doped reduced graphene ...

    Indian Academy of Sciences (India)

    The heteroatom-doped graphene/reduced graphene oxide (rGO)is very promising and the nitrogen-doped rGO (N-rGO) is emerging as a new inexpensive electrocatalyst foroxygen reduction reaction (ORR). Herein, we describe the effect of the chemical nature and amount of nitrogenin N-rGO towards ORR in acidic solution ...

  3. Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

    2018-04-24

    A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

  4. Catholyte-Free Electrocatalytic CO2 Reduction to Formate.

    Science.gov (United States)

    Lee, Wonhee; Kim, Young Eun; Youn, Min Hye; Jeong, Soon Kwan; Park, Ki Tae

    2018-04-16

    Electrochemical reduction of carbon dioxide (CO 2 ) into value-added chemicals is a promising strategy to reduce CO 2 emission and mitigate climate change. One of the most serious problems in electrocatalytic CO 2 reduction (CO 2 R) is the low solubility of CO 2 in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte-free electrocatalytic CO 2 reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm -2 , despite the decrease in CO 2 solubility. Furthermore, a significantly high formate concentration of 41.5 g L -1 is obtained as a one-path product at 343 K with high PCD (51.7 mA cm -2 ) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Electrocatalytic oxidative determination of reserpine at electrochemically functionalized single walled carbon nanotube with polyaniline

    International Nuclear Information System (INIS)

    Dar, Riyaz Ahmad; Naikoo, Gowhar Ahmad; Pitre, Krishna Sadashive

    2013-01-01

    Graphical abstract: Electrode oxidation mechanism of reserpine at PANI modified-SWCNT/CPE. -- Highlights: • Electropolymerization of polyaniline at SWCNT/CPE. • CV, EIS, CC SEM techniques were used for characterization of electrode. • Electrode showed electrocatalytic activity towards anodic oxidation of reserpine. • Oxidation process as irreversible and adsorption-controlled. • Reserpine in bark of Rauwolfia serpentina and in its pharmaceutical formulations. -- Abstract: In the present work a polyaniline film was successfully deposited by electropolymerization on single walled carbon nanotube paste electrode. The electrode was characterized using cyclic voltammetry, electrochemical impedance spectroscopy, chronocoulometry and scanning electron microscopy. The modified electrode showed electrocatalytic behaviour towards the anodic oxidation of reserpine. The adsorptive stripping voltammetric behaviour of reserpine at polyaniline film modified single walled carbon nanotube paste electrode (modified-SWCNTPE) was investigated and validated in pharmaceuticals and biological fluids by cyclic voltammetry (CV) and adsorptive stripping differential pulse voltammetry (AdSDPV) in 0.02 M phosphate buffer in the pH range of 2.5–8.5. Cyclic voltammetry has shown that the oxidation process is irreversible over the pH range studied and exhibited an adsorption-controlled behaviour. Further, the overall electrode process is mainly diffusion controlled with adsorption effects. The proposed more sensitive AdSDPV method allow quantitation over the range 0.085 μg mL −1 to 0.87 μg mL −1 with the detection limit of 0.407 ng mL −1 and has been successfully used to determine reserpine in bark of Rauwolfia serpentina and in its pharmaceutical formulations

  6. Greater-confinement disposal

    International Nuclear Information System (INIS)

    Trevorrow, L.E.; Schubert, J.P.

    1989-01-01

    Greater-confinement disposal (GCD) is a general term for low-level waste (LLW) disposal technologies that employ natural and/or engineered barriers and provide a degree of confinement greater than that of shallow-land burial (SLB) but possibly less than that of a geologic repository. Thus GCD is associated with lower risk/hazard ratios than SLB. Although any number of disposal technologies might satisfy the definition of GCD, eight have been selected for consideration in this discussion. These technologies include: (1) earth-covered tumuli, (2) concrete structures, both above and below grade, (3) deep trenches, (4) augered shafts, (5) rock cavities, (6) abandoned mines, (7) high-integrity containers, and (8) hydrofracture. Each of these technologies employ several operations that are mature,however, some are at more advanced stages of development and demonstration than others. Each is defined and further described by information on design, advantages and disadvantages, special equipment requirements, and characteristic operations such as construction, waste emplacement, and closure

  7. More features, greater connectivity.

    Science.gov (United States)

    Hunt, Sarah

    2015-09-01

    Changes in our political infrastructure, the continuing frailties of our economy, and a stark growth in population, have greatly impacted upon the perceived stability of the NHS. Healthcare teams have had to adapt to these changes, and so too have the technologies upon which they rely to deliver first-class patient care. Here Sarah Hunt, marketing co-ordinator at Aid Call, assesses how the changing healthcare environment has affected one of its fundamental technologies - the nurse call system, argues the case for wireless such systems in terms of what the company claims is greater adaptability to changing needs, and considers the ever-wider range of features and functions available from today's nurse call equipment, particularly via connectivity with both mobile devices, and ancillaries ranging from enuresis sensors to staff attack alert 'badges'.

  8. Greater oil investment opportunities

    International Nuclear Information System (INIS)

    Arenas, Ismael Enrique

    1997-01-01

    Geologically speaking, Colombia is a very attractive country for the world oil community. According to this philosophy new and important steps are being taken to reinforce the oil sector: Expansion of the exploratory frontier by including a larger number of sedimentary areas, and the adoption of innovative contracting instruments. Colombia has to offer, Greater economic incentives for the exploration of new areas to expand the exploratory frontier, stimulation of exploration in areas with prospectivity for small fields. Companies may offer Ecopetrol a participation in production over and above royalties, without it's participating in the investments and costs of these fields, more favorable conditions for natural gas seeking projects, in comparison with those governing the terms for oil

  9. Ternary Hollow Mesoporous TiN/N-Graphene/Pt Hybrid Results in Enhanced Electrocatalytic Performance for Methanol Oxidation and Oxygen Reduction Reaction

    International Nuclear Information System (INIS)

    Liu, Baocang; Huo, Lili; Zhang, Geng; Zhang, Jun

    2016-01-01

    Highlights: • A novel hollow mesoporous ternary @M-TiN/N-G/Pt electrocatalysts were synthesized. • The @M-TiN/N-G/Pt electrocatalysts displayed outstanding activity and stability toward MOR and ORR. • The activity and stability of @M-TiN/N-G/Pt electrocatalysts were higher than Pt/TiN, @M-TiN/Pt, and Pt/C catalysts. • The excellent electrocatalytic performance rooted in its unique configuration. • Several reasons were proposed to explain the enhanced electrocatalytic performance of @M-TiN/N-G/Pt. - Abstract: A novel hollow mesoporous TiN/N-graphene (N-G) hybrid architecture (@M-TiN/N-G) composed of N-doped graphene wrapped mesoporous TiN nanoparticle shells was constructed for the first time. It can be used as an efficient support for creating a highly efficient ternary @M-TiN/N-G/Pt electrocatalyst with superior catalytic activity and stability for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) through decorating well-dispersed Pt nanoparticles on @M-TiN/N-G surface. By optimizing the content of N-G in catalysts, the @M-TiN/N-G/Pt catalysts display superior catalytic activity and stability toward MOR and ORR to traditional Pt/C and graphene-free Pt/TiN and @M-TiN/Pt catalysts. The various characterization results reveal that the outstanding electrocatalytic performance of @M-TiN/N-G/Pt catalyst roots in its large surface area, high porosity, strong interaction among Pt, TiN, and N-G, excellent electron transfer property facilitated by N-doped graphene, and small size of Pt and TiN nanocrystals. The synthetic approach may be available for constructing other graphene based hollow metal nitrides, carbides, and phosphides for various electrocatalytic applications.

  10. High electrocatalytic performance of nitrogen-doped carbon nanofiber-supported nickel oxide nanocomposite for methanol oxidation in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Al-Enizi, Abdullah M. [Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia); Elzatahry, Ahmed A., E-mail: aelzatahry@ksu.edu.sa [Materials Science and Technology Program, College of Arts and Science, Qatar University, Doha 2713 (Qatar); Advanced Technology and New Materials Research Institute, City of Scientific Research and Technology Applications, New Borg El-Arab City, Alexandria 21934 (Egypt); Abdullah, Aboubakr M., E-mail: bakr@qu.edu.qa [Center for Advanced Materials, Qatar University, Doha 2713 (Qatar); Vinu, Ajayan [Future Industries Institute, University of South Australia, Building X-X2-09, Mawson Lakes Campus, Mawson Lakes 5095 SA (Australia); Iwai, Hideo [Materials Analysis Station, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki, 305-0047 (Japan); Al-Deyab, Salem S. [Petrochemical Research Chair, Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia)

    2017-04-15

    Highlights: • A mixture of Polyvinylpyrrolidone (PVP), graphene and emeraldine base polyaniline (PANi) was electrospun and used as starting materials to prepare a nitrogen-doped carbon nanofiber (N-CNF). • Nickel oxide was loaded on the N-CNF to form a nanocomposite which was calcined later at different temperatures. • The effect of calcination temperature on the electrocatalytic behavior of the nanocomposite was studied which shows that the nanocomposite calcined at 500 °C was proved to be very high compared to the other calcination temperatures. • The stability of catalyst was excellent and its resistance to the adsorption of the intermediates generated from the methanol oxidation was very high. - Abstract: Nitrogen-Doped Carbon Nanofiber (N-CNF)–supported NiO composite was prepared by electrospinning a sol-gel mixture of graphene and polyaniline (PANi) with aqueous solutions of Polyvinylpyrrolidone (PVP) followed by a high-temperature annealing process. The electrospun was stabilized for 2 h at 280 °C, carbonized for 5 h at 1200 °C then loaded by 10% NiO. The electrocatalytic activities of the produced nanocomposite have been studied using cyclic voltammetry, and chronoamperometry. Also, N-CNF was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area (BET), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and scanning-electron microscopy (SEM). The obtained N-doped carbon nanofiber was found to have a nitrogen content of 2.6 atomic% with a diameter range of (140–160) nm, and a surface area (393.3 m{sup 2} g{sup −1}). In addition, it showed a high electrocatalytic behavior towards methanol oxidation reaction in alkaline medium and high stability and resistivity to the adsorption of intermediates.

  11. Influence of co-electrodeposited Gold particles on the electrocatalytic properties of CoHCF thin films

    International Nuclear Information System (INIS)

    Kumar, Alam Venugopal Narendra; Joseph, James

    2014-01-01

    The electrochemical modification of solid electrodes with metal hexacyanoferrate thin films for enhancing the interfacial properties has created interest for over the past three decades. The preparation of Prussian blue (PB) Au nano composites for the enhancement in the electrocatalytic properties of PB on glassy carbon electrode has been reported by us. The incorporation of Au nano particles in Cobalt hexacyanoferrate (CoHCF) films on Glassy carbon by co-electrodeposition is expected to benefit its interfacial electron transfer properties. The present work describes the effect on the interfacial properties by incorporated Au particles in CoHCF (CoHCF(Au)) modified electrodes. The CoHCF(Au) modified electrodes were characterized by UV-Vis spectrophotometry, Cyclic Voltammetry, AC Impedance, FE-SEM etc., Influence on the electrocatalytic properties of CoHCF(Au) films have been explored by performing two important reactions i) Hydrazine elecrtro-oxidation ii) Oxygen evolution reaction. Our results reveal that CoHCF(Au) modified GC electrode perform better in terms of charge transport in the redox film and also for the electrooxidation of hydrazine in comparision with simple CoHCF modified electrodes. By using the current-transient technique (chrono method i vs t curve) the hydrazine diffusion coefficient (D 0 ) were calculated. Diffusion coefficient of hydrazine was approximately three times higher on CoHCF(Au) electrode, 9.5 × 10 −5 cm 2 s −1 compared with simple CoHCF modified electrode, 3.3× 10 −5 cm 2 s −1 . Similarly, we also discuss results which reveal that CoHCF(Au) electrodes enhances electrocatalytic activity in splitting water to oxygen in 0.1 M NaOH solution compared to simple CoHCF and Au deposited on GC electrodes

  12. Nitrogen doped graphene supported palladium-cobalt as a promising catalyst for methanol oxidation reaction: Synthesis, characterization and electrocatalytic performance

    International Nuclear Information System (INIS)

    Kiyani, Roya; Rowshanzamir, Soosan; Parnian, Mohammad Javad

    2016-01-01

    In this work, palladium and palladium-cobalt supported on nitrogen doped graphene as anode materials in direct methanol fuel cells is reported. A simple and low temperature solvothermal method is used to directly prepare nanoflower-like NG and then, Pd and Pd−Co nanoparticles are precipitated onto the surface of NG using a modified polyol reduction method. The synthesized electrocatalysts are characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) are used to measure electrocatalytic methanol oxidation activity and the durability of electrocatalysts. The results show that Pd−Co/NG has better electrocatalytic activity than Pd/NG toward methanol oxidation reaction (MOR) in alkaline media that is related at the presence of cobalt atoms. In addition, chronoamperometric results indicate that Pd−Co/NG is more stable than commercial Pt/C for MOR. - Highlights: • Nitrogen doped graphene (NG) was prepared by a simple solvothermal method. • Pd and Pd−Co nanoparticles were deposited on NG by polyol reduction method. • Promoting effects of cobalt over Pd/NG for MOR were investigated. • Higher activity and enhanced durability was observed for Pd−Co/NG catalyst.

  13. Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea

    International Nuclear Information System (INIS)

    Xu, Xiao; Zhou, Yingke; Yuan, Tao; Li, Yawei

    2013-01-01

    A facile hydrothermal reaction of graphene oxide with urea was used to produce nitrogen doped graphene, and Pt nanoparticles were deposited on the obtained nitrogen doped graphene by the NaBH 4 reduction route. The morphology and microstructure of the synthesized catalysts were characterized by transmission electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy, while the functional groups on the surface of the catalysts were investigated by the Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra. Cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the methanol electrocatalytic oxidation activity and durability of Pt catalysts supported on the nitrogen doped graphene. The results showed that nitrogen doping and reduction of GO were achieved simultaneously by the facile hydrothermal reaction, which had beneficial effects for the deposition process and electrocatalytic activity of Pt nanoparticles. The Pt catalysts supported on the nitrogen doped graphene substrate presented excellent activity and durability of methanol oxidation reaction, which might be promising for application in direct methanol fuel cells

  14. Electrocatalytic aerobic epoxidation of alkenes: Experimental and DFT investigation

    International Nuclear Information System (INIS)

    Magdesieva, Tatiana V.; Borisova, Nataliya E.; Dolganov, Alexander V.; Ustynyuk, Yuri A.

    2012-01-01

    A new method for electrocatalytic aerobic epoxidation of alkenes catalyzed by binuclear Cu(II) complexes with azomethine ligands based on 2,6-diformyl-4-tert-butylphenol is described. In acetonitrile–water (5%), at the potential of Cu II /Cu I redox couple (–0.8 V vs. Ag/AgCl/KCl) at room temperature the epoxide is obtained in an average yield of around 50%. Contrary to the majority of known epoxidations, no strong oxidants are involved and no free hydrogen peroxide is formed in the reaction, thus making it ecologically friendly. The DFT quantum-chemical modeling of the reaction mechanism revealed that a copper hydroperoxo-complex rather than hydrogen peroxide or a copper oxo-complex oxidizes alkene. The process is very selective since neither products of hydroxylation of benzene ring in styrene nor of allylic oxidation of cyclohexene were detected.

  15. Electrocatalytic oxidation of methanol on (Pb) lead modified by Pt, Pt-Ru and Pt-Sn microparticles dispersed into poly(o-phenylenediamine) film

    Energy Technology Data Exchange (ETDEWEB)

    Golikand, Ahmad Nozad; Maragheh, Mohammad Ghannadi; Irannejad, Leila [Jaber Ibn Hayan Research Lab., Atomic Energy Organization of Iran (AEOI), Tehran (Iran); Golabi, Seyed Mehdi [Electroanalytical Chemistry Lab., Faculty of Chemistry, University of Tabriz, Tabriz (Iran)

    2005-08-18

    The electrocatalytic oxidation of methanol at a (Pb) lead electrode modified by Pt, Pt-Ru and Pt-Sn microparticles dispersed into poly(o-phenylenediamine) (PoPD) film has been investigated using cyclic voltammetry as analytical technique and 0.5M sulfuric acid as supporting electrolyte. It has been shown that the presence of PoPD film increases considerably the efficiency of deposited Pt and Pt alloys microparticles toward the electrocatalytic oxidation of methanol. The catalytic activity of Pt particles is further enhanced when Ru and especially Sn, is co-deposited in the polymer film. The effects of various parameters such as concentration of methanol, medium temperature as well as the long term stability of modified electrodes have also been investigated. (author)

  16. Electrocatalytic reduction of dioxygen by cobalt porphyrin-modified glassy carbon electrode with single-walled carbon nanotubes and nafion in aqueous solutions

    International Nuclear Information System (INIS)

    Choi, Ayoung; Jeong, Haesang; Kim, Songmi; Jo, Suhee; Jeon, Seungwon

    2008-01-01

    Cobalt porphyrin (CoP)-modified glassy carbon electrode (GCE) with single-walled carbon nanotubes (SWNTs) and Nafion demonstrated a higher electrocatalytic activity for the reduction of dioxygen in 0.1 M H 2 SO 4 solution. Cyclic and hydrodynamic voltammetry at the CoP-SWNTs/GCE-modified electrodes in O 2 -saturated aqueous solutions was used to study the electrocatalytic pathway. Compared with the CoP/GCE-modified electrodes, the reduction potential of dioxygen at the CoP-SWNTs/GCE-modified electrodes was shifted to the positive direction and the limiting current was greatly increased. Especially, the Co(TMPP)-SWNTs/GCE-modified electrode was catalyzed effectively by the 4e - reduction of dioxygen to water, because hydrodynamic voltammetry revealed the transference of approximately four electrons for dioxygen reduction and the minimal generation of hydrogen peroxide in the process of dioxygen reduction

  17. Electrocatalytic properties of monometallic and bimetallic nanoparticles-incorporated polypyrrole films for electro-oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Selvaraj, V.; Alagar, M. [Department of Chemical Engineering, Alagappa College of Technology, Anna University, Chennai 600025 (India); Hamerton, I. [Chemistry Division, School of Biomedical and Molecular Sciences, University of Surrey, Guildford, Surrey GU2 7XH (United Kingdom)

    2006-10-06

    Oxidative electrochemical polymerization of pyrrole at indium-doped tin oxide (ITO) is accomplished from a neat monomer solution with a supporting electrolyte (0.3M n-tetrabutyl ammonium tetrafluoroborate) by multiple-scan cyclic voltammetry. Polypyrrole (Ppy) films containing nanometer-sized platinum and Pt/Pd bimetallic particles are electro-synthesized on ITO glass plates by voltammetric cycling between -0.1 and +1V (versus Ag/AgCl/3M NaCl). The electrocatalytic oxidation of methanol on the nanoparticle-modified polypyrrole films is studied by means of electrochemical techniques. The modified electrode exhibits significant eletrocatalytic activity for methanol oxidation. The enhanced electrocatalytic activities may be due to the uniform dispersion of nanoparticles in the polypyrrole film and a synergistic effect of the highly-dispersed metal particles so that the polypyrrole film reduces electrode poisoning by adsorbed CO species. The monometallic (Pt) and bimetallic (Pt/Pd) nanoparticles are uniformly dispersed in polypyrrole matrixes, as confirmed by scanning electron microscopic and atomic force microscopic analysis. Energy dispersive X-ray analysis is used to characterize the composition of metal present in the nanoparticle-modified electrodes. (author)

  18. Facile synthesis of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide with enhanced electrocatalytic properties

    Science.gov (United States)

    Li, Shan-Shan; Zheng, Jie-Ning; Ma, Xiaohong; Hu, Yuan-Yuan; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

    2014-05-01

    A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media.A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S12 and Tables S1 and S2. See DOI: 10.1039/c3nr06808k

  19. Electro-catalytic properties of tri-(Fe, Co and Ni shungite composites

    Directory of Open Access Journals (Sweden)

    Bazarbay Serikbayev

    2012-03-01

    Full Text Available The article presents the results of electrochemical investigations obtained on carbon paste electrodes (CPE of shungite from the land Koksu. Electrochemical and electro-catalytic properties of shungite modified with iron, cobalt and nickel were compared.

  20. Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

    KAUST Repository

    Nurlaela, Ela; Shinagawa, Tatsuya; Qureshi, Muhammad; Dhawale, Dattatray Sadashiv; Takanabe, Kazuhiro

    2016-01-01

    The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER

  1. Heterogeneous electron transfer kinetics and electrocatalytic behaviour of mixed self-assembled ferrocenes and SWCNT layers

    CSIR Research Space (South Africa)

    Nkosi, D

    2010-01-01

    Full Text Available The electron transfer dynamics and electrocatalytic behaviour of ferrocene-terminated self-assembled monolayers (SAMs), co-adsorbed with single-walled carbon nanotubes (SWCNTs) on a gold electrode, have been interrogated for the first time...

  2. Covalent attachment of thionine onto gold electrode modified with cadmium sulfide nanoparticles: Improvement of electrocatalytic and photelectrocatalytic reduction of hydrogen peroxide

    International Nuclear Information System (INIS)

    Salimi, Abdollah; Rahmatpanah, Rojzin; Hallaj, Rahman; Roushani, Mahmoud

    2013-01-01

    A newly developed strategy based on gold (Au) electrode modified with cadmium sulfide nanoparticles (CdSnp) and thionine (Th) was proposed toward electrocatalytic and photoelectrocatalytic hydrogen peroxide (H 2 O 2 ) reduction. At first, a thin film of CdS nanoparticles was electrodeposited onto Au electrode. Then, the CdS/Au electrode was modified with mercaptoacetic acid (MAA), which not only acts as a stabilizing agent to prevent the chalcogenide CdS nanocrystals from aggregation but also as a linker for subsequent attachment of Th onto the CdS nanoparticles. The effective covalent immobilization of Th was achieved through amide bond formation reaction between -NH 2 groups of Th and -COOH groups of MAA, using dicyclohexylcarbodiimide (DCC) as condensation agent. The Au/CdS/Th modified electrode showed a well-defined redox couple with surface confined characteristics at wide pH range (2–12). The heterogeneous electron transfer rate constant (k s ) and the surface coverage of immobilized Th on the modified electrode was obtained as 0.12 s −1 and 4.35 × 10 −9 mole cm −2 , respectively. The electrocatalytic activity and stability of the modified electrode toward hydrogen peroxide reduction was investigated and it was found that the Au/CdS/Th electrode illustrates excellent electrocatalytic activity toward H 2 O 2 reduction at reduced overpotential. The detection limit, sensitivity and catalytic rate constant (k cat ) of the modified electrode toward H 2 O 2 were 55 nM, 3.4 μA μM −1 cm −2 and 3.75 (±0.1) × 10 3 M −1 s −1 , respectively, at linear concentration range up to 10 mM. Upon light irradiation, about two-fold improvements were attained in sensitivity and detection limit of the modified electrode toward H 2 O 2 electrocatalytic determination

  3. Ultrafine Iridium Oxide Nanorods Synthesized by Molten Salt Method toward Electrocatalytic Oxygen and Hydrogen Evolution Reactions

    International Nuclear Information System (INIS)

    Ahmed, Jahangeer; Mao, Yuanbing

    2016-01-01

    Highlights: • Ultrafine iridium oxide nanorods were synthesized by a molten salt method at 650 °C. • They show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions. • These results are comparable with, and in most cases, higher than reported data in the literature. • This study reports a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure. • These IrO_2 NRs are expected to serve as a benchmark to develop active electrocatalysts. - Abstract: Ultrafine iridium oxide nanorods (IrO_2 NRs) were successfully synthesized using a molten salt method at 650 °C. The structural and morphological characterizations of these IrO_2 NRs were carried out by powder X-ray diffraction, Raman spectroscopy and electron microscopic techniques. Compared to commercial IrO_2 nanoparticles (IrO_2 NPs) and previous reports, these IrO_2 NRs show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions by passing either N_2 or O_2 gas in a 0.5 M KOH electrolyte before electrochemical measurements, including cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Specifically, the current densities from the as-synthesized IrO_2 NRs and commercial IrO_2 NPs were measured in 0.5 M KOH electrolyte to be 70 and 58 (OER, deaerated, at 0.6 V versus Ag/AgCl), 71 and 61 (OER, O_2, from −0.10 to 1.0 V versus Ag/AgCl at 50 mV/s), and 25 and 14 (HER, deaerated, at −1.4 V versus Ag/AgCl) mA/cm"2, respectively. These results are comparable with, and in most cases, higher than reported data in the literature. Therefore, the current study reports not only a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure, and it is expected that these IrO_2 NRs can serve as a benchmark in the development of active OER and HER (photo)electrocatalysts for various applications.

  4. Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons

    Science.gov (United States)

    Hahn, Christopher; Hatsukade, Toru; Kim, Youn-Geun; Vailionis, Arturas; Baricuatro, Jack H.; Higgins, Drew C.; Nitopi, Stephanie A.; Soriaga, Manuel P.; Jaramillo, Thomas F.

    2017-01-01

    In this study we control the surface structure of Cu thin-film catalysts to probe the relationship between active sites and catalytic activity for the electroreduction of CO2 to fuels and chemicals. Here, we report physical vapor deposition of Cu thin films on large-format (∼6 cm2) single-crystal substrates, and confirm epitaxial growth in the , , and orientations using X-ray pole figures. To understand the relationship between the bulk and surface structures, in situ electrochemical scanning tunneling microscopy was conducted on Cu(100), (111), and (751) thin films. The studies revealed that Cu(100) and (111) have surface adlattices that are identical to the bulk structure, and that Cu(751) has a heterogeneous kinked surface with (110) terraces that is closely related to the bulk structure. Electrochemical CO2 reduction testing showed that whereas both Cu(100) and (751) thin films are more active and selective for C–C coupling than Cu(111), Cu(751) is the most selective for >2e− oxygenate formation at low overpotentials. Our results demonstrate that epitaxy can be used to grow single-crystal analogous materials as large-format electrodes that provide insights on controlling electrocatalytic activity and selectivity for this reaction. PMID:28533377

  5. High Cellular Monocyte Activation in People Living With Human Immunodeficiency Virus on Combination Antiretroviral Therapy and Lifestyle-Matched Controls Is Associated With Greater Inflammation in Cerebrospinal Fluid

    NARCIS (Netherlands)

    Booiman, Thijs; Wit, Ferdinand W.; Maurer, Irma; de Francesco, Davide; Sabin, Caroline A.; Harskamp, Agnes M.; Prins, Maria; Garagnani, Paolo; Pirazzini, Chiara; Franceschi, Claudio; Fuchs, Dietmar; Gisslén, Magnus; Winston, Alan; Reiss, Peter; Kootstra, Neeltje A.; Schouten, J.; Kooij, K. W.; van Zoest, R. A.; Elsenga, B. C.; Janssen, F. R.; Heidenrijk, M.; Zikkenheiner, W.; van der Valk, M.; Booiman, T.; Harskamp-Holwerda, A. M.; Boeser-Nunnink, B.; Maurer, I.; Mangas Ruiz, M. M.; Girigorie, A. F.; Villaudy, J.; Frankin, E.; Pasternak, A.; Berkhout, B.; van der Kuyl, T.; Portegies, P.; Schmand, B. A.; Geurtsen, G. J.; ter Stege, J. A.; Klein Twennaar, M.; Majoie, C. B. L. M.; Caan, M. W. A.; Su, T.; Weijer, K.; Bisschop, P. H. L. T.; Kalsbeek, A.; Wezel, M.; Visser, I.; Ruhé, H. G.; Franceschi, C.; Garagnani, P.

    2017-01-01

    Increased monocyte activation and intestinal damage have been shown to be predictive for the increased morbidity and mortality observed in treated people living with human immunodeficiency virus (PLHIV). A cross-sectional analysis of cellular and soluble markers of monocyte activation, coagulation,

  6. Porphyrinic metal-organic framework/macroporous carbon composites for electrocatalytic applications

    International Nuclear Information System (INIS)

    Yin, Duanduan; Liu, Jian; Bo, Xiangjie; Li, Mian; Guo, Liping

    2017-01-01

    Graphical abstract: Zr-PorMOF/MPC composites were prepared, which used to detect H 2 O 2 and simultaneously detect UA, XA and HX Display Omitted -- Highlights: •Preparing Zr-PorMOF/MPC composites by a simple one-step solvothermal reaction. •Enhanced electrocatalytic activity at Zr-PorMOF/MPC than Zr-PorMOF and MPC. •A low detection limit, short response time and low applied potential towards H 2 O 2 reduction. •Simultaneous determination of UA, XA and HX. -- Abstract: In this work, a novel porphyrinic metal-organic framework-based composite has been successfully synthesized by a simple one-step solvothermal method through growing Zr-PorMOF on macroporous carbon (MPC). Porphyrin-base MOFs combining the structural adjustable of MOFs and the specific catalytic activity of biomimetic catalysts play an important role in electrocatalysis. A series of characterization show that the roles of MPC as follow: (1) MPC could avoid the agglomeration of Zr-PorMOF particles and increase the specific surface area; (2) MPC could improve the electrochemical stability of Zr-PorMOF particles; (3) MPC could reduce the electron transfer resistance. Therefore, MPC plays the role of the conductive bridges to provide facile charge transport. The obtained Zr-PorMOF/MPC composites exhibit much better electrocatalytic activity for the reduction of hydrogen peroxide (H 2 O 2 ) than the pristine Zr-PorMOF due to the synergy of Zr-PorMOF and MPC. This enzyme-free H 2 O 2 sensor shows two linear relationships in the ranges 0.5–137 μM (R 2 = 0.991, sensitivity = 66 μA mM −1 ) and 137–3587 μM (R 2 = 0.993, sensitivity = 16 μA mM −1 ), with a low over-potential at −0.2 V, a fast response time within 1 s and a low limit of detection (LOD) of 0.18 μM. Moreover, Zr-PorMOF/MPC composites were used to simultaneously detect uric acid (UA), xanthine (XA) and hypoxanthine (HX). These three substances are degradation products of purine metabolism. In addition, Zr-PorMOF/MPC composites

  7. The graphene nanopowder for electro-catalytic oxidation of dopamine and uric acid in the presence of ascorbic acid

    Institute of Scientific and Technical Information of China (English)

    Yuan; Bu; Wenle; Dai; Nan; Li; Xinran; Zhao; Xia; Zuo

    2013-01-01

    The graphene nanopowder for electro-catalytic oxidation of dopamine and uric acid in the presence of ascorbic acid has been investigated by cyclic voltammetry,linear polarization and chronoamperometry.The graphene nanopowder modified electrode was prepared using the drop coating method,which displayed excellent electrocatalytic activity towards the oxidation of dopamine and uric acid compared with the bare glassy carbon electrode in phosphate buffer solution at pH=7.0.Linear responses for dopamine and uric acid were obtained in the ranges of3.3μmol/L to 249.1μmol/L and 6.7μmol/L to 386.3μmol/L with detection limits of 1.5μmol/L and 2.7μmol/L(S/N=3),respectively.The response time was less than 2 s in case of dopamine and 3 s in case of uric acid,respectively.The results demonstrated that the graphene nanopowder had potential for detecting dopamine and uric acid.

  8. Microwave-Assisted Synthesis of Co3(PO42 Nanospheres for Electrocatalytic Oxidation of Methanol in Alkaline Media

    Directory of Open Access Journals (Sweden)

    Prabhakarn Arunachalam

    2017-04-01

    Full Text Available Low-cost and high-performance advanced electrocatalysts for direct methanol fuel cells are of key significance for the improvement of environmentally-pleasant energy technologies. Herein, we report the facile synthesis of cobalt phosphate (Co3(PO42 nanospheres by a microwave-assisted process and utilized as an electrocatalyst for methanol oxidation. The phase formation, morphological surface structure, elemental composition, and textural properties of the synthesized (Co3(PO42 nanospheres have been examined by powder X-ray diffraction (XRD, Fourier transform-infrared spectroscopy (FT-IR, field emission-scanning electron microscopy (FE-SEM, high-resolution transmission electron microscopy (HRTEM, X-ray photoelectron spectroscopy (XPS, and nitrogen adsorption-desorption isotherm investigations. The performance of an electrocatalytic oxidation of methanol over a Co3(PO42 nanosphere-modified electrode was evaluated in an alkaline solution using cyclic voltammetry (CV and chronopotentiometry (CP techniques. Detailed studies were made for the methanol oxidation by varying the experimental parameters, such as catalyst loading, methanol concentration, and long-term stability for the electro-oxidation of methanol. The good electrocatalytic performances of Co3(PO42 should be related to its good surface morphological structure and high number of active surface sites. The present investigation illustrates the promising application of Co3(PO42 nanospheres as a low-cost and more abundant electrocatalyst for direct methanol fuel cells.

  9. Live Faecalibacterium prausnitzii induces greater TLR2 and TLR2/6 activation than the dead bacterium in an apical anaerobic co-culture system.

    Science.gov (United States)

    Maier, Eva; Anderson, Rachel C; Altermann, Eric; Roy, Nicole C

    2018-02-01

    Inappropriate activation of intestinal innate immune receptors, such as toll-like receptors (TLRs), by pathogenic bacteria is linked to chronic inflammation. In contrast, a "tonic" level of TLR activation by commensal bacteria is required for intestinal homeostasis. A technical challenge when studying this activation in vitro is the co-culturing of oxygen-requiring mammalian cells with obligate anaerobic commensal bacteria. To overcome this, we used a novel apical anaerobic co-culture system to successfully adapt a TLR activation assay to be conducted in conditions optimised for both cell types. Live Faecalibacterium prausnitzii, an abundant obligate anaerobe of the colonic microbiota, induced higher TLR2 and TLR2/6 activation than the dead bacterium. This enhanced TLR induction by live F. prausnitzii, which until now has not previously been described, may contribute to maintenance of gastrointestinal homeostasis. This highlights the importance of using physiologically relevant co-culture systems to decipher the mechanisms of action of live obligate anaerobes. © 2017 John Wiley & Sons Ltd.

  10. Preparation and electrochemical property of TiO_2/Nano-graphite composite anode for electro-catalytic degradation of ceftriaxone sodium

    International Nuclear Information System (INIS)

    Guo, Xiaolei; Li, Dong; Wan, Jiafeng; Yu, Xiujuan

    2015-01-01

    Titanium dioxide/Nano-graphite (TiO_2/Nano-G) composite was synthesized by a sol-gel method and TiO_2/Nano-G electrode was prepared in hot-press approach. The composite was characterized by X-ray photoelectron spectroscopy (XPS), fourier transform infrared (FT-IR), scanning electrons microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrochemical performance of the TiO_2/Nano-G anode electrode was investigated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electro-catalytic performance was evaluated by the yield of ·OH radicals, degradation of methyl orange and ceftriaxone sodium. The results demonstrated that TiO_2 nanoparticles were dispersed on the surface and interlamination of the Nano-G uniformly, TiO_2/Nano-G electrode owned higher electro-catalytic oxidation activity and stability than Nano-G electrode. Degradation rate of ceftriaxone sodium within 120 min by TiO_2(40)/Nano-G electrode was 97.7%. And ·OH radicals given by TiO_2/Nano-G electrode was higher than that of Nano-G electrode and DSA (Ti/IrO_2-RuO_2) electrode. The excellent electro-catalytic performance could be ascribed to the admirable conductive property of the Nano-G and more production of ·OH offered by TiO_2(40)/Nano-G electrode.

  11. Effect of the leaching of Ru-Se-Fe and Ru-Mo-Fe obtained by mechanical alloying on electrocatalytical behavior for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Ezeta, A.; Arce, E.M.; Solorza, O.; Gonzalez, R.G.; Dorantes, H.

    2009-01-01

    In the present work, Ru-Se-Fe and Ru-Mo-Fe alloyed nanoparticles were synthesized from high purity powders (Ru, Se and Mo) by means of the high-energy mechanical alloying. Fe was integrated to the alloys because of the erosion of the mill balls. The ORR electrocatalytic performance of the alloys (lixiviated or not) was evaluated in a rotating disc electrode (RDE) at room temperature. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used for the structure characterization of the materials. Small-particle clusters with granular morphology and nanometric sizes were obtained in all the cases. According to the Tafel parameters from the RDE results, a first order ORR is present in both electrocatalytic systems through a 4e - global multielectron transference to form water: O 2 + 4H + + e - → H 2 O. The electrocatalytic activity showed that the mechanical alloying enabled to obtain nanoparticle electrocatalysts with good ORR performance. Lixiviation of the mechanical alloying powders not improves the catalytical responses.

  12. High Cellular Monocyte Activation in People Living With Human Immunodeficiency Virus on Combination Antiretroviral Therapy and Lifestyle-Matched Controls Is Associated With Greater Inflammation in Cerebrospinal Fluid

    NARCIS (Netherlands)

    Booiman, Thijs; Wit, Ferdinand W N M; Maurer, Irma; De Francesco, Davide; Sabin, Caroline A; Harskamp, Agnes M; Prins, Maria; Garagnani, Paolo; Pirazzini, Chiara; Franceschi, Claudio; Fuchs, Dietmar; Gisslén, Magnus; Winston, Alan; Reiss, Peter; Kootstra, Neeltje A; Kalsbeek, A.

    2017-01-01

    BACKGROUND: Increased monocyte activation and intestinal damage have been shown to be predictive for the increased morbidity and mortality observed in treated people living with human immunodeficiency virus (PLHIV). METHODS: A cross-sectional analysis of cellular and soluble markers of monocyte

  13. Physical Activity Might Be of Greater Importance for Good Spinal Control Than If You Have Had Pain or Not: A Longitudinal Study.

    Science.gov (United States)

    Aasa, Ulrika; Lundell, Sara; Aasa, Björn; Westerståhl, Maria

    2015-12-01

    Longitudinal design. A cohort followed in 3 waves of data collection. The aim of the study was to describe the relationships between the performance of 2 tests of spinal control at the age of 52 years and low back pain, physical activity level, and fitness earlier in life, as well as to describe the cross-sectional relationships between these measures. Altered spinal control has been linked to pain; however, other stimuli may also lead to inability to control the movements of the spine. Participants answered questions about physical activity and low back pain, and performed physical fitness tests at the age of 16, 34, and 52 years. The fitness test battery included tests of endurance in the back and abdominal muscles, a submaximal bicycle ergometer test to estimate maximal oxygen uptake, and measurements of hip flexion, thoracic spine flexibility, and anthropometrics. Two tests were aggregated to a physical fitness index. At the age of 52, also 2 tests of spinal control, the standing Waiter's bow (WB) and the supine double leg lower (LL) were performed. Logistic regression analyses showed that higher back muscle endurance at the age of 34 years could positively predict WB performance at 52 years and higher physical fitness at the age of 34 could positively predict LL performance at 52 years. Regarding cross-sectional relationships, an inability to perform the WB correctly was associated with lower physical fitness, flexibility and physical activity, and larger waist circumference. An inability to correctly perform the LL was associated with lower physical fitness. One-year prevalence of pain was not significantly associated with WB or LL test performance. An active life resulting in higher physical fitness is related to better spinal control in middle-aged men and women. This further strengthens the importance of physical activity throughout the life span. 3.

  14. Clobazam and its active metabolite N-desmethylclobazam display significantly greater affinities for α₂- versus α₁-GABA(A-receptor complexes.

    Directory of Open Access Journals (Sweden)

    Henrik Sindal Jensen

    Full Text Available Clobazam (CLB, a 1,5-benzodiazepine (BZD, was FDA-approved in October 2011 for the adjunctive treatment of seizures associated with Lennox-Gastaut syndrome (LGS in patients 2 years and older. BZDs exert various CNS effects through allosteric modulation of GABAA receptors. The structurally distinct, 1,4-BZD clonazepam (CLN is also approved to treat LGS. The precise mechanisms of action and clinical efficacy of both are unknown. Data show that the GABAA α₁-subunit-selective compound zolpidem [ZOL] exhibits hypnotic/sedative effects. Conversely, data from knock-in mice carrying BZD binding site mutations suggest that the α₂ subunit mediates anticonvulsant effects, without sedative actions. Hence, the specific pattern of interactions across the GABAA receptor complexes of BZDs might be reflected in their clinical efficacies and adverse effect profiles. In this study, GABAA-receptor binding affinities of CLB, N-desmethylclobazam (N-CLB, the major metabolite of CLB, CLN, and ZOL were characterized with native receptors from rat-brain homogenates and on cloned receptors from HEK293 cells transfected with combinations of α (α₁, α₂, α₃, or α₅, β₂, and γ₂ subtypes. Our results demonstrate that CLB and N-CLB have significantly greater binding affinities for α₂- vs. α₁-receptor complexes, a difference not observed for CLN, for which no distinction between α₂ and α₁ receptors was observed. Our experiments with ZOL confirmed the high preference for α₁ receptors. These results provide potential clues to a new understanding of the pharmacologic modes of action of CLB and N-CLB.

  15. Activity-dependent expression of miR-132 regulates immediate-early gene induction during olfactory learning in the greater short-nosed fruit bat, Cynopterus sphinx.

    Science.gov (United States)

    Mukilan, Murugan; Ragu Varman, Durairaj; Sudhakar, Sivasubramaniam; Rajan, Koilmani Emmanuvel

    2015-04-01

    The activity-dependent expression of immediate-early genes (IEGs) and microRNA (miR)-132 has been implicated in synaptic plasticity and the formation of long-term memory (LTM). In the present study, we show that olfactory training induces the expression of IEGs (EGR-1, C-fos, C-jun) and miR-132 at similar time scale in olfactory bulb (OB) of Cynopterus sphinx. We examined the role of miR-132 in the OB using antisense oligodeoxynucleotide (AS-ODN) and demonstrated that a local infusion of AS-ODN in the OB 2h prior to training impaired olfactory memory formation in C. sphinx. However, the infusion of AS-ODN post-training did not cause a deficit in memory formation. Furthermore, the inhibition of miR-132 reduced the olfactory training-induced expression of IEGs and post synaptic density protein-95 (PSD-95) in the OB. Additionally, we show that miR-132 regulates the activation of calcium/calmodulin-dependent protein kinase-II (CaMKII) and cAMP response element binding protein (CREB), possibly through miR-148a. These data suggest that olfactory training induces the expression of miR-132 and IEGs, which in turn activates post-synaptic proteins that regulate olfactory memory formation. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. Effect of recycling activities on the heating value of solid waste: case study of the Greater Vancouver Regional District (Metro Vancouver).

    Science.gov (United States)

    Abedini, Ali R; Atwater, James W; Fu, George Yuzhu

    2012-08-01

    Two main goals of the integrated solid waste management system (ISWMS) of Metro Vancouver (MV) include further recycling of waste and energy recovery via incineration of waste. These two very common goals, however, are not always compatible enough to fit in an ISWMS depending on waste characteristics and details of recycling programs. This study showed that recent recycling activities in MV have negatively affected the net heating value (NHV) of municipal solid waste (MSW) in this regional district. Results show that meeting MV's goal for additional recycling of MSW by 2015 will further reduce the NHV of waste, if additional recycling activities are solely focused on more extensive recycling of packaging materials (e.g. paper and plastic). It is concluded that 50% additional recycling of paper and plastic in MV will increase the overall recycling rate to 70% (as targeted by the MV for 2015) and result in more than 8% reduction in NHV of MSW. This reduction translates to up to 2.3 million Canadian dollar (CAD$) less revenue at a potential waste-to-energy (WTE) plant with 500 000 tonnes year(-1) capacity. Properly designed recycling programmes, however, can make this functional element of ISWMS compatible with green goals of energy recovery from waste. Herein an explanation of how communities can increase their recycling activities without affecting the feasibility of potential WTE projects is presented.

  17. Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.

    2015-10-20

    Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.

  18. Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.; Manjunath, K.; Samrat, D.; Reddy, Viswanath; Ramakrishnappa, T.; Nagaraju, Doddahalli H.

    2015-01-01

    Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.

  19. Background synaptic activity in rat entorhinal cortex shows a progressively greater dominance of inhibition over excitation from deep to superficial layers.

    Directory of Open Access Journals (Sweden)

    Stuart David Greenhill

    Full Text Available The entorhinal cortex (EC controls hippocampal input and output, playing major roles in memory and spatial navigation. Different layers of the EC subserve different functions and a number of studies have compared properties of neurones across layers. We have studied synaptic inhibition and excitation in EC neurones, and we have previously compared spontaneous synaptic release of glutamate and GABA using patch clamp recordings of synaptic currents in principal neurones of layers II (L2 and V (L5. Here, we add comparative studies in layer III (L3. Such studies essentially look at neuronal activity from a presynaptic viewpoint. To correlate this with the postsynaptic consequences of spontaneous transmitter release, we have determined global postsynaptic conductances mediated by the two transmitters, using a method to estimate conductances from membrane potential fluctuations. We have previously presented some of this data for L3 and now extend to L2 and L5. Inhibition dominates excitation in all layers but the ratio follows a clear rank order (highest to lowest of L2>L3>L5. The variance of the background conductances was markedly higher for excitation and inhibition in L2 compared to L3 or L5. We also show that induction of synchronized network epileptiform activity by blockade of GABA inhibition reveals a relative reluctance of L2 to participate in such activity. This was associated with maintenance of a dominant background inhibition in L2, whereas in L3 and L5 the absolute level of inhibition fell below that of excitation, coincident with the appearance of synchronized discharges. Further experiments identified potential roles for competition for bicuculline by ambient GABA at the GABAA receptor, and strychnine-sensitive glycine receptors in residual inhibition in L2. We discuss our results in terms of control of excitability in neuronal subpopulations of EC neurones and what these may suggest for their functional roles.

  20. Universal electrode interface for electrocatalytic oxidation of liquid fuels.

    Science.gov (United States)

    Liao, Hualing; Qiu, Zhipeng; Wan, Qijin; Wang, Zhijie; Liu, Yi; Yang, Nianjun

    2014-10-22

    Electrocatalytic oxidations of liquid fuels from alcohols, carboxylic acids, and aldehydes were realized on a universal electrode interface. Such an interface was fabricated using carbon nanotubes (CNTs) as the catalyst support and palladium nanoparticles (Pd NPs) as the electrocatalysts. The Pd NPs/CNTs nanocomposite was synthesized using the ethylene glycol reduction method. It was characterized using transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, voltammetry, and impedance. On the Pd NPs/CNTs nanocomposite coated electrode, the oxidations of those liquid fuels occur similarly in two steps: the oxidations of freshly chemisorbed species in the forward (positive-potential) scan and then, in the reverse scan (negative-potential), the oxidations of the incompletely oxidized carbonaceous species formed during the forward scan. The oxidation charges were adopted to study their oxidation mechanisms and oxidation efficiencies. The oxidation efficiency follows the order of aldehyde (formaldehyde) > carboxylic acid (formic acid) > alcohols (ethanol > methanol > glycol > propanol). Such a Pd NPs/CNTs nanocomposite coated electrode is thus promising to be applied as the anode for the facilitation of direct fuel cells.

  1. Electrocatalytic upgrading of biomass pyrolysis oils to chemical and fuel

    Science.gov (United States)

    Lam, Chun Ho

    The present project's aim is to liquefy biomass through fast pyrolysis and then upgrade the resulting "bio-oil" to renewable fuels and chemicals by intensifying its energy content using electricity. This choice reflects three points: (a) Liquid hydrocarbons are and will long be the most practical fuels and chemical feedstocks because of their energy density (both mass and volume basis), their stability and relative ease of handling, and the well-established infrastructure for their processing, distribution and use; (b) In the U.S., the total carbon content of annually harvestable, non-food biomass is significantly less than that in a year's petroleum usage, so retention of plant-captured carbon is a priority; and (c) Modern technologies for conversion of sunlight into usable energy forms---specifically, electrical power---are already an order of magnitude more efficient than plants are at storing solar energy in chemical form. Biomass fast pyrolysis (BFP) generates flammable gases, char, and "bio-oil", a viscous, corrosive, and highly oxygenated liquid consisting of large amounts of acetic acid and water together with hundreds of other organic compounds. With essentially the same energy density as biomass and a tendency to polymerize, this material cannot practically be stored or transported long distances. It must be upgraded by dehydration, deoxygenation, and hydrogenation to make it both chemically and energetically compatible with modern vehicles and fuels. Thus, this project seeks to develop low cost, general, scalable, robust electrocatalytic methods for reduction of bio-oil into fuels and chemicals.

  2. Electrocatalytic oxidation of cellulose at a gold electrode.

    Science.gov (United States)

    Sugano, Yasuhito; Latonen, Rose-Marie; Akieh-Pirkanniemi, Marceline; Bobacka, Johan; Ivaska, Ari

    2014-08-01

    The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Formation, Characteristics and Electrocatalytic Properties of Nanoporous Metals Formed by Dealloying of Ternary-Noble Alloys

    Science.gov (United States)

    Vega Zuniga, Adrian A.

    Nanoporous metals formed by electrochemical dealloying of silver from Ag-Au-Pt alloys, with 77 at.% silver and platinum contents of 1, 2 and 3 at.%, have been studied. The presence of platinum, which is immobile relative to gold, refine the ligament size and stabilized the nanostructure against coarsening, even under experimental conditions that would be expected to promote coarsening (e.g., exposure to high temperature, longer dealloying times). By adding only 1 at.% Pt to the alloy precursor, the ligament/pore size was reduced by 50% with respect to that in nanoporous gold (NPG), which was formed on a Ag-Au alloy with the same silver content as ternary alloys. A further decrease in the ligament size was observed by increasing the platinum content of the precursor; however, most of the improvement occurred with 1 at.% Pt. The adsorbate-induced surface segregation of platinum was also investigated for these nanoporous metals. By exposing freshly-dealloyed nanostructures to moderate temperatures in the presence of air, platinum segregated to the ligament surface; in contrast, in an inert atmosphere (Ar-H 2), platinum mostly reverted to the bulk of the ligaments. This thermally activated process was thermodynamically driven by the interaction between platinum and oxygen; however, at the desorption temperature of oxygen, platinum de-segregated from the surface. Moreover, the co-segregation of platinum and oxygen hindered the thermal coarsening of the ligaments. Finally, the electrocatalytic abilities of these nanostructures were studied towards methanol and ethanol electro-oxidation, in alkaline and acidic media, showing significantly improved response in comparison to that observed in NPG. The synergistic effect between gold and platinum atoms and the smaller feature size of the nanostructures were directly associated with this behaviour. In alkaline electrolyte, the nanostructure formed on the alloy with 1 at.% Pt showed higher catalytic response than the other two

  4. Greater Independence in Activities of Daily Living is Associated with Higher Health-Related Quality of Life Scores in Nursing Home Residents with Dementia

    Directory of Open Access Journals (Sweden)

    Charice S. Chan

    2015-06-01

    Full Text Available Health-related quality of life (HRQL for nursing home residents is important, however, the concept of quality of life is broad, encompasses many domains and is difficult to assess in people with dementia. Basic activities of daily living (ADL are measured routinely in nursing homes using the Resident Assessment Instrument-Minimum Data Set Version 2.0 (RAI-MDS and Functional Independence Measure (FIM instrument. We examined the relationship between HRQL and ADL to assess the future possibility of ADL dependency level serving as a surrogate measure of HRQL in residents with dementia. To assess ADL, measures derived from the RAI-MDS and FIM data were gathered for 111 residents at the beginning of our study and at 6-month follow-up. Higher scores for independence in ADL were correlated with higher scores for a disease-specific HRQL measure, the Quality of Life—Alzheimer’s Disease Scale. Preliminary evidence suggests that FIM-assessed ADL is associated with HRQL for these residents. The associations of the dressing and toileting items with HRQL were particularly strong. This finding suggests the importance of ADL function in HRQL. The RAI-MDS ADL scales should be used with caution to evaluate HRQL.

  5. PRELIMINARY RESULTS OF ATMOSPHERIC DEPOSITION OF MAJOR AND TRACE ELEMENTS IN THE GREATER AND LESSER CAUCASUS MOUNTAINS STUDIED BY THE MOSS TECHNIQUE AND NEUTRON ACTIVATION ANALYSIS

    Directory of Open Access Journals (Sweden)

    S. Shetekauri

    2015-05-01

    Full Text Available The method of moss biomonitoring of atmospheric deposition of trace elements was applied for the first time in the western Caucasus Mountains to assess the environmental situation in this region. The sixteen moss samples have been collected in 2014 summer growth period along altitudinal gradients in the range of altitudes from 600 m to 2665 m. Concentrations of Na, Mg, Al, Cl, K, Ca, Ti, V, Mn, Fe, Zn, As, Br, Rb, Mo, Cd, I, Sb, Ba, La, Sm, W, Au, and U determined by neutron activation analysis in the moss samples are reported. A comparison with the data for moss collected in Norway (pristine area was carried out.  Multivariate statistical analysis of the results was used for assessment pollution sources in the studied part of the Caucasus. The increase in concentrations of most of elements with rising altitude due to gradually disappearing vegetation cover and wind erosion of soil was observed. A comparison with the available data for moss collected in the Alps at the same altitude (~ 2500 m was performed.

  6. Effective Degradation of Aqueous Tetracycline Using a Nano-TiO2/Carbon Electrocatalytic Membrane

    Directory of Open Access Journals (Sweden)

    Zhimeng Liu

    2016-05-01

    Full Text Available In this work, an electrocatalytic membrane was prepared to degrade aqueous tetracycline (TC using a carbon membrane coated with nano-TiO2 via a sol-gel process. SEM, XRD, EDS, and XPS were used to characterize the composition and structure of the electrocatalytic membrane. The effect of operating conditions on the removal rate of tetracycline was investigated systematically. The results show that the chemical oxygen demand (COD removal rate increased with increasing residence time while it decreased with increasing the initial concentration of tetracycline. Moreover, pH had little effect on the removal of tetracycline, and the electrocatalytic membrane could effectively remove tetracycline with initial concentration of 50 mg·L−1 (pH, 3.8–9.6. The 100% tetracycline and 87.8% COD removal rate could be achieved under the following operating conditions: tetracycline concentration of 50 mg·L−1, current density of 1 mA·cm−2, temperature of 25 °C, and residence time of 4.4 min. This study provides a new and feasible method for removing antibiotics in water with the synergistic effect of electrocatalytic oxidation and membrane separation. It is evident that there will be a broad market for the application of electrocatalytic membrane in the field of antibiotic wastewater treatment.

  7. Synthesis of Platinum-Nickel Hydroxide Nanocomposites for Electrocatalytic Reduction of Water

    KAUST Repository

    Wang, Lei

    2016-11-25

    Water electrolysis represents a promising solution for storage of renewable but intermittent electrical energy in hydrogen molecules. This technology is however challenged by the lack of efficient electrocatalysts for the hydrogen and oxygen evolution reactions. Here we report on the synthesis of platinum-nickel hydroxide nanocomposites and their electrocatalytic applications for water reduction. An in situ reduction strategy taking advantage of the Ni(II)/Ni(III) redox has been developed to enable and regulate the epitaxial growth of Pt nanocrystals on single-layer Ni(OH)2 nanosheets. The obtained nanocomposites (denoted as Pt@2D-Ni(OH)2) exhibit an improvement factor of 5 in catalytic activity and a reduction of up to 130 mV in overpotential compared to Pt for the hydrogen evolution reaction (HER). A combination of electron microscopy/spectroscopy characterization, electrochemical studies and density functional calculations was employed to uncover the structures of the metal-hydroxide interface and understand the mechanisms of catalytic enhancement.

  8. Enhanced electrocatalytic oxidation of isoniazid at electrochemically modified rhodium electrode for biological and pharmaceutical analysis.

    Science.gov (United States)

    Cheemalapati, Srikanth; Chen, Shen-Ming; Ali, M Ajmal; Al-Hemaid, Fahad M A

    2014-09-01

    A simple and sensitive electrochemical method has been proposed for the determination of isoniazid (INZ). For the first time, rhodium (Rh) modified glassy carbon electrode (GCE) has been employed for the determination of INZ by linear sweep voltammetry technique (LSV). Compared with the unmodified electrode, the proposed Rh modified electrode provides strong electrocatalytic activity toward INZ with significant enhancement in the anodic peak current. Scanning electron microscopy (SEM) and field emission scanning electron microscopy (FESEM) results reveal the morphology of Rh particles. With the advantages of wide linearity (70-1300μM), good sensitivity (0.139μAμM(-1)cm(-2)) and low detection limit (13μM), this proposed sensor holds great potential for the determination of INZ in real samples. The practicality of the proposed electrode for the detection of INZ in human urine and blood plasma samples has been successfully demonstrated using LSV technique. Through the determination of INZ in commercially available pharmaceutical tablets, the practical applicability of the proposed method has been validated. The recovery results are found to be in good agreement with the labeled amounts of INZ in tablets, thus showing its great potential for use in clinical and pharmaceutical analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Characterization and electrocatalytic properties of sonochemical synthesized PdAg nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Godinez-Garcia, Andres, E-mail: agodinez@qro.cinvestav.mx [Depto. Materiales, Centro de Investigacion y de Estudios Avanzados del IPN, Libramiento norponiente 2000, Fracc. Real de Juriquilla, C.P. 76230 Santiago de Queretaro, Qro. (Mexico); Perez-Robles, Juan Francisco [Depto. Materiales, Centro de Investigacion y de Estudios Avanzados del IPN, Libramiento norponiente 2000, Fracc. Real de Juriquilla, C.P. 76230 Santiago de Queretaro, Qro. (Mexico); Martinez-Tejada, Hader Vladimir [Grupo de Energia y Termodinamica, Universidad Pontificia Bolivariana, Medellin, Antioquia C.P. 050031 (Colombia); Solorza-Feria, Omar [Depto. Quimica, CINVESTAV-IPN, Av. IPN 2508, A. P. 14-740, 07360 D.F. Mexico (Mexico)

    2012-06-15

    High intensity ultrasound was used in the synthesis of PdAg nanoparticles. PdAg nanoparticles were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS), scanning transmission electron microscopy (STEM) and high-resolution transmission electron microscopy (HRTEM). Catalytic properties for oxygen reduction reaction (ORR) were determined by electrochemical techniques of cyclic voltammetry (CV) and thin-film rotating disk electrode (TF-RDE). Finally the electrocatalyst was tested as a cathode in a single polymer electrolyte membrane fuel cell (PEMFC). Sonochemical synthesis (SS) decreased the overpotential required for the ORR and increased the double-layer capacitance (DLC) respect to the sodium borohydride reduction method due to a better distribution on vulcan carbon support. The electrocatalytic activity of the nanometric bimetallic electrocatalyst for the ORR in acid media showed a favorable multielectron charge transfer process (n = 4e{sup -}) to water formation. The performance of the membrane electrode assembly (MEA) prepared with dispersed PdAg/C as a cathode catalyst in a single PEMFC is lower in comparison to platinum. - Highlights: Black-Right-Pointing-Pointer Sonochemical synthesized PdAg nanoparticles supported on carbon were produced. Black-Right-Pointing-Pointer The material showed catalytic properties for the oxygen reduction reaction (ORR). Black-Right-Pointing-Pointer The ORR favored the pathway to water formation.

  10. Electrocatalytic oxidation of alcohols on single gold particles in highly ordered SiO2 cavities

    International Nuclear Information System (INIS)

    Li, Na; Zhou, Qun; Tian, Shu; Zhao, Hong; Li, Xiaowei; Adkins, Jason; Gu, Zhuomin; Zhao, Lili; Zheng, Junwei

    2013-01-01

    In the present work, we report a new and simple approach for preparing a highly ordered Au (1 1 1) nanoparticle (NP) array in SiO 2 cavities on indium-doped tin oxide (ITO) electrodes. We fabricated a SiO 2 cavity array on the surface of an ITO electrode using highly ordered self-assembly of polystyrene spheres as a template. Gold NPs were electrodeposited at the bottom of the SiO 2 cavities, and single gold NPs dominated with (1 1 1) facets were generated in each cavity by annealing the electrode at a high temperature. Such (1 1 1) facets were the predominate trait of the single gold particle which exhibited considerable electrocatalytic activity toward oxidation of methanol, ethanol, and glycerol. This has been attributed to the formation of incipient hydrous oxides at unusually low potential on the specific (1 1 1) facet of the gold particles. Moreover, each cavity of the SiO 2 possibly behaves as an independent electrochemical cell in which the methanol molecules are trapped; this produces an environment advantageous to catalyzing electrooxidation. The oxidation of methanol on the electrodes is a mixed control mechanism (both by diffusion and electrode kinetics). This strategy both provided an approach to study electrochemical reactions on a single particle in a microenvironment and may supply a way to construct alcohols sensors

  11. Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

    Directory of Open Access Journals (Sweden)

    Mingyan Wang

    2017-07-01

    Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

  12. Synthesis of Platinum-Nickel Hydroxide Nanocomposites for Electrocatalytic Reduction of Water

    KAUST Repository

    Wang, Lei; Zhu, Yihan; Zeng, Zhenhua; Lin, Chong; Giroux, Michael; Jiang, Lin; Han, Yu; Greeley, Jeffrey; Wang, Chao; Jin, Jian

    2016-01-01

    Water electrolysis represents a promising solution for storage of renewable but intermittent electrical energy in hydrogen molecules. This technology is however challenged by the lack of efficient electrocatalysts for the hydrogen and oxygen evolution reactions. Here we report on the synthesis of platinum-nickel hydroxide nanocomposites and their electrocatalytic applications for water reduction. An in situ reduction strategy taking advantage of the Ni(II)/Ni(III) redox has been developed to enable and regulate the epitaxial growth of Pt nanocrystals on single-layer Ni(OH)2 nanosheets. The obtained nanocomposites (denoted as Pt@2D-Ni(OH)2) exhibit an improvement factor of 5 in catalytic activity and a reduction of up to 130 mV in overpotential compared to Pt for the hydrogen evolution reaction (HER). A combination of electron microscopy/spectroscopy characterization, electrochemical studies and density functional calculations was employed to uncover the structures of the metal-hydroxide interface and understand the mechanisms of catalytic enhancement.

  13. Electrodeposition of palladium and reduced graphene oxide nanocomposites on foam-nickel electrode for electrocatalytic hydrodechlorination of 4-chlorophenol

    International Nuclear Information System (INIS)

    Liu, Yong; Liu, Lan; Shan, Jun; Zhang, Jingdong

    2015-01-01

    Highlights: • Pd and reduced graphene oxide are deposited on foam-Ni via electrodeposition. • Pd particles supported on RGO possess large active surface area. • Pd/RGO/foam-Ni shows high electrocatalytic activity for dechlorination of 4-CP. • 100% 4-CP can be removed on Pd/RGO/foam-Ni under optimum ECH conditions. - Abstract: A high-performance palladium (Pd) and reduced graphene oxide (RGO) composite electrode was prepared on foam-nickel (foam-Ni) via two-step electrodeposition processes. The scanning electron microscopic (SEM) observation showed that the obtained Pd/RGO/foam-Ni composite electrode displayed a uniform and compact morphology. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopic (XPS) analysis confirmed the successful deposition of Pd and RGO on nickel substrate. The cyclic voltammetric (CV) measurements indicated that the presence of RGO greatly enhanced the active surface area of Pd particles deposited on foam-Ni. The as-deposited Pd/RGO/foam-Ni electrode was applied to electrocatalytic hydrodechlorination (ECH) of 4-chlorophenol (4-CP). Various factors influencing the dechlorination of 4-CP such as dechlorination current, initial concentration of 4-CP, Na 2 SO 4 concentration and initial pH were systematically investigated. The thermodynamic analysis showed that the dechlorination reaction of 4-CP at different temperatures followed the first-order kinetics and the activation energy for 4-CP dechlorination on Pd/RGO/foam-Ni electrode was calculated to be 51.96 kJ mol −1 . Under the optimum conditions, the dechlorination efficiency of 4-CP could reach 100% after 60-min ECH treatment. Moreover, the prepared Pd/RGO/foam-Ni composite electrode showed good stability for recycling utilization in ECH of 4-CP

  14. Self-assembly of hollow MoS{sub 2} microflakes by one-pot hydrothermal synthesis for efficient electrocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Aishi; Cui, Renjie; He, Yanna; Wang, Qi [Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023 (China); Zhang, Jian, E-mail: iamjzhang@njupt.edu.cn [Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023 (China); Yang, Jianping [School of Science, Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 (China); Li, Xing’ao, E-mail: lxahbmy@126.com [Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023 (China); School of Science, Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 (China)

    2017-07-31

    Highlights: • A new hollow MoS{sub 2} microflakes are prepared by hydrothermal synthesis firstly. • SEM and TEM study show the structural nature of hollow microflakes in depth. • The unique hollow structures have large surface area owing to the cavity. • The hollow microflakes show better HER performance than their solid counterparts. - Abstract: Molybdenum disulfide (MoS{sub 2}) has emerged as a promising non-precious metal catalyst for hydrogen evolution reaction (HER) in recent years. Some strategies including nanotechnology as well as atom doping have been employed in the preparing of electrocatalysts for high-activity and stability. To the best of our knowledge, hollow MoS{sub 2} microflakes assembled from ultrathin nanosheets have not been prepared previously. In this work, a simple, facile and environmentally friendly hydrothermal synthesis was utilized for the fabrication of hollow MoS{sub 2} microflakes for the first time. The unique hollow structures have fascinating properties, such as the large surface and low density. The morphology and structure of MoS{sub 2} microflakes were confirmed by XRD, SEM, TEM and Raman. The composition of these materials was identified by the X-ray photoelectron spectroscopy. Notably, the as-prepared hollow MoS{sub 2} microflakes showed better electrocatalytic activity than other samples. The hollow flake-like structure can not only increase the active edge sites owing to the large specific surface area, but also enhance the electron transport to improve the electrocatalytic activity. Benefiting from these factors, the hollow MoS{sub 2} microflakes exhibited electrocatalytic activity and excellent stability with a low overpotential about 85 mV and a Tafel slope of 59 mV per decade.

  15. Towards versatile and sustainable hydrogen production via electrocatalytic water splitting: Electrolyte engineering

    KAUST Repository

    Shinagawa, Tatsuya

    2016-12-17

    Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. The electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances where water splitting reaction is conducted, required solution conditions such as the identity and molarity of ions may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate developing efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), electrode stability, and/or indirectly impacts the performance by influencing concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions.

  16. Towards versatile and sustainable hydrogen production via electrocatalytic water splitting: Electrolyte engineering

    KAUST Repository

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    2016-01-01

    Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. The electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances where water splitting reaction is conducted, required solution conditions such as the identity and molarity of ions may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate developing efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), electrode stability, and/or indirectly impacts the performance by influencing concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions.

  17. Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

    Directory of Open Access Journals (Sweden)

    Motoko Harada, Hidenori Noguchi, Nikolas Zanetakis, Satoru Takakusagi, Wenbo Song and Kohei Uosaki

    2011-01-01

    Full Text Available Multilayers of gold nanoclusters (GNCs coated with a thin Pd layer were constructed using GNCs modified with self-assembled monolayers (SAMs of mercaptoundecanoic acid and a polyallylamine hydrochloride (PAH multilayer assembly, which has been reported to act as a three-dimensional electrode. SAMs were removed from GNCs by electrochemical anodic decomposition and then a small amount of Pd was electrochemically deposited on the GNCs. The kinetics of the oxygen reduction reaction (ORR on the Pd modified GNC/PAH multilayer assembly was studied using a rotating disk electrode, and a significant increase in the ORR rate was observed after Pd deposition. Electrocatalytic activities in alkaline and acidic solutions were compared both for the GNC multilayer electrode and Pd modified GNC electrode.

  18. Unexpected effect of drying method on the microstructure and electrocatalytic properties of bentonite/alpha-nickel hydroxide nanocomposite

    Science.gov (United States)

    Nunes, Cícero V.; Danczuk, Marins; Bortoti, Andressa A.; Gonçalves, Josué M.; Araki, Koiti; Anaissi, Fauze J.

    2015-11-01

    The degree of crystallinity, morphology and electrochemical properties of a nanocomposite formed by stabilized alpha-Ni(OH)2 nanoparticles and bentonite nanoflakes is strongly influenced by the vacuum drying process, either at room temperature or by freeze-drying (lyophilization). Alpha-Ni(OH)2 nanoparticles induced the formation of intercalation nanocomposites exhibiting higher structural organization than in the precursor clay. Also, lyophilization process preserved the structure of the nanocomposites in aqueous suspension and/or induced the disaggregation of nanoflakes, producing materials with lower degree of crystallinity, larger interlamellar distances and electrochemically more active than those obtained by conventional vacuum drying. In fact, the lyophilized materials exhibited more than twice as large density of current for electrocatalytic oxidation of methanol (37 against 14 mA cm-2) indicating its potentiality for development of sensors and fuel cells.

  19. Improving the electrocatalytic properties of Pd-based catalyst for direct alcohol fuel cells: effect of solid solution.

    Science.gov (United States)

    Wen, Cuilian; Wei, Ying; Tang, Dian; Sa, Baisheng; Zhang, Teng; Chen, Changxin

    2017-07-07

    The tolerance of the electrode against the CO species absorbed upon the surface presents the biggest dilemma of the alcohol fuel cells. Here we report for the first time that the inclusion of (Zr, Ce)O 2 solid solution as the supporting material can significantly improve the anti-CO-poisoning as well as the activity of Pd/C catalyst for ethylene glycol electro-oxidation in KOH medium. In particular, the physical origin of the improved electrocatalytic properties has been unraveled by first principle calculations. The 3D stereoscopic Pd cluster on the surface of (Zr, Ce)O 2 solid solution leads to weaker Pd-C bonding and smaller CO desorption driving force. These results support that the Pd/ZrO 2 -CeO 2 /C composite catalyst could be used as a promising effective candidate for direct alcohol fuel cells application.

  20. Electrochemical deposition of gold-platinum alloy nanoparticles on an indium tin oxide electrode and their electrocatalytic applications

    Energy Technology Data Exchange (ETDEWEB)

    Song Yan; Ma Yuting; Wang Yuan [Department of Chemistry, Soochow University, Suzhou, Jiangsu 215123 (China); Di Junwei, E-mail: djw@suda.edu.c [Department of Chemistry, Soochow University, Suzhou, Jiangsu 215123 (China); Tu Yifeng [Department of Chemistry, Soochow University, Suzhou, Jiangsu 215123 (China)

    2010-07-01

    Gold-platinum (Au-Pt) hybrid nanoparticles (Au-PtNPs) were successfully deposited on an indium tin oxide (ITO) surface using a direct electrochemical method. The resulting nanoparticles were characterized by scanning electron microscopy (SEM), UV-vis spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), and electrochemical methods. It was found that the size of the Au-PtNPs depends on the number of electrodeposition cycles. Au-PtNPs obtained by 20 electrodeposition cycles had a cauliflower-shaped structure with an average diameter of about 60 nm. These Au-PtNPs exhibited alloy properties. Electrochemical measurements showed that the charge transfer resistivity was significantly decreased for the Au-PtNPs/ITO electrode. Additionally, the Au-PtNPs displayed an electrocatalytic activity for nitrite oxidation and oxygen reduction. The Au-PtNPs/ITO electrodes reported herein could possibly be used as electrocatalysts and sensors.

  1. Electrochemical and Computational Studies on the Electrocatalytic Effect of Conducting Polymers toward the Redox Reactions of Thiadiazole-Based Thiolate Compounds

    KAUST Repository

    Rodríguez-Calero, Gabriel G.

    2010-04-08

    We have studied the electrocatalytic effects of polythiophene-based conducting polymers toward the redox reactions of the dilithium salt of the thiadiazole-based dithiol compound 2,5-dimercapto-1,3,4-thiodiazole (DMcT-2Li) via cyclic voltammetry (CV), rotating-disk electrode voltammetry, and electrochemical impedance spectroscopy (EIS). We have found that the electrocatalytic activity of the conducting polymers is strongly influenced by the potential range over which the polymers are electrically conductive (i.e., window of conductivity), which was tuned by employing different electron-donating groups at the 3- or 3,4-positions of polythiophene (PTh). Both poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), whose windows of conductivity exhibited a good overlap with the formal potential for the dimerization process of DMcT-2Li; E0′ d (?0.54 V versus Ag/Ag+) exhibited electrocatalytic activity toward both the oxidation and reduction processes of DMcT-2Li. On the other hand, PTh, poly(3-methylthiophene) (PMTh), and poly(3,4- dimethoxythiophene) (PDMTh), whose windows of conductivity did not overlap with E0′d, did not exhibit electrocatalytic activity. The standard charge transfer rate constants for the dimerization process of DMcT-2Li at PEDOT, PProDOT, and PDMTh film-modified glassy carbon electrodes (GCEs) were estimated to be 7.4 - 10?4, 3.2 - 10?4, and 6.9 - 10?5 cm/s while the rate constant was 6.3 - 10?5 cm/s at an unmodified GCE. Moreover, EIS studies for PEDOT, PProDOT, and PDMTh film-modified GCEs indicated the smallest charge transfer resistance for a PEDOT film and highest for a PDMTh film at E0′d, indicating that the higher the electrical conductivity of a film at E 0′d the higher the electrocatalytic activity toward the redox reactions of DMcT-2Li. These results clearly indicate that in order to accelerate the redox reactions of DMcT-2Li (and likely of other organosulfur compounds) the window of conductivity

  2. Electrochemical and Computational Studies on the Electrocatalytic Effect of Conducting Polymers toward the Redox Reactions of Thiadiazole-Based Thiolate Compounds

    KAUST Repository

    Rodríguez-Calero, Gabriel G.; Lowe, Michael A.; Kiya, Yasuyuki; Abruña, Héctor D.

    2010-01-01

    We have studied the electrocatalytic effects of polythiophene-based conducting polymers toward the redox reactions of the dilithium salt of the thiadiazole-based dithiol compound 2,5-dimercapto-1,3,4-thiodiazole (DMcT-2Li) via cyclic voltammetry (CV), rotating-disk electrode voltammetry, and electrochemical impedance spectroscopy (EIS). We have found that the electrocatalytic activity of the conducting polymers is strongly influenced by the potential range over which the polymers are electrically conductive (i.e., window of conductivity), which was tuned by employing different electron-donating groups at the 3- or 3,4-positions of polythiophene (PTh). Both poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), whose windows of conductivity exhibited a good overlap with the formal potential for the dimerization process of DMcT-2Li; E0′ d (?0.54 V versus Ag/Ag+) exhibited electrocatalytic activity toward both the oxidation and reduction processes of DMcT-2Li. On the other hand, PTh, poly(3-methylthiophene) (PMTh), and poly(3,4- dimethoxythiophene) (PDMTh), whose windows of conductivity did not overlap with E0′d, did not exhibit electrocatalytic activity. The standard charge transfer rate constants for the dimerization process of DMcT-2Li at PEDOT, PProDOT, and PDMTh film-modified glassy carbon electrodes (GCEs) were estimated to be 7.4 - 10?4, 3.2 - 10?4, and 6.9 - 10?5 cm/s while the rate constant was 6.3 - 10?5 cm/s at an unmodified GCE. Moreover, EIS studies for PEDOT, PProDOT, and PDMTh film-modified GCEs indicated the smallest charge transfer resistance for a PEDOT film and highest for a PDMTh film at E0′d, indicating that the higher the electrical conductivity of a film at E 0′d the higher the electrocatalytic activity toward the redox reactions of DMcT-2Li. These results clearly indicate that in order to accelerate the redox reactions of DMcT-2Li (and likely of other organosulfur compounds) the window of conductivity

  3. The electrocatalytic application of RuO2 in direct borohydride fuel cells

    International Nuclear Information System (INIS)

    Yang, Xiaodong; Wei, Xiaozhu; Liu, Ce; Liu, Yongning

    2014-01-01

    A high electrocatalytic activity of RuO 2 has been found for oxygen reduction reaction (ORR) in the cathode of direct borohydride fuel cells (DBFCs). The electron transfer number n during the ORR changes from 3.58 to 3.86 and the percentage of the intermediate product H 2 O 2 decreases from 20.8% to 7.2% correspondingly when the disk potential scans negatively from −0.39 V to −0.8 V versus Hg/HgO. Peak power densities of 425 mW cm −2 has been obtained at 60 °C, when RuO 2 has been used as a cathodic catalyst in DBFCs. RuO 2 displays low sensitivity to the BH 4 − oxidation in DBFCs. Moreover, RuO 2 , as a cathodic catalyst, demonstrates a superb stability during a 200-h durability test. The identical X-ray diffraction (XRD) patterns of the RuO 2 before and after the durability test also prove its stability. - Highlights: • RuO 2 exhibits oxygen reduction reaction (ORR) activity in an alkaline solution. • RuO 2 provides 3.58–3.86 electron transfer number during the ORR. • Direct borohydride fuel cell (DBFC) with RuO 2 cathode displays a peak power density of 425 mW cm −2 at 60 °C. • DBFC with RuO 2 cathode exhibits a superb stability during a 200-h durability test

  4. The electrocatalytical reduction of m-nitrophenol on palladium nanoparticles modified glassy carbon electrodes

    International Nuclear Information System (INIS)

    Shi Qiaofang; Diao Guowang

    2011-01-01

    Highlights: ► The deposition of palladium on a GC electrode was performed by cyclic voltammetry. ► SEM images showed palladium nanoparticles deposited on a glassy carbon (GC) electrode. ► The Pd/GC electrode can effectively catalyze m-nitrophenol in aqueous media. ► The reduction of m-nitrophenol on the Pd/GC electrode depended on potential and pH. ► XPS spectra of the Pd/GC electrodes demonstrated the presence of palladium. - Abstract: Palladium nanoparticles modified glassy carbon electrodes (Pd/GC) were prepared via the electrodeposition of palladium on a glassy carbon (GC) electrode using cyclic voltammetry in different sweeping potential ranges. The scanning electron microscope images of palladium particles on the GC electrodes indicate that palladium particles with diameters of 20–50 nm were homogeneously dispersed on the GC electrode at the optimal deposition conditions, which can effectively catalyze the reduction of m-nitrophenol in aqueous solutions, but their catalytic activities are strongly related to the deposition conditions of Pd. The X-ray photoelectron spectroscopy spectra of the Pd/GC electrode confirmed that 37.1% Pd was contained in the surface composition of the Pd/GC electrode. The cyclic voltammograms of the Pd/GC electrode in the solution of m-nitrophenol show that the reduction peak of m-nitrophenol shifts towards the more positive potentials, accompanied with an increase in the peak current compared to the bare GC electrode. The electrocatalytic activity of the Pd/GC electrode is affected by pH values of the solution. In addition, the electrolysis of m-nitrophenol under a constant potential indicates that the reduction current of m-nitrophenol on the Pd/GC electrode is approximately 20 times larger than that on the bare GC electrode.

  5. Enhancement of oxidative electrocatalytic properties of platinum nanoparticles by supporting onto mixed WO{sub 3}/ZrO{sub 2} matrix

    Energy Technology Data Exchange (ETDEWEB)

    Rutkowska, Iwona A., E-mail: ilinek@chem.uw.edu.pl; Wadas, Anna; Kulesza, Pawel J., E-mail: pkulesza@chem.uw.edu.pl

    2016-12-01

    Highlights: • The electrocatalytic system utilizing Pt nanoparticles dispersed on mixed metal oxide (WO{sub 3}/ZrO{sub 2}) system is proposed. • The system is characterized by high activity toward oxidations of ethanol, methanol and acetaldehyde in acid medium. • The enhancement effect is facilitated by presence of hydroxyl groups, high mobility of protons and improved distribution of electrons. • Strong interactions between Pt and the mixed oxide WO{sub 3}/ZrO{sub 2} support are postulated. - Abstract: Nanostructured mixed metal (W, Zr) oxide matrices (in a form of layered intercalated films of WO{sub 3} and ZrO{sub 2}) are considered here for supporting and activating catalytic platinum nanoparticles toward electrooxidation of ethanol. Remarkable increases of electrocatalytic (voltammetric, chronoamperometric) currents measured in 0.5 mol dm{sup −3} H{sub 2}SO{sub 4} (containing 0.5 mol dm{sup −3} ethanol) have been observed. Comparison has been made to the behavior of methanol and acetaldehyde under analogous conditions. The enhancement effects are interpreted in terms of specific interactions between platinum nanoparticles and the metal oxide species, high acidity of the mixed oxide sites, as well as high population of surface hydroxyl groups and high mobility of protons existing in close vicinity of Pt catalytic sites. The metal oxide nanostructures are expected to interact competitively (via the surface hydroxyl groups) with adsorbates of the undesirable reaction intermediates, including CO, facilitating their desorption (“third body effect”), or even oxidative removal (e.g., of CO to CO{sub 2}). The fact that the partially reduced tungsten oxide (H{sub x}WO{sub 3}) component is characterized by fast electron transfers coupled to proton displacements tends to improve the overall charge propagation at the electrocatalytic interface.

  6. The influence of nitrate concentrations and acidity on the electrocatalytic reduction of nitrate on platinum

    NARCIS (Netherlands)

    Groot, de M.T.; Koper, M.T.M.

    2004-01-01

    A study was performed to determine the influence of nitrate concentration and acidity on the reaction rate and selectivity of the electrocatalytic nitrate reduction on platinum. There are two different nitrate reduction mechanisms on platinum: a direct mechanism (0.4–0.1 V vs. SHE) and an indirect

  7. Electron transport and electrocatalytic properties of MWCNT/nickel nanocomposites: hydrazine and diethylaminoethanethiol as analytical probes

    CSIR Research Space (South Africa)

    Adekunle, AS

    2010-06-01

    Full Text Available of the electrodes with the Ni and NiO nanoparticles was confirmed by techniques such as FTIR, FESEM, HRSEM, TEM, XRD, EDX and cyclic voltammetry (CV). The electrocatalytic oxidation of DEAET and hydrazine on the modified electrodes was investigated using CV...

  8. Pt nanoparticles embedded on reduced graphite oxide with excellent electrocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Saravanan, Gengan, E-mail: saravanan3che@gmail.com [Central University of Tamil Nadu, Department of Chemistry, Thiruvarur, 610101 (India); Mohan, Subramanian, E-mail: sanjnamohan@yahoo.com [EMFT Division, CSIR-Central Electrochemical Research Institute, Tamilnadu, Karaikudi 630 006 (India)

    2016-11-15

    Graphical abstract: RGO/Nano Pt: This study explore the electrocatalytic oxidation performance of reduced graphite oxide (RGO) anchored with nano Pt. This graphene composite reveal superior electrooxidation performance that is associated with the flexible RGO matrix and the uniform distribution of Pt particles, which enhances surface area, fast electron transfer, uniform particle size distribution; consequently, the RGO matrix provides more stability to Pt particles during electrooxidation process. Display Omitted - Highlights: • Greener electrochemical method applied to prepare well-dispersed Pt-rGO. • Pt-rGO large surface area excellent charge transfer better catalytic activity. • Low-cost highly efficient carbon-based electrodes for direct formic acid fuel cell. • rGO an excellent support to anchor Pt nanoparticles on its surface. • Pt-rGO distinctly enhanced current density towards formic acid electrooxidation. - Abstract: Economically viable electrochemical approach has been developed for the synthesis of Pt nanoparticles through electrodeposition technique on the surface of Reduced Graphite Oxide (RGO). Pt nanoparticles embedded Reduced Graphite Oxide on Glassy Carbon Electrode are employed (Pt-rGO/GCE) for electrooxidation of formic acid. Scanning Electron Microscopy (SEM) image and Transmission Electron Microscopy (TEM) image shows that reduced graphite oxide act as an excellent support to anchor the Pt nanoparticles. Cyclic voltammetry results confirmed that Pt-rGO/GCE enhanced current density as many folds than that of bare platinum electrode for electrooxidation of formic acid. X-ray diffraction (XRD) patterns for Pt-graphene composites illustrate that peaks at 69.15 and 23° for Pt (220) and graphene carbon (002) respectively. {sup 13}C NMR spectrum of the electrochemically reduced graphite oxide resonance contains only one peak at 133 ppm which retains graphitic sp{sup 2} carbon and does not contain any oxygenated carbon and the carbonyl

  9. Metal modified tungsten carbide (WC) for catalytic and electrocatalytic applications

    Science.gov (United States)

    Mellinger, Zachary J.

    that the binding energies for methanol and methoxy as well as ethanol and ethoxy on one monolayer (ML) Pd/WC are more similar to Pd than to WC. This predicts that the ML Pd/WC surface should have catalytic properties more similar to Pd than to WC. Ultra--high vacuum (UHV) experiments were then performed to determine the reaction products and pathways for methanol and ethanol on Pd(111), WC, and Pd/WC surfaces. These studies showed that the WC surface was very active toward the O--H bond cleavage to produce a methoxy intermediate, although WC was also undesirable because it was active for C--O bond scission and less active for the C--H bond scission. Adding Pd on WC enhanced the scission of the C--H bonds of methoxy while removing the C--O bond scission reaction pathway, suggesting a synergistic effect of using Pd/WC as electrocatalysts for methanol and ethanol decomposition. Dissociation of water, which is important for CO tolerance, was also investigated using UHV techniques with the conclusion that both the WC and Pd/WC surfaces dissociated water. The predictions from UHV studies was verified in electrochemical experiments using cyclic voltammetry (CV) and chronoamperometry (CA) measurements of electro--oxidation of methanol and ethanol in an alkaline environment. These experiments showed that Pd/WC was electrochemically active towards methanol and ethanol decomposition and has greater electrochemical stability over time than pure Pd, potentially due to higher CO tolerance for Pd/WC.

  10. Graphene Quantum Dots Electrochemistry and Sensitive Electrocatalytic Glucose Sensor Development

    Directory of Open Access Journals (Sweden)

    Sanju Gupta

    2017-09-01

    Full Text Available Graphene quantum dots (GQDs, derived from functionalized graphene precursors are graphene sheets a few nanometers in the lateral dimension having a several-layer thickness. They are zero-dimensional materials with quantum confinement and edge site effects. Intense research interest in GQDs is attributed to their unique physicochemical phenomena arising from the sp2-bonded carbon nanocore surrounded with edged plane functional moieties. In this work, GQDs are synthesized by both solvothermal and hydrothermal techniques, with the optimal size of 5 nm determined using high-resolution transmission electron microscopy, with additional UV-Vis absorption and fluorescence spectroscopy, revealing electronic band signatures in the blue-violet region. Their potential in fundamental (direct electron transfer and applied (enzyme-based glucose biosensor electrochemistry has been practically realized. Glucose oxidase (GOx was immobilized on glassy carbon (GC electrodes modified with GQDs and functionalized graphene (graphene oxide and reduced form. The cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy are used for characterizing the direct electron transfer kinetics and electrocatalytical biosensing. The well-defined quasi-reversible redox peaks were observed under various electrochemical environment and conditions (pH, concentration, scan rate to determine the diffusion coefficient (D and first-order electron transfer rate (kET. The cyclic voltammetry curves showed homogeneous ion transport behavior for GQD and other graphene-based samples with D ranging between 8.45 × 10−9 m2 s−1 and 3 × 10−8 m2 s−1 following the order of GO < rGO < GQD < GQD (with FcMeOH as redox probe < GOx/rGO < GOx/GO < HRP/GQDs < GOx/GQDs. The developed GOx-GQDs biosensor responds efficiently and linearly to the presence of glucose over concentrations ranging between 10 μM and 3 mM with a limit of detection of 1.35 μM and

  11. Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Pengcheng; Zhou, Yingke, E-mail: zhouyk888@hotmail.com; Hu, Min; Chen, Jian

    2017-01-15

    Highlights: • Nitrogen-doped carbon nanotube supporting ultrafine NiO nanoparticles with high dispersity are facile synthesized. • The nitrogen doping, calcination temperature and NiO loading present great effects on the catalyst morphology, structure and electrochemical performance. • NiO-NCNT-3x-400 demonstrates remarkable catalytic activity and stability for the methanol electrolytic oxidation reaction. - Abstract: Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

  12. Preparation of three-dimensional porous Cu film supported on Cu foam and its electrocatalytic performance for hydrazine electrooxidation in alkaline medium

    International Nuclear Information System (INIS)

    Liu, Ran; Ye, Ke; Gao, Yinyi; Long, Ziyao; Cheng, Kui; Zhang, Wenping; Wang, Guiling; Cao, Dianxue

    2016-01-01

    Highlights: • A binder-free Cu/Cu foam electrode is prepared by an electrochemical method. • The electrode owns a novel three-dimensional porous structure. • The electrode exhibits superior catalytic activity for hydrazine electrooxidation. - Abstract: A three-dimensional porous copper film is directly deposited on Cu foam by an electrodeposition method using hydrogen bubbles as dynamic template (denoted as Cu/Cu foam). Its electrocatalytic activity toward hydrazine electrooxidation is tested by linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Compared with Cu foam, hydrazine electrooxidation on the Cu/Cu foam electrode shows that the onset oxidation potential displays a ~100 mV negative shift, the current density at −0.6 V raises about 14 times, the apparent activation energy and the charge transfer resistance reduce significantly. The increasing electrocatalytic performance for hydrazine electrooxidation is mainly caused by the highly porous structure of the Cu/Cu foam electrode which can provide a large surface area and make electrolyte access the electrocatalyst surfaces more easily. Hydrazine electrooxidation on the Cu/Cu foam electrode proceeds through a near 4-electron process.

  13. Fabrication of graphene-fullerene hybrid by self-assembly and its application as support material for methanol electrocatalytic oxidation reaction

    Science.gov (United States)

    Zhang, Xuan; Zhang, Jia-Wei; Xiang, Ping-Hua; Qiao, Jinli

    2018-05-01

    Graphene-fullerene hybrids were facilely fabricated by self-assembly of graphene oxide (GO) and multi-substituted fulleropyrrolidines (PyrC60). The hybrids (GO-PyrC60) were applied as support materials to deposit Pd nanoparticle catalyst by a simple hydrothermal co-reduction approach. The as-prepared electrocatalysts (Pd/RGO-PyrC60) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. The RGO-PyrC60 hybrid supported Pd catalyst with the optimal ratio of RGO to PyrC60, exhibited much enhanced electrocatalytic activity and stability toward methanol oxidation reaction (MOR) compared to the RGO alone supported Pd as well as commercial Pd/C. The introduction of fulleropyrrolidine as spacer between graphene layers could increase the electrocatalytic activity and improve the long-term stability. This strategy may contribute to developing graphene-fullerene hydrids as effective support materials for advanced electrocatalysts.

  14. Greater Leisure Time Physical Activity Is Associated with Lower Allostatic Load in White, Black, and Mexican American Midlife Women: Findings from the National Health and Nutrition Examination Survey, 1999 through 2004.

    Science.gov (United States)

    Upchurch, Dawn M; Rainisch, Bethany Wexler; Chyu, Laura

    2015-01-01

    Allostatic load is a useful construct to understand how social and environmental conditions get under the skin to affect health. To date, few studies have examined health-enhancing lifestyle behaviors and their potential benefits in reducing allostatic load. The purpose of this study was to investigate the contributions of leisure time physical activity on level of allostatic load among White, Black, and Mexican American midlife women. Data were from the National Health and Nutrition Examination Survey, 1999 through 2004 (n = 1,680, women ages 40-59). All analyses were weighted. Negative binomial regression was used to model a summative count measure of allostatic load (M = 2.30). Models were also computed to estimate adjusted predicted allostatic load for given levels of physical activity, and by race/ethnicity for each age category (40-44, 45-49, 50-54, 55-59), controlling for other demographics and medication use. Higher levels of physical activity were associated significantly with lower levels of allostatic load, independent of demographics. Compared with White women ages 40 to 44, all other racial/ethnic-by-age groups had significantly higher allostatic load. Higher socioeconomic status was associated with a lower allostatic load. Adjusted prediction models demonstrated associations between greater levels of physical activity and lower allostatic load for all ages and racial/ethnic groups. Our findings suggest physical activity may ameliorate some of the effects of cumulative physiological dysregulation and subsequent disease burden in midlife women. Programs and policies that encourage and promote healthy aging and provide opportunities for a diversity of women to engage in health-enhancing lifestyle practices such as physical activity are recommended. Copyright © 2015 Jacobs Institute of Women's Health. Published by Elsevier Inc. All rights reserved.

  15. Synthesis and Electrocatalytic Performance of Multi-Component Nanoporous PtRuCuW Alloy for Direct Methanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    Xiaoting Chen

    2015-06-01

    Full Text Available We have prepared a multi-component nanoporous PtRuCuW (np-PtRuCuW electrocatalyst via a combined chemical dealloying and mechanical alloying process. The X-ray diffraction (XRD, transmission electron microscopy (TEM and electrochemical measurements have been applied to characterize the microstructure and electrocatalytic activities of the np-PtRuCuW. The np-PtRuCuW catalyst has a unique three-dimensional bi-continuous ligament structure and the length scale is 2.0 ± 0.3 nm. The np-PtRuCuW catalyst shows a relatively high level of activity normalized to mass (467.1 mA mgPt−1 and electrochemically active surface area (1.8 mA cm−2 compared to the state-of-the-art commercial PtC and PtRu catalyst at anode. Although the CO stripping peak of np-PtRuCuW 0.47 V (vs. saturated calomel electrode, SCE is more positive than PtRu, there is a 200 mV negative shift compared to PtC (0.67 V vs. SCE. In addition, the half-wave potential and specific activity towards oxygen reduction of np-PtRuCuW are 0.877 V (vs. reversible hydrogen electrode, RHE and 0.26 mA cm−2, indicating a great enhancement towards oxygen reduction than the commercial PtC.

  16. Clean hydrogen generation through the electrocatalytic oxidation of ethanol in a Proton Exchange Membrane Electrolysis Cell (PEMEC): Effect of the nature and structure of the catalytic anode

    Science.gov (United States)

    Lamy, Claude; Jaubert, Thomas; Baranton, Stève; Coutanceau, Christophe

    2014-01-01

    The electrocatalytic oxidation of ethanol was investigated in a Proton Exchange Membrane Electrolysis Cell (PEMEC) working at low temperature (20°C) on several Pt-based catalysts (Pt/C, PtSn/C, PtSnRu/C) in order to produce very clean hydrogen by electrolysis of a biomass compound. The electrocatalytic activity was determined by cyclic voltammetry and the rate of hydrogen evolution was measured for each catalyst at different current densities. The cell voltages UEtOH were recorded as a function of time for each current density. At 100 mA cm-2, i.e. 0.5 A with the 5 cm2 surface area PEMEC used, the cell voltage did not exceed 0.9 V for an evolution rate of about 220 cm3 of hydrogen per hour and the electrical energy consumed was less than 2.3 kWh (Nm3)-1, i.e. less than one half of the energy needed for water electrolysis (4.7 kWh (Nm3)-1 at UH2O = 2 V). This result is valid for the decomposition of any organic compound, particularly those originated from biomass resource, provided that their electro-oxidation rate is sufficient (>100 mA cm-2) at a relatively low cell voltage (Ucell < 1 V) which necessitates the development of efficient electrocatalysts for the electrochemical decomposition of this compound.

  17. Electrografting of N’,N’-dimethylphenothiazin-5-ium-3,7-diamine (Azure A) diazonium salt forming electrocatalytic organic films on gold or graphene oxide gold hybrid electrodes

    International Nuclear Information System (INIS)

    Gómez-Anquela, C.; Revenga-Parra, M.; Abad, J.M.; Marín, A. García; Pau, J.L.; Pariente, F.; Piqueras, J.; Lorenzo, E.

    2014-01-01

    Electroactive films containing redox active phenothiazine moieties are covalently bound onto gold and graphene oxide gold hybrid electrodes, using reductive redox grafting of N’,N’-dimethylphenothiazin-5-ium-3,7-diamine (Azure A) diazonium salt. The grafting procedure is based on continuous voltammetric potential sweep of solutions containing the phenothiazine diazonium salt previously generated in situ. Control of the film thickness, electroactivity and stability can easily be exerted through appropriate choice of the concentration and number of potential scans performed. Cyclic Voltammetry, Electrochemical Quartz Crystal Microbalance (EQCM) and Spectroscopic Ellipsometry are used to characterize the growth process as well as the viscoelastic properties of the resulting stable electrografted films. The electron transfer reactions through the films are mediated by the presence of the Azure A redox moieties, which show a quasi-reversible electrochemical response and exhibit a potent electrocatalytic effect toward the oxidation of NADH. This electrocatalytic model has been used to compare the properties of Azure A electrografted films generated on gold electrodes with those obtained on hybrid electrodes composed by graphene oxide modified gold electrodes

  18. Manganese catalysts with bulky bipyridine ligands for the electrocatalytic reduction of carbon dioxide: eliminating dimerization and altering catalysis.

    Science.gov (United States)

    Sampson, Matthew D; Nguyen, An D; Grice, Kyle A; Moore, Curtis E; Rheingold, Arnold L; Kubiak, Clifford P

    2014-04-09

    With the goal of improving previously reported Mn bipyridine electrocatalysts in terms of increased activity and reduced overpotential, a bulky bipyridine ligand, 6,6'-dimesityl-2,2'-bipyridine (mesbpy), was utilized to eliminate dimerization in the catalytic cycle. Synthesis, electrocatalytic properties, X-ray diffraction (XRD) studies, and infrared spectroelectrochemistry (IR-SEC) of Mn(mesbpy)(CO)3Br and [Mn(mesbpy)(CO)3(MeCN)](OTf) are reported. Unlike previously reported Mn bipyridine catalysts, these Mn complexes exhibit a single, two-electron reduction wave under nitrogen, with no evidence of dimerization. The anionic complex, [Mn(mesbpy)(CO)3](-), is formed at 300 mV more positive potential than the corresponding state is formed in typical Mn bipyridine catalysts. IR-SEC experiments and chemical reductions with KC8 provide insights into the species leading up to the anionic state, specifically that both the singly reduced and doubly reduced Mn complexes form at the same potential. When formed, the anionic complex binds CO2 with H(+), but catalytic activity does not occur until a ~400 mV more negative potential is present. The Mn complexes show high activity and Faradaic efficiency for CO2 reduction to CO with the addition of weak Brønsted acids. IR-SEC experiments under CO2/H(+) indicate that reduction of a Mn(I)-CO2H catalytic intermediate may be the cause of this unusual "over-reduction" required to initiate catalysis.

  19. Multistage electrodeposition of supported platinum-based nanostructured systems for electrocatalytic applications

    CSIR Research Space (South Africa)

    Mkwizu, TS

    2011-05-01

    Full Text Available .R. Modibedi and Mkhulu K. Mathe* *kmathe@csir.co.za 219th ECS Meeting, 1 ? 6 May, 2011, Montreal, Canada Multistage Electrodeposition of Supported Platinum-based Nanostructured Systems for Electrocatalytic Applications Overview ? Acknowledgements... of constituent elements of the given electrode surface. ? Applications areas: Fuel cells, electrochemical sensors, electrolyzers Introduction e- A B 5 Introduction Atomic-level processes during electrocatalysis www...

  20. Electrocatalytic Determination of Isoniazid by a Glassy Carbon Electrode Modified with Poly (Eriochrome Black T)

    OpenAIRE

    Karim Asadpour-Zeynali; Venus Baghalabadi

    2017-01-01

    In this work poly eriochrome black T (EBT) was electrochemically synthesized on the glassy carbon electrode as electrode modifier. On the modified electrode, voltammetric behavior of isoniazid (INH) was investigated. The poly (EBT)-modified glassy carbon electrode has excellent electrocatalytic ability for the electrooxidation of isoniazid. This fact was appeared as a reduced overpotential of INH oxidation in a wide operational pH range from 2 to 13. It has been found that the catalytic peak ...

  1. Quantifying the Electrocatalytic Turnover of Vitamin B12-Mediated Dehalogenation on Single Soft Nanoparticles.

    Science.gov (United States)

    Cheng, Wei; Compton, Richard G

    2016-02-12

    We report the electrocatalytic dehalogenation of trichloroethylene (TCE) by single soft nanoparticles in the form of Vitamin B12 -containing droplets. We quantify the turnover number of the catalytic reaction at the single soft nanoparticle level. The kinetic data shows that the binding of TCE with the electro-reduced vitamin in the Co(I) oxidation state is chemically reversible. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Study of reactivities of electro-catalytic oxidation of organic substrates with Ru(IV) complex

    International Nuclear Information System (INIS)

    Madurro, J.M.; Oliveira, S.M. de; Campos, J.L.

    1988-01-01

    An electrocatalytic procedure for the oxidation of olefines, ketones, heterocycles and ethers using the Ru IV oxidant RuO (bpy) (trpy) 2+ (bpy is 2,2 - bipyridine; trpy is 2,2', 2''' - terpyridine), is described. The relative reactivities of the substrates are determined by analysis of the exponential i x t curves, using simple linear and exponential least-square programme. Mechanistics considerations based on the observed relative reactivities are discussed. (M.J.C.) [pt

  3. Fabrication of electrocatalytic Ta nanoparticles by reactive sputtering and ion soft landing

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Moser, Trevor; Engelhard, Mark; Browning, Nigel D.; Laskin, Julia

    2016-11-07

    About 40 years ago, it was shown that tungsten carbide exhibits similar catalytic behavior to Pt for certain commercially relevant reactions, thereby suggesting the possibility of cheaper and earth-abundant substitutes for costly and rare precious metal catalysts. In this work, reactive magnetron sputtering of Ta in the presence of three model hydrocarbons (2-butanol, heptane, and m-xylene) combined with gas aggregation and ion soft landing was employed to prepare organic-inorganic hybrid nanoparticles (NPs) on surfaces for evaluation of catalytic activity and durability. The electro-catalytic behavior of the NPs supported on glassy carbon was evaluated in acidic aqueous solution by cyclic voltammetry. The Ta-heptane and Ta-xylene NPs were revealed to be active and robust toward promotion of the oxygen reduction reaction, an important process occurring at the cathode in fuel cells. In comparison, pure Ta and Ta-butanol NPs were essentially unreactive. Characterization techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were applied to probe how different sputtering conditions such as the flow rates of gases, sputtering current, and aggregation length affect the properties of the NPs. AFM images reveal the focused size of the NPs as well as their preferential binding along the step edges of graphite surfaces. In comparison, TEM images of the same NPs on carbon grids show that they bind randomly to the surface with some agglomeration but little coalescence. The TEM images also reveal morphologies with crystalline cores surrounded by amorphous regions for NPs formed in the presence of 2-butanol and heptane. In contrast, NPs formed in the presence of m-xylene are amorphous throughout. XPS spectra indicate that while the percentage of Ta, C, and O in the NPs varies depending on the sputtering conditions and hydrocarbon employed, the electron binding energies of the elements are similar

  4. In situ preparation of NiS2/CoS2 composite electrocatalytic materials on conductive glass substrates with electronic modulation for high-performance counter electrodes of dye-sensitized solar cells

    Science.gov (United States)

    Li, Faxin; Wang, Jiali; Zheng, Li; Zhao, Yaqiang; Huang, Niu; Sun, Panpan; Fang, Liang; Wang, Lei; Sun, Xiaohua

    2018-04-01

    The electrocatalytic composite materials of honeycomb structure NiS2 nanosheets loaded with metallic CoS2 nanoparticles are in situ prepared on F doped SnO2 conductive glass (FTO) substrates used as counter electrodes of DSSCs through chemical bath deposition (CBD) and sulfidizing process. Single crystalline NiS2 honeycomb structure array lay a foundation for the large surface area of NiS2/CoS2 composite CEs. The formed NiS2/CoS2 nanointerface modulates electronic structure of composite CEs from the synergetic interactions between CoS2 nanoparticles and NiS2 nanosheets, which dramatically improves the electrocatalytic activity of NiS2/CoS2 composite CEs; Metallic CoS2 nanoparticles covering NiS2 nanosheets electrodes adjusts the electrodes' structure and then reduces the series resistance (Rs) and the Nernst diffusion resistance (Zw) of counter electrodes. The improvement of these areas greatly enhances the electrocatalytic performance of CEs and the short circuit current density (Jsc) and Fill factor (FF) of DSSCs. Impressively, the DSSC based on NiS2/CoS2-0.1 CE shows the best photovoltaic performance with photovoltaic conversion efficiency of 8.22%, which is 24.36% higher than that (6.61%) of the DSSC with Pt CE. And the NiS2/CoS2-0.1 CE also displays a good stability in the iodine based electrolyte. This work indicates that rational construction of composite electrocatalytic materials paves an avenue for high-performance counter electrodes of DSSCs.

  5. Progress and Perspective of Electrocatalytic CO2 Reduction for Renewable Carbonaceous Fuels and Chemicals.

    Science.gov (United States)

    Zhang, Wenjun; Hu, Yi; Ma, Lianbo; Zhu, Guoyin; Wang, Yanrong; Xue, Xiaolan; Chen, Renpeng; Yang, Songyuan; Jin, Zhong

    2018-01-01

    The worldwide unrestrained emission of carbon dioxide (CO 2 ) has caused serious environmental pollution and climate change issues. For the sustainable development of human civilization, it is very desirable to convert CO 2 to renewable fuels through clean and economical chemical processes. Recently, electrocatalytic CO 2 conversion is regarded as a prospective pathway for the recycling of carbon resource and the generation of sustainable fuels. In this review, recent research advances in electrocatalytic CO 2 reduction are summarized from both experimental and theoretical aspects. The referred electrocatalysts are divided into different classes, including metal-organic complexes, metals, metal alloys, inorganic metal compounds and carbon-based metal-free nanomaterials. Moreover, the selective formation processes of different reductive products, such as formic acid/formate (HCOOH/HCOO - ), monoxide carbon (CO), formaldehyde (HCHO), methane (CH 4 ), ethylene (C 2 H 4 ), methanol (CH 3 OH), ethanol (CH 3 CH 2 OH), etc. are introduced in detail, respectively. Owing to the limited energy efficiency, unmanageable selectivity, low stability, and indeterminate mechanisms of electrocatalytic CO 2 reduction, there are still many tough challenges need to be addressed. In view of this, the current research trends to overcome these obstacles in CO 2 electroreduction field are summarized. We expect that this review will provide new insights into the further technique development and practical applications of CO 2 electroreduction.

  6. Electrocatalytic reduction of nitrite using ferricyanide; Application for its simple and selective determination

    International Nuclear Information System (INIS)

    Ojani, Reza; Raoof, Jahan-Bakhsh; Zarei, Ebrahim

    2006-01-01

    The electrocatalytic reduction of nitrite has been studied by ferricyanide at the surface of carbon paste electrode. Cyclic voltammetry and chronoamperometry techniques were used to investigate the suitability of ferricyanide as a mediator for the electrocatalytic nitrite reduction in aqueous solution with various pH. Results showed that pH 0.00 is the most suitable for this purpose. In the optimum pH, the electrocatalytic ability about 700 mV can be seen and the homogeneous second-order rate constant (k s ) for nitrite coupled catalytically to ferricyanide was calculated 2.75 x 10 3 M -1 s -1 by Nicholson-Shain method. Also, electron transfer coefficients (α) for ferricyanide was determined by using various electrochemical approaches such as Tafel plot in the absence and presence of nitrite 0.556 and 0.760, respectively. The catalytic reduction peak current was linearly dependent on the nitrite concentration and the linearity range obtained was 5.00 x 10 -5 to 1.00 x 10 -3 M. Detection limit has been found to be 2.63 x 10 -5 M (2σ). This method has been applied as a selective, simple and precise method for determination of nitrite in real sample

  7. Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering.

    Science.gov (United States)

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    2017-04-10

    Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  8. Preparation and characterization of osmium hexacyanoferrate films and their electrocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Chen, S.-M. [Department of Chemical Engineering, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei, Taiwan 106 (China)]. E-mail: smchen78@ms15.hinet.net; Liao, C.-J. [Department of Chemical Engineering, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei, Taiwan 106 (China)

    2004-11-15

    Osmium hexacyanoferrate films have been prepared using repeated cyclic voltammetry, and the deposition process and the films' electrocatalytic properties in electrolytes containing various cations have been investigated. The cyclic voltammograms recorded the deposition of osmium hexacyanoferrate films directly from the mixing of Os{sup 3+} and Fe(CN){sub 6}{sup 3-} ions from solutions containing various cations. An electrochemical quartz crystal microbalance, cyclic voltammetry, and UV-visible spectroscopy were used to study the growth mechanism of the osmium hexacyanoferrate films. The osmium hexacyanoferrate films showed a single redox couple, and the redox reactions included 'electron transfer' and 'proton transfer' with a formal potential that demonstrates a proton effect in acidic solutions up to a 12 M aqueous HCl solution. The electrochemical and electrochemical quartz crystal microbalance results indicate that the redox process was confined to the immobilized osmium hexacyanoferrate film. The electrocatalytic reduction of dopamine, epinephrine, norepinephrine, S{sub 2}O{sub 3}{sup 2-}, and SO{sub 5}{sup 2-} by the osmium hexacyanoferrate films was performed. The preparation and electrochemical properties of co-deposited osmium(III) hexacyanoferrate and copper(II) hexacyanoferrate films were determined, and their two redox couples showed formal potentials that demonstrated a proton effect and an alkaline cation effect, respectively. Electrocatalytic reactions on the hybrid films were also investigated.

  9. Electrocatalytic properties of three new POMs-based inorganic–organic frameworks with flexible zwitterionic dicarboxylate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Yanli; Li, Ling; Mu, Bao; Li, Changxia; Huang, Rudan, E-mail: huangrd@bit.edu.cn

    2017-05-15

    Three POMs–based inorganic–organic frameworks, namely, [Cu{sub 2}(L){sub 2}(SiW{sub 12}O{sub 40})(H{sub 2}O){sub 2}]·6H{sub 2}O (1), [Co{sub 2}(L){sub 2}(SiW{sub 12}O{sub 40})(H{sub 2}O){sub 8}]·8H{sub 2}O (2) and [Ni{sub 2}(L){sub 2}(SiW{sub 12}O{sub 40})(H{sub 2}O){sub 8}]·6H{sub 2}O (3), (L=1,1′-(1,4-phenylene-bis(methylene))-bis(pyridine-3-carboxylic acid)), have been synthesized and characterized by elemental analyses, IR, XRPD, TG, and single crystal X-ray diffraction. Compound 1 contains 1D double chains decorated by (Cu{sub 2}(L){sub 4}(H{sub 2}O){sub 2}) units and the 1D chains and POMs are stacked to yield 2D frameworks. Compound 2 displays a 2D network constructed from 1D zigzag chains and POMs arranged in ABAB mode. Compound 3 consists of big square girds and the POMs are dispersed in the middle of the two adjacent girds, forming 2D networks. Compounds 1–3 all show structural integrity in aqueous solutions at different pH values and in common organic solvents. Additionally, the fluorescence and electrochemical properties of compounds 1–3 are also investigated. Compounds 1–3 exhibit good electrocatalytic activities for the reduction of NaNO{sub 2} and H{sub 2}O{sub 2}. - Highlights: • Compound 1–3 all contain different 1D chains. The noncovalent interaction of metal–organic moieties from compounds 1–3 and POMs to construct three new host–guest supramolecular compounds. • Compounds 1–3 show good electrocatalytic activities towards the reduction of NaNO{sub 2} and H{sub 2}O{sub 2}. • Compounds 1–3 all show structural integrity in aqueous solutions at different pH values and in common organic solvents. • Compounds 1–3 may be promising luminescent materials due to their luminescent properties.

  10. Synthesis of Pd@Pt Core-shell Nanoparticles based on Photochemical Seed Growth Method and Co-reduction Method and the Electrocatalytic Performance

    Directory of Open Access Journals (Sweden)

    Li Shanshan

    2016-01-01

    Full Text Available A series of Pd@Pt nanoparticles were synthesized based on electrochemical seed growth method and co-reduction method in polyethylene-glycol and acetone solution system. The TEM/HR-TEM and XPS characterization proved that the prepared composite nanoparticles present core-shell structure and analyzed the chemical state of the particles. The electrocatalytic performance of Pd@Pt particles was studied by using the electrochemical workstation. The results showed that the Pd@Pt/C catalyst of different molar ratios of Pd to Pt exhibited preferable catalytic activity and stability for the methanol catalytic oxidation reaction. Among which, the Pd@Pt nanoparticles (Pd:Pt=1:1 prepared by co-reduction method, presented highest catalytic activity, which is 2 times higher than that of Pt/C catalyst. The high catalytic activity produced by the core-shell structure was briefly discussed.

  11. [Autoerotic fatalities in Greater Dusseldorf].

    Science.gov (United States)

    Hartung, Benno; Hellen, Florence; Borchard, Nora; Huckenbeck, Wolfgang

    2011-01-01

    Autoerotic fatalities in the Greater Dusseldorf area correspond to the relevant medicolegal literature. Our results included exclusively young to middle-aged, usually single men who were found dead in their city apartments. Clothing and devices used showed a great variety. Women's or fetish clothing and complex shackling or hanging devices were disproportionately frequent. In most cases, death occurred due to hanging or ligature strangulation. There was no increased incidence of underlying psychiatric disorders. In most of the deceased no or at least no remarkable alcohol intoxication was found. Occasionally, it may be difficult to reliably differentiate autoerotic accidents, accidents occurring in connection with practices of bondage & discipline, dominance & submission (BDSM) from natural death, suicide or homicide.

  12. Planning for greater confinement disposal

    International Nuclear Information System (INIS)

    Gilbert, T.L.; Luner, C.; Meshkov, N.K.; Trevorrow, L.E.; Yu, C.

    1985-01-01

    A report that provides guidance for planning for greater-confinement disposal (GCD) of low-level radioactive waste is being prepared. The report addresses procedures for selecting a GCD technology and provides information for implementing these procedures. The focus is on GCD; planning aspects common to GCD and shallow-land burial are covered by reference. Planning procedure topics covered include regulatory requirements, waste characterization, benefit-cost-risk assessment and pathway analysis methodologies, determination of need, waste-acceptance criteria, performance objectives, and comparative assessment of attributes that support these objectives. The major technologies covered include augered shafts, deep trenches, engineered structures, hydrofracture, improved waste forms, and high-integrity containers. Descriptive information is provided, and attributes that are relevant for risk assessment and operational requirements are given. 10 refs., 3 figs., 2 tabs

  13. Carbon-Coated Perovskite BaMnO3 Porous Nanorods with Enhanced Electrocatalytic Perporites for Oxygen Reduction and Oxygen Evolution

    International Nuclear Information System (INIS)

    Xu, Yujiao; Tsou, Alvin; Fu, Yue; Wang, Jin; Tian, Jing-Hua; Yang, Ruizhi

    2015-01-01

    A thin carbon layer has been introduced to coat on the perovskite BaMnO 3 nanorods by a facile method, which exhibit significantly enhanced electrocatalytic activity for both the ORR and OER with excellent stability. - Highlights: • A non-rare-earth element based perovskite BaMnO 3 nanorods as an active electrocatalyst for the ORR and OER have been prepared and investigated for the first time. • A thin carbon-coating layer with thickness of approximately 10 nm has been successfully introduced to enhance the electrical conductivity and the electrocatalytic activities of the bare perovskite for both ORR and OER. • The stabilities of bare BaMnO 3 nanorods for both ORR and OER have also been improved dramatically with the help of carbon coating, especially for the OER process. - Abstract: Highly efficient, low-cost catalysts, especially with bifunctional electrocatalytic capabilities for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are vital for the wide commercialization of fuel cells and metal-air batteries. In this study, BaMnO 3 - a non-rare-earth element based perovskite nanorods have been prepared and investigated for the first time, and a thin carbon-coating with a thickness of approximately 10 nm has been successfully introduced to enhance the electrical conductivity of the bare perovskite. Electrochemical tests reveal that bare BaMnO 3 nanorods exhibit very good catalytic activity. More interestingly, a remarkably enhanced ORR activity for the perovskite BaMnO 3 nanorods was observed after coating with a thin layer of carbon, which dominated with a direct four-electron pathway. Meanwhile, the OER process has also been enhanced extraordinarily with the carbon-coating, reaching a maximum of 14.8 mA cm −2 at 1.0 V (vs. Ag/AgCl), which is far superior to both the bare BaMnO 3 nanorods and commercial Pt/C (20 wt%) catalysts. Furthermore, the stabilities of bare BaMnO 3 nanorods for both ORR and OER have also been improved

  14. Electrocatalytic properties of carbon-supported Pt-Ru catalysts with the high alloying degree for formic acid electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu.; Zhou, Yiming; Tang, Yawen; Lu, Tianhong [College of Chemistry and Environmental Science, Nanjing Normal University, Nanjing 210097 (China)

    2010-07-01

    A series of carbon-supported bimetallic Pt-Ru catalysts with high alloying degree and different Pt/Ru atomic ratio have been prepared by a chemical reduction method in the H{sub 2}O/ethanol/tetrahydrofuran (THF) mixture solvent. The structural and electronic properties of catalysts are characterized using X-ray reflection (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM). The electrooxidation of formic acid on these Pt-Ru nanoparticles are investigated by using cyclic voltammetry, chronoamperometry and CO-stripping measurements. The results of electrochemical measurements illustrate that the alloying degree and Pt/Ru atomic ratio of Pt-Ru catalyst play an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for formic acid electrooxidation due to the bifunctional mechanism and the electronic effect. Since formic acid is an intermediate in the methanol electrooxidation on Pt electrode in acidic electrolyte, the observation provides an additional fundamental understanding of the structure-activity relationship of Pt-Ru catalyst for methanol electrooxidation. (author)

  15. Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

    Science.gov (United States)

    Valenti, Giovanni; Boni, Alessandro; Melchionna, Michele; Cargnello, Matteo; Nasi, Lucia; Bertoni, Giovanni; Gorte, Raymond J.; Marcaccio, Massimo; Rapino, Stefania; Bonchio, Marcella; Fornasiero, Paolo; Prato, Maurizio; Paolucci, Francesco

    2016-12-01

    Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50 mV overpotential). The Tafel slope of ~130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure.

  16. electrocatalytic reduction of oxygen at vapor phase polymerized poly ...

    African Journals Online (AJOL)

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    ABSTRACT. We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to ...

  17. Electrocatalytic reduction of oxygen at vapor phase polymerized ...

    African Journals Online (AJOL)

    We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to study the ...

  18. Waste management in Greater Vancouver

    Energy Technology Data Exchange (ETDEWEB)

    Carrusca, K. [Greater Vancouver Regional District, Burnaby, BC (Canada); Richter, R. [Montenay Inc., Vancouver, BC (Canada)]|[Veolia Environmental Services, Vancouver, BC (Canada)

    2006-07-01

    An outline of the Greater Vancouver Regional District (GVRD) waste-to-energy program was presented. The GVRD has an annual budget for solid waste management of $90 million. Energy recovery revenues from solid waste currently exceed $10 million. Over 1,660,00 tonnes of GVRD waste is recycled, and another 280,000 tonnes is converted from waste to energy. The GVRD waste-to-energy facility combines state-of-the-art combustion and air pollution control, and has processed over 5 million tonnes of municipal solid waste since it opened in 1988. Its central location minimizes haul distance, and it was originally sited to utilize steam through sales to a recycle paper mill. The facility has won several awards, including the Solid Waste Association of North America award for best facility in 1990. The facility focuses on continual improvement, and has installed a carbon injection system; an ammonia injection system; a flyash stabilization system; and heat capacity upgrades in addition to conducting continuous waste composition studies. Continuous air emissions monitoring is also conducted at the plant, which produces a very small percentage of the total air emissions in metropolitan Vancouver. The GVRD is now seeking options for the management of a further 500,000 tonnes per year of solid waste, and has received 23 submissions from a range of waste energy technologies which are now being evaluated. It was concluded that waste-to-energy plants can be located in densely populated metropolitan areas and provide a local disposal solution as well as a source of renewable energy. Other GVRD waste reduction policies were also reviewed. refs., tabs., figs.

  19. Electrocatalytic oxidation of hydrogen peroxide on a platinum electrode in the imitation of oxidative drug metabolism of lidocaine.

    Science.gov (United States)

    Nouri-Nigjeh, Eslam; Bruins, Andries P; Bischoff, Rainer; Permentier, Hjalmar P

    2012-10-21

    Electrochemistry in combination with mass spectrometry has shown promise as a versatile technique not only in the analytical assessment of oxidative drug metabolism, but also for small-scale synthesis of drug metabolites. However, electrochemistry is generally limited to reactions initiated by direct electron transfer. In the case of substituted-aromatic compounds, oxidation proceeds through a Wheland-type intermediate where resonance stabilization of the positive charge determines the regioselectivity of the anodic substitution reaction, and hence limits the extent of generating drug metabolites in comparison with in vivo oxygen insertion reactions. In this study, we show that the electrocatalytic oxidation of hydrogen peroxide on a platinum electrode generates reactive oxygen species, presumably surface-bound platinum-oxo species, which are capable of oxygen insertion reactions in analogy to oxo-ferryl radical cations in the active site of Cytochrome P450. Electrochemical oxidation of lidocaine at constant potential in the presence of hydrogen peroxide produces both 3- and 4-hydroxylidocaine, suggesting reaction via an arene oxide rather than a Wheland-type intermediate. No benzylic hydroxylation was observed, thus freely diffusing radicals do not appear to be present. The results of the present study extend the possibilities of electrochemical imitation of oxidative drug metabolism to oxygen insertion reactions.

  20. Effects of reducibility of graphene oxide nanosheets on preparation of AgNPs/GO nanocomposites and their electrocatalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Dou, Yanpeng; Peng, Junjun, E-mail: john-peng@whu.edu.cn; Li, Wei; Li, Ming; Liu, Huihong; Zhang, Hanmin [Wuhan Textile University, College of Chemistry and Chemical Engineering (China)

    2015-12-15

    Silver nanoparticles/graphene oxide (AgNPs/GO) nanocomposites were prepared in a solution of AgNO{sub 3} and GO. The GO serves not only as a reductant but also as a substrate to support the as-reduced silver nanoparticles. The reducibility of GO was investigated by analyzing the influence factors such as pH, duration, the reaction temperature, and the weight ratio of AgNO{sub 3} and GO in the AgNP/GO nanocomposite mixture, which were evaluated by the UV–vis absorption spectroscopy. The results demonstrated that Ag nanoparticles with an average diameter of 5–10 nm were uniformly dispersed on the surface of GO nanosheets under the optimum synthesis conditions of pH between 8 and 11, weight ratio of AgNO{sub 3} and GO between 55 % and 60 %, and at 80 °C for 6 h. Moreover, the obtained AgNPs/GO nanocomposites exhibit good electrocatalytic activity for the reduction of p-nitrophenol to 4-(hydroxyamino) phenol.

  1. Electrocatalytic Study of Paracetamol at a Single-Walled Carbon Nanotube/Nickel Nanocomposite Modified Glassy Carbon Electrode

    Directory of Open Access Journals (Sweden)

    Koh Sing Ngai

    2015-01-01

    Full Text Available A rapid, simple, and sensitive method for the electrochemical determination of paracetamol was developed. A single-walled carbon nanotube/nickel (SWCNT/Ni nanocomposite was prepared and immobilized on a glassy carbon electrode (GCE surface via mechanical attachment. This paper reports the voltammetry study on the effect of paracetamol concentration, scan rate, pH, and temperature at a SWCNT/Ni-modified electrode in the determination of paracetamol. The characterization of the SWCNT/Ni/GCE was performed by cyclic voltammetry. Variable pressure scanning electron microscopy (VPSEM and energy dispersive X-ray (EDX spectrometer were used to examine the surface morphology and elemental profile of the modified electrode, respectively. Cyclic voltammetry showed significant enhancement in peak current for the determination of paracetamol at the SWCNT/Ni-modified electrode. A linear calibration curve was obtained for the paracetamol concentration between 0.05 and 0.50 mM. The SWCNT/Ni/GCE displayed a sensitivity of 64 mA M−1 and a detection limit of 1.17 × 10−7 M in paracetamol detection. The proposed electrode can be applied for the determination of paracetamol in real pharmaceutical samples with satisfactory performance. Results indicate that electrodes modified with SWCNT and nickel nanoparticles exhibit better electrocatalytic activity towards paracetamol.

  2. A study of the electro-catalytic oxidation of methanol on a cobalt hydroxide modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Jafarian, M.; Mahjani, M.G.; Heli, H.; Gobal, F.; Khajehsharifi, H.; Hamedi, M.H.

    2003-01-01

    Cobalt hydroxide modified glassy carbon electrodes (CHM/GC) prepared by the anodic deposition in presence of tartrate ions have been used for the electro-catalytic oxidation of methanol in alkaline solutions where the methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (IS) have been employed. In CV studies, in the presence of methanol the peak current of the oxidation of cobalt hydroxide increase is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of methanol is being catalysed through the mediated electron transfer across the cobalt hydroxide layer comprising of cobalt ions of various valence states. A mechanism based on the electro-chemical generation of Co(IV) active sites and their subsequent consumptions by methanol have been discussed and the corresponding rate law under the control of charge transfer has been developed and kinetic parameters have been derived. In this context the charge transfer resistance accessible both theoretically and through the IS studies have been used as a criteria. Under the CA regimes the reaction followed a Cottrellian behaviour

  3. Electrochemical and electrocatalytic studies of toluidine blue immobilized on a silica gel surface coated with niobium oxide

    Directory of Open Access Journals (Sweden)

    Santos Antonio S.

    2002-01-01

    Full Text Available The electrochemical behavior of toluidine blue (TB adsorbed on a silica surface modified with niobium oxide (SN was investigated using a modified carbon paste electrode. The presence of SN gave the electrode high stability, avoiding the leaching out of the mediator from the electrode surface. The formal potential (E0' of the adsorbed TB was --113 mV vs. SCE, indicating a shift of almost 100 mV towards more positive potential values, compared to TB dissolved in aqueous solution or adsorbed on carbon paste. The stability and formal potential remained constant upon changing the solution pH in the range 5 to 8. In these solution pH values the electrocatalytic activity remained almost constant with a sensitivity of 1.2 10-4 A L mol-1 cm-2 and a K Mapp of 4.9 10-5 mol L-1. A linear response range for NADH concentration between 2.0 10-4 and 4.0 10-3 mol L-1 at pH 7.0, with a detection limit of 3.4 10-5 mol L-1 was observed for the sensor. A response time of 2 s and a precision of 1.0 %, expressed as relative standard deviation for 10 replicates, were observed for the sensor developed.

  4. The electrocatalytic oxidation of carbohydrates at a nickel/carbon paper electrode fabricated by the filtered cathodic vacuum arc technique

    International Nuclear Information System (INIS)

    Fu, Yingyi; Wang, Tong; Su, Wen; Yu, Yanan; Hu, Jingbo

    2015-01-01

    The direct electrochemical behaviour of carbohydrates at a nickel/carbon paper electrode with a novel fabrication method is investigated. The investigation is used for verification the feasibility of using monosaccharides and disaccharides in the application of fuel cell. The selected monosaccharides are glucose, fructose and galactose; the disaccharides are sucrose, maltose and lactose. The modified nickel/carbon paper electrode was prepared using a filtered cathodic vacuum arc technique. The morphology image of the nickel thin film on the carbon paper surface was characterized by scanning electron microscopy (SEM). The existence of nickel was verified by X-ray photoelectron spectroscopy (XPS). The contact angle measurement was also used to characterize the modified electrode. Cyclic voltammetry (CV) was employed to evaluate the electrochemical behaviour of monosaccharides and disaccharides in an alkaline aqueous solution. The modified electrode exhibits good electrocatalytic activities towards carbohydrates. In addition, the stability of the nickel/carbon paper electrode with six sugars was also investigated. The good catalytic effects of the nickel/carbon paper electrode allow for the use of carbohydrates as fuels in fuel cell applications

  5. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.

    2015-08-25

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

  6. Preparation, characterization and electrocatalytic behavior of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate hybrid film-modified electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Chu, H.-W.; Thangamuthu, R. [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan (China); Chen, S.-M. [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan (China)], E-mail: smchen78@ms15.hinet.net

    2008-02-15

    Polynuclear mixed-valent hybrid films of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate (ZnO/ZnHCF-RuOHCF) have been deposited on electrode surfaces from H{sub 2}SO{sub 4} solution containing Zn(NO{sub 3}){sub 2}, RuCl{sub 3} and K{sub 3}[Fe(CN){sub 6}] by potentiodynamic cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide and ruthenium oxide hexacyanoferrate (RuOHCF) in the hybrid film. The effect of type of monovalent cations on the redox behavior of hybrid film was investigated. In pure supporting electrolyte, electrochemical responses of Ru{sup II/III} redox transition occurring at negative potential region resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF-RuOHCF hybrid film was investigated towards oxidation of epinephrine, dopamine and L-cysteine, and reduction of S{sub 2}O{sub 8}{sup 2-} and SO{sub 5}{sup 2-} as well as IO{sub 3}{sup -} using cyclic voltammetry and rotating ring disc electrode (RRDE) techniques.

  7. Electrochemical Detection of E. coli O157:H7 in Water after Electrocatalytic and Ultraviolet Treatments Using a Polyguanine-Labeled Secondary Bead Sensor

    Directory of Open Access Journals (Sweden)

    Michael G. Beeman

    2018-05-01

    Full Text Available The availability of clean drinking water is a significant problem worldwide. Many technologies exist for purifying drinking water, however, many of these methods require chemicals or use simple methods, such as boiling and filtering, which may or may not be effective in removing waterborne pathogens. Present methods for detecting pathogens in point-of-use (POU sterilized water are typically time prohibitive or have limited ability differentiating between active and inactive cells. This work describes a rapid electrochemical sensor to differentially detect the presence of active Escherichia coli (E. coli O157:H7 in samples that have been partially or completely sterilized using a new POU electrocatalytic water purification technology based on superradicals generated by defect laden titania (TiO2 nanotubes. The sensor was also used to detect pathogens sterilized by UV-C radiation for a comparison of different modes of cell death. The sensor utilizes immunomagnetic bead separation to isolate active bacteria by forming a sandwich assay comprised of antibody functionalized secondary magnetic beads, E. coli O157:H7, and polyguanine (polyG oligonucleotide functionalized secondary polystyrene beads as an electrochemical tag. The assay is formed by the attachment of antibodies to active receptors on the membrane of E. coli, allowing the sensor to differentially detect viable cells. Ultravioloet (UV-C radiation and an electrocatalytic reactor (ER with integrated defect-laden titania nanotubes were used to examine the sensors’ performance in detecting sterilized cells under different modes of cell death. Plate counts and flow cytometry were used to quantify disinfection efficacy and cell damage. It was found that the ER treatments shredded the bacteria into multiple fragments, while UV-C treatments inactivated the bacteria but left the cell membrane mostly intact.

  8. Electrochemical Detection of E. coli O157:H7 in Water after Electrocatalytic and Ultraviolet Treatments Using a Polyguanine-Labeled Secondary Bead Sensor.

    Science.gov (United States)

    Beeman, Michael G; Nze, Ugochukwu C; Sant, Himanshu J; Malik, Hammad; Mohanty, Swomitra; Gale, Bruce K; Carlson, Krista

    2018-05-10

    The availability of clean drinking water is a significant problem worldwide. Many technologies exist for purifying drinking water, however, many of these methods require chemicals or use simple methods, such as boiling and filtering, which may or may not be effective in removing waterborne pathogens. Present methods for detecting pathogens in point-of-use (POU) sterilized water are typically time prohibitive or have limited ability differentiating between active and inactive cells. This work describes a rapid electrochemical sensor to differentially detect the presence of active Escherichia coli (E. coli) O157:H7 in samples that have been partially or completely sterilized using a new POU electrocatalytic water purification technology based on superradicals generated by defect laden titania (TiO₂) nanotubes. The sensor was also used to detect pathogens sterilized by UV-C radiation for a comparison of different modes of cell death. The sensor utilizes immunomagnetic bead separation to isolate active bacteria by forming a sandwich assay comprised of antibody functionalized secondary magnetic beads, E. coli O157:H7, and polyguanine (polyG) oligonucleotide functionalized secondary polystyrene beads as an electrochemical tag. The assay is formed by the attachment of antibodies to active receptors on the membrane of E. coli , allowing the sensor to differentially detect viable cells. Ultravioloet (UV)-C radiation and an electrocatalytic reactor (ER) with integrated defect-laden titania nanotubes were used to examine the sensors’ performance in detecting sterilized cells under different modes of cell death. Plate counts and flow cytometry were used to quantify disinfection efficacy and cell damage. It was found that the ER treatments shredded the bacteria into multiple fragments, while UV-C treatments inactivated the bacteria but left the cell membrane mostly intact.

  9. Epitaxial growth of zigzag PtAu alloy surface on Au nano-pentagrams with enhanced Pt utilization and electrocatalytic performance toward ethanol oxidation reaction

    International Nuclear Information System (INIS)

    Du, Cheng; Gao, Xiaohui; Zhuang, Zhihua; Cheng, Chunfeng; Zheng, Fuqin; Li, Xiaokun; Chen, Wei

    2017-01-01

    Highlights: • PtAu nanoalloy surface is heteroepitaxially grown on the pre-synthesized Au nano-pentagrams. • The PtAu/Au nano-pentagrams exhibit excellent electrocatalytic activity for ethanol oxidation. • The charge transfer resistance of PtAu/Au is lower than that of commercial Pt/C. • The durability and anti-poisoning ability of PtAu/Au is much better than those of commercial Pt/C - Abstract: Improving Pt utilization is of fundamental importance for many significant processes in energy conversion, which is strongly dependent on the surface structure of used catalysts. Based on the traditional Pt-on-Au system which has been proved to be an ideal nanostructure for improving the catalytic activity and stability of Pt, and the recent follow-up studies on this system, we introduce here a new strategy for fabricating Pt surface with high-index facets over the Pt-on-Au system. To achieve this goal, we elaborately designed and fabricated a unique zigzag PtAu alloy nanosurface on Au nano-pentagrams (PtAu/Au NPs) through epitaxial growth of Pt along the high-index facets on the pre-synthesized Au nano-pentagrams. Owing to the surface electronic interaction between Au and Pt and the exposed high-index facets from the unique morphology of zigzag PtAu alloy nanosurface, the as-prepared PtAu/Au NPs exhibited excellent electrocatalytic performance toward ethanol oxidation reaction (EOR) in alkaline condition. The specific activity (8.3 mA cm"−"2) and mass activity (4.4 A mg"−"1) obtained from PtAu/Au NPs are about 5.2 and 5.5 times, respectively, higher than those from commercial Pt/C for EOR.

  10. Fundamental limitation of electrocatalytic methane conversion to methanol

    DEFF Research Database (Denmark)

    Arnarson, Logi; Schmidt, Per Simmendefeldt; Pandey, Mohnish

    2018-01-01

    binding energies on the surface. Based on a simple kinetic model we can conclude that in order to obtain sufficient activity oxygen has to bind weakly to the surface but there is an upper limit to retain selectivity. Few potentially interesting candidates are found but this relatively simple description...

  11. Study on preparation of SnO2-TiO2/Nano-graphite composite anode and electro-catalytic degradation of ceftriaxone sodium.

    Science.gov (United States)

    Guo, Xiaolei; Wan, Jiafeng; Yu, Xiujuan; Lin, Yuhui

    2016-12-01

    In order to improve the electro-catalytic activity and catalytic reaction rate of graphite-like material, Tin dioxide-Titanium dioxide/Nano-graphite (SnO 2 -TiO 2 /Nano-G) composite was synthesized by a sol-gel method and SnO 2 -TiO 2 /Nano-G electrode was prepared in hot-press approach. The composite was characterized by X-ray photoelectron spectroscopy, fourier transform infrared, Raman, N 2 adsorption-desorption, scanning electrons microscopy, transmission electron microscopy and X-ray diffraction. The electrochemical performance of the SnO 2 -TiO 2 /Nano-G anode electrode was investigated via cyclic voltammetry and electrochemical impedance spectroscopy. The electro-catalytic performance was evaluated by the degradation of ceftriaxone sodium and the yield of ·OH radicals in the reaction system. The results demonstrated that TiO 2 , SnO 2 and Nano-G were composited successfully, and TiO 2 and SnO 2 particles dispersed on the surface and interlamination of the Nano-G uniformly. The specific surface area of SnO 2 modified anode was higher than that of TiO 2 /Nano-G anode and the degradation rate of ceftriaxone sodium within 120 min on SnO 2 -TiO 2 /Nano-G electrode was 98.7% at applied bias of 2.0 V. The highly efficient electro-chemical property of SnO 2 -TiO 2 /Nano-G electrode was attributed to the admirable conductive property of the Nano-G and SnO 2 -TiO 2 /Nano-G electrode. Moreover, the contribution of reactive species ·OH was detected, indicating the considerable electro-catalytic activity of SnO 2 -TiO 2 /Nano-G electrode. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Graphene wrapped porous Co_3O_4/NiCo_2O_4 double-shelled nanocages with enhanced electrocatalytic performance for glucose sensor

    International Nuclear Information System (INIS)

    Xue, Bei; Li, Kezhi; Feng, Lei; Lu, Jinhua; Zhang, Leilei

    2017-01-01

    Highlights: • Graphene wrapped Co_3O_4/NiCo_2O_4 DSNCs has been prepared for detection of glucose. • Sensing performance was improved by synergy between electrocatalytic activity and efficient electron transport. • The sensor has excellent sensing performance with high sensitivity and low detection limit. • The developed method was successfully applied to detect glucose in human serum. - Abstract: Graphene (G) wrapped porous Co_3O_4/NiCo_2O_4 double-shelled nanocages (Co_3O_4/NiCo_2O_4 DSNCs@G) were prepared by the formation of Co_3O_4/NiCo_2O_4 DSNCs using zeolite imidazole frameworks-67 as template with the subsequent calcination and package of G by hydrothermal method. The abundant accessible active sites provided by the porous structure of Co_3O_4/NiCo_2O_4 DSNCs and efficient electron transport pathways for electrocatalytic reaction offered by the high conductive G worked very well together in a ferocious synergy, which endowed Co_3O_4/NiCo_2O_4 DSNCs@G with excellent electrocatalytic behaviors for determining glucose. A comparison between Co_3O_4/NiCo_2O_4 DSNCs without G packing and Co_3O_4/NiCo_2O_4 DSNCs@G showed that former had linear response window concentrations of 0.01-3.52 mM (correlation coefficient = 0.999), detection limit of 0.744 μM (S/N = 3) and sensitivity of 0.196 mA mM"−"1 cm"−"2, whereas the latter exhibited linear response window concentrations of 0.01-3.52 mM (correlation coefficient = 0.999), detection limit of 0.384 μM (S/N = 3) and sensitivity of 0.304 mA mM"−"1 cm"−"2. The combination of Co_3O_4/NiCo_2O_4 DSNCs and G was a meaningful strategy to fabricate high-performance non-enzyme glucose sensors with low detection limit, good selectivity and high sensitivity.

  13. Nano-structured Ni(II)-curcumin modified glassy carbon electrode for electrocatalytic oxidation of fructose

    International Nuclear Information System (INIS)

    Elahi, M. Yousef; Mousavi, M.F.; Ghasemi, S.

    2008-01-01

    A nano-structured Ni(II)-curcumin (curcumin: 1,7-bis[4-hydroxy-3-methoxyphenyl]-1,6-heptadiene-3,5-dione) film is electrodeposited on a glassy carbon electrode in alkaline solution. The morphology of polyNi(II)-curcumin (NC) was investigated by scanning electron microscopy (SEM). The SEM results show NC has a nano-globular structure in the range 20-50 nm. Using cyclic voltammetry, linear sweep voltammetry, chronoamperometry, steady-state polarization measurements and electrochemical impedance spectroscopy (EIS) showed that the nano-structure NC film acts as an efficient material for the electrocatalytic oxidation of fructose. According to the voltammetric studies, the increase in the anodic peak current and subsequent decrease in the corresponding cathodic current, fructose was oxidized on the electrode surface via an electrocatalytic mechanism. The EIS results show that the charge-transfer resistance has as a function of fructose concentration, time interval and applied potential. The increase in the fructose concentration and time interval in fructose solution results in enhanced charge transfer resistance in Nyquist plots. The EIS results indicate that fructose electrooxidation at various potentials shows different impedance behaviors. At lower potentials, a semicircle is observed in the first quadrant of impedance plot. With further increase of the potential, a transition of the semicircle from the first to the second quadrant occurs. Also, the results obtained show that the rate of fructose electrooxidation depends on concentration of OH - . Electron transfer coefficient, diffusion coefficient and rate constant of the electrocatalytic oxidation reaction are obtained. The modified electrode was used as a sensor for determination of fructose with a good dynamic range and a low detection limit

  14. Copper-Based Metal-Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols.

    Science.gov (United States)

    Albo, Jonathan; Vallejo, Daniel; Beobide, Garikoitz; Castillo, Oscar; Castaño, Pedro; Irabien, Angel

    2017-03-22

    The electrocatalytic reduction of CO 2 has been investigated using four Cu-based metal-organic porous materials supported on gas diffusion electrodes, namely, (1) HKUST-1 metal-organic framework (MOF), [Cu 3 (μ 6 -C 9 H 3 O 6 ) 2 ] n ; (2) CuAdeAce MOF, [Cu 3 (μ 3 -C 5 H 4 N 5 ) 2 ] n ; (3) CuDTA mesoporous metal-organic aerogel (MOA), [Cu(μ-C 2 H 2 N 2 S 2 )] n ; and (4) CuZnDTA MOA, [Cu 0.6 Zn 0.4 (μ-C 2 H 2 N 2 S 2 )] n . The electrodes show relatively high surface areas, accessibilities, and exposure of the Cu catalytic centers as well as favorable electrocatalytic CO 2 reduction performance, that is, they have a high efficiency for the production of methanol and ethanol in the liquid phase. The maximum cumulative Faradaic efficiencies for CO 2 conversion at HKUST-1-, CuAdeAce-, CuDTA-, and CuZnDTA-based electrodes are 15.9, 1.2, 6, and 9.9 %, respectively, at a current density of 10 mA cm -2 , an electrolyte-flow/area ratio of 3 mL min cm -2 , and a gas-flow/area ratio of 20 mL min cm -2 . We can correlate these observations with the structural features of the electrodes. Furthermore, HKUST-1- and CuZnDTA-based electrodes show stable electrocatalytic performance for 17 and 12 h, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Nonaqueous electrocatalytic water oxidation by a surface-bound Ru(bda)(L)₂ complex.

    Science.gov (United States)

    Sheridan, Matthew V; Sherman, Benjamin D; Wee, Kyung-Ryang; Marquard, Seth L; Gold, Alexander S; Meyer, Thomas J

    2016-04-21

    The rate of electrocatalytic water oxidation by the heterogeneous water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], , (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate) on metal oxide surfaces is greatly enhanced relative to water as the solvent. In these experiments with propylene carbonate (PC) as the nonaqueous solvent, water is the limiting reagent. Mechanistic studies point to atom proton transfer (APT) as the rate limiting step in water oxidation catalysis.

  16. Investigating radical cation chain processes in the electrocatalytic Diels-Alder reaction.

    Science.gov (United States)

    Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels-Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.

  17. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hyunjoo; Habas, Susan; Somorjai, Gabor; Yang, Peidong

    2007-12-14

    Single crystalline surface such as (100), (111), (110) has been studied as an idealized platform for electrocatalytic reactions since the atomic arrangement affects a catalytic property. The secondary metal deposition on these surfaces also alters the catalytic property often showing improvement such as poisoning decrease. On the other hand, electrocatalysts used for practical purpose usually have a size on the order of nanometers. Therefore, linking the knowledge from single crystalline studies to nanoparticle catalysts is of enormous importance. Recently, the Pt nanoparticles which surface structure was preferentially oriented was synthesized and used as electrocatalysts. Here, we demonstrate a rational design of a binary metallic nanocatalyst based on the single crystalline study.

  18. Electrocatalytic oxidation of methanol: study with Pt:Mo dispersed catalysts

    Directory of Open Access Journals (Sweden)

    Oliveira Neto Almir

    2000-01-01

    Full Text Available The electrocatalytic oxidation of methanol on Pt:Mo dispersed on carbon prepared using an alternative method recently developed in this laboratory was investigated. The EDX analysis confirmed that the simultaneous reduction of the precursor salts of Pt and Mo leads to the presence of these materials at the nominal composition initially calculated. The addition of Mo to Pt causes an increase of the oxidation currents, but does not improve the catalytic effect for methanol oxidation. Tafel plots for various methanol concentrations showed the presence of two slopes. On line differential electrochemical mass spectrometry (DEMS was used to investigate the distribution of products and intermediates in methanol oxidation.

  19. Ni-O4 species anchored on N-doped graphene-based materials as molecular entities and electrocatalytic performances for oxygen reduction reaction

    Science.gov (United States)

    Jang, Dawoon; Lee, Seungjun; Shin, Yunseok; Ohn, Saerom; Park, Sunghee; Lim, Donggyu; Park, Gilsoo; Park, Sungjin

    2017-12-01

    The generation of molecular active species on the surface of nano-materials has become promising routes to produce efficient electrocatalysts. Development of cost-effective catalysts with high performances for oxygen reduction reaction (ORR) is an important challenge for fuel cell and metal-air battery applications. In this work, we report a novel hybrid produced by room-temperature solution processes using Ni-based organometallic molecules and N-doped graphene-based materials. Chemical and structural characterizations reveal that Ni-containing species are well-dispersed on the surface of graphene network as molecular entity. The hybrid shows excellent electrocatalytic performances for ORR in basic medium with an onset potential of 0.87 V (vs. RHE), superior durability and good methanol tolerance.

  20. Topotactic transition of α-Co(OH)2 to β-Co(OH)2 anchored on CoO nanoparticles during electrochemical water oxidation: synergistic electrocatalytic effects.

    Science.gov (United States)

    Kundu, Sumana; Malik, Bibhudatta; Prabhakaran, Amrutha; Pattanayak, Deepak K; Pillai, Vijayamohanan K

    2017-08-29

    Herein, we report a single step, anionic surfactant-assisted, low temperature-hydrothermal synthetic strategy of CoO nanoparticles anchored on β-Co(OH) 2 nanosheets which show a low overpotential (295 mV @ 10 mA cm -2 ) for the oxygen evolution reaction (OER). They also demonstrate much better kinetic parameters compared to the state-of-the-art RuO 2 . Interestingly, under the OER operational conditions (in alkaline medium), the topotactic transformation of α-Co(OH) 2 to a stable Brucite-like β-Co(OH) 2 phase leads to a synergistic interaction between the β-Co(OH) 2 sheets on the CoO nanoparticles for enhancing the OER electrocatalytic activity.

  1. Characterization and electrocatalytic application of silver modified polypyrrole electrodes

    Directory of Open Access Journals (Sweden)

    A. DEKANSKI

    2005-02-01

    Full Text Available Silver modified polypyrrole electrodeswere preparedwith the aim of testing them for the electrooxidation of formaldehyde in alkaline solution. The modification of polypyrrole by immersion in aqueous AgNO3 solution was studied by cyclic voltammetry and vacuum techniques (AES and XPS. The influence of time of immersion and the thickness of the polypyrrole film, prepared by electrochemical polymerization, on the modification of the polymer were examined. The results acquired from both electrochemical and spectroscopic examinations show that immersion of a polypyrrole electrode in a AgNO3 solution results in its modificationwith silver, which is deposited in the elemental state on the surface. The quantity of silver deposited depends not only on the immersion time but also on the thickness of the polymer film. A modified PPy/Ag electrode exhibits catalytic activity for the electrooxidation of CH2O in NaOH. In spite of the low quantity of silver, the activity of the electrode for this reaction is comparable to that of a polycrystalline silver electrode.

  2. Electrocatalytic analysis of superoxide anion radical using nitrogen-doped graphene supported Prussian Blue as a biomimetic superoxide dismutase

    International Nuclear Information System (INIS)

    Liu, Tingting; Niu, Xiangheng; Shi, Libo; Zhu, Xiang; Zhao, Hongli; Lana, Minbo

    2015-01-01

    Graphical abstract: Prussian Blue (PB) cubes supported on nitrogen-doped graphene sheets (NGS) were synthesized using a simple and scalable method, and the utilization of the PB-NGS hybrid as an efficient superoxide dismutase mimic in the electrochemical sensing of O 2 ·− was demonstrated. - Highlights: • Facile and scalable synthesis of Prussian Blue cubes supported on nitrogen-doped graphene; • Nitrogen-doped graphene supported Prussian Blue as an efficient biomimetic superoxide dismutase for the electrocatalytic sensing of superoxide anion; • Good sensitivity, excellent selectivity and attractive long-term stability for superoxide anion sensing. - Abstract: Considering the double-sided roles of superoxide anion radical, monitoring of its track in living systems is attracting increasing academic and practical interest. Here we synthesized Prussian Blue (PB) cubes that were supported on nitrogen-doped graphene sheets (NGS) using a facile and scalable method, and explored their potential utilization in the electrochemical sensing of superoxide anion. As an efficient superoxide dismutase mimic, direct electron transfer of the prepared PB-NGS hybrid immobilized on a screen-printed gold electrode was harvested in physiological media. With the bifunctional activities, the synthetic mimic could catalyze the dismutation of superoxide anion via the redox cycle of active iron. By capturing the electro-reduction amperometric responses of superoxide anion radical to hydrogen peroxide in the cathodic polarization, highly sensitive determination (a sensitivity of as high as 0.32 μA cm −2 μM −1 ) of the target was achieved, with no interference from common coexisting species including ascorbic acid, dopamine, and uric acid observed. Compared to natural superoxide dismutases, the artificial enzyme mimic exhibited favorable activity stability, indicating its promising applications in the in vivo long-term monitoring of superoxide anion

  3. Electrocatalytic reduction of carbon dioxide under plasma DBD process

    International Nuclear Information System (INIS)

    Amouroux, Jacques; Cavadias, Simeon

    2017-01-01

    Carbon dioxide can be converted, by reaction with hydrogen, into fine chemicals and liquid fuels such as methanol and DME. Methane production by the Sabatier reaction opens the way of carbon recycling for a circular economy of carbon resources. The catalytic process of methanation of carbon dioxide produces two molecules of water as a by-product. A current limitation in the CO 2 methanation is the ageing of catalysts, mainly due to water adsorption during the process. To avoid this adsorption, the process is operated at high temperature (300 °C–400 °C), leading to carbon deposition on the catalyst and its deactivation. To overcome this problem, a methanation plasma-catalytic process has been developed, which achieves high CO 2 conversion rate (80%), and a selectivity close to 100%, working from room temperature to 150 °C, instead of 300 °C–400 °C for the thermal catalytic process. The main characteristics of this process are high-voltage pulses of few nanoseconds duration, activating the adsorption of CO 2 in bent configuration and the polarization of the catalyst. The key step in this process is the desorption of water from the polarized catalyst. The high CO 2 conversion at low temperature could be explained by the creation of a plasma inside the nanopores of the catalyst. (paper)

  4. Electrocatalytic reduction of carbon dioxide under plasma DBD process

    Science.gov (United States)

    Amouroux, Jacques; Cavadias, Simeon

    2017-11-01

    Carbon dioxide can be converted, by reaction with hydrogen, into fine chemicals and liquid fuels such as methanol and DME. Methane production by the Sabatier reaction opens the way of carbon recycling for a circular economy of carbon resources. The catalytic process of methanation of carbon dioxide produces two molecules of water as a by-product. A current limitation in the CO2 methanation is the ageing of catalysts, mainly due to water adsorption during the process. To avoid this adsorption, the process is operated at high temperature (300 °C-400 °C), leading to carbon deposition on the catalyst and its deactivation. To overcome this problem, a methanation plasma-catalytic process has been developed, which achieves high CO2 conversion rate (80%), and a selectivity close to 100%, working from room temperature to 150 °C, instead of 300 °C-400 °C for the thermal catalytic process. The main characteristics of this process are high-voltage pulses of few nanoseconds duration, activating the adsorption of CO2 in bent configuration and the polarization of the catalyst. The key step in this process is the desorption of water from the polarized catalyst. The high CO2 conversion at low temperature could be explained by the creation of a plasma inside the nanopores of the catalyst.

  5. Ultrathin bismuth nanosheets from in situ topotactic transformation for selective electrocatalytic CO2 reduction to formate.

    Science.gov (United States)

    Han, Na; Wang, Yu; Yang, Hui; Deng, Jun; Wu, Jinghua; Li, Yafei; Li, Yanguang

    2018-04-03

    Electrocatalytic carbon dioxide reduction to formate is desirable but challenging. Current attention is mostly focused on tin-based materials, which, unfortunately, often suffer from limited Faradaic efficiency. The potential of bismuth in carbon dioxide reduction has been suggested but remained understudied. Here, we report that ultrathin bismuth nanosheets are prepared from the in situ topotactic transformation of bismuth oxyiodide nanosheets. They process single crystallinity and enlarged surface areas. Such an advantageous nanostructure affords the material with excellent electrocatalytic performance for carbon dioxide reduction to formate. High selectivity (~100%) and large current density are measured over a broad potential, as well as excellent durability for >10 h. Its selectivity for formate is also understood by density functional theory calculations. In addition, bismuth nanosheets were coupled with an iridium-based oxygen evolution electrocatalyst to achieve efficient full-cell electrolysis. When powered by two AA-size alkaline batteries, the full cell exhibits impressive Faradaic efficiency and electricity-to-formate conversion efficiency.

  6. Ruthenium(III) diphenyldithiocarbamate as mediator for the electrocatalytic oxidation of sulfhydryl compounds at graphite electrode

    International Nuclear Information System (INIS)

    Nalini, B.; Sriman Narayanan, S.

    1998-01-01

    Ruthenium(III) diphenyldithiocarbamate was used as mediator to modify graphite electrode by abrasive method. The modified electrode was characterized electrochemically by cyclic voltammetry. The electrode was scanned between 0.0 V to +0.8 V. An anodic peak at + 0.39 V and a cathodic peak at +0.24 V have been observed for a scan rate of 100 mV/s. The electrode has been characterized at various scan rate and pHs in 0.1 M KNO 3 solution. Sulfhydryl compounds, cysteine and glutathione, were electro catalytically oxidised at the modified electrode. pH variation was studied to optimize the conditions for their estimation. Linear response for cysteine is in the range of 0.00-15.20 ppm, with a correlation coefficient (r), of 0.9993. The linear range for glutathione is 0.00-30.40 ppm, with a value of 0.999 for r. The electrocatalytic oxidation of both cysteine and glutathione gave reproducible current values with a standard deviation of 0.1686 for 10 repetitive determinations. The stability and reproducibility of the electrode for the determination of cysteine and glutathione were also discussed. The electrocatalytic oxidation of the sulfhydryl compounds were also studied in hydrodynamic environment. (author)

  7. Hydroxyacetone: A Glycerol-Based Platform for Electrocatalytic Hydrogenation and Hydrodeoxygenation Processes.

    Science.gov (United States)

    Sauter, Waldemar; Bergmann, Olaf L; Schröder, Uwe

    2017-08-10

    Here, we propose the use of hydroxyacetone, a dehydration product of glycerol, as a platform for the electrocatalytic synthesis of acetone, 1,2-propanediol, and 2-propanol. 11 non-noble metals were investigated as electrode materials in combination with three different electrolyte compositions toward the selectivity, Coulombic efficiency (CE), and reaction rates of the electrocatalytic hydrogenation (formation of 1,2-propanediol) and hydrodeoxygenation (formation of acetone and propanol) of hydroxyacetone. With a selectivity of 84.5 %, a reaction rate of 782 mmol h -1  m -2 and a CE of 32 % (for 0.09 m hydroxyacetone), iron electrodes, in a chloride electrolyte, yielded the best 1,2 propanediol formation. A further enhancement of the performance can be achieved upon increasing the educt concentration to 0.5 m, yielding a reaction rate of 2248.1 mmol h -1  m -2 and a CE of 64.5 %. Acetone formation was optimal at copper and lead electrodes in chloride solution, with lead showing the lowest tendency of side product formation. 2-propanol formation can be achieved using a consecutive oxidation of the formed acetone (at iron electrodes). 1-propanol formation was observed only in traces. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Hydrogen peroxide as a sustainable energy carrier: Electrocatalytic production of hydrogen peroxide and the fuel cell

    International Nuclear Information System (INIS)

    Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D.

    2012-01-01

    This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal–oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

  9. Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell.

    Science.gov (United States)

    Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D

    2012-11-01

    This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

  10. Electro-catalytic oxidation of reactive Orange 107 using cerium doped oxides of Nd3+ nanoparticle

    International Nuclear Information System (INIS)

    Rajkumar, K.; Muthukumar, M.; Mangalaraja, R.V.

    2011-01-01

    A new rare earth doped cerium oxide powder was used as a catalyst to investigate the removal of colour and TOC from simulated wastewater of Reactive Orange 107. The electro oxidation process was carried out in the reactor in presence of an electrolyte NaCl. Graphite electrode was used as anode and cathode and electrolysis were carried out at a current density of 34.96 mAcm -2 with a catalyst concentration of 0.05g L -1 . In order to find the efficiency of nanocatalyst, experiments were also conducted without catalyst. From the experiment, it was found that complete colour removal was achieved on electrocatalytic oxidation as well as electro oxidation. When comparing the above processes, catalytic oxidation shows more efficient than electro oxidation. With respect to the degradation of the dye, catalytic oxidation shows more TOC removal than the oxidation taken place without catalyst. It infers that even though the electro-catalytic oxidation process achieves complete decolouration but it does not achieve complete mineralisation. The FTIR and GCMS studies confirmed the formation of by-products. (author)

  11. In Situ Surface-Enhanced Raman Spectroscopy Study of the Electrocatalytic Effect of PtFe/C Nanocatalyst on Ethanol Electro-Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    A. C. Gómez-Monsiváis

    2017-03-01

    Full Text Available Currently, the ethanol electro-oxidation reaction has attracted considerable attention in fuel cells because of new green ethanol synthetic methods based on biomass processes that have emerged. In this study, PtFe/C and Pt/C nanoparticles were synthesized by a chemical reduction method and tested in the ethanol electro-oxidation reaction. Furthermore, the electrocatalytic effect of the PtFe bimetallic catalyst was analyzed by in situ surface-enhanced Raman spectroscopy (SERS coupled to an electrochemical cell. X-ray diffractograms showed typical face-centered cubic structures with crystallite sizes of 3.31 and 3.94 for Pt/C and PtFe/C, respectively. TEM micrographs revealed nanoparticle sizes of 2 ± 0.4 nm and 3 ± 0.6 nm for Pt/C and PtFe/C respectively. PtFe/C exhibited a Pt90Fe10 composition by both X-ray fluorescence and energy-dispersive X-ray spectroscopy. A better electrocatalytic activity as function of concentration was obtained through the incorporation of a small amount of Fe into the Pt lattice and the presence of Fe2+/Fe3+ (observed by X-ray photoelectron spectroscopy. According to SERS experiments, the presence of these iron species promotes the chemisorption of ethanol, the formation of formic acid as main product and renewal of the catalytic sites, resulting in current densities that were at least three fold higher than the values obtained for the Pt/C nanocatalyst.

  12. Electrocatalytic studies of osmium-ruthenium carbonyl cluster compounds for their application as methanol-tolerant cathodes for oxygen reduction reaction and carbon monoxide-tolerant anodes for hydrogen oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Borja-Arco, E.; Uribe-Godinez, J.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

    2006-07-01

    This paper provided details of an electrokinetic study of novel electrocatalytic materials capable of performing both the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). Osmium-ruthenium carbonyl cluster compounds (Os{sub x}Ru{sub 3}(CO){sub n}) were synthesized by chemical condensation in non-polar organic solvents at different boiling points and refluxing temperatures. Three different non-polar organic solvents were used: (1) n-nonane; o-xylene; and 1,2-dichlorobenzene. The electrocatalysts were characterized by Fourier Transform Infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A rotating disk electrode technique was used to analyze the materials. Results of the analysis showed that the materials performed ORR in both the presence and absence of carbon monoxide (CO), and that electrocatalysts were not poisoned by the presence of CO. Cyclic voltamperometry for the disk electrodes showed that the electrochemical behaviour of the compounds in the acid electrolyte was similar in the presence or absence of methanol. The Tafel slope, exchange current density and the transfer coefficient were also investigated. The electrokinetic parameters for the ORR indicated that the materials with the highest electrocatalytic activity were synthesized in 1,2-dichlorobenzene. Electrocatalytic activity during HOR were prepared in n-nonane. It was concluded that the new materials are good candidates for use as both a cathode and an anode in proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). 7 refs., 2 tabs., 7 figs.

  13. Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes

    NARCIS (Netherlands)

    Kondratenko, E.V.; Mul, Guido; Baltrusaitis, Jonas; Larrazábal, G.O.; Pérez-Ramírez, J.

    2013-01-01

    This review highlights recent developments and future perspectives in carbon dioxide usage for the sustainable production of energy and chemicals and to reduce global warming. We discuss the heterogeneously catalysed hydrogenation, as well as the photocatalytic and electrocatalytic conversion of CO2

  14. Electrocatalytic Oxidation of Hydroxylamine at a Quinizarine Modified Glassy Carbon Electrode: Application to Differential Pulse Voltammetry Detection of Hydroxylamine

    OpenAIRE

    MAZLOUMARDAKANI, Mohammad; KARAMI, Payam EBRAHIMI

    2014-01-01

    The electrocatalytic behavior of hydroxylamine was studied on a glassy carbon electrode modified by electrodeposition of quinizarine, using cyclic voltammetry, chronoamperometry, and rotating disk voltammetry as diagnostic techniques. Cyclic voltammetry showed that the catalytic current of the system depends on the concentration of hydroxylamine. The magnitude of the peak current for quinizarine increased sharply in the presence of hydroxylamine and proportional to hydroxylamine conc...

  15. Characterization and Electrocatalytic Properties of Titanium-Based Ru0.3Co0.7−xCex Mixed Oxide Electrodes for Oxygen Evolution in Alkaline Solution

    Directory of Open Access Journals (Sweden)

    Hongjun Wu

    2011-01-01

    Full Text Available Ti-supported RuO2-Co3O4-CeO2 (Ru0.3Co0.7−xCex oxide, 0≤x≤0.7 electrodes were prepared by sol-gel process. The phase structure, surface morphology, and microstructure of the oxide layer were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Electrocatalytic activity and oxygen evolution reaction (OER kinetics on these electrodes in 1.0 mol⋅dm−3 KOH solution were studied by recording open-circuit potential, cyclic voltammetry, and polarisation curves. The results showed that the appropriate content of CeO2 could reduce the grain size and increase active surface area. The electrocatalytic activity shows a strong dependence on the CeO2 content in the film. Catalytic performance of mixed oxide electrodes with 40 mol % CeO2 was the best, with the greatest voltammetric charge, 86.23 mC⋅cm−2, and the smallest apparent activation energy for OER at 0.60 V was 22.76 kJ⋅mol−1.

  16. Greater confinement disposal of radioactive wastes

    International Nuclear Information System (INIS)

    Trevorrow, L.E.; Gilbert, T.L.; Luner, C.; Merry-Libby, P.A.; Meshkov, N.K.; Yu, C.

    1985-01-01

    Low-level radioactive waste (LLW) includes a broad spectrum of different radionuclide concentrations, half-lives, and hazards. Standard shallow-land burial practice can provide adequate protection of public health and safety for most LLW. A small volume fraction (approx. 1%) containing most of the activity inventory (approx. 90%) requires specific measures known as greater-confinement disposal (GCD). Different site characteristics and different waste characteristics - such as high radionuclide concentrations, long radionuclide half-lives, high radionuclide mobility, and physical or chemical characteristics that present exceptional hazards - lead to different GCD facility design requirements. Facility design alternatives considered for GCD include the augered shaft, deep trench, engineered structure, hydrofracture, improved waste form, and high-integrity container. Selection of an appropriate design must also consider the interplay between basic risk limits for protection of public health and safety, performance characteristics and objectives, costs, waste-acceptance criteria, waste characteristics, and site characteristics

  17. Assessing Human Impacts on the Greater Akaki River, Ethiopia ...

    African Journals Online (AJOL)

    We assessed the impacts of human activities on the Greater Akaki River using physicochemical parameters and macroinvertebrate metrics. Physicochemical samples and macroinvertebrates were collected bimonthly from eight sites established on the Greater Akaki River from February 2006 to April 2006. Eleven metrics ...

  18. Plasma leptin concentrations are greater in type II diabetic patients and stimulate monocyte chemotactic peptide-1 synthesis via the mitogen-activated protein kinase/extracellular signal-regulated kinase pathway

    Directory of Open Access Journals (Sweden)

    Jin Joo Cha

    2012-09-01

    Conclusions: Overall, these findings suggest that activation of leptin synthesis may promote MCP-1 activation in a diabetic environment via the MAPK pathway in VSMCs and that it possibly contributes to the acceleration of atherosclerosis.

  19. Electrocatalytic Performance of Carbon Supported WO3-Containing Pd–W Nanoalloys for Oxygen Reduction Reaction in Alkaline Media

    Directory of Open Access Journals (Sweden)

    Nan Cui

    2018-05-01

    Full Text Available In this paper, we report that WOx containing nanoalloys exhibit stable electrocatalytic performance in alkaline media, though bulk WO3 is easy to dissolve in NaOH solution. Carbon supported oxide-rich Pd–W alloy nanoparticles (PdW/C with different Pd:W atom ratios were prepared by the reduction–oxidation method. Among the catalysts, the oxide-rich Pd0.8W0.2/C (Pd/W = 8:2, atom ratio exhibits the highest catalytic activity for the oxygen reduction reaction. The X-ray photoelectron spectroscopy data shows that ~40% of Pd atoms and ~60% of the W atoms are in their oxide form. The Pd 3d5/2 binding energy of the oxide-rich Pd–W nanoalloys is higher than that of Pd/C, indicating the electronic structure of Pd is affected by the strong interaction between Pd and W/WO3. Compare to Pd/C, the onset potential of the oxygen reduction reaction at the oxide-rich Pd0.8W0.2/C shifts to a higher potential. The current density (mA·mg Pd−1 at the oxide-rich Pd0.8W0.2/C is ~1.6 times of that at Pd/C. The oxide-rich Pd0.8W0.2/C also exhibits higher catalytic stability than Pd/C, which demonstrates that it is a prospective candidate for the cathode of fuel cells operating with alkaline electrolyte.

  20. Immobilization of hydrogenase on carbon nanotube polyelectrolytes as heterogeneous catalysts for electrocatalytic interconversion of protons and hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jiang; Wu, Wen-Jie; Fang, Fang [Fudan University, Department of Chemistry (China); Zorin, Nikolay A. [Russian Academy of Sciences, Institute of Basic Biological Problems (Russian Federation); Chen, Meng; Qian, Dong-Jin, E-mail: djqian@fudan.edu.cn [Fudan University, Department of Chemistry (China)

    2016-08-15

    Immobilization of active enzymes on the surfaces of electrodes and nanomaterials is important in the fields of bioscience, and biotechnology. In this study, we investigated electrocatalytic properties of the interconversion of protons and hydrogen by means of hydrogenase (H{sub 2}ase)-functionalized carbon nanotube polyelectrolyte composites. Multiwalled carbon nanotube polyelectrolytes (MWNT-PEs) were synthesized through a diazonium and an addition reaction with poly(4-vinylpyridine) (P4VP), followed by another addition reaction with either methyl iodide (CH{sub 3}I) or N-methyl-N′-benzyl bromide bipyridinium (VBenBr) to produce MWNT-P4VPMe or MWNT-P4VPBenV polyelectrolytes, respectively. The MWNT-PE@H{sub 2}ase bio-nanocomposites were then prepared by means of MWNT-PEs as substrates to bind with H{sub 2}ase. The redox current density of the MWNT-PE@H{sub 2}ase-modified electrodes increased with a decrease in pH values of the Ar-saturated electrolyte solution owing to the catalytic reduction of protons (H{sub 2} production); further, it increased with the increasing pH values of the H{sub 2}-saturated solution owing to the catalytic oxidation of hydrogen. The reversible color change between blue-colored and colorless viologen (catalyzed by the MWNT-PE@H{sub 2}ase bio-nanocomposites) suggested that they may be developed as nano-biosensors for molecular H{sub 2}. The as-synthesized bio-nanocomposites showed strong long-term stability and high bioactivity.Graphical Abstract.

  1. Preparation of Cerium (III) 12-tungstophosphoric acid/ordered mesoporous carbon composite modified electrode and its electrocatalytic properties

    International Nuclear Information System (INIS)

    Liu Lin; Ndamanisha, Jean Chrysostome; Bai Jing; Guo Liping

    2010-01-01

    In this work, a novel structured Cerium (III) 12-tungstophosphoric acid (CePW)/ordered mesoporous carbon (OMC) composite is synthesized. The characterization of the material by the Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical characterization shows that the novel CePW/OMC composite has improved properties based on the combination of CePW and OMC properties. CePW/OMC can be used to modify the glassy carbon (GC) electrode and the CePW/OMC/GC modified electrode shows an enhanced electrocatalytic activity. This property can be applied in the determination of some biomolecules. Especially, the detection and determination of the guanine (G) in the presence of adenine (A) is achieved. The catalytic current of G versus its concentration shows a good linearity with two good linear ranges from 4.0 x 10 -6 to 8.0 x 10 -5 M and from 8.0 x 10 -5 to 1.9 x 10 -3 M (correlation coefficient = 0.999 and 0.996) with a detection limit of 5.7 x 10 -9 M (S/N = 3). The linear range for adenine is 4.0 x 10 -6 -7.0 x 10 -4 M with a detection limit of 7.45 x 10 -8 M. With good stability and reproducibility, the present CePW/OMC/GC modified electrode should be a good model for constructing a novel and promising electrochemical sensing platform for further electrochemical detection of other biomolecules.

  2. Electrocatalytical oxidation and sensitive determination of acetaminophen on glassy carbon electrode modified with graphene–chitosan composite

    International Nuclear Information System (INIS)

    Zheng, Meixia; Gao, Feng; Wang, Qingxiang; Cai, Xili; Jiang, Shulian; Huang, Lizhang; Gao, Fei

    2013-01-01

    The electrochemical behaviors of acetaminophen (ACOP) on a graphene–chitosan (GR–CS) nanocomposite modified glassy carbon electrode (GCE) were investigated by cyclic voltammetry (CV), chronocoulometry (CC) and differential pulse voltammetry (DPV). Electrochemical characterization showed that the GR–CS nanocomposite had excellent electrocatalytic activity and surface area effect. As compared with bare GCE, the redox signal of ACOP on GR–CS/GCE was greatly enhanced. The values of electron transfer rate constant (k s ), diffusion coefficient (D) and the surface adsorption amount (Γ ⁎ ) of ACOP on GR–CS/GCE were determined to be 0.25 s −1 , 3.61 × 10 −5 cm 2 s −1 and 1.09 × 10 −9 mol cm −2 , respectively. Additionally, a 2e − /2H + electrochemical reaction mechanism of ACOP was deduced based on the acidity experiment. Under the optimized conditions, the ACOP could be quantified in the range from 1.0 × 10 −6 to 1.0 × 10 −4 M with a low detection limit of 3.0 × 10 −7 M based on 3S/N. The interference and recovery experiments further showed that the proposed method is acceptable for the determination of ACOP in real pharmaceutical preparations. Highlights: ► A chitosan–graphene nanocomposite modified glassy carbon electrode was prepared. ► The modified electrode was electrochemically characterized by CV and EIS. ► Electro-oxidation of acetaminophen was examined on the modified electrode. ► Sensing analysis of the modified electrode toward acetaminophen was studied

  3. Electrocatalytic oxidation of hydrazine at overoxidized polypyrrole film modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Majidi, Mir Reza [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of); Jouyban, Abolghasem [Faculty of Pharmacy and Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz 51664 (Iran, Islamic Republic of); Asadpour-Zeynali, Karim [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of)]. E-mail: asadpour@tabrizu.ac.ir

    2007-06-20

    Electrocatalytic oxidation of hydrazine (HZ) was studied on an overoxidized polypyrrole (OPPy) modified glassy carbon electrode using cyclic voltammetry and chronoamperometry techniques. The OPPy-modified glassy carbon electrode has very high catalytic ability for electrooxidation of HZ, which appeared as a reduced overpotential in a wide operational pH range of 5-10. The overall numbers of electrons involved in the catalytic oxidation of HZ, the number of electrons involved in the rate-determining and diffusion coefficient of HZ were estimated using cyclic voltammetry and chronoamperometry. It has been shown that using the OPPy-modified electrode, HZ can be determined by cyclic voltammetry and amperometry with limit of detection 36 and 3.7 {mu}M, respectively. The results of the analysis suggest that the proposed method promises accurate results and could be employed for the routine determination of HZ.

  4. Exploring the origins of the apparent "electrocatalytic" oxidation of kojic acid at graphene modified electrodes.

    Science.gov (United States)

    Figueiredo-Filho, Luiz C S; Brownson, Dale A C; Fatibello-Filho, Orlando; Banks, Craig E

    2013-08-21

    We explore the recent reports that the use of graphene modified electrodes gives rise to the electrocatalytic oxidation of kojic acid. It is demonstrated that large quantifiable voltammetric signatures are observed on bare/unmodified graphitic electrodes, which are shown to be analytically useful and superior to those observed at graphene modified alternatives. This work is of importance as it shows that control experiments are critical and must be undertaken before "electrocatalysis" is conferred when investigating graphene in electrochemistry. In terms of the electroanalytical response of graphene modified electrodes, a bare edge plane pyrolytic graphite electrode is shown to give rise to an improved linear range and limit of detection, questioning the need to modify electrodes with graphene.

  5. Direct synthesis of graphene nanosheets support Pd nanodendrites for electrocatalytic formic acid oxidation

    Institute of Scientific and Technical Information of China (English)

    杨苏东; 陈琳

    2015-01-01

    We report a solvothermal method preparation of dendritic Pd nanoparticles (DPNs) and spherical Pd nanoparticles (SPNs) supported on reduced graphene oxide (RGO). Drastically different morphologies of Pd NPs with nanodendritic structures or spherical structures were observed on graphene by controlling the reduction degree of graphene oxide (GO) un-der mild conditions. In addition to being a commonplace substrate, GO plays a more important role that relies on its surface groups, which serves as a shape-directing agent to direct the dendritic growth. As a result, the obtained DPNs/RGO catalyst exhibits a significantly enhanced electro-catalytic behavior for the oxidation of formic acid compared to the SPNs/RGO catalyst.

  6. Rapid synthesis of dendritic Pt/Pb nanoparticles and their electrocatalytic performance toward ethanol oxidation

    Science.gov (United States)

    Zhang, Ke; Xu, Hui; Yan, Bo; Wang, Jin; Gu, Zhulan; Du, Yukou

    2017-12-01

    This article reports a rapid synthetic method for the preparation of dendritic platinum-lead bimetallic catalysts by using an oil bath for 5 min in the presence of hexadecyltrimethylammonium chloride (CTAC) and ascorbic acid (AA). CTAC acts as a shape-direction agent, and AA acts as a reducing agent during the reaction process. A series of physical techniques are used to characterize the morphology, structure and electronic properties of the dendritic Pt/Pb nanoparticles, indicating the Pt/Pb dendrites are porous, highly alloying, and self-supported nanostructures. Various electrochemical techniques were also investigated the catalytic performance of the Pt/Pb catalysts toward the ethanol electrooxidation reaction. Cyclic voltammetry and chronoamperometry indicated that the synthesized dendritic Pt/Pb nanoparticles possessed much higher electrocatalytic performance than bulk Pt catalyst. This study may inspire the engineering of dendritic bimetallic catalysts, which are expected to have great potential applications in fuel cells.

  7. Novel antimony doped tin oxide/carbon aerogel as efficient electrocatalytic filtration membrane

    Directory of Open Access Journals (Sweden)

    Zhimeng Liu

    2016-05-01

    Full Text Available A facile method was developed to prepare antimony doped tin oxide (Sb-SnO2/carbon aerogel (CA for use as an electrocatalytic filtration membrane. The preparation process included synthesis of a precursor sol, impregnation, and thermal decomposition. The Sb-SnO2, which was tetragonal in phase with an average crystallite size of 10.8 nm, was uniformly distributed on the CA surface and firmly attached via carbon-oxygen-tin chemical bonds. Preliminary filtration tests indicated that the Sb-SnO2/CA membrane had a high rate of total organic carbon removal for aqueous tetracycline owing to its high current efficiency and electrode stability.

  8. Electrocatalytic reduction of H2O2 by Pt nanoparticles covalently bonded to thiolated carbon nanostructures

    International Nuclear Information System (INIS)

    You, Jung-Min; Kim, Daekun; Jeon, Seungwon

    2012-01-01

    Highlights: ► Novel thiolated carbon nanostructures – platinum nanoparticles [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] have been synthesized, and [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] denotes as t-GO-pt and t-MWCNT-Pt in manuscript, respectively. ► The modified electrode denoted as PDDA/t-GO-pt/GCE was used for the electrochemical determination of H 2 O 2 for the first time. ► The results show that PDDA/t-GO-pt nanoparticles have the promising potential as the basic unit of the electrochemical biosensors for the detection of H 2 O 2 . ► The proposed H 2 O 2 biosensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s. - Abstract: Glassy carbon electrodes were coated with thiolated carbon nanostructures – multi-walled carbon nanotubes and graphene oxide. The subsequent covalent addition of platinum nanoparticles and coating with poly(diallydimethylammonium chloride) resulted in biosensors that detected hydrogen peroxide through its electrocatalytic reduction. The sensors were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H 2 O 2 . The Pt nanoparticles covalently bonded to the thiolated carbon nanostructures were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Cyclic voltammetry and amperometry were used to characterize the biosensors’ performances. The sensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s, thus demonstrating their potential for use in H 2 O 2 analysis.

  9. Electrocatalytic behaviour of hybrid cobalt–manganese hexacyanoferrate film on glassy carbon electrode

    International Nuclear Information System (INIS)

    Vinu Mohan, A.M.; Rambabu, Gutru; Aswini, K.K.; Biju, V.M.

    2014-01-01

    A thin film of hybrid cobalt–manganese hexacyanoferrate (CoMnHCF), a redox mediator was electrodeposited on a glassy carbon (GC) electrode and was employed as an amperometric sensor towards L-Tryptophan (L-Trp). The hybrid film was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction technique (XRD), scanning electron microscope–energy dispersive X-ray spectroscopy (SEM–EDAX), and electrochemical techniques. The atomic absorption spectroscopic analysis provided the stoichiometry of the hybrid film to be K 1.74-y Co y Mn 0.78 [Fe(CN) 6 ], y ≤ 0.68. The electrochemical impedance study revealed the excellent charge transfer properties of GC/CoMnHCF electrode. The voltammetric investigations demonstrated exceptional electrocatalytic properties of the hybrid film modified electrode when compared to that of bare GC, GC/CoHCF and GC/MnHCF electrodes, towards the L-Trp oxidation. The kinetic parameters such as electron transfer coefficient, the electron transfer rate constant, the diffusion coefficient and the catalytic rate constant for the electrooxidation process of L-Trp were investigated. The amperometric detection of L-Trp employing GC/CoMnHCF electrode possessed a good sensitivity of 10 × 10 −2 A M −1 cm −2 in a wide range of detection (2–200 μM) at a reduced overpotential of 680 mV. In addition, the proposed amperometric method was applied to the detection of L-Trp in commercial milk samples with reproducible results. - Highlights: • A hybrid cobalt–manganese hexacyanoferrate film was prepared. • The hybrid film possesses excellent charge transfer properties. • The hybrid film exhibits excellent electrocatalytic properties towards Tryptophan. • Tryptophan detection is possible from commercial milk samples

  10. Electrodeposition of tantalum on carbon black in non-aqueous solution and its electrocatalytic properties

    International Nuclear Information System (INIS)

    Jo, Ara; Lee, Youngmi; Lee, Chongmok

    2016-01-01

    In this work, we synthesized tantalum (Ta) nanoclusters on carbon black (Ta/CB) via simple electrodeposition in non-aqueous solvent, acetonitrile (ACN) at ambient temperature. Transmission electron microscopy (TEM) images showed that the electrodeposited Ta nanoclusters consisted of tiny Ta nanoparticles. X-ray photoelectron spectroscopy (XPS) result represented that the outermost Ta formed the native oxide on Ta/CB due to its ambient exposure to air. Electrochemical catalytic properties of prepared Ta/CB on glassy carbon electrode (Ta/CB/GC) were investigated toward reductions of oxygen and hydrogen peroxide, and oxidations of ascorbic acid and dopamine. For oxygen reduction reaction (ORR) in acid, Ta/CB/GC represented a decent electrocatalytic performance which was better or comparable to bare Pt. The operational stability in acidic condition was maintained up to 500 repetitive potential cycles presumably due to the protective native Ta oxide layer. Ta/CB/GC also showed high amperometric sensitivity (4.5 (±0.1_6) mA mM"−"1 cm"−"2, n = 5) for reduction of hydrogen peroxide in 0.1 M phosphate buffer solution (PBS, pH 7.4). In addition, Ta/CB/GC was demonstrated for the possibility of simultaneous detection of ascorbic acid and dopamine using differential pulse voltammetry (DPV). - Highlights: • We electrodeposited Ta nanoclusters (Ta/CB/GC) in acetonitrile at room temperature. • The Ta/CB/GC showed better or comparable performance to bare Pt for ORR. • The Ta/CB/GC showed high sensitivity for reduction of hydrogen peroxide at pH 7.4. • The Ta/CB/GC showed possible simultaneous detection of ascorbic acid and dopamine. • We extended the applicability of Ta electrode material for various electrocatalytic reactions.

  11. Electrodeposition of tantalum on carbon black in non-aqueous solution and its electrocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Ara; Lee, Youngmi, E-mail: youngmilee@ewha.ac.kr; Lee, Chongmok, E-mail: cmlee@ewha.ac.kr

    2016-08-24

    In this work, we synthesized tantalum (Ta) nanoclusters on carbon black (Ta/CB) via simple electrodeposition in non-aqueous solvent, acetonitrile (ACN) at ambient temperature. Transmission electron microscopy (TEM) images showed that the electrodeposited Ta nanoclusters consisted of tiny Ta nanoparticles. X-ray photoelectron spectroscopy (XPS) result represented that the outermost Ta formed the native oxide on Ta/CB due to its ambient exposure to air. Electrochemical catalytic properties of prepared Ta/CB on glassy carbon electrode (Ta/CB/GC) were investigated toward reductions of oxygen and hydrogen peroxide, and oxidations of ascorbic acid and dopamine. For oxygen reduction reaction (ORR) in acid, Ta/CB/GC represented a decent electrocatalytic performance which was better or comparable to bare Pt. The operational stability in acidic condition was maintained up to 500 repetitive potential cycles presumably due to the protective native Ta oxide layer. Ta/CB/GC also showed high amperometric sensitivity (4.5 (±0.1{sub 6}) mA mM{sup −1} cm{sup −2}, n = 5) for reduction of hydrogen peroxide in 0.1 M phosphate buffer solution (PBS, pH 7.4). In addition, Ta/CB/GC was demonstrated for the possibility of simultaneous detection of ascorbic acid and dopamine using differential pulse voltammetry (DPV). - Highlights: • We electrodeposited Ta nanoclusters (Ta/CB/GC) in acetonitrile at room temperature. • The Ta/CB/GC showed better or comparable performance to bare Pt for ORR. • The Ta/CB/GC showed high sensitivity for reduction of hydrogen peroxide at pH 7.4. • The Ta/CB/GC showed possible simultaneous detection of ascorbic acid and dopamine. • We extended the applicability of Ta electrode material for various electrocatalytic reactions.

  12. Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

    Science.gov (United States)

    Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

    2017-08-30

    One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

  13. Dynamics of electrocatalytic oxidation of ethylene glycol, methanol and formic acid at MWCNT platform electrochemically modified with Pt/Ru nanoparticles

    CSIR Research Space (South Africa)

    Maxakato, NW

    2010-03-01

    Full Text Available Comparative electrocatalytic behavior of functionalized multiwalled carbon nanotubes (fMWCNTs) electrodecorated with Pt/Ru nanoparticles towards the oxidation of methanol (MeOH), ethylene glycol (EG) and formic acid (FA) has been investigated...

  14. Formation, surface characterization, and electrocatalytic application of self-assembled monolayer films of tetra-substituted manganese, iron, and cobalt benzylthio phthalocyanine complexes

    CSIR Research Space (South Africa)

    Akinbulu, IA

    2011-10-01

    Full Text Available characteristics of the films were interrogated by cyclic voltammetry. Significant passivation of voltammetry processes associated with bare gold surface (gold oxidation and underpotential deposition of copper) confirmed formation of the films. Electrocatalytic...

  15. Social Entrepreneurship and Shrinking Regions paper thoughts: “What motivates social entrepreneurs to be active in promoting sustainable social services in shrinking rural regions? A case study of Greater Twente.

    NARCIS (Netherlands)

    Benneworth, Paul Stephen; Velderman, Willem-Jan; Stienstra, Martin R.

    2016-01-01

    There is an increasing realisation that advanced economies are suffering from a new wave of rural depopulation as a consequence of a ‘perfect storm’ of rural outmigration and falling birth-rates. The issue of managed decline (i.e. rural demolition) has actively been proposed as the only inevitable

  16. Effect of the structural characteristics of binary Pt-Ru and ternary Pt-Ru-M fuel cell catalysts on the activity of ethanol electrooxidation in acid medium.

    Science.gov (United States)

    Antolini, Ermete

    2013-06-01

    In view of their possible use as anode materials in acid direct ethanol fuel cells, the electrocatalytic activity of Pt-Ru and Pt-Ru-M catalysts for ethanol oxidation has been investigated. This minireview examines the effects of the structural characteristics of Pt-Ru, such as the degree of alloying and Ru oxidation state, on the electrocatalytic activity for ethanol oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis and electrocatalytic activity of Au/Pt bimetallic nanodendrites for ethanol oxidation in alkaline medium.

    Science.gov (United States)

    Han, Xinyi; Wang, Dawei; Liu, Dong; Huang, Jianshe; You, Tianyan

    2012-02-01

    Gold/Platinum (Au/Pt) bimetallic nanodendrites were successfully synthesized through seeded growth method using preformed Au nanodendrites as seeds and ascorbic acid as reductant. Cyclic voltammograms (CVs) of a series of Au/Pt nanodendrites modified electrodes in 1M KOH solution containing 1M ethanol showed that the electrocatalyst with a molar ratio (Au:Pt) of 3 exhibited the highest peak current density and the lowest onset potential. The peak current density of ethanol electro-oxidation on the Au(3)Pt(1) nanodendrites modified glassy carbon electrode (Au(3)Pt(1) electrode) is about 16, 12.5, and 4.5 times higher than those on the polycrystalline Pt electrode, polycrystalline Au electrode, and Au nanodendrites modified glassy carbon electrode (Au dendrites electrode), respectively. The oxidation peak potential of ethanol electro-oxidation on the Au(3)Pt(1) electrode is about 299 and 276 mV lower than those on the polycrystalline Au electrode and Au dendrites electrode, respectively. These results demonstrated that the Au/Pt bimetallic nanodendrites may find potential application in alkaline direct ethanol fuel cells (ADEFCs). Copyright © 2011 Elsevier Inc. All rights reserved.

  18. Facile synthesis, dielectric properties and electrocatalytic activities of PMMA-NiFe2O4 nanocomposite

    International Nuclear Information System (INIS)

    Maji, Pranabi; Choudhary, Ram Bilash

    2017-01-01

    The paper deals with the dielectric and catalytic properties of poly (methyl methacrylate)-nikel ferrite (PMMA-NiFe 2 O 4 ) nanocomposite. The nanocomposite was prepared by using a general and facile synthesis strategy. Fourier transform infrared (FTIR) and X-ray diffraction (XRD) spectra confirmed the formation of PMMA-NiFe 2 O 4 nanocomposite. Field effect scanning electron microscopic (FESEM) and transmission electron microscopic (TEM) images revealed that NiFe 2 O 4 nanoparticles were uniformly distributed and were tightly adhered with PMMA matrix owing to surface modification with 3-methacryloyloxy propyl trimethoxy silane (KH-570). Thermal stability was enhanced by incorporation of NiFe 2 O 4 nanofillers. The nanocomposite showed high dielectric constant and low dielectric loss. The achieved dielectric and thermal property inferred the potential application of this material in energy storage and embedded electronics devices. Further, the as prepared nanocomposite also offered a remarkable electrochemical performance towards hydrogen peroxide (H 2 O 2 ) sensing. - Highlights: • PMMA-NiFe 2 O 4 nanocomposite was synthesized via free radical polymerization. • The nanocomposite exhibited high value of dielectric constant (51) and tanδ (0.3). • Thermal stability of the PMMA matrix was improved by the incorporation of NiFe 2 O 4. • The H 2 O 2 detection limit was estimated 44 μM when signal to noise (S/N) ration was 3. • The electrochemical sensitivity of H 2 O 2 was calculated 0.6727 μA mM -1 .

  19. Oxidized multi walled carbon nanotubes for improving the electrocatalytic activity of a benzofuran derivative modified electrode

    Directory of Open Access Journals (Sweden)

    Mohammad Mazloum-Ardakani

    2016-01-01

    Full Text Available In the present paper, the use of a novel carbon paste electrode modified by 7,8-dihydroxy-3,3,6-trimethyl-3,4-dihydrodibenzo[b,d]furan-1(2H-one (DTD and oxidized multi-walled carbon nanotubes (OCNTs is described for determination of levodopa (LD, acetaminophen (AC and tryptophan (Trp by a simple and rapid method. At first, the electrochemical behavior of DTD is studied, then, the mediated oxidation of LD at the modified electrode is investigated. At the optimum pH of 7.4, the oxidation of LD occurs at a potential about 330 mV less positive than that of an unmodified carbon paste electrode. Based on differential pulse voltammetry (DPV, the oxidation current of LD exhibits a linear range between 1.0 and 2000.0 μM of LD with a detection limit (3σ of 0.36 μM. DPV was also used for simultaneous determination of LD, AC and Trp at the modified electrode. Finally, the proposed electrochemical sensor was used for determinations of these substances in human serum sample.

  20. Electrocatalytic activity of Cu2O nanocubes-based electrode for ...

    Indian Academy of Sciences (India)

    sensitive, selective, and fast amperometric sensing of glucose, which is promising for the future development of non-enzymatic ... sensors have attracted much attention because of their ... addition of 0.1 M L-ascorbic acid, the colour changed.

  1. Partially Hydrogenated Graphene Materials Exhibit High Electrocatalytic Activities Related to Unintentional Doping with Metallic Impurities

    Czech Academy of Sciences Publication Activity Database

    Jankovský, O.; Libánská, A.; Bouša, D.; Sedmidubský, D.; Matějková, Stanislava; Sofer, Z.

    2016-01-01

    Roč. 22, č. 25 (2016), s. 8627-8634 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GA15-09001S Institutional support: RVO:61388963 Keywords : electrocatalysis * electrochemistry * graphene * hydrogenation * sensing Subject RIV: CA - Inorganic Chemistry Impact factor: 5.317, year: 2016

  2. Influence of different carbon nanostructures on the electrocatalytic activity and stability of Pt supported electrocatalysts

    DEFF Research Database (Denmark)

    Stamatin, Serban Nicolae; Borghei, Maryam; Andersen, Shuang Ma

    2014-01-01

    Commercially available graphitized carbon nanofibers and multi-walled carbon nanotubes, two carbon materials with very different structure, have been functionalized in a nitric–sulfuric acid mixture. Further on, the materials have been platinized by a microwave assisted polyol method. The relative...

  3. Cobalt coatings: deposition on a nickel substrate and electrocatalytic activity for alkaline water electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Brossard, L. (Inst. de Recherche d' Hydro-Quebec (IREQ), Varennes, Quebec (Canada))

    1992-02-01

    The deposition of cobalt on a nickel substrate in 30 wt% KOH aqueous solution containing dissolved cobalt was investigated. The effect of the applied cathodic current density (i{sub a}) and the dissolved-cobalt concentration in the electrolyte on the deposition rate suggests that the rate-determining step is the diffusion of the dissolved cobalt in the solution. The faradic efficiency of the cobalt deposition reaction and the coating morphology are linked to i{sub a}, while the evolution rate of both oxygen and hydrogen in 30 wt% KOH at 70degC is dependent on the coating morphology. (orig.).

  4. Electrocatalytic activity of atomic layer deposited Pt–Ru catalysts onto N-doped carbon nanotubes

    DEFF Research Database (Denmark)

    Johansson, Anne-Charlotte Elisabeth Birgitta; Larsen, Jackie Vincent; Verheijen, Marcel A.

    2014-01-01

    (ethylcyclopentadienyl)ruthenium (Ru(EtCp)2), respectively. O2 was used as the reactant in both processes. The composition of the catalysts was easily tuned by varying the Pt-to-Ru ALD cycle ratio. The catalysts were tested toward the CO oxidation and methanol oxidation reaction (MOR) in a three-electrode electrochemical set...

  5. Electrocatalytic activity of atomic layer deposited Pt-Ru catalysts onto N-doped carbon nanotubes

    NARCIS (Netherlands)

    Johansson, A.-C.; Larsen, J.V.; Verheijen, M.A.; Haugshøj, K.B.; Clausen, H.; Kessels, W.M.M.; Christensen, L.H.; Thomsen, E.V.

    2014-01-01

    Pt-Ru catalysts of various compositions, between 0 and 100 at.% of Ru, were deposited onto N-doped multi-walled carbon nanotubes (N-CNTs) by atomic layer deposition (ALD) at 250 C. The Pt and Ru precursors were trimethyl(methylcyclopentadienyl)platinum (MeCpPtMe3) and

  6. Assembly of Modified Ferritin Proteins on Carbon Nanotubes and its Electrocatalytic Activity for Oxygen Reduction

    Science.gov (United States)

    Kim, Jae-Woo; Lillehei, Peter T.; Park, Cheol

    2012-01-01

    Highly effective dispersions of carbon nanotubes (CNTs) can be made using a commercially available buffer solution. Buffer solutions of 3-(N-morpholino)-propanesulfonic acid (MOPS), which consists of a cyclic ring with nitrogen and oxygen heteroatoms, a charged group, and an alkyl chain greatly enhance the dispersibility and stability of CNTs in aqueous solutions. Additionally, the ability of biomolecules, especially cationized Pt-cored ferritins, to adhere onto the well-dispersed CNTs in the aqueous buffer solution is also improved. This was accomplished without the use of surfactant molecules, which are detrimental to the electrical, mechanical, and other physical properties of the resulting products. The assembled Pt-cored ferritin proteins on the CNTs were used as an electrocatalyst for oxygen reduction

  7. Multifunctional electrocatalytic hybrid carbon nanocables with highly active edges on their walls

    Czech Academy of Sciences Publication Activity Database

    Gusmao, R.; Sofer, Z.; Nováček, M.; Luxa, J.; Matějková, Stanislava; Pumera, M.

    2016-01-01

    Roč. 8, č. 12 (2016), s. 6700-6711 ISSN 2040-3364 Institutional support: RVO:61388963 Keywords : metallic impurities * graphene oxide * selective detection Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 7.367, year: 2016

  8. Modeling the active site of [FeFe]-hydrogenase: Electro-catalytic ...

    Indian Academy of Sciences (India)

    The mechanistic aspects of relevant electro–catalytic proton reductions have been discussed in detail. ... in the presence of a weak acid.4 This prompted us to investigate whether .... shifted to lower magnetic field strengths than those in parent ...

  9. Greater trochanteric pain syndrome diagnosis and treatment.

    Science.gov (United States)

    Mallow, Michael; Nazarian, Levon N

    2014-05-01

    Lateral hip pain, or greater trochanteric pain syndrome, is a commonly seen condition; in this article, the relevant anatomy, epidemiology, and evaluation strategies of greater trochanteric pain syndrome are reviewed. Specific attention is focused on imaging of this syndrome and treatment techniques, including ultrasound-guided interventions. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. Highly improved electrocatalytic behavior of sulfite at carbon ionic liquid electrode: Application to the analysis of some real samples

    International Nuclear Information System (INIS)

    Safavi, Afsaneh; Maleki, Norouz; Momeni, Safieh; Tajabadi, Fariba

    2008-01-01

    The electrocatalytic oxidation of sulfite was investigated at carbon ionic liquid electrode (CILE). This electrode is a very good alternative to previously described electrodes because the electrocatalytic effect is achieved without any electrode modification. Comparative experiments were carried out using carbon paste electrode (CPE) and glassy carbon electrode (GCE). At CILE, highly reproducible and well-defined cyclic voltammograms were obtained for sulfite with a peak potential of 0.55 V vs. Ag/AgCl. Sulfite oxidation at CILE does not result in deactivation of the electrode surface. The kinetic parameters for this irreversible heterogeneous electron transfer process were determined. Under optimal experimental conditions, the peak current response increased linearly with sulfite concentration over the range of 6-1000 μM. The detection limit of the method was 4 μM. The method was applied to the determination of sulfite in mineral water, grape juice and non-alcoholic beer samples

  11. Assembly of crosslinked oxo-cyanoruthenate and zirconium oxide bilayers: Application in electrocatalytic films based on organically modified silica with templated pores

    International Nuclear Information System (INIS)

    Rutkowska, Iwona A.; Sek, Jakub P.; Mehdi, B. Layla; Kulesza, Pawel J.; Cox, James A.

    2014-01-01

    Electrochemical deposition of crosslinked oxo-cyanoruthenate, Ru-O/CN-O, from a mixture of RuCl 3 and K 4 Ru(CN) 6 is known to yield a film on glassy carbon that promotes oxidations by a combination of electron and oxygen transfer. Layer-by-layer (LbL) deposition of this species at a film formed by cycling of the electrode potential in a ZrO 2 solution systematically increases the number of catalytically active sites of the Ru-O/CN-O on the electrode. The evaluation of the electrocatalytic activity was by cyclic voltammetric oxidation of cysteine at pH 2. Plots of the anodic peak current vs. the square root of scan rate were indicative of linear diffusion control of this oxidation, even in the absence of ZrO 2 , but the slopes of these linear plots increased with bilayer number, n, of (ZrO 2 | Ru-O/CN-O) n . The latter observation is hypothesized to be due to an increased number of active sites for a given geometric electrode area, but proof requires further study. To optimize utilization of the catalyst and to provide a size-exclusion characteristic to the electrode, the study was extended to LbL deposition of the composite in 50-nm pores of an organically modified silica film deposited by electrochemically assisted sol-gel processing using surface-bound poly(styrene sulfonate) nanospheres as a templating agent

  12. Charge transfer-resistance in nitrogen-doped/undoped graphene: Its influence on the electro-catalytic reduction of H2O2

    International Nuclear Information System (INIS)

    Magerusan, Lidia; Pogacean, Florina; Socaci, Crina; Coros, Maria; Rosu, Marcela-Corina; Pruneanu, Stela

    2016-01-01

    Nitrogen doped (N-Gr) and undoped (TRGO) graphene were chemically synthesized and characterized by TEM, STEM-EDX and XPS. The electrochemical reduction of H 2 O 2 was investigated with bare glassy carbon (GC) electrode and with GC modified with each graphene sample. The active area of TRGO/GC and N-Gr/GC modified electrodes were found to be 0.75 and 0.295 cm 2 , respectively. Both were considerably larger than that of bare GC (0.07 cm 2 ). We carefully looked at the kinetic of interfacial electron transfer process and found that the charge-transfer resistance (R ct ) of TRGO/GC electrode (7.83 × 10 6 Ω) was significantly lower than that of N-Gr/GC electrode (4.81 × 10 7 Ω) or bare GC (1.74 × 10 9 Ω). Interestingly, although TRGO/GC electrode had the largest active area and the smallest charge transfer resistance, it did not promote the H 2 O 2 electrochemical reduction. In contrast, N-Gr/GC modified electrode exhibited an enhanced electro-catalytic activity towards H 2 O 2 reduction, which was related to the presence of heterogeneous atoms into the sp 2 carbon network.

  13. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

    Science.gov (United States)

    Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

    2015-12-01

    Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

  14. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

    International Nuclear Information System (INIS)

    Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

    2015-01-01

    Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611}high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H_2PtCl_6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells. (paper)

  15. The NuSTAR Extragalactic Survey: First Direct Measurements of the Greater Than Or Similar To 10 Kev X-Ray Luminosity Function For Active Galactic Nuclei At z > 0.1

    DEFF Research Database (Denmark)

    Aird, J.; Alexander, D. M.; Ballantyne, D. R.

    2015-01-01

    We present the first direct measurements of the rest-frame 10-40 keV X-ray luminosity function (XLF) of active galactic nuclei (AGNs) based on a sample of 94 sources at 0.1 ... program. Our results are consistent with the strong evolution of the AGN population seen in prior, lower-energy studies of the XLF. However, different models of the intrinsic distribution of absorption, which are used to correct for selection biases, give significantly different predictions for the total...... component (with a relative normalization of R ∼ 2 at all luminosities) can bring extrapolations of the XLF from 2-10 keV into agreement with our NuSTAR sample. Ultimately, X-ray spectral analysis of the NuSTAR sources is required to break this degeneracy between the distribution of absorbing column...

  16. The skin migratory stage of the schistosomulum of Schistosoma mansoni has a surface showing greater permeability and activity in membrane internalisation than other forms of skin or mechanical schistosomula.

    Science.gov (United States)

    DE Jesus Jeremias, Wander; DA Cunha Melo, Jose Renan; Baba, Elio Hideo; Coelho, Paulo Marcos Zech; Kusel, John Robert

    2015-08-01

    Skin schistosomula can be prepared by collecting them after isolated mouse skin have been penetrated by cercariae in vitro. The schistosomula can also migrate out of isolated mouse skin penetrated by cercariae in vitro and from mouse skin penetrated by cercariae in vivo. Schistosomula can also be produced from cercariae applied through a syringe or in a vortex. When certain surface properties of the different forms of schistosomula were compared, those migrating from mouse skin penetrated by cercariae in vivo or in vitro had greatly increased permeability to membrane impermeant molecules such as Lucifer yellow and high molecular weight dextrans. These migrating forms also possessed surfaces which showed greatly enhanced uptake into internal membrane vesicles of the dye FM 143, a marker for endocytosis. This greatly enhanced activity and permeability of the surfaces of tissue migrating schistosomula is likely to be of great importance in the adaptation to the new host.

  17. A nano-structured Ni(II)-chelidamic acid modified gold nanoparticle self-assembled electrode for electrocatalytic oxidation and determination of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Gholivand, Mohammad Bagher, E-mail: mbgholivand@yahoo.com [Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of); Azadbakht, Azadeh [Department of Chemistry, Faculty of Basic Science, Khorramabad Branch, Islamic Azad University, Khorramabad (Iran, Islamic Republic of)

    2012-10-01

    A nano-structured Ni(II)-chelidamic acid (2,6-dicarboxy-4-hydroxypyridine) film was electrodeposited on a gold nanoparticle-cysteine-gold electrode. The morphology of Ni(II)-chelidamic acid gold nanoparticle self-assembled electrode was investigated by scanning electron microscopy (SEM). Electrocatalytic oxidation of methanol on the surface of modified electrode was studied by cyclic voltammetry and chronoamperometry methods. The hydrodynamic amperometry at a rotating modified electrode at constant potential versus reference electrode was used for detection of methanol. Under optimized conditions the calibration plots are linear in the concentration range 0-50 mM with a detection limit of 15 {mu}M. The formed matrix in our work possessed a 3D porous network structure with a large effective surface area, high catalytic activity and behaved like microelectrode ensembles. The modified electrode indicated reproducible behavior and a high level stability during the experiments, making it particularly suitable for analytical purposes. - Highlights: Black-Right-Pointing-Pointer The Au electrode modified with thin Ni(II)/CHE-AuNP film shows stable and reproducible behavior. Black-Right-Pointing-Pointer Long stability and excellent electrochemical reversibility were observed. Black-Right-Pointing-Pointer This modified electrode shows excellent catalytic activity for methanol oxidation. Black-Right-Pointing-Pointer Combination of unique properties of AuNP and Ni(II)/CHE resulted in improvement of current responses.

  18. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

    Science.gov (United States)

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-02-01

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs.

  19. Electrocatalytic glucose oxidation via hybrid nanomaterial catalyst of multi-wall TiO2 nanotubes supported Ni(OH)2 nanoparticles: Optimization of the loading level

    International Nuclear Information System (INIS)

    Gu, Yingying; Liu, Yicheng; Yang, Haihong; Li, Benqiang; An, Yarui

    2015-01-01

    Highlights: • Multi-wall TiO 2 nanotube supported Ni(OH) 2 nanoparticles, Ni(OH) 2 /TNTs, was prepared and investigated as anode electro-catalysts for glucose oxidation. • Ni(OH) 2 -24.2%/TNTs obtains the best catalytic activity. • Compared with Ni(OH) 2, the current density of Ni(OH) 2 -24.2%/TNTs increased 5.9 times in 0.1 M NaOH solution. - Abstract: The novel hybrid nanomaterial catalyst of multi-wall TiO 2 nanotube supported Ni(OH) 2 nanoparticles (Ni(OH) 2 /TNTs) was prepared through hydrothermal method and investigated as anode electro-catalysts for glucose oxidation. The nanostructure was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), thermogravimetry-differential thermal analysis (TGA) and nitrogen adsorption-desorption (BET-BJH). The electrochemical performance was measured by a range of electrochemical measurements. Compared with Ni(OH) 2 , the current density of Ni(OH) 2 /TNTs modified GC electrode increased 5.9 times in 0.1 M NaOH solution. The results indicated that the synthesized nanoparticles exhibited good electro-catalytic activity and stability for glucose oxidation. Meanwhile, the hybrid nanomaterial of Ni(OH) 2 /TNTs may be a potential candidate catalyst for direct glucose fuel cell

  20. The Manipulation of Hydrophobicity in Catalyst Design for Applications of Aerobic Alcohols Oxidation and Electrocatalytic Water Oxidation

    KAUST Repository

    Chen, Batian

    2016-05-17

    Hydrophobicity is the generalized characteristic of non-polar substances that brings about their exclusion from aqueous phases. This property, entropic in its nature, drives key self-assembly and phase separation processes in water. Protein folding, the formation of DNA double helix, the existence of lipid bilayers and the wetting properties of leaf surfaces are all due to hydrophobic interactions. Inspired by Nature, we aimed to use hydrophobicity for creating novel and improved catalytic systems. (I) A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. (II) An enzyme-inspired catalytic system based on a rationally designed multifunctional surfactant was developed. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically. (III) Development of a facile means of photo/electrocatalytic water splitting is one of the main barriers to establishing of a solar hydrogen economy. Of the two half-reactions involved in splitting water into O2 and H2, water oxidation presents the most challenge due to its mechanistic complexity. A practical water oxidation catalyst must be highly active, yet inexpensive and indefinitely stable under harsh oxidative conditions. Here, I shall describe the synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine, (BimH)3. A wide range of catalysts differing in their electronic properties

  1. Impact of solute concentration on the electrocatalytic conversion of dissolved gases in buffered solutions

    KAUST Repository

    Shinagawa, Tatsuya

    2015-04-24

    To maintain local pH levels near the electrode during electrochemical reactions, the use of buffer solutions is effective. Nevertheless, the critical effects of the buffer concentration on electrocatalytic performances have not been discussed in detail. In this study, two fundamental electrochemical reactions, oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR), on a platinum rotating disk electrode are chosen as model gas-related aqueous electrochemical reactions at various phosphate concentrations. Our detailed investigations revealed that the kinetic and limiting diffusion current densities for both the ORR and HOR logarithmically decrease with increasing solute concentration (log|jORR|=-0.39c+0.92,log|jHOR|=-0.35c+0.73). To clarify the physical aspects of this phenomenon, the electrolyte characteristics are addressed: with increasing phosphate concentration, the gas solubility decrease, the kinematic viscosity of the solution increase and the diffusion coefficient of the dissolved gases decrease. The simulated limiting diffusion currents using the aforementioned parameters match the measured ones very well (log|jORR|=-0.43c+0.99,log|jHOR|=-0.40c+0.54), accurately describing the consequences of the electrolyte concentration. These alterations of the electrolyte properties associated with the solute concentration are universally applicable to other aqueous gas-related electrochemical reactions because the currents are purely determined by mass transfer of the dissolved gases. © 2015 The Authors.

  2. Electrocatalytic Determination of Isoniazid by a Glassy Carbon Electrode Modified with Poly (Eriochrome Black T

    Directory of Open Access Journals (Sweden)

    Karim Asadpour-Zeynali

    2017-06-01

    Full Text Available In this work poly eriochrome black T (EBT was electrochemically synthesized on the glassy carbon electrode as electrode modifier. On the modified electrode, voltammetric behavior of isoniazid (INH was investigated. The poly (EBT-modified glassy carbon electrode has excellent electrocatalytic ability for the electrooxidation of isoniazid. This fact was appeared as a reduced overpotential of INH oxidation in a wide operational pH range from 2 to 13. It has been found that the catalytic peak current depends on the concentration of INH and solution pH. The number of electrons involved in the rate determining step was found 1. The diffusion coefficient of isoniazid was also estimated using chronoamperometry technique. The experimental results showed that the mediated oxidation peak current of isoniazid is linearly dependent on the concentration of isoniazid in the ranges of 8.0 × 10-6 – 1.18 × 10-3 M and 2.90 × 10-5 M – 1.67× 10-3 M with differential pulse voltammetry (DPV and amperometry methods, respectively. The detection limits (S/N = 3 were found to be 6.0 μM and 16.4 μM by DPV and amperometry methods, respectively. This developed method was applied to the determination of isoniazid in tablet samples with satisfactory results.

  3. Self-consistent nonlocal feedback theory for electrocatalytic swimmers with heterogeneous surface chemical kinetics

    Science.gov (United States)

    Nourhani, Amir; Crespi, Vincent H.; Lammert, Paul E.

    2015-06-01

    We present a self-consistent nonlocal feedback theory for the phoretic propulsion mechanisms of electrocatalytic micromotors or nanomotors. These swimmers, such as bimetallic platinum and gold rods catalyzing decomposition of hydrogen peroxide in aqueous solution, have received considerable theoretical attention. In contrast, the heterogeneous electrochemical processes with nonlocal feedback that are the actual "engines" of such motors are relatively neglected. We present a flexible approach to these processes using bias potential as a control parameter field and a locally-open-circuit reference state, carried through in detail for a spherical motor. While the phenomenological flavor makes meaningful contact with experiment easier, required inputs can also conceivably come from, e.g., Frumkin-Butler-Volmer kinetics. Previously obtained results are recovered in the weak-heterogeneity limit and improved small-basis approximations tailored to structural heterogeneity are presented. Under the assumption of weak inhomogeneity, a scaling form is deduced for motor speed as a function of fuel concentration and swimmer size. We argue that this form should be robust and demonstrate a good fit to experimental data.

  4. High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Towards Hydrogen Evolution Reaction

    KAUST Repository

    Coy, Emerson

    2017-08-22

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced price and similar catalytic properties. However, most of the studied structures to date neglect long lasting chemical and structural stability, focusing only on electrochemical efficiency. Herein we report on a new approach to easily deposit and control the micro/nanostructure of thin film electrodes based on niobium carbide (NbC) and their electrocatalytic response. We will show that, by improving the mechanical properties of the NbC electrodes, microstructure and mechanical resilience can be obtained whilst maintaining high electro catalytic response. We also address the influence of other parameters such as conductivity and chemical composition on the overall performance of the thin film electrodes. Finally, we show that nanocomposite NbC electrodes are promising candidates towards HER , and furthermore, that the methodology presented here is suitable to produce other transition metal carbides (TM-C) with improved catalytic and mechanical properties.

  5. Coupled slow and fast surface dynamics in an electrocatalytic oscillator: Model and simulations

    International Nuclear Information System (INIS)

    Nascimento, Melke A.; Nagao, Raphael; Eiswirth, Markus; Varela, Hamilton

    2014-01-01

    The co-existence of disparate time scales is pervasive in many systems. In particular for surface reactions, it has been shown that the long-term evolution of the core oscillator is decisively influenced by slow surface changes, such as progressing deactivation. Here we present an in-depth numerical investigation of the coupled slow and fast surface dynamics in an electrocatalytic oscillator. The model consists of four nonlinear coupled ordinary differential equations, investigated over a wide parameter range. Besides the conventional bifurcation analysis, the system was studied by means of high-resolution period and Lyapunov diagrams. It was observed that the bifurcation diagram changes considerably as the irreversible surface poisoning evolves, and the oscillatory region shrinks. The qualitative dynamics changes accordingly and the chaotic oscillations are dramatically suppressed. Nevertheless, periodic cascades are preserved in a confined region of the resistance vs. voltage diagram. Numerical results are compared to experiments published earlier and the latter reinterpreted. Finally, the comprehensive description of the time-evolution in the period and Lyapunov diagrams suggests further experimental studies correlating the evolution of the system's dynamics with changes of the catalyst structure

  6. A novel advanced oxidation process——wet electrocatalytic oxidation for high concentrated organic wastewater treatment

    Institute of Scientific and Technical Information of China (English)

    DAI QiZhou; ZHOU MingHua; LEI LeCheng; ZHANG Xing Wang

    2007-01-01

    A novel advanced oxidation process-wet electrocatalytic oxidation(WEO)was studied with p-nitrophenol as model pollutant and β-PbO2 electrode as the anode.Compared with the effect of the individual wet air oxidation(WAO)and electrochemical oxidation(EO),the effect of WEO showed synergistic effect on COD removal under the conditions of temperature 160℃,C=1000mg·L-1,PN2=0.50MPa,Po2=0.9 MPa,current density=3 mA·cm-2,Na2SO4 3 g·L-1.And the synergistic factor got the best value of 0.98 within 120 min after 180 min treatment.The synergistic factor was studied after 120 min treatment at 100℃,120℃,140℃and 160℃,and the effect of 120℃was the best with the value of 1.26.Possible mechanism for the synergistic effect was discussed based on the analysis of free-radical generation and intermediates detected by HPLC and GC/MS.

  7. Photo-electrocatalytic hydrogen generation at dye-sensitised electrodes functionalised with a heterogeneous metal catalyst

    International Nuclear Information System (INIS)

    Hoogeveen, Dijon A.; Fournier, Maxime; Bonke, Shannon A.; Fang, Xi-Ya; Mozer, Attila J.; Mishra, Amaresh; Bäuerle, Peter; Simonov, Alexandr N.; Spiccia, Leone

    2016-01-01

    Dye-sensitised photocathodes promoting hydrogen evolution are usually coupled to a catalyst to improve the reaction rate. Herein, we report on the first successful integration of a heterogeneous metal particulate catalyst, viz., Pt aggregates electrodeposited from acidic solutions on the surface of a NiO-based photocathode sensitised with a p-type perylenemonoimid-sexithiophene-triphenylamine dye (PMI-6T-TPA). The platinised dye-NiO electrodes generate photocurrent density of ca −0.03 mA cm −2 (geom.) with 100% faradaic efficiency for the H 2 evolution at 0.059 V vs. reversible hydrogen electrode under 1 sun visible light irradiation (AM1.5G, 100 mW cm −2 , λ > 400 nm) for more than 10 hours in 0.1 M H 2 SO 4 (aq.). The Pt-free dye-NiO and dye-free Pt-modified NiO cathodes show no photo-electrocatalytic hydrogen evolution under these conditions. The performance of these Pt-modified PMI-6T-TPA-based photoelectrodes compares well to that of previously reported dye-sensitised photocathodes for H 2 evolution.

  8. Simultaneous bilateral isolated greater trochanter fracture

    Directory of Open Access Journals (Sweden)

    Maruti Kambali

    2013-01-01

    Full Text Available A 48-year-old woman sustained simultaneous isolated bilateral greater trochanteric fracture, following a road traffic accident. The patient presented to us 1 month after the injury. She presented with complaints of pain in the left hip and inability to walk. Roentgenograms revealed displaced comminuted bilateral greater trochanter fractures. The fracture of the left greater trochanter was reduced and fixed internally using the tension band wiring technique. The greater trochanter fracture on the right side was asymptomatic and was managed conservatively. The patient regained full range of motion and use of her hips after a postoperative follow-up of 6 months. Isolated fractures of the greater trochanter are unusual injuries. Because of their relative rarity and the unsettled controversy regarding their etiology and pathogenesis, several methods of treatment have been advocated. Furthermore, the reports of this particular type of injury are not plentiful and the average textbook coverage afforded to this entity is limited. In our study we discuss the mechanism of injury and the various treatment options available.

  9. A Pt-Co3O4-CD electrocatalyst with enhanced electrocatalytic performance and resistance to CO poisoning achieved by carbon dots and Co3O4 for direct methanol fuel cells.

    Science.gov (United States)

    Sun, Yue; Zhou, Yunjie; Zhu, Cheng; Hu, Lulu; Han, Mumei; Wang, Aoqi; Huang, Hui; Liu, Yang; Kang, Zhenhui

    2017-05-04

    Highly efficient electrocatalysts remain huge challenges in direct methanol fuel cells (DMFCs). Here, a Pt-Co 3 O 4 -CDs/C composite was fabricated as an anode electrocatalyst with low Pt content (12 wt%) by using carbon dots (CDs) and Co 3 O 4 nanoparticles as building blocks. The Pt-Co 3 O 4 -CDs/C composite catalyst shows a significantly enhanced electrocatalytic activity (1393.3 mA mg -1 Pt), durability (over 4000 s) and CO-poisoning tolerance. The superior catalytic activity should be attributed to the synergistic effect of CDs, Pt and Co 3 O 4 . Furthermore, the Pt-Co 3 O 4 -CDs/C catalyst was integrated into a single cell, which exhibits a maximum power density of 45.6 mW cm -2 , 1.7 times the cell based on the commercial 20 wt% Pt/C catalyst.

  10. Greater Confinement Disposal trench and borehole operations status

    International Nuclear Information System (INIS)

    Harley, J.P. Jr.; Wilhite, E.L.; Jaegge, W.J.

    1987-01-01

    Greater Confinement Disposal (GCD) facilities have been constructed within the operating burial ground at the Savannah River Plant (SRP) to dispose of the higher activity fraction of SRP low-level waste. GCD practices of waste segregation, packaging, emplacement below the root zone, and waste stabilization are being used in the demonstration. 2 refs., 2 figs., 2 tabs

  11. Vertically aligned single-walled carbon nanotubes as low-cost and high electrocatalytic counter electrode for dye-sensitized solar cells.

    Science.gov (United States)

    Dong, Pei; Pint, Cary L; Hainey, Mel; Mirri, Francesca; Zhan, Yongjie; Zhang, Jing; Pasquali, Matteo; Hauge, Robert H; Verduzco, Rafael; Jiang, Mian; Lin, Hong; Lou, Jun

    2011-08-01

    A novel dye-sensitized solar cell (DSSC) structure using vertically aligned single-walled carbon nanotubes (VASWCNTs) as the counter electrode has been developed. In this design, the VASWCNTs serve as a stable high surface area and highly active electrocatalytic counter-electrode that could be a promising alternative to the conventional Pt analogue. Utilizing a scalable dry transfer approach to form a VASWCNTs conductive electrode, the DSSCs with various lengths of VASWCNTs were studied. VASWCNTs-DSSC with 34 μm original length was found to be the optimal choice in the present study. The highest conversion efficiencies of VASWCNTs-DSSC achieved 5.5%, which rivals that of the reference Pt DSSC. From the electrochemical impedance spectroscopy analysis, it shows that the new DSSC offers lower interface resistance between the electrolyte and the counter electrode. This reproducible work emphasizes the promise of VASWCNTs as efficient and stable counter electrode materials in DSSC device design, especially taking into account the low-cost merit of this promising material.

  12. Synthesis of a novel Au nanoparticles decorated Ni-MOF/Ni/NiO nanocomposite and electrocatalytic performance for the detection of glucose in human serum.

    Science.gov (United States)

    Chen, Jingyuan; Xu, Qin; Shu, Yun; Hu, Xiaoya

    2018-07-01

    A nonenzymatic glucose electrochemical sensor was constructed based on Au nanoparticles (AuNPs) decorated Ni metal-organic-framework (MOF)/Ni/NiO nanocomposite. Ni-MOF/Ni/NiO nanocomposite was synthesized by one-step calcination of Ni-MOF. Then AuNPs were loaded onto the Ni-based nanocomposites' surface through electrostatic adsorption. Through characterization by transmission electron microscopy (TEM), high resolution TEM (HRTEM) and energy disperse spectroscopy (EDS) mapping, it is found that the AuNPs were well distributed on the surface of Ni-based nanocomposite. Cyclic voltammetric (CV) study showed the electrocatalytic activity of Au-Ni nanocomposite was highly improved after loading AuNPs onto it. Amperometric study demonstrated that the Au-Ni nanocomposites modified glassy carbon electrode (GCE) exhibited a high sensitivity of 2133.5 mA M -1 cm -2 and a wide linear range (0.4-900 μM) toward the oxidation of glucose with a detection limit as low as 0.1 μM. Moreover, the reproducibility, selectivity and stability of the sensor all exhibited outstanding performance. We applied the as-fabricated high performance sensor to measure the glucose levels in human serum and obtained satisfactory results. It is believed that AuNPs decorated Ni MOF/Ni/NiO nanocomposite provides a new platform for developing highly performance electrochemical sensors in practical applications. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. Electrocatalytic properties of functionalized carbon nanotubes with titanium dioxide and benzofuran derivative/ionic liquid for simultaneous determination of isoproterenol and serotonin

    International Nuclear Information System (INIS)

    Mazloum-Ardakani, Mohammad; Khoshroo, Alireza

    2014-01-01

    Highlights: • TiO 2 and benzofuran derivative were uniformly deposited onto carbon nanotubes • This nanocomposite can be used as a sensor in isoproterenol detection • This sensor shows a great enhancement in sensitivity, selectivity and stability - Abstract: In this paper we report synthesis and application of functionalized multiwalled carbon nanotubes (CNTs) with titanium dioxide nanoparticles (TiO 2 ), 9-(1,3-dithiolan-2-yl)-6,7-dihydroxy-3,3-dimethyl-3,4-dihydrodibenzo[b,d] furan-1(2H)-one (benzofuran derivative (DDF)) and 1-butyl-3-methylimidazolium tetrafluoroborate (IL) as high sensitive sensors for simultaneous determination of isoproterenol (IP) and serotonin (5-HT) using glassy carbon electrode. The modified electrode was characterized by different methods including a scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS) and voltammetry. A pair of well-defined redox peaks of DDF was obtained at the modified glassy carbon electrode by direct electron transfer between the DDF and the electrode. Dramatically enhanced electrocatalytic activity was exemplified at the modified electrode, as an electrochemical sensor to study the electro oxidation of IP and 5-HT. The differential pulse voltammetry data showed that the obtained anodic peak currents were linearly dependent on the IP and 5-HT concentrations in the range of 0.1–1300.0 and 1.0–650.0 μM, respectively. The applicability of the modified electrode was demonstrated by simultaneous determination of IP and 5-HT in human serum

  14. Greater trochanteric fracture with occult intertrochanteric extension.

    Science.gov (United States)

    Reiter, Michael; O'Brien, Seth D; Bui-Mansfield, Liem T; Alderete, Joseph

    2013-10-01

    Proximal femoral fractures are frequently encountered in the emergency department (ED). Prompt diagnosis is paramount as delay will exacerbate the already poor outcomes associated with these injuries. In cases where radiography is negative but clinical suspicion remains high, magnetic resonance imaging (MRI) is the study of choice as it has the capability to depict fractures which are occult on other imaging modalities. Awareness of a particular subset of proximal femoral fractures, namely greater trochanteric fractures, is vital for both radiologists and clinicians since it has been well documented that they invariably have an intertrochanteric component which may require surgical management. The detection of intertrochanteric or cervical extension of greater trochanteric fractures has been described utilizing MRI but is underestimated with both computed tomography (CT) and bone scan. Therefore, if MRI is unavailable or contraindicated, the diagnosis of an isolated greater trochanteric fracture should be met with caution. The importance of avoiding this potential pitfall is demonstrated in the following case of an elderly woman with hip pain and CT demonstrating an isolated greater trochanteric fracture who subsequently returned to the ED with a displaced intertrochanteric fracture.

  15. Butterfly valves: greater use in power plants

    International Nuclear Information System (INIS)

    McCoy, M.

    1975-01-01

    Improvements in butterfly valves, particularly in the areas of automatic control and leak tightness are described. The use of butterfly valves in nuclear power plants is discussed. These uses include service in component cooling, containment cooling, and containment isolation. The outlook for further improvements and greater uses is examined. (U.S.)

  16. Greater Somalia, the never-ending dream?

    DEFF Research Database (Denmark)

    Zoppi, Marco

    2015-01-01

    This paper provides an historical analysis of the concept of Greater Somalia, the nationalist project that advocates the political union of all Somali-speaking people, including those inhabiting areas in current Djibouti, Ethiopia and Kenya. The Somali territorial unification project of “lost...

  17. Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide.

    Science.gov (United States)

    Guo, Si-Xuan; Li, Fengwang; Chen, Lu; MacFarlane, Douglas R; Zhang, Jie

    2018-04-18

    Electrochemical reduction of CO 2 is a promising method to convert CO 2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo 12 O 40 ] 3- (PMo). Metallic Ag is formed upon reduction of Ag + . Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO 2 reduction was evaluated in a CO 2 saturated dimethylformamide medium containing 0.1 M [ n-Bu 4 N]PF 6 and 0.5% (v/v) added H 2 O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO 2 to CO with an onset potential of -1.70 V versus Fc 0/+ , which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90% were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec -1 suggests that rapid formation of *CO 2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO 2 (and presumably CO 2 •- ) and hence promotes the formation of CO 2 •- .

  18. Conductive Boron-Doped Graphene as an Ideal Material for Electrocatalytically Switchable and High-Capacity Hydrogen Storage.

    Science.gov (United States)

    Tan, Xin; Tahini, Hassan A; Smith, Sean C

    2016-12-07

    Electrocatalytic, switchable hydrogen storage promises both tunable kinetics and facile reversibility without the need for specific catalysts. The feasibility of this approach relies on having materials that are easy to synthesize, possessing good electrical conductivities. Graphitic carbon nitride (g-C 4 N 3 ) has been predicted to display charge-responsive binding with molecular hydrogen-the only such conductive sorbent material that has been discovered to date. As yet, however, this conductive variant of graphitic carbon nitride is not readily synthesized by scalable methods. Here, we examine the possibility of conductive and easily synthesized boron-doped graphene nanosheets (B-doped graphene) as sorbent materials for practical applications of electrocatalytically switchable hydrogen storage. Using first-principle calculations, we find that the adsorption energy of H 2 molecules on B-doped graphene can be dramatically enhanced by removing electrons from and thereby positively charging the adsorbent. Thus, by controlling charge injected or depleted from the adsorbent, one can effectively tune the storage/release processes which occur spontaneously without any energy barriers. At full hydrogen coverage, the positively charged BC 5 achieves high storage capacities up to 5.3 wt %. Importantly, B-doped graphene, such as BC 49 , BC 7 , and BC 5 , have good electrical conductivity and can be easily synthesized by scalable methods, which positions this class of material as a very good candidate for charge injection/release. These predictions pave the route for practical implementation of electrocatalytic systems with switchable storage/release capacities that offer high capacity for hydrogen storage.

  19. Utilization of wind energy in greater Hanover

    International Nuclear Information System (INIS)

    Sahling, U.

    1993-01-01

    Since the beginning of the Eighties, the association of communities of Greater Hanover has dealt intensively with energy and ecopolitical questions in the scope of regional planning. Renewable energy sources play a dominant role in this context. This brochure is the third contribution to the subject ''Energy policy and environmental protection''. Experts as well as possibly interested parties are addressed especially. For all 8 contributions contained, separate entries have been recorded in this database. (BWI) [de

  20. Small cities face greater impact from automation

    OpenAIRE

    Frank, Morgan R.; Sun, Lijun; Cebrian, Manuel; Youn, Hyejin; Rahwan, Iyad

    2017-01-01

    The city has proven to be the most successful form of human agglomeration and provides wide employment opportunities for its dwellers. As advances in robotics and artificial intelligence revive concerns about the impact of automation on jobs, a question looms: How will automation affect employment in cities? Here, we provide a comparative picture of the impact of automation across U.S. urban areas. Small cities will undertake greater adjustments, such as worker displacement and job content su...

  1. The Greater Sekhukhune-CAPABILITY outreach project.

    Science.gov (United States)

    Gregersen, Nerine; Lampret, Julie; Lane, Tony; Christianson, Arnold

    2013-07-01

    The Greater Sekhukhune-CAPABILITY Outreach Project was undertaken in a rural district in Limpopo, South Africa, as part of the European Union-funded CAPABILITY programme to investigate approaches for capacity building for the translation of genetic knowledge into care and prevention of congenital disorders. Based on previous experience of a clinical genetic outreach programme in Limpopo, it aimed to initiate a district clinical genetic service in Greater Sekhukhune to gain knowledge and experience to assist in the implementation and development of medical genetic services in South Africa. Implementing the service in Greater Sekhukhune was impeded by a developing staff shortage in the province and pressure on the health service from the existing HIV/AIDS and TB epidemics. This situation underscores the need for health needs assessment for developing services for the care and prevention of congenital disorders in middle- and low-income countries. However, these impediments stimulated the pioneering of innovate ways to offer medical genetic services in these circumstances, including tele-teaching of nurses and doctors, using cellular phones to enhance clinical care and adapting and assessing the clinical utility of a laboratory test, QF-PCR, for use in the local circumstances.

  2. Operational technology for greater confinement disposal

    International Nuclear Information System (INIS)

    Dickman, P.T.; Vollmer, A.T.; Hunter, P.H.

    1984-12-01

    Procedures and methods for the design and operation of a greater confinement disposal facility using large-diameter boreholes are discussed. It is assumed that the facility would be located at an operating low-level waste disposal site and that only a small portion of the wastes received at the site would require greater confinement disposal. The document is organized into sections addressing: facility planning process; facility construction; waste loading and handling; radiological safety planning; operations procedures; and engineering cost studies. While primarily written for low-level waste management site operators and managers, a detailed economic assessment section is included that should assist planners in performing cost analyses. Economic assessments for both commercial and US government greater confinement disposal facilities are included. The estimated disposal costs range from $27 to $104 per cubic foot for a commercial facility and from $17 to $60 per cubic foot for a government facility. These costs are based on average site preparation, construction, and waste loading costs for both contact- and remote-handled wastes. 14 figures, 22 tables

  3. Optical and electro-catalytic properties of bundled ZnO nanowires grown on a ITO substrate

    International Nuclear Information System (INIS)

    Xia Cao; Wang Ning; Wang Long

    2010-01-01

    Bundled wurtzite zinc oxide (ZnO) nanowires were fabricated in a facile manner on an ITO-conducting substrate via a microemulsion route without using any hard template or external electric/magnetic field. Structure and properties of the as-prepared ZnO electrode were investigated using scanning electron microscopy, X-ray diffraction, photoluminescence, Raman spectroscopy, as well as electrochemical tests. The ZnO electrode shows excellent optical and electrocatalytic ability, which may find further applications such as optoelectronics or as sensors as well as other modern industrial areas.

  4. Greater happiness for a greater number: Is that possible in Austria?

    NARCIS (Netherlands)

    R. Veenhoven (Ruut)

    2011-01-01

    textabstractWhat is the final goal of public policy? Jeremy Bentham (1789) would say: greater happiness for a greater number. He thought of happiness as subjective enjoyment of life; in his words as “the sum of pleasures and pains”. In his time the happiness of the great number could not be measured

  5. Greater happiness for a greater number: Is that possible? If so how? (Arabic)

    NARCIS (Netherlands)

    R. Veenhoven (Ruut); E. Samuel (Emad)

    2012-01-01

    textabstractWhat is the final goal of public policy? Jeremy Bentham (1789) would say: greater happiness for a greater number. He thought of happiness as subjective enjoyment of life; in his words as “the sum of pleasures and pains”. In his time, the happiness of the great number could not be

  6. Greater happiness for a greater number: Is that possible in Germany?

    NARCIS (Netherlands)

    R. Veenhoven (Ruut)

    2009-01-01

    textabstractWhat is the final goal of public policy? Jeremy Bentham (1789) would say: greater happiness for a greater number. He thought of happiness as subjective enjoyment of life; in his words as “the sum of pleasures and pains”. In his time the Happiness of the great number could not be measured

  7. Search for greater stability in nuclear regulation

    International Nuclear Information System (INIS)

    Asselstine, J.K.

    1985-01-01

    The need for greater stability in nuclear regulation is discussed. Two possible approaches for dealing with the problems of new and rapidly changing regulatory requirements are discussed. The first approach relies on the more traditional licensing reform initiatives that have been considered off and on for the past decade. The second approach considers a new regulator philosophy aimed at the root causes of the proliferation of new safety requirements that have been imposed in recent years. For the past few years, the concepts of deregulation and regulatory reform have been in fashion in Washington, and the commercial nuclear power program has not remained unaffected. Many look to these concepts to provide greater stability in the regulatory program. The NRC, the nuclear industry and the administration have all been avidly pursuing regulatory reform initiatives, which take the form of both legislative and administrative proposals. Many of these proposals look to the future, and, if adopted, would have little impact on currently operating nuclear power plants or plants now under construction