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Sample records for methanol tolerant oxygen-reduction

  1. Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

    Science.gov (United States)

    Huang, K.; Bi, K.; Liang, C.; Lin, S.; Zhang, R.; Wang, W. J.; Tang, H. L.; Lei, M.

    2015-06-01

    A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells.

  2. Emerging methanol-tolerant AlN nanowire oxygen reduction electrocatalyst for alkaline direct methanol fuel cell.

    Science.gov (United States)

    Lei, M; Wang, J; Li, J R; Wang, Y G; Tang, H L; Wang, W J

    2014-08-11

    Replacing precious and nondurable Pt catalysts with cheap materials is a key issue for commercialization of fuel cells. In the case of oxygen reduction reaction (ORR) catalysts for direct methanol fuel cell (DMFC), the methanol tolerance is also an important concern. Here, we develop AlN nanowires with diameters of about 100-150 nm and the length up to 1 mm through crystal growth method. We find it is electrochemically stable in methanol-contained alkaline electrolyte. This novel material exhibits pronounced electrocatalytic activity with exchange current density of about 6.52 × 10(-8) A/cm(2). The single cell assembled with AlN nanowire cathodic electrode achieves a power density of 18.9 mW cm(-2). After being maintained at 100 mA cm(-2) for 48 h, the AlN nanowire-based single cell keeps 92.1% of the initial performance, which is in comparison with 54.5% for that assembled with Pt/C cathode. This discovery reveals a new type of metal nitride ORR catalyst that can be cheaply produced from crystal growth method.

  3. Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance

    Directory of Open Access Journals (Sweden)

    Carmelo Lo Vecchio

    2015-11-01

    Full Text Available Next generation cathode catalysts for direct methanol fuel cells (DMFCs must have high catalytic activity for the oxygen reduction reaction (ORR, a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/TinO2n–1 were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB and 30% Pd/Vulcan (Pd/Vul were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/TinO2n–1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/TinO2n–1 catalysts in DMFC cathodes.

  4. Core/shell AgNi/PtAgNi nanoparticles as methanol-tolerant oxygen reduction electrocatalysts

    International Nuclear Information System (INIS)

    Wu, Dengfeng; Cheng, Daojian

    2015-01-01

    A core/shell AgNi/PtAgNi nanoparticle (NP) was synthesized via a new seed-mediated growth method in organic solvent medium. The as-synthesized AgNi/PtAgNiNP exhibits an AgNi core coated with PtAgNi shell, which was confirmed by transmission electron microscopy (TEM), ultraviolet–visible absorption spectroscopy and X-ray Photoelectron Spectroscopy (XPS). The AgNi/PtAgNiNPs/C catalyst possesses higher oxygen reduction reaction (ORR) activity and better durability compared with the commercial Pt/C catalyst. It is found that the ORR polarization curve of the AgNi/PtAgNiNPs/C catalyst shows an onset potential of 0.91 V vs. RHE, which is superior to the commercial Pt/C (0.88 V vs. RHE). In addition, the AgNi/PtAgNiNPs/C catalyst shows much better durability than the commercial Pt/C catalyst. More interestingly, the AgNi/PtAgNiNPs/C catalyst displays much higher methanol tolerance than the commercial Pt/C catalyst in 0.1 M KOH solution in the presence of 0.5 M methanol. Our results show that core/shell AgNi/PtAgNiNPs possess selective activity for ORR even in the presence of methanol, showing potential application as methanol-tolerant cathode catalysts in direct methanol fuel cells.

  5. Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

    OpenAIRE

    K. Huang; K. Bi; C. Liang; S. Lin; R. Zhang; W. J. Wang; H. L. Tang; M. Lei

    2015-01-01

    A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45?nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR acti...

  6. Electrochemically reduced graphene-oxide supported bimetallic nanoparticles highly efficient for oxygen reduction reaction with excellent methanol tolerance

    Science.gov (United States)

    Yasmin, Sabina; Cho, Sung; Jeon, Seungwon

    2018-03-01

    We report a simple and facile method for the fabrication of bimetallic nanoparticles on electrochemically reduced graphene oxide (ErGO) for electrocatalytic oxygen reduction reaction (ORR) in alkaline media. First, reduced graphene oxide supported palladium and manganese oxide nanoparticle (rGO/Pd-Mn2O3) catalyst was synthesized via a simple chemical method at room temperature; then, it was electrochemically reduced for oxidation reduction reaction (ORR) in alkaline media. The chemical composition and morphological properties of ErGO/Pd-Mn2O3 was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The TEM images reveals that, nano-sized Pd and Mn2O3 particles were disperse on the ErGO sheet without aggregation. The as-prepared ErGO/Pd-Mn2O3 was employed for ORR in alkaline media which shows higher ORR activity with more positive onset and half-wave potential, respectively. Remarkably, ErGO/Pd-Mn2O3 reduced oxygen via four-electron transfer pathway with negligible amount of intermediate peroxide species (HO2-). Furthermore, the higher stability and excellent methanol tolerance of the ErGO/Pd-Mn2O3 compared to commercial Pt/C (20 wt%) catalyst, indicating its suitability for fuel cells.

  7. High Performance and Cost-Effective Direct Methanol Fuel Cells: Fe-N-C Methanol-Tolerant Oxygen Reduction Reaction Catalysts.

    Science.gov (United States)

    Sebastián, David; Serov, Alexey; Artyushkova, Kateryna; Gordon, Jonathan; Atanassov, Plamen; Aricò, Antonino S; Baglio, Vincenzo

    2016-08-09

    Direct methanol fuel cells (DMFCs) offer great advantages for the supply of power with high efficiency and large energy density. The search for a cost-effective, active, stable and methanol-tolerant catalyst for the oxygen reduction reaction (ORR) is still a great challenge. In this work, platinum group metal-free (PGM-free) catalysts based on Fe-N-C are investigated in acidic medium. Post-treatment of the catalyst improves the ORR activity compared with previously published PGM-free formulations and shows an excellent tolerance to the presence of methanol. The feasibility for application in DMFC under a wide range of operating conditions is demonstrated, with a maximum power density of approximately 50 mW cm(-2) and a negligible methanol crossover effect on the performance. A review of the most recent PGM-free cathode formulations for DMFC indicates that this formulation leads to the highest performance at a low membrane-electrode assembly (MEA) cost. Moreover, a 100 h durability test in DMFC shows suitable applicability, with a similar performance-time behavior compared to common MEAs based on Pt cathodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Simple one-pot synthesis of platinum-palladium nanoflowers with enhanced catalytic activity and methanol-tolerance for oxygen reduction in acid media

    International Nuclear Information System (INIS)

    Zheng, Jie-Ning; He, Li-Li; Chen, Fang-Yi; Wang, Ai-Jun; Xue, Meng-Wei; Feng, Jiu-Ju

    2014-01-01

    Graphical abstract: PtPd nanoflowers were fabricated by one-pot solvothermal co-reduction method in oleylamine system, which exhibited the improved electrocatalytic activity and higher methanol tolerance for oxygen reduction, compared with commercial Pt and Pd black catalysts. - Highlights: • Bimetallic alloyed PtPd nanoflowers are prepared by a simple one-pot solvothermal co-reduction method. • PtPd nanoflowers display high catalytic performance for ORR dominated by a four-electron pathway. • PtPd nanoflowers show good methanol tolerance for ORR. - Abstract: In this work, bimetallic alloyed platinum-palladium (PtPd) nanoflowers are fabricated by one-pot solvothermal co-reduction of Pt (II) acetylacetonate and Pd (II) acetylacetonate in oleylamine system. The as-prepared nanostructures show the enhanced electrocatalytic activity for oxygen reduction reaction (ORR), dominated by a four-electron pathway based on the Koutecky-Levich plots, mainly owing to the inhibition of the formation of Pt–OH ad via the downshift of d-band center for Pt. Meanwhile, PtPd nanoflowers display good methanol tolerance and improved stability for ORR. The chronoamperometry test reveals that the current of PtPd nanoflowers remains 45.9% of its original value within 6000 s, much higher than those of commercial Pt (36.7%) and Pd (32.2%) black catalysts. Therefore, PtPd nanoflowers with unique interconnected structures can be used as a promising cathode catalyst in direct methanol fuel cells

  9. Rhodium based clusters for oxygen reduction and hydrogen oxidation in 0.5 M H2SO4, tolerant to methanol and carbon monoxide, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Jimenez-Sandoval, O.; Borja-Arco, E.; Altamirano-Gutierrez, A. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional, Queritaro (Mexico); Castellanos, R.H. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-Queretaro, Queretaro (Mexico)

    2008-07-01

    Rhodium (Rh6(CO)16) and novel Rh-based clusters were prepared using thermolysis techniques under different conditions in N2 and H2 reaction media, as well as in n-nonane, o-xylene, 1,2-dichlorobenzene and dimethylsulfoxide. The clusters were used as novel electrocatalysts for oxygen reduction reaction (ORR) in the absence and presence of 1.0 and 2.0 M methanol solutions. The catalysts were also used for hydrogen oxidation reaction (HOR) with pure hydrogen (H2) and in the presence of carbon monoxide (CO). Rotating disk electrode measurements were used to analyze the materials. The study showed that the electrocatalyst support ratio plays a significant role in the electrochemical behaviour of the materials. Rh6(CO)16 and Rh2(1,2-DCB) presented the best electrocatalytic behaviour for ORR and HOR in the absence and presence of methanol and CO. The study demonstrated that the rhodium-based materials are capable of performing ORR and HOR while being tolerant of both methanol and CO. 3 refs., 3 figs.

  10. Preparation of Bimetallic Pd-Co Nanoparticles on Graphene Support for Use as Methanol Tolerant Oxygen Reduction Electrocatalysts

    Directory of Open Access Journals (Sweden)

    R. N. Singh

    2012-12-01

    Full Text Available Graphene-supported (40-x wt% Pd x wt% Co (0≤x≤13.33 alloys/composites have been prepared by a microwave-assisted polyol reduction method and been investigated for their structural and electrocatalytic properties for the oxygen reduction reaction (ORR in 0.5 M H2SO4 at 298 K. The study demonstrated that the bimetallic Pd-Co composite nanoparticles are, in fact, alloy nanoparticles with fcc crystalline structure. Partial substitution of Pd by Co (from 3.64 to 13.33 wt% in 40 wt% Pd/graphene decreases the lattice parameter as well as the crystallite size and increases the apparent catalytic activity, the latter, however, being the greatest with 8 wt% Co. The ORR activity of the active 32 wt% Pd 8wt% Co is found to be considerably low when it was deposited on the support multiwall carbon nanotubes under similar conditions. The rotating disk electrode study indicated that the ORR on 32 wt% Pd 8 wt% Co/GNS in 0.5 M H2SO4 follows approximately the four-electron pathway.

  11. Oxygen reduction reaction at MWCNT-modified nanoscale iron(II) tetrasulfophthalocyanine: remarkable performance over platinum and tolerance toward methanol in alkaline medium

    CSIR Research Space (South Africa)

    Fashedemi, OO

    2015-04-01

    Full Text Available A nanoscale iron(II) tetrasulfophthalocyanine (nanoFeTSPc) catalyst obtained by co-ordinating with hexadecyltrimethylammonium bromide and subsequently anchored onto multi-walled carbon nanotubes (MWCNTs) for oxygen reduction reaction (ORR) has been...

  12. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    International Nuclear Information System (INIS)

    Tritsaris, Georgios A.; Norskov, Jens K.; Rossmeisl, Jan

    2011-01-01

    Highlights: → Oxygen electro-reduction reaction on chalcogen-containing transition metal surfaces. → Evaluation of catalytic performance with density functional theory. → Ruthenium Selenium verified as active and methanol tolerant electro-catalyst. → Water boils at -10000 K. - Abstract: We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated.

  13. A study of Rh xS y/C and RuSe x/C as methanol-tolerant oxygen reduction catalysts for mixed-reactant fuel cell applications

    International Nuclear Information System (INIS)

    Papageorgopoulos, Dimitrios C.; Liu, Fang; Conrad, Olaf

    2007-01-01

    For efficient operation, mixed-reactant fuel cells utilise highly selective anode and cathode electrocatalysts. While platinum and its alloys are the most widely used ORR electrocatalysts in conventional DMFCs, they suffer from both their very high activity for methanol oxidation and their inherent cost. Platinum-free precious metal chalcogenides have been suggested as alternatives with comparable oxygen reduction activity in the presence of methanol. Of these, commercially available carbon supported rhodium sulphide and developmental ruthenium selenium were electrochemically tested and assessed for their potential as selective ORR cathode catalysts. Both materials exhibited oxygen reduction activity approaching that of platinum, albeit at potentials 150 and 80 mV more negative. The three materials' ability to maintain their oxygen reduction activity in the presence of methanol ranks ruthenium selenium > rhodium sulphide >> platinum

  14. Chalcogenide metal centers for oxygen reduction reaction: Activity and tolerance

    International Nuclear Information System (INIS)

    Feng Yongjun; Gago, Aldo; Timperman, Laure; Alonso-Vante, Nicolas

    2011-01-01

    This mini-review summarizes materials design methods, oxygen reduction kinetics, tolerance to small organic molecules and fuel cell performance of chalcogenide metal catalysts, particularly, ruthenium (Ru x Se y ) and non-precious transition metals (M x X y : M = Co, Fe and Ni; X = Se and S). These non-platinum catalysts are potential alternatives to Pt-based catalysts because of their comparable catalytic activity (Ru x Se y ), low cost, high abundance and, in particular, a high tolerance to small organic molecules. Developing trends of synthesis methods, mechanism of oxygen reduction reaction and applications in direct alcohol fuel cells as well as the substrate effect are highlighted.

  15. 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.

  16. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    DEFF Research Database (Denmark)

    Tritsaris, Georgios; Nørskov, Jens Kehlet; Rossmeisl, Jan

    2011-01-01

    We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability...... of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated....

  17. The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yuhao; Reddy, Ramana G. [Department of Metallurgical and Materials Engineering, The University of Alabama, P.O. Box 870202, Tuscaloosa, AL 35487 (United States)

    2007-02-01

    The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 C, 635 C and 980 C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H{sub 2}SO{sub 4} solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 C or 635 C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC. (author)

  18. CoPd x oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

    International Nuclear Information System (INIS)

    Mustain, William E.; Kepler, Keith; Prakash, Jai

    2007-01-01

    The electrochemical activity of carbon-supported cobalt-palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm 2 single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 deg. C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPd x PEMFC system with varying composition reveals that a nominal cobalt-palladium atomic ratio of 1:3, CoPd 3 , exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd 3 has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd 3 catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd 3 catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt

  19. A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

    Science.gov (United States)

    Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

    2018-06-01

    The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

  20. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Liu, Baocang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Gong, Xia [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Dafang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhang, Jun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2016-12-15

    Graphical abstract: Ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities (NDs) catalysts, are successfully synthesized by using a facile method. The as-obtained ternary catalysts manifest superior catalytic activity and stability both in terms of surface and mass specific activities toward the methanol oxidation and oxygen reduction reactions, as compared to the binary catalysts and the commercial Pt/C catalysts. - Highlights: • Ternary RuMPt catalysts are synthesized by using a facile method. • The catalysts manifest superior catalytic activity towards the MOR and ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg{sup −1}) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  1. Microwave Assisted Synthesis of Osmium Electrocatalysts for the Oxygen Reduction Reaction in the Absence and Presence of Aqueous Methanol

    Directory of Open Access Journals (Sweden)

    Edgar Borja-Arco

    2011-01-01

    Full Text Available Osmium electrocatalysts for the oxygen reduction reaction (ORR were prepared by microwave irradiation of Os3(CO12 at different experimental conditions. The materials obtained were structurally characterized by FT-IR, micro-Raman spectroscopy and X-ray diffraction. Their chemical compositions were obtained by EDS. The electrocatalytic properties for the oxygen reduction reaction were evaluated by rotating disk electrode measurements in 0.5 mol L-1 H2SO4, in the absence and presence of aqueous methanol. The kinetic parameters, such as Tafel slope, exchange current density, and charge transfer coefficient are reported.

  2. Oxygen reduction and methanol oxidation behaviour of SiC based Pt nanocatalysts for proton exchange membrane fuel cells

    DEFF Research Database (Denmark)

    Dhiman, Rajnish; Stamatin, Serban Nicolae; Andersen, Shuang Ma

    2013-01-01

    for carbon based commercial catalyst, when HClO4 is used as electrolyte. The Pt (110) & Pt (111) facets are shown to have higher electrochemical activities than Pt (100) facets. To the best of our knowledge, methanol oxidation studies and the comparison of peak deconvolutions of the H desorption region in CV...... and methanol oxidation reactions of SiC supported catalysts and measured them against commercially available carbon based catalysts. The deconvolution of the hydrogen desorption signals in CV cycles shows a higher contribution of Pt (110) & Pt (111) peaks compared to Pt (100) for SiC based supports than...... cyclic studies are here reported for the first time for SiC based catalysts. The reaction kinetics for the oxygen reduction and for methanol oxidation with Pt/SiC are observed to be similar to the carbon based catalysts. The SiC based catalyst shows a higher specific surface activity than BASF (Pt...

  3. An Investigation of Palladium Oxygen Reduction Catalysts for the Direct Methanol Fuel Cell

    Directory of Open Access Journals (Sweden)

    G. F. Álvarez

    2011-01-01

    Full Text Available A comparative study of Pd and Pt was carried out in DMFC using different methanol concentrations and under different operating conditions. Cell performance was compared at methanol concentrations of 1, 3, 5, and 7 M and at temperatures of 20, 40, and 60°C. Homemade Pd nanoparticles were prepared on Vulcan XC-72R using ethylene glycol as the reducing agent at pH 11. The resulting catalyst, Pd/C, with metal nanoparticles of approximately 6 nm diameter, was tested as a cathode catalyst in DMFC. At methanol concentrations of 5 M and higher, the Pd cathode-based cell performed better than that with Pt at 60°C with air.

  4. Methanol resistant ruthenium electrocatalysts for oxygen reduction synthesized by pyrolysis of Ru{sub 3}(CO){sub 12} in different atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Altamirano-Gutierrez, A.; Jimenez-Sandoval, O.; Uribe-Godinez, J.; Borja-Arco, E. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro, Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Castellanos, R.H. [Universidad del Papaloapan, Campus Tuxtepec, Circuito Central No. 200, Col. Parque Industrial, Tuxtepec, Oax. 68301 (Mexico); Olivares-Ramirez, J.M. [Universidad Tecnologica de San Juan del Rio, Av. La Palma No. 125, Col. Vista Hermosa, San Juan del Rio, Qro. 76800 (Mexico)

    2009-10-15

    Novel ruthenium electrocatalysts for the oxygen reduction reaction (ORR) were prepared by pyrolysis of Ru{sub 3}(CO){sub 12} in three atmospheres: neutral (N{sub 2}), partially oxidative (air) and partially reductive (70:30 N{sub 2}/H{sub 2}), at temperatures in the 80-700 C range. The materials were characterized by FT-IR spectroscopy, X-ray diffraction and scanning electron microscopy. A thermogravimetric analysis of the Ru{sub 3}(CO){sub 12} precursor in the three atmospheres was also performed. The electrocatalytic properties of the materials were evaluated by rotating disk electrode measurements in 0.5 mol L{sup -1} H{sub 2}SO{sub 4}. The kinetic parameters, such as the Tafel slope, exchange current density and charge transfer coefficient, are reported. The catalysts prepared in N{sub 2} and N{sub 2}/H{sub 2}, in general, show a higher performance than those synthesized in air. In the two nitrogen containing atmospheres, a pyrolysis temperature of 360 C seems to lead to better electrocatalytic properties for the ORR. The new electrocatalysts are also tolerant to methanol concentrations as high as 2.0 mol L{sup -1}. (author)

  5. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  6. A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum.

    Science.gov (United States)

    Yang, Zehui; Nakashima, Naotoshi

    2015-07-20

    The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance.

  7. Enhancing the methanol tolerance of platinum nanoparticles for the cathode reaction of direct methanol fuel cells through a geometric design.

    Science.gov (United States)

    Feng, Yan; Ye, Feng; Liu, Hui; Yang, Jun

    2015-11-18

    Mastery over the structure of nanoparticles might be an effective way to enhance their performance for a given application. Herein we demonstrate the design of cage-bell nanostructures to enhance the methanol tolerance of platinum (Pt) nanoparticles while remaining their catalytic activity for oxygen reduction reaction. This strategy starts with the synthesis of core-shell-shell nanoparticles with Pt and silver (Ag) residing respectively in the core and inner shell regions, which are then agitated with saturated sodium chloride (NaCl) solution to eliminate the Ag component from the inner shell region, leading to the formation of bimetallic nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a metal shell with nano-channels, which exhibit superior methanol-tolerant property in catalyzing oxygen reduction reaction due to the different diffusion behaviour of methanol and oxygen in the porous metal shell of cage-bell structured nanoparticles. In particular, the use of remarkably inexpensive chemical agent (NaCl) to promote the formation of cage-bell structured particles containing a wide spectrum of metal shells highlights its engineering merit to produce highly selective electrocatalysts on a large scale for the cathode reaction of direct methanol fuel cells.

  8. l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

    Science.gov (United States)

    Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

    2017-10-15

    In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Oxygen reduction reaction on a highly-alloyed Pt-Ni supported carbon electrocatalyst in acid solution

    CSIR Research Space (South Africa)

    Zheng, H

    2010-08-31

    Full Text Available Alloyed electrocatalysts such as PtNi/C[1-2], PtCo/C[3], PtCr/C[4], PtFe/C [5-6], and non-alloyed Pt-TiO2/C were reportedly investigated for methanol tolerance during Oxygen reduction reaction (ORR). The high methanol tolerance...

  10. 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.

  11. Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells.

    Science.gov (United States)

    Kim, Jiyoung; Jang, Jin-Sung; Peck, Dong-Hyun; Lee, Byungrok; Yoon, Seong-Ho; Jung, Doo-Hwan

    2016-08-15

    Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF) was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC). The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR) activities and the electrochemical double layer compared with common carbon black (CB). To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF-supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA) of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

  12. Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    Jiyoung Kim

    2016-08-01

    Full Text Available Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC. The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR activities and the electrochemical double layer compared with common carbon black (CB. To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF–supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

  13. Cuprous oxide nanoparticles dispersed on reduced graphene oxide as an efficient electrocatalyst for oxygen reduction reaction.

    Science.gov (United States)

    Yan, Xiao-Yan; Tong, Xi-Li; Zhang, Yue-Fei; Han, Xiao-Dong; Wang, Ying-Yong; Jin, Guo-Qiang; Qin, Yong; Guo, Xiang-Yun

    2012-02-11

    Cuprous oxide (Cu(2)O) nanoparticles dispersed on reduced graphene oxide (RGO) were prepared by reducing copper acetate supported on graphite oxide using diethylene glycol as both solvent and reducing agent. The Cu(2)O/RGO composite exhibits excellent catalytic activity and remarkable tolerance to methanol and CO in the oxygen reduction reaction. This journal is © The Royal Society of Chemistry 2012

  14. High performance platinum single atom electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

    2017-07-01

    For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

  15. Combinatorial discovery of new methanol-tolerant non-noble metal cathode electrocatalysts for direct methanol fuel cells.

    Science.gov (United States)

    Yu, Jong-Sung; Kim, Min-Sik; Kim, Jung Ho

    2010-12-14

    Combinatorial synthesis and screening were used to identify methanol-tolerant non-platinum cathode electrocatalysts for use in direct methanol fuel cells (DMFCs). Oxygen reduction consumes protons at the surface of DMFC cathode catalysts. In combinatorial screening, this pH change allows one to differentiate active catalysts using fluorescent acid-base indicators. Combinatorial libraries of carbon-supported catalyst compositions containing Ru, Mo, W, Sn, and Se were screened. Ternary and quaternary compositions containing Ru, Sn, Mo, Se were more active than the "standard" Alonso-Vante catalyst, Ru(3)Mo(0.08)Se(2), when tested in liquid-feed DMFCs. Physical characterization of the most active catalysts by powder X-ray diffraction, gas adsorption, and X-ray photoelectron spectroscopy revealed that the predominant crystalline phase was hexagonal close-packed (hcp) ruthenium, and showed a surface mostly covered with oxide. The best new catalyst, Ru(7.0)Sn(1.0)Se(1.0), was significantly more active than Ru(3)Se(2)Mo(0.08), even though the latter contained smaller particles.

  16. Study of electrocatalytic properties of iridium carbonyl cluster and rhodium carbonyl cluster compounds for the oxygen reduction and hydrogen oxidation reactions in 0.5 MH{sub 2}SO{sub 4} in presence and absence of methanol and carbon monoxide, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Borja-Arco, E.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

    2006-07-01

    The suitability of carbonyl cluster compounds as a substitute to platinum (Pt) in fuel cell catalysts was investigated. Iridium (Ir{sub 4}(CO){sub 12} and rhodium (Rh{sub 6}(CO){sub 116}) cluster compounds were investigated as potential new electrocatalysts for oxygen reduction reaction (ORR) in the presence and absence of methanol at different concentrations, as well as for the hydrogen oxidation reaction (HOR) with pure hydrogen and a hydrogen/carbon monoxide mixture. The materials were studied using room temperature rotating disk electrode (RDE) measurements and cyclic and linear sweep voltammetry techniques (LSV). Tafel slope and exchange current density were calculated using the LSV polarization curves. Cyclic voltamperometry results suggested that the electrocatalysts were tolerant to methanol. However, electrochemical behaviour of the materials altered in the presence of CO, and peaks corresponding to CO oxidation were observed in both cases. The rhodium carbonyl showed a higher current density for the ORR than the iridium carbonyl. The current potential curves in the presence of methanol were similar to those obtained without methanol. Results confirmed the tolerance properties of the materials to perform the ORR. Decreased current density values were observed during HOR, and were attributed to changes in the hydrogen solubility and diffusion coefficient due to the presence of CO. The Tafel slopes indicated that the mechanics of the HOR were Heyrovsky-Volmer. Results showed that the materials are capable of performing both ORR and HOR in an acid medium. It was noted that the iridium carbonyl cluster followed a 4-electron transfer mechanism towards the formation of water. It was concluded that the compounds are suitable for use as both cathodes and anodes in proton exchange membrane fuel cells (PEMFCs) and as cathodes in direct methanol fuel cells (DMFCs). 3 refs., 2 tabs., 3 figs.

  17. Intermetallic Pd 3 Pb nanowire networks boost ethanol oxidation and oxygen reduction reactions with significantly improved methanol tolerance

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Qiurong [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA; Zhu, Chengzhou [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA; Key Laboratory of Pesticide and Chemical Biology; Bi, Cuixia [Institute of Crystal Materials; Shandong University; Jinan 250100; P. R. China; Xia, Haibing [Institute of Crystal Materials; Shandong University; Jinan 250100; P. R. China; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; Richland; USA; Du, Dan [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA; Key Laboratory of Pesticide and Chemical Biology; Lin, Yuehe [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA

    2017-01-01

    Intermetallic nanocrystals are currently receiving extensive attention due to their well-defined crystal structures, highly ordered atomic distribution and superior structural stability that endow them with optimized catalytic activities, stabilities and high selectivity for use as electrocatalysts for fuel cells.

  18. Low content of Pt supported on Ni-MoCx/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

    Science.gov (United States)

    Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui

    2017-08-01

    Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.

  19. Oxygen Reduction on Platinum

    DEFF Research Database (Denmark)

    Nesselberger, Markus

    . The influence of the ion adsorption strength, which is observed in the “particle size studies” on the oxygen reduction rate on Pt/C catalysts, is further investigated under similar reaction conditions by infrared spectroscopy. The designed in situ electrochemical ATR-FTIR setup features a high level...... of instrument automation and online data treatment, and provides welldefined mass transport conditions enabling kinetic measurements. A modified electrochemical / spectroscopic interface is presented allowing the exclusive investigation of the Pt/C catalyst layer. Three types of potential dependent adsorption...... adsorption on Pt does not block the ORR directly. Instead, the onset of oxide formation with the concomitant conversion of the anion adsorbate layer is the decisive blocking mechanism....

  20. Low content of Pt supported on Ni-MoC{sub x}/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui, E-mail: diamond_wangyanhui@163.com

    2017-08-01

    Highlights: • Ni-MoC{sub x}/C catalyst support was synthesized by a two-step method. • 10Pt/Ni-MoC{sub x}/C was an active and durable low Pt catalyst for MOR, ORR and HER. • The high stability of 10Pt/Ni-MoC{sub x}/C was ascribed to the anchoring effect of MoC{sub x}. • High activity of 10Pt/Ni-MoC{sub x}/C was due to a synergistic of Pt, Ni, MoO{sub x} and MoC{sub x}. - Abstract: Nickel and molybdenum carbide modified carbon black (Ni-MoC{sub x}/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoC{sub x}/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoC{sub x}/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoC{sub x}/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoC{sub x}/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoC{sub x}/C reached 68.4 m{sup 2} g{sup −1}, which was higher than that of 20Pt/C (63.2 m{sup 2} g{sup −1}). The enhanced stability and activity of 10Pt/Ni-MoC{sub x}/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoC{sub x} formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoO{sub x} and MoC{sub x}. These findings indicated that 10Pt/Ni-MoC{sub x}/C was a promising electrocatalyst for direct methanol fuel cells.

  1. Spillover effect induced Pt-TiO2/C as ethanol tolerant oxygen reduction reaction catalyst for direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Meenakshi, S.; Nishanth, K.G.; Sridhar, P.; Pitchumani, S.

    2014-01-01

    Hypo-hyper-d-electronic interactive nature is used to develop a new carbon supported HT-Pt-TiO 2 composite catalyst comprising Pt and Ti in varying atomic ratio, namely 1:1, 2:1 and 3:1. The electro-catalysts are characterized by XRD, TEM, SEM-EDAX, Cyclic Voltammetry (CV) and Linear sweep voltammetry (LSV) techniques. HT-Pt-TiO 2 /C catalysts exhibit significant improvement in oxygen reduction reaction (ORR) over Pt/C. The effect of composition towards ORR with and without ethanol has been studied. The direct ethanol fuel cell (DEFC) with HT-Pt-TiO 2 /C cathode catalyst exhibits an enhanced peak power density of 41 mW cm −2 , whereas 21 mW cm −2 is obtained for the DEFCs with carbon-supported Pt catalyst operating under identical conditions

  2. Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

    2018-01-01

    Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

  3. Fabrication of MEA based on optimum amount of Co in PdxCo/C alloy nanoparticles as a new cathode for oxygen reduction reaction in passive direct methanol fuel cells

    International Nuclear Information System (INIS)

    Gharibi, Hussein; Golmohammadi, Farhad; Kheirmand, Mehdi

    2013-01-01

    Highlights: ► The optimal amount of Pd/Co in the catalyst layer reduces the polarization resistance in comparison with Pd alone. ► The Pd/Co in catalyst layer increases the Pd utilization in the ORR. ► The DMFC test results indicate that the MEA prepared from Pd 3 Co/C cathode exhibits best performance. -- Abstract: Carbon supported Pd and Pd x Co alloy electrocatalysts of different Pd x Co atomic ratios (x = 1, 2, 3 and 10) were prepared by the impregnation synthesis method at room temperature without heat treatment by ethylene glycol (EG) reduction. As prepared Pd x Co bimetallic nanoparticles show a single-phase face-centered-cubic (fcc) disordered structure. The performance of these electrodes in the ORR was measured with cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), chronoamperometry (CA), inductive coupled plasma (ICP), X-ray diffraction (XRD); scanning electron microscopy coupled to energy dispersive X-ray (SEM–EDX) and transmission electron microscope (TEM). For synthesized Pd x Co/C electrocatalysts, the highest catalytic activity for the ORR, was found for a Pd:Co atomic ratio of 3:1 in acid media at the presence and absence of methanol with optimal Pd–Pd bond distance (0.2729 nm). Since the Pd x Co/C alloy electrocatalysts are inactive for the adsorption and oxidation of methanol, it can act as a methanol-tolerant ORR catalyst in a direct methanol fuel cell (DMFC). A membrane-electrode assembly (MEA) has been prepared by employing of the Pd 3 Co/C as a cathode for passive direct methanol fuel cell and characterized by polarization curves and impedance diagrams. The DMFC test results indicate that the MEA prepared from Pd 3 Co/C cathode exhibits better performance compared to the MEA prepared from Pt/C (Electrochem) and an in-house Pd/C catalyst synthesized, in terms of maximum power density and minimum charge transfer resistance

  4. Carbon-supported cubic CoSe2 catalysts for oxygen reduction reaction in alkaline medium

    International Nuclear Information System (INIS)

    Feng Yongjun; Alonso-Vante, Nicolas

    2012-01-01

    Highlights: ► Cubic CoSe 2 a non-precious metal electrocatalyst for oxygen reduction in KOH. ► The catalyst shows four-electron transfer pathway in overall reaction. ► Catalyst has higher methanol tolerance than commercial Pt/C catalyst. - Abstract: A Carbon-supported CoSe 2 nanocatalyst has been developed as an alternative non-precious metal electrocatalyst for oxygen reduction reaction (ORR) in alkaline medium. The catalyst was prepared via a surfactant-free route and its electrocatalytic activity for the ORR has been investigated in detail in 0.1 M KOH electrolyte at 25 °C using rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. The prepared catalyst showed promising catalytic activity towards ORR in a four-electron transfer pathway and higher tolerance to methanol compared to commercial Pt/C catalyst in 0.1 M KOH. To some extent, the increase of CoSe 2 loading on the electrode favors a faster reduction of H 2 O 2 intermediate to H 2 O.

  5. Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

    Science.gov (United States)

    Zhu, Yimin; Zelenay, Piotr

    2006-03-21

    A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

  6. Porous boron doped diamonds as metal-free catalysts for the oxygen reduction reaction in alkaline solution

    Science.gov (United States)

    Suo, Ni; Huang, Hao; Wu, Aimin; Cao, Guozhong; Hou, Xiaoduo; Zhang, Guifeng

    2018-05-01

    Porous boron doped diamonds (BDDs) were obtained on foam nickel substrates with a porosity of 80%, 85%, 90% and 95% respectively by hot filament chemical vapor deposition (HFCVD) technology. Scanning electron microscopy (SEM) reveals that uniform and compact BDDs with a cauliflower-like morphology have covered the overall frame of the foam nickel substrates. Raman spectroscopy shows that the BDDs have a poor crystallinity due to heavily doping boron. X-ray photoelectron spectroscopy (XPS) analysis effectively demonstrates that boron atoms can be successfully incorporated into the crystal lattice of diamonds. Electrochemical measurements indicate that the oxygen reduction potential is unaffected by the specific surface area (SSA), and both the onset potential and the limiting diffusion current density are enhanced with increasing SSA. It is also found that the durability and methanol tolerance of the boron doped diamond catalysts are attenuated as the increasing of SSA. The SSA of the catalyst is directly proportional to the oxygen reduction activity and inversely to the durability and methanol resistance. These results provide a reference to the application of porous boron doped diamonds as potential cathodic catalysts for the oxygen reduction reaction in alkaline solution by adjusting the SSA.

  7. Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Zhu, Chengzhou [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Song, Junhua [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99352 USA; Xiao, Biwei [Energy and Environmental Directory, Pacific Northwest National Laboratory, Richland WA 99352 USA; Du, Dan [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Lin, Yuehe [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA

    2017-07-11

    The development of active, durable, and low-cost catalysts to replace noble metal-based materials is highly desirable to promote the sluggish oxygen reduction reaction in fuel cells. Herein, nitrogen and fluorine-codoped three-dimensional carbon nanowire aerogels, composed of interconnected carbon nanowires, were synthesized for the first time by a hydrothermal carbonization process. Owing to their porous nanostructures and heteroatom-doping, the as-prepared carbon nanowire aerogels, with optimized composition, present excellent electrocatalytic activity that is comparable to commercial Pt/C. Remarkably, the aerogels also exhibit superior stability and methanol tolerance. This synthesis procedure paves a new way to design novel heteroatomdoped catalysts.

  8. A high-performance mesoporous carbon supported nitrogen-doped carbon electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Xu, Jingjing; Lu, Shiyao; Chen, Xu; Wang, Jianan; Zhang, Bo; Zhang, Xinyu; Xiao, Chunhui; Ding, Shujiang

    2017-12-01

    Investigating low-cost and highly active electrocatalysts for oxygen reduction reactions (ORR) is of crucial importance for energy conversion and storage devices. Herein, we design and prepare mesoporous carbon supported nitrogen-doped carbon by pyrolysis of polyaniline coated on CMK-3. This electrocatalyst exhibits excellent performance towards ORR in alkaline media. The optimized nitrogen-doped mesoporous electrocatalyst show an onset potential (E onset) of 0.95 V (versus reversible hydrogen electrode (RHE)) and half-wave potential (E 1/2) of 0.83 V (versus RHE) in 0.1 M KOH. Furthermore, the as-prepared catalyst presents superior durability and methanol tolerance compared to commercial Pt/C indicating its potential applications in fuel cells and metal-air batteries.

  9. Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

    Science.gov (United States)

    Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

    2014-01-01

    Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

  10. 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

  11. Development of silver-gas diffusion electrodes for the oxygen reduction reaction by electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Salomé, Sónia; Rego, Rosa; Oliveira, M. Cristina, E-mail: mcris@utad.pt

    2013-12-16

    Silver-gas diffusion electrodes (Ag-GDE) were prepared by direct deposition of the catalyst onto a carbon paper support by electrodeposition. This deposition technique, under potentiostatic and galvanostatic mode, allows the production of well dispersed ultra-low Ag loading levels. The catalytic activity of the prepared materials towards the oxygen reduction reaction (ORR) was investigated in the alkaline solution and its tolerance to methanol was evaluated. Based on an Ag-ink prepared from the electrodeposit material and RDE experiments, it was concluded that the ORR occurs via a four-electron pathway on the Ag electrodeposit. The combination of reasonably high catalytic activity, efficiency, low price, facile and green synthesis makes the electrodeposited Ag-GDE attractive for the ORR in alkaline fuel cells. - Highlights: • A facile and simple way to successfully prepare catalyzed gas diffusion electrodes. • Ultra-low loadings of Ag-GDEs can be achieved. • Good tolerance to methanol and a high mass activity (3.14 mA{sub Ag} mg{sup −1}). • ORR occurs via a four-electron pathway.

  12. Synthesis and characterization of Pd-Ni nanoalloy electrocatalysts for oxygen reduction reaction in fuel cells

    International Nuclear Information System (INIS)

    Zhao, Juan; Sarkar, Arindam; Manthiram, Arumugam

    2010-01-01

    Carbon-supported Pd-Ni nanoalloy electrocatalysts with different Pd/Ni atomic ratios have been synthesized by a modified polyol method, followed by heat treatment in a reducing atmosphere at 500-900 deg. C. The samples have been characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), rotating disk electrode (RDE) measurements, and single-cell proton exchange membrane fuel cell (PEMFC) tests for oxygen reduction reaction (ORR). XRD and TEM data reveal an increase in the degree of alloying and particle size with increasing heat-treatment temperature. XPS data indicate surface segregation with Pd enrichment on the surface of Pd 80 Ni 20 after heat treatment at ≥500 deg. C, suggesting possible lattice strains in the outermost layers. Electrochemical data based on CV, RDE, and single-cell PEMFC measurement show that Pd 80 Ni 20 heated at 500 deg. C has the highest mass catalytic activity for ORR among the Pd-Ni samples investigated, with stability and catalytic activity significantly higher than that found with Pd. With a lower cost, the Pd-Ni catalysts exhibit higher tolerance to methanol than Pt, offering an added advantage in direct methanol fuel cells (DMFC).

  13. Steady state oxygen reduction and cyclic voltammetry

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Karlberg, Gustav; Jaramillo, Thomas

    2008-01-01

    The catalytic activity of Pt and Pt3Ni for the oxygen reduction reaction is investigated by applying a Sabatier model based on density functional calculations. We investigate the role of adsorbed OH on the activity, by comparing cyclic voltammetry obtained from theory with previously published ex...

  14. A bio-inspired N-doped porous carbon electrocatalyst with hierarchical superstructure for efficient oxygen reduction reaction

    Science.gov (United States)

    Miao, Yue-E.; Yan, Jiajie; Ouyang, Yue; Lu, Hengyi; Lai, Feili; Wu, Yue; Liu, Tianxi

    2018-06-01

    The bio-inspired hierarchical "grape cluster" superstructure provides an effective integration of one-dimensional carbon nanofibers (CNF) with isolated carbonaceous nanoparticles into three-dimensional (3D) conductive frameworks for efficient electron and mass transfer. Herein, a 3D N-doped porous carbon electrocatalyst consisting of carbon nanofibers with grape-like N-doped hollow carbon particles (CNF@NC) has been prepared through a simple electrospinning strategy combined with in-situ growth and carbonization processes. Such a bio-inspired hierarchically organized conductive network largely facilitates both the mass diffusion and electron transfer during the oxygen reduction reactions (ORR). Therefore, the metal-free CNF@NC catalyst demonstrates superior catalytic activity with an absolute four-electron transfer mechanism, strong methanol tolerance and good long-term stability towards ORR in alkaline media.

  15. Heavily Graphitic-Nitrogen Self-doped High-porosity Carbon for the Electrocatalysis of Oxygen Reduction Reaction

    Science.gov (United States)

    Feng, Tong; Liao, Wenli; Li, Zhongbin; Sun, Lingtao; Shi, Dongping; Guo, Chaozhong; Huang, Yu; Wang, Yi; Cheng, Jing; Li, Yanrong; Diao, Qizhi

    2017-11-01

    Large-scale production of active and stable porous carbon catalysts for oxygen reduction reaction (ORR) from protein-rich biomass became a hot topic in fuel cell technology. Here, we report a facile strategy for synthesis of nitrogen-doped porous nanocarbons by means of a simple two-step pyrolysis process combined with the activation of zinc chloride and acid-treatment process, in which kidney bean via low-temperature carbonization was preferentially adopted as the only carbon-nitrogen sources. The results show that this carbon material exhibits excellent ORR electrocatalytic activity, and higher durability and methanol-tolerant property compared to the state-of-the-art Pt/C catalyst for the ORR, which can be mainly attributed to high graphitic-nitrogen content, high specific surface area, and porous characteristics. Our results can encourage the synthesis of high-performance carbon-based ORR electrocatalysts derived from widely-existed natural biomass.

  16. A Universal Method to Engineer Metal Oxide-Metal-Carbon Interface for Highly Efficient Oxygen Reduction.

    Science.gov (United States)

    Lv, Lin; Zha, Dace; Ruan, Yunjun; Li, Zhishan; Ao, Xiang; Zheng, Jie; Jiang, Jianjun; Chen, Hao Ming; Chiang, Wei-Hung; Chen, Jun; Wang, Chundong

    2018-03-27

    Oxygen is the most abundant element in the Earth's crust. The oxygen reduction reaction (ORR) is also the most important reaction in life processes and energy converting/storage systems. Developing techniques toward high-efficiency ORR remains highly desired and a challenge. Here, we report a N-doped carbon (NC) encapsulated CeO 2 /Co interfacial hollow structure (CeO 2 -Co-NC) via a generalized strategy for largely increased oxygen species adsorption and improved ORR activities. First, the metallic Co nanoparticles not only provide high conductivity but also serve as electron donors to largely create oxygen vacancies in CeO 2 . Second, the outer carbon layer can effectively protect cobalt from oxidation and dissociation in alkaline media and as well imparts its higher ORR activity. In the meanwhile, the electronic interactions between CeO 2 and Co in the CeO 2 /Co interface are unveiled theoretically by density functional theory calculations to justify the increased oxygen absorption for ORR activity improvement. The reported CeO 2 -Co-NC hollow nanospheres not only exhibit decent ORR performance with a high onset potential (922 mV vs RHE), half-wave potential (797 mV vs RHE), and small Tafel slope (60 mV dec -1 ) comparable to those of the state-of-the-art Pt/C catalysts but also possess long-term stability with a negative shift of only 7 mV of the half-wave potential after 2000 cycles and strong tolerance against methanol. This work represents a solid step toward high-efficient oxygen reduction.

  17. Ruthenium cluster-like chalcogenide as a methanol tolerant cathode catalyst in air-breathing laminar flow fuel cells

    International Nuclear Information System (INIS)

    Whipple, Devin T.; Jayashree, Ranga S.; Egas, Daniela; Alonso-Vante, Nicolas; Kenis, Paul J.A.

    2009-01-01

    This paper reports the incorporation of a cluster-like Ru x Se y as a methanol tolerant cathode catalyst in a laminar flow fuel cell. The effect on cell performance of several concentrations of methanol in the cathode stream was investigated for the Ru x Se y catalyst and compared to a conventional platinum catalyst. While the Pt catalyst exhibited up to ∼80% drop in power density, the Ru x Se y catalyst showed no decrease in performance when the cathode was exposed to methanol. At several methanol concentrations the Ru x Se y catalyst performed better than the Pt catalyst. This demonstration of a methanol tolerant catalyst in a laminar flow fuel cell opens up the way for further miniaturization of the cell design and simplification of its operation as the need for an electrolyte stream to prevent fuel crossover has been eliminated.

  18. Enhanced electrocatalysis performance of amorphous electrolytic carbon from CO2 for oxygen reduction by surface modification in molten salt

    International Nuclear Information System (INIS)

    Chen, Zhigang; Gu, Yuxing; Du, Kaifa; Wang, Xu; Xiao, Wei; Mao, Xuhui; Wang, Dihua

    2017-01-01

    Highlights: •The potential of electrolytic carbon as catalyst for oxygen reduction was evaluated. •A molten salt method for electrolytic-carbon modification was demonstrated. •The electrolytic carbon was activated for the ORR by the molten salt sulfidation. •Sulfur and cobalt dual modification further improved the ORR activity of the carbon. -- Abstract: The electrolytic carbon (E-carbon) derived from greenhouse gas CO 2 in molten carbonates at mild temperature possesses high electrical conductivity and suitable specific surface area. In this work, its potential as catalyst is investigated towards oxygen reduction reaction (ORR). It is revealed that the pristine E-carbon has no electrocatalytic activity for the ORR due to its high surface content of carboxyl group. The carbon was then treated in a Li 2 SO 4 containing Li 2 CO 3 -Na 2 CO 3 -K 2 CO 3 molten salt at 550 °C. Sulfur modified E-carbon was obtained in the melt via a galvanic sulfidation reaction, in which Li 2 SO 4 served as a nontoxic sulfur source and an oxidant. The sulfur modified E-carbon showed a significantly improved electrocatalytic activity. Subsequently, a sulfur/cobalt dual modified carbon with much higher catalysis activity was successfully prepared by treating an E-carbon/CoSO 4 composite in the same melt. The dual modified E-carbon showed excellent catalytic performance with activity close to the commercial Pt/C catalyst but a high tolerance towards methanol.

  19. Three-dimensional iron, nitrogen-doped carbon foams as efficient electrocatalysts for oxygen reduction reaction in alkaline solution

    International Nuclear Information System (INIS)

    Ma, Yanjiao; Wang, Hui; Feng, Hanqing; Ji, Shan; Mao, Xuefeng; Wang, Rongfang

    2014-01-01

    Graphical abstract: Three-dimentional Fe, N-doped carbon foams prepared by two steps exhibited comparable catalytic activity for oxygen reduction reaction to commercial Pt/C due to the unique structure and the synergistic effect of Fe and N atoms. - Highlights: • Three-dimensional Fe, N-doped carbon foam (3D-CF) were prepared. • 3D-CF exhibits comparable catalytic activity to Pt/C for oxygen reduction reaction. • The enhanced activity of 3D-CF results of its unique structure. - Abstract: Three-dimensional (3D) Fe, N-doped carbon foams (3D-CF) as efficient cathode catalysts for the oxygen reduction reaction (ORR) in alkaline solution are reported. The 3D-CF exhibit interconnected hierarchical pore structure. In addition, Fe, N-doped carbon without porous strucuture (Fe-N-C) and 3D N-doped carbon without Fe (3D-CF’) are prepared to verify the electrocatalytic activity of 3D-CF. The electrocatalytic performance of as-prepared 3D-CF for ORR shows that the onset potential on 3D-CF electrode positively shifts about 41 mV than those of 3D-CF’ and Fe-N-C respectively. In addition, the onset potential on 3D-CF electrode for ORR is about 27 mV more negative than that on commercial Pt/C electrode. 3D-CF also show better methanol tolerance and durability than commercial Pt/C catalyst. These results show that to synthesize 3D hierarchical pores with high specific surface area is an efficient way to improve the ORR performance

  20. Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts

    Science.gov (United States)

    Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P.; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

    2015-03-01

    The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions

  1. Scalable preparation of sized-controlled Co-N-C electrocatalyst for efficient oxygen reduction reaction

    Science.gov (United States)

    Ai, Kelong; Li, Zelun; Cui, Xiaoqiang

    2017-11-01

    Heat-treated metal-nitrogen-carbon (M-N-C) materials are emerging as promising non-precious catalysts to replace expensive Pt-based materials for oxygen reduction reaction (ORR) in energy conversion and storage devices. Despite recent progress, their activity and durability are still far from satisfactory. The activity site and particle size are among the most important factors for the ORR activity of M-N-C catalysts. Extensive efforts have been made to reveal the correlation of active site and activity. However, it remains unclear to what extent the particle size will influence the ORR activity of M-N-C materials. Moreover, to the best of our knowledge, controllable synthesis of M-N-C catalysts with high-density activity sites remains elusive. Herein, we develop a straightforward method to produce a monodisperse and size-controlled Co-N-C (Nano-P-ZIF-67) electrocatalyst, and systemically investigate its catalytic mechanisms. Only by optimizing the particle size, Nano-P-ZIF-67 outperforms the commercial 20 wt% Pt/C regarding all evaluating indicators for ORR catalysts in alkaline media including higher catalytic activity, durability, and stronger methanol tolerance. Nano-P-ZIF-67 is assembled into a cell, and the cell shows a power density of 45.5 mW/cm2, which is the highest value among currently studied cathode catalysts. We expect Nano-P-ZIF-67 to be a highly interesting candidate for the next generation of ORR catalysts.

  2. Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

    Science.gov (United States)

    Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

    2018-03-01

    Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

  3. A Pt-free Electrocatalyst Based on Pyrolized Vinazene-Carbon Composite for Oxygen Reduction Reaction

    International Nuclear Information System (INIS)

    Akinpelu, Akeem; Merzougui, Belabbes; Bukola, Saheed; Azad, Abdul-Majeed; Basheer, Rafil A.; Swain, Greg M.; Chang, Qiaowan; Shao, Minhua

    2015-01-01

    The 2-vinyl-4, 5-dicyanoimidazole (Vinazene) was used as a nitrogen precursor to synthesize a promising non-precious metal (NPM) catalyst for oxygen reduction reaction (ORR). Vinazene together with an iron source was impregnated into a carbon matrix and pyrolyzed at 900 °C in N 2 atmosphere. The structure of the resulting Fe–N–C nanocomposite was analyzed by X-ray photoelectron spectroscopy, Raman spectroscopy and X-ray diffraction. Both rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) experiments showed excellent ORR activity for the obtained catalyst with low H 2 O 2 formation (∼3.0%) in 0.1 M KOH. The catalyst was found to be rich in mesoporous structure along with high percentage of pyrrolic-N function with surface area of about 673 m 2 g −1 and pore size of 4.2 nm. In addition to its excellent ORR activity, the catalyst showed remarkable tolerance towards methanol oxidation and demonstrates good stability over 10,000 potential cycles (0.6–1.0 V Vs RHE). We believe that this N-rich Vinazene molecule will be beneficial to further development of nitrogen doped carbon electrocatalysts

  4. Ordered hierarchically porous carbon codoped with iron and nitrogen as electrocatalyst for the oxygen reduction reaction.

    Science.gov (United States)

    Deng, Chengwei; Zhong, Hexiang; Yao, Lan; Liu, Sisi; Xu, Zhuang; Zhang, Huamin

    2014-12-01

    N-doped carbon catalysts have attracted great attention as potential alternatives to expensive Pt-based catalysts used in fuel cells. Herein, an ordered hierarchically porous carbon codoped with N and Fe (Fe-NOHPC) is prepared by an evaporation-induced self-assembly process followed by carbonization under ammonia. The soft template and Fe species promote the formation of the porous structure and facilitate the oxygen reduction reaction (ORR).The catalyst possesses an ordered hierarchically porous structure with a large surface area (1172.5 m(2) g(-1) ) and pore volume of 1.03 cm(3) g(-1) . Compared to commercial 20% Pt/C, it exhibits better ORR catalytic activity and higher stability as well as higher methanol tolerance in an alkaline electrolyte, which demonstrates its potential use in fuel cells as a nonprecious cathode catalyst. The N configuration, Fe species, and pore structure of the catalysts are believed to correlate with its high catalytic activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synergistically enhanced activity of nitrogen-doped carbon dots/graphene composites for oxygen reduction reaction

    Science.gov (United States)

    Liu, Hui; Zhao, Qingshan; Liu, Jingyan; Ma, Xiao; Rao, Yuan; Shao, Xiaodong; Li, Zhongtao; Wu, Wenting; Ning, Hui; Wu, Mingbo

    2017-11-01

    With rapid dissociative adsorption of oxygen, nitrogen-doped carbon nanomaterials have been demonstrated to be efficient alternative catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we developed a mild hydrothermal strategy to construct nitrogen-doped carbon dots/graphene (NCDs-NG) composites towards ORR. Carbon dots (CDs) were derived from petroleum coke via acid oxidation while graphene oxide (GO) was obtained from graphite by modified Hummer's method. Graphene was employed as a conductive substrate to disperse CDs during hydrothermal reducing reaction while ammonia was utilized as N source to dope both graphene and CDs. The synergistic effects, i.e. CDs as pillars for graphene and catalytic sites for ORR, the high conductivity of graphene, the quick O2 adsorption on doped pyridinic nitrogen endow the NCDs-NG composites with enhanced ORR catalytic performance in alkaline electrolyte. The onset potential of -95 mV and kinetic current density of 12.7 mA cm-2 at -0.7 V (vs. Ag/AgCl) can be compared to those of the commercial 20 wt% Pt/C catalyst. The electron transfer number is about 3.9, revealing a four-electron pathway for ORR. The optimal NCDs-NG catalyst shows superior durability and methanol tolerance than 20 wt% Pt/C. This work demonstrates a feasible and effective strategy to prepare metal-free efficient ORR electrocatalysts for fuel cell applications.

  6. Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jie; Chen, Jinwei, E-mail: jwchen@scu.edu.cn; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin, E-mail: rl.wang@scu.edu.cn

    2016-12-15

    Graphical abstract: A hybrid catalyst was prepared via a quite green and simple method to achieve an one-pot synthesis of the N-doping carbon, tungsten carbides, and iron/cobalt carbides. It exhibited comparable electrocatalytic activity, higher durability and ability to methanol tolerance compared with commercial Pt/C to ORR. - Highlights: • A novel type of hybrid Fe/Co/WC@NC catalysts have been successfully synthesized. • The hybrid catalyst also exhibited better durability and methanol tolerance. • Multiple effective active sites of Fe{sub 3}C, Co{sub 3}C, WC, and NC help to improve catalytic performance. - Abstract: This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe{sub 3}C and Co{sub 3}C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe{sub 3}C, and Co{sub 3}C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.

  7. Electronic modification of Pt via Ti and Se as tolerant cathodes in air-breathing methanol microfluidic fuel cells.

    Science.gov (United States)

    Ma, Jiwei; Habrioux, Aurélien; Morais, Cláudia; Alonso-Vante, Nicolas

    2014-07-21

    We reported herein on the use of tolerant cathode catalysts such as carbon supported Pt(x)Ti(y) and/or Pt(x)Se(y) nanomaterials in an air-breathing methanol microfluidic fuel cell. In order to show the improvement of mixed-reactant fuel cell (MRFC) performances obtained with the developed tolerant catalysts, a classical Pt/C nanomaterial was used for comparison. Using 5 M methanol concentration in a situation where the fuel crossover is 100% (MRFC-mixed reactant fuel cell application), the maximum power density of the fuel cell with a Pt/C cathodic catalyst decreased by 80% in comparison with what is observed in the laminar flow fuel cell (LFFC) configuration. With Pt(x)Ti(y)/C and Pt(x)Se(y)/C cathode nanomaterials, the performance loss was only 55% and 20%, respectively. The evaluation of the tolerant cathode catalysts in an air-breathing microfluidic fuel cell suggests the development of a novel nanometric system that will not be size restricted. These interesting results are the consequence of the high methanol tolerance of these advanced electrocatalysts via surface electronic modification of Pt. Herein we used X-ray photoelectron and in situ FTIR spectroscopies to investigate the origin of the high methanol tolerance on modified Pt catalysts.

  8. Substrate effect on oxygen reduction electrocatalysis

    International Nuclear Information System (INIS)

    Timperman, L.; Feng, Y.J.; Vogel, W.; Alonso-Vante, N.

    2010-01-01

    The oxygen reduction reaction (ORR) was investigated on carbon (XC-72) supported platinum nanoparticles, generated via the carbonyl chemical route and on oxide composites supported platinum generated via the UV-photo-deposition technique in sulfuric acid medium. The behavior of Pt/C was examined using a careful dosing of the catalyst loading spanning the range from 4.3 to 131 μg cm -2 . The ORR electrochemical response of Pt/C (in line with recent literature data) is put into contrast with the Pt/oxide-composite systems. Our results point out that it is possible to use smaller amounts of catalyst for the ORR when platinum atoms interact with the oxide (anatase) surface of the substrate composite. Evidence of the incipient metal-substrate interaction is discussed in the light of the results of XRD experiments.

  9. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

    Science.gov (United States)

    Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

    2015-01-01

    Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

  10. Synthesis of Pd₃Co₁@Pt/C core-shell catalysts for methanol-tolerant cathodes of direct methanol fuel cells.

    Science.gov (United States)

    Aricò, Antonino S; Stassi, Alessandro; D'Urso, Claudia; Sebastián, David; Baglio, Vincenzo

    2014-08-18

    A composite Pd-based electrocatalyst consisting of a surface layer of Pt (5 wt.%) supported on a core Pd3Co1 alloy (95 wt.%) and dispersed as nanoparticles on a carbon black support (50 wt.% metal content) was prepared by using a sulphite-complex route. The structure, composition, morphology, and surface properties of the catalyst were investigated by XRD, XRF, TEM, XPS and low-energy ion scattering spectroscopy (LE-ISS). The catalyst showed an enrichment of Pt on the surface and a smaller content of Co in the outermost layers. These characteristics allow a decrease the Pt content in direct methanol fuel cell cathode electrodes (from 1 to 0.06 mg cm(-2)) without significant decay in performance, due also to a better tolerance to methanol permeated through the polymer electrolyte membrane. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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.

  12. Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

    Science.gov (United States)

    Qi, Chunling; Zhang, Li; Xu, Guancheng; Sun, Zhipeng; Zhao, Aihua; Jia, Dianzeng

    2018-01-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in efficient energy conversion and storage solutions. Here, Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures (denoted as Co@Co3O4/NCs) are prepared via a simple two-step and in situ approach by carbonization and subsequent oxidation of Co-MOF containing high contents of carbon and nitrogen. When evaluated as electrocatalyst towards both ORR and OER in a KOH electrolyte solution, the as-fabricated Co@Co3O4/NC-2 exhibits similar ORR catalytic activity to the commercial Pt/C catalyst, but superior stability and good methanol tolerance. Furthermore, the as-fabricated catalysts also show promising catalytic activity for OER. The effective catalytic activities originate from the synergistic effects between well wrapped Co@Co3O4 nanoparticles and nitrogen doped carbon structures.

  13. Uric acid-derived Fe3C-containing mesoporous Fe/N/C composite with high activity for oxygen reduction reaction in alkaline medium

    Science.gov (United States)

    Ma, Jun; Xiao, Dejian; Chen, Chang Li; Luo, Qiaomei; Yu, Yue; Zhou, Junhao; Guo, Changding; Li, Kai; Ma, Jie; Zheng, Lirong; Zuo, Xia

    2018-02-01

    In this work, a category of Fe3C-containing Fe/N/C mesoporous material has been fabricated by carbonizing the mixture of uric acid, Iron (Ⅲ) chloride anhydrous and carbon support (XC-72) under different pyrolysis temperature. Of all these samples, pyrolysis temperature (800 °C) becomes the most crucial factor in forming Fe3C active sites which synergizes with high content of graphitic N to catalyze oxygen reduction reaction (ORR). X-ray absorption fine structure spectroscopy (XAFS) is used to exhibit that the space structure around Fe atoms in the catalyst. This kind of catalyst possesses comparable ORR properties with commercial 20% Pt/C (onset potential is 0 V vs. Ag/AgCl in 0.1 M KOH), the average transfer electron number is 3.84 reflecting the 4-electron process. Moreover, superior stability and methanol tolerance deserve to be mentioned.

  14. Covalent versus Charge Transfer Modification of Graphene/Carbon-Nanotubes with Vitamin B1: Co/N/S-C Catalyst toward Excellent Oxygen Reduction.

    Science.gov (United States)

    Vij, Varun; Tiwari, Jitendra N; Kim, Kwang S

    2016-06-29

    High-performance nonprecious cathodic catalysts for oxygen reduction are highly demanded for low-temperature polymer electrolyte membrane fuel cells (PEMFCs). Here, we report a noble-meta- free, nitrogen and sulfur codoped graphene(G)/carbon-nanotube(CNT) material decorated with Co nanoparticles (NPs), which serve as catalytic sites for excellent oxygen reduction reaction (ORR) in basic and acidic media. Out of the cathodic catalysts synthesized by either covalent (cov) or charge transfer (CT) modification of graphen oxide (GO) with thiamine (Th: Vitamin B1), ThG/CNT/Co-cov shows more promising ORR properties than ThG/CNT/Co-CT. Catalyst ThG/CNT/Co-cov exhibits onset/halfwave potentials of 0.95/0.86 V in 0.1 M KOH and 0.92/0.83 V in 0.1 M HClO4, which are comparable to those of commercial catalyst Pt/C (0.95/0.86 V). As compared to Pt/C, our catalyst shows higher current densities of 6.72 mA cm(-2) in basic medium and 7.08 mA cm(-2) in acidic medium at 0.55 V (vs reversible hydrogen electrode (RHE)). It also exhibits better catalytic stability and methanol tolerance. High catalytic efficiency and stability of ThG/CNT/Co-cov show a promising prospect of materialization of PEMFCs for clean energy production.

  15. N- and S-doped high surface area carbon derived from soya chunks as scalable and efficient electrocatalysts for oxygen reduction

    Science.gov (United States)

    Rana, Moumita; Arora, Gunjan; Gautam, Ujjal K.

    2015-02-01

    Highly stable, cost-effective electrocatalysts facilitating oxygen reduction are crucial for the commercialization of membrane-based fuel cell and battery technologies. Herein, we demonstrate that protein-rich soya chunks with a high content of N, S and P atoms are an excellent precursor for heteroatom-doped highly graphitized carbon materials. The materials are nanoporous, with a surface area exceeding 1000 m2 g-1, and they are tunable in doping quantities. These materials exhibit highly efficient catalytic performance toward oxygen reduction reaction (ORR) with an onset potential of -0.045 V and a half-wave potential of -0.211 V (versus a saturated calomel electrode) in a basic medium, which is comparable to commercial Pt catalysts and is better than other recently developed metal-free carbon-based catalysts. These exhibit complete methanol tolerance and a performance degradation of merely ˜5% as compared to ˜14% for a commercial Pt/C catalyst after continuous use for 3000 s at the highest reduction current. We found that the fraction of graphitic N increases at a higher graphitization temperature, leading to the near complete reduction of oxygen. It is believed that due to the easy availability of the precursor and the possibility of genetic engineering to homogeneously control the heteroatom distribution, the synthetic strategy is easily scalable, with further improvement in performance.

  16. Facile preparation of three-dimensional Co1-xS/sulfur and nitrogen-codoped graphene/carbon foam for highly efficient oxygen reduction reaction

    Science.gov (United States)

    Liang, Hui; Li, Chenwei; Chen, Tao; Cui, Liang; Han, Jingrui; Peng, Zhi; Liu, Jingquan

    2018-02-01

    Because of the urgent need for renewable resources, oxygen reduction reaction (ORR) has been widely studied. Finding efficient and low cost non-precious metal catalyst is increasingly critical. In this study, melamine foam is used as template to obtain porous sulfur and nitrogen-codoped graphene/carbon foam with uniformly distributed cobalt sulfide nanoparticles (Co1-xS/SNG/CF) which is prepared by a simple infiltration-drying-sulfuration method. It is noteworthy that melamine foam not only works as a three-dimensional support skeleton, but also provides a nitrogen source without any environmental pollution. Such Co1-xS/SNG/CF catalyst shows excellent oxygen reduction catalytic performance with an onset potential of only 0.99 V, which is the same as that of Pt/C catalyst (Eonset = 0.99 V). Furthermore, the stability and methanol tolerance of Co1-xS/SNG/CF are more outstanding than those of Pt/C catalyst. Our work manifests a facile method to prepare S and N-codoped 3D graphene network decorated with Co1-xS nanoparticles, which may be utilized as potential alternative to the expensive Pt/C catalysts toward ORR.

  17. Hexadecacarbonylhexarhodium as a novel electrocatalyst for oxygen reduction and hydrogen oxidation in the presence of fuel cell contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro. Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Hernandez-Castellanos, R. [Universidad Tecnologica de San Juan del Rio, Av. La Palma No. 125, Col. Vista Hermosa, San Juan del Rio, Qro. 76800 (Mexico)

    2010-11-01

    The electrocatalytic activity for oxygen reduction and hydrogen oxidation of a discrete metal carbonyl cluster with a well defined molecular and crystal structure, Rh{sub 6}(CO){sub 16}, is reported. The exchange current density of this compound for oxygen reduction is one order of magnitude higher than that of platinum, and its resistance degree to PEM fuel cell contaminants such as methanol and CO is as high as 2 mol L{sup -1} and 0.5%, respectively. These properties make the metal complex a potential alternative for use as electrode in polymer electrolyte membrane fuel cells. (author)

  18. Ultramicroelectrode studies of oxygen reduction in polyelectrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

    1997-12-31

    A study on the oxygen reduction reaction in a solid state electrochemical cell was presented. The oxygen reduction reaction is a rate limiting reaction in the operation of solid polymer electrolyte fuel cells which use H{sub 2} and O{sub 2}. Interest in the oxygen reduction reaction of platinum electrodes in contact with Nafion electrolytes stems from its role in fuel cell technology. The kinetics of the oxygen reduction reaction in different polyelectrolyte membranes, such as Nafion and non-Nafion membranes, were compared. The electrode kinetics and mass transport parameters of the oxygen reduction reaction in polyelectrolyte membranes were measured by ultramicroelectrode techniques. The major difference found between these two classes of membrane was the percentage of water, which is suggestive of superior electrochemical mass transport properties of the non-Nafion membranes. 2 refs. 1 fig.

  19. Porous VO(x)N(y) nanoribbons supported on CNTs as efficient and stable non-noble electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Huang, K; Bi, K; Lu, Y K; Zhang, R; Liu, J; Wang, W J; Tang, H L; Wang, Y G; Lei, M

    2015-11-30

    Novel nanocomposites of carbon nanotubes supported porous VO(x)N(y) nonoribbons (VO(x)N(y)-CNTs) have been synthesized by the annealing of the sol-gel mixture of CNTs and V2O5 under NH3 atmosphere as well as the ageing process in air. Besides the morphological and structural characterizations revealed by TEM, SEAD, EDS, XRD and XPS measurements, typical electrochemical tests including cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry have been employed to determine the oxygen reduction reaction (ORR) performance of VO(x)N(y)-CNTs. Inspiringly, the results indicate that VO(x)N(y)-CNTs catalyst exhibits a 0.4 mA/cm(2) larger diffusion-limited current density, a 0.10  V smaller onset potential value, a 10.73% less of ORR current decay and an excellent methanol-tolerance compared with commercial Pt/C catalyst. Therefore, we have reasonable grounds to believe that this new VO(x)N(y)-CNTs nanocomposites can be regarded as a promising non-precious methanol-tolerant ORR catalyst candidate for alkaline fuel cells.

  20. Porous carbon supported Fe-N-C composite as an efficient electrocatalyst for oxygen reduction reaction in alkaline and acidic media

    Science.gov (United States)

    Liu, Baichen; Huang, Binbin; Lin, Cheng; Ye, Jianshan; Ouyang, Liuzhang

    2017-07-01

    In recent years, non-precious metal electrocatalysts for oxygen reduction reaction (ORR) have attracted tremendous attention due to their high catalytic activity, long-term stability and excellent methanol tolerance. Herein, the porous carbon supported Fe-N-C catalysts for ORR were synthesized by direct pyrolysis of ferric chloride, 6-Chloropyridazin-3-amine and carbon black. Variation of pyrolysis temperature during the synthesis process leads to the difference in ORR catalytic activity. High pyrolysis temperature is beneficial to the formation of the "N-Fe" active sites and high electrical conductivity, but the excessive temperature will cause the decomposition of nitrogen-containing active sites, which are revealed by Raman, TGA and XPS. A series of synthesis and characterization experiments with/without nitrogen or iron in carbon black indicate that the coordination of iron and nitrogen plays a crucial role in achieving excellent ORR performances. Electrochemical test results show that the catalyst pyrolyzed at 800 °C (Fe-N-C-800) exhibits excellent ORR catalytic activity, better methanol tolerance and higher stability compared with commercial Pt/C catalyst in both alkaline and acidic conditions.

  1. One-step preparation of N-doped graphene/Co nanocomposite as an advanced oxygen reduction electrocatalyst

    International Nuclear Information System (INIS)

    Bai, Fo; Huang, Hao; Tan, Yanlei; Hou, Changmin; Zhang, Ping

    2015-01-01

    Graphical abstract: N-doped graphene/Co nanocomposites were synthesized through one-step pyrolysis process and the product exhibits high performance for ORR and excellent stability in alkaline medium. - Highlights: • N-doped graphene/Co nano-composite is directly synthesized by a one-step method from Co(NO3)2∙6H2O, glucose and dicyandiamide (DCDA). • The electrocatalytic performance of as-prepared NG/Co-0.5 shows the peak potential positively shifts about 10 mV than commercial Pt/C electrode. • The material shows an excellent stability and tolerance to methanol poisoning effects in alkaline medium. - Abstract: N-doped graphene/Co nanocomposites (NG/Co NPs) have been prepared by a simple one-step pyrolysis of Co(NO 3 ) 2 ∙6H 2 O, glucose and dicyandiamide (DCDA). The products with nitrogen doped and suitable graphitic degree perform high electrocatalytic activity (with the reduction peak at −0.099 V vs Ag/AgCl) and near four-electron selectivity for the oxygen reduction reaction (ORR), with excellent stability and durability in alkaline medium comparable to a commercial Pt/C catalyst. Owing to the superb ORR performance, low cost and facile preparation, the catalysts of NG/Co NPs have great potential applications in fuel cells, metal-air batteries and ORR-related electrochemical industries

  2. Solution-based synthesis and design of late transition metal chalcogenide materials for oxygen reduction reaction (ORR).

    Science.gov (United States)

    Gao, Min-Rui; Jiang, Jun; Yu, Shu-Hong

    2012-01-09

    Late transition metal chalcogenide (LTMC) nanomaterials have been introduced as a promising Pt-free oxygen reduction reaction (ORR) electrocatalysts because of their low cost, good ORR activity, high methanol tolerance, and facile synthesis. Herein, an overview on the design and synthesis of LTMC nanomaterials by solution-based strategies is presented along with their ORR performances. Current solution-based synthetic approaches towards LTMC nanomaterials include a hydrothermal/solvothermal approach, single-source precursor approach, hot-injection approach, template-directed soft synthesis, and Kirkendall-effect-induced soft synthesis. Although the ORR activity and stability of LTMC nanomaterials are still far from what is needed for practical fuel-cell applications, much enhanced electrocatalytic performance can be expected. Recent advances have emphasized that decorating the surface of the LTMC nanostructures with other functional nanoparticles can lead to much better ORR catalytic activity. It is believed that new synthesis approaches to LTMCs, modification techniques of LTMCs, and LTMCs with desirable morphology, size, composition, and structures are expected to be developed in the future to satisfy the requirements of commercial fuel cells. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Improving biomass-derived carbon by activation with nitrogen and cobalt for supercapacitors and oxygen reduction reaction

    Science.gov (United States)

    Zhang, Man; Jin, Xin; Wang, Linan; Sun, Mengjia; Tang, Yang; Chen, Yongmei; Sun, Yanzhi; Yang, Xiaojin; Wan, Pingyu

    2017-07-01

    Biomass-derived carbon by activation with nitrogen and cobalt (denoted as NPACCo) was prepared by one-pot pyrolysis of pomelo peel with melamine, cobalt nitrate and potassium hydroxide, followed by acid leaching. NPACCo possesses high content of quaternary-N (2.5%) and pyridinic-N (1.7%), co-existences of amorphous and short-range ordered carbon, high specific surface area and pore structure with majority of micropores and small mesopores. As electrode material of supercapacitors, NPACCo exhibits high specific capacitance and good rate capability. At ultrahigh rate of 50 A g-1 (135 mA cm-2), the capacitance of NPACCo remains 246 F g-1, which is 6.3, 1.9 and 3.2 times as high as that of other three materials (PC, PAC and NPAC). The as-assembled symmetric supercapacitor of NPACCo delivers high energy density, high power density and excellent cycling stability. With respect to oxygen reduction reaction (ORR), NPACCo exhibits high onset potential (0.87 V), high half-wave potential (0.78 V), excellent methanol tolerance and low yield of H2O2. The ORR properties of NPACCo are comparable or superior to those of commercial Pt/C. This investigation of pomelo peel-based NPACCo would be valuable for development of both supercapacitor and ORR.

  4. Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction.

    Science.gov (United States)

    Li, Qiheng; Chen, Wenxing; Xiao, Hai; Gong, Yue; Li, Zhi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Cheong, Weng-Chon; Shen, Rongan; Fu, Ninghua; Gu, Lin; Zhuang, Zhongbin; Chen, Chen; Wang, Dingsheng; Peng, Qing; Li, Jun; Li, Yadong

    2018-06-01

    Heteroatom-doped Fe-NC catalyst has emerged as one of the most promising candidates to replace noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular-level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole-thiophene copolymer pyrolysis strategy to synthesize Fe-isolated single atoms on sulfur and nitrogen-codoped carbon (Fe-ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe-ISA/SNC shows a volcano-type curve with the increase of sulfur doping. The optimized Fe-ISA/SNC exhibits a half-wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe-isolated single atoms on nitrogen codoped carbon (Fe-ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe-ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X-ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate-limiting reductive release of OH* and therefore improved the overall ORR efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

    Science.gov (United States)

    Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

    2018-01-31

    The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

  6. Promotional effect of phosphorus doping on the activity of the Fe-N/C catalyst for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Hu, Yang; Zhu, Jianbin; Lv, Qing

    2015-01-01

    Cost-effective, active and stable electrocatalysts for the oxygen reduction reaction (ORR) are highly desirable for the wide-spread adoption of technologies such as fuel cells and metal-air batteries. Among the already reported non-precious metal catalysts, carbon-supported transition metal...... to that for the undoped Fe-N/C catalyst. The activity and durability of the catalysts are demonstrated in direct methanol fuel cells....

  7. Selective electrocatalysts toward a prototype of the membraneless direct methanol fuel cell.

    Science.gov (United States)

    Feng, Yan; Yang, Jinhua; Liu, Hui; Ye, Feng; Yang, Jun

    2014-01-22

    Mastery over the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the design and fabrication of Pt-based nanomaterials with enhanced catalytic activity and superior selectivity toward the reactions in direct methanol fuel cells (DMFCs) upon the deep understanding of the mechanisms of these electrochemical reactions. In particular, the ternary Au@Ag2S-Pt nanocomposites display superior methanol oxidation reaction (MOR) selectivity due to the electronic coupling effect among different domains of the nanocomposites, while the cage-bell structured Pt-Ru nanoparticles exhibit excellent methanol tolerance for oxygen reduction reaction (ORR) at the cathode because of the differential diffusion of methanol and oxygen in the porous Ru shell of the cage-bell nanoparticles. The good catalytic selectivity of these Pt-based nanomaterials via structural construction enables a DMFC to be built without a proton exchange membrane between the fuel electrode and the oxygen electrode.

  8. 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.

  9. 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.

  10. Surface tailored single walled carbon nanotubes as catalyst support for direct methanol fuel cell

    Science.gov (United States)

    Kireeti, Kota V. M. K.; Jha, Neetu

    2017-10-01

    A strategy for tuning the surface property of Single Walled Carbon Nanotubes (SWNTs) for enhanced methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) along with methanol tolerance is presented. The surface functionality is tailored using controlled acid and base treatment. Acid treatment leads to the attachment of carboxylic carbon (CC) fragments to SWNT making it hydrophilic (P3-SWNT). Base treatment of P3-SWNT with 0.05 M NaOH reduces the CCs and makes it hydrophobic (P33-SWNT). Pt catalyst supported on the P3-SWNT possesses enhanced MOR whereas that supported on P33-SWNT not only enhances ORR kinetics but also possess good tolerance towards methanol oxidation as verified by the electrochemical technique.

  11. Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

    2016-05-01

    Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. High content of pyridinic- and pyrrolic-nitrogen-modified carbon nanotubes derived from blood biomass for the electrocatalysis of oxygen reduction reaction in alkaline medium

    International Nuclear Information System (INIS)

    Zheng, Jie; Guo, Chaozhong; Chen, Chunyan; Fan, Mingzhi; Gong, Jianping; Zhang, Yanfang; Zhao, Tianxin; Sun, Yuelin; Xu, Xiaofan; Li, Mengmeng; Wang, Ran; Luo, Zhongli; Chen, Changguo

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: •An ORR electrocatalyst was fabricated from blood biomass and carbon nanotube. •The N-CNT catalyst exhibits good ORR activity, methanol resistance and stability. •The pyrolysis process produces high contents of pyridinic and pyrrolic N species. •The pyridinic-N group may play more important role in the active sites for ORR. -- Abstract: Here we present a facile synthetic route to design nitrogen-doped nanostructured carbon-based electrocatalyst for oxygen reduction reaction (ORR) by the copyrolysis of blood biomass from pig and carbon nanotubes (CNTs) at high temperatures. The nitrogen-doped CNTs obtained at 800 °C not only results in excellent ORR activity with four-electron transfer selectivity in alkaline medium, but also exhibits superior methanol-tolerant property and long-term stability. It is confirmed that high-temperature pyrolysis processes can facilitate to produce higher contents of pyridinic- and pyrrolic-N binding groups in electrocatalysts, contributing to the enhancement of ORR performance in terms of onset potential, half-wave potential, and limited current density. We also propose that the planar-N configuration may be the active site that is responsible for the improved ORR electrocatalytic performance. The straight-forward and cheap synthesis of the active and stable electrocatalyst makes it a promising candidate for electrochemical power sources such as fuel cells or metal-air batteries

  13. Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as oxygen reduction reaction electrocatalyst for polymer electrolyte membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Imran Jafri, Razack; Sujatha, N.; Ramaprabhu, S. [Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre (NFMTC), Department of Physics, Indian Institute of Technology Madras, Chennai (India); Rajalakshmi, N. [Center for Fuel Cell Technology (ARCI), Madavakkam, Chennai (India)

    2009-08-15

    Bi-functional catalysts based on Au supported on oxide based nanomaterials for use in fuel cells were evaluated by electrochemical methods for oxygen reduction reaction (ORR) in Polymer Electrolyte Membrane Fuel Cell (PEMFC). Metal oxide coated multi walled carbon nanotubes (MWNTs) (MnO{sub 2}/MWNT and ZnO/MWNT) were prepared by reduction of potassium permanganate and oxidation of Zn powder on MWNT surface respectively. Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT were prepared by chemical reduction of chloroauric acid on MnO{sub 2}/MWNT and ZnO/MWNT. The samples were characterized and linear sweep voltammetric studies were performed in N{sub 2} saturated, O{sub 2} saturated and methanol containing 1 M KOH solution and the results have been discussed. A single fuel cell was also constructed using Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as ORR electrocatalysts. A maximum power density of 45 mW/cm{sup 2} and 56 mW/cm{sup 2} was obtained with Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT respectively. Additionally, the methanol tolerance of these electrocatalysts has been investigated and results have been discussed. (author)

  14. Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan

    2012-01-01

    In this work, we extend the activity volcano for oxygen reduction from the face-centered cubic (fcc) metal (111) facet to the (100) facet. Using density functional theory calculations, we show that the recent findings of constant scaling between OOH* and OH* holds on the fcc metal (100) facet......, as well. Using this fact, we show the existence of a universal activity volcano to describe oxygen reduction electrocatalysis with a minimum overpotential, ηmin = 0.37 ± 0.1 V. Specifically, we find that the (100) facet of Pt is found to bind oxygen intermediates too strongly and is not active for oxygen...... reduction reaction (ORR). In contrast, Au(100) is predicted to be more active than Au(111) and comparable in activity to Pt alloys. Using this activity volcano, we further predict that Au alloys that bind OH more strongly could display improved ORR activity on the (100) facet. We carry out a computational...

  15. Oxygen reduction on nanocrystalline ruthenia-local structure effects

    DEFF Research Database (Denmark)

    Abbott, Daniel F.; Mukerjee, Sanjeev; Petrykin, Valery

    2015-01-01

    Nanocrystalline ruthenium dioxide and doped ruthenia of the composition Ru1-xMxO2 (M = Co, Ni, Zn) with 0 ≤ x ≤ 0.2 were prepared by the spray-freezing freeze-drying technique. The oxygen reduction activity and selectivity of the prepared materials were evaluated in alkaline media using the RRDE ...

  16. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nandan, Ravi, E-mail: aerawat27@gmail.com; Nanda, Karuna Kar [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India)

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  17. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer

    Science.gov (United States)

    Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

    2016-01-01

    Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated.Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic

  18. High-Performance Direct Methanol Fuel Cells with Precious-Metal-Free Cathode.

    Science.gov (United States)

    Li, Qing; Wang, Tanyuan; Havas, Dana; Zhang, Hanguang; Xu, Ping; Han, Jiantao; Cho, Jaephil; Wu, Gang

    2016-11-01

    Direct methanol fuel cells (DMFCs) hold great promise for applications ranging from portable power for electronics to transportation. However, apart from the high costs, current Pt-based cathodes in DMFCs suffer significantly from performance loss due to severe methanol crossover from anode to cathode. The migrated methanol in cathodes tends to contaminate Pt active sites through yielding a mixed potential region resulting from oxygen reduction reaction and methanol oxidation reaction. Therefore, highly methanol-tolerant cathodes must be developed before DMFC technologies become viable. The newly developed reduced graphene oxide (rGO)-based Fe-N-C cathode exhibits high methanol tolerance and exceeds the performance of current Pt cathodes, as evidenced by both rotating disk electrode and DMFC tests. While the morphology of 2D rGO is largely preserved, the resulting Fe-N-rGO catalyst provides a more unique porous structure. DMFC tests with various methanol concentrations are systematically studied using the best performing Fe-N-rGO catalyst. At feed concentrations greater than 2.0 m, the obtained DMFC performance from the Fe-N-rGO cathode is found to start exceeding that of a Pt/C cathode. This work will open a new avenue to use nonprecious metal cathode for advanced DMFC technologies with increased performance and at significantly reduced cost.

  19. Iron(II) phthalocyanine covalently functionalized graphene as a highly efficient non-precious-metal catalyst for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Liu, Ying; Wu, Yan-Ying; Lv, Guo-Jun; Pu, Tao; He, Xing-Quan; Cui, Li-Li

    2013-01-01

    Graphical abstract: The fabricated FePc-Gr catalyst for ORR exhibited high activity, favoring a direct 4-electron process, good stability and selectivity, all of which should be attributed to its high conductivity, the synergistic effect between FePc and graphene, as well as the formation of stable FePc-Gr composite through covalent bonding and π–π interaction. - Abstract: A novel iron(II) phthalocyanine covalently modified graphene (FePc-Gr) was synthesized by reduction of the product obtained through an amidation reaction between carboxyl-functionalized graphene oxide (CFGO) and iron(II) tetra-aminophthalocyanine (FeTAPc). The FePc-Gr hybird was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS), respectively. The electrocatalytic properties of FePc-Gr toward the oxygen reduction reaction (ORR) were evaluated using cyclic voltammetry (CV) and linear sweep voltammetry methods. The peak potential of the ORR on the FePc-Gr catalyst was found to be about −0.12 V vs. SCE in 0.1 M NaOH solution, which was 180 and 360 mV more positive than that on FeTAPc and bare GCE, respectively. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements revealed that the ORR mechanism was nearly via a direct four-electron pathway to water on FePc-Gr. The current still remained 83.5% of its initial after chronoamperometric test for 10,000 s. Nevertheless, Pt/C catalyst only retained 40.5% of its initial current. The peak potential and peak current changed slightly when 3 M methanol was introduced. So the FePc-Gr composite catalyst for ORR exhibited high activity, good stability and methanol-tolerance, which could be used as a promising Pt-free catalyst for ORR in alkaline direct methanol fuel cell (DMFC)

  20. Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian, E-mail: anjx@163.com; Shen, Yuhua, E-mail: s_yuhua@163.com

    2017-01-30

    Graphical abstract: This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass simultaneously for environment clean. And the typical sample exhibits excellent catalytic performance toward ORR, which is similar to that of commercial Pt/C. - Highlights: • This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass. • The HPC/RGO composite not only prevents the aggregation of RGO, but also takes advantage of the synergy between them. • This method was accessible, without using any activator, which is an effective strategy for the large scale application of FCs. - Abstract: Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) –doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m{sup 2}/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and

  1. Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction.

    Science.gov (United States)

    Niu, Wenhan; Li, Ligui; Liu, Xiaojun; Wang, Nan; Liu, Ji; Zhou, Weijia; Tang, Zhenghua; Chen, Shaowei

    2015-04-29

    Thermally removable nanoparticle templates were used for the fabrication of self-supported N-doped mesoporous carbons with a trace amount of Fe (Fe-N/C). Experimentally Fe-N/C was prepared by pyrolysis of poly(2-fluoroaniline) (P2FANI) containing a number of FeO(OH) nanorods that were prepared by a one-pot hydrothermal synthesis and homogeneously distributed within the polymer matrix. The FeO(OH) nanocrystals acted as rigid templates to prevent the collapse of P2FANI during the carbonization process, where a mesoporous skeleton was formed with a medium surface area of about 400 m(2)/g. Subsequent thermal treatments at elevated temperatures led to the decomposition and evaporation of the FeO(OH) nanocrystals and the formation of mesoporous carbons with the surface area markedly enhanced to 934.8 m(2)/g. Electrochemical measurements revealed that the resulting mesoporous carbons exhibited apparent electrocatalytic activity for oxygen reduction reactions (ORR), and the one prepared at 800 °C (Fe-N/C-800) was the best among the series, with a more positive onset potential (+0.98 V vs RHE), higher diffusion-limited current, higher selectivity (number of electron transfer n > 3.95 at +0.75 V vs RHE), much higher stability, and stronger tolerance against methanol crossover than commercial Pt/C catalysts in a 0.1 M KOH solution. The remarkable ORR performance was attributed to the high surface area and sufficient exposure of electrocatalytically active sites that arose primarily from N-doped carbons with minor contributions from Fe-containing species.

  2. Amorphous metallic alloys for oxygen reduction reaction in a polymer electrolyte membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Huerta, R.; Guerra-Martinez, I.; Lopez, J.S. [Inst. Politecnico Nacional, ESIQIE, Mexico City (Mexico). Lab. de Electroquimica; Pierna, A.R. [Basque Country Univ., San Sebastian (Spain). Dept. of Chemical Engineering and Environment; Solorza-Feria, O. [Inst. Politenico Nacional, Centro de Investigacion y de Estudios Avanzados, Mexico City (Mexico). Dept. de Quimica

    2010-07-15

    Direct methanol fuel cells (DMFC) and polymer electrolyte membrane fuel cells (PEMFC) represent an important, environmentally clean energy source. This has motivated extensive research on the synthesis, characterization and evaluation of novel and stable oxygen reduction electrocatalysts for the direct four-electron transfer process to water formation. Studies have shown that amorphous alloyed compounds can be used as electrode materials in electrochemical energy conversion devices. Their use in PEMFCs can optimize the electrocatalyst loading in the membrane electrode assembly (MEA). In this study, amorphous metallic PtSn, PtRu and PtRuSn alloys were synthesized by mechanical milling and used as cathodes for the oxygen reduction reaction (ORR) in sulphuric acid and in a single PEM fuel cell. Two different powder morphologies were observed before and after the chemical activation in a hydrofluoric acid (HF) solution at 25 degrees C. The kinetics of the ORR on the amorphous catalysts were investigated. The study showed that the amorphous metallic PtSn electrocatalyst was the most active of the 3 electrodes for the cathodic reaction. Fuel cell experiments were conducted at various temperatures at 30 psi for hydrogen (H{sub 2}) and at 34 psi for oxygen (O{sub 2}). MEAs made of Nafion 115 and amorphous metallic PtSn dispersed on carbon powder in a PEMFC had a power density of 156 mW per cm{sup 2} at 0.43V and 80 degrees C. 12 refs., 1 tab., 5 figs.

  3. A Polycarboxyl-Decorated FeIII -Based Xerogel-Derived Multifunctional Composite (Fe3 O4 /Fe/C) as an Efficient Electrode Material towards Oxygen Reduction Reaction and Supercapacitor Application.

    Science.gov (United States)

    Devi, Bandhana; Venkateswarulu, Mangili; Kushwaha, Himmat Singh; Halder, Aditi; Koner, Rik Rani

    2018-05-02

    Low cost, non-noble metal catalysts with a good oxygen reduction reaction (ORR) activity comparable to that of platinum and also having good energy storage properties are highly desirable but challenging. Several challenges are associated with the development of such materials. Herein, we demonstrate a new polycarboxyl-functionalised Fe III -based gel material, synthesised following a solvothermal method and the development of its composite (Fe 3 O 4 /Fe/C) by annealing at optimised temperature. The developed composite displayed excellent electrocatalytic activity for the oxygen reduction reaction with an onset potential of 0.87 V (vs. RHE) and a current density value of -5 mA cm -2 , which are comparable with commercial 20 wt % Pt/C. In addition, as one of the most desirable properties, the composite exhibits a better methanol tolerance and greater durability than Pt/C. The same material was explored as an energy storage material for supercapacitors, which showed a specific capacitance of 245 F g -1 at a current density of 1 A g -1 . It is expected that this Fe 3 O 4 /Fe/C composite with a disordered graphitised carbon matrix will pave a horizon for developing energy conversion and energy storage devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Charge transfer induced activity of graphene for oxygen reduction

    International Nuclear Information System (INIS)

    Shen, Anli; Xia, Weijun; Dou, Shuo; Wang, Shuangyin; Zhang, Lipeng; Xia, Zhenhai

    2016-01-01

    Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR. (paper)

  5. Determination of rate constants for the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Racz, A.; Walter, T.; Stimming, U. [Munich Technical Univ., Garching (Germany). Dept. of Physics

    2008-07-01

    The oxygen reduction reaction (ORR) in fuel cells is a complex and fundamental electrochemical reaction. However, greater insight is needed into this multi-electron reaction in order to develop efficient and innovative catalysts. The rotating ring disc electrode (RRDE) is a useful tool for studying reaction intermediates of the ORR and to better understand the reaction pathway. Carbon materials such as carbon nanofilaments-platelets (CNF-PL) have high electrical conductivity and may be considered for fuel cells. In particular Pt and RuSe{sub x}, deposited on CNF-PL materials could act as efficient catalysts in fuel cells. This study used the RRDE to evaluate the oxygen reduction kinetics of these catalysts in oxygen-saturated, diluted sulphuric acid at room temperature. Kinetic data and hydrogen peroxide formation were determined by depositing a thin-film of the catalyst on the Au disc. The values for the constants k1, k2 and k3 were obtained using diagnostic criteria and expressions to calculate the rate constants of the cathodic oxygen reduction reaction for RuSe on new carbon supports. A potential dependency of the constants k1 and k2 for RuSe{sub x}/CNF-PL was observed. The transition of the Tafel slopes for this catalyst was obtained. 4 refs., 1 fig.

  6. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    Science.gov (United States)

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-02-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  7. 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.

  8. Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

    Science.gov (United States)

    Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

    2014-11-21

    Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

  9. Enhanced Oxygen Reduction Reaction by In Situ Anchoring Fe2N Nanoparticles on Nitrogen-Doped Pomelo Peel-Derived Carbon

    Directory of Open Access Journals (Sweden)

    Yiqing Wang

    2017-11-01

    Full Text Available The development of effective oxygen electrode catalysts for renewable energy technologies such as metal-air batteries and fuel cells remains challenging. Here, we prepared a novel high-performance oxygen reduction reaction (ORR catalyst comprised of Fe2N nanoparticles (NPs in situ decorated over an N-doped porous carbon derived from pomelo peel (i.e., Fe2N/N-PPC. The decorated Fe2N NPs provided large quantities of Fe-N-C bonding catalytic sites. The as-obtained Fe2N/N-PPC showed superior onset and half-wave potentials (0.966 and 0.891 V, respectively in alkaline media (0.1 M KOH compared to commercial Pt/C through a direct four-electron reaction pathway. Fe2N/N-PPC also showed better stability and methanol tolerance than commercial Pt/C. The outstanding ORR performance of Fe2N/N-PPC was attributed to its high specific surface area and the synergistic effects of Fe2N NPs. The utilization of agricultural wastes as a precursor makes Fe2N/N-PPC an ideal non-precious metal catalyst for ORR applications.

  10. N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

    Science.gov (United States)

    Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

    2017-08-01

    It is still a great challenge in preparing non-precious metal catalysts with high activity and long-term stability to substitute for precious metal catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we report a novel and facile catalyst-N, S co-doped carbon spheres with highly dispersed CoO (CoO@NS-CSs), where biomass glucose spheres act as carbon precursor and H2S, NH3 derived from the decomposition of thiourea not only provide N, S sources but also can etch carbon spheres to produce nanoporous structure. CoO@NS-CSs catalyst exhibits excellent ORR activity with a high onset potential of 0.946 V vs. RHE (reversible hydrogen electrode) and a half-wave potential of 0.821 V vs. RHE through a four-electron pathway in alkaline solution, which is comparable to commercial Pt/C catalyst (onset potential: 0.926 V vs. RHE, half-wave potential: 0.827 V vs. RHE). Furthermore, both the long-term stability and methanol-tolerance of CoO@NS-CSs catalyst are superior to those of commercial Pt/C catalyst. The excellent ORR performance of CoO@NS-CSs catalyst can be attributed to its micro-mesopore structure, high specific surface area (667 m2 g-1), and highly dispersed CoO. This work manifests that the obtained CoO@NS-CSs catalyst is promising to be applied to fuel cells.

  11. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed; Merzougui, Belabbes A.; Akinpelu, Akeem; Laoui, Tahar; Hedhili, Mohamed N.; Swain, Greg M.; Shao, Minhua

    2014-01-01

    Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

  12. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed

    2014-11-01

    Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts\\' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

  13. Facile preparation of efficient electrocatalysts for oxygen reduction reaction: One-dimensional meso/macroporous cobalt and nitrogen Co-doped carbon nanofibers

    Science.gov (United States)

    Yoon, Ki Ro; Choi, Jinho; Cho, Su-Ho; Jung, Ji-Won; Kim, Chanhoon; Cheong, Jun Young; Kim, Il-Doo

    2018-03-01

    Efficient electrocatalyst for oxygen reduction reaction (ORR) is an essential component for stable operation of various sustainable energy conversion and storage systems such as fuel cells and metal-air batteries. Herein, we report a facile preparation of meso/macroporous Co and N co-doped carbon nanofibers (Co-Nx@CNFs) as a high performance and cost-effective electrocatalyst toward ORR. Co-Nx@CNFs are simply obtained from electrospinning of Co precursor and bicomponent polymers (PVP/PAN) followed by temperature controlled carbonization and further activation step. The prepared Co-Nx@CNF catalyst carbonized at 700 °C (Co-Nx@CNF700) shows outstanding ORR performance, i.e., a low onset potential (0.941 V) and half wave potential (0.814 V) with almost four-electron transfer pathways (n= 3.9). In addition, Co-Nx@CNF700 exhibits a superior methanol tolerance and higher stability (>70 h) in Zn-air battery in comparison with Pt/C catalyst (∼30 h). The outstanding performance of Co-Nx@CNF700 catalysts is attributed to i) enlarged surface area with bimodal porosity achieved by leaching of inactive species, ii) increase of exposed ORR active Co-Nx moieties and graphitic edge sites, and iii) enhanced electrical conductivity and corrosion resistance due to the existence of numerous graphitic flakes in carbon matrix.

  14. Recent advances in the kinetics of oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Adzic, R.

    1996-07-01

    Oxygen reduction is considered an important electrocatalytic reaction; the most notable need remains improvement of the catalytic activity of existing metal electrocatalysts and development of new ones. A review is given of new advances in the understanding of reaction kinetics and improvements of the electrocatalytic properties of some surfaces, with focus on recent studies of relationship of the surface properties to its activity and reaction kinetics. The urgent need is to improve catalytic activity of Pt and synthesize new, possibly non- noble metal catalysts. New experimental techniques for obtaining new level of information include various {ital in situ} spectroscopies and scanning probes, some involving synchrotron radiation. 138 refs, 18 figs, 2 tabs.

  15. Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

    International Nuclear Information System (INIS)

    Smirnov, Evgeny; Peljo, Pekka; Scanlon, Micheál D.; Girault, Hubert H.

    2016-01-01

    ABSTRACT: Functionalization of a soft or liquid-liquid interface by a one gold nanoparticle thick “nanofilm” provides a conductive pathway to facilitate interfacial electron transfer from a lipophilic electron donor to a hydrophilic electron acceptor in a process known as interfacial redox catalysis. The gold nanoparticles in the nanofilm are charged by Fermi level equilibration with the lipophilic electron donor and act as an interfacial reservoir of electrons. Additional thermodynamic driving force can be provided by electrochemically polarising the interface. Using these principles, the biphasic reduction of oxygen by a lipophilic electron donor, decamethylferrocene, dissolved in α,α,α-trifluorotoluene was catalysed at a gold nanoparticle nanofilm modified water-oil interface. A recently developed microinjection technique was utilised to modify the interface reproducibly with the mirror-like gold nanoparticle nanofilm, while the oxidised electron donor species and the reduction product, hydrogen peroxide, were detected by ion transfer voltammetry and UV/vis spectroscopy, respectively. Metallization of the soft interface allowed the biphasic oxygen reduction reaction to proceed via an alternative mechanism with enhanced kinetics and at a significantly lower overpotential in comparison to a bare soft interface. Weaker lipophilic reductants, such as ferrocene, were capable of charging the interfacial gold nanoparticle nanofilm but did not have sufficient thermodynamic driving force to significantly elicit biphasic oxygen reduction.

  16. Improved Charge Transfer in a Mn2O3@Co1.2Ni1.8O4 Hybrid for Highly Stable Alkaline Direct Methanol Fuel Cells with Good Methanol Tolerance.

    Science.gov (United States)

    Liu, Yan; Chen, Yuanzhen; Li, Sai; Shu, Chenyong; Fang, Yuan; Song, Bo

    2018-03-21

    A three-dimensional Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 hybrid was synthesized via facile two-step processes and employed as a cathode catalyst in direct methanol fuel cells (DMFCs) for the first time. Because of the unique architecture with ultrathin and porous nanosheets of the Co 1.2 Ni 1.8 O 4 shell, this composite exhibits better electrochemical performance than the pristine Mn 2 O 3 . Remarkably, it shows excellent methanol tolerance, even in a high concentration solution. The DMFC was assembled with Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 , polymer fiber membranes, and PtRu/C as the cathode, membrane, and anode, respectively. The power densities of 57.5 and 70.5 mW cm -2 were recorded at 18 and 28 °C, respectively, especially the former is the best result reported in the literature at such a low temperature. The stability of the Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 catalyzed cathode was evaluated, and the results show that this compound possesses excellent stability in a high methanol concentration. The improved electrochemical activity could be attributed to the narrow band gap of the hybrid, which accelerates the electrons jumping from the valence band to the conduction band. Therefore, Mn III could be oxidized into Mn IV more easily, simultaneously providing an electron to the absorbed oxygen.

  17. Highly effective and CO-tolerant PtRu electrocatalysts supported on poly(ethyleneimine) functionalized carbon nanotubes for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Cheng, Yi; Jiang, San Ping

    2013-01-01

    A highly efficient and CO tolerant PtRu electrocatalysts supported on amino-rich, cationic poly(ethyleneimine) polyelectrolyte functionalized multi-walled carbon nanotubes (PtRu/PEI-MWCNTs) has been developed. The catalysts were characterized by thermogravimetric analysis, Raman spectroscopy, cyclic voltammograms, CO stripping, chronoamperometry, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The PtRu particles with average size ∼2.5 nm are well dispersed on PEI-MWCNTs. The peak current for the methanol oxidation reaction on 40% PtRu/PEI-MWCNTs is 636mAmg Pt −1 , 5.7 times higher than 112mA mg Pt −1 measured on the 40% PtRu supported on acid treated MWCNTs (PtRu/AO-MWCNTs) under identical conditions. PtRu/PEI-MWCNTs catalysts exhibit a superior electrocatalytic activity and stability for the methanol oxidation reaction due to its high tolerance toward CO poisoning as compared with PtRu/AO-MWCNTs for direct methanol fuel cells

  18. Graphene-derived Fe/Co-N-C catalyst in direct methanol fuel cells: Effects of the methanol concentration and ionomer content on cell performance

    Science.gov (United States)

    Park, Jong Cheol; Choi, Chang Hyuck

    2017-08-01

    Non-precious metal catalysts (typically Fe(Co)-N-C catalysts) have been widely investigated for use as cost-effective cathode materials in low temperature fuel cells. Despite the high oxygen reduction activity and methanol-tolerance of graphene-based Fe(Co)-N-C catalysts in an acidic medium, their use in direct methanol fuel cells (DMFCs) has not yet been successfully implemented, and only a few studies have investigated this topic. Herein, we synthesized a nano-sized graphene-derived Fe/Co-N-C catalyst by physical ball-milling and a subsequent chemical modification of the graphene oxide. Twelve membrane-electrode-assemblies are fabricated with various cathode compositions to determine the effects of the methanol concentration, ionomer (i.e. Nafion) content, and catalyst loading on the DMFC performance. The results show that a graphene-based catalyst is capable of tolerating a highly-concentrated methanol feed up to 10.0 M. The optimized electrode composition has an ionomer content and catalyst loading of 66.7 wt% and 5.0 mg cm-2, respectively. The highest maximum power density is ca. 32 mW cm-2 with a relatively low PtRu content (2 mgPtRu cm-2). This study overcomes the drawbacks of conventional graphene-based electrodes using a nano-sized graphene-based catalyst and further shows the feasibility of their potential applications in DMFC systems.

  19. Establishment and application of a modified membrane-blot assay for Rhizomucor miehei lipases aimed at improving their methanol tolerance and thermostability.

    Science.gov (United States)

    He, Dong; Luo, Wen; Wang, Zhiyuan; Lv, Pengmei; Yuan, Zhenhong; Huang, Shaowei; Xv, Jingliang

    2017-07-01

    Directed evolution has been proved an effective way to improve the stability of proteins, but high throughput screening assays for directed evolution with simultaneous improvement of two or more properties are still rare. In this study, we aimed to establish a membrane-blot assay for use in the high-throughput screening of Rhizomucor miehei lipases (RMLs). With the assistance of the membrane-blot screening assay, a mutant E47K named G10 that showed improved thermal stability was detected in the first round of error-prone PCR. Using G10 as the parent, two variants G10-11 and G10-20 that showed improved thermal stability and methanol tolerance without loss of activity compared to the wild type RML were obtained. The T 50 60 -value of G10-11 and G10-20 increased by 12°C and 6.5°C, respectively. After incubation for 1h, the remaining residual activity of G10-11 and G10-20 was 63.45% and 74.33%, respectively, in 50% methanol, and 15.98% and 30.22%, respectively, in 80% methanol. Thus, we successfully developed a membrane-blot assay that could be used for the high-throughput screening of RMLs with improved thermostability and methanol tolerance. Based on our findings, we believe that our newly developed membrane-blot assay will have potential applications in directed evolution in the future. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Gopalan, Srikanth [Boston Univ., MA (United States)

    2013-03-31

    In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

  1. Fe/N/C hollow nanospheres by Fe(iii)-dopamine complexation-assisted one-pot doping as nonprecious-metal electrocatalysts for oxygen reduction

    Science.gov (United States)

    Zhou, Dan; Yang, Liping; Yu, Linghui; Kong, Junhua; Yao, Xiayin; Liu, Wanshuang; Xu, Zhichuan; Lu, Xuehong

    2015-01-01

    In this work, a series of hollow carbon nanospheres simultaneously doped with N and Fe-containing species are prepared by Fe3+-mediated polymerization of dopamine on SiO2 nanospheres, carbonization and subsequent KOH etching of the SiO2 template. The electrochemical properties of the hollow nanospheres as nonprecious-metal electrocatalysts for oxygen reduction reaction (ORR) are characterized. The results show that the hollow nanospheres with mesoporous N-doped carbon shells of ~10 nm thickness and well-dispersed Fe3O4 nanoparticles prepared by annealing at 750 °C (Fe/N/C HNSs-750) exhibit remarkable ORR catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst, and high selectivity towards 4-electron reduction of O2 to H2O. Moreover, it displays better electrochemical durability and tolerance to methanol crossover effect in an alkaline medium than the Pt/C. The excellent catalytic performance of Fe/N/C HNSs-750 towards ORR can be ascribed to their high specific surface area, mesoporous morphology, homogeneous distribution of abundant active sites, high pyridinic nitrogen content, graphitic nitrogen and graphitic carbon, as well as the synergistic effect of nitrogen and iron species for catalyzing ORR.In this work, a series of hollow carbon nanospheres simultaneously doped with N and Fe-containing species are prepared by Fe3+-mediated polymerization of dopamine on SiO2 nanospheres, carbonization and subsequent KOH etching of the SiO2 template. The electrochemical properties of the hollow nanospheres as nonprecious-metal electrocatalysts for oxygen reduction reaction (ORR) are characterized. The results show that the hollow nanospheres with mesoporous N-doped carbon shells of ~10 nm thickness and well-dispersed Fe3O4 nanoparticles prepared by annealing at 750 °C (Fe/N/C HNSs-750) exhibit remarkable ORR catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst, and high selectivity towards 4-electron reduction of O2 to H2O

  2. Oxygen reduction kinetics on mixed conducting SOFC model cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Baumann, F.S.

    2006-07-01

    The kinetics of the oxygen reduction reaction at the surface of mixed conducting solid oxide fuel cell (SOFC) cathodes is one of the main limiting factors to the performance of these promising systems. For ''realistic'' porous electrodes, however, it is usually very difficult to separate the influence of different resistive processes. Therefore, a suitable, geometrically well-defined model system was used in this work to enable an unambiguous distinction of individual electrochemical processes by means of impedance spectroscopy. The electrochemical measurements were performed on dense thin film microelectrodes, prepared by PLD and photolithography, of mixed conducting perovskite-type materials. The first part of the thesis consists of an extensive impedance spectroscopic investigation of La0.6Sr0.4Co0.8Fe0.2O3 (LSCF) microelectrodes. An equivalent circuit was identified that describes the electrochemical properties of the model electrodes appropriately and enables an unambiguous interpretation of the measured impedance spectra. Hence, the dependencies of individual electrochemical processes such as the surface exchange reaction on a wide range of experimental parameters including temperature, dc bias and oxygen partial pressure could be studied. As a result, a comprehensive set of experimental data has been obtained, which was previously not available for a mixed conducting model system. In the course of the experiments on the dc bias dependence of the electrochemical processes a new and surprising effect was discovered: It could be shown that a short but strong dc polarisation of a LSCF microelectrode at high temperature improves its electrochemical performance with respect to the oxygen reduction reaction drastically. The electrochemical resistance associated with the oxygen surface exchange reaction, initially the dominant contribution to the total electrode resistance, can be reduced by two orders of magnitude. This &apos

  3. Hierarchical hybrid of Ni{sub 3}N/N-doped reduced graphene oxide nanocomposite as a noble metal free catalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Li, Yingjun; Li, Yetong [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Huang, Keke [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Zhang, Jun, E-mail: cejzhang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2017-04-01

    Highlights: • Hybrid of Ni{sub 3}N/N-RGO catalysts are synthesized by using a two-step method. • The catalysts manifest superior catalytic activity towards the ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: Novel nickel nitride (Ni{sub 3}N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni{sub 3}N/N-RGO nanocomposites are obtained. The Ni{sub 3}N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni{sub 3}N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni{sub 3}N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni{sub 3}N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni{sub 3}N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.

  4. Spherical α-MnO2 Supported on N-KB as Efficient Electrocatalyst for Oxygen Reduction in Al–Air Battery

    Directory of Open Access Journals (Sweden)

    Kui Chen

    2018-04-01

    Full Text Available Traditional noble metal platinum (Pt is regarded as a bifunctional oxygen catalyst due to its highly catalytic efficiency, but its commercial availability and application is often restricted by high cost. Herein, a cheap and effective catalyst mixed with α-MnO2 and nitrogen-doped Ketjenblack (N-KB (denoted as MnO2-SM150-0.5 is examined as a potential electrocatalyst in oxygen reduction reactions (ORR and oxygen evolution reactions (OER. This α-MnO2 is prepared by redox reaction between K2S2O8 and MnSO4 in acid conditions with a facile hydrothermal process (named the SM method. As a result, MnO2-SM150-0.5 exhibits a good catalytic performance for ORR in alkaline solution, and this result is comparable to a Pt/C catalyst. Moreover, this catalyst also shows superior durability and methanol tolerance compared with a Pt/C catalyst. It also displays a discharge voltage (~1.28 V at a discharge density of 50 mA cm−2 in homemade Al–air batteries that is higher than commercial 20% Pt/C (~1.19 V. The superior electrocatalytic performance of MnO2-SM150-0.5 could be attributed to its higher Mn3+/Mn4+ ratio and the synergistic effect between MnO2 and the nitrogen-doped KB. This study provides a novel strategy for the preparation of an MnO2-based composite electrocatalyst.

  5. Synergistic increase of oxygen reduction favourable Fe-N coordination structures in a ternary hybrid of carbon nanospheres/carbon nanotubes/graphene sheets.

    Science.gov (United States)

    Zhang, Shiming; Liu, Bin; Chen, Shengli

    2013-11-14

    A Fe/N co-doped ternary nanocarbon hybrid, with uniform bamboo-like carbon nanotubes (CNTs) in situ grown on/between the single/few-layer graphene sheets interspaced by carbon nanosphere aggregates, was prepared through a one-pot heat treatment of a precursor mixture containing graphene oxide, Vulcan XC-72 carbon nanospheres, nitrogen rich melamine and small amounts of Fe ions. Physical characterization including electron microscopic images, N2 adsorption-desorption isotherms, pore size distribution, XPS, XRD, Mössbauer spectra, and EDX revealed that the 0-D/1-D/2-D ternary hybrid architecture not only offered an optimized morphology for high dispersion of each nanocarbon moiety, while the carbon nanosphere interspaced graphene sheets have provided a platform for efficient reaction between Fe ions and melamine molecules, resulting in uniform nucleation and growth of CNTs and formation of high density Fe-N coordination assemblies that have been believed to be the active centers for the oxygen reduction reaction (ORR) in carbon-based nonprecious metal electrocatalysts. In the absence of graphene oxides or carbon nanospheres, a similar heat treatment was found to result in large amounts of elemental Fe and Fe carbides and entangled CNTs with wide diameter distributions. As a result, the ternary Fe/N-doped nanocarbon hybrid exhibits ORR activity much higher than the Fe-N doped single or binary nanocarbon materials prepared under similar heat treatment conditions, and approaching that of the state-of-the-art carbon-supported platinum catalyst (Pt/C) in acidic media, as well as superior stability and methanol tolerance to Pt/C.

  6. Nitrogen-Doped Carbon Nanoparticles for Oxygen Reduction Prepared via a Crushing Method Involving a High Shear Mixer

    Directory of Open Access Journals (Sweden)

    Lei Shi

    2017-09-01

    Full Text Available The disposal of agricultural wastes such as fresh banana peels (BPs is an environmental issue. In this work, fresh BPs were successfully transformed into nitrogen-doped carbon nanoparticles (N-CNPs by using a high shear mixer facilitated crushing method (HSM-FCM followed by carbonization under Ar atmosphere. Ammonia-activated N-CNPs (N-CNPs-NH3 were prepared via subsequent ammonia activation treatments at a high temperature. The as-prepared N-CNPs and N-CNPs-NH3 materials both exhibited high surface areas (above 700 m2/g and mean particle size of 50 nm. N-CNPs-NH3 showed a relatively higher content of pyridinic and graphitic N compared to N-CNPs. In alkaline media, N-CNPs-NH3 showed superior performances as an oxygen reduction reaction (ORR catalyst (E0 = −0.033 V, J = 2.4 mA/cm2 compared to N-CNPs (E0 = 0.07 V, J = 1.8 mA/cm2. In addition, N-CNPs-NH3 showed greater oxygen reduction stability and superior methanol crossover avoidance than a conventional Pt/C catalyst. This study provides a novel, simple, and scalable approach to valorize biomass wastes by synthesizing highly efficient electrochemical ORR catalysts.

  7. The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum

    DEFF Research Database (Denmark)

    Verdaguer Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E.L.

    2012-01-01

    The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction...

  8. Investigation of a Pt-Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Castro Luna, A. M.; Bonesi, A.; Triaca, W. E.; Blasi, A. Di; Stassi, A.; Baglio, V.; Antonucci, V.; Arico, A. S.

    2010-01-01

    Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt-Fe/C), with a particle size of about 2-3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt-Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm 2 DEFC single cells at 60 and 80 o C. An improvement in single cell performance was observed in the presence of the Pt-Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm -2 at 2 bar rel. cathode pressure and 80 o C.

  9. Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

    Science.gov (United States)

    Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

    2018-01-01

    Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

  10. Two-Dimensional N,S-Codoped Carbon/Co 9 S 8 Catalysts Derived from Co(OH) 2 Nanosheets for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang [School of Mechanical; Zhu, Chengzhou [School of Mechanical; Song, Junhua [School of Mechanical; Feng, Shuo [School of Mechanical; Du, Dan [School of Mechanical; Key Laboratory of Pesticide and Chemical; Engelhard, Mark H. [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Xiao, Dongdong [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Li, Dongsheng [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Lin, Yuehe [School of Mechanical

    2017-10-12

    Investigation of highly active and cost-efficient electrocatalysts for oxygen reduction reaction is of great importance in a wide range of clean energy devices, including fuel cells and metal-air batteries. Herein, the simultaneous formation of Co9S8 and N,S-codoped carbon was achieved in a dual templates system. First, Co(OH)2 nanosheets and tetraethyl orthosilicate were utilized to direct the formation of two-dimensional carbon precursors, which were then dispersed into thiourea solution. After subsequent pyrolysis and templates removal, N/S-codoped porous carbon sheets confined Co9S8 catalysts (Co9S8/NSC) were obtained. Owing to the morphological and compositional advantages as well as the synergistic effects, the resultant Co9S8/NSC catalysts with modified doping level and pyrolysis degree exhibit superior ORR catalytic activity and long-term stability compared with the state-of-the-art Pt/C catalyst in alkaline media. Remarkably, the as-prepared carbon composites also reveal exceptional tolerance of methanol, indicating their potential applications in fuel cells.

  11. Preparation of Ag4Bi2O5/MnO2 Corn/Cob Like Nano Material as a Superior Catalyst for Oxygen Reduction Reaction in Alkaline Solution

    Directory of Open Access Journals (Sweden)

    Xun Zeng

    2017-12-01

    Full Text Available Ag4Bi2O5/MnO2 nano-sized material was synthesized by a co-precipitation method in concentrated KOH solution. The morphology characterization indicates that MnO2 nanoparticles with a size of 20 nm are precipitated on the surface of nano Ag4Bi2O5, forming a structure like corn on the cob. The obtained material with 60% Mn offers slightly higher initial potential (0.098 V vs. Hg/HgO and limiting current density (−5.67 mA cm−2 at a rotating speed of 1600 rpm compared to commercial Pt/C (−0.047 V and −5.35 mA cm−2, respectively. Furthermore, the obtained material exhibits superior long-term durability and stronger methanol tolerance than commercial Pt/C. The remarkable features suggest that the Ag4Bi2O5/MnO2 nano-material is a very promising oxygen reduction reaction catalyst.

  12. Transforming waste biomass with an intrinsically porous network structure into porous nitrogen-doped graphene for highly efficient oxygen reduction.

    Science.gov (United States)

    Zhou, Huang; Zhang, Jian; Amiinu, Ibrahim Saana; Zhang, Chenyu; Liu, Xiaobo; Tu, Wenmao; Pan, Mu; Mu, Shichun

    2016-04-21

    Porous nitrogen-doped graphene with a very high surface area (1152 m(2) g(-1)) is synthesized by a novel strategy using intrinsically porous biomass (soybean shells) as a carbon and nitrogen source via calcination and KOH activation. To redouble the oxygen reduction reaction (ORR) activity by tuning the doped-nitrogen content and type, ammonia (NH3) is injected during thermal treatment. Interestingly, this biomass-derived graphene catalyst exhibits the unique properties of mesoporosity and high pyridine-nitrogen content, which contribute to the excellent oxygen reduction performance. As a result, the onset and half-wave potentials of the new metal-free non-platinum catalyst reach -0.009 V and -0.202 V (vs. SCE), respectively, which is very close to the catalytic activity of the commercial Pt/C catalyst in alkaline media. Moreover, our catalyst has a higher ORR stability and stronger CO and CH3OH tolerance than Pt/C in alkaline media. Importantly, in acidic media, the catalyst also exhibits good ORR performance and higher ORR stability compared to Pt/C.

  13. Significant advantages of sulfur-doped graphene in neutral media as electrocatalyst for oxygen reduction comparing with Pt/C

    Science.gov (United States)

    Shi, Xinxin; Zhang, Jiaona; Huang, Tinglin

    2018-02-01

    Sulfur-doped graphene (SDG) has been found to be an efficient electrocatalyst for oxygen reduction reaction. However, previous studies on the catalytic activity of SDG have been mainly confined to O2-saturated alkaline media which is a typical alkaline fuel cell environment. Air-cathode microbial fuel cells (ACMFCs), as a novel energy conversion and wastewater treatment technology, use the oxygen from air as cathodic reactant in neutral media with low concentration of O2. Thus, it is meaningful to explore the catalytic performance of SDG in such ACMFC environment. The result showed that in ACMFC environment, the peak current density of SDG in CV test was surprisingly 4.5 times higher than that of Pt/C, indicating a much stronger catalytic activity of SDG. Moreover, SDG exhibited a stronger tolerance against the crossover of glucose (a typical anodic fuel in ACMFC) and better stability than Pt/C in neutral media.

  14. Tolerance

    DEFF Research Database (Denmark)

    Tønder, Lars

    is linked to a different set of circumstances than the ones suggested by existing models in contemporary democratic theory. Reorienting the discussion of tolerance, the book raises the question of how to disclose new possibilities within our given context of affect and perception. Once we move away from......Tolerance: A Sensorial Orientation to Politics is an experiment in re-orientation. The book is based on the wager that tolerance exceeds the more prevalent images of self-restraint and repressive benevolence because neither precludes the possibility of a more “active tolerance” motivated...... by the desire to experiment and to become otherwise. The objective is to discuss what gets lost, conceptually as well as politically, when we neglect the subsistence of active tolerance within other practices of tolerance, and to develop a theory of active tolerance in which tolerance's mobilizing character...

  15. Hydrothermal synthesis of highly crystalline RuS2 nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

    International Nuclear Information System (INIS)

    Li, Yanjuan; Li, Nan; Yanagisawa, Kazumichi; Li, Xiaotian; Yan, Xiao

    2015-01-01

    Highlights: • Highly crystalline RuS 2 nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS 2 with average particle size of 14.8 nm. • RuS 2 nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl − . - Abstract: Highly crystalline ruthenium sulfide (RuS 2 ) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS 2 and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S 2 2− . Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS 2 nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS 2 is active towards oxygen reduction reaction. Although the activity of RuS 2 is lower than that of Pt/C, the RuS 2 catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl −

  16. Tolerance

    DEFF Research Database (Denmark)

    Tønder, Lars

    Tolerance: A Sensorial Orientation to Politics is an experiment in re-orientation. The book is based on the wager that tolerance exceeds the more prevalent images of self-restraint and repressive benevolence because neither precludes the possibility of a more “active tolerance” motivated by the d...... these alternatives by returning to the notion of tolerance as the endurance of pain, linking this notion to exemplars and theories relevant to the politics of multiculturalism, religious freedom, and free speech....

  17. Importance of the support and the grade of Pt in the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Enriquez M, O.; Fernandez V, S.M.

    2004-01-01

    The technology of the fuel cells type Proton Exchange Membrane (PEM), needs to define clearly the influence of the different involved parameters, this is made in general using methods of electrochemical impedance, in which the involved reactions can be presupposed. Another form of making is identifying experimentally the influence of the different parameters. In this work the obtained results are reported with for the oxygen reduction reaction using as electro catalyst platinum analytical grade and fuel cell grade and like support graphite and vulcan. It was found that as much the support as the particle size modify the over potential for the oxygen reduction reaction (Orr). (Author)

  18. 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)

  19. A new method to synthesize sulfur-doped graphene as effective metal-free electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhai, Chunyang; Sun, Mingjuan [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Zhu, Mingshan, E-mail: mingshanzhu@yahoo.com [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Song, Shaoqing [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China); Jiang, Shujuan, E-mail: sjjiang@ecit.edu.cn [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China)

    2017-06-15

    Highlights: • S doped graphene was facile synthesized by one-pot solvothermal method. • DMSO acted as S source as well as reaction solvent. • S-RGO worked as an efficient metal-free electrocatalyst for ORR. • S-RGO acted as a promising candidate instead of Pt-based catalyst. - Abstract: The exploration of a metal-free catalyst with highly efficient yet low-cost for the oxygen-reduction reaction (ORR) is under wide spread investigation. In this paper, by using dimethyl sulfoxide (DMSO) as S source as well as solvent, we report a new, low-cost, and facile solvothermal route to synthesize S-doped reduced graphene oxide (S-RGO). The existence of S element in the framework of RGO was solidly confirmed by energy-dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). The as-synthesized S-RGO can be worked as an efficient metal-free electrocatalyst for ORR. Moreover, compared to commercial Pt/C electrocatalyst, the S-RGO displays superior resistance to crossover effect and stability by evaluating the addition of methanol and CO poisoning experiment. This result not only shows S-RGO as a promising candidate instead of Pt-based catalyst for ORR, but also provides a new approach for the preparation of metal-free electrocatalyst in future.

  20. MIL-100-Fe derived N-doped Fe/Fe3C@C electrocatalysts for efficient oxygen reduction reaction

    Science.gov (United States)

    Guo, Dakai; Han, Sancan; Wang, Jiacheng; Zhu, Yufang

    2018-03-01

    N-doped porous Fe/Fe3C@C electrocatalysts were prepared by the pyrolysis of the hexamethylenetetramine (HMT)-incorporated MIL-100-Fe at different temperatures (700-1000 °C) under N2 atmosphere. Rotary evaporation of MIL-100-Fe and HMT solution could make more N-enriched HMT molecules enter into the pores of MIL-100-Fe, thus improving nitrogen contents of the final pyrolyzed samples. All pyrolyzed samples show porous textures with middle specific surface areas. The X-ray photoelectron spectroscopy (XPS) results demonstrate the successful introduction of N atoms into carbon framework. Sample Fe-N2-800 prepared by annealing the precursors with the HMT/MIL-100-Fe weight ratio of 2 at 800 °C exhibits the best electrocatalytic activity towards the oxygen reduction reaction (ORR) in terms of onset potential and current density because of high graphitic N and pyridinic N content. The enwrapped Fe/Fe3C nanoparticles and Fe-Nx active sites in these samples could also boost the ORR activity synergistically. Moreover, sample Fe-N2-800 demonstrates a dominant four electron reduction process, as well as excellent long-term operation stability and methanol crossover resistance. Thus, the N-doped Fe/Fe3C@C composites derived from the HMT-incorporated MIL-100-Fe are promising electrocatalysts to replace Pt/C for ORR in practical applications.

  1. Targeted design of α-MnO2 based catalysts for oxygen reduction

    Czech Academy of Sciences Publication Activity Database

    Lehtimäki, M.; Hoffmannová, Hana; Boytsová, O.; Bastl, Zdeněk; Bush, M.; Halck, N. B.; Rossmeisl, J.; Krtil, Petr

    2016-01-01

    Roč. 191, FEB 2016 (2016), s. 452-461 ISSN 0013-4686 EU Projects: European Commission(XE) 214936 - ELCAT Institutional support: RVO:61388955 Keywords : electrocatalysis * oxygen reduction * MnO2 Subject RIV: CG - Electrochemistry Impact factor: 4.798, year: 2016

  2. Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

    2014-01-01

    Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low‐temperature fuel cells. A novel type of catalysts prepared by high‐pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting...

  3. Oxygen Reduction Reaction on Pt Overlayers Deposited onto a Gold Film: Ligand, Strain, and Ensemble Effect

    DEFF Research Database (Denmark)

    Deng, Yu-Jia; Tripkovic, Vladimir; Rossmeisl, Jan

    2016-01-01

    We study the oxygen reduction reaction (ORR), the catalytic process occurring at the cathode in fuel cells, on Pt layers prepared by electrodeposition onto an Au substrate. Using a nominal Pt layer by layer deposition method previously proposed, imperfect layers of Pt on Au are obtained. The ORR...

  4. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

    2010-01-01

    We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

  5. Thermodynamic driving force effects in the oxygen reduction catalyzed by a metal-free porphyrin

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Samec, Zdeněk

    2012-01-01

    Roč. 82, SI (2012), s. 457-462 ISSN 0013-4686 R&D Projects: GA ČR GAP208/11/0697 Institutional research plan: CEZ:AV0Z40400503 Keywords : oxygen reduction * metal-free porphyrin * electrocatalysis Subject RIV: CG - Electrochemistry Impact factor: 3.777, year: 2012

  6. Targeted design of α-MnO2 based catalysts for oxygen reduction

    DEFF Research Database (Denmark)

    Lehtimaeki, Matti; Hoffmannova, Hana; Boytsova, Olga

    2016-01-01

    The paper focuses on theoretical and experimental aspects of an oxide surface optimization for oxygen reduction reaction (ORR). Various doped α-MnO2 based electrocatalysts were prepared by microwave-assisted hydrothermal synthesis and electrochemically characterized to validate density functional...

  7. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions

    DEFF Research Database (Denmark)

    Vallejo, Federico Calle; Martinez, Jose Ignacio; Rossmeisl, Jan

    2011-01-01

    Low-temperature fuel cells are appealing alternatives to the conventional internal combustion engines for transportation applications. However, in order for them to be commercially viable, effective, stable and low-cost electrocatalysts are needed for the Oxygen Reduction Reaction (ORR) at the ca...

  8. Oxygen reduction by decamethylferrocene at liquid/liquid interfaces catalyzed by dodecylaniline

    Czech Academy of Sciences Publication Activity Database

    Su, B.; Hatay, I.; Li, F.; Partovi-Nia, R.; Samec, Zdeněk; Ersöz, M.; Girault, H. H.

    2010-01-01

    Roč. 639, 1-2 (2010), s. 102-108 ISSN 1572-6657 R&D Projects: GA ČR(CZ) GA203/07/1257; GA MŠk OC 177 Institutional research plan: CEZ:AV0Z40400503 Keywords : oxygen reduction * proton reduction * voltammetry Subject RIV: CG - Electrochemistry Impact factor: 2.732, year: 2010

  9. Efficient oxygen reduction reaction using ruthenium tetrakis(diaquaplatinum)octacarboxyphthalocyanine catalyst supported on MWCNT platform

    CSIR Research Space (South Africa)

    Maxakato, NW

    2011-02-01

    Full Text Available -1 Electroanalysis 2011, 23, No. 2, 325 ? 329 Efficient Oxygen Reduction Reaction Using Ruthenium Tetrakis(diaquaplatinum)Octacarboxyphthalocyanine Catalyst Supported on MWCNT Platform Nobanathi W. Maxakato,a Solomon A. Mamuru,a Kenneth I. Ozoemena*a, b a...

  10. Ruthenium supported on nitrogen-doped carbon nanotubes for the oxygen reduction reaction in alkaline

    CSIR Research Space (South Africa)

    Mabena, LF

    2012-10-01

    Full Text Available between 0 and 10 wt.%. The activity of the prepared nanocatalysts toward the oxygen reduction reaction (ORR) was characterized using the rotating disk electrode and voltammetry techniques. The ORR activity was higher at lower concentrations of Ru on N...

  11. Fuel cell electrocatalsis : oxygen reduction on Pt-based nanoparticle catalysts

    NARCIS (Netherlands)

    Vliet, Dennis Franciscus van der

    2010-01-01

    The thesis contains a discussion on the subject of the Oxygen Reduction Reaction (ORR) on Pt-alloy nanoparticle catalysts in the Rotating Disk Electrode (RDE) method. An insight in some of the difficulties of this method is given with proper solutions and compensations for these problems. Pt3Co,

  12. Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction

    NARCIS (Netherlands)

    Hartnig, C.B.; Koper, M.T.M.

    2002-01-01

    We present a molecular dynamics simulation of solvent reorganization in the first electron transfer step in the oxygen reduction reaction, i.e. O2+e-¿O2-, modeled as taking place in the outer Helmholtz plane. The first electron transfer step is usually considered the rate-determining step from many

  13. Beyond the top of the volcano? A unified approach to electrocatalytic oxygen reduction and oxygen evolution

    Czech Academy of Sciences Publication Activity Database

    Busch, M.; Halck, N. B.; Kramm, U. I.; Siehrostami, S.; Krtil, Petr; Rossmeisl, J.

    2016-01-01

    Roč. 29, NOV 2016 (2016), s. 126-135 ISSN 2211-2855 Institutional support: RVO:61388955 Keywords : hydrogen evolution * catalytic-activity * Electrocatalysis * Oxygen reduction * Oxygen evolution * Volcano * Density functional theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.343, year: 2016

  14. Oxygen reduction on carbon supported platinum catalysts in high temperature polymer electrolytes

    DEFF Research Database (Denmark)

    Qingfeng, Li; Bergqvist, R. S.; Hjuler, H. A.

    1999-01-01

    Oxygen reduction on carbon supported platinum catalysts has been investigated in H3PO4, H3PO4-doped Nafion and PBI polymer electrolytes in a temperature range from 80 to 190°C. Compared with pure H3PO4, using the H3PO4 doped Nafion and PBI polymer electrolytes can significantly improve the oxygen...

  15. Slat templated formation of efficient oxygen reduction electrocatalyst with a fluidic precursor

    Science.gov (United States)

    Tan, Yao

    2018-05-01

    Development of cost-effective and efficient oxygen reduction catalyst is critical for the commercialization of proton exchange membrane fuel cell. Metal and nitrogen co-doped carbon is recognized as a promising alternative to traditional platinum-based oxygen reduction catalyst. Herein, we report a novel metal and nitrogen co-doped carbon catalyst with an ionic liquid precursor. Salt template, which can be easily removed with mild treatment after the synthesis, is used to generate abundant mesopores in the resulting catalyst. We show that the novel catalyst shows a superior activity comparable to commercial Pt/C catalyst. Furthermore, the important role of the mesopore for the activity of the catalyst is demonstrated.

  16. Understanding the Oxygen Reduction Reaction on a Y/Pt(111) Single Crystal

    DEFF Research Database (Denmark)

    Ulrikkeholm, Elisabeth Therese; Johansson, Tobias Peter; Malacrida, Paolo

    2014-01-01

    Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation of this tec......Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation...... using electrochemical measurements, low energy electron diffraction, ion scattering spectroscopy, angle resolved X-ray photoelectron spectroscopy, temperature programmed desorption of CO, and synchrotron based X-ray absorption spectroscopy and surface sensitive X-ray diffraction. These measurements were...

  17. Pt Catalyst Supported within TiO2 Mesoporous Films for Oxygen Reduction Reaction

    International Nuclear Information System (INIS)

    Huang, Dekang; Zhang, Bingyan; Bai, Jie; Zhang, Yibo; Wittstock, Gunther; Wang, Mingkui; Shen, Yan

    2014-01-01

    In this study, dispersed Pt nanoparticles into mesoporous TiO 2 thin films are fabricated by a facile electrochemical deposition method as electro-catalysts for oxygen reduction reaction. The mesoporous TiO 2 thin films coated on the fluorine-doped tin oxide glass by screen printing allow a facile transport of reactants and products. The structural properties of the resulted Pt/TiO 2 electrode are evaluated by field emission scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy. Cyclic voltammetry measurements are performed to study the electrochemical properties of the Pt/TiO 2 electrode. Further study demonstrates the stability of the Pt catalyst supported within TiO 2 mesoporous films for the oxygen reduction reaction

  18. 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 ...

  19. Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

    Energy Technology Data Exchange (ETDEWEB)

    Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy; Myers, Deborah J.; Karabacak, Tansel

    2017-08-24

    Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

  20. Structure and Stability of Pt-Y Alloy Particles for Oxygen Reduction Studied by Electron Microscopy

    DEFF Research Database (Denmark)

    Deiana, Davide; Wagner, Jakob Birkedal; Hansen, Thomas Willum

    2015-01-01

    Platinum-yttrium alloy nanoparticles show both a high activity and stability for the oxygen reduction reaction. The catalysts were prepared by magnetron sputter aggregation and mass filtration providing a model catalyst system with a narrow size distribution. The structure and stability of nanost...... the catalyst after reaction and after aging tests shows the development of a core-shell type structure after being exposed to reaction conditions....

  1. Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

    OpenAIRE

    Preuss, Kathrin; Kannuchamy, Vasanth Kumar; Marinovic, Adam; Isaacs, Mark; Wilson, Karen; Abrahams, Isaac; Titirici, Maria-Magdalena

    2016-01-01

    We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a po...

  2. Oxygen reduction on carbon supported platinum catalysts in high temperature polymer electrolytes

    DEFF Research Database (Denmark)

    Qingfeng, Li; Hjuler, Hans Aage; Bjerrum, Niels

    2000-01-01

    Oxygen reduction on carbon supported platinum catalysts has been investigated in H3PO4, H3PO4-doped Nafion and polybenzimidazole (PBI) polymer electrolytes in a temperature range up to 190 degrees C. Compared with pure H3PO4, the combination of H3PO4 and polymer electrolytes can significantly...... membrane fuel cell based on H3PO4-doped PBI for operation at temperatures between 150 and 200 degrees C. (C) 2000 Elsevier Science Ltd. All rights reserved....

  3. Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

    International Nuclear Information System (INIS)

    Tarasevich, M.R.; Chalykh, A.E.; Bogdanovskaya, V.A.; Kuznetsova, L.N.; Kapustina, N.A.; Efremov, B.N.; Ehrenburg, M.R.; Reznikova, L.A.

    2006-01-01

    Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O 2 molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed

  4. Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

    Science.gov (United States)

    Jiang, Rongzhong; Tran, Dat T; McClure, Joshua P; Chu, Deryn

    2015-08-26

    In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst.

  5. Noncovalently functionalized graphitic mesoporous carbon as a stable support of Pt nanoparticles for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Yuyan; Zhang, Sheng; Kou, Rong; Wang, Chongmin; Viswanathan, Vilayanur; Liu, Jun; Wang, Yong; Lin, Yuehe [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Wang, Xiqing; Dai, Sheng [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

    2010-04-02

    We report a durable electrocatalyst support, highly graphitized mesoporous carbon (GMPC), for oxygen reduction in polymer electrolyte membrane (PEM) fuel cells. GMPC is prepared through graphitizing the self-assembled soft-template mesoporous carbon (MPC) under high temperature. Heat-treatment at 2800 C greatly improves the degree of graphitization while most of the mesoporous structures and the specific surface area of MPC are retained. GMPC is then noncovalently functionalized with poly(diallyldimethylammonium chloride) (PDDA) and loaded with Pt nanoparticles by reducing Pt precursor (H{sub 2}PtCl{sub 6}) in ethylene glycol. Pt nanoparticles of {proportional_to}3.0 nm in diameter are uniformly dispersed on GMPC. Compared to Pt supported on Vulcan XC-72 carbon black (Pt/XC-72), Pt/GMPC exhibits a higher mass activity towards oxygen reduction reaction (ORR) and the mass activity retention (in percentage) is improved by a factor of {proportional_to}2 after 44 h accelerated degradation test under the potential step (1.4-0.85 V) electrochemical stressing condition which focuses on support corrosion. The enhanced activity and durability of Pt/GMPC are attributed to the graphitic structure of GMPC which is more resistant to corrosion. These findings demonstrate that GMPC is a promising oxygen reduction electrocatalyst support for PEM fuel cells. The approach reported in this work provides a facile, eco-friendly promising strategy for synthesizing stable metal nanoparticles on hydrophobic support materials. (author)

  6. Oxygen reduction kinetics on graphite cathodes in sediment microbial fuel cells.

    Science.gov (United States)

    Renslow, Ryan; Donovan, Conrad; Shim, Matthew; Babauta, Jerome; Nannapaneni, Srilekha; Schenk, James; Beyenal, Haluk

    2011-12-28

    Sediment microbial fuel cells (SMFCs) have been used as renewable power sources for sensors in fresh and ocean waters. Organic compounds at the anode drive anodic reactions, while oxygen drives cathodic reactions. An understanding of oxygen reduction kinetics and the factors that determine graphite cathode performance is needed to predict cathodic current and potential losses, and eventually to estimate the power production of SMFCs. Our goals were to (1) experimentally quantify the dependence of oxygen reduction kinetics on temperature, electrode potential, and dissolved oxygen concentration for the graphite cathodes of SMFCs and (2) develop a mechanistic model. To accomplish this, we monitored current on polarized cathodes in river and ocean SMFCs. We found that (1) after oxygen reduction is initiated, the current density is linearly dependent on polarization potential for both SMFC types; (2) current density magnitude increases linearly with temperature in river SMFCs but remains constant with temperature in ocean SMFCs; (3) the standard heterogeneous rate constant controls the current density temperature dependence; (4) river and ocean SMFC graphite cathodes have large potential losses, estimated by the model to be 470 mV and 614 mV, respectively; and (5) the electrochemical potential available at the cathode is the primary factor controlling reduction kinetic rates. The mechanistic model based on thermodynamic and electrochemical principles successfully fit and predicted the data. The data, experimental system, and model can be used in future studies to guide SMFC design and deployment, assess SMFC current production, test cathode material performance, and predict cathode contamination.

  7. Simultaneous reduction and nitrogen functionalization of graphene oxide using lemon for metal-free oxygen reduction reaction

    Science.gov (United States)

    Begum, Halima; Ahmed, Mohammad Shamsuddin; Cho, Sung; Jeon, Seungwon

    2017-12-01

    Inspire by the vision of finding a simple and green method for simultaneous reduction and nitrogen (N)-functionalization of graphene oxide (GO), a N-rich reduced graphene oxide (rGO) has been synthesized through a facile and ecofriendly hydrothermal strategy while most of the existing methods are involving with multiple steps and highly toxic reducing agents that are harmful to human health and environment. In this paper, the simultaneous reduction and N-functionalization of GO using as available lemon juice (denoted as Lem-rGO) for metal-free electrocatalysis towards oxygen reduction reaction (ORR) is described. The proposed method is based on the reduction of GO using of the reducing and the N-precursor capability of ascorbic acid and citric acid as well as the nitrogenous compounds, respectively, that containing in lemon juice. The resultant Lem-rGO has higher reduction degree, higher specific surface area and better crystalline nature with N-incorporation than that of well investigated ascorbic acid and citric acid treated rGO. As a result, it shows better ORR electrocatalytic activity in respect to the improved onset potential, electron transfer rate and kinetics than those typical rGO catalysts. Moreover, it shows a significant tolerance to the anodic fuels and durability than the Pt/C during ORR.

  8. Novel RuCoSe as non-platinum catalysts for oxygen reduction reaction in microbial fuel cells

    Science.gov (United States)

    Rozenfeld, Shmuel; Schechter, Michal; Teller, Hanan; Cahan, Rivka; Schechter, Alex

    2017-09-01

    Microbial electrochemical cells (MECs) are explored for the conversion of acetate directly to electrical energy. This device utilizes a Geobacter sulfurreducens anode and a novel RuCoSe air cathode. RuCoSe synthesized in selected compositions by a borohydride reduction method produces amorphous structures of powdered agglomerates. Oxygen reduction reaction (ORR) was measured in a phosphate buffer solution pH 7 using a rotating disc electrode (RDE), from which the kinetic current (ik) was measured as a function of potential and composition. The results show that ik of RuxCoySe catalysts increases in the range of XRu = 0.25 > x > 0.7 and y < 0.15 for all tested potentials. A poisoning study of RuCoSe and Pt catalysts in a high concentration acetate solution shows improved tolerance of RuCoSe to this fuel at acetate concentration ≥500 mM. MEC discharge plots under physiological conditions show that ∼ RuCo2Se (sample S3) has a peak power density of 750 mW cm-2 which is comparable with Pt 900 mW cm-2.

  9. The Mechanisms of Oxygen Reduction in the Terminal Reducing Segment of the Chloroplast Photosynthetic Electron Transport Chain.

    Science.gov (United States)

    Kozuleva, Marina A; Ivanov, Boris N

    2016-07-01

    The review is dedicated to ascertainment of the roles of the electron transfer cofactors of the pigment-protein complex of PSI, ferredoxin (Fd) and ferredoxin-NADP reductase in oxygen reduction in the photosynthetic electron transport chain (PETC) in the light. The data regarding oxygen reduction in other segments of the PETC are briefly analyzed, and it is concluded that their participation in the overall process in the PETC under unstressful conditions should be insignificant. Data concerning the contribution of Fd to the oxygen reduction in the PETC are examined. A set of collateral evidence as well as results of direct measurements of the involvement of Fd in this process in the presence of isolated thylakoids led to the inference that this contribution in vivo is negligible. The increase in oxygen reduction rate in the isolated thylakoids in the presence of either Fd or Fd plus NADP + under increasing light intensity was attributed to the increase in oxygen reduction executed by the membrane-bound oxygen reductants. Data are presented which imply that a main reductant of the O 2 molecule in the terminal reducing segment of the PETC is the electron transfer cofactor of PSI, phylloquinone. The physiological significance of characteristic properties of oxygen reductants in this segment of the PETC is discussed. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  10. One-step synthesis of high-yield biodiesel from waste cooking oils by a novel and highly methanol-tolerant immobilized lipase.

    Science.gov (United States)

    Wang, Xiumei; Qin, Xiaoli; Li, Daoming; Yang, Bo; Wang, Yonghua

    2017-07-01

    This study reported a novel immobilized MAS1 lipase from marine Streptomyces sp. strain W007 for synthesizing high-yield biodiesel from waste cooking oils (WCO) with one-step addition of methanol in a solvent-free system. Immobilized MAS1 lipase was selected for the transesterification reactions with one-step addition of methanol due to its much more higher biodiesel yield (89.50%) when compared with the other three commercial immobilized lipases (biodiesel yield (95.45%) was acquired with one-step addition of methanol under the optimized conditions. Moreover, it was observed that immobilized MAS1 lipase retained approximately 70% of its initial activity after being used for four batch cycles. Finally, the obtained biodiesel was further characterized using FT-IR, 1 H and 13 C NMR spectroscopy. These findings indicated that immobilized MAS1 lipase is a promising catalyst for biodiesel production from WCO with one-step addition of methanol under high methanol concentration. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Temperature Dependence of the Oxygen Reduction Mechanism in Nonaqueous Li–O 2 Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bin [Energy; Xu, Wu [Energy; Zheng, Jianming [Energy; Yan, Pengfei [Environmental; Walter, Eric D. [Environmental; Isern, Nancy [Environmental; Bowden, Mark E. [Environmental; Engelhard, Mark H. [Environmental; Kim, Sun Tai [Energy; Department; Read, Jeffrey [Power; Adams, Brian D. [Energy; Li, Xiaolin [Energy; Cho, Jaephil [Department; Wang, Chongmin [Environmental; Zhang, Ji-Guang [Energy

    2017-10-11

    The temperature dependence of the oxygen reduction mechanism in Li-O2 batteries was investigated using carbon nanotube-based air electrodes and 1,2-dimethoxyethane-based electrolyte within a temperature range of 20C to 40C. It is found that the discharge capacity of the Li-O2 batteries decreases from 7,492 mAh g-1 at 40C to 2,930 mAh g-1 at 0C. However, a sharp increase in capacity was found when the temperature was further decreased and a very high capacity of 17,716 mAh g-1 was observed at 20C at a current density of 0.1 mA cm-2. When the temperature increases from 20C to 40C, the morphologies of the Li2O2 formed varied from ultra-small spherical particles to small flakes and then to large flake-stacked toroids. The lifetime of superoxide and the solution pathway play a dominate role on the battery capacity in the temperature range of -20C to 0C, but the electrochemical kinetics of oxygen reduction and the surface pathway dominate the discharge behavior in the temperature range of 0C to 40C. These findings provide fundamental understanding on the temperature dependence of oxygen reduction process in a Li-O2 battery and will enable a more rational design of Li-O2 batteries.

  12. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    International Nuclear Information System (INIS)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone; Chorkendorff, Ib

    2012-01-01

    Highlights: ► Impedance spectroscopy of Cu/Pt(1 1 1) near-surface alloy and Pt(1 1 1). ► Presence of oxygen changes little the adsorption dynamics. ► Adsorption dynamics similar on alloy and Pt(1 1 1). ► Electrosorption phenomena on alloy shifted in potential, relative to Pt(1 1 1). - Abstract: The adsorption dynamics of *OH and *O species at Pt(1 1 1) and Cu/Pt(1 1 1) near-surface alloy (NSA) surfaces in oxygen-free and O 2 -saturated 0.1 M HClO 4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(1 1 1) surface resulting in weaker bonding to adsorbates like *OH, *H or *O. This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16 V towards more positive potentials can be clearly monitored in absence of O 2 and under the oxygen reduction reaction (ORR) conditions for the Cu/Pt(1 1 1) NSA. In both cases, for Pt(1 1 1) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when oxygen reduction takes place at the surface. A ∼5-fold improvement in the ORR activity over the Pt(1 1 1) at 0.9 V (RHE) was measured for the Cu/Pt(1 1 1) near-surface alloy.

  13. 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

  14. Polypyrrole/Co-tetraphenylporphyrin modified carbon fibre paper as a fuel cell electrocatalyst of oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Weimin; Chen, Jun; Wagner, Pawel; Wallace, Gordon G. [ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Wollongong NSW 2522 (Australia); Swiegers, Gerhard F. [CSIRO Molecular and Health Technologies, Bag 10, Clayton VIC 3169 (Australia)

    2008-04-15

    A thin-layer of polypyrrole (PPy) film, immobilized with neutral 5,10,15,20-tetraphenylporphyrinato cobalt (II) (Co-TPP), was successfully and uniformly deposited onto mesoporous carbon fibre paper (CFP) via vapor-phase polymerization. The resulting PPy/Co-TPP-modified carbon fibre paper (PPy/Co-TPP-CFP) electrode was characterized by cyclic voltammetry, SEM and EDX-ray mapping. Its electrochemical stability and long-term electrocatalytic performance were investigated in a half-fuel cell testing system. The electrode displayed significant electrocatalytic performance for oxygen reduction at 0.0 V (vs. Ag/AgCl), with notable long-term stability. (author)

  15. The effect of temperature and pressure on the oxygen reduction reactions in polyelectrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

    1997-12-31

    The effect of temperature and pressure on the oxygen reduction reaction in polyelectrolyte membranes was described. Polyelectrolytes chosen for the experiment differed in composition, weight and flexibility of the polymer chains. The study was conducted in a solid state electrochemical cell at temperatures between 30 and 95 degrees C and in the pressure range of 1 to 5 atm. The solubility of oxygen in these membranes was found to follow Henry`s Law, while the diffusion coefficient decreased with pressure. The effect of temperature on the solubility of oxygen and the diffusion coefficient of oxygen in the membranes was similar to that observed in solution electrolytes. 2 refs., 3 figs.

  16. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Masud, Jahangir [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2010-12-15

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

  17. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Ohsaka, Takeo

    2009-01-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H 2 O as the final product.

  18. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

    2010-01-01

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

  19. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: mrmche@yahoo.com; Ohsaka, Takeo [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: ohsaka@echem.titech.ac.jp

    2009-10-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H{sub 2}O as the final product.

  20. Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

    Science.gov (United States)

    Orellana, Walter

    2012-07-01

    The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

  1. Electro catalyst of platinum prepared by CVD for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R.

    2004-01-01

    In this work it is reported the preparation and characterization of platinum films obtained by the technique of chemical vapor deposition at low pressure, better well-known as LPCVD for their initials in English (Low Pressure Chemical Vapor Deposition). The technique has several industrial applications and in this work it is explored their possible use to prepare applicable electrocatalysts in fuel cells. The films were characterized by XRD, SEM, EDS and they were proven for to determine their acting in the Oxygen reduction reaction (Orr) in sulfuric acid 0.5 M, the results show that the material presents good activity for the reaction in study. (Author)

  2. One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

    KAUST Repository

    Varga, Tamá s; Varga, Á gnes Tí mea; Ballai, Gergő; Haspel, Henrik; Kukovecz, Á kos; Kó nya, Z.

    2018-01-01

    Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close

  3. Electrodeposition of Pd based binary catalysts on Carbon paper via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Direct alcohol fuel cells (DAFCs) continue to extensive attention as potential power sources for portable and stationary applications. The oxygen reduction reaction (ORR) involving the four electron transfer remains a challenge for DAFCs due to its...

  4. Influence of Chemical and Physical Properties of Activated Carbon Powders on Oxygen Reduction and Microbial Fuel Cell Performance

    KAUST Repository

    Watson, Valerie J.; Nieto Delgado, Cesar; Logan, Bruce E.

    2013-01-01

    Commercially available activated carbon (AC) powders made from different precursor materials (coal, peat, coconut shell, hardwood, and phenolic resin) were electrochemically evaluated as oxygen reduction catalysts and tested as cathode catalysts

  5. Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

    KAUST Repository

    Seo, J.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

    2013-01-01

    The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine

  6. Oxygen reduction at platinum nanoparticles supported on carbon cryogel in alkaline solution

    Directory of Open Access Journals (Sweden)

    N. R. ELEZOVIC

    2007-07-01

    Full Text Available The oxygen reduction reaction was investigated in 0.1 M NaOH solution, on a porous coated electrode formed of Pt particles supported on carbon cryogel. The Pt/C catalyst was characterized by the X-ray diffraction (XRD, transmission electron microscopy (TEM and cyclic voltammetry techniques. The results demonstrated a successful reduction of Pt to metallic form and homogenous Pt particle size distribution with a mean particle size of about 2.7 nm. The ORR kinetics was investigated by linear sweep polarization at a rotating disc electrode. The results showed the existence of two E – log j regions, usually referred to polycrystalline Pt in acid and alkaline solution. At low current densities (lcd, the Tafel slope was found to be close to –2.3RT/F, while at high current densities (hcd it was found to be close to –2×2.3RT/F. It is proposed that the main path in the ORR mechanism on Pt particles was the direct four-electron process, with the transfer of the first electron as the rate determining step. If the activities are expressed through the specific current densities, a small enhancement of the catalytic activity for Pt/C was observed compared to that of polycrystalline Pt. The effect of the Pt particle size on the electrocatalysis of oxygen reduction was ascribed to the predominant (111 facets of the platinum crystallites.

  7. KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

    Science.gov (United States)

    He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

    In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

  8. Cross-Linked CoMoO4/rGO Nanosheets as Oxygen Reduction Catalyst

    Directory of Open Access Journals (Sweden)

    Jiaqi Fu

    2017-12-01

    Full Text Available Development of inexpensive and robust electrocatalysts towards oxygen reduction reaction (ORR is crucial for the cost-affordable manufacturing of metal-air batteries and fuel cells. Here we show that cross-linked CoMoO4 nanosheets and reduced graphene oxide (CoMoO4/rGO can be integrated in a hybrid material under one-pot hydrothermal conditions, yielding a composite material with promising catalytic activity for oxygen reduction reaction (ORR. Cyclic voltammetry (CV and linear sweep voltammetry (LSV were used to investigate the efficiency of the fabricated CoMoO4/rGO catalyst towards ORR in alkaline conditions. The CoMoO4/rGO composite revealed the main reduction peak and onset potential centered at 0.78 and 0.89 V (vs. RHE, respectively. This study shows that the CoMoO4/rGO composite is a highly promising catalyst for the ORR under alkaline conditions, and potential noble metal replacement cathode in fuel cells and metal-air batteries.

  9. Surface coverage of Pt atoms on PtCo nanoparticles and catalytic kinetics for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Rongzhong, E-mail: rongzhong.jiang@us.army.mi [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States); Rong, Charles; Chu, Deryn [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States)

    2011-02-01

    The surface coverage of Pt atoms on PtCo nanoparticles and its effect on catalytic kinetics for oxygen reduction were investigated. The PtCo nanoparticles with different surface coverage of Pt atoms were synthesized with various methods, including normal chemical method, microemulsion synthesis, and ultrasound-assisted microemulsion. A model of Pt atoms filling into a spherical nanoparticle was proposed to explain the relationship of surface metal atoms and nanoparticle size. The catalytic activity of the PtCo nano-particles is highly dependent on the synthetic methods, even if they have the same chemical composition. The PtCo nano-particles synthesized with ultrasound-assisted microemulsion showed the highest activity, which is attributed to an increase of active surface coverage of Pt atoms on the metal nanoparticles. The rate of oxygen reduction at 0.5 V (vs. SCE) catalyzed by the PtCo synthesized with ultrasound-assisted micro-emulsion was about four times higher than that of the PtCo synthesized with normal chemical method. As demonstrated with rotating-ring disk electrode measurement, the PtCo nano-particles can catalyze oxygen 4-electron reduction to water without intermediate H{sub 2}O{sub 2} detected.

  10. Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells

    International Nuclear Information System (INIS)

    Freguia, Stefano; Rabaey, Korneel; Yuan Zhiguo; Keller, Juerg

    2007-01-01

    Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m -3 (cathode total volume) or 50 W m -3 (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kg COD m -3 d -1 , which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials

  11. Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Freguia, Stefano; Rabaey, Korneel; Yuan, Zhiguo; Keller, Juerg [The University of Queensland, St. Lucia, Qld (Australia). Advanced Wastewater Management Centre

    2007-12-01

    Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m{sup -3} (cathode total volume) or 50 W m{sup -3} (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kg{sub COD} m{sup -3} d{sup -1}, which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials. (author)

  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. Nanostructured Mn{sub x}O{sub y} for oxygen reduction reaction (ORR) catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Delmondo, Luisa, E-mail: luisa.delmondo@polito.it [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Salvador, Gian Paolo; Muñoz-Tabares, José Alejandro; Sacco, Adriano; Garino, Nadia; Castellino, Micaela [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Gerosa, Matteo; Massaglia, Giulia [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Chiodoni, Angelica; Quaglio, Marzia [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy)

    2016-12-01

    Highlights: • Good performance catalysts for oxygen reduction reaction. • Nanostructured low-cost catalysts respect to platinum ones. • Synthesis using environmental benign chemical reagents. - Abstract: In the field of fuel cells, oxygen plays a key role as the final electron acceptor. To facilitate its reduction (Oxygen Reduction Reaction—ORR), a proper catalyst is needed and platinum is considered the best one due to its low overpotential for this reaction. By considering the high price of platinum, alternative catalysts are needed and manganese oxides (Mn{sub x}O{sub y}) can be considered promising substitutes. They are inexpensive, environmental friendly and can be obtained into several forms; most of them show significant electro-catalytic performance, even if strategies are needed to increase their efficiency. In particular, by developing light and high-surface area materials and by optimizing the presence of catalytic sites, we can obtain a cathode with improved electro-catalytic performance. In this case, nanofibers and xerogels are two of the most promising nanostructures that can be used in the field of catalysis. In this work, a study of the morphological and catalytic behavior of Mn{sub x}O{sub y} nanofibers and xerogels is proposed. Nanofibers were obtained by electrospinning, while xerogels were prepared by sol-gel and freeze drying techniques. Despite of the different preparation approaches, the obtained nanostructured manganese oxides exhibited similar catalytic performance for the ORR, comparable to those obtained from Pt catalysts.

  14. Heteroatom-doped porous carbon from methyl orange dye wastewater for oxygen reduction

    Directory of Open Access Journals (Sweden)

    Yiqing Wang

    2018-04-01

    Full Text Available Banana peel-derived porous carbon (BPPC was prepared from banana peel and used as an adsorbent for methyl orange (MO wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO50 exhibited a high specific surface area of 1774.3 m2/g. Heteroatom-doped porous carbon (PC was successfully synthesized from the BPPC absorbed MO at high temperature and used for oxygen reduction. The BPPC-MO50 displayed the highest ORR onset potential among all carbon-based electrocatalysts, i.e., 0.93 V vs. reversible hydrogen electrode (RHE. This is the first report to describe porous carbon-activated materials from agriculture and forestry waste that is used for adsorption of dyes from wastewater via an enhanced heteroatom (N,S content. These results may contribute to the sustainable development of dye wastewater treatment by transforming saturated PC into an effective material and has potential applications in fuel cells or as energy sources. Keywords: Banana peel, Dye wastewater, Porous carbon, Heteroatom doping, Oxygen reduction reaction

  15. Promotion of multi-electron transfer for enhanced photocatalysis: A review focused on oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Changhua [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); College of Chemistry and Biology, Beihua University, Jilin 132013 (China); Zhang, Xintong, E-mail: xtzhang@nenu.edu.cn [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); Liu, Yichun [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China)

    2015-12-15

    Highlights: • Oxygen reduction reaction (ORR) in photocatalysis process is focused. • Multi-electron transfer ORR is reviewed. • This review provides a guide to access to enhanced photocatalysis via multi-electron transfer. - Abstract: Semiconductor photocatalysis has attracted significant interest for solar light induced environmental remediation and solar fuel generation. As is well known, photocatalytic performance is determined by three steps: photoexcitation, separation and transport of photogenerated charge carriers, and surface reactions. To achieve higher efficiency, significant efforts have been made on improvement of efficiency of above first two steps, which have been well documented in recent review articles. In contrast, this review intends to focus on strategies moving onto the third step of improvement for enhanced photocatalysis wherein active oxygen species including superoxide radical, hydrogen peroxide, hydroxyl radical are in situ detected. Particularly, surface electron-transfer reduction of oxygen over single component photocatalysts is reviewed and systems enabling multi-electron transfer induced oxygen reduction reaction (ORR) are highlighted. It is expected this review could provide a guideline for readers to better understand the critical role of ORR over photocatalyst in charge carrier separation and transfer and obtain reliable results for enhanced aerobic photocatalysis.

  16. Experimental Elucidation of the Oxygen Reduction Volcano in Base on a Pt Alloy Single Crystal

    DEFF Research Database (Denmark)

    Jensen, Kim Degn; Tymoczko, Jakub; Bandarenka, Aliaksandr S.

    2016-01-01

    and base.[1,2] In our earlier studies, we mapped out the experimental Sabatier volcano for the oxygen reduction reaction in 0.1 M HClO4 using the Cu/Pt(111) near-surface alloy system, see Figure 1 for near-surface alloy schematic.[3,4] In this study, as those of [3,4], we found that by changing...... the subsurface coverage of Cu we could tune the surface binding of the key reaction intermediate, OH; we thus monitored the OH binding energy shift through the observable shifts in the base voltammograms in both acidic and alkaline media. Further, we elucidate the experimental oxygen reduction volcano in 0.1 M...... to Pt(111). However, all surfaces show a ~4 fold improvement in activity in 0.1 M KOH, relative to the same surface in 0.1 M HClO4. At the peak of the volcano the surface exhibits an exceptionally high specific activity of 90 mA/cm2 at 0.9 V with respect to the reversible hydrogen electrode. Thus, our...

  17. Preparation of nitrogen-doped graphitic carboncages as electrocatalyst for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Yan, Jing; Meng, Hui; Yu, Wendan; Yuan, Xiaoli; Lin, Worong; Ouyang, Wenpeng; Yuan, Dingsheng

    2014-01-01

    Nitrogen-doped carbon nanomaterials have been attracted increasing research interests in lithium-O 2 and Zinc-O 2 batteries, ultracapacitors and fuel cells. Herein, nitrogen-doped graphitic carboncages (N-GCs) have been prepared by mesoporous Fe 2 O 3 as a catalyst and lysine as a nitrogen doped carbon source. Due to the catalysis of Fe 2 O 3 , the N-GCs have a high graphitization degree at a low temperature, which is detected by X-ray diffraction and Raman spectrometer. Simultaneously, the heteroatom nitrogen is in-situ doped into carbon network. Therefore, the excellent electrocatalysis performance for oxygen reduction reaction is expected. The electrochemical measurement indicates that The N-GCs for oxygen reduction reaction in O 2 -saturated 0.1 mol L −1 KOH show a four-electron transfer process and exhibit excellent electrocatalytic activity (E ORR = -0.05 V vs. Ag/AgCl) and good stability (i/i 0 = 90% at -0.35 V after 4000 s with a rotation rate of 1600 rpm)

  18. Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

    Science.gov (United States)

    Cheng, Fangyi; Chen, Jun

    2012-03-21

    Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

  19. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    DEFF Research Database (Denmark)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

    2012-01-01

    The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *O....... This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16V towards more positive potentials can be clearly monitored in absence of O2 and under the oxygen reduction reaction (ORR) conditions...... for the Cu/Pt(111) NSA. In both cases, for Pt(111) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when...

  20. 3D graphene preparation via covalent amide functionalization for efficient metal-free electrocatalysis in oxygen reduction

    Science.gov (United States)

    Ahmed, Mohammad Shamsuddin; Kim, Young-Bae

    2017-02-01

    3D and porous reduced graphene oxide (rGO) catalysts have been prepared with sp3-hybridized 1,4-diaminobutane (sp3-DABu, rGO-sp3-rGO) and sp2-hybridized 1,4-diaminobenzene (sp2-DABe, rGO-sp2-rGO) through a covalent amidation and have employed as a metal-free electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. Both compounds have used as a junction between functionalized rGO layers to improve electrical conductivity and impart electrocatalytic activity to the ORR resulting from the interlayer charge transfer. The successful amidation and the subsequent reduction in the process of catalyst preparation have confirmed by X-ray photoelectron spectroscopy. A hierarchical porous structure is also confirmed by surface morphological analysis. Specific surface area and thermal stability have increased after successful the amidation by sp3-DABu. The investigated ORR mechanism reveals that both functionalized rGO is better ORR active than nonfunctionalized rGO due to pyridinic-like N content and rGO-sp3-rGO is better ORR active than rGO-sp2-rGO due to higher pyridinic-like N content and π-electron interaction-free interlayer charge transfer. Thus, the rGO-sp3-rGO has proven as an efficient metal-free electrocatalyst with better electrocatalytic activity, stability, and tolerance to the crossover effect than the commercially available Pt/C for ORR.

  1. Carbon supported Pd-Co-Mo alloy as an alternative to Pt for oxygen reduction in direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Ch. Venkateswara [National Centre for Catalysis Research, Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, TN (India); Viswanathan, B., E-mail: bvnathan@acer.iitm.ernet.i [National Centre for Catalysis Research, Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, TN (India)

    2010-03-01

    Carbon black (CDX975) supported Pd and Pd-Co-Mo alloy nanoparticles are prepared by the reduction of metal precursors with hydrazine in reverse microemulsion of water/Triton-X-100/propanol-2/cyclohexane. The as-synthesized Pd-Co-Mo/CDX975 is heat treated at 973, 1073 and 1173 K to promote alloy formation. The prepared materials are characterized by powder XRD and EDX. Face-centred cubic structure of Pd is evident from XRD. The chemical composition of the respective elements in the catalysts is evaluated from the EDX analysis and observed that it is in good agreement with initial metal precursor concentrations. Oxygen reduction measurements performed by linear sweep voltammetry indicate the good catalytic activity of Pd-Co-Mo alloys compared to Pd. This is due to the suppression of (hydr)oxy species on Pd surface by the presence of alloying elements, Co and Mo. Among the investigated catalysts, heat-treated Pd-Co-Mo/CDX975 at 973 K exhibited good ORR activity compared to the catalysts heat treated at 1073 and 1173 K. This is due to the small crystallite size and high surface area. Rotating disk electrode (RDE) measurements indicated the comparable ORR activity of heat-treated Pd-Co-Mo/CDX975 at 973 K with that of commercial Pt/C. Kinetic analysis reveals that the ORR on Pd-Co-Mo/CDX975 follows the four-electron pathway leading to water. Moreover, Pd-Co-Mo/CDX975 exhibited substantially higher ethanol tolerance during the ORR than Pt/C. Good dispersion of metallic nanoparticles on the carbon support is observed from HRTEM images. Single-cell direct ethanol fuel cell tests indicated the comparable performance of Pd-Co-Mo/CDX975 with that of commercial Pt/C. Stability under DEFC operating conditions for 50 h indicated the good stability of Pd-Co-Mo/CDX975 compared with that of Pt/C.

  2. Oxygen reduction at electrodeposited ZnO layers in alkaline solution

    International Nuclear Information System (INIS)

    Prestat, M.; Vucko, F.; Lescop, B.; Rioual, S.; Peltier, F.; Thierry, D.

    2016-01-01

    Zinc oxide (ZnO) layers were electrodeposited from an aqueous nitrate bath at 62 °C on copper substrates. At −0.9 V (vs. saturated calomel reference electrode), the growth rate is 600 nm min −1 . In the early stages of the deposition, the layers are porous. At longer deposition times, the surface becomes dense and rough. The wurtzite crystalline structure is confirmed by XRD measurements and the chemical composition of the ZnO surface was assessed by EDX and XPS. The oxygen reduction reaction (ORR) was investigated at room temperature in a 10 −3 M KOH solution with KCl as supporting electrolyte. The ORR onset potential is found to be much larger than that of platinum taken as reference electrocatalyst. Rotating ring-disk electrode experiments evidence a negligible production of hydrogen peroxide as intermediate product of the reaction. The latter follows thus a direct four-electron pathway at pH ∼11.

  3. Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

    2015-01-01

    Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

  4. Rational design of competitive electrocatalysts for the oxygen reduction reaction in hydrogen fuel cells

    Science.gov (United States)

    Stolbov, Sergey; Alcántara Ortigoza, Marisol

    2012-02-01

    The large-scale application of one of the most promising clean and renewable sources of energy, hydrogen fuel cells, still awaits efficient and cost-effective electrocatalysts for the oxygen reduction reaction (ORR) occurring on the cathode. We demonstrate that truly rational design renders electrocatalysts possessing both qualities. By unifying the knowledge on surface morphology, composition, electronic structure and reactivity, we solve that sandwich-like structures are an excellent choice for optimization. Their constituting species couple synergistically yielding reaction-environment stability, cost-effectiveness and tunable reactivity. This cooperative-action concept enabled us to predict two advantageous ORR electrocatalysts. Density functional theory calculations of the reaction free-energy diagrams confirm that these materials are more active toward ORR than the so far best Pt-based catalysts. Our designing concept advances also a general approach for engineering materials in heterogeneous catalysis.

  5. Controllable synthesis of Co3O4 nanocrystals as efficient catalysts for oxygen reduction reaction

    Science.gov (United States)

    Li, Baoying; Zhang, Yihe; Du, Ruifeng; Liu, Lei; Yu, Xuelian

    2018-03-01

    The electrochemical oxygen reduction reaction (ORR) has received great attention due to its importance in fuel cells and metal-air batteries. Here, we present a simple approach to prepare non-noble metal catalyst-Co3O4 nanocrystals (NCs). The particle size and shape were simply controlled by different types and concentrations of metal precursor. Furthermore, different sizes and shapes of Co3O4 NCs are explored as electrocatalysts for ORR, and it has been observed that particles with a similar shape, and smaller particle size led to greater catalytic current densities because of the greater surface area. For particles with a comparable size, the shape or crystalline structure governed the activity of the electrocatalytic reactions. Most importantly, the 9 nm-Co3O4 were demonstrated to act as low-cost catalysts for the ORR with a similar performance to that of Pt catalysts.

  6. Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

    KAUST Repository

    Ohnishi, R.; Katayama, M.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

    2013-01-01

    Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

  7. Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

    Science.gov (United States)

    Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

    2015-03-11

    Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode.

  8. Modified Graphene as Electrocatalyst towards Oxygen Reduction Reaction for Fuel Cells

    International Nuclear Information System (INIS)

    Qazzazie, D; Yurchenko, O; Beckert, M; Mülhaupt, R; Urban, G

    2014-01-01

    This paper reports modified graphene-based materials as metal-free electrocatalysts for oxygen reduction reaction (ORR) with outstanding electrocatalytic activity in alkaline conditions. Nitrogen-doped graphene samples are synthesized by a novel procedure. The defect density in the structure of the prepared materials is investigated by Raman spectroscopy. Further structural characterization by X-ray photoelectron spectroscopy reveals the successful nitrogen doping of graphene. The electrochemical characterization of graphene and nitrogen-doped graphene in 0.1 M KOH solution demonstrates the material's electrocatalytic activity towards ORR. For graphene an onset potential of – 0.175 V vs. Ag/AgCl reference electrode is determined, while for nitrogen-doped graphene the determined onset potential is – 0.160 V. Thus, the electrocatalytic activity of nitrogen-doped graphene towards ORR is enhanced which can be ascribed to the effect of nitrogen doping

  9. Modified Graphene as Electrocatalyst towards Oxygen Reduction Reaction for Fuel Cells

    Science.gov (United States)

    Qazzazie, D.; Beckert, M.; Mülhaupt, R.; Yurchenko, O.; Urban, G.

    2014-11-01

    This paper reports modified graphene-based materials as metal-free electrocatalysts for oxygen reduction reaction (ORR) with outstanding electrocatalytic activity in alkaline conditions. Nitrogen-doped graphene samples are synthesized by a novel procedure. The defect density in the structure of the prepared materials is investigated by Raman spectroscopy. Further structural characterization by X-ray photoelectron spectroscopy reveals the successful nitrogen doping of graphene. The electrochemical characterization of graphene and nitrogen-doped graphene in 0.1 M KOH solution demonstrates the material's electrocatalytic activity towards ORR. For graphene an onset potential of - 0.175 V vs. Ag/AgCl reference electrode is determined, while for nitrogen-doped graphene the determined onset potential is - 0.160 V. Thus, the electrocatalytic activity of nitrogen-doped graphene towards ORR is enhanced which can be ascribed to the effect of nitrogen doping.

  10. Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

    KAUST Repository

    Ohnishi, R.

    2013-03-12

    Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

  11. An Oxygen Reduction Study of Graphene-Based Nanomaterials of Different Origin

    Directory of Open Access Journals (Sweden)

    Jaana Lilloja

    2016-07-01

    Full Text Available The aim of this study is to compare the electrochemical behaviour of graphene-based materials of different origin, e.g., commercially available graphene nanosheets from two producers and reduced graphene oxide (rGO towards the oxygen reduction reaction (ORR using linear sweep voltammetry, rotating disc electrode and rotating ring-disc electrode methods. We also investigate the effect of catalyst ink preparation using two different solvents (2-propanol containing OH− ionomer or N,N-dimethylformamide on the ORR. The graphene-based materials are characterised by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Clearly, the catalytic effect depends on the origin of graphene material and, interestingly, the electrocatalytic activity of the catalyst material for ORR is lower when using the OH− ionomer in electrode modification. The graphene electrodes fabricated with commercial graphene show better ORR performance than rGO in alkaline solution.

  12. Pt Monolayer Shell on Nitrided Alloy Core—A Path to Highly Stable Oxygen Reduction Catalyst

    Directory of Open Access Journals (Sweden)

    Jue Hu

    2015-07-01

    Full Text Available The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC. Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared PtMLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability of the PtMLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.

  13. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Hyung Chul; Hwang, Gyeong S., E-mail: gshwang@che.utexas.edu [Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Manogaran, Dhivya [Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712 (United States); Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho [Energy Lab, Samsung Advanced Institute of Technology, Samsung Electronics Co., Ltd., Suwon (Korea, Republic of); Kwon, Kyungjung [Department of Energy and Mineral Resources Engineering, Sejong University, Seoul 143-747 (Korea, Republic of)

    2013-11-28

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd{sub 3}Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd{sub 3}Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

  14. Structure, activity, and stability of platinum alloys as catalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Vej-Hansen, Ulrik Grønbjerg

    In this thesis I present our work on theoretical modelling of platinum alloys as catalysts for the Oxygen Reduction Reaction (ORR). The losses associated with the kinetics of the ORR is the main bottleneck in low-temperature fuel cells for transport applications, and more active catalysts...... are essential for wide-spread use of this technology. platinum alloys have shown great promise as more active catalysts, which are still stable under reaction conditions. We have investigated these systems on multiple scales, using either Density Functional Theory (DFT) or Effective Medium Theory (EMT......), depending on the length and time scales involved. Using DFT, we show how diffusion barriers in transition metal alloys in the L12 structure depend on the alloying energy, supporting the assumption that an intrinsically more stable alloy is also more stable towards diffusion-related degradation...

  15. Evidence of enzymatic catalysis of oxygen reduction on stainless steels under marine biofilm.

    Science.gov (United States)

    Faimali, Marco; Benedetti, Alessandro; Pavanello, Giovanni; Chelossi, Elisabetta; Wrubl, Federico; Mollica, Alfonso

    2011-04-01

    Cathodic current trends on stainless steel samples with different surface percentages covered by biofilm and potentiostatically polarized in natural seawater were studied under oxygen concentration changes, temperature increases, and additions of enzymic inhibitors to the solution. The results showed that on each surface fraction covered by biofilm the oxygen reduction kinetics resembled a reaction catalyzed by an immobilised enzyme with high oxygen affinity (apparent Michaelis-Menten dissociation constant close to K(O(2))(M)  ≈ 10 μM) and low activation energy (W ≈ 20 KJ mole(-1)). The proposed enzyme rapidly degraded when the temperature was increased above the ambient (half-life time of ∼1 day at 25°C, and of a few minutes at 50°C). Furthermore, when reversible enzymic inhibitors (eg sodium azide and cyanide) were added, the cathodic current induced by biofilm growth was inhibited.

  16. The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction

    International Nuclear Information System (INIS)

    Delacote, Cyril; Lewera, Adam; Pisarek, Marcin; Kulesza, Pawel J.; Zelenay, Piotr; Alonso-Vante, Nicolas

    2010-01-01

    This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru x Se y . The catalysts were obtained by thermal decomposition of Ru 3 (CO) 12 and Fe(CO) 5 in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

  17. Fabrication of high surface area graphene electrodes with high performance towards enzymatic oxygen reduction

    International Nuclear Information System (INIS)

    Di Bari, Chiara; Goñi-Urtiaga, Asier; Pita, Marcos; Shleev, Sergey; Toscano, Miguel D.; Sainz, Raquel; De Lacey, Antonio L.

    2016-01-01

    High surface area graphene electrodes were prepared by simultaneous electrodeposition and electroreduction of graphene oxide. The electrodeposition process was optimized in terms of pH and conductivity of the solution and the obtained graphene electrodes were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy and electrochemical methods (cyclic voltammetry and impedance spectroscopy). Electrodeposited electrodes were further functionalized to carry out covalent immobilization of two oxygen-reducing multicopper oxidases: laccase and bilirubin oxidase. The enzymatic electrodes were tested as direct electron transfer based biocathodes and catalytic currents as high as 1 mA/cm 2 were obtained. Finally, the mechanism of the enzymatic oxygen reduction reaction was studied for both enzymes calculating the Tafel slopes and transfer coefficients.

  18. Nitrogen-Doped Carbon Nanotube and Graphene Materials for Oxygen Reduction Reactions

    Directory of Open Access Journals (Sweden)

    Qiliang Wei

    2015-09-01

    Full Text Available Nitrogen-doped carbon materials, including nitrogen-doped carbon nanotubes (NCNTs and nitrogen-doped graphene (NG, have attracted increasing attention for oxygen reduction reaction (ORR in metal-air batteries and fuel cell applications, due to their optimal properties including excellent electronic conductivity, 4e− transfer and superb mechanical properties. Here, the recent progress of NCNTs- and NG-based catalysts for ORR is reviewed. Firstly, the general preparation routes of these two N-doped carbon-allotropes are introduced briefly, and then a special emphasis is placed on the developments of both NCNTs and NG as promising metal-free catalysts and/or catalyst support materials for ORR. All these efficient ORR electrocatalysts feature a low cost, high durability and excellent performance, and are thus the key factors in accelerating the widespread commercialization of metal-air battery and fuel cell technologies.

  19. 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

  20. Oxygen reduction activity of N-doped carbon-based films prepared by pulsed laser deposition

    Science.gov (United States)

    Hakoda, Teruyuki; Yamamoto, Shunya; Kawaguchi, Kazuhiro; Yamaki, Tetsuya; Kobayashi, Tomohiro; Yoshikawa, Masahito

    2010-12-01

    Carbon-based films with nitrogen species on their surface were prepared on a glassy carbon (GC) substrate for application as a non-platinum cathode catalyst for polymer electrolyte fuel cells. Cobalt and carbon were deposited in the presence of N 2 gas using a pulsed laser deposition method and then the metal Co was removed by HCl-washing treatment. Oxygen reduction reaction (ORR) activity was electrochemically determined using a rotating disk electrode system in which the film samples on the GC substrate were replaceable. The ORR activity increased with the temperature of the GC substrate during deposition. A carbon-based film prepared at 600 °C in the presence of N 2 at 66.7 Pa showed the highest ORR activity among the tested samples (0.66 V vs. NHE). This film was composed of amorphous carbons doped with pyridine type nitrogen atoms on its surface.

  1. Oxygen Reduction Reaction on PtCo Nanocatalyst: (Bi)sulfate Anion Poisoning

    Science.gov (United States)

    Liu, Jie; Huang, Yan

    2018-05-01

    Pt alloy electrocatalysts are susceptible to anion adsorption in the working environment of fuel cells. In this work, the unavoidable bisulfate and sulfate ((bi)sulfate) poisoning of the oxygen reduction reaction (ORR) on a common PtCo nanocatalyst was studied by the rotating disk electrode (RDE) technique, for the first time to the best of our knowledge. The specific activity decreases linearly with the logarithm of (bi)sulfate concentration under various high potentials. This demonstrates that the (bi)sulfate adsorption does not affect the free energy of ORR activation at a given potential. Moreover, it is speculated that these two conditions, the adsorption of one O2 molecule onto two Pt sites and this adsorption as a rate-determining step of ORR reaction, are unlikely to exist simultaneously.

  2. Limiting Current of Oxygen Reduction on Gas-Diffusion Electrodes for Phosphoric Acid Fuel Cells

    DEFF Research Database (Denmark)

    Li, Qingfeng; Gang, Xiao; Hjuler, Hans Aage

    1994-01-01

    on polytetrafluorine-ethyl bonded gas-diffusion electordes in phosphoric acid with and without fluorinated additives. This provides an alternative to estimate the film thickness by combining it with the acid-adsorption measurements and the porosity analysis of the catalyst layer. It was noticed that the limiting......Various models have been devoted to the operation mechanism of porous diffusion electrodes. They are, however, suffering from the lack of accuracy concerning the acid-film thickness on which they are based. In the present paper the limiting current density has been measured for oxygen reduction...... current density can be accomplished either by gas-phase diffusion or liquid-phase diffusion, and it is the latter that can be used in the film-thickness estimation. It is also important to mention that at such a limiting condition, both the thin-film model and the filmed agglomerate model reach the same...

  3. Effect of solvent on Se-modified ruthenium/carbon catalyst for oxygen reduction

    Directory of Open Access Journals (Sweden)

    Chuanxiang Zhang

    2014-12-01

    Full Text Available Se-modified ruthenium supporting on carbon (Sex–Ru/C electrocatalyst was prepared by solvothermal one-step synthesis method. The reaction mechanism was revealed after discussing impact of different solvents (i-propanol and EG in solvotermal reaction. The result showed that the grain size of Se-modified ruthenium electrocatalyst was as small as 1 to 3 nm and highly dispersed on carbon surface. X-ray photoelectron spectroscopy (XPS presented that selenium mainly existed in the catalyst in the form of elemental selenium and selenium oxides when the solvent was EG and i-propanol, respectively. The oxygen reduction reaction (ORR performance was improved by appearance of selenium oxides.

  4. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    International Nuclear Information System (INIS)

    Ham, Hyung Chul; Hwang, Gyeong S.; Manogaran, Dhivya; Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Kwon, Kyungjung

    2013-01-01

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd 3 Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd 3 Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts

  5. A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

    Science.gov (United States)

    Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

    2017-09-01

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

  6. Correlating Structure and Oxygen Reduction Activity on Y/Pt(111) and Gd/Pt(111) Single Crystals

    DEFF Research Database (Denmark)

    Ulrikkeholm, Elisabeth Therese; Pedersen, Anders Filsøe; Johansson, Tobias Peter

    2015-01-01

    Polymer Electrolyte Membrane Fuel Cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the Oxygen Reduction Reaction (ORR) at the PEMFC cathode prevents the commercialisation of this tech......Polymer Electrolyte Membrane Fuel Cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the Oxygen Reduction Reaction (ORR) at the PEMFC cathode prevents the commercialisation...... of this technology. Improving the activity of Pt by alloying it with other metals could decrease the loading of Pt at the cathode to a level comparable to Pt-group metal loading in internal combustion engines. PtxY and PtxGd exhibit exceptionally high activity for oxygen reduction, both in the polycrystalline form...

  7. First principles investigation of the activity of thin film Pt, Pd and Au surface alloys for oxygen reduction

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Rossmeisl, Jan

    2015-01-01

    Further advances in fuel cell technologies are hampered by kinetic limitations associated with the sluggish cathodic oxygen reduction reaction. We have investigated a range of different formulations of binary and ternary Pt, Pd and Au thin films as electrocatalysts for oxygen reduction. The most...... active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys...

  8. Hydrothermal synthesis of highly crystalline RuS{sub 2} nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yanjuan [Key Laboratory of Marine Chemistry Theory and Technology, Minisry of Education Ocean University of China, Qingdao, 266100 (China); College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Li, Nan, E-mail: lin@jlu.edu.cn [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yanagisawa, Kazumichi [Research Laboratory of Hydrothermal Chemistry, Kochi University, Kochi 780-8520 (Japan); Li, Xiaotian [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yan, Xiao [Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun 130012 (China)

    2015-05-15

    Highlights: • Highly crystalline RuS{sub 2} nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} with average particle size of 14.8 nm. • RuS{sub 2} nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}. - Abstract: Highly crystalline ruthenium sulfide (RuS{sub 2}) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S{sub 2}{sup 2−}. Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS{sub 2} nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS{sub 2} is active towards oxygen reduction reaction. Although the activity of RuS{sub 2} is lower than that of Pt/C, the RuS{sub 2} catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}.

  9. Template-free synthesis of hierarchical yolk-shell Co and N codoped porous carbon microspheres with enhanced performance for oxygen reduction reaction

    Science.gov (United States)

    Chao, Shujun; Cui, Qian; Wang, Kui; Bai, Zhengyu; Yang, Lin; Qiao, Jinli

    2015-08-01

    The structures and compositions of materials have important influences on their performance. Herein, hierarchically structured yolk-shell Co and N codoped porous carbon microspheres (YS-Co/N-PCMs) have been successfully synthesized by using low-cost melamine, formaldehyde and cobalt acetate as raw materials via a facile template-free hydrothermal method and a subsequent pyrolysis. The formation process of the yolk-shell precursor is systematically investigated, involving a morphological evolution process from solid microspheres, ultrathin and wrinkled shells wrap, to yolk-shell structure formation. More importantly, the unique structure combines the favorable features towards oxygen reduction reaction (ORR), such as high surface area, sufficient Co-Nx and graphitic N active sites and suitable pore structures. As a result, the YS-Co/N-PCMs catalyst shows high catalytic activity for ORR in alkaline media for fuel cells, which not only outperforms commercial Pt-based catalysts in terms of resistance to methanol crossover and long-time stability, but is also better than many non-precious metal doped carbon-based catalysts reported previously. In addition, the YS-Co/N-PCMs catalyst also has high catalytic activity toward oxygen evolution reaction (OER). Therefore, the YS-Co/N-PCMs catalyst may serve as a promising alternative to Pt/C catalyst for ORR and OER in alkaline media.

  10. Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium

    International Nuclear Information System (INIS)

    Feng Yongjun; He Ting; Alonso-Vante, Nicolas

    2009-01-01

    We investigated the effect of CoSe 2 /C nanoparticle loading rate on oxygen reduction reaction (ORR) activity and H 2 O 2 production using the rotating disk electrode and the rotating ring-disk electrode techniques. We prepared carbon-supported CoSe 2 nanoparticles with different nominal loading rates and evaluated these samples by means of powder X-ray diffraction. All the catalysts had an OCP value of 0.81 V vs. RHE. H 2 O 2 production during the ORR process decreased with an increase in catalytic layer thickness. This decrease was related to the CoSe 2 loading on the disk electrode. H 2 O 2 production also decreased with increasing catalytic site density, a phenomenon related to the CoSe 2 loading rate on the carbon substrate. The cathodic current density significantly increased with increasing catalytic layer thickness, but decreased with increasing catalytic site density. In the case of 20 wt% CoSe 2 /C nanoparticles at 22 μg cm -2 , we determined that the transfer process involves about 3.5 electrons.

  11. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries

    International Nuclear Information System (INIS)

    Sun, Shanshan; Miao, He; Xue, Yejian; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2016-01-01

    In this paper, the hybrid catalysts of manganese oxide decorated by silver nanoparticles (Ag-MnO x ) are fully investigated and show the excellent oxygen reduction reaction (ORR) activity. The Ag-MnO 2 is synthesized by a facile strategy of the electroless plating of silver on the manganese oxide. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the ORR activities of the catalysts are systematically investigated by the rotating disk electrode (RDE) and aluminum-air battery technologies. The Ag nanoparticles with the diameters at about 10 nm are anchored on the surface of α-MnO 2 and a strong interaction between Ag and MnO 2 components in the hybrid catalyst are confirmed. The electrochemical tests show that the activity and stability of the 50%Ag-MnO 2 composite catalyst (the mass ratio of Ag/MnO 2 is 1:1) toward ORR are greatly enhanced comparing with single Ag or MnO 2 catalyst. Moreover, the peak power density of the aluminum-air battery with 50%Ag-MnO 2 can reach 204 mW cm −2 .

  12. Effect of different chemical modification of carbon nanotubes for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Dumitru, Anca; Mamlouk, M.; Scott, K.

    2014-01-01

    The electrochemical reduction of oxygen on chemically modified multi-walled carbon nanotubes (CNTs) electrodes in 1 M KOH solution has been studied using the rotating ring disc electrode (RDE). The surface modification of CNTs has been estimated by XPS and Raman spectroscopy. The effect of different oxygen functionalities on the surface of carbon nanotube for the oxygen reduction reaction (ORR) is considered in terms of the number of electrons (n) involved. Electrochemical studies indicate that in the case of the modification of CNTs with citric acid and diazonium salts the n values were close to two in the measured potential range, and the electrochemical reduction is limited to the production of peroxide as the final product. In the case of the modification of carbon nanotubes with peroxymonosulphuric acid, in the measured potential range, the n value is close to 4 indicating the four-electron pathway for the ORR. By correlating ORR measurements with the XPS analysis, we propose that the increase in electrocatalytic activity towards the ORR, for CNT can be attributed to the increase in C-O groups on the surface of CNTs after modification with peroxymonosulphuric acid

  13. Enhanced oxygen reduction activity on surface-decorated perovskite thin films for solid oxide fuel cells

    KAUST Repository

    Mutoro, Eva; Crumlin, Ethan J.; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

    2011-01-01

    Surface-decoration of perovskites can strongly affect the oxygen reduction activity, and therefore is a new and promising approach to improve SOFC cathode materials. In this study, we demonstrate that a small amount of secondary phase on a (001) La 0.8Sr 0.2CoO 3-δ (LSC) surface can either significantly activate or passivate the electrode. LSC (001) microelectrodes prepared by pulsed laser deposition on a (001)-oriented yttria-stabilized zirconia (YSZ) substrate were decorated with La-, Co-, and Sr-(hydr)oxides/carbonates. "Sr"-decoration with nanoparticle coverage in the range from 50% to 80% of the LSC surface enhanced the surface exchange coefficient, k q, by an order of magnitude while "La"- decoration and "Co"-decoration led to no change and reduction in k q, respectively. Although the physical origin for the enhancement is not fully understood, results from atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy suggest that the observed k q enhancement for "Sr"-decorated surfaces can be attributed largely to catalytically active interface regions between surface Sr-enriched particles and the LSC surface. © 2011 The Royal Society of Chemistry.

  14. 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...

  15. Investigations of Pd-Cu electrocatalyst for oxygen reduction reaction in acidic media with RDE method

    Energy Technology Data Exchange (ETDEWEB)

    Fouda-Onana, F.; Bah, S.; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

    2008-07-01

    The kinetics of the oxygen reduction reaction (ORR) has been studied extensively with different platinum bi-metallic alloys such as Pt-Fe, Pt-Ni, Pt-Co. However, palladium-based bi-metallic alloys are being considered as a substitute for platinum in electrocatalysts. This paper reported on a study that investigated the ORR on bi-metallic Pd-Cu electrocatalyst. Different contents in Cu were analyzed and an optimal Cu composition leading to the highest ORR activity was found. A mechanism of the ORR kinetics for this catalyst was introduced based on the value of the Tafel slope. A smooth increase in surface area up to 50 per cent Cu was observed to a constant value of 23 cm{sup 2}. Such behaviour was due to the high dispersion of Pd as Cu increased and segregated. A volcano-shape was found between the kinetic current, activation energy and the Cu composition. The maximum exchange current density and the lowest activation energy were found for Pd50Cu50, which corresponded to the highest surface area. All Pd-Cu alloys presented a higher kinetic current than Pd alone. 3 refs., 1 tab., 3 figs.

  16. PTFE effect on the electrocatalysis of the oxygen reduction reaction in membraneless microbial fuel cells.

    Science.gov (United States)

    Guerrini, Edoardo; Grattieri, Matteo; Faggianelli, Alessio; Cristiani, Pierangela; Trasatti, Stefano

    2015-12-01

    Influence of PTFE in the external Gas Diffusion Layer (GDL) of open-air cathodes applied to membraneless microbial fuel cells (MFCs) is investigated in this work. Electrochemical measurements on cathodes with different PTFE contents (200%, 100%, 80% and 60%) were carried out to characterize cathodic oxygen reduction reaction, to study the reaction kinetics. It is demonstrated that ORR is not under diffusion-limiting conditions in the tested systems. Based on cyclic voltammetry, an increase of the cathodic electrochemical active area took place with the decrease of PTFE content. This was not directly related to MFC productivity, but to the cathode wettability and the biocathode development. Low electrodic interface resistances (from 1 to 1.5 Ω at the start, to near 0.1 Ω at day 61) indicated a negligible ohmic drop. A decrease of the Tafel slopes from 120 to 80 mV during productive periods of MFCs followed the biological activity in the whole MFC system. A high PTFE content in the cathode showed a detrimental effect on the MFC productivity, acting as an inhibitor of ORR electrocatalysis in the triple contact zone.

  17. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.

    2010-11-04

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  18. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    International Nuclear Information System (INIS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-01-01

    Highlights: • The screened M-G structures are very thermodynamically stable, and the stability is even higher than that of the corresponding bulk metal surfaces. • The binding energies of ORR intermediates suggest that they are not linear dependence, which are different form the cases found on some metal-based catalysts. • The Au-, Co-, and Ag-G structures could be used as the ORR catalysts. - Abstract: Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  19. Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

    Science.gov (United States)

    Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

    2018-06-26

    It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

  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. Co- and defect-rich carbon nanofiber films as a highly efficient electrocatalyst for oxygen reduction

    Science.gov (United States)

    Kim, Il To; Song, Myeong Jun; Shin, Seoyoon; Shin, Moo Whan

    2018-03-01

    Many efforts are continuously devoted to developing high-efficiency, low-cost, and highly scalable oxygen reduction reaction (ORR) electrocatalysts to replace precious metal catalysts. Herein, we successfully synthesize Co- and defect-rich carbon nanofibers (CNFs) using an efficient heat treatment approach involving the pyrolysis of electrospun fibers at 370 °C under air. The heat treatment process produces Co-decorated CNFs with a high Co mass ratio, enriched pyridinic N, Co-pyridinic Nx clusters, and defect-rich carbon structures. The synergistic effects from composition and structural changes in the designed material increase the number of catalytically active sites for the ORR in an alkaline solution. The prepared Co- and defect-rich CNFs exhibit excellent ORR activities with a high ORR onset potential (0.954 V vs. RHE), a large reduction current density (4.426 mA cm-2 at 0.40 V), and a nearly four-electron pathway. The catalyst also exhibits a better long-term durability than commercial Pt/C catalysts. This study provides a novel hybrid material as an efficient ORR catalyst and important insight into the design strategy for CNF-based hybrid materials as electrochemical electrodes.

  2. Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

    Science.gov (United States)

    Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

    2014-12-01

    Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

  3. S- and N-Doped Graphene Nanomaterials for the Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Luis Miguel Rivera

    2017-09-01

    Full Text Available In the current work, heteroatom-doped graphene materials containing different atomic ratios of nitrogen and sulphur were employed as electrocatalysts for the oxygen reduction reaction (ORR in acidic and alkaline media. To this end, the hydrothermal route and different chemical reducing agents were employed to synthesize the catalytic materials. The physicochemical characterization of the catalysts was performed by several techniques, such as X-ray diffraction, Raman spectroscopy and elemental analysis; meanwhile, the electrochemical performance of the materials toward the ORR was analyzed by linear sweep voltammetry (LSV, rotating disk electrode (RDE and rotating ring-disk electrode (RRDE techniques. The main results indicate that the ORR using heteroatom-doped graphene is a direct four-electron pathway, for which the catalytic activity is higher in alkaline than in acidic media. Indeed, a change of the reaction mechanism was observed with the insertion of N into the graphenic network, by the rate determining step changes from the first electrochemical step (formation of adsorbed OOH on glassy carbon to the removal of adsorbed O (Oad from the N-graphene surface. Moreover, the addition of sulphur atoms into the N-graphene structure increases the catalytic activity toward the ORR, as the desorption of Oad is accelerated.

  4. Investigation of Au-Pt/C electro-catalysts for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Lin Rui; Zhang Haiyan; Zhao Tiantian; Cao Chunhui; Yang Daijun; Ma Jianxin

    2012-01-01

    Highlights: ► Au-Pt core shell catalyst. ► Seed-mediated growth method. ► Au-Pt (2:4)/C best activity toward ORR. ► Four-electron pathway in acid solution. ► Single cell performance. - Abstract: Carbon-supported Au-Pt core shell nano-structured catalysts were synthesized by the seed-mediated growth method. The nano-structured catalysts were characterized by UV–vis spectroscopy, X-ray photoelectron spectra (XPS) and transmission electron microscopy (TEM) techniques. The oxygen reduction reaction (ORR) activity of the Au-Pt/C was tested by means of linear sweep voltammetry (LSV) by employing rotating disk electrode (RDE). It revealed that Au-Pt (2:4)/C (atomic ratio) catalyst exhibited the best catalytic activity toward ORR. Au-Pt (2:4)/C proceeded by an approximately four-electron pathway in acid solution, through which molecular oxygen was directly reduced to water. The stability of Au-Pt (2:4)/C is tested by cyclic voltammetry for 500 cycles. The performance of the membrane electrode assembly (MEA) prepared by Au-Pt (2:4)/C as the cathode catalyst in a single proton exchange membrane fuel cell (PEMFC) generated a maximum power density of 479 mW cm −2 at 0.431 V using H 2 and O 2 at 80 °C.

  5. Theoretical predictions for hexagonal BN based nanomaterials as electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Lyalin, Andrey; Nakayama, Akira; Uosaki, Kohei; Taketsugu, Tetsuya

    2013-02-28

    The catalytic activity for the oxygen reduction reaction (ORR) of both the pristine and defect-possessing hexagonal boron nitride (h-BN) monolayer and H-terminated nanoribbon have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active by nitrogen doping. It is shown that the energetics of adsorption of O(2), O, OH, OOH, and H(2)O on N atom impurities in the h-BN monolayer (N(B)@h-BN) is quite similar to that known for a Pt(111) surface. The specific mechanism of destructive and cooperative adsorption of ORR intermediates on the surface point defects is discussed. It is demonstrated that accounting for entropy and zero-point energy (ZPE) corrections results in destabilization of the ORR intermediates adsorbed on N(B)@h-BN, while solvent effects lead to their stabilization. Therefore, entropy, ZPE and solvent effects partly cancel each other and have to be taken into account simultaneously. Analysis of the free energy changes along the ORR pathway allows us to suggest that a N-doped h-BN monolayer can demonstrate catalytic properties for the ORR under the condition that electron transport to the catalytically active center is provided.

  6. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

    Science.gov (United States)

    Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka; Li, Jingkun; Jia, Qingying; Stamatin, Serban; Harrington, George F; Lyth, Stephen Mathew; Krtil, Petr; Mukerjee, Sanjeev; Fonda, Emiliano; Jaouen, Frédéric

    2017-10-16

    Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN 4 C 12 , CoN 3 C 10,porp and CoN 2 C 5 . The O 2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O 2 -adsorption strength, we conclude that cobalt-based moieties bind O 2 too weakly for efficient O 2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

  7. Palladium nanoparticles/defective graphene composites as oxygen reduction electrocatalysts: A first-principles study

    KAUST Repository

    Liu, Xin

    2012-02-02

    The impact of graphene substrate-Pd nanoparticle interaction on the O, OH, and OOH adsorption that is directly related to the electrocatalytic performance of these composites in oxygen reduction reaction (ORR) has been investigated by first-principles-based calculations. The calculated binding energy of a Pd 13 nanoparticle on a single vacancy graphene is as high as -6.10 eV, owing to the hybridization between the dsp states of the Pd particles with the sp 2 dangling bonds at the defect sites. The strong interaction results in the averaged d-band center of the deposited Pd nanoparticles shifted away from the Fermi level from -1.02 to -1.45 eV. Doping the single vacancy graphene with B or N will further tune the average d-band center and also the activity of the composite toward O, OH, and OOH adsorption. The adsorption energies of O, OH, and OOH are reduced from -4.78, -4.38, and -1.56 eV on the freestanding Pd 13 nanoparticle to -4.57, -2.66, and -1.39 eV on Pd 13/single vacancy graphene composites, showing that the defective graphene substrate will not only stabilize the Pd nanoparticles but also reduce the adsorption energies of the O-containing species to the Pd particle, and so as the poisoning of the ORR active sites. © 2011 American Chemical Society.

  8. Polyaniline-Derived Ordered Mesoporous Carbon as an Efficient Electrocatalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Kai Wan

    2015-06-01

    Full Text Available Nitrogen-doped ordered mesoporous carbon was synthesized by using polyaniline as the carbon source and SBA-15 as the template. The microstructure, composition and electrochemical behavior were extensively investigated by the nitrogen sorption isotherm, X-ray photoelectron spectroscopy, cyclic voltammetry and rotating ring-disk electrode. It is found that the pyrolysis temperature yielded a considerable effect on the pore structure, elemental composition and chemical configuration. The pyrolysis temperature from 800 to 1100 °C yielded a volcano-shape relationship with both the specific surface area and the content of the nitrogen-activated carbon. Electrochemical tests showed that the electrocatalytic activity followed a similar volcano-shape relationship, and the carbon catalyst synthesized at 1000 °C yielded the best performance. The post-treatment in NH3 was found to further increase the specific surface area and to enhance the nitrogen doping, especially the edge-type nitrogen, which favored the oxygen reduction reaction in both acid and alkaline media. The above findings shed light on electrocatalysis and offer more strategies for the controllable synthesis of the doped carbon catalyst.

  9. Oxygen reduction at platimun/ionomer interface: effects of phase separation of ionomer

    Energy Technology Data Exchange (ETDEWEB)

    Chlistunoff, Jerzy [Los Alamos National Laboratory

    2008-01-01

    Oxygen reduction reaction (ORR) at the interface between platinum and recast ionomers (Nafion EW 1100 and 950 and 6F-40) was studied at different temperatures (20--80{sup o}C) and humidities (10--100%) employing smooth Pt and Pt-black-covered ultramicroelectrodes. ORR was strongly inhibited on smooth electrodes. The inhibition increased with the reduction time, temperature and humidity, but was absent for Nafion EW 1100 in contact with liquid water. It was attributed to the hydrophobic component of ionomer blocking both active sites and oxygen transport. It was postulated that the dynamic changes in interfacial phase separation of ionomer are facilitated by the attractive interactions between the hydrophobic component of ionomer and bare platinum and between oxide-covered Pt and the hydrophilic component of ionomer. These interactions were also proposed to be responsible for the differences in ORR voltammetry for films prepared and equilibrated under different conditions. The decrease in ORR inhibition, Nafion EW 950> Nafion EW 1100> 6F-40, was correlated with physical and molecular properties of the ionomers. The lack of inhibition for Pt-black-covered electrodes was attributed to the more random distribution of ionomer chains and the high activation barriers for the ionomer restructuring at rough interfaces.

  10. Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

    Science.gov (United States)

    Miller, R. O.

    1975-01-01

    With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

  11. Oxygen reduction reaction of Pt–In alloy: Combined theoretical and experimental investigations

    International Nuclear Information System (INIS)

    Pašti, Igor A.; Gavrilov, Nemanja M.; Baljozović, Miloš; Mitrić, Miodrag; Mentus, Slavko V.

    2013-01-01

    Graphical abstract: Upon DFT prediction of improved electrocatalytic activity of Pt–In alloys toward ORR, the alloy Pt-10 at% In was synthesized on glassy carbon disc, simultaneously with pure Pt reference catalyst. Improved catalytic activity of the alloy was evidenced by voltammetry on RDE in 0.1 mol dm −3 KOH solution. -- Highlights: •The adsorption of O atoms on Pt–In alloys model surfaces was investigated by DFT. •The improvement of catalytic activity toward ORR was predicted by DFT. •Pt-10 at% In alloy was synthesized on glassy carbon disk surface. •By voltammetry on RDE improvement of activity toward ORR was evidenced. -- Abstract: By means of the density functional theory (DFT) calculations, using the adsorption energy of oxygen on single crystal surfaces as criterion, it was predicted that the alloying of Pt with In should improve kinetics of oxygen reduction reaction (ORR). To prove this, the Pt–In alloy having nominal composition Pt 9 In was synthesized by heating H 2 PtCl 6 –InCl 3 mixture in hydrogen stream. The XRD characterization confirmed that Pt–In alloy was formed. The electrochemical measurements by rotating disk technique in alkaline 0.1 mol dm −3 KOH solution evidenced faster ORR kinetics for factor 2.6 relative to the one on pure platinum. This offers the possibility of searching for new ORR electrocatalysts by alloying platinum with p-elements

  12. High Oxygen Reduction Reaction Performances of Cathode Materials Combining Polyoxometalates, Coordination Complexes, and Carboneous Supports.

    Science.gov (United States)

    Zhang, Shuangshuang; Oms, Olivier; Hao, Long; Liu, Rongji; Wang, Meng; Zhang, Yaqin; He, Hong-Yan; Dolbecq, Anne; Marrot, Jérôme; Keita, Bineta; Zhi, Linjie; Mialane, Pierre; Li, Bin; Zhang, Guangjin

    2017-11-08

    A series of carbonaceous-supported precious-metal-free polyoxometalate (POM)-based composites which can be easily synthesized on a large scale was shown to act as efficient cathode materials for the oxygen reduction reaction (ORR) in neutral or basic media via a four-electron mechanism with high durability. Moreover, exploiting the versatility of the considered system, its activity was optimized by the judicious choice of the 3d metals incorporated in the {(PW 9 ) 2 M 7 } (M = Co, Ni) POM core, the POM counterions and the support (thermalized triazine-based frameworks (TTFs), fluorine-doped TTF (TTF-F), reduced graphene oxide, or carbon Vulcan XC-72. In particular, for {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F, the overpotential required to drive the ORR compared well with those of Pt/C. This outstanding ORR electrocatalytic activity is linked with two synergistic effects due to the binary combination of the Cu and Ni centers and the strong interaction between the POM molecules and the porous and highly conducting TTF-F framework. To our knowledge, {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F represents the first example of POM-based noble-metal-free ORR electrocatalyst possessing both comparable ORR electrocatalytic activity and much higher stability than that of Pt/C in neutral medium.

  13. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.; Mutoro, Eva; Ahn, Sung-Jin; la O’ , Gerardo Jose; Leonard, Donovan N.; Borisevich, Albina; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

    2010-01-01

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  14. Synthesis of 2D Nitrogen-Doped Mesoporous Carbon Catalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Zhipeng Yu

    2017-02-01

    Full Text Available 2D nitrogen-doped mesoporous carbon (NMC is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR. The effect of the synthesis conditions on the silica template and carbon is extensively investigated. In this work, we employ dual templates—viz. graphene oxide and triblock copolymer F127—to control the textural features of a 2D silica film. The silica is then used as a template to direct the synthesis of a 2D nitrogen-doped mesoporous carbon. The resultant nitrogen-doped mesoporous carbon is characterized by transmission electron microscopy (TEM, nitrogen ad/desorption isotherms, X-ray photoelectron spectroscopy (XPS, cyclic voltammetry (CV, and rotating disk electrode measurements (RDE. The electrochemical test reveals that the obtained 2D-film carbon catalyst yields a highly electrochemically active surface area and superior electrocatalytic activity for the ORR compared to the 3D-particle. The superior activity can be firstly attributed to the difference in the specific surface area of the two catalysts. More importantly, the 2D-film morphology makes more active sites accessible to the reactive species, resulting in a much higher utilization efficiency and consequently better activity. Finally, it is noted that all the carbon catalysts exhibit a higher ORR activity than a commercial Pt catalyst, and are promising for use in fuel cells.

  15. Recent developments of nano-structured materials as the catalysts for oxygen reduction reaction

    Science.gov (United States)

    Kang, SungYeon; Kim, HuiJung; Chung, Yong-Ho

    2018-04-01

    Developments of high efficient materials for electrocatalyst are significant topics of numerous researches since a few decades. Recent global interests related with energy conversion and storage lead to the expansion of efforts to find cost-effective catalysts that can substitute conventional catalytic materials. Especially, in the field of fuel cell, novel materials for oxygen reduction reaction (ORR) have been noticed to overcome disadvantages of conventional platinum-based catalysts. Various approaching methods have been attempted to achieve low cost and high electrochemical activity comparable with Pt-based catalysts, including reducing Pt consumption by the formation of hybrid materials, Pt-based alloys, and not-Pt metal or carbon based materials. To enhance catalytic performance and stability, numerous methods such as structural modifications and complex formations with other functional materials are proposed, and they are basically based on well-defined and well-ordered catalytic active sites by exquisite control at nanoscale. In this review, we highlight the development of nano-structured catalytic materials for ORR based on recent findings, and discuss about an outlook for the direction of future researches.

  16. 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....

  17. Highly dispersed TaOx nanoparticles prepared by electrodeposition as oxygen reduction electrocatalysts for polymer electrolyte fuel cells

    KAUST Repository

    Seo, Jeongsuk; Zhao, Lan; Cha, Dong Kyu; Takanabe, Kazuhiro; Katayama, Masao; Kubota, Jun; Domen, Kazunari

    2013-01-01

    for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFCs). Electrodeposition conditions of Ta complexes and subsequent various heat treatments for the deposited TaOx were examined for the best performance of the ORR. TaOx particles

  18. Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

    KAUST Repository

    Seo, J.

    2013-11-13

    The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine oxide nanoparticles exhibited a distinctively high onset potential different from that of the bulky oxide particles.

  19. Kinetics of sodium borohydride direct oxidation and oxygen reduction in sodium hydroxide electrolyte - Part II. O-2 reduction

    Czech Academy of Sciences Publication Activity Database

    Chatenet, M.; Micoud, F.; Roche, I.; Chainet, E.; Vondrák, Jiří

    2006-01-01

    Roč. 51, č. 25 (2006), s. 5452-5458 ISSN 0013-4686 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction selectivity * platinum * silver Subject RIV: CA - Inorganic Chemistry Impact factor: 2.955, year: 2006

  20. Heterogeneous electron transfer and oxygen reduction reaction at nanostructured iron(II) phthalocyanine and its MWCNTs nanocomposites

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-05-01

    Full Text Available species within the porous layers of MWCNTs. Electron transfer process is much easier at the EPPGE-MWCNT and EPPGE-MWCNT-nanoFePc compared to the other electrodes. The best response for oxygen reduction reaction was at the EPPGE-MWCNTnanoFePc, yielding a 4...

  1. Enhancement of oxygen reduction at Fe tetrapyridyl porphyrin by pyridyl-N coordination to transition metal ions

    International Nuclear Information System (INIS)

    Maruyama, Jun; Baier, Claudia; Wolfschmidt, Holger; Bele, Petra; Stimming, Ulrich

    2012-01-01

    One of the promising candidates as noble-metal-free electrode catalysts for polymer electrolyte fuel cells (PEFCs) is a carbon material with nitrogen atoms coordinating iron ions embedded on the surface (Fe-N x moiety) as the active site, although the activity is insufficient compared to conventional platinum-based electrocatalysts. In order to obtain fundamental information on the activity enhancement, a simple model of the Fe-N x active site was formed by adsorbing 5,10,15,20-Tetrakis(4-pyridyl)-21H,23H-porphine iron(III) chloride (FeTPyPCl) on the basal plane of highly oriented pyrolytic graphite (HOPG), and cathodic oxygen reduction was investigated on the surface in 0.1 M HClO 4 . The catalytic activity for oxygen reduction was enhanced by loading transition metal ions (Co 2+ , Ni 2+ , Cu 2+ ) together with FeTPyPCl. The X-ray photoelectron spectrum of the surface suggested that the metal was coordinated by the pyridine-N. The enhancement effect of the transition metals was supported by two different measurements: oxygen reduction at HOPG in 0.1 M HClO 4 dissolving FeTPyPCl and the metal ions; oxygen reduction in 0.1 M HClO 4 at the subsequently well-rinsed and dried HOPG. The ultraviolet–visible spectrum for the solution also suggested the coordination between the pyridyl-N and the metal ions. The oxygen reduction enhancement was attributed to the electronic interaction between the additional transition metal and the Fe center of the porphyrin through the coordination bonds. These results implied that the improvement of the activity of the noble-metal-free catalyst would be possible by the proper introduction of the transition metal ions around the active site.

  2. Evaluation of reaction selectivity at various Pt/C electrocatalysts using a porous microelectrode in the presence of methanol and oxygen

    International Nuclear Information System (INIS)

    Shironita, Sayoko; Zhang, Weiqi; Sakai, Tsukasa; Umeda, Minoru

    2014-01-01

    Pt is most useful metal for various electrochemical reactions as an electrocatalyst. In a direct methanol fuel cell, Pt performs a catalytic activity for both the methanol oxidation reaction and oxygen reduction reaction; therefore, a Pt-based catalyst is used as an anode and a cathode. For the coexistence of methanol and oxygen due to methanol crossover through an electrolyte membrane during the cell operation, the direct methanol fuel cell performance decreases. However, if a higher selective reaction electrocatalyst can be developed, the cell performance will not be suppressed. In this study, the reaction selectivities of seven types of Pt supported on carbon (Pt/C) electrocatalysts were evaluated using a porous microelectrode in the presence of methanol and oxygen. As a result, some Pt/C catalysts showed a methanol oxidation selectivity, while the other catalysts showed an oxygen reduction selectivity. It was found that the percentage of edge-atom in the Pt particle is related to the methanol oxidation selectivity or the oxygen reduction selectivity. Moreover, each current density decreases with the increasing chemical shift in the Pt binding energy

  3. 1995 world methanol conference

    International Nuclear Information System (INIS)

    Anon.

    1995-01-01

    The 20 papers contained in this volume deal with the global markets for methanol, the production of MTBE, integrating methanol production into a coal-to-SNG complex, production of methanol from natural gas, catalysts for methanol production from various synthesis gases, combined cycle power plants using methanol as fuel, and economics of the methanol industry. All papers have been processed for inclusion on the data base

  4. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department

    2017-09-26

    To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.

  5. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk

    2014-12-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  6. Effect of pH and Water Structure on the Oxygen Reduction Reaction on platinum electrodes

    International Nuclear Information System (INIS)

    Briega-Martos, Valentín; Herrero, Enrique; Feliu, Juan M.

    2017-01-01

    The oxygen reduction reaction (ORR) at different pH values has been studied at platinum single crystal electrodes using the hanging meniscus rotating disk electrode (HMRDE) configuration. The use of NaF/HClO 4 mixtures allows investigating the reaction up to pH = 6 in solutions with enough buffering capacity and in the absence of anion specific adsorption. The analysis of the currents shows that the kinetic current density measured at 0.85 V for the Pt(111) electrode follows a volcano curve with the maximum located around pH = 9. This maximum activity for pH = 9 can be related to the effects of the electrode charge and/or water structure in the ORR. On the other hand, the catalytic activity for the other basal planes shows a monotonic behavior with a small dependence of the activity with pH. For stepped surfaces with (111) terraces, the behavior with pH changes gets closer to that of the Pt(111) surface as the terrace length increases. Additionally, the ORR curves show a dependence of the limiting diffusion current with pH. It is observed that the limiting current density diminishes as the pH increases in a potential region where hydrogen peroxide is readily reduced. These results suggest the existence of a bifurcation point in the mechanism previous to peroxide formation, in which OOH • is proposed as the bifurcation intermediate. The reduction of OOH • requires proton addition and would be more difficult at neutral pH values, justifying the diminution of the limiting currents.

  7. Nitrogen-doped graphene-wrapped iron nanofragments for high-performance oxygen reduction electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jang Yeol [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Kim, Na Young [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of); Shin, Dong Yun [Chungbuk National University, Department of Environmental Engineering (Korea, Republic of); Park, Hee-Young [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of); Lee, Sang-Soo [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Joon Kwon, S. [Korea Institute of Science and Technology, Nanophotonics Research Center (Korea, Republic of); Lim, Dong-Hee [Chungbuk National University, Department of Environmental Engineering (Korea, Republic of); Bong, Ki Wan [Korea University, Department of Chemical and Biological Engineering (Korea, Republic of); Son, Jeong Gon, E-mail: jgson@kist.re.kr [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Kim, Jin Young, E-mail: jinykim@kist.re.kr [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of)

    2017-03-15

    Transition metals, such as iron (Fe)- or cobalt (Co)-based nanomaterials, are promising electrocatalysts for oxygen reduction reactions (ORR) in fuel cells due to their high theoretical activity and low cost. However, a major challenge to using these metals in place of precious metal catalysts for ORR is their low efficiency and poor stability, thus new concepts and strategies should be needed to address this issue. Here, we report a hybrid aciniform nanostructures of Fe nanofragments embedded in thin nitrogen (N)-doped graphene (Fe@N-G) layers via a heat treatment of graphene oxide-wrapped iron oxide (Fe{sub 2}O{sub 3}) microparticles with melamine. The heat treatment leads to transformation of Fe{sub 2}O{sub 3} microparticles to nanosized zero-valent Fe fragments and formation of core-shell structures of Fe nanofragments and N-doped graphene layers. Thin N-doped graphene layers massively promote electron transfer from the encapsulated metals to the graphene surface, which efficiently optimizes the electronic structure of the graphene surface and thereby triggers ORR activity at the graphene surface. With the synergistic effect arising from the N-doped graphene and Fe nanoparticles with porous aciniform nanostructures, the Fe@N-G hybrid catalyst exhibits high catalytic activity, which was evidenced by high E{sub 1/2} of 0.82 V, onset potential of 0.93 V, and limiting current density of 4.8 mA cm{sup −2} indicating 4-electron ORR, and even exceeds the catalytic stability of the commercial Pt catalyst.

  8. Lanthanides-based graphene catalysts for high performance hydrogen evolution and oxygen reduction

    International Nuclear Information System (INIS)

    Shinde, S.S.; Sami, Abdul; Lee, Jung-Ho

    2016-01-01

    Highlights: • Facile, scalable in-situ synthesis of lanthanide (La, Eu, Yb) doped graphene frameworks. • Efficient electrocatalytic performance towards HER and ORR. • Eu-Gr hybrid shows HER performance; onset & overpotential (81 & 160 mV), & Tafel slope (52 mV dec −1 ). • Eu-Gr exhibits superior activity of ORR; onset potential (0.92 V), electron transfer number (4.03). • Excellent long-term stability in HER and ORR, comparable to those of commercial Pt/C catalysts. - Abstract: The design of efficient electrocatalysts for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) has received enormous consideration due to their effectiveness in modern renewable energy technologies such as fuel cells, electrolyzers, and metal–air batteries. Herein, we present a facile method to fabricate lanthanides (L = La, Eu, Yb)-doped graphene materials as catalyst for the HER and ORR that show desirable electrocatalytic activities as well as long-term stability. The Eu-graphene hybrid has showed unbeatable HER performance such as small values of onset potential (81 mV), overpotential (160 mV), and Tafel slope (52 mV dec −1 ), along with a high exchange current density (7.55 × 10 −6 A cm −2 ). The L-graphenes also exhibit superior electrocatalytic activity for ORR, including small Tafel slopes (96, 66, and 105 mV dec −1 for La-Gr, Eu-Gr, and Yb-Gr, respectively), positive onset potential (∼0.83–0.92 V), high electron transfer numbers (∼3.84–4.03), and excellent enduring strength, analogous to those of viable Pt/C catalysts. The excellent electrocatalytic performance is attributed to the synergistic effect of abundant edges and doping sites, high electrical conductivity, large active surface areas and fast charge transfer; which renders lanthanide-based graphene hybrids as potentially great candidate for energy conversion systems.

  9. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk; Anjum, Dalaver H.; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2014-01-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  10. New highly active oxygen reduction electrode for PEM fuel cell and Zn/air battery applications (NORA). Final report

    Energy Technology Data Exchange (ETDEWEB)

    Thiele, D.; Zuettel, A.

    2008-04-15

    This illustrated final report for the Swiss Federal Office of Energy (SFOE) presents the results of a project concerning a new, highly active oxygen reduction electrode for PEM fuel cell and zinc/air battery applications. The goal of this project was, according to the authors, to increase the efficiency of the oxygen reduction reaction by lowering the activation polarisation through the right choice of catalyst and by lowering the concentration polarisation. In this work, carbon nanotubes are used as support material. The use of these nanotubes grown on perovskites is discussed. Theoretical considerations regarding activation polarisation are discussed and alternatives to the use of platinum are examined. The results of experiments carried out are presented in graphical and tabular form. The paper is completed with a comprehensive list of references.

  11. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)

    2017-09-26

    It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability

  12. Electrocatalytic activity of silver decorated ceria microspheres for the oxygen reduction reaction and their application in aluminium-air batteries.

    Science.gov (United States)

    Sun, Shanshan; Xue, Yejian; Wang, Qin; Li, Shihua; Huang, Heran; Miao, He; Liu, Zhaoping

    2017-07-11

    Nanosheet-constructing porous CeO 2 microspheres with silver nanoparticles anchored on the surface were developed as a highly efficient oxygen reduction reaction (ORR) catalyst. The aluminum-air batteries applying Ag-CeO 2 as the ORR catalyst exhibit a high output power density and low degradation rate of 345 mW cm -2 and 2.6% per 100 h, respectively.

  13. Graphene layer encapsulated metal nanoparticles as a new type of non-precious metal catalysts for oxygen reduction

    DEFF Research Database (Denmark)

    Hu, Yang; Zhong, Lijie; Jensen, Jens Oluf

    2016-01-01

    Cheap and efficient non-precious metal catalysts for oxygen reduction have been a focus of research in the field of low-temperature fuel cells. This review is devoted to a brief summary of the recent work on a new type of catalysts, i.e., the graphene layer encapsulated metal nanoparticles....... The discussion is focused on the synthesis, structure, mechanism, performance, and further research....

  14. Durability of carbon-supported manganese oxide nanoparticles for the oxygen reduction reaction (ORR) in alkaline medium

    Czech Academy of Sciences Publication Activity Database

    Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

    2008-01-01

    Roč. 38, č. 9 (2008), s. 1195-1201 ISSN 0021-891X R&D Projects: GA AV ČR KJB4813302; GA ČR GA104/02/0731 Grant - others:CNRS(FR) 18105 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction * rotating ring-disc electrode * carbon-supported manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.540, year: 2008

  15. Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

    2015-01-01

    Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter , which is vital in high performance fuel cells, batteries and nanodevices.

  16. Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

    Science.gov (United States)

    Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

    2010-07-20

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

  17. Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells

    KAUST Repository

    la O', Gerardo Jose; Ahn, Sung-Jin; Crumlin, Ethan; Orikasa, Yuki; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

    2010-01-01

    Figure Presented The active ingredient: La0.8Sr 0.2CoO3-δ (LSC) epitaxial thin films are prepared on (001 )-oriented yttria-stabilized zirconia (YSZ) single crystals with a gadolinium-doped ceria (GDC) buffer layer (see picture). The LSC epitaxial films exhibit better oxygen reduction kinetics than bulk LSC. The enhanced activity is attributed in part to higher oxygen nonstoichiometry. © 2010 Wiley-VCH Verlag GmbH & Co. KCaA, Weinheim.

  18. Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells

    KAUST Repository

    la O', Gerardo Jose

    2010-06-22

    Figure Presented The active ingredient: La0.8Sr 0.2CoO3-δ (LSC) epitaxial thin films are prepared on (001 )-oriented yttria-stabilized zirconia (YSZ) single crystals with a gadolinium-doped ceria (GDC) buffer layer (see picture). The LSC epitaxial films exhibit better oxygen reduction kinetics than bulk LSC. The enhanced activity is attributed in part to higher oxygen nonstoichiometry. © 2010 Wiley-VCH Verlag GmbH & Co. KCaA, Weinheim.

  19. One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

    KAUST Repository

    Varga, Tamás

    2018-03-14

    Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close to the ideal particle size for oxygen reduction reaction (ORR) were formed, i.e., with diameter of 3–4 nm (500 and 600 °C) and 6 nm (700 °C). X-ray photoelectron spectroscopy confirmed the successful introduction of both pyridinic and pyrrolic type nitrogen moieties into the graphene layers, which indicates a strong interaction between the nanoparticles and the graphene layers. The electrocatalytic activity of glassy carbon electrodes (GCE) modified with the synthesized Pt/NG samples for oxygen reduction was compared to that of a platinum/carbon black catalyst modified electrode in acidic and alkaline media. Based on the measured limiting current densities and calculated electron transfer number, the highest activity was measured in acidic and alkaline media on the samples annealed at 600 and 700 °C, respectively.

  20. A proposed agglomerate model for oxygen reduction in the catalyst layer of proton exchange membrane fuel cells

    International Nuclear Information System (INIS)

    Zhang, Xiaoxian; Gao, Yuan; Ostadi, Hossein; Jiang, Kyle; Chen, Rui

    2014-01-01

    Highlights: • We developed a new agglomerate model to describe oxygen reduction reaction. • We showed how to calculate the model parameters from catalyst layer structure. • We verified the agglomerate model. - Abstract: Oxygen diffusion and reduction in the catalyst layer of PEM fuel cell is an important process in fuel cell modelling, but models able to link the reduction rate to catalyst-layer structure are lack; this paper makes such an effort. We first link the average reduction rate over the agglomerate within a catalyst layer to a probability that an oxygen molecule, which is initially on the agglomerate surface, will enter and remain in the agglomerate at any time in the absence of any electrochemical reaction. We then propose a method to directly calculate distribution function of this probability and apply it to two catalyst layers with contrasting structures. A formula is proposed to describe these calculated distribution functions, from which the agglomerate model is derived. The model has two parameters and both can be independently calculated from catalyst layer structures. We verify the model by first showing that it is an improvement and able to reproduce what the spherical model describes, and then testing it against the average oxygen reductions directly calculated from pore-scale simulations of oxygen diffusion and reaction in the two catalyst layers. The proposed model is simple, but significant as it links the average oxygen reduction to catalyst layer structures, and its two parameters can be directly calculated rather than by calibration

  1. Influence of Chemical and Physical Properties of Activated Carbon Powders on Oxygen Reduction and Microbial Fuel Cell Performance

    KAUST Repository

    Watson, Valerie J.

    2013-06-03

    Commercially available activated carbon (AC) powders made from different precursor materials (coal, peat, coconut shell, hardwood, and phenolic resin) were electrochemically evaluated as oxygen reduction catalysts and tested as cathode catalysts in microbial fuel cells (MFCs). AC powders were characterized in terms of surface chemistry and porosity, and their kinetic activities were compared to carbon black and platinum catalysts in rotating disk electrode (RDE) tests. Cathodes using the coal-derived AC had the highest power densities in MFCs (1620 ± 10 mW m-2). Peat-based AC performed similarly in MFC tests (1610 ± 100 mW m-2) and had the best catalyst performance, with an onset potential of Eonset = 0.17 V, and n = 3.6 electrons used for oxygen reduction. Hardwood based AC had the highest number of acidic surface functional groups and the poorest performance in MFC and catalysis tests (630 ± 10 mW m-2, Eonset = -0.01 V, n = 2.1). There was an inverse relationship between onset potential and quantity of strong acid (pKa < 8) functional groups, and a larger fraction of microporosity was negatively correlated with power production in MFCs. Surface area alone was a poor predictor of catalyst performance, and a high quantity of acidic surface functional groups was determined to be detrimental to oxygen reduction and cathode performance. © 2013 American Chemical Society.

  2. Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

    Science.gov (United States)

    O'Laoire, Cormac Micheal

    Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li

  3. Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

    DEFF Research Database (Denmark)

    Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf

    2018-01-01

    Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at lo...

  4. Facile Synthesis of N-Doped Graphene-Like Carbon Nanoflakes as Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction

    Science.gov (United States)

    Gu, Daguo; Zhou, Yao; Ma, Ruguang; Wang, Fangfang; Liu, Qian; Wang, Jiacheng

    2018-06-01

    A series of N-doped carbon materials (NCs) were synthesized by using biomass citric acid and dicyandiamide as renewable raw materials via a facile one-step pyrolysis method. The characterization of microstructural features shows that the NCs samples are composed of few-layered graphene-like nanoflakes with controlled in situ N doping, which is attributed to the confined pyrolysis of citric acid within the interlayers of the dicyandiamide-derived g-C3N4 with high nitrogen contents. Evidently, the pore volumes of the NCs increased with the increasing content of dicyandiamide in the precursor. Among these samples, the NCs nanoflakes prepared with the citric acid/dicyandiamide mass ratio of 1:6, NC-6, show the highest N content of 6.2 at%, in which pyridinic and graphitic N groups are predominant. Compared to the commercial Pt/C catalyst, the as-prepared NC-6 exhibits a small negative shift of 66 mV at the half-wave potential, demonstrating excellent electrocatalytic activity in the oxygen reduction reaction. Moreover, NC-6 also shows better long-term stability and resistance to methanol crossover compared to Pt/C. The efficient and stable performance are attributed to the graphene-like microstructure and high content of pyridinic and graphitic doped nitrogen in the sample, which creates more active sites as well as facilitating charge transfer due to the close four-electron reaction pathway. The superior electrocatalytic activity coupled with the facile synthetic method presents a new pathway to cost-effective electrocatalysts for practical fuel cells or metal-air batteries.

  5. Template-free synthesis of three-dimensional nanoporous N-doped graphene for high performance fuel cell oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Tang, Sheng; Zhou, Xuejun; Xu, Nengneng; Bai, Zhengyu; Qiao, Jinli; Zhang, Jiujun

    2016-01-01

    Highlights: • 3-D porous N-doped graphene was prepared using one-step silica template-free method. • High specific surface area of 920 m 2 g −1 was achieved for 3-D porous N-doped graphene. • Much higher ORR activity was observed for N-doped graphene than S-doped one in 0.1 M KOH. • The as-prepared catalyst gave a peak power density of 275 mW cm −2 as zinc–air battery cathode. - Abstract: Three-dimensional nanoporous nitrogen-doped graphene (3D-PNG) has been synthesized through a facial one-step synthesis method without additional silica template. The as-prepared 3D-PNGwas used as an electrocatalyst for the oxygen reduction reaction (ORR), which shows excellent electrochemistry performance, demonstrated by half-cell electrochemical evaluation in 0.1 M KOH including prominent ORR activity, four electron-selectivity and remarkable methanol poisoning stability compared to commercial 20%Pt/C catalyst. The physical and surface properties of 3D-PNG catalyst were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and BET surface area analysis. The experiments show that 3D-PNG catalyst possesses super-large specific surface area reaching 920 m 2 g −1 , which is superior to our most recently reported 3D-PNG synthesized by silica template (670 m 2 g −1 ) and other doped graphene catalysts in literature. When used for constructing a zinc–air battery cathode, such an 3D-PNG catalyst can give a discharge peak power density of 275 mW cm −2 . All the results announce a unique procedure to product high-efficiency graphene-based non-noble metal catalyst materials for electrochemical energy devices including both fuel cells and metal–air batteries.

  6. Reactive template synthesis of nitrogen-doped graphene-like carbon nanosheets derived from hydroxypropyl methylcellulose and dicyandiamide as efficient oxygen reduction electrocatalysts

    Science.gov (United States)

    Hu, Chun; Zhou, Yao; Ma, Ruguang; Liu, Qian; Wang, Jiacheng

    2017-03-01

    Oxygen reduction reaction (ORR) plays a dominant role in proton exchange membrane fuel cells (PEMFCs). Thus, the design and preparation of efficient ORR electrocatalysts is of high importance. In this work, we successfully prepared a series of nitrogen-doped graphene-like carbon nanosheets (NCNSs) with large pore volumes of up to 1.244 cm3 g-1 and high level of N dopants (5.3-6.8 at%) via a one-step, in-situ reactive template strategy by co-pyrolysis of hydroxypropyl methylcellulose (HPMC) and dicyandiamide (DICY) as the precursors at 1000 °C. The DICY-derived graphitic carbon nitride (g-C3N4) nanosheets could act as the hard template for the confined growth of 2D carbon nanosheets, and the further increase in the pyrolysis temperature could directly remove off the g-C3N4 template by complete decomposition and simultaneously dope N atoms within the carbon nanosheets. The pyridinic and graphitic nitrogen groups are dominant among various N functional groups in the NCNSs. The NCNS_1:10 prepared with the HPMC/DICY mass ratio of 1/10 can be used as the metal-free ORR electrocatalysts with optimal activity (onset potential: -0.1 V vs. SCE; limiting current density: 4.8 mA cm-2) in O2-saturated 0.1 M KOH electrolyte among the NCNSs. Moreover, the NCNS_1:10 demonstrates a dominant four-electron reduction process, as well as excellent long-term operation stability and outstanding methanol crossover resistance. The excellent ORR activity of the NCNS_1:10 should be mainly owing to high contents of pyridinic and graphitic N dopants, large pore volume, hierarchical structures, and microstructural defects.

  7. Incorporation of Pt, Ru and Pt-Ru nanoparticles into ordered mesoporous carbons for efficient oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Stojmenović, Marija; Momčilović, Milan; Gavrilov, Nemanja; Pašti, Igor A.; Mentus, Slavko; Jokić, Bojan; Babić, Biljana

    2015-01-01

    Ordered mesoporous carbon, volume-doped up to 3 w.% with Pt, Ru and Pt-Ru nanoparticles was synthesized by evaporation-induced self-assembly method, under acidic conditions. The content of incorporated metal was determined by EDX analysis. The X-ray diffractometry confirmed the existence of highly dispersed metallic phases in doped samples. Specific surface area was determined by N 2 -physisorption measurements to range between 452 and 545 m 2 g −1 . Raman spectroscopy of investigated materials indicated highly disordered carbon structure with crystallite sizes around 1.4 nm. In a form of thin-layer electrode on glassy carbon support, in 0.1 M KOH solution, the prepared materials displayed high activity toward oxygen reduction reaction (ORR) in alkaline media, with onset potentials more positive than −0.10 V vs. SCE. The kinetics of O 2 reduction was found to be affected by both the specific surface area and the concentration of metal dopants. The ethanol tolerance of (Pt, Ru)-doped OMCs was found to be higher than that of common Pt/C ORR catalysts. Presented study provides a new route for the synthesis of active and selective ORR catalysts in alkaline media, being competitive with, or superior to, the existing ones in terms of performance and price

  8. Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

    Science.gov (United States)

    Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

    2015-12-01

    Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

  9. Development of PdM (M = Ni, Cu, Ag) electrocatalysts for oxygen reduction reaction in alkaline medium in the absence and presence of alcohol

    International Nuclear Information System (INIS)

    Isidoro, Roberta Alvarenga

    2015-01-01

    Pd/C, Pd Cu/C, Pd Ni/C and Pd Ag/C electrocatalysts were produced by microwave method to be used as cathode in alkaline fuel cell in the absence and presence of alcohol. This method showed to be effective for the materials production, the particles exhibited good dispersion in carbon support and it produced electrocatalysts with a particle size of about 3.5 nm, according to XRD and TEM analysis. In cyclic voltammetry is observed that Pd Cu/C and Pd Ni/C electrocatalysts has higher active area with higher amount of Cu and Ni, respectively. Rotating ring disk analysis in the electrocatalysts showed that the amount of peroxide produced was at most 4%. This data is similar to Koutecky-Levich analysis, once for both the ORR occurs via 4 electrons. Materials stability analysis showed that they kept or improve performance in ORR, comparing the data before and after 1000 voltammetric cycles. Tolerance tests in methanol and ethanol were performed in a half cell in all electrocatalysts compositions. In presence of methanol and ethanol the compositions 50:50, to all materials studied, showed less influence in the presence of alcohol in ORR linear scan. In alkaline fuel cell Pd Ag/C 70:30 showed better performance for ORR in presence of methanol and Pd Ni/C 70:30 showed better performance for ORR in ethanol presence. (author)

  10. 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

  11. Optimization of the Pd-Fe-Mo Catalysts for Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

    International Nuclear Information System (INIS)

    Lee, Yeayeon; Jang, Jeongseok; Lee, Jin Goo; Jeon, Ok Sung; Kim, Hyeong Su; Hwang, Ho Jung; Shul, Yong Gun

    2016-01-01

    Highlights: • Pd-Mo-Fe catalysts show high catalytic activity and stability for oxygen-reduction reactions in acid media. • The optimum compositions were 7.5:1.5:1.0 for Pd-Fe-Mo, and the optimum temperatures were 500 °C. • The Pd-Fe-Mo catalysts were successfully applied to the PEMFC cathode, showing ∼500 mA cm −1 at 0.6 V. • The lattice constant was strongly related to the activity and stability of the catalysts for oxygen-reduction reactions. - Abstract: Highly active and durable non-platinum catalysts for oxygen-reduction reaction (ORR) have been developed for energy conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this study, Pd-Fe-Mo catalyst is reported as a non-platinum catalyst for ORR. The atomic ratio and annealing temperatures are controlled on the catalysts to understand interplay between their physical and chemical properties and electrochemical activities. The Pd-Fe-Mo catalyst optimized with 7.5:1.5:1.0 of the atomic ratio and 500 °C of the annealing temperature shows 32.18 mA mg −1 PGM (PGM: platinum group metal) of the kinetic current density at 0.9 V for ORR, which is comparable to that of commercial Pt/C catalyst. The current density is degraded to 6.20 mA mg −1 PGM after 3000 cycling of cyclic voltammetry, but it is greatly enhanced value compared to other non-platinum catalysts. In actual application to PEMFCs, the 20% Pd-Fe-Mo catalyst supported on carbons exhibits a high performance of 506 mA cm −2 at 0.6 V. The results suggest that the Pd-Fe-Mo catalyst can be a good candidate for non-platinum ORR catalysts.

  12. Metal-free and Oxygen-free Graphene as Oxygen Reduction Catalysts for Highly Efficient Fuel Cells

    Science.gov (United States)

    2013-06-30

    analysis was carried out by a TA instrument with a heating rate of 10 °C in N2. The Raman spectra were collected on a Raman spectrometer (Renishaw...kinematics viscosity for KOH (v = 0.01 cm 2 s -1 ) and CO2 is concentration of O2 in the solution (CO2 = 1.2 × 10 -6 mol cm -3 ). The constant 0.2 is...functionalizing graphene to impart electrocatalytic activity for oxygen reduction reaction (ORR) in fuel cells. Raman and X-ray photoelectron spectroscopic

  13. Enzymatic versus Inorganic Oxygen Reduction Catalysts: Comparison of the Energy Levels in a Free-Energy Scheme

    DEFF Research Database (Denmark)

    Kjærgaard, Christian Hauge; Rossmeisl, Jan; Nørskov, Jens Kehlet

    2010-01-01

    In this paper, we present a method to directly compare the energy levels of intermediates in enzymatic and inorganic oxygen reduction catalysts. We initially describe how the energy levels of a Pt(111) catalyst, operating at pH = 0, are obtained. By a simple procedure, we then convert the energy...... levels of cytochrome c oxidase (CcO) models obtained at physiological pH = 7 to the energy levels at pH = 0, which allows for comparison. Furthermore, we illustrate how different bias voltages will affect the free-energy landscapes of the catalysts. This allows us to determine the so-called theoretical...

  14. Process for obtaining methanol. Verfahren zur Gewinnung von Methanol

    Energy Technology Data Exchange (ETDEWEB)

    Link, H; Watson, A

    1983-12-08

    Synthetic gas is generated and converted to methanol in a reactor. After the separation of the crude methanol, there is a multi-stage methanol distillation. Condensate occurring during distillation is at least partly fed back before the methanol synthesis.

  15. Enhanced methanol oxidation and oxygen reduction reactions on palladium-decorated FeCo@Fe/C core–shell nanocatalysts in alkaline medium

    CSIR Research Space (South Africa)

    Fashedemi, OO

    2013-12-01

    Full Text Available . Zhong, J. Luo, B. Fang, B. N. Wanjala, P. N. Njoki, R. Loukrakpam and J. Yin, Nanotechnology, 2010, 21, 062001. 39 C. L. Lee, H. P. Chiou, C. M. Syu, C. R. Liu, C. C. Yang and C. C. Syu, Int. J. Hydrogen Energy, 2011, 36, 12706–12714. 40 K. J. Mayrhofer..., 12, 1102–1106. 2 Y. W. Lee, M. Kim, Y. Kim, S. W. Kang, J. H. Lee and S. W. Han, J. Phys. Chem. C, 2010, 114, 7689–7693. 3 C. Zhu, S. Guo and S. Dong, J. Mater. Chem., 2012, 22, 14851–14855. 4 C. Jeyabharathi, P. Venkateshkhumar, J. Mathiyarasau and K...

  16. Studies on the heterogeneous electron transport and oxygen reduction reaction at metal (Co, Fe) octabutylsulphonylphthalocyanines supported on multi-walled carbon nanotube modified graphite electrode

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-09-01

    Full Text Available Heterogeneous electron transfer dynamics and oxygen reduction reaction (ORR) activities using octabutylsulphonylphthalocyanine complexes of iron (FeOBSPc) and cobalt (CoOBSPc) supported on multi-walled carbon nanotube (MWCNT) platforms have been...

  17. Iron (II) tetrakis(diaquaplatinum) octacarboxyphthalocyanine supported on multi-walled carbon nanotubes as effective electrocatalyst for oxygen reduction reaction in alkaline medium

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-11-01

    Full Text Available Oxygen reduction reaction (ORR) in alkaline medium at iron (II) tetrakis (diaquaplatinum) octacarboxyphthalocyanine (PtFeOCPc) catalyst supported on multi-walled carbon nanotubes (MWCNTs) has been described. The ORR followed the direct 4-electron...

  18. Improvement of activated carbons as oxygen reduction catalysts in neutral solutions by ammonia gas treatment and their performance in microbial fuel cells

    KAUST Repository

    Watson, Valerie J.; Nieto Delgado, Cesar; Logan, Bruce E.

    2013-01-01

    Commercially available activated carbon (AC) powders from different precursor materials (peat, coconut shell, coal, and hardwood) were treated with ammonia gas at 700 C to improve their performance as oxygen reduction catalysts in neutral p

  19. Oxidation of CO and Methanol on Pd-Ni Catalysts Supported on Different Chemically-Treated Carbon Nanofibers

    Directory of Open Access Journals (Sweden)

    Juan Carlos Calderón

    2016-10-01

    Full Text Available In this work, palladium-nickel nanoparticles supported on carbon nanofibers were synthesized, with metal contents close to 25 wt % and Pd:Ni atomic ratios near to 1:2. These catalysts were previously studied in order to determine their activity toward the oxygen reduction reaction. Before the deposition of metals, the carbon nanofibers were chemically treated in order to generate oxygen and nitrogen groups on their surface. Transmission electron microscopy analysis (TEM images revealed particle diameters between 3 and 4 nm, overcoming the sizes observed for the nanoparticles supported on carbon black (catalyst Pd-Ni CB 1:2. From the CO oxidation at different temperatures, the activation energy Eact for this reaction was determined. These values indicated a high tolerance of the catalysts toward the CO poisoning, especially in the case of the catalysts supported on the non-chemically treated carbon nanofibers. On the other hand, apparent activation energy Eap for the methanol oxidation was also determined finding—as a rate determining step—the COads diffusion to the OHads for the catalysts supported on carbon nanofibers. The results here presented showed that the surface functional groups only play a role in the obtaining of lower particle sizes, which is an important factor in the obtaining of low CO oxidation activation energies.

  20. Methanol Fuel Cell

    Science.gov (United States)

    Voecks, G. E.

    1985-01-01

    In proposed fuel-cell system, methanol converted to hydrogen in two places. External fuel processor converts only part of methanol. Remaining methanol converted in fuel cell itself, in reaction at anode. As result, size of fuel processor reduced, system efficiency increased, and cost lowered.

  1. Influence of Micropore and Mesoporous in Activated Carbon Air-cathode Catalysts on Oxygen Reduction Reaction in Microbial Fuel Cells

    International Nuclear Information System (INIS)

    Liu, Yi; Li, Kexun; Ge, Baochao; Pu, Liangtao; Liu, Ziqi

    2016-01-01

    In this study, carbon samples with different micropore and mesoporous structures are prepared as air-cathode catalyst layer to explore the role of pore structure on oxygen reduction reaction. The results of linear sweep voltammetry and power density show that the commercially-produced activated carbon (CAC) has the best electrochemical performance, and carbon samples with only micropore or mesoporous show lower performance than CAC. Nitrogen adsorption-desorption isotherms analysis confirm that CAC has highest surface area (1616 m 2 g −1 ) and a certain amount of micropore and mesoporous. According to Tafel plot and rotating disk electrode, CAC behaves the highest kinetic activity and electron transfer number, leading to the improvement of oxygen reduction reaction. The air permeability test proves that mesoporous structure enhance oxygen permeation. Carbon materials are also analyzed by In situ Fourier Transform Infrared Spectroscopy and H 2 temperature programmed reduction, which indicate that micropore provide active sites for catalysis. In a word, micropore and mesoporous together would improve the electrochemical performance of carbon materials.

  2. An investigation on the electrocatalytic properties of polypyrrole films on the kinetics of oxygen reduction reaction in PEMFC

    Energy Technology Data Exchange (ETDEWEB)

    Saremi, M.; Sharifi Asl, S.; Kazemi, Sh. [Tehran Univ., Tehran (Iran, Islamic Republic of). School of Metallurgy and Material Science Engineering

    2008-07-01

    A proton exchange membrane (PEM) fuel cell has high power density, low weight, very short start-up time and no leakage of electrolytes. However, there are some disadvantages when operating the PEM fuel cell at room temperature. Many studies involving the widespread commercial use of Pt-based electrocatalysts search for low-cost electrocatalysts for the oxygen reduction reaction. In recent years, much attention has been placed on the use of electrocatalysis for the conducting polymer electrode. Polypyrrole has attracted much attention as an advanced conducting material because of its good environmental stability, easy synthesis and high conductivity. This study examined the effect of the polypyrrole catalyst in a PEMFC cathode. The electropolymerization of pyrrole was carried out in a 3-electrode cell using pure hydrogen and oxygen as the reactants. Tests were carried out at room temperature and cell impedance was measured. The polymer was formed galvanostatically in a 0.1 M pyrrole with a 0.15 KCl aqueous solution with a 20 mA/cm{sup 2} current density. The effect of operating voltage and oxygen mass transport was examined by EIS method, which separates these two phenomena. The study showed that polypyrrole has a catalytic effect for oxygen reduction reaction in PEMFC comparable to a Pt catalyzed electrode. Although the cell potential with polypyrrole was slightly lower than a Pt coated cell, it was found to be more economical. 8 refs., 2 figs.

  3. Interface-modulated approach toward multilevel metal oxide nanotubes for lithium-ion batteries and oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    Jiashen Meng; Chaojiang Niu; Xiong Liu; Ziang Liu; Hongliang Chen; Xuanpeng Wang; Jiantao Li

    2016-01-01

    Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis,chemical sensing,drug delivery,and energy storage.However,the controlled synthesis of multilevel nanotubes remains a great challenge.Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment.This versatile strategy can be effectively applied to fabricate wire-in-tube and tubein-tube nanotubes of various metal oxides.These multilevel nanotubes possess a large specific surface area,fast mass transport,good strain accommodation,and high packing density,which are advantageous for lithium-ion batteries (LIBs)and the oxygen reduction reaction (ORR).Specifically,shrinkable CoMn2O4 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of ~565 mAh.g-1 at a high rate of 2 A.g-1,maintaining 89% of the latter after 500 cycles.Further,as an oxygen reduction reaction catalyst,these nanotubes also exhibit excellent stability with about 92% current retention after 30,000 s,which is higher than that of commercial Pt/C (81%).Therefore,this feasible method may push the rapid development of one-dimensional (1D) nanomaterials.These multifunctional nanotubes have great potential in many frontier fields.

  4. Evaluation of the participation of ferredoxin in oxygen reduction in the photosynthetic electron transport chain of isolated pea thylakoids.

    Science.gov (United States)

    Kozuleva, Marina A; Ivanov, Boris N

    2010-07-01

    The contribution to reduction of oxygen by ferredoxin (Fd) to the overall reduction of oxygen in isolated pea thylakoids was studied in the presence of Fd versus Fd + NADP(+). The overall rate of electron transport was measured using a determination of Photosystem II quantum yield from chlorophyll fluorescence parameters, and the rate of oxidation of Fd was measured from the light-induced redox changes of Fd. At low light intensity, increasing Fd concentration from 5 to 30 microM in the absence of NADP(+) increased the proportion of oxygen reduction by Fd from 25-35 to 40-60% in different experiments. This proportion decreased with increasing light intensity. When NADP(+) was added in the presence of 15 microM Fd, which was optimal for the NADP(+) reduction rate, the participation of Fd in the reduction of oxygen was low, no more than 10%, and it also decreased with increasing light intensity. At high light intensity, the overall oxygen reduction rates in the presence of Fd + NADP(+) and in the presence of Fd alone were comparable. The significance of reduction of dioxygen either by water-soluble Fd or by the membrane-bound carriers of the photosynthetic electron transport chain for redox signaling under different light intensities is discussed.

  5. General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

    Science.gov (United States)

    Gryszel, Maciej; Sytnyk, Mykhailo; Jakešová, Marie; Romanazzi, Giuseppe; Gabrielsson, Roger; Heiss, Wolfgang; Głowacki, Eric Daniel

    2018-04-25

    Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H 2 O 2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O 2 to H 2 O 2 , with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H 2 O to O 2 . We found increased H 2 O 2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O 2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

  6. First principles investigation of the activity of thin film Pt, Pd and Au surface alloys for oxygen reduction

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Rossmeisl, Jan

    2015-01-01

    driving force for surface segregation, diffusion to defects or surface self-assembling. On the basis of stability and activity analysis we conclude that the near surface alloy of Pd in Pt and some PdAu binary and PtPdAu ternary thin films with a controlled amount of Au are the best catalysts for oxygen......Further advances in fuel cell technologies are hampered by kinetic limitations associated with the sluggish cathodic oxygen reduction reaction. We have investigated a range of different formulations of binary and ternary Pt, Pd and Au thin films as electrocatalysts for oxygen reduction. The most...... active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys...

  7. Electrocatalysis of oxygen reduction on nitrogen-containing multi-walled carbon nanotube modified glassy carbon electrodes

    International Nuclear Information System (INIS)

    Vikkisk, Merilin; Kruusenberg, Ivar; Joost, Urmas; Shulga, Eugene; Tammeveski, Kaido

    2013-01-01

    Highlights: ► Pyrolysis in the presence of urea was used for nitrogen doping of carbon nanotubes. ► N-doped carbon nanotubes were used as catalysts for the oxygen reduction reaction. ► N-doped carbon material showed a high catalytic activity for ORR in alkaline media. ► N-containing CNT material is an attractive cathode catalyst for alkaline membrane fuel cells. - Abstract: The electrochemical reduction of oxygen was studied on nitrogen-doped multi-walled carbon nanotube (NCNT) modified glassy carbon (GC) electrodes employing the rotating disk electrode (RDE) method. Nitrogen doping was achieved by simple pyrolysis of the carbon nanotube material in the presence of urea. The surface morphology and composition of the NCNT samples were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed a rather uniform distribution of NCNTs on the GC electrode substrate. The XPS analysis showed a successful doping of carbon nanotubes with nitrogen species. The RDE results revealed that in alkaline solution the N-doped nanotube materials showed a remarkable electrocatalytic activity towards oxygen reduction. At low overpotentials the reduction of oxygen followed a two-electron pathway on undoped carbon nanotube modified GC electrodes, whereas on NCNT/GC electrodes a four-electron pathway of O 2 reduction predominated. The results obtained are significant for the development of nitrogen-doped carbon-based cathodes for alkaline membrane fuel cells.

  8. One-step Synthesis of Pt Nanoparticles Highly Loaded on Graphene Aerogel as Durable Oxygen Reduction Electrocatalyst

    International Nuclear Information System (INIS)

    Huang, Qinghong; Tao, Feifei; Zou, Liangliang; Yuan, Ting; Zou, Zhiqing; Zhang, Haifeng; Zhang, Xiaogang; Yang, Hui

    2015-01-01

    Synthesis of highly active and durable Pt based catalysts with a high metal loading for fuel cells’ applications still remains a big challenge. The three-dimensional (3D) graphene aerogel (GA) not only possess the intrinsic property of graphene, but also have abundant pore architecture for anchoring metal nanoparticles, thus would be suitable as metal catalysts’ support. This work reports a simple and mild one-step co-reduction synthesis of Pt nanoparticles highly loaded on 3D GA and the use as durable oxygen reduction catalyst. Both X-ray diffraction and TEM measurements confirm that Pt nanoparticles (ca. 60 wt.% Pt loading) with an average diameter of ca. 3.2 nm are uniformly decorated on the homogeneously interconnected pores of 3D GA even after a heat treatment at 300 °C. Such a Pt/GA catalyst exhibits significantly enhanced electrocatalytic activity and improved durability for the oxygen reduction reaction. The enhancement in both catalytic activity and durability may result from the unique 3-D architecture structure of GA, the uniform dispersion of Pt nanoparticles, and the interaction between the Pt nanoparticles and GA. The GA-supported Pt can serve as a highly active catalyst for fuel cell applications

  9. Facile synthesis of silver nanoparticles supported on three dimensional graphene oxide/carbon black composite and its application for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Yuan, Lizhi; Jiang, Luhua; Liu, Jing; Xia, Zhangxun; Wang, Suli; Sun, Gongquan

    2014-01-01

    Graphical abstract: - Highlights: • Ag nanoparticles were prepared using GO as reductant without any stabilizers. • A composite support with a 3D structure was constructed by GO and carbon black. • The Ag/GO/C composite shows enhanced ORR activity compared with Ag/GO. - Abstract: A 3D graphene oxide/carbon sphere supported silver composite (Ag/GO/C) was synthesized using graphene oxide as the reducing agent. The reducing process of Ag + was monitored by the ultra violet-visible (UV-vis) absorption spectrometer and the physical properties of the Ag/GO/C composite were characterized by Fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the dispersive Ag nanoparticles are anchored uniformly on the surface of GO sheets with a mean size of about 6.9 nm. With introducing carbon black, the Ag nanoparticles aggregated slightly. Compared with its counterpart Ag/GO, the Ag/GO/C composite showed a significantly enhanced activity towards the oxygen reduction reaction in alkaline media. The enhancement can be ascribed to the 3D composite support, which not only improves the electrical conductivity, but also enforces the mass transport in the catalyst layer facilitating the reactants access to the active sites. Moreover, the Ag/GO/C composite exhibits good tolerance to alcohols, carbonates and tetramethylammonium hydroxide. This work is expected to open a new pathway to use GO as a reducing agent to synthesize electrocatalysts without surfactants

  10. A Highly Active and Alcohol-Tolerant Cathode Electrocatalyst Containing Ag Nanoparticles Supported on Graphene

    International Nuclear Information System (INIS)

    Jiang, Rongzhong; Moton, Elizabeth; McClure, Joshua P.; Bowers, Zachary

    2014-01-01

    A highly active oxygen reduction reaction (ORR) catalyst was synthesized by supporting Ag nano-particles on graphene nano platelets (Ag/GNP) via ultrasound treatment. The Ag/GNP catalyzes the O 2 molecule through a 4-electron reduction to water in 0.1 M KOH electrolyte. The half-wave potential for the ORR on Ag/GNP is similar to a Pt black coated electrode (i.e -0.27 V at Ag/GNP, and -0.18 V at 40% Pt/C vs.SCE). The kinetic rate for the ORR on Ag/GNP is 3.16 × 10 −2 cm · s −1 at -0.4 V vs. SCE. The effect of alcohols and other impurities on the ORR catalytic activity for Ag/GNP was examined and found to be highly tolerant to methanol, ethanol and ethylene glycol. The Ag/GNP catalyst is also tolerant to tetraalkyl ammonium hydroxides; i.e. functional groups related to the chemical structure of common alkaline electrolyte membranes

  11. Temperature dependence of the oxygen reduction kinetics on Ru{sub x}Se{sub y}/C catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Leveratto, D.; Racz, A.; Savinova, E.R.; Stimming, U. [Technische Universitaet Muenchen, Department of Physics E19, James-Franck-Str. 1, D-85748 Garching (Germany)

    2006-07-15

    The temperature dependence of the oxygen reduction kinetics on carbon-supported Ru{sub x}Se{sub y} catalysts is studied using a rotating disc electrode in 0.5 M H{sub 2}SO{sub 4} in the temperature interval from 25 C to 65 C. When the absolute value of the overpotential is below ca. 0.65 V, the reaction is limited by a one-electron charge transfer step, where the transfer coefficient is independent of the temperature and equal to 0.44. The apparent activation enthalpy at zero overpotential is 0.49 eV and the pre-exponential factor is independent of the temperature. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  12. 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.

  13. From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

    Science.gov (United States)

    Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

    2017-07-01

    Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

  14. Direct synthesis of Fe3 C-functionalized graphene by high temperature autoclave pyrolysis for oxygen reduction.

    Science.gov (United States)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Huang, Yunjie; Cleemann, Lars N; Xing, Wei; Bjerrum, Niels J; Li, Qingfeng

    2014-08-01

    We present a novel approach to direct fabrication of few-layer graphene sheets with encapsulated Fe3 C nanoparticles from pyrolysis of volatile non-graphitic precursors without any substrate. This one-step autoclave approach is facile and potentially scalable for production. Tested as an electrocatalyst, the graphene-based composite exhibited excellent catalytic activity towards the oxygen reduction reaction in alkaline solution with an onset potential of ca. 1.05 V (vs. the reversible hydrogen electrode) and a half-wave potential of 0.83 V, which is comparable to the commercial Pt/C catalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Lukasz JOZWIAK

    2017-02-01

    Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14406

  16. Pt monolayer shell on hollow Pd core electrocatalysts: Scale up synthesis, structure, and activity for the oxygen reduction reaction

    Directory of Open Access Journals (Sweden)

    Vukmirovic Miomir B.

    2013-01-01

    Full Text Available We report on synthesis, characterization and the oxygen reduction reaction (ORR kinetics of Pt monolayer shell on Pd(hollow, or Pd-Au(hollow core electrocatalysts. Comparison between the ORR catalytic activity of the electrocatalysts with hollow cores and those of Pt solid and Pt hollow nanoparticles has been obtained using the rotating disk electrode technique. Hollow nanoparticles were made using Ni or Cu nanoparticles as sacrificial templates. The Pt ORR specific and mass activities of the electrocatalysts with hollow cores were found considerably higher than those of the electrocatalysts with the solid cores. We attribute this enhanced Pt activity to the smooth surface morphology and hollow-induced lattice contraction, in addition to the mass-saving geometry of hollow particles.

  17. The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: nicolas.alonso.vante@univ-poitiers.f [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)

    2010-11-01

    This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

  18. Effect of ordering of PtCu₃ nanoparticle structure on the activity and stability for the oxygen reduction reaction.

    Science.gov (United States)

    Hodnik, Nejc; Jeyabharathi, Chinnaiah; Meier, Josef C; Kostka, Alexander; Phani, Kanala L; Rečnik, Aleksander; Bele, Marjan; Hočevar, Stanko; Gaberšček, Miran; Mayrhofer, Karl J J

    2014-07-21

    In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts.

  19. Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

    Science.gov (United States)

    Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

    2018-02-09

    Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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.

  1. Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells

    Science.gov (United States)

    Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang

    2015-06-01

    Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.

  2. The Methanol Economy Project

    Energy Technology Data Exchange (ETDEWEB)

    Olah, George [Univ. of Southern California, Los Angeles, CA (United States); Prakash, G. K. [Univ. of Southern California, Los Angeles, CA (United States)

    2014-02-01

    The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO2 capture using supported amines, co-electrolysis of CO2 and water to formate and syngas, decomposition of formate to CO2 and H2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

  3. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  4. Methanol fuel update

    International Nuclear Information System (INIS)

    Colledge, R.; Spacek, J.

    1992-01-01

    An overview is presented of methanol fuel developments, with particular reference to infrastructure, supply and marketing. Methanol offers reduced emissions, easy handling, is cost effective, can be produced from natural gas, coal, wood, or municipal waste, is a high performance fuel, is safer than gasoline, and contributes to energy security. Methanol supply, environmental benefits, safety/health issues, economics, passenger car economics, status of passenger car technology, buses, methanol and the prosperity initiative, challenges to implementation, and the role of government and original equipment manufacturers are discussed. Governments must assist in the provision of methanol refuelling infrastructure, and in providing an encouraging regulatory atmosphere. Discriminatory and inequitable taxing methods must be addressed, and an air quality agenda must be defined to allow the alternative fuel industry to respond in a timely manner

  5. Dietary methanol and autism.

    Science.gov (United States)

    Walton, Ralph G; Monte, Woodrow C

    2015-10-01

    The authors sought to establish whether maternal dietary methanol during pregnancy was a factor in the etiology of autism spectrum disorders. A seven item questionnaire was given to women who had given birth to at least one child after 1984. The subjects were solicited from a large primary care practice and several internet sites and separated into two groups - mothers who had given birth to a child with autism and those who had not. Average weekly methanol consumption was calculated based on questionnaire responses. 550 questionnaires were completed by women who gave birth to a non-autistic child. On average these women consumed 66.71mg. of methanol weekly. 161 questionnaires were completed by women who had given birth to an autistic child. The average estimated weekly methanol consumption for this group was 142.31mg. Based on the results of the Wilcoxon rank sum-test, we see a significant difference between the reported methanol consumption rates of the two groups. This study suggests that women who have given birth to an autistic child are likely to have had higher intake of dietary sources of methanol than women who have not. Further investigation of a possible link of dietary methanol to autism is clearly warranted. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

  6. Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT

    DEFF Research Database (Denmark)

    Hansen, Heine Anton; Rossmeisl, Jan; Nørskov, Jens Kehlet

    2008-01-01

    The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells but not in ac......The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells...... but not in acidic PEM fuel cells. Based on density functional theory calculations we investigate the electrochemically most stable surface structures as a function of pH and electrostatic potential for Pt(111), Ag(111) and Ni(111), and we construct surface Pourbaix diagrams. We study the oxygen reduction reaction......, on the other hand, is constant vs. the standard hydrogen electrode (SHE). For Ag, this means that where the potential for dissolution and ORR are about the same at pH = 0, Ag becomes more stable relative to RHE as pH is increased. Hence the pH dependent stability offers an explanation for the possible use...

  7. Optimization of Ru{sub x}Se{sub y} electrocatalyst loading for oxygen reduction in a PEMFC

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Huerta, R.G. [Instituto Politecnico Nacional, Laboratorio de Electroquimica y Corrosion ESIQIE, UPALP, 07738 Mexico, D.F., Mexico (Mexico); Guzman-Guzman, A.; Solorza-Feria, O. [Depto. Quimica, Centro de Investigacion y de Estudios Avanzados del IPN, A. Postal 14-740, 07360 Mexico D.F., Mexico (Mexico)

    2010-11-15

    The synthesis, characterization and optimization of Ru{sub x}Se{sub y} catalyst loading as a cathode electrode for a single polymer electrolyte membrane fuel cell, PEMFC were investigated. Ru{sub x}Se{sub y} catalyst was synthesized via a decarbonylation of Ru{sub 3}(CO){sub 12} and elemental selenium in 1,6-hexanediol under refluxing conditions for 2 h. The powder electrocatalyst was characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and examined for the oxygen reduction reaction (ORR) in 0.5M H{sub 2}SO{sub 4} by rotating disk electrode (RDE) and in membrane-electrode assemblies, MEAs for a single PEMFC. Results indicate the formation of agglomerates of crystalline particles with nanometric size embedded in an amorphous phase. The catalyst exhibited high current density and lower overpotential for the ORR compared to that of Ru{sub x} cluster catalyst. Dispersed Ru{sub x}Se{sub y} catalyst loading on Vulcan carbon was optimized as a cathode electrode by performance testing in a single H{sub 2}-O{sub 2} fuel cell. (author)

  8. Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soo, Li Ting, E-mail: nicolesoo90@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Loh, Kee Shyuan, E-mail: ksloh@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Mohamad, Abu Bakar, E-mail: drab@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Daud, Wan Ramli Wan, E-mail: wramli@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Wong, Wai Yin, E-mail: waiyin.wwy@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); School of Engineering, Taylor' s University' s Lakeside Campus, No. 1, Jalan Taylor' s, 46500 Subang Jaya, Selangor (Malaysia)

    2016-08-25

    A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

  9. Proton conductive Pt-Co nanoparticles anchoring on citric acid functionalized graphene for efficient oxygen reduction reaction

    Science.gov (United States)

    Zhao, Yige; Liu, Jingjun; Wu, Yijun; Wang, Feng

    2017-08-01

    Designing highly efficient electro-catalysts for the oxygen reduction reaction (ORR) has been regarded as a demanding task in the development of renewable energy sources. However, little attention has been paid on improving Pt-based catalysts by promoting proton transfer from the electrolyte solutions to the catalyst layer at the cathode. Herein, we design proton conductive Pt-Co alloy nanoparticles anchoring on citric acid functionalized graphene (Pt-Co/CA-G) catalysts for efficient ORR. The facile modification approach for graphene can introduce oxygenated functional groups on the graphene surface to promote proton transfer as well as keeping the high electron conductivity without destroying the graphene original structure. The electrochemical results show that the Pt-Co/CA-G catalyst exhibits more excellent ORR activity and stability than the commercial Pt/C catalyst, which can be attributed to its improved proton transfer ability. The fast proton transfer comes from the hydrogen-bonding networks formed by the interaction between the oxygenated functional groups and water molecules. This work provides not only a novel and simple approach to modify graphene but also an effective strategy to improve Pt-based catalysts for the ORR.

  10. Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

    Science.gov (United States)

    Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

    2018-01-01

    A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

  11. Operando Soft X-ray Absorption Spectroscopic Study on a Solid Oxide Fuel Cell Cathode during Electrochemical Oxygen Reduction.

    Science.gov (United States)

    Nakamura, Takashi; Oike, Ryo; Kimura, Yuta; Tamenori, Yusuke; Kawada, Tatsuya; Amezawa, Koji

    2017-05-09

    An operando soft X-ray absorption spectroscopic technique, which enabled the analysis of the electronic structures of the electrode materials at elevated temperature in a controlled atmosphere and electrochemical polarization, was established and its availability was demonstrated by investigating the electronic structural changes of an La 2 NiO 4+δ dense-film electrode during an electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K under an atmospheric pressure of 100 ppm O 2 /He, 0.1 % O 2 /He, and 1 % O 2 /He gas mixtures. Considerable spectral changes were observed in the O K-edge X-ray absorption spectra upon changing the PO2 and application of electrical potential, whereas only small spectral changes were observed in Ni L-edge X-ray absorption spectra. A pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied partial density of states of Ni 3d-O 2p hybridization, increased or decreased with cathodic or anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopic technique developed in this study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Nb-doped TiO2 cathode catalysts for oxygen reduction reaction of polymer electrolyte fuel cells

    KAUST Repository

    Arashi, Takuya

    2014-09-01

    Nb-doped TiO2 particles were studied as electrocatalysts for the oxygen reduction reaction (ORR) under acidic conditions. The Nb-doped TiN nanoparticles were first synthesized by meso-porous C3N4 and then fully oxidized to Nb-doped TiO2 by immersing in 0.1 M H 2SO4 at 353 K for 24 h. Although the ORR activity of the as-obtained sample was low, a H2 treatment at relatively high temperature (1173 K) dramatically improved the ORR performance. An onset potential as high as 0.82 VRHE was measured. No degradation of the catalysts was observed during the oxidation-reduction cycles under the ORR condition for over 127 h. H2 treatment at temperatures above 1173 K caused the formation of a Ti4O7 phase, resulting in a decrease in ORR current. Elemental analysis indicated that the Nb-doped TiO 2 contained 25 wt% residual carbon. Calcination in air at 673 or 973 K eliminated the residual carbon in the catalyst, which was accompanied by a dramatic decrease in ORR activity. This post-calcination process may reduce the conductivity of the sample by filling the oxygen vacancies, and the carbon residue in the particle aggregates may enhance the electrocatalytic activity for ORR. The feasibility of using conductive oxide materials as electrocatalysts is discussed. © 2013 Elsevier B.V.

  13. Effects of grain boundaries at the electrolyte/cathode interfaces on oxygen reduction reaction kinetics of solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Min Gi; Koo, Ja Yang; Ahn, Min Woo; Lee, Won Young [Dept. of Mechanical Engineering, Sungkyunkwan University, Suwon (Korea, Republic of)

    2017-04-15

    We systematically investigated the effects of grain boundaries (GBs) at the electrolyte/cathode interface of two conventional electrolyte materials, i.e., yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC). We deposited additional layers by pulsed laser deposition to control the GB density on top of the polycrystalline substrates, obtaining significant improvements in peak power density (two-fold for YSZ and three-fold for GDC). The enhanced performance at high GB density in the additional layer could be ascribed to the accumulation of oxygen vacancies, which are known to be more active sites for oxygen reduction reactions (ORR) than grain cores. GDC exhibited a higher enhancement than YSZ, due to the easier formation, and thus higher concentration, of oxygen vacancies for ORR. The strong relation between the concentration of oxygen vacancies and the surface exchange characteristics substantiated the role of GBs at electrolyte/cathode interfaces on ORR kinetics, providing new design parameters for highly performing solid oxide fuel cells.

  14. Core-Shell Structuring of Pure Metallic Aerogels towards Highly Efficient Platinum Utilization for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Cai, Bin; Hübner, René; Sasaki, Kotaro; Zhang, Yuanzhe; Su, Dong; Ziegler, Christoph; Vukmirovic, Miomir B; Rellinghaus, Bernd; Adzic, Radoslav R; Eychmüller, Alexander

    2018-03-05

    The development of core-shell structures remains a fundamental challenge for pure metallic aerogels. Here we report the synthesis of Pd x Au-Pt core-shell aerogels composed of an ultrathin Pt shell and a composition-tunable Pd x Au alloy core. The universality of this strategy ensures the extension of core compositions to Pd transition-metal alloys. The core-shell aerogels exhibited largely improved Pt utilization efficiencies for the oxygen reduction reaction and their activities show a volcano-type relationship as a function of the lattice parameter of the core substrate. The maximum mass and specific activities are 5.25 A mg Pt -1 and 2.53 mA cm -2 , which are 18.7 and 4.1 times higher than those of Pt/C, respectively, demonstrating the superiority of the core-shell metallic aerogels. The proposed core-based activity descriptor provides a new possible strategy for the design of future core-shell electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Obtaining of platinum-titanium alloys by sol-gel and their performance for the detachment reactions and oxygen reduction

    International Nuclear Information System (INIS)

    Regueira R, B. I.

    2011-01-01

    In the present work, platinum-titanium (Pt-Ti) alloys were prepared, characterized and evaluated in acid media as bifunctional electrocatalysts for the oxygen evolution reaction (Oer) and oxygen reduction reactions (Orr) in acid media. The alloys were synthesized by sol-gel method, heating the gel at temperatures of 400 and 600 C. The alloys characterization was realized by X-ray diffraction, scanning electron microscopy and EDS. Both alloys were formed by agglomerates of nanometer particles. The particle sizes were lower for the alloy obtained at 400 C (120 nm to 257 nm) compared to the alloy prepared at 600 C (555 nm to 833 nm). Cyclic and linear voltammetry techniques were used for the electrochemical evaluation of the alloy obtained at both temperatures for the Oer and Orr, in a 0.5 M sulfuric acid solution. The materials have response for both electrochemical reactions, therefore the best performance was for the Pt-Ti alloy, obtained at 400 C and it was stable for the oxygen evolution reaction. The alloy obtained at 400 C presents satisfactory electrocatalytic characteristics to be used as bifunctional material in a unified regenerative fuel cell. (Author)

  16. Magneli phase Ti4O7 electrode for oxygen reduction reaction and its implication for zinc-air rechargeable batteries

    International Nuclear Information System (INIS)

    Li Xiaoxia; Zhu, Aaron Li; Qu Wei; Wang Haijiang; Hui, Rob; Zhang Lei; Zhang Jiujun

    2010-01-01

    In this paper, Magneli phase Ti 4 O 7 was successfully synthesized using a TiO 2 reduction method, and characterized using X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The electrode coated with this Ti 4 O 7 material showed activities for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). For the ORR, several parameters, including overall electron transfer number, kinetic constants, electron transfer coefficient, and percentage H 2 O 2 production, were obtained using the rotating ring-disk electrode (RRDE) technique and the Koutecky-Levich theory. The overall electron transfer number was found to be between 2.3 and 2.9 in 1, 4, and 6 M KOH electrolytes, suggesting that the ORR process on the Ti 4 O 7 electrode was a mixed process of 2- and 4-electron transfer pathways. Electrochemical durability tests, carried out in highly concentrated KOH electrolyte, confirmed that this Ti 4 O 7 is a stable electrode material, suggesting that it should be a feasible candidate for the air-cathodes of zinc-air batteries. To understand the stability of this material, Raman and XPS spectra were also collected for the Ti 4 O 7 samples before and after the stability tests. The results and analysis revealed that a thin layer of TiO 2 formed on the Ti 4 O 7 surface, which may have prevented further oxidation into the bulk of the Ti 4 O 7 electrode.

  17. Electrochemical kinetics and X-ray absorption spectroscopy investigations of select chalcogenide electrocatalysts for oxygen reduction reaction applications

    International Nuclear Information System (INIS)

    Ziegelbauer, Joseph M.; Murthi, Vivek S.; O'Laoire, Cormac; Gulla, Andrea F.; Mukerjee, Sanjeev

    2008-01-01

    Transition metal-based chalcogenide electrocatalysts exhibit a promising level of performance for oxygen reduction reaction applications while offering significant economic benefits over the state of the art Pt/C systems. The most active materials are based on Ru x Se y clusters, but the toxicity of selenium will most likely limit their embrace by the marketplace. Sulfur-based analogues do not suffer from toxicity issues, but suffer from substantially less activity and stability than their selenium brethren. The structure/property relationships that result in these properties are not understood due to ambiguities regarding the specific morphologies of Ru x S y -based chalcogenides. To clarify these properties, an electrochemical kinetics study was interpreted in light of extensive X-ray diffraction, scanning electron microscopy, and in situ X-ray absorption spectroscopy evaluations. The performance characteristics of ternary M x Ru y S z /C (M = Mo, Rh, or Re) chalcogenide electrocatalysts synthesized by the now-standard low-temperature nonaqueous (NA) route are compared to commercially available (De Nora) Rh- and Ru-based systems. Interpretation of performance differences is made in regards to bulk and surface properties of these systems. In particular, the overall trends of the measured activation energies in respect to increasing overpotential and the gross energy values can be explained in regards to these differences

  18. Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Soo, Li Ting; Loh, Kee Shyuan; Mohamad, Abu Bakar; Daud, Wan Ramli Wan; Wong, Wai Yin

    2016-01-01

    A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

  19. Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

    Science.gov (United States)

    Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

    2017-07-01

    We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

  20. Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

    2017-10-01

    The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

  1. Synthesis and Characterization of Pt-Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction.

    Science.gov (United States)

    Yang, Xuan; Roling, Luke T; Vara, Madeline; Elnabawy, Ahmed O; Zhao, Ming; Hood, Zachary D; Bao, Shixiong; Mavrikakis, Manos; Xia, Younan

    2016-10-12

    Engineering the elemental composition of metal nanocrystals offers an effective strategy for the development of catalysts or electrocatalysts with greatly enhanced activity. Herein, we report the synthesis of Pt-Ag alloy nanocages with an outer edge length of 18 nm and a wall thickness of about 3 nm. Such nanocages with a composition of Pt 19 Ag 81 could be readily prepared in one step through the galvanic replacement reaction between Ag nanocubes and a Pt(II) precursor. After 10 000 cycles of potential cycling in the range of 0.60-1.0 V as in an accelerated durability test, the composition of the nanocages changed to Pt 56 Ag 44 , together with a specific activity of 1.23 mA cm -2 toward oxygen reduction, which was 3.3 times that of a state-of-the-art commercial Pt/C catalyst (0.37 mA cm -2 ) prior to durability testing. Density functional theory calculations attributed the increased activity to the stabilization of the transition state for breaking the O-O bond in molecular oxygen. Even after 30 000 cycles of potential cycling, the mass activity of the nanocages only dropped from 0.64 to 0.33 A mg -1 Pt , which was still about two times that of the pristine Pt/C catalyst (0.19 A mg -1 Pt ).

  2. Evaluation and Enhancement of the Oxygen Reduction Reaction Activity on Hafnium Oxide Nanoparticles Assisted by L(+)-lysine

    International Nuclear Information System (INIS)

    Chisaka, Mitsuharu; Itagaki, Noriaki

    2016-01-01

    Evaluation of the oxygen reduction reaction (ORR) on oxide compounds is difficult owing to the insulating nature of oxides. In this study, various amounts of L(+)-lysine were added to the precursor dispersion for the hydrothermal synthesis of hafnium oxide nanoparticles on reduced graphene oxide sheets (HfO_x–rGO) to coat the HfO_x catalysts with layers of carbon, thereby increasing the conductivity and number of active sites. When the mass ratio of L(+)-lysine to GO, R, was above 26, carbon layers were formed and the amount monotonically increased with increasing R, as noted by cyclic voltammogrametry. X-ray photoelectron spectroscopy and rotating disk electrode analyses revealed that pyrolysis produced ORR-active oxygen defects, whose formation was proposed to involve carbothermal reduction. When 53 ≤ R ≤ 210, HfO_x–rGO contained a similar amount of oxygen defects and ORR activity, as represented by an onset potential of 0.9 V versus the reversible hydrogen electrode in 0.1 mol dm"−"3 H_2SO_4. However, the number of active sites depended on R due to the amount of L(+)-lysine-derived carbon layers that increased both the number of active sites and resistivity towards oxygen diffusion.

  3. A novel method for synthesis of phosphomolybdic acid-modified Pd/C catalysts for oxygen reduction reaction

    Science.gov (United States)

    Zhu, Mingyuan; Gao, Xiaoling; Luo, Guangqin; Dai, Bin

    2013-03-01

    This manuscript reports a convenient method for immobilizing phosphomolybdic acid (HPMo) on polyaniline (PAN-) functionalized carbon supports. The obtained HPMo-PAN-C sample is used as the support to prepare a Pd/HPMo-PAN-C catalyst. The samples are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction analysis. The results suggest that HPMo retains its Keggin structure and that the presence of HPMo reduces the average particle size of the Pd nano-particles in the obtained Pd/HPMo-PAN-C catalyst. Electro-chemical measurements in 0.5 M HClO4 solution reveal that the Pd/HPMo-PAN-C catalyst has higher catalytic activity for oxygen reduction reactions than does a Pd/C catalyst prepared using a similar procedure. The stability of the Pd/HPMo-PAN-C catalyst is evaluated by multiple-cycle voltammetry techniques; the mass catalytic activity decreases by only 10% after 100 scanning cycles.

  4. O-, N-Atoms-Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts.

    Science.gov (United States)

    Yang, Yang; Mao, Kaitian; Gao, Shiqi; Huang, Hao; Xia, Guoliang; Lin, Zhiyu; Jiang, Peng; Wang, Changlai; Wang, Hui; Chen, Qianwang

    2018-05-28

    Manganese (Mn) is generally regarded as not being sufficiently active for the oxygen reduction reaction (ORR) compared to other transition metals such as Fe and Co. However, in biology, manganese-containing enzymes can catalyze oxygen-evolving reactions efficiently with a relative low onset potential. Here, atomically dispersed O and N atoms coordinated Mn active sites are incorporated within graphene frameworks to emulate both the structure and function of Mn cofactors in heme-copper oxidases superfamily. Unlike previous single-metal catalysts with general M-N-C structures, here, it is proved that a coordinated O atom can also play a significant role in tuning the intrinsic catalytic activities of transition metals. The biomimetic electrocatalyst exhibits superior performance for the ORR and zinc-air batteries under alkaline conditions, which is even better than that of commercial Pt/C. The excellent performance can be ascribed to the abundant atomically dispersed Mn cofactors in the graphene frameworks, confirmed by various characterization methods. Theoretical calculations reveal that the intrinsic catalytic activity of metal Mn can be significantly improved via changing local geometry of nearest coordinated O and N atoms. Especially, graphene frameworks containing the Mn-N 3 O 1 cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Platinum Iron Intermetallic Nanoparticles Supported on Carbon Formed In Situ by High-Pressure Pyrolysis for Efficient Oxygen Reduction

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

    2016-01-01

    Carbon-supported PtFe alloy catalysts are synthesized by the one-step, high-temperature pyrolysis of Pt, Fe, and C precursors. As a result of the high temperature, the formed PtFe nanoparticles possess highly ordered, face-centered tetragonal, intermetallic structures with a mean size of ≈11.8 nm....... At 0.9 V versus the reversible hydrogen electrode, the PtFe nanoparticles show a 6.8 times higher specific activity than the reference Pt/C catalyst towards the oxygen reduction reaction (ORR) as well as excellent stability, most likely because of the durable intermetallic structure and the preleaching...... treatment of the catalyst. During these preliminary syntheses, we found that a portion of the PtFe nanoparticles is buried in the in situ formed carbon phase, which limits Pt utilization in the catalyst and results in a mass-specific activity equivalent to the commercial Pt/C catalyst. Moreover...

  6. Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

    Directory of Open Access Journals (Sweden)

    Nagappan Ramaswamy

    2012-01-01

    Full Text Available Complex electrochemical reactions such as Oxygen Reduction Reaction (ORR involving multi-electron transfer is an electrocatalytic inner-sphere electron transfer process that exhibit strong dependence on the nature of the electrode surface. This criterion (along with required stability in acidic electrolytes has largely limited ORR catalysts to the platinum-based surfaces. New evidence in alkaline media, discussed here, throws light on the involvement of surface-independent outer-sphere electron transfer component in the overall electrocatalytic process. This surface non-specificity gives rise to the possibility of using a wide-range of non-noble metal surfaces as electrode materials for ORR in alkaline media. However, this outer-sphere process predominantly leads only to peroxide intermediate as the final product. The importance of promoting the electrocatalytic inner-sphere electron transfer by facilitation of direct adsorption of molecular oxygen on the active site is emphasized by using pyrolyzed metal porphyrins as electrocatalysts. A comparison of ORR reaction mechanisms between acidic and alkaline conditions is elucidated here. The primary advantage of performing ORR in alkaline media is found to be the enhanced activation of the peroxide intermediate on the active site that enables the complete four-electron transfer. ORR reaction schemes involving both outer- and inner-sphere electron transfer mechanisms are proposed.

  7. Durability of template-free Fe-N-C foams for electrochemical oxygen reduction in alkaline solution

    Science.gov (United States)

    Mufundirwa, Albert; Harrington, George F.; Smid, Břetislav; Cunning, Benjamin V.; Sasaki, Kazunari; Lyth, Stephen M.

    2018-01-01

    Due to the high cost and limited availability of platinum, the development of non-platinum-group metals (non-PGM) catalysts is of paramount importance. A promising alternative to Pt are Fe-N-C-based materials. Here we present the synthesis, characterization and electrochemistry of a template-free nitrogen-doped carbon foam, impregnated with iron. This low-cost and gram-scale method results in materials with micron-scale pore size and large surface area (1600 m2g-1). When applied as an oxygen reduction reaction (ORR) electrocatalyst in alkaline solution, the Fe-N-C foams display extremely high initial activity, slightly out-performing commercially available non-PGM catalysts (NCP-2000, Pajarito Powder). The load-cycle durability in alkaline solution is investigated, and the performance steadily degrades over 60,000 potential cycles, whilst the commercial catalyst is remarkably stable. The post-operation catalyst microstructure is elucidated by transmission electron microscopy (TEM), to provide insight into the degradation processes. The resulting images suggest that potential cycling leads to leaching of atomically dispersed Fe-N2/4 sites in all the catalysts, whereas encapsulated iron nanoparticles are protected.

  8. Study of gold-platinum and platinum-gold surface modification and its influence on hydrogen evolution and oxygen reduction

    Directory of Open Access Journals (Sweden)

    BRANIMIR N. GRGUR

    2005-02-01

    Full Text Available Surface modification of the electrodes was conducted from sulfuric acid solutions containing the corresponding metal–chloride complexes using cyclic voltammetry. Comparing the charges of the hydrogen underpotential deposition region, and the corresponding oxide reduction regions, it is concluded that a platinum overlayer on gold forms 3D islands, while gold on platinum forms 2D islands. Foreign metals present in an amount of up to one monolayer exert an influence on the change in reaction rate with respect to both hydrogen evolution (HER and oxygen reduction (ORR reactions. Aplatinum overlayer on a gold substrate increases the activity forHER and for ORR, compared with pure gold. These results can be understood in terms of a simple model, in which the change in the H and OH binding energies are directly proportional to the shift of the d-bond center of the overlayer. On the contrary, a gold layer on platinum slightly decreases the activity for both reactions compared with pure platinum.

  9. 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.

  10. Manganese dioxide-supported silver bismuthate as an efficient electrocatalyst for oxygen reduction reaction in zinc-oxygen batteries

    International Nuclear Information System (INIS)

    Sun, Yanzhi; Yang, Meng; Pan, Junqing; Wang, Pingyuan; Li, Wei; Wan, Pingyu

    2016-01-01

    In this paper, we present a new efficient composite electrocatalyst, manganese dioxide-supported silver bismuthate (Ag 4 Bi 2 O 5 /MnO 2 ), for oxygen reduction reaction (ORR) in alkaline media. The new electrocatalyst was characterized with scanning electron microscope (SEM), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Electrochemical measurements indicate that the Ag 4 Bi 2 O 5 /MnO 2 composite is a very efficient electrocatalyst for ORR in alkaline media. The physical and electrochemical characterization results suggest that the high activity is ascribed to the support effects from MnO 2 and the synergetic effects among Ag 4 Bi 2 O 5 and MnO 2 . The analysis of rotating disk electrode (RDE) results shows that the ORR occurs via a four-electron pathway on the surface of the Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst. This electrocatalyst was further tested in a designed zinc–oxygen (Zn–O 2 ) battery. This battery can offer a discharge time of 225 h at 120 mA cm −2 , increasing by more than 492% as compared with pure MnO 2 electrocatalyst. It demonstrates that this inexpensive Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst is a viable alternative to platinum electrocatalyst for energy conversion devices.

  11. Tailored Combination of Low Dimensional Catalysts for Efficient Oxygen Reduction and Evolution in Li-O2 Batteries.

    Science.gov (United States)

    Yoon, Ki Ro; Kim, Dae Sik; Ryu, Won-Hee; Song, Sung Ho; Youn, Doo-Young; Jung, Ji-Won; Jeon, Seokwoo; Park, Yong Joon; Kim, Il-Doo

    2016-08-23

    The development of efficient bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key issue pertaining high performance Li-O2 batteries. Here, we propose a heterogeneous electrocatalyst consisting of LaMnO3 nanofibers (NFs) functionalized with RuO2 nanoparticles (NPs) and non-oxidized graphene nanoflakes (GNFs). The Li-O2 cell employing the tailored catalysts delivers an excellent electrochemical performance, affording significantly reduced discharge/charge voltage gaps (1.0 V at 400 mA g(-1) ), and superior cyclability for over 320 cycles. The outstanding performance arises from (1) the networked LaMnO3 NFs providing ORR/OER sites without severe aggregation, (2) the synergistic coupling of RuO2 NPs for further improving the OER activity and the electrical conductivity on the surface of the LaMnO3 NFs, and (3) the use of GNFs providing a fast electronic pathway as well as improved ORR kinetics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhuang [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Li, Mian [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Fan, Liquan; Han, Jianan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Xiong, Yueping, E-mail: ypxiong@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China)

    2017-04-15

    Highlights: • Novel Fe/Ni-N-CNFs electrocatalysts are prepared by electrospinning technique. • The Fe1Ni1-N-CNFs catalyst exhibits the excellent ORR and OER catalytic activity. • Synergy of Fe/Ni alloy is responsible for the excellent catalytic performance. - Abstract: The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-N{sub x} and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

  13. Critical appraisal on the role of catalysts for the oxygen reduction reaction in lithium-oxygen batteries

    International Nuclear Information System (INIS)

    Lodge, Andrew W.; Lacey, Matthew J.; Fitt, Matthew; Garcia-Araez, Nuria; Owen, John R.

    2014-01-01

    This work reports a detailed characterization of the reduction of oxygen in pyrrolidinium-based ionic liquids for application to lithium-oxygen batteries. It is found that, in the absence of Li + , all electron transfer kinetics are fast, and therefore, the reactions are limited by the mass transport rate. Reversible reduction of O 2 to O 2 • − and O 2 • − to O 2 2− take place at E 0 = 2.1 V and 0.8 V vs. Li + /Li, respectively. In the presence of Li + , O 2 is reduced to LiO 2 first and then to Li 2 O 2 . The solubility product constant of Li 2 O 2 is found to be around 10 −51 , corroborating the hypothesis that electrode passivation by Li 2 O 2 deposition is an important issue that limits the capacity delivered by lithium-oxygen batteries. Enhancing the rate of Li 2 O 2 formation by using different electrode materials would probably lead to faster electrode passivation and hence smaller charge due to oxygen reduction (smaller capacity of the battery). On the contrary, soluble redox catalysts can not only increase the reaction rate of Li 2 O 2 formation but also avoid electrode passivation since the fast diffusion of the soluble redox catalyst would displace the formation of Li 2 O 2 at a sufficient distance from the electrode surface

  14. Nb-doped TiO2 cathode catalysts for oxygen reduction reaction of polymer electrolyte fuel cells

    KAUST Repository

    Arashi, Takuya; Seo, Jeongsuk; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2014-01-01

    Nb-doped TiO2 particles were studied as electrocatalysts for the oxygen reduction reaction (ORR) under acidic conditions. The Nb-doped TiN nanoparticles were first synthesized by meso-porous C3N4 and then fully oxidized to Nb-doped TiO2 by immersing in 0.1 M H 2SO4 at 353 K for 24 h. Although the ORR activity of the as-obtained sample was low, a H2 treatment at relatively high temperature (1173 K) dramatically improved the ORR performance. An onset potential as high as 0.82 VRHE was measured. No degradation of the catalysts was observed during the oxidation-reduction cycles under the ORR condition for over 127 h. H2 treatment at temperatures above 1173 K caused the formation of a Ti4O7 phase, resulting in a decrease in ORR current. Elemental analysis indicated that the Nb-doped TiO 2 contained 25 wt% residual carbon. Calcination in air at 673 or 973 K eliminated the residual carbon in the catalyst, which was accompanied by a dramatic decrease in ORR activity. This post-calcination process may reduce the conductivity of the sample by filling the oxygen vacancies, and the carbon residue in the particle aggregates may enhance the electrocatalytic activity for ORR. The feasibility of using conductive oxide materials as electrocatalysts is discussed. © 2013 Elsevier B.V.

  15. N-doped graphene coupled with Co nanoparticles as an efficient electrocatalyst for oxygen reduction in alkaline media

    Science.gov (United States)

    Zhang, Geng; Lu, Wangting; Cao, Feifei; Xiao, Zhidong; Zheng, Xinsheng

    2016-01-01

    Development of low-cost and highly efficient electrocatalysts for oxygen reduction reaction (ORR) is still a great challenge for the large-scale application of fuel cells and metal-air batteries. Herein, a noble metal-free ORR electrocatalyst in the form of N-doped graphene coupled with part of Co nanoparticles encased in N-doped graphitic shells (named as SUCo-0.03-800) is prepared by facile one-step pyrolysis of the mixture of sucrose, urea and cobalt nitrate. The novel structure is confirmed by High Resolution-TEM, XRD, XPS and Raman spectroscopy. SUCo-0.03-800 presents comparable ORR catalytic activity to commercial Pt/C catalyst with a dominating four-electron pathway under alkaline conditions, and both of its mass activity and volume activity also outperform Co-free N-doped graphene and other Co/N-C hybrids with higher Co content, which may probably be ascribed to the high specific surface area, novel structure and synergistic effect between encased Co nanoparticles and N-doped graphitic shell. Additionally, SUCo-0.03-800 also shows outstanding stability and improved selectivity towards ORR, making it a promising alternative to Pt with potential application in fuel cells and metal-air batteries.

  16. 57Fe-Mössbauer spectroscopy and electrochemical activities of graphitic layer encapsulated iron electrocatalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Zhong, Lijie; Frandsen, Cathrine; Mørup, Steen

    2018-01-01

    Graphitic layer encapsulated iron based nanoparticles (G@FeNPs) have recently been disclosed as an interesting type of highly active electrocatalysts for the oxygen reduction reaction (ORR). However, the complex composition of the metal-containing components and their contributions in catalysis r...

  17. 2D Ultrathin Core-shell Pd@Ptmonolayer Nanosheets: Defect-Mediated Thin Film Growth and Enhanced Oxygen Reduction Performance

    KAUST Repository

    Wang, Wenxin

    2015-06-16

    An operational strategy for the synthesis of atomically smooth Pt skin by a defect-mediated thin film growth method is reported. Extended ultrathin core-shell structured Pd@Ptmonolayer nanosheets (thickness below 5 nm) exhibit a seven-fold enhancement in mass-activity and surprisingly good durability toward oxygen reduction reaction as compared with the commercial Pt/C catalyst.

  18. Synthesis of self-supported non-precious metal catalysts for oxygen reduction reaction with preserved nanostructures from the polyaniline nanofiber precursor

    DEFF Research Database (Denmark)

    Hu, Yang; Zhao, Xiao; Huang, Yunjie

    2013-01-01

    Non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) are an active subject of recent research on proton exchange membrane fuel cells. In this study, we report a new approach to preparation of self-supported and nano-structured NPMCs using pre-prepared polyaniline (PANI...

  19. 2D Ultrathin Core-shell Pd@Ptmonolayer Nanosheets: Defect-Mediated Thin Film Growth and Enhanced Oxygen Reduction Performance

    KAUST Repository

    Wang, Wenxin; Zhao, Yunfeng; Ding, Yi

    2015-01-01

    An operational strategy for the synthesis of atomically smooth Pt skin by a defect-mediated thin film growth method is reported. Extended ultrathin core-shell structured Pd@Ptmonolayer nanosheets (thickness below 5 nm) exhibit a seven-fold enhancement in mass-activity and surprisingly good durability toward oxygen reduction reaction as compared with the commercial Pt/C catalyst.

  20. Carbon-supported manganese oxide nanoparticles as electrocatalysts for the Oxygen Reduction Reaction (ORR) in alkaline medium: Physical characterizations and ORR mechanism

    Czech Academy of Sciences Publication Activity Database

    Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

    2007-01-01

    Roč. 111, č. 3 (2007), s. 1434-1443 ISSN 1932-7447 R&D Projects: GA ČR GA104/02/0731; GA AV ČR KJB4813302 Institutional research plan: CEZ:AV0Z40320502 Keywords : Oxygen Reduction Reaction Subject RIV: CA - Inorganic Chemistry

  1. The Influence of Particle Shape and Size on the Activity of Platinum Nanoparticles for Oxygen Reduction Reaction: A Density Functional Theory Study

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Cerri, Isotta; Bligaard, Thomas

    2014-01-01

    We present first principle investigation of the influence of platinum nanoparticle shape and size on the oxygen reduction reaction activity. We compare the activities of nanoparticles with specific shapes (tetrahedron, octahedron, cube and truncated octahedron) with that of equilibrium particle s...

  2. Mechanistic model of the oxygen reduction catalyzed by a metal-free porphyrin in one- and two-phase liquid systems

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Záliš, Stanislav; Samec, Zdeněk

    2013-01-01

    Roč. 110, NOV 2013 (2013), s. 816-821 ISSN 0013-4686 R&D Projects: GA ČR GAP208/11/0697 Institutional support: RVO:61388955 Keywords : oxygen reduction * metal -free porphyrin * catalysis Subject RIV: CG - Electrochemistry Impact factor: 4.086, year: 2013

  3. Defective graphene supported MPd12 (M = Fe, Co, Ni, Cu, Zn, Pd) nanoparticles as potential oxygen reduction electrocatalysts: A first-principles study

    KAUST Repository

    Liu, Xin

    2013-01-24

    We studied the electronic structure of MPd12 (M = Fe, Co, Ni, Cu, Zn, Pd) nanoparticles deposited on graphene substrates and their reactivity toward O adsorption, which are directly related to the catalytic performance of these composites in oxygen reduction reaction, by first-principles-based calculations. We found that the alloying between M and Pd can enhance the stability of nanoparticles and promote their oxygen reduction activity to be comparable with that of Pt(111). The defective graphene substrate can provide anchoring sites for these nanoparticles by forming strong metal-substrate interaction. The interfacial interaction can contribute to additional stability and further tune the averaged d-band center of the deposited alloy nanoparticles, resulting in strong interference on the O adsorption. As the O adsorption on these composites is weakened, the oxygen reduction reaction kinetics over these composites will also be promoted. These composites are thus expected to exhibit both high stability and superior catalytic performance in oxygen reduction reaction. © 2013 American Chemical Society.

  4. Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes

    International Nuclear Information System (INIS)

    Le Bozec, N.

    2000-01-01

    Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

  5. The Asian methanol market

    International Nuclear Information System (INIS)

    Nagase, Hideki

    1995-01-01

    For the purpose of this presentation, Asia has been broadly defined as a total of 15 countries, namely Japan, Korea, Taiwan, China, Hong Kong, the Philippines, Thailand, Malaysia, Singapore, Indonesia, Myanmar, India, Vietnam, Australia and New Zealand. In 1994 and the first half of 1995, the methanol industry and its derivative industries experienced hard time, because of extraordinarily high methanol prices. In spite of this circumstance, methanol demand in Asian countries has been growing steadily and remarkably, following Asian high economic growth. Most of this growth in demand has been and will continue to be met by outside supply. However, even with increased import of methanol from outside of Asia, as a result of this growth, Asian trade volume will be much larger in the coming years. Asian countries must turn their collective attention to making logistics and transportation for methanol and its derivatives more efficient in the Asian region to make better use of existing supply resources. The author reviews current economic growth as his main topic, and explains the forecast of the growth of methanol demand and supply in Asian countries in the near future

  6. Integrated methanol synthesis

    International Nuclear Information System (INIS)

    Jaeger, W.

    1982-01-01

    This invention concerns a plant for methanol manufacture from gasified coal, particularly using nuclear power. In order to reduce the cost of the hydrogen circuits, the methanol synthesis is integrated in the coal gasification plant. The coal used is gasified with hydration by means of hydrogen and the crude gas emerging, after cooling and separating the carbon dioxide and hydrogen sulphide, is mixed with the synthetic gas leaving the methane cracking furnace. This mixture is taken to the methanol synthesis and more than 90% is converted into methanol in one pass. The gas mixture remaning after condensation and separation of methanol is decomposed into three fractions in low temperature gas decomposition with a high proportion of unconverted carbon monoxide. The flow of methane is taken to the cracking furnace with steam, the flow of hydrogen is taken to the hydrating coal gasifier, and the flow of carbon monoxide is taken to the methanol synthesis. The heat required for cracking the methane can either be provided by a nuclear reactor or by the coke left after hydrating gasification. (orig./RB) [de

  7. The Effect of Support on Advanced Pt-based Cathodes towards the Oxygen Reduction Reaction. State of the Art

    International Nuclear Information System (INIS)

    Luo, Yun; Alonso-Vante, Nicolas

    2015-01-01

    Graphical abstract: TOC: This mini-review summarizes advanced Pt catalysts towards enhanced ORR activity and stability. Tunable ORR activity and stability can be achieved in tailoring Pt active center, depending on nature of supporting materials. - Highlights: • Substrate effect leads to ORR activity and stability enhancement of catalyst centers. • Carbon-based materials and oxide-carbon composite influences favorably the Pt electronic environment. • Pt surface modification induced via ligand effect, geometric effect, metal-substrate strong interaction, and interaction of rare earth oxide and Pt surface atoms. • Sources for enhancement of ORR activity and stability were identified. - Abstract: This work summarizes the advanced materials developed by various research groups for improving the stability of platinum (Pt), and Pt-based catalysts center toward the oxygen reduction reaction (ORR) in acid medium. The ORR stability enhancement of Pt catalytic center can be classified according to the different nature of the supporting materials, namely, carbon-, oxide-based-, and oxide-carbon composites. The enhancement and stability of a catalytic center can be related to either its electronic modification induced by a strong interaction with the support, another metal (alloy), or to geometric effects. In addition, other parameters come into play, the size, the morphology of the catalytic center, the temperature, the dispersion, and mass loading, along with the measuring methods. This mini-review mainly focusses on the stability improvement, depending on the substrate nature. This latter can be further modified via functionalization or by the chemical interaction nature between the substrate and catalyst.

  8. Fabrication of iron-doped cobalt oxide nanocomposite films by electrodeposition and application as electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jingxuan; Wang, Xuemei; Qin, Dongdong; Xue, Zhonghua; Lu, Xiaoquan, E-mail: luxq@nwnu.edu.cn

    2014-11-30

    Highlights: • We fabricated the Fe-doped Co{sub 3}O{sub 4} nanofilms for the first time by potentiostatic electrodeposition method. • The Fe was doped homogeneously in the nanofilms by this method. • Among the different concentration ratios of Co{sup 2+}/Fe{sup 2+}, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. • The Fe-doped Co{sub 3}O{sub 4} nanofilms in this work exhibit good electrocatalytic activity toward oxygen reduction and appear to be promising cathodic electrocatalyst in alkaline fuel cells. - Abstract: In this work, Fe-doped Co{sub 3}O{sub 4} nanofilms were fabricated by electrodeposition on FTO glass substrates for the first time. The structures of the as-prepared nanofilms were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Characterization results demonstrate that Fe was doped homogeneously in the nanofilms. As the different concentration ratios of Fe{sup 2+}/Co{sup 2+} were explored, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. It is considered that the difference in the catalytic activities for the ORR of the samples may be due to the fact that the joining of iron changed the catalyst surface's electric state and enhanced the acidity of cobalt centers, on the other hand, the doping process probably modified the absorption property of the nanofilms. The experimental results suggest that the Fe-doped Co{sub 3}O{sub 4} nanofilms in this work exhibit favorable electrocatalytic activity toward ORR and appear to be promising cathodic electrocatalyst in alkaline fuel cells.

  9. Mechanochemical synthesis of Co and Ni decorated with chemically deposited Pt as electrocatalysts for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Flores-Rojas, E.; Cabañas-Moreno, J.G.; Pérez-Robles, J.F.; Solorza-Feria, O.

    2016-01-01

    High energy milling in combination with galvanic displacement were used for the preparation of bimetallic nanocatalysts. Co and Ni monometallic powders milled for 30 and 20 h, respectively were both produced in air atmosphere and used as precursors for the preparation of M-Pt (M = Co,Ni) compounds. Nanosized monometallic powders were physically supported on Vulcan carbon, and covered with 20 wt%Pt through a Galvanic Displacement Reaction (GDR) to produce Co-20Pt/C and Ni-20Pt/C electrocatalysts. XRD was used for phase identification on milled powders and for demonstrating structural transformations of Co powders during milling. Results on unmilled metallic Co powder show a predominant HCP structure modifying to a FCC structure after milling. Ni powders maintain their same FCC structure. Energy Dispersive X-Ray Spectometry (EDX) was used for chemical composition analysis on milled powders at several milling times. Scanning Transmission Electron Microscopy (STEM) show the formation of heterogeneous particle with ∼10 nm in size for both electrocatalysts. The electrocatalytic activity was evaluated by Cyclic Voltammetry (CV) and steady state Rotating Disk Electrode (RDE) for the Oxygen Reduction Reaction (ORR) in 0.1 M HClO_4. The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the cathodic reaction. - Highlights: • Monometallic powders of Co, and Ni were used as precursors for the preparation of M-Pt (M = Co,Ni) electrocatalysts. • Nanosized monometallic powders were decorated with Pt by a Galvanic Displacement Reaction. • The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the ORR reaction.

  10. Lignin-derived electrospun carbon nanofiber mats with supercritically deposited Ag nanoparticles for oxygen reduction reaction in alkaline fuel cells

    International Nuclear Information System (INIS)

    Lai, Chuilin; Kolla, Praveen; Zhao, Yong; Fong, Hao; Smirnova, Alevtina L.

    2014-01-01

    Highlights: • Electrospun carbon nanofiber mats were prepared from a natural product of lignin. • The freestanding mats were flexible with BET specific surface area of ∼583 m 2 /g. • The mats were surface-deposited with Ag nanoparticles via the scCO 2 method. • Novel electrocatalytic systems of Ag/ECNFs exhibited high activities towards ORR. - Abstract: Ag nanoparticles (AgNPs) (11, 15, and 25 wt.%) were deposited on the surface of the freestanding and mechanically flexible mats consisting of lignin-derived electrospun carbon nanofibers (ECNFs) by the supercritical CO 2 method followed by the thermal treated at 180 °C. The electrochemical activity of Ag/ECNFs electrocatalyst systems towards oxygen reduction reaction (ORR) was studied in 0.1 M KOH aqueous solution using the rotating disk/rotating ring disk electrode (RDE/RRDE) technique. The SEM, TEM, and XRD results indicated that, the spherical AgNPs were uniformly distributed on the ECNF surface with sizes in the range of 2-10 nm. The electrocatalytic results revealed that, all of the Ag/ECNFs systems exhibited high activity in ORR and demonstrated close-to-theoretical four-electron pathway. In particular, the mass activity of 15 wt.% Ag/ECNFs system was the highest (119 mA mg −1 ), exceeding that of HiSPEC 4100™ commercial Pt/C catalyst (98 mA mg −1 ). This study suggested that the lignin-derived ECNF mats surface-deposited with AgNPs would be promising as cost-effective and highly efficient electrocatalyst for ORR in alkaline fuel cells

  11. Pt-Ag cubic nanocages with wall thickness less than 2 nm and their enhanced catalytic activity toward oxygen reduction.

    Science.gov (United States)

    Sun, Xiaojun; Yang, Xuan; Zhang, Yun; Ding, Yong; Su, Dong; Qin, Dong

    2017-10-12

    We report a facile synthesis of Pt-Ag nanocages with walls thinner than 2 nm by depositing a few atomic layers of Pt as conformal shells on Ag nanocubes and then selectively removing the Ag template via wet etching. In a typical process, we inject a specific volume of aqueous H 2 PtCl 6 into a mixture of Ag nanocubes, ascorbic acid (H 2 Asc), NaOH, and poly(vinylpyrrolidone) in water under ambient conditions. At an initial pH of 11.9, the Pt(iv) precursor is quickly reduced by an ascorbate monoanion, a strong reducing agent derived from the neutralization of H 2 Asc with NaOH. The newly formed Pt atoms are deposited onto the edges and then corners and side faces of Ag nanocubes, leading to the generation of Ag@Pt core-shell nanocubes with a conformal Pt shell of approximately three atomic layers (or, about 0.6 nm in thickness) when 0.4 mL of 0.2 mM H 2 PtCl 6 is involved. After the selective removal of Ag in the core using an etchant based on a mixture of Fe(NO 3 ) 3 and HNO 3 , we transform the core-shell nanocubes into Pt-Ag alloy nanocages with an ultrathin wall thickness of less than 2 nm. We further demonstrate that the as-obtained nanocages with a composition of Pt 42 Ag 58 exhibit an enhanced catalytic activity toward the oxygen reduction reaction, with a mass activity of 0.30 A mg -1 and a specific activity of 0.93 mA cm -2 , which are 1.6 and 2.5 times, respectively, greater than those of a commercial Pt/C catalyst.

  12. High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

    Science.gov (United States)

    Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

    2018-02-26

    The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

  13. Ga-Doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Lim, JeongHoon; Shin, Hyeyoung; Kim, MinJoong; Lee, Hoin; Lee, Kug-Seung; Kwon, YongKeun; Song, DongHoon; Oh, SeKwon; Kim, Hyungjun; Cho, EunAe

    2018-04-11

    Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mg Pt -1 ) and a 17.3-fold improvement in the specific activity (2.53 mA cm -2 ) compared to the commercial Pt/C (0.106 A mg Pt -1 and 0.146 mA cm -2 ). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications.

  14. Iridium-decorated palladium-platinum core-shell catalysts for oxygen reduction reaction in proton exchange membrane fuel cell.

    Science.gov (United States)

    Wang, Chen-Hao; Hsu, Hsin-Cheng; Wang, Kai-Ching

    2014-08-01

    Carbon-supported Pt, Pd, Pd-Pt core-shell (Pt(shell)-Pd(core)/C) and Ir-decorated Pd-Pt core-shell (Ir-decorated Pt(shell)-Pd(core)/C) catalysts were synthesized, and their physical properties, electrochemical behaviors, oxygen reduction reaction (ORR) characteristics and proton exchange membrane fuel cell (PEMFC) performances were investigated herein. From the XRD patterns and TEM images, Ir-decorated Pt(shell)-Pd(core)/C has been confirmed that Pt was deposited on the Pd nanoparticle which had the core-shell structure. Ir-decorated Pt(shell)-Pd(core)/C has more positive OH reduction peak than Pt/C, which is beneficial to weaken the binding energy of Pt-OH during the ORR. Thus, Ir-decorated Pt(shell)-Pd(core)/C has higher ORR activity than Pt/C. The maximum power density of H2-O2 PEMFC using Ir-decorated Pt(shell)-Pd(core)/C is 792.2 mW cm(-2) at 70°C, which is 24% higher than that using Pt/C. The single-cell accelerated degradation test of PEMFC using Ir-decorated Pt(shell)-Pd(core)/C shows good durability by the potential cycling of 40,000 cycles. This study concludes that Ir-decorated Pt(shell)-Pd(core)/C has the low Pt content, but it can facilitate the low-cost and high-efficient PEMFC. Copyright © 2013 Elsevier Inc. All rights reserved.

  15. Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

    Science.gov (United States)

    Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

    2017-06-20

    An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

  16. Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability

    Directory of Open Access Journals (Sweden)

    Ariel Jackson

    2018-01-01

    Full Text Available Improving the performance of oxygen reduction reaction (ORR electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs. Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mgPt−1 at 0.9 V versus the reversible hydrogen electrode (RHE, which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mgPt−1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s−1, maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

  17. Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability.

    Science.gov (United States)

    Jackson, Ariel; Strickler, Alaina; Higgins, Drew; Jaramillo, Thomas Francisco

    2018-01-12

    Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mg Pt -1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mg Pt -1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s -1 ), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

  18. ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hao; Yin, Feng-Xiang; Chen, Biao-Hua; He, Xiao-Bo; Lv, Peng-Liang; Ye, Cai-Yun; Liu, Di-Jia

    2017-05-01

    Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wa Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.

  19. Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

    Science.gov (United States)

    Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

    2017-08-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO 2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Mechanochemical synthesis of Co and Ni decorated with chemically deposited Pt as electrocatalysts for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Flores-Rojas, E.; Cabañas-Moreno, J.G. [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Pérez-Robles, J.F. [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Dpto. Ciencia de los Materiales, CINVESTAV-IPN Unidad Queretaro, Libramiento Norponiente No. 2000 Fracc. Real de Juriquilla, 76230, Queretaro (Mexico); Solorza-Feria, O., E-mail: osolorza@cinvestav.mx [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Depto. Química, CINVESTAV-IPN, 07360, México City (Mexico)

    2016-11-01

    High energy milling in combination with galvanic displacement were used for the preparation of bimetallic nanocatalysts. Co and Ni monometallic powders milled for 30 and 20 h, respectively were both produced in air atmosphere and used as precursors for the preparation of M-Pt (M = Co,Ni) compounds. Nanosized monometallic powders were physically supported on Vulcan carbon, and covered with 20 wt%Pt through a Galvanic Displacement Reaction (GDR) to produce Co-20Pt/C and Ni-20Pt/C electrocatalysts. XRD was used for phase identification on milled powders and for demonstrating structural transformations of Co powders during milling. Results on unmilled metallic Co powder show a predominant HCP structure modifying to a FCC structure after milling. Ni powders maintain their same FCC structure. Energy Dispersive X-Ray Spectometry (EDX) was used for chemical composition analysis on milled powders at several milling times. Scanning Transmission Electron Microscopy (STEM) show the formation of heterogeneous particle with ∼10 nm in size for both electrocatalysts. The electrocatalytic activity was evaluated by Cyclic Voltammetry (CV) and steady state Rotating Disk Electrode (RDE) for the Oxygen Reduction Reaction (ORR) in 0.1 M HClO{sub 4}. The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the cathodic reaction. - Highlights: • Monometallic powders of Co, and Ni were used as precursors for the preparation of M-Pt (M = Co,Ni) electrocatalysts. • Nanosized monometallic powders were decorated with Pt by a Galvanic Displacement Reaction. • The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the ORR reaction.

  1. Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

    International Nuclear Information System (INIS)

    Yaldagard, Maryam; Jahanshahi, Mohsen; Seghatoleslami, Naser

    2014-01-01

    Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C

  2. Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

    Energy Technology Data Exchange (ETDEWEB)

    Yaldagard, Maryam, E-mail: m_yaldagard@yahoo.com [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of); Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Jahanshahi, Mohsen, E-mail: mjahan@nit.um.ac.ir [Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Seghatoleslami, Naser, E-mail: Slami@um.ac.ir [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of)

    2014-10-30

    Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C.

  3. Shedding Light on the Oxygen Reduction Reaction Mechanism in Ether-Based Electrolyte Solutions: A Study Using Operando UV-Vis Spectroscopy.

    Science.gov (United States)

    Hirshberg, Daniel; Sharon, Daniel; Afri, Michal; Lavi, Ronit; Frimer, Aryeh A; Metoki, Noa; Eliaz, Noam; Kwak, Won-Jin; Sun, Yang-Kook; Aurbach, Doron

    2018-04-04

    Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

  4. Electrocatalysts of platinum, cobalt and nickel prepared by mechanical alloying for the oxygen reduction reaction in H2SO4 0.5M

    International Nuclear Information System (INIS)

    Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R.

    2007-01-01

    Metallic powders of Pt, Co and Nickel were processed by mechanical alloyed and electrocatalysts were synthesized for the oxygen reduction reaction, applicable in fuel cells. The structural and morphological characterization was carried out using X-ray Diffraction, scanning electron microscopy and transmission electron microscopy. It was found that the alloyed powders formed agglomerates that consist of crystalline particles of nano metric size. Its were obtained polarization curves by the Electrode of Rotational Disk technique in a solution of H 2 SO 4 0.5 M, used as electrolyte, to evaluate the electrocatalytic activity of mechanically alloyed powders. Tafel graphics were built to determine the kinetic parameters of each electro catalyst. The PtCoNi alloy exhibited the biggest electrocatalytic activity, with the smallest over potential for the oxygen reduction reaction. (Author)

  5. 2D ultrathin core-shell Pd@Ptmonolayer nanosheets: defect-mediated thin film growth and enhanced oxygen reduction performance

    Science.gov (United States)

    Wang, Wenxin; Zhao, Yunfeng; Ding, Yi

    2015-07-01

    An operational strategy for the synthesis of atomically smooth Pt skin by a defect-mediated thin film growth method is reported. Extended ultrathin core-shell structured d@Ptmonolayer nanosheets (thickness below 5 nm) exhibit nearly seven-fold enhancement in mass-activity and surprisingly good durability toward oxygen reduction reaction as compared with the commercial Pt/C catalyst.An operational strategy for the synthesis of atomically smooth Pt skin by a defect-mediated thin film growth method is reported. Extended ultrathin core-shell structured d@Ptmonolayer nanosheets (thickness below 5 nm) exhibit nearly seven-fold enhancement in mass-activity and surprisingly good durability toward oxygen reduction reaction as compared with the commercial Pt/C catalyst. Electronic supplementary information (ESI) available: Sample preparation, physical and electrochemical characterization, Fig. S1 to S11. See DOI: 10.1039/c5nr02748a

  6. Electrocatalysts with platinum, cobalt and nickel preparations by mechanical alloyed and CVD for the reaction of oxygen reduction

    International Nuclear Information System (INIS)

    Garcia C, M. A.

    2008-01-01

    In this research, the molecular oxygen reduction reaction (ORR) was investigated on electrocatalysts of Co, Ni, Pt and their alloys CoNi, PtCo, PtNi and PtCoNi by using H 2 SO 4 0.5 and KOH 0.5 M solutions as electrolytes. The electrocatalysts were synthesized by Mechanical Alloying (MA) and Chemical Vapor Deposition (CVD) processes. For MA, metallic powders were processed during 20 h of milling in a high energy SPEX 8000 mill. For CVD, a hot-wall reactor was utilized and Co, Ni and Pt acetilactetonates were used as precursors. Films were deposited at a total pressure of 1 torr and temperatures of 400-450 C. Electrocatalysts were characterized by X-Ray Diffraction (XRD). Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Energy Dispersive X-Ray Spectroscopy (EDS). Electrocatalysts prepared by mechanical alloying showed a homogeneously dispersed agglomeration of particles with nano metric size. Electrocatalysts obtained by CVD showed, in some cases, non uniform films, with particles of nano metric size, as well. The electrocatalytic performance was evaluated by using the Rotating Disk Electrode technique (RDE). Electrocatalysts prepared by MA showed higher activity than those obtained by CVD. All electrocatalysts were evaluated in alkaline media. Only electrocatalysts containing Pt were evaluated in acid media, because those materials with Co, Ni and their alloys showed instability in acidic media. Most electrocatalysts followed a mechanism for the ORR producing a certain proportion of H 2 O 2 . All electrocatalysts, exhibited a fair or good electrocatalytic activity in comparison with other similar reported materials. It was found that MA and CVD are appropriate processes to prepare electrocatalysts for the ORR with particles of nano metric size and performing with an acceptable catalytic activity. PtCoNi 70-23-7% by MA and PtCoNi-CVD electrocatalysts showed the highest activity in alkaline media, while in acidic electrolyte PtCoNi 70

  7. The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts.

    Science.gov (United States)

    Fortunelli, Alessandro; Goddard Iii, William A; Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Jaramillo-Botero, Andrés

    2015-07-01

    Recently Debe et al. reported that Pt 3 Ni 7 leads to extraordinary Oxygen Reduction Reaction (ORR) activity. However, several reports show that hardly any Ni remains in the layers of the catalysts close to the surface ("Pt-skin effect"). This paradox that Ni is essential to the high catalytic activity with the peak ORR activity at Pt 3 Ni 7 while little or no Ni remains close to the surface is explained here using large-scale first-principles-based simulations. We make the radical assumption that processing Pt-Ni catalysts under ORR conditions would leach out all Ni accessible to the solvent. To simulate this process we use the ReaxFF reactive force field, starting with random alloy particles ranging from 50% Ni to 90% Ni and containing up to ∼300 000 atoms, deleting the Ni atoms, and equilibrating the resulting structures. We find that the Pt 3 Ni 7 case and a final particle radius around 7.5 nm lead to internal voids in communication with the exterior, doubling the external surface footprint, in fair agreement with experiment. Then we examine the surface character of these nanoporous systems and find that a prominent feature in the surface of the de-alloyed particles is a rhombic structure involving 4 surface atoms which is crystalline-like but under-coordinated. Using density-functional theory, we calculate the energy barriers of ORR steps on Pt nanoporous catalysts, focusing on the O ad -hydration reaction (O ad + H 2 O ad → OH ad + OH ad ) but including the barriers of O 2 dissociation (O 2ad → O ad + O ad ) and water formation (OH ad + H ad → H 2 O ad ). We find that the reaction barrier for the O ad -hydration rate-determining-step is reduced significantly on the de-alloyed surface sites compared to Pt(111). Moreover we find that these active sites are prevalent on the surface of particles de-alloyed from a Pt-Ni 30 : 70 initial composition. These simulations explain the peak in surface reactivity at Pt 3 Ni 7 , and provide a rational guide to

  8. 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

  9. Highly dispersed TaOx nanoparticles prepared by electrodeposition as oxygen reduction electrocatalysts for polymer electrolyte fuel cells

    KAUST Repository

    Seo, Jeongsuk

    2013-06-06

    Based on the chemical stability of group IV and V elements in acidic solutions, TaOx nanoparticles prepared by electrodeposition in an ethanol-based Ta plating bath at room temperature were investigated as novel nonplatinum electrocatalysts for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFCs). Electrodeposition conditions of Ta complexes and subsequent various heat treatments for the deposited TaOx were examined for the best performance of the ORR. TaOx particles on carbon black (CB), electrodeposited at a constant potential of -0.5 V Ag/AgCl for 10 s and then heat-treated by pure H2 flow at 523 K for 1 h, showed excellent catalytic activity with an onset potential of 0.93 VRHE (for 2 μA cm-2) for the ORR. Surface characterizations of the catalysts were performed by scanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). The loading amounts of the electrodeposited material on the CB were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). All the physical results suggested that high dispersion of TaOx particles on the CB surface with 2-3 nm size was critical and key for high activity. The chemical identity and modified surface structure for the deposited TaOx catalysts before and after H 2 heat treatment were analyzed by X-ray photoelectron spectroscopy (XPS). The formation of more exposed active sites on the electrode surface and enhanced electroconductivity of the tantalum oxide promoted from the H 2 treatment greatly improved the ORR performance of the electrodeposited TaOx nanoparticles on CB. Finally, the highly retained ORR activity after an accelerated durability test in an acidic solution confirmed and proved the chemical stability of the oxide nanoparticles. The high utilization of the electrodeposited TaOx nanoparticles uniformly dispersed on CB for the ORR was comparable to that of commercial Pt/CB catalysts

  10. Oxygen reduction reaction of (C-PCTNB@CNTs): A nitrogen and phosphorus dual-doped carbon electro-catalyst derived from polyphosphazenes

    Science.gov (United States)

    Dar, Sami Ullah; Ud Din, Muhammad Aizaz; Hameed, Muhammad Usman; Ali, Shafqat; Akram, Raheel; Wu, Zhanpeng; Wu, Dezhen

    2018-01-01

    This research describes the synthesis of a novel type of poly [cyclotriphosphazene-co-1,3,5-triol nitrobenzene] (PCTNB) microspheres with uniform size and diameter of more than 2 μm having well characterization. These microspheres are further used to wrap the CNTs by a facile route using template based non-covalent method to form PCTNB@CNTs composite. This composite is further well analyzed before it is subjected to pyrolysis. The direct carbonization of the PCTNB@CNTs is performed at 600 °C at a rate of 5 °C/min under N2 atmosphere to render the N, P, O doped carbonized PCTNB@CNTs having enhanced electronic features to be applied as an ORR electrocatalysts in fuel cells accompanied by TEM, XPS, Raman, FT-IR, TGA and BET analyses. Here, we have designed a metal-free, N, P, O doped (C-PCTNB@CNTs) electro-catalyst which exhibit significantly high ORR performance in acidic PEM cells showing much higher onset potential of (0.94 V) and half-wave potential of (0.85 V) with electron transfer number (n) 3.9 at 0.4-0.7 V as compared to other non-metallic electro-catalysts. Thus, (C-PCTNB@CNTs) is a metal-free, methanol tolerant carbon-based ORR catalyst, and it opens up new avenues for clean energy generation for affordable and durable fuel cells.

  11. Composite of TiN nanoparticles and few-walled carbon nanotubes and its application to the electrocatalytic oxygen reduction reaction

    KAUST Repository

    Isogai, Shunsuke

    2011-11-30

    Nanoparticles meet nanotubes! Direct synthesis of TiN nanoparticles in a three-dimensional network of few-walled carbon nanotubes (FWCNTs) was achieved by using mesoporous graphitic carbon nitride (C 3N 4) as both a hard template and a nitrogen source. The TiN/FWCNT composite showed high performance for the oxygen reduction reaction in acidic media. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Oxygen reduction reaction properties of nitrogen-incorporated nanographenes synthesized using in-liquid plasma from mixture of ethanol and iron phthalocyanine

    Science.gov (United States)

    Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

    2018-04-01

    Nanographenes were synthesized using in-liquid plasma from a mixture of iron phthalocyanine and ethanol. In a previous study, micrometer-scale flakes with nitrogen incorporation were obtained. A nonprecious metal catalytic activity was observed with 3.13 electrons in an oxygen reduction reaction under an acidic solute condition. Large-surface-area, high-graphene-crystallinity, and iron-carbon-bonding sites were found owing to a high catalytic activity in Fe-N/nanographene.

  13. Direct Methanol Fuel Cell, DMFC

    Directory of Open Access Journals (Sweden)

    Amornpitoksuk, P.

    2003-09-01

    Full Text Available Direct Methanol Fuel Cell, DMFC is a kind of fuel cell using methanol as a fuel for electric producing. Methanol is low cost chemical substance and it is less harmful than that of hydrogen fuel. From these reasons it can be commercial product. The electrocatalytic reaction of methanol fuel uses Pt-Ru metals as the most efficient catalyst. In addition, the property of membrane and system designation are also effect to the fuel cell efficient. Because of low power of methanol fuel cell therefore, direct methanol fuel cell is proper to use for the energy source of small electrical devices and vehicles etc.

  14. Improvement of activated carbons as oxygen reduction catalysts in neutral solutions by ammonia gas treatment and their performance in microbial fuel cells

    KAUST Repository

    Watson, Valerie J.

    2013-11-01

    Commercially available activated carbon (AC) powders from different precursor materials (peat, coconut shell, coal, and hardwood) were treated with ammonia gas at 700 C to improve their performance as oxygen reduction catalysts in neutral pH solutions used in microbial fuel cells (MFCs). The ammonia treated ACs exhibited better catalytic performance in rotating ring-disk electrode tests than their untreated precursors, with the bituminous based AC most improved, with an onset potential of Eonset = 0.12 V (untreated, Eonset = 0.08 V) and n = 3.9 electrons transferred in oxygen reduction (untreated, n = 3.6), and the hardwood based AC (treated, E onset = 0.03 V, n = 3.3; untreated, Eonset = -0.04 V, n = 3.0). Ammonia treatment decreased oxygen content by 29-58%, increased nitrogen content to 1.8 atomic %, and increased the basicity of the bituminous, peat, and hardwood ACs. The treated coal based AC cathodes had higher maximum power densities in MFCs (2450 ± 40 mW m-2) than the other AC cathodes or a Pt/C cathode (2100 ± 1 mW m-2). These results show that reduced oxygen abundance and increased nitrogen functionalities on the AC surface can increase catalytic performance for oxygen reduction in neutral media. © 2013 Elsevier B.V. All rights reserved.

  15. 2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

    Science.gov (United States)

    Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

    2016-08-01

    Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets

  16. Methanol from biomass and hydrogen

    International Nuclear Information System (INIS)

    Anon.

    1989-01-01

    For Hawaii in the near term, the only liquid fuels indigenous sources will be those that can be made from biomass, and of these, methanol is the most promising. In addition, hydrogen produced by electrolysis can be used to markedly increase the yield of biomass methanol. This paper calculates cost of producing methanol by an integrated system including a geothermal electricity facility plus a plant producing methanol by gasifying biomass and adding hydrogen produced by electrolysis. Other studies cover methanol from biomass without added hydrogen and methanol from biomass by steam and carbon dioxide reforming. Methanol is made in a two-step process: the first is the gasification of biomass by partial oxidation with pure oxygen to produce carbon oxides and hydrogen, and the second is the reaction of gases to form methanol. Geothermal steam is used to generate the electricity used for the electrolysis to produce the added hydrogen

  17. Oxygen Reduction Kinetics of La2-xSrxNiO 4+delta Electrodes for Solid Oxide Fuel Cells

    Science.gov (United States)

    Guan, Bo

    In the development of intermediate temperature solid oxide fuel cell (IT-SOFC), mixed ionic-electronic conductors (MIEC) have drawn big interests due to their both ionic and electronic species transport which can enlarge the 3-dimension of the cathode network. This thesis presents an investigation of MIEC of Ruddlesden-popper (RP) phases like K2NiF4 type La2NiO4+delta (LNO)-based oxides which have interesting transport, catalytic properties and suitable thermal expansion coefficients. The motivation of this present work is to further understand the fundamental of the effect of Sr doing on the oxygen reduction reaction (ORR) kinetics of LNO cathode. Porous symmetrical cells of La2-xSrxNiO4+delta (0≤x≤0.4) were fabricated and characterized by electrochemical impedance spectroscopy (EIS) in different PO2 from temperature range of 600˜800°C. The spectra were analyzed based on the impedance model introduced by Adler et al. The rate determining steps (RDS) for ORR were proposed and the responsible reasons were discussed. The overall polarization resistances of doped samples increase with Sr level. Surface oxygen exchange and bulk ionic diffusion co-control the ORR kinetics. With high Sr content (x=0.3, 0.4), oxygen ion transfer resistance between nickelate/electrolyte is observed. However for porous symmetrical cells it is hard to associate the resistance from EIS directly to each ORR elementary processes because of the difficulty in describing the microstructure of the porous electrode. The dense electrode configuration was adopted in this thesis. By using the dense electrode, the surface area, the thickness of electrode, the interface between electrode and electrolyte and lastly the 3PB are theoretically well-defined. Through this method, there is a good chance to distinguish the contribution of surface exchange from other processes. Dense and thin electrode layers in thickness of ˜40 mum are fabricated by using a novel spray modified pressing method. Negligible

  18. Methanol production by Mycobacterium smegmatis

    International Nuclear Information System (INIS)

    Weisman, L.S.; Ballou, C.E.

    1988-01-01

    Mycobacterium smegmatis cells produce [ 3 H]methanol when incubated with [methyl- 3 H]methionine. The methanol is derived from S-adenosylmethionine rather than methyltetrahydrofolate. M. smegmatis cells carboxymethylate several proteins, and some of the methanol probably results from their demethylation, but most of the methanol may come from an unidentified component with a high gel mobility. Although methanol in the medium reached 19 μM, it was not incorporated into the methylated mannose polysaccharide, a lipid carrier in this organism

  19. Hot new gamble on methanol

    Energy Technology Data Exchange (ETDEWEB)

    Hatton, J.

    1981-10-01

    Methanol from coal, wood, or natural gas is being considered as an extender or an alternative source of gasoline. Firms such as Nova and Celanese are gambling millions on the proposition that methanol is a crucial steppingstone to the fuels and chemicals of the future. With a new process developed by Mobil Oil, methanol from coal could be converted into gasoline. By the 1990s Imperial Oil Ltd. expects there will be at least one methanol plant using Alberta coal. These and other plans by the Alberta and British Columbia governments and by Canadian industry to produce methanol are reported.

  20. Methanol commercial aviation fuel

    International Nuclear Information System (INIS)

    Price, R.O.

    1992-01-01

    Southern California's heavy reliance on petroleum-fueled transportation has resulted in significant air pollution problems within the south Coast Air Basin (Basin) which stem directly from this near total dependence on fossil fuels. To deal with this pressing issue, recently enacted state legislation has proposed mandatory introduction of clean alternative fuels into ground transportation fleets operating within this area. The commercial air transportation sector, however, also exerts a significant impact on regional air quality which may exceed emission gains achieved in the ground transportation sector. This paper addresses the potential, through the implementation of methanol as a commercial aviation fuel, to improve regional air quality within the Basin and the need to flight test and demonstrate methanol as an environmentally preferable fuel in aircraft turbine engines

  1. Methanol and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Gauthier-Lafaye, J.; Perron, R.

    1987-01-01

    The overall focus of the book is on homogeneous catalysed processes which were seen to offer the most promising routes to C/sub 2/ oxygenates. The first three chapters review the industrial synthesis and applications of carbon monoxide such as in the manufacture of gasoline (e.g. Fischer-Tropsch, Mobil processes), organic chemicals (e.g. ethanol, acetic acid, etc.), industrial importance of C/sub 2/ oxygenates, and use of methanol as a future feedstock are discussed. The next six chapters are each concerned with the production of a particular C/sub 2/ oxygenate and a detailed analysis of the methods and catalysts used. The hydrocarbonylation of methanol occupies a large chapter (136 references) with a comparative examination of the catalysts available, and their modification to increase selectivity to either acetylaldehyde or ethanol. Following chapters examine the synthesis of ethyl acetate, acetic acid, acetic anhydride, vinyl acetate, ethylene glycol and oxalic acid.

  2. Nitrofurantoin methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Venu R. Vangala

    2011-03-01

    Full Text Available The antibiotic nitrofurantoin {systematic name: (E-1-[(5-nitro-2-furylmethylideneamino]imidazolidine-2,4-dione} crystallizes as a methanol monosolvate, C8H6N4O5·CH4O. The nitrofurantoin molecule adopts a nearly planar conformation (r.m.s. deviation = 0.0344 Å. Hydrogen bonds involve the co-operative N—H...O—H...O heterosynthons between the cyclic imide of nitrofurantoin and methanol O—H groups. There are also C—H...O hydrogen bonds involving the nitrofurantoin molecules which support the key hydrogen-bonding synthon. The overall crystal packing is further assisted by weak C—H...O interactions, giving a herringbone pattern.

  3. Oxygen reduction kinetics and transport properties of (Ba,Sr)(Co,Fe)O3-δ solid oxide fuel cell cathode materials

    International Nuclear Information System (INIS)

    Wang, Lei; Merkle, Rotraut; Baumann, Frank S.; Maier, Joachim; Fleig, Juergen

    2007-01-01

    Full text: The oxygen reduction at the surface of cathode materials is crucial for the performance of solid oxide fuel cells (SOFC), but a detailed understanding of the mechanism is not available yet. (Ba x Sr 1-x )(Co 1-y Fe y )O 3-δ shows strongly improved oxygen reduction rates compared to previously applied perovskite cathode materials. In this work, surface rate constants as well as bulk transport properties are studied. (Ba x Sr 1-x )(Co 1-y Fe y )O 3-δ with 0≤x≤0.5, 0.2≤y≤1 was synthesized by the Pechini method. Oxygen stoichoimetry was obtained from thermo-gravimetric analysis, confirming that Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ has an exceptionally low oxygen content which is generally smaller than 2.5. Dense thin films were grown by pulsed laser deposition (PLD) and patterned into circular microelectrodes by photolithography. The surface resistance R s , which dominate the overall electrode resistance, were measured by impedance spectroscopy on individual microelectrodes at different T, pO 2 and applied electrical bias. PLD technique greatly helps to study the oxygen reduction kinetics since only measurements on dense thin films allow to record absolute R s values without interference from morphology effects. These R s values were found to be much lower than those for (La,Sr)(Co,Fe)O 3-δ . The variation of the surface reaction rates with A-site and B-site composition was studied and correlations with bulk materials properties such as oxygen nonstoichiometry, ionic mobility or oxidation enthalpy were examined. Plausible reaction mechanisms as well as possible reasons for the high absolute surface reaction rates will be discussed

  4. Effect of cathode porosity on the Lithium-air cell oxygen reduction reaction – A rotating ring-disk electrode investigation

    International Nuclear Information System (INIS)

    Seo, Jeongwook; Sankarasubramanian, Shrihari; Singh, Nikhilendra; Mizuno, Fuminori; Takechi, Kensuke; Prakash, Jai

    2017-01-01

    The kinetics of the oxygen reduction reaction (ORR) on the practical air cathode in a Lithium-air cell, which is conventionally composed of porous carbon with or without catalysts supported on it, was investigated. The mechanism and kinetics of the oxygen reduction reaction (ORR) was studied on a porous carbon electrode in an oxygen saturated solution of 0.1 M Lithium bis-trifluoromethanesulfonimide (LiTFSI) in Dimethoxyethane (DME) using cyclic voltammetery (CV) and the rotating ring-disk electrode (RRDE) technique. The oxygen reduction and evolution reactions were found to occur at similar potentials to those observed on a smooth, planar glassy carbon (GC) electrode. The effect of porosity and the resultant increase in surface area were readily observed in the increase in the transient time required for the intermediates to reach the ring and the much larger disk currents (compared to smooth, planar GC) recorded respectively. The RRDE data was analyzed using a kinetic model previously developed by us and the rate constants for the elementary reactions were calculated. The rates constant for the electrochemical reactions were found to be similar in magnitude to the rate constants calculated for smooth GC disks. The porosity of the electrode was found to decrease the rate of desorption of the intermediate and the product and delay their diffusion by shifting it from a Fickian regime in the electrolyte bulk to the Knudsen regime in the film pores. Thus, it is shown that the effect of the electrode porosity on the kinetics of the ORR is physical rather than electrochemical.

  5. Kinetics of oxygen reduction in perovskite cathodes for solid oxide fuel cells: A combined modeling and experimental approach

    Science.gov (United States)

    Miara, Lincoln James

    unknown rate constants (kad, k des, k1, k1¯ ), and parameters (Ds, Q°, n) arising from the governing equations are estimated from a combination of experiments, mathematical analysis, and numerical data analysis. In the second system, dense patterned films of cathode with composition: La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF-6428) were fabricated on Ga-doped CeO2 coated YSZ substrates. These samples were analyzed by EIS over a temperature and pO 2 range of 600--800 °C and 10-3--1.00 atm, respectively. To understand the EIS results, a 2-dimensional model was developed which accounted for surface oxygen exchange, and both surface and bulk transport of oxygen to the electrolyte interface. The results were obtained by numerically solving a stationary partial differential equation describing the oxygen vacancy distribution in the cathode. From these results, the model impedance was derived and then fitted to the experimental EIS results. From the fitting results the contributions to the impedance from each of the processes were estimated. Also, the surface exchange rate was estimated over the experimental operating conditions. Finally, the results suggest that the surface diffusion occurred by an interstitial type mechanism in this material. The cathode surface is intimately involved in most of the oxygen reduction processes; however, the surface structure and chemistry is typically treated as an extension of the bulk without consideration of the actual surface properties. Recent evidence suggests that significant changes occur to the surface during operation which in turn leads to changes in electrochemical performance. To investigate these phenomena, well-oriented thin films (250 nm in thickness) of Sr-doped lanthanum manginite (LSM) films were grown on single crystals of YSZ (111). Films which were cathodically biased with a -1 V applied dc potential were compared to control samples. The cathodic bias results in both an enhancement in electrochemical performance and a change in

  6. Deciphering Periodic Methanol Masers

    Science.gov (United States)

    Stecklum, Bringfried; Caratti o Garatti, Alessio; Henning, Thomas; Hodapp, Klaus; Hopp, Ulrich; Kraus, Alex; Linz, Hendrik; Sanna, Alberto; Sobolev, Andrej; Wolf, Verena

    2018-05-01

    Impressive progress has been made in recent years on massive star formation, yet the involved high optical depths even at submm/mm wavelengths make it difficult to reveal its details. Recently, accretion bursts of massive YSOs have been identified to cause flares of Class II methanol masers (methanol masers for short) due to enhanced mid-IR pumping. This opens a new window to protostellar accretion variability, and implies that periodic methanol masers hint at cyclic accretion. Pinning down the cause of the periodicity requires joint IR and radio monitoring. We derived the first IR light curve of a periodic maser host from NEOWISE data. The source, G107.298+5.639, is an intermediate-mass YSO hosting methanol and water masers which flare every 34.5 days. Our recent joint K-band and radio observations yielded first but marginal evidence for a phase lag between the rise of IR and maser emission, respectively, and revealed that both NEOWISE and K-band light curves are strongly affected by the light echo from the ambient dust. Both the superior resolution of IRAC over NEOWISE and the longer wavelengths compared to our ground-based imaging are required to inhibit the distractive contamination by the light echo. Thus, we ask for IRAC monitoring of G107 to cover one flare cycle, in tandem with 100-m Effelsberg and 2-m Wendelstein radio and NIR observations to obtain the first high-quality synoptic measurements of this kind of sources. The IR-maser phase lag, the intrinsic shape of the IR light curves and their possible color variation during the cycle allow us to constrain models for the periodic maser excitation. Since methanol masers are signposts of intermediate-mass and massive YSOs, deciphering their variability offers a clue to the dynamics of the accretion-mediated growth of massive stars and their feedback onto the immediate natal environment. The Spitzer light curve of such a maser-hosting YSO would be a legacy science product of the mission.

  7. One-pot, green, rapid synthesis of flowerlike gold nanoparticles/reduced graphene oxide composite with regenerated silk fibroin as efficient oxygen reduction electrocatalysts.

    Science.gov (United States)

    Xu, Shengjie; Yong, Liu; Wu, Peiyi

    2013-02-01

    Flowerlike gold nanoparticles (Au NPs)/reduced graphene oxide (RGO) composites were fabricated by a facile, one-pot, environmentally friendly method in the presence of regenerated silk fibroin (RSF). The influences of reaction time, temperature, and HAuCl(4): RGO ratio on the morphology of Au NPs loaded on RGO sheets were discussed and a tentative mechanism for the formation of flowerlike Au NPs/RGO composite was proposed. In addition, the flowerlike Au NPs/RGO composite showed superior catalytic performance for oxygen reduction reaction (ORR) to Au/RGO composites with other morphologies. Our work provides an alternative facile and green approach to synthesize functional metal/RGO composites.

  8. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis

    DEFF Research Database (Denmark)

    Su, Hai-Yan; Gorlin, Yelena; Man, Isabela Costinela

    2012-01-01

    Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen...... reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn2O3 and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V...

  9. Comparison between the Oxygen Reduction Reaction Activity of Pd5Ce and Pt5Ce

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Zheng, Jian; Rizzi, Gian Andrea

    2015-01-01

    A set of electrochemical and X-ray spectroscopy measurements have been used conjointly with density functional theory (DFT) simulations to study the activity and stability of Pd5Ce for the oxygen reduction reaction. A polycrystalline Pd5Ce rod has been selected as a model catalyst to test if resu......-Pd5Ce is more facile, requires less atom rearrangement, than transformation from Pt5Ce to Pt3Ce, which might explain the kinetic stability of Pt5Ce at low temperatures....

  10. Electro catalyst of platinum prepared by CVD for the oxygen reduction reaction; Electrocatalizador de platino preparado por CVD para la reaccion de reduccion de oxigeno

    Energy Technology Data Exchange (ETDEWEB)

    Garcia C, M.A.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Vargas G, J.R. [IPN, ESIQIE, 07300 Mexico D.F. (Mexico)

    2004-07-01

    In this work it is reported the preparation and characterization of platinum films obtained by the technique of chemical vapor deposition at low pressure, better well-known as LPCVD for their initials in English (Low Pressure Chemical Vapor Deposition). The technique has several industrial applications and in this work it is explored their possible use to prepare applicable electrocatalysts in fuel cells. The films were characterized by XRD, SEM, EDS and they were proven for to determine their acting in the Oxygen reduction reaction (Orr) in sulfuric acid 0.5 M, the results show that the material presents good activity for the reaction in study. (Author)

  11. The (p, ρ, T) of (methanol + benzene) and (methanol + ethylbenzene)

    International Nuclear Information System (INIS)

    Naziev, Yashar M.; Shahverdiyev, Astan N.; Hasanov, Vaqif H.

    2005-01-01

    The (p, ρ, T) of methanol, ethylbenzene and (methanol + benzene) and (methanol + ethylbenzene) at temperatures between (290 and 500) K and pressures in the range (0.1 to 60) MPa have been measured with a magnetic suspension densimeter with an uncertainty of ±0.1%. Our measurements with methanol deviate from the literature values by less than 0.2%. The (p, ρ, T) measurements were fitted with experimental uncertainties by an empirical equation. The temperature and mole fraction dependence of the coefficients of the equation of state are presented

  12. Formaldehyde, methanol and hydrocarbon emissions from methanol-fueled cars

    International Nuclear Information System (INIS)

    Williams, R.L.; Lipari, F.; Potter, R.A.

    1990-01-01

    Exhaust and evaporative emissions tests were conducted on several methanol- and gasoline-fueled vehicles. Separate samples for chromatographic analysis of formaldehyde, methanol, and individual hydrocarbons were collected in each of the three phases of the driving cycle and in each of the two portions of the evaporative emissions test. One vehicle, equipped with an experimental variable-fuel engine, was tested using methanol/gasoline fuel mixtures of 100, 85, 50, 15, and 0 percent methanol. Combustion-generated hydrocarbons were lowest using methanol fuel, and increased several-fold as the gasoline fraction was increased. Gasoline components in the exhaust increased from zero as the gasoline fraction of the fuel was increased. On the other hand, formaldehyde emissions were several times higher using methanol fuel than they were using gasoline. A dedicated methanol car and the variable-fuel car gave similar emissions patterns when they both were tested using methanol fuel. The organic-carbon composition of the exhaust was 85-90 percent methanol, 5-7 percent formaldehyde, and 3-9 percent hydrocarbons. Several cars that were tested using gasoline emitted similar distributions of hydrocarbons, even through the vehicles represented a broad range of current and developmental engine families and emissions control systems

  13. Electrochemical formation of a Pt/Zn alloy and its use as a catalyst for oxygen reduction reaction in fuel cells.

    Science.gov (United States)

    Sode, Aya; Li, Winton; Yang, Yanguo; Wong, Phillip C; Gyenge, Elod; Mitchell, Keith A R; Bizzotto, Dan

    2006-05-04

    The characterization of an electrochemically created Pt/Zn alloy by Auger electron spectroscopy is presented indicating the formation of the alloy, the oxidation of the alloy, and the room temperature diffusion of the Zn into the Pt regions. The Pt/Zn alloy is stable up to 1.2 V/RHE and can only be removed with the oxidation of the base Pt metal either electrochemically or in aqua regia. The Pt/Zn alloy was tested for its effectiveness toward oxygen reduction. Kinetics of the oxygen reduction reaction (ORR) were measured using a rotating disk electrode (RDE), and a 30 mV anodic shift in the potential of ORR was found when comparing the Pt/Zn alloy to Pt. The Tafel slope was slightly smaller than that measured for the pure Pt electrode. A simple procedure for electrochemically modifying a Pt-containing gas diffusion electrode (GDE) with Zn was developed. The Zn-treated GDE was pressed with an untreated GDE anode, and the created membrane electrode assembly was tested. Fuel cell testing under two operating conditions (similar anode and cathode inlet pressures, and a larger cathode inlet pressure) indicated that the 30 mV shift observed on the RDE was also evident in the fuel cell tests. The high stability of the Pt/Zn alloy in acidic environments has a potential benefit for fuel cell applications.

  14. Anodically-grown TiO_2 nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Sacco, Adriano; Garino, Nadia; Lamberti, Andrea; Pirri, Candido Fabrizio; Quaglio, Marzia

    2017-01-01

    Highlights: • Anodically-grown TiO_2 nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO_2 nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO_2 NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  15. Thermoelectric properties of Sr0.61Ba0.39Nb2O6-δ ceramics in different oxygen-reduction conditions

    Science.gov (United States)

    Li, Yi; Liu, Jian; Wang, Chun-Lei; Su, Wen-Bin; Zhu, Yuan-Hu; Li, Ji-Chao; Mei, Liang-Mo

    2015-04-01

    The thermoelectric properties of Sr0.61Ba0.39Nb2O6-δ ceramics, reduced in different conditions, are investigated in the temperature range from 323 K to 1073 K. The electrical transport behaviors of the samples are dominated by the thermal-activated polaron hopping in the low temperature range, the Fermi glass behavior in the middle temperature range, and the Anderson localized behavior in the high temperature range. The thermal conductivity presents a plateau at high-temperatures, indicating a glass-like thermal conduction behavior. Both the thermoelectric power factor and the thermal conductivity increase with the increase of the degree of oxygen-reduction. Taking these two factors into account, the oxygen-reduction can still contribute to promoting the thermoelectric figure of merit. The highest ZT value is obtained to be ˜0.19 at 1073 K in the heaviest oxygen reduced sample. Project supported by the National Basic Research Program of China (Grant No. 2013CB632506) and the National Natural Science Foundation of China (Grant Nos. 51202132 and 51002087).

  16. Anodically-grown TiO{sub 2} nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sacco, Adriano, E-mail: adriano.sacco@iit.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Garino, Nadia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Lamberti, Andrea, E-mail: andrea.lamberti@polito.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Pirri, Candido Fabrizio [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Quaglio, Marzia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy)

    2017-08-01

    Highlights: • Anodically-grown TiO{sub 2} nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO{sub 2} nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO{sub 2} NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  17. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

    Science.gov (United States)

    Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

    2015-11-16

    Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

    Science.gov (United States)

    Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

    2018-06-01

    Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

  19. Development of methanol evaporation plate to reduce methanol crossover in a direct methanol fuel cell

    Science.gov (United States)

    Zhang, Ruiming

    This research focuses on methanol crossover reduction in direct methanol fuel cells (DMFC) through separating the methanol vapor from its liquid phase and feeding the vapor passively at low temperature range. Membrane electrode assemblies (MEAs) were fabricated by using commercial available membrane with different thickness at different anode catalyst loading levels, and tested under the operating conditions below 100°C in cell temperature and cathode exit open to ambient pressure. Liquid methanol transport from the anode through the membrane into cathode ("methanol crossover") is identified as one of the major efficiency losses in a DMFC. It is known that the methanol crossover rate in the vapor phase is much lower than in liquid phase. Vapor feed can be achieved by heating the liquid methanol to elevated temperatures (>100°C), but other issues limit the performance of the cell when operating above 100°C. High temperature membranes and much more active cathode catalyst structures are required, and a complex temperature control system must be employed. However, methanol vapor feed can also occur at a lower temperature range (evaporation through a porous body. The methanol crossover with this vapor feed mode is lower compared with the direct liquid methanol feed. A new method of using a methanol evaporation plate (MEP) to separate the vapor from its liquid phase to reduce the liquid methanol crossover at low temperature range is developed. A MEP plays the roles of liquid/vapor methanol phase separation and evaporation in a DMFC. The goal of this study is to develop a MEP with the proper properties to achieve high methanol phase separation efficiency and fast methanol evaporation rate over a wide range of temperature, i.e., from room temperature up to near boiling temperature (100°C). MEP materials were selected and characterized. MEPs made from three different types were tested extensively with different MEA and porous back layer configurations. The benefits of

  20. Methanol as an energy carrier

    Energy Technology Data Exchange (ETDEWEB)

    Biedermann, P.; Grube, T.; Hoehlein, B. (eds.)

    2006-07-01

    For the future, a strongly growing energy demand is expected in the transport sector worldwide. Economically efficient oil production will run through a maximum in the next decade. Higher fuel prices and an environmentally desirable reduction of emissions will increase the pressure for reducing fuel consumption and emissions in road traffic. These criteria show the urgent necessity of structural changes in the fuel market. Due to its advantages concerning industrial-scale production, storage and global availability, methanol has the short- to medium-term potential for gaining increased significance as a substitution product in the energy market. Methanol can be produced both from fossil energy sources and from biomass or waste materials through the process steps of synthesis gas generation with subsequent methanol synthesis. Methanol has the potential to be used in an environmentally friendly manner in gasoline/methanol mixtures for flexible fuel vehicles with internal combustion engines and in diesel engines with pure methanol. Furthermore, it can be used in fuel cell vehicles with on-board hydrogen production in direct methanol fuel cell drives, and in stationary systems for electricity and heat generation as well as for hydrogen production. Finally, in portable applications it serves as an energy carrier for electric power generation. In this book, the processes for the production and use of methanol are presented and evaluated, markets and future options are discussed and issues of safety and environmental impacts are addressed by a team of well-known authors. (orig.)

  1. Methanol synthesis beyond chemical equilibrium

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Winkelman, J. G. M.; Wilbers, E.; Assink, D.; Lemmens, K. P. J.; Heeres, H. J.

    2013-01-01

    In commercial methanol production from syngas, the conversion is thermodynamically limited to 0.3-0.7 leading to large recycles of non-converted syngas. This problem can be overcome to a significant extent by in situ condensation of methanol during its synthesis which is possible nowadays due to the

  2. Methylnaltrexone bromide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Xinbo Zhou

    2012-03-01

    Full Text Available In the title compound [systematic name: (4R,4aS,7aR,12bS-3-cyclopropylmethyl-4a,9-hydroxy-7-oxo-2,3,4,4a,5,6,7,7a-octahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-3-ium bromide methanol monosolvate], C21H26NO4+·Br−·CH3OH, two of the three six-membered rings adopt chair conformations while the third, which contains a C=C double bond, adopts an approximate half-boat conformation. The 2,3-dihydrofuran ring adopts an envelope conformation. In the crystal, the components are linked by O—H...O and O—H...Br hydrogen bonds. The absolute stereochemistry was inferred from one of the starting materials.

  3. Electro-deposition of Pd on Carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Modibedi, Remegia M.; Mathe, Mkhulu K.; Motsoeneng, Rapelang G.; Khotseng, Lindiwe E.; Ozoemena, Kenneth I.; Louw, Eldah K.

    2014-01-01

    Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions using the electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substrates for the electrodeposition of the metal. Supported nanostructured Pd electrodes were characterized using electrochemical methods and scanning electron microscopy. Carbon paper and Ni foam produced good quality deposits with some agglomeration on Ni foam. The EDX profiles confirmed the presence of Pd particles. Cyclic voltammograms of the electrodeposited Pd on substrates showed features characteristic of polycrystalline Pd electrodes. In the acidic electrolyte a very weak oxygen reduction reaction (ORR) activity was observed on Pd/Carbon paper electrode when compared to Pd/Ni foam electrode. The Pd/Ni foam electrode showed improved ORR activity in alkaline medium

  4. Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

    Science.gov (United States)

    Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

    2018-05-01

    Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

  5. A polyacrylonitrile copolymer-silica template for three-dimensional hierarchical porous carbon as a Pt catalyst support for the oxygen reduction reaction.

    Science.gov (United States)

    Liu, Minmin; Li, Jian; Cai, Chao; Zhou, Ziwei; Ling, Yun; Liu, Rui

    2017-08-01

    Herein, we report a novel route to construct a hierarchical three-dimensional porous carbon (3DC) through a copolymer-silica assembly. In the synthesis, silica acts as a hard template and leads to the formation of an interconnected 3D macropore, whereas styrene-co-acrylonitrile polymer has been used as both a carbon source and a soft template for micro- and meso-pores. The obtained 3DC materials possess a large surface area (∼550.5 m 2 g -1 ), which facilitates high dispersion of Pt nanoparticles on the carbon support. The 3DC-supported Pt electrocatalyst shows excellent performance in the oxygen reduction reaction (ORR). The easy processing ability along with the characteristics of hierarchical porosity offers a new strategy for the preparation of carbon nanomaterials for energy application.

  6. Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

    Science.gov (United States)

    Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

    2017-10-01

    Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

  7. Density functional study on the mechanism for the highly active palladium monolayer supported on titanium carbide for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Mao, Jianjun; Zhang, Yanxing; Chu, Xingli; Li, Shasha; Yang, Zongxian

    2016-01-01

    The adsorption, diffusion, and dissociation of O 2 on the palladium monolayer supported on TiC(001) surface, MLPd/TiC(001), are investigated using ab initio density functional theory calculations. Strong adhesion of palladium monolayer to the TiC(001) support, accompanied by a modification of electronic structure of the supported palladium, is evidenced. Compared with Pt(111) surface, the MLPd/TiC(001) can enhance the adsorption of O 2 , leading to comparable dissociation barrier and a smaller diffusion barrier of O 2 . Whilst the adsorption strength of atomic O (the dissociation product of O 2 ) on MLPd/TiC(001) is similar to that on the Pt(111) surface, possessing high mobility, our theoretical results indicate that MLPd/TiC(001) may serve as a good catalyst for the oxygen reduction reaction.

  8. Defect-induced Catalysis toward the Oxygen Reduction Reaction in Single-walled Carbon Nanotube: Nitrogen doped and Non-nitrogen doped

    International Nuclear Information System (INIS)

    Lu, Di; Wu, Dan; Jin, Jian; Chen, Liwei

    2016-01-01

    Single-walled carbon nanotubes (SWNTs) are post-treated by argon (Ar) or ammonia (NH 3 ) plasma irradiation to introduce defects that are potentially related to catalysis towards the oxygen reduction reaction (ORR). Electrochemical characterization in alkali medium suggests that the plasma irradiated SWNTs demonstrate enhanced catalytic activity toward the ORR with a positively shifted threshold potential. Moreover the enhanced desired four-electron pathway catalytic activity, which exhibited as the positive shifted threshold potential, is independent of the nitrogen dopant. The nature of the defects is probed with Raman and X-ray photoelectron spectroscopy. The results indicate that the non-nitrogen doped defects of SWNTs contribute to the actual active site for the ORR.

  9. Enhancement of the oxygen reduction on nitride stabilized pt-M (M=Fe, Co, and Ni) core–shell nanoparticle electrocatalysts

    KAUST Repository

    Kuttiyiel, Kurian A.; Choi, YongMan; Hwang, Sun-Mi; Park, Gu-Gon; Yang, Tae-Hyun; Su, Dong; Sasaki, Kotaro; Liu, Ping; Adzic, Radoslav R.

    2015-01-01

    Given the harsh operating conditions in hydrogen/oxygen fuel cells, the stability of catalysts is one of the critical questions affecting their commercialization. We describe a distinct class of oxygen reduction (ORR) core–shell electrocatalysts comprised of nitride metal cores enclosed by thin Pt shells that is easily synthesized. The synthesis is reproducible and amenable to scale up. Our theoretical analysis and the experimental data indicate that metal nitride nanoparticle cores could significantly enhance the ORR activity as well as the durability of the core–shell catalysts as a consequence of combined geometrical, electronic and segregation effects on the Pt shells. In addition to its fuel cells application, this class of catalysts holds promise to significantly contribute in resolving the problem of platinum scarcity and furthermore indicates the guidelines for future research and development.

  10. Enhancement of the oxygen reduction on nitride stabilized pt-M (M=Fe, Co, and Ni) core–shell nanoparticle electrocatalysts

    KAUST Repository

    Kuttiyiel, Kurian A.

    2015-04-01

    Given the harsh operating conditions in hydrogen/oxygen fuel cells, the stability of catalysts is one of the critical questions affecting their commercialization. We describe a distinct class of oxygen reduction (ORR) core–shell electrocatalysts comprised of nitride metal cores enclosed by thin Pt shells that is easily synthesized. The synthesis is reproducible and amenable to scale up. Our theoretical analysis and the experimental data indicate that metal nitride nanoparticle cores could significantly enhance the ORR activity as well as the durability of the core–shell catalysts as a consequence of combined geometrical, electronic and segregation effects on the Pt shells. In addition to its fuel cells application, this class of catalysts holds promise to significantly contribute in resolving the problem of platinum scarcity and furthermore indicates the guidelines for future research and development.

  11. High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

    Energy Technology Data Exchange (ETDEWEB)

    Song, Ping; Barkholtz, Heather M.; Wang, Ying; Xu, Weilin; Liu, Dijia; Zhuang, Lin

    2017-12-01

    We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives of Pt-based catalysts with best performance/price.

  12. Graphene-cobaltite-Pd hybrid materials for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells.

    Science.gov (United States)

    Sharma, Chandra Shekhar; Awasthi, Rahul; Singh, Ravindra Nath; Sinha, Akhoury Sudhir Kumar

    2013-12-14

    Hybrid materials comprising of Pd, MCo2O4 (where M = Mn, Co or Ni) and graphene have been prepared for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells. Structural and electrochemical characterizations were carried out using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, chronoamperometry and cyclic, CO stripping, and linear sweep voltammetries. The study revealed that all the three hybrid materials are active for both methanol oxidation (MOR) and oxygen reduction (ORR) reactions in 1 M KOH. However, the Pd-MnCo2O4/GNS hybrid electrode exhibited the greatest MOR and ORR activities. This active hybrid electrode has also outstanding stability under both MOR and ORR conditions, while Pt- and other Pd-based catalysts undergo degradation under similar experimental conditions. The Pd-MnCo2O4/GNS hybrid catalyst exhibited superior ORR activity and stability compared to even Pt in alkaline solutions.

  13. Highly regenerable carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres as oxygen reduction electrocatalyst and magnetic adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Wenqiang [Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, and Institute for Advanced Study, Tongji University, Shanghai 201804 (China); School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Liu, Minmin; Cai, Chao [Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, and Institute for Advanced Study, Tongji University, Shanghai 201804 (China); Zhou, Haijun, E-mail: zhouhaijun@just.edu.cn [School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Liu, Rui, E-mail: ruiliu@tongji.edu.cn [Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, and Institute for Advanced Study, Tongji University, Shanghai 201804 (China)

    2017-02-15

    We present the synthesis and multifunctional utilization of core-satellite carbon-Fe{sub 3}O{sub 4} nanoparticles to serve as the enabling platform for a range of applications including oxygen reduction reaction (ORR) and magnetic adsorbent. Starting from polydopamine (PDA) nanoparticles and Fe(NO{sub 3}){sub 3}, carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. The synergistic combination of Fe{sub 3}O{sub 4} and N-doped carbon endows the nanocomposite with high electrochemical activity in ORR and mainly four electrons transferred in reaction process. Furthermore, carbon-Fe{sub 3}O{sub 4} nanoparticles used as magnetic adsorbent exhibit the efficient removal of Rhodamine B from an aqueous solution. The recovery and reuse of the adsorbent is demonstrated 5 times without any detectible loss in activity. - Graphical abstract: Starting from polydopamine (PDA) nanoparticles and Fe(NO{sub 3}){sub 3}, carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. The nanocomposites serve as the enabling platform for a range of applications including oxygen reduction reaction (ORR) and magnetic adsorbent. - Highlights: • Carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. • Polydopamine and Fe(NO{sub 3}){sub 3} are precursors for N-doped carbon source and Fe{sub 3}O{sub 4} nanoparticles, respectively. • The nanocomposites exhibit high electrochemical activity in ORR. • The nanocomposites effectively adsorb organic dyes with magnetic recovery and good recycle property.

  14. Hydrothermal synthesis of Fe_2O_3/polypyrrole/graphene oxide composites as highly efficient electrocatalysts for oxygen reduction reaction in alkaline electrolyte

    International Nuclear Information System (INIS)

    Ren, Suzhen; Ma, Shaobo; Yang, Ying; Mao, Qing; Hao, Ce

    2015-01-01

    Graphical abstract: Fe_2O_3/polypyrrole/graphene oxide electrocatalysts for oxygen reduction reaction (ORR) are successfully prepared through one simple polypyrrole-assisted hydrothermal method and possess very high ORR activity and are able to selectively reduce O_2 to water through the four-electron transfer reaction mechanism in alkaline electrolyte. - Abstract: Advantages in low cost, and excellent catalytic activity of Fe-based nanomaterials dispersed on nitrogen-doped graphene supports render them to be good electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Here, Fe_2O_3/polypyrrole/graphene oxide (Fe_2O_3/Ppy/GO) composites with the Fe_2O_3 embedded in the Ppy modified GO are synthesized using hydrothermal method. With an optimal iron atom content ratio of 1.6% in graphene oxide and heat treatment at 800 °C, the Fe_2O_3/Ppy/GO exhibited enhanced catalytic performance for ORR with the onset potential of −0.1 V (vs SCE), cathodic potential of −0.24 V (vs SCE), an approximate 4e"− transfer process in O_2-saturated 0.1 M KOH, and superior stability that only reduced 5% catalytic activity after 5000 cycles. The decisive factors in improving the electrocatalytic and durable performance are the intimate and large contact interfaces between nanocrystallines of Fe_2O_3 and Ppy/GO, in addition to the high electron withdrawing/storing ability and the high conductivity of GO doped with nitrogen from Ppy during the hydrothermal reaction. The Fe_2O_3/Ppy/GO showed significantly improved ORR properties and confirmed that Fe-N-C-based electrocatalysts played a key role in fuel cells.

  15. Hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum nanocomposite as an efficient electrocatalyst for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Li, Zesheng; Liu, Zhisen; Li, Bolin; Liu, Zhenghui; Li, Dehao; Wang, Hongqiang; Li, Qingyu

    2016-01-01

    Graphical abstract: Newfashioned hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum (HMG/WC/Pt) nanocomposite with interesting three-dimensional architecture bas been successfully fabricated as an efficient electrocatalyst for the oxygen reduction reaction. - Highlights: • Hollow hemisphere-shaped macroporous graphene is proposed as ORR catalyst support. • Honeycomb-like macroporous graphene/WC/Pt electrocatalyst is firsy prepared for ORR. • The present electrocatalyst exhibited greatly enhanced ORR catalytic activity and stability. - Abstract: Hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum (HMG/WC/Pt) nanocomposite has been synthesized as an efficient electrocatalyst for the oxygen reduction reaction (ORR). The HMG/WC/Pt sample has been systematically characterized by the X-ray diffraction (XRD), Scanning electron microscope (SEM) and Transmission electron microscopy (TEM). The analysis results indicate that the sample has an interesting three-dimensional hollow hemisphere-shaped macroporous architecture. The results also demonstrate the successful integration of WC and Pt nanoparticles on the HMG, in which the WC nanoparticles are in size of about 10 nm and the Pt nanoparticles are in size of about 3 nm. The as-prepared HMG/WC/Pt electrode displays excellent electrocatalytic performances for the ORR in 0.1 mol L −1 HClO 4 electrolyte. The mass activity (i m at 0.9 V) of HMG/WC/Pt is 206 mA mg −1 Pt, which is about 85% higher than that of Pt/C (112 mA mg −1 Pt). It also displayed a very high activity retention of 84.5% after 2000 cyclic voltammetry cycles for the HMG/WC/Pt, while that of the Pt/C is only 70.5%. The HMG/WC/Pt nanocomposite would be a promising electrocatalytic material for the ORR in Fuel cell applications.

  16. Identification of marine methanol-utilizing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, M; Iwaki, H; Kouno, K; Inui, T

    1980-01-01

    A taxonomical study of 65 marine methanol-utilizing bacteria is described. They were Gram-negative, non-spore-forming rods with a polar flagellum and had marine bacterial properties and required vitamin B/sub 12/ for growth. All of them assimilated fructose in addition to C/sub 1/-compounds and produced acid oxidatively from fructose. Twenty-four strains assimilated only C/sub 1/-compounds. They were resistant to penicillin, oxytetracycline and 0/129 substance (Vibrio stat), and tolerant to 12% NaCl. Guanine-cytosine contents of deoxyribonucleic acid in typical strains fell in the range of 43.8 to 47.6%. Other morphological and physiological properties were almost the same as those of terrestrial methanol-utilizers. Bacteria in the first group (41 strains) were facultative methylotrophs and were divided into three subgroups by the assimilation of methylated amines, that is, subgroup I (30 strains) assimilated mono-, di- and tri-methylamine, subgroup II (9 strains) assimilated only mono-methylamine, the bacteria of subgroups I and II were named Alteromonas thalassomethanolica sp. nov. and subgroup III (2 strains) did not assimilate methylated amines, and was tentatively assigned as Alteromonas sp. The second group of bacteria (24 strains) was obligate methylotrophs, named Methylomonas thalassica sp. nov. and was divided into subgroup IV (15 strains) which assimilated mono-, di and tri-methylamine and subgroup V (9 strains) which assimilated mono-methylamine.

  17. Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

    Science.gov (United States)

    Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

    2016-05-18

    PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

  18. Tuning of size and shape of Au–Pt nanocatalysts for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Hunyadi Murph, Simona E.; Murphy, Catherine J.; Colon-Mercado, Hector R.; Torres, Ricardo D.; Heroux, Katie J.; Fox, Elise B.; Thompson, Lucas B.; Haasch, Richard T.

    2011-01-01

    In this article, we report the precise control of the size, shape, and surface morphology of Au–Pt nanocatalysts (cubes, blocks, octahedrons, and dogbones) synthesized via a seed-mediated approach. Gold “seeds” of different aspect ratios (1–4.2), grown by a silver-assisted approach, were used as templates for high-yield production of novel Au–Pt nanocatalysts at a low temperature (40 °C). Characterization by electron microscopy (SEM, TEM, HRTEM), energy dispersive X-ray analysis, UV–Vis spectroscopy, zeta-potential (surface charge), atomic force microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma mass spectrometry were used to better understand their physico-chemical properties, preferred reactivities and underlying nanoparticle growth mechanism. A rotating disk electrode was employed to evaluate the Au–Pt nanocatalysts electrochemical performance in the oxygen reduction reaction (ORR) and the methanol oxidation reaction of direct methanol fuel cells. The results indicate the Au–Pt dogbones are partially and in some cases completely unaffected by methanol poisoning during the evaluation of the ORR. The ORR performance of the octahedron particles in the absence of MeOH is superior to that of the Au–Pt dogbones and Pt-black; however, its performance is affected by the presence of MeOH.

  19. TUNING OF SIZE AND SHAPE OF AU-PT NANOCATALYST FOR DIRECT METHANOL FUEL CELLS

    Energy Technology Data Exchange (ETDEWEB)

    Murph, S.

    2011-04-20

    In this paper, we report the precise control of the size, shape and surface morphology of Au-Pt nanocatalysts (cubes, blocks, octahedrons and dogbones) synthesized via a seed-mediated approach. Gold 'seeds' of different aspect ratios (1 to 4.2), grown by a silver-assisted approach, were used as templates for high-yield production of novel Au-Pt nanocatalysts at a low temperature (40 C). Characterization by electron microscopy (SEM, TEM, HRTEM), energy dispersive X-ray analysis (EDX), UV-Vis spectroscopy, zeta-potential (surface charge), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS) were used to better understand their physico-chemical properties, preferred reactivities and underlying nanoparticle growth mechanism. A rotating disk electrode was used to evaluate the Au-Pt nanocatalysts electrochemical performance in the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) of direct methanol fuel cells. The results indicate the Au-Pt dogbones are partially and in some cases completely unaffected by methanol poisoning during the evaluation of the ORR. The ORR performance of the octahedron particles in the absence of MeOH is superior to that of the Au-Pt dogbones and Pt-black, however its performance is affected by the presence of MeOH.

  20. Importance of the support and the grade of Pt in the oxygen reduction reaction; Importancia del soporte y del grado del Pt en la reaccion de reduccion de oxigeno

    Energy Technology Data Exchange (ETDEWEB)

    Enriquez M, O.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2004-07-01

    The technology of the fuel cells type Proton Exchange Membrane (PEM), needs to define clearly the influence of the different involved parameters, this is made in general using methods of electrochemical impedance, in which the involved reactions can be presupposed. Another form of making is identifying experimentally the influence of the different parameters. In this work the obtained results are reported with for the oxygen reduction reaction using as electro catalyst platinum analytical grade and fuel cell grade and like support graphite and vulcan. It was found that as much the support as the particle size modify the over potential for the oxygen reduction reaction (Orr). (Author)

  1. Identifying Activity Descriptors for CO2 Electro-Reduction to Methanol on Rutile (110) Surfaces

    DEFF Research Database (Denmark)

    Bhowmik, Arghya; Hansen, Heine Anton; Vegge, Tejs

    2015-01-01

    Electrocatalytic reduction of CO2 to liquid fuels using energy from renewable sources has the potential to form the basis of a carbon neutral sustainable energy system, while integrating seamlessly in the established infrastructure1. Storing intermittent renewable energy in a chemical fuel...... towards electrocatalytic production of methanol. We would like to acknowledge the Lundbeck Foundation for financial support of this work. References: 1. Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl. Acad. Sci. U. S. A.103,15729–35 (2006......., Ali, I., Jansen, M. & Omanovic, S. Electrochemical reduction of CO 2 in an aqueous electrolyte employing an iridium/ruthenium-oxide electrode. Can. J. Chem. Eng. (2014). doi:10.1002/cjce.22110 6. Nørskov, J. K. et al. Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. J. Phys...

  2. Growth of Bacillus methanolicus in 2 M methanol at 50 °C: the effect of high methanol concentration on gene regulation of enzymes involved in formaldehyde detoxification by the ribulose monophosphate pathway.

    Science.gov (United States)

    Bozdag, Ahmet; Komives, Claire; Flickinger, Michael C

    2015-07-01

    Bacillus methanolicus MGA3 is a Gram-positive aerobic methylotroph growing optimally at 50-53°C. Methylotrophy in B. methanolicus is encoded on pBM19 and by two chromosomal copies of the methanol dehydrogenase (mdh), hexulose phosphate synthase (hps) and phosphohexuloisomerase (phi) genes. However, there are no published studies on the regulation of methylotrophy or the dominant mechanism of detoxification of intracellular formaldehyde in response to high methanol concentration. The µ max of B. methanolicus MGA3 was assessed on methanol, mannitol and glucose. B. methanolicus achieved a µ max at 25 mM initial methanol of 0.65 ± 0.007 h(-1), which decreased to 0.231 ± 0.004 h(-1) at 2 M initial methanol. Slow growth was also observed with initial methanol concentrations of >2 M. The µ max on mannitol and glucose are 0.532 ± 0.002 and 0.336 ± 0.003 h(-1), respectively. Spiking cultures with additional methanol (100 mM) did not disturb the growth rate of methanol-grown cells, whereas, a 50 mM methanol spike halted the growth in mannitol. Surprisingly, growth in methanol was inhibited by 1 mM formaldehyde, while mannitol-grown cells tolerated 2 mM. Moreover, mannitol-grown cells removed formaldehyde faster than methanol-grown cells. Further, we show that methanol oxidation in B. methanolicus MGA3 is mainly carried out by the pBM19-encoded mdh. Formaldehyde and formate addition down-regulate the mdh and hps genes in methanol-grown cells. Similarly, they down-regulate mdh genes in mannitol-grown cells, but up-regulate hps. Phosphofructokinase (pfk) is up-regulated in both methanol and mannitol-grown cells, which suggests that pfk may be a possible synthetic methylotrophy target to reduce formaldehyde growth toxicity at high methanol concentrations.

  3. Adaptation of the autotrophic acetogen Sporomusa ovata to methanol accelerates the conversion of CO2 to organic products

    DEFF Research Database (Denmark)

    Tremblay, Pier-Luc; Höglund, Daniel; Koza, Anna

    2015-01-01

    , and biochemical studies revealed that the molecular mechanisms responsible for the novel characteristics of the adapted strain were associated with the methanol oxidation pathway and the Wood-Ljungdahl pathway of acetogens along with biosynthetic pathways, cell wall components, and protein chaperones. The results...... to grow quicker autotrophically with methanol, a toxic C1 compound, as the sole substrate. Better growth on different concentrations of methanol and with H2-CO2 indicated the adapted strain had a more efficient autotrophic metabolism and a higher tolerance to solvent. The growth rate on methanol...

  4. Batch extractive distillation for high purity methanol

    International Nuclear Information System (INIS)

    Zhang Weijiang; Ma Sisi

    2006-01-01

    In this paper, the application in chemical industry and microelectronic industry, market status and the present situation of production of high purity methanol at home and abroad were introduced firstly. Purification of industrial methanol for high purity methanol is feasible in china. Batch extractive distillation is the best separation technique for purification of industrial methanol. Dimethyl sulfoxide was better as an extractant. (authors)

  5. Synergy of Cobalt and Silver Microparticles Electrodeposited on Glassy Carbon for the Electrocatalysis of the Oxygen Reduction Reaction: An Electrochemical Investigation

    Directory of Open Access Journals (Sweden)

    Claudio Zafferoni

    2015-08-01

    Full Text Available The combination of two different metals, each of them acting on different steps of the oxygen reduction reaction (ORR, yields synergic catalytic effects. In this respect, the electrocatalytic effect of silver is enhanced by the addition of cobalt, which is able to break the O–O bond of molecular oxygen, thus accelerating the first step of the reduction mechanism. At the same time, research is to further reduce the catalyst’s cost, reducing the amount of Ag, which, even though being much less expensive than Pt, is still a noble metal. From this point of view, using a small amount of Ag together with an inexpensive material, such as graphite, represents a good compromise. The aim of this work was to verify if the synergic effects are still operating when very small amounts of cobalt (2–10 μg·cm−2 are added to the microparticles of silver electrodeposited on glassy carbon, described in a preceding paper from us. To better stress the different behaviour observed when cobalt and silver are contemporarily present in the deposit, the catalytic properties of cobalt alone were investigated. The analysis was completed by the Levich plots to evaluate the number of electrons involved and by Tafel plots to show the effects on the reaction mechanism.

  6. Nitrogen-Doped Hollow Carbon Spheres with Embedded Co Nanoparticles as Active Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Ruohao Xing

    2018-02-01

    Full Text Available Transition metal (Fe, Co, Ni complexes on carbon nanomaterials are promising candidates as electrocatalysts towards the oxygen reduction reaction (ORR. In this paper, nitrogen-doped hollow carbon spheres with embedded Co nanoparticles were successfully prepared via a controllable synthesis strategy. The morphology characterization shows that the hollow carbon spheres possess an average diameter of ~150 nm with a narrow size distribution and a shell thickness of ~14.5 nm. The content of N doping ranges from 2.1 to 6.6 at.% depending on the calcination temperature from 900 to 1050 °C. Compared with commercial Pt/C, the Co-containing nitrogen-doped hollow carbon spheres prepared at 900 °C (CoNHCS-900 as an ORR electrocatalyst shows a half-wave potential shift of only ∆E1/2 = 55 mV, but a superior stability of about 90.2% maintenance after 20,000 s in the O2-saturated 0.1 M KOH at a rotating speed of 1600 rpm. This could be ascribed to the synergistic effects of N-containing moieties, Co-Nx species, and Co nanoparticles, which significantly increase the density of active sites and promote the charge transfer during the ORR process.

  7. Microwave-Assisted Synthesis of Reduced Graphene Oxide/SnO2 Nanocomposite for Oxygen Reduction Reaction in Microbial Fuel Cells.

    Science.gov (United States)

    Garino, Nadia; Sacco, Adriano; Castellino, Micaela; Muñoz-Tabares, José Alejandro; Chiodoni, Angelica; Agostino, Valeria; Margaria, Valentina; Gerosa, Matteo; Massaglia, Giulia; Quaglio, Marzia

    2016-02-01

    We report on an easy, fast, eco-friendly, and reliable method for the synthesis of reduced graphene oxide/SnO2 nanocomposite as cathode material for application in microbial fuel cells (MFCs). The material was prepared starting from graphene oxide that has been reduced to graphene during the hydrothermal synthesis of the nanocomposite, carried out in a microwave system. Structural and morphological characterizations evidenced the formation of nanocomposite sheets, with SnO2 crystals of few nanometers integrated in the graphene matrix. Physico-chemical analysis revealed the formation of SnO2 nanoparticles, as well as the functionalization of the graphene by the presence of nitrogen atoms. Electrochemical characterizations put in evidence the ability of such composite to exploit a cocatalysis mechanism for the oxygen reduction reaction, provided by the presence of both SnO2 and nitrogen. In addition, the novel composite catalyst was successfully employed as cathode in seawater-based MFCs, giving electrical performances comparable to those of reference devices employing Pt as catalyst.

  8. High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

    Science.gov (United States)

    Chhina, H.; Campbell, S.; Kesler, O.

    The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H 2SO 4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.

  9. High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Chhina, H. [Automotive fuel cell corporation, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Department of Mechanical and Industrial Engineering, 5 King' s College Road, University of Toronto, Toronto, Ontario (Canada); Campbell, S. [Automotive fuel cell corporation, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, 5 King' s College Road, University of Toronto, Toronto, Ontario (Canada)

    2008-04-15

    The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 C and compared to that of HiSpec 4000 trademark Pt/Vulcan XC-72R in 0.5 M H{sub 2}SO{sub 4}. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000 trademark. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization. (author)

  10. M3C (M: Fe, Co, Ni) Nanocrystals Encased in Graphene Nanoribbons: An Active and Stable Bifunctional Electrocatalyst for Oxygen Reduction and Hydrogen Evolution Reactions.

    Science.gov (United States)

    Fan, Xiujun; Peng, Zhiwei; Ye, Ruquan; Zhou, Haiqing; Guo, Xia

    2015-07-28

    Transition metal carbide nanocrystalline M3C (M: Fe, Co, Ni) encapsulated in graphitic shells supported with vertically aligned graphene nanoribbons (VA-GNRs) are synthesized through a hot filament chemical vapor deposition (HF-CVD) method. The process is based on the direct reaction between iron group metals (Fe, Co, Ni) and carbon source, which are facilely get high purity carbide nanocrystals (NCs) and avoid any other impurity at relatively low temperature. The M3C-GNRs exhibit superior enhanced electrocatalystic activity for oxygen reduction reaction (ORR), including low Tafel slope (39, 41, and 45 mV dec(-1) for Fe3C-GNRs, Co3C-GNRs, and Ni3C-GNRs, respectively), positive onset potential (∼0.8 V), high electron transfer number (∼4), and long-term stability (no obvious drop after 20 000 s test). The M3C-GNRs catalyst also exhibits remarkable hydrogen evolution reaction (HER) activity with a large cathodic current density of 166.6, 79.6, and 116.4 mA cm(-2) at an overpotential of 200 mV, low onset overpotential of 32, 41, and 35 mV, small Tafel slope of 46, 57, and 54 mV dec(-1) for Fe3C-GNRs, Co3C-GNRs, and Ni3C-GNRs, respectively, as well as an excellent stability in acidic media.

  11. Deoxyribonucleic acid directed metallization of platinum nanoparticles on graphite nanofibers as a durable oxygen reduction catalyst for polymer electrolyte fuel cells

    Science.gov (United States)

    Peera, S. Gouse; Sahu, A. K.; Arunchander, A.; Nath, Krishna; Bhat, S. D.

    2015-11-01

    Effective surface functionalization to the hydrophobic graphite nanofibers (GNF) is performed with the biomolecule, namely deoxy-ribo-nucleic-acid (DNA) via π-π interactions. Pt nanoparticles are impregnated on GNF-DNA composite by ethylene glycol reduction method (Pt/GNF-DNA) and its effect on electro catalytic activity for oxygen reduction reaction (ORR) is systemically studied. Excellent dispersion of Pt nanoparticles over GNF-DNA surfaces with no evidence on particle aggregation is a remarkable achievement in this study. This result in higher electro chemical surface area of the catalyst, enhanced ORR behavior with significant enhancement in mass activity. The catalyst is validated in H2-O2 polymer electrolyte fuel cell (PEFC) and a peak power density of 675 mW cm-2 is achieved at a load current density of 1320 mA cm-2 with a minimal catalyst loading of 0.1 mg cm-2 at a cell temperature of 70 °C and 2 bar absolute pressure. Repeated potential cycling up to 10000 cycles in acidic media is also performed for this catalyst and found excellent stability with only 60 mV drop in the ORR half wave potential. The superior behavior of Pt/GNF-DNA catalyst is credited to the robust fibrous structure of GNF and its effective surface functionalization process via π-π interaction.

  12. N/S/B-doped graphitized carbon encased Fe species as a highly active and durable catalyst towards oxygen reduction reaction.

    Science.gov (United States)

    Li, Guang-Lan; Cheng, Guang-Chun; Chen, Wen-Wen; Liu, Cai-Di; Yuan, Li-Fang; Yang, Bei-Bei; Hao, Ce

    2018-03-15

    Exploring cost-effective, high-performance and durable non-precious metal catalysts is of great significance for the acceleration of sluggish oxygen reduction reaction (ORR). Here, we report an intriguing heteroatom-doped graphitized carbon encased Fe species composite by introducing N, S and B sequentially. The experimental approach was designed ingeniously for that the FeCl 3 ·6H 2 O could catalyze thiourea to synthesize N, S co-doped carbon materials which would further react with H 3 BO 3 and NH 3 (emerged at the heat-treatment process) to prepare N, S and B co-doped carbon materials (Fe-N/S/B-C). The Fe-N/S/B-C exhibits an impressive ORR activity for its half-wave potential of -0.1 V, which is 36 mV or 19 mV higher than that of the corresponding single or dual doped counterparts (Fe-N-C or Fe-N/S-C) and 31 mV positive than that of Pt/C catalyst, respectively. Further chronoamperometric measurement and accelerated aging test confirm the excellent electrochemical durability of Fe-N/S/B-C with the stable core-shell structure. The remarkable ORR performance and facile preparation method enable Fe-N/S/B-C as a potential candidate in electrochemical energy devices. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. (La1-xSrx)0.98MnO3 perovskite with A-site deficiencies toward oxygen reduction reaction in aluminum-air batteries

    Science.gov (United States)

    Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-02-01

    The strontium doped Mn-based perovskites have been proposed as one of the best oxygen reduction reaction catalysts (ORRCs) to substitute the noble metal. However, few studies have investigated the catalytic activities of LSM with the A-site deficiencies. Here, the (La1-xSrx)0.98MnO3 (LSM) perovskites with A-site deficiencies are prepared by a modified solid-liquid method. The structure, morphology, valence state and oxygen adsorption behaviors of these LSM samples are characterized, and their catalytic activities toward ORR are studied by the rotating ring-disk electrode (RRDE) and aluminum-air battery technologies. The results show that the appropriate doping with Sr and introducing A-site stoichiometry can effectively tailor the Mn valence and increase the oxygen adsorption capacity of LSM. Among all the LSM samples in this work, the (La0.7Sr0.3)0.98MnO3 perovskite composited with 50% carbon (50%LSM30) exhibits the best ORR catalytic activity due to the excellent oxygen adsorption capacity. Also, this catalyst has much higher durability than that of commercial 20%Pt/C. Moreover, the maximum power density of the aluminum-air battery using 50%LSM30 as the ORRC can reach 191.3 mW cm-2. Our work indicates that the LSM/C composite catalysts with A-site deficiencies can be used as a promising ORRC in the metal-air batteries.

  14. Electrodeposited ultrafine NbOx, ZrOx, and TaO x nanoparticles on carbon black supports for oxygen reduction electrocatalysts in acidic media

    KAUST Repository

    Seo, Jeongsuk

    2013-09-06

    A remarkable electrocatalytic activity was obtained for the oxygen reduction reaction (ORR) in acidic solutions on ultrafine nano-oxide catalysts based on group IV or V elements. By potentiostatic electrodepostion in nonaqueous solutions at 298 K followed by heat treatment in H2 gas, highly dispersed fine nanoparticles of NbOx, ZrOx, and TaOx with sizes of less than 5 nm were prepared and deposited on carbon black (CB) loaded electrodes. These oxide nanoparticles showed high catalytic activities with high onset potentials of 0.96 VRHE (NbOx), 1.02 VRHE (ZrOx), and 0.93 V RHE (TaOx) for the ORR. Owing to the high chemical stability of group IV and V oxides, the catalysts were very stable during the ORR in acidic solutions. Surface characterization and chemical identification were performed using scanning transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). All results clearly indicate the formation of nano-oxide electrocatalysts that show an outstanding ORR performance, whereas the bulk oxides are not active because of the absence of electronic conductivity. The present work demonstrates potential candidates for highly stable, non-noble-metal cathode catalysts for polymer electrolyte fuel cells (PEFCs), where the catalysts are exposed to highly acidic and oxidizing conditions. © 2013 American Chemical Society.

  15. Synergistic Effect of Nitrogen Doping and MWCNT Intercalation for the Graphene Hybrid Support for Pt Nanoparticles with Exemplary Oxygen Reduction Reaction Performance

    Directory of Open Access Journals (Sweden)

    Kang Fu

    2018-04-01

    Full Text Available The potential of graphene–multi-walled-carbon nanotube (G-M hybrids prepared by the one-pot modified Hummers method followed by thermal annealing has been demonstrated by employing one as an electrocatalyst support for oxygen reduction reaction (ORR. N doping effectively modified the electronic structure of the G-M hybrid support, which was beneficial for the uniform distribution of Pt nanoparticles, and ORR activities were further improved. The newly prepared Pt/N-G-M catalyst demonstrated higher electrochemical activity than Pt/G-M and Pt/G catalysts. Even compared with commercial 20 wt % Pt/C (JM20, Pt/N-G-M delivered a better half-wave potential and mass activity. In terms of the durability test, Pt/N-G-M maintained 72.7% of its initial electrochemical active surface area (ECSA after 2000 repeated potential cycles between 0 and 1.2 V in acidic media in relation to the 44.4% retention for JM20. Moreover, the half-wave potential for Pt/N-G-M showed only a minimal change, significantly superior to the 139 mV of loss for JM20. It is expected that Pt/N-G-M can be the potential candidate as a highly efficient and durable catalyst if utilized in proton exchange membrane fuel cells (PEMFCs.

  16. Preparation and characterization of electronically conducting polypyrrole-montmorillonite nanocomposite and its potential application as a cathode material for oxygen reduction

    International Nuclear Information System (INIS)

    Rajapakse, R.M.G.; Murakami, Kenji; Bandara, H.M.N.; Rajapakse, R.M.M.Y.; Velauthamurti, K.; Wijeratne, S.

    2010-01-01

    Simple wet chemical processes were deployed to prepare low-cost conducting nanocomposites based on natural clays with 2:1 layered structures such as sodium montmorillonite (MMT). Ce(IV) modified MMT was used for the spontaneous polymerization of pyrrole within clay interlayers. The resulted clay-conducting polypyrrole nanocomposites containing the reduced form of the oxidising agent, have been extensively characterized by X-ray diffraction (XRD) technique for interlayer spacing variations and by Fourier transform infra red (FT-IR) spectroscopy to study the interactions between the clay and polymer functional groups. DC polarization technique with both blocking and non-blocking electrodes was used to distinguish between the ionic and electronic transport numbers and to recognize the type of mobile ionic species. AC impedance analysis further resolved the electrical conduction of these materials. Bulk conductivity analysis implied that the polypyrrole (PPY) formed within Ce(IV) modified MMT posses dominant electronic conductivity. The low-cost, light-weight and stable polymer-clay nanocomposite prepared by Ce(IV) intercalated MMT, [Ce(III)-PPY-MMT], seems to be a promising cathode material for oxygen reduction and hence may find applications in fuel cell industries.

  17. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei; Gehrig, Dominik; Zhang, Fan; Lu, Chenbao; Zhang, Chao; Cai, Ming; Wang, Yuanyuan; Laquai, Fré dé ric; Zhuang, Xiaodong; Feng, Xinliang

    2016-01-01

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  18. In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

    Science.gov (United States)

    Liu, Qiunan; Yang, Tingting; Du, Congcong; Tang, Yongfu; Sun, Yong; Jia, Peng; Chen, Jingzhao; Ye, Hongjun; Shen, Tongde; Peng, Qiuming; Zhang, Liqiang; Huang, Jianyu

    2018-05-14

    We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu 2 O and then to Cu; in the latter, NaO 2 formed first, followed by its disproportionation to Na 2 O 2 and O 2 . Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO 2 . Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O 2 batteries.

  19. Facile Synthesis of Quasi-One-Dimensional Au/PtAu Heterojunction Nanotubes and Their Application as Catalysts in an Oxygen-Reduction Reaction.

    Science.gov (United States)

    Cai, Kai; Liu, Jiawei; Zhang, Huan; Huang, Zhao; Lu, Zhicheng; Foda, Mohamed F; Li, Tingting; Han, Heyou

    2015-05-11

    An intermediate-template-directed method has been developed for the synthesis of quasi-one-dimensional Au/PtAu heterojunction nanotubes by the heterogeneous nucleation and growth of Au on Te/Pt core-shell nanostructures in aqueous solution. The synthesized porous Au/PtAu bimetallic nanotubes (PABNTs) consist of porous tubular framework and attached Au nanoparticles (AuNPs). The reaction intermediates played an important role in the preparation, which fabricated the framework and provided a localized reducing agent for the reduction of the Au and Pt precursors. The Pt7 Au PABNTs showed higher electrocatalytic activity and durability in the oxygen-reduction reaction (ORR) in 0.1 M HClO4 than porous Pt nanotubes (PtNTs) and commercially available Pt/C. The mass activity of PABNTs was 218 % that of commercial Pt/C after an accelerated durability test. This study demonstrates the potential of PABNTs as highly efficient electrocatalysts. In addition, this method provides a facile strategy for the synthesis of desirable hetero-nanostructures with controlled size and shape by utilizing an intermediate template. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. General Solvent-dependent Strategy toward Enhanced Oxygen Reduction Reaction in Graphene/Metal Oxide Nanohybrids: Effects of Nitrogen-containing Solvent

    Science.gov (United States)

    Kao, Wei-Yao; Chen, Wei-Quan; Chiu, Yu-Hsiang; Ho, Yu-Hsuan; Chen, Chun-Hu

    2016-11-01

    A general solvent-dependent protocol directly influencing the oxygen reduction reaction (ORR) in metal oxide/graphene nanohybrids has been demonstrated. We conducted the two-step synthesis of cobalt oxide/N-doped graphene nanohybrids (CNG) with solvents of water, ethanol, and dimethylformamide (DMF), representing tree typical categories of aqueous, polar organic, and organic N-containing solvents commonly adopted for graphene nanocomposites preparation. The superior ORR performance of the DMF-hybrids can be attributed to the high nitrogen-doping, aggregation-free hybridization, and unique graphene porous structures. As DMF is the more effective N-source, the spectroscopic results support a catalytic nitrogenation potentially mediated by cobalt-DMF coordination complexes. The wide-distribution of porosity (covering micro-, meso-, to macro-pore) and micron-void assembly of graphene may further enhance the diffusion kinetics for ORR. As the results, CNG by DMF-synthesis exhibits the high ORR activities close to Pt/C (i.e. only 8 mV difference of half-wave potential with electron transfer number of 3.96) with the better durability in the alkaline condition. Additional graphene hybrids comprised of iron and manganese oxides also show the superior ORR activities by DMF-synthesis, confirming the general solvent-dependent protocol to achieve enhanced ORR activities.

  1. Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

    Science.gov (United States)

    Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

    2014-01-22

    Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

  2. The Use of an Edible Mushroom-Derived Renewable Carbon Material as a Highly Stable Electrocatalyst towards Four-Electron Oxygen Reduction

    Directory of Open Access Journals (Sweden)

    Chaozhong Guo

    2015-12-01

    Full Text Available The development of highly stable and efficient electrocatalysts for sluggish oxygen reduction reaction (ORR is exceedingly significant for the commercialization of fuel cells but remains a challenge. We here synthesize a new nitrogen-doped biocarbon composite material (N-BC@CNP-900 as a nitrogen-containing carbon-based electrocatalyst for the ORR via facile all-solid-state multi-step pyrolysis of bioprotein-enriched enoki mushroom as a starting material, and inexpensive carbon nanoparticles as the inserting matrix and conducting agent at controlled temperatures. Results show that the N-BC@CNP-900 catalyst exhibits the best ORR electrocatalytic activity with an onset potential of 0.94 V (versus reversible hydrogen electrode, RHE and high stability. Meanwhile, this catalyst significantly exhibits good selectivity of the four-electron reaction pathway in an alkaline electrolyte. It is notable that pyridinic- and graphtic-nitrogen groups that play a key role in the enhancement of the ORR activity may be the catalytically active structures for the ORR. We further propose that the pyridinic-nitrogen species can mainly stabilize the ORR activity and the graphitic-nitrogen species can largely enhance the ORR activity. Besides, the addition of carbon support also plays an important role in the pyrolysis process, promoting the ORR electrocatalytic activity.

  3. The Use of an Edible Mushroom-Derived Renewable Carbon Material as a Highly Stable Electrocatalyst towards Four-Electron Oxygen Reduction.

    Science.gov (United States)

    Guo, Chaozhong; Sun, Lingtao; Liao, Wenli; Li, Zhongbin

    2015-12-23

    The development of highly stable and efficient electrocatalysts for sluggish oxygen reduction reaction (ORR) is exceedingly significant for the commercialization of fuel cells but remains a challenge. We here synthesize a new nitrogen-doped biocarbon composite material (N-BC@CNP-900) as a nitrogen-containing carbon-based electrocatalyst for the ORR via facile all-solid-state multi-step pyrolysis of bioprotein-enriched enoki mushroom as a starting material, and inexpensive carbon nanoparticles as the inserting matrix and conducting agent at controlled temperatures. Results show that the N-BC@CNP-900 catalyst exhibits the best ORR electrocatalytic activity with an onset potential of 0.94 V ( versus reversible hydrogen electrode, RHE) and high stability. Meanwhile, this catalyst significantly exhibits good selectivity of the four-electron reaction pathway in an alkaline electrolyte. It is notable that pyridinic- and graphtic-nitrogen groups that play a key role in the enhancement of the ORR activity may be the catalytically active structures for the ORR. We further propose that the pyridinic-nitrogen species can mainly stabilize the ORR activity and the graphitic-nitrogen species can largely enhance the ORR activity. Besides, the addition of carbon support also plays an important role in the pyrolysis process, promoting the ORR electrocatalytic activity.

  4. Rudimentary simple, single step fabrication of nano-flakes like AgCd alloy electro-catalyst for oxygen reduction reaction in alkaline fuel cell

    International Nuclear Information System (INIS)

    Bhandary, Nimai; Basu, Suddhasatwa; Ingole, Pravin P.

    2016-01-01

    In this work, for the first time, we report rudimentary simple, single step fabrication of an electro-catalyst based on AgCd alloy nanoparticles with flakes like geometry which shows highly efficient activity towards oxygen reduction reaction (ORR). A simple potentiostatic deposition method has been employed for co-depositing AgCd alloy nanostructures with flakes like shapes along with dendrites on the surface of carbon fibre paper. The chemico-physical properties of the catalyst are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDXS). Electro-catalytic activity of AgCd alloy based electro-catalyst towards ORR is studied in alkaline medium by cyclic voltammetry and rotating ring disk electrode (RRDE) technique. Electrochemical in-situ FTIR measurements are also performed to identify the species generated during ORR process. Based on the results from electro-catalysis experiment, it is concluded that nano-alloyed AgCd electrodeposited on carbon paper shows excellent activity for ORR, following four electron pathways with H_2O_2 yield less than 15%. The combination of low cost of Ag and Cd, fast and facile method of its fabrication and higher activity towards ORR makes the AgCd electro-catalyst an attractive catalyst of choice for alkaline fuel cell.

  5. Effect of cationic molecules on the oxygen reduction reaction on fuel cell grade Pt/C (20 wt%) catalyst in potassium hydroxide (aq, 1 mol dm(-3)).

    Science.gov (United States)

    Ong, Ai Lien; Inglis, Kenneth K; Whelligan, Daniel K; Murphy, Sam; Varcoe, John R

    2015-05-14

    This study investigates the effect of 1 mmol dm(-3) concentrations of a selection of small cationic molecules on the performance of a fuel cell grade oxygen reduction reaction (ORR) catalyst (Johnson Matthey HiSPEC 3000, 20 mass% Pt/C) in aqueous KOH (1 mol dm(-3)). The cationic molecules studied include quaternary ammonium (including those based on bicyclic systems) and imidazolium types as well as a phosphonium example: these serve as fully solubilised models for the commonly encountered head-groups in alkaline anion-exchange membranes (AAEM) and anion-exchange ionomers (AEI) that are being developed for application in alkaline polymer electrolyte fuel cells (APEFCs), batteries and electrolysers. Both cyclic and hydrodynamic linear sweep rotating disk electrode voltammetry techniques were used. The resulting voltammograms and subsequently derived data (e.g. apparent electrochemical active surface areas, Tafel plots, and number of [reduction] electrons transferred per O2) were compared. The results show that the imidazolium examples produced the highest level of interference towards the ORR on the Pt/C catalyst under the experimental conditions used.

  6. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei

    2016-10-11

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  7. A facile template approach for the synthesis of mesoporous Fe3C/Fe-N-doped carbon catalysts for efficient and durable oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    Shuai Li; Bo Li; Liang Ma; Jia Yang; Hangxun Xu

    2017-01-01

    Facile synthetic approaches toward the development of efficient and durable nonprecious metal catalysts for the oxygen reduction reaction (ORR) are very important for commercializing advanced electrochemical devices such as fuel cells and metal-air batteries.Here we report a novel template approach to synthesize mesoporous Fe-N-doped carbon catalysts encapsulated with Fe3C nanoparticles.In this approach,the layer-structured FeOCl was first used as a template for the synthesis of a three-dimensional polypyrrole (PPy) structure.During the removal of the FeOCl template,the Fe3+ can be absorbed by PPy and then converted into Fe3C nanoparticles and Fe-N-C sites during the pyrolyzing process.As a result,the as-prepared catalysts could exhibit superior electrocatalytic ORR performance to the commercial Pt/C catalyst in alkaline solutions.Furthermore,the Zn-air battery assembled using the mesoporous carbon catalyst as the air electrode could surpass the commercial Pt/C catalyst in terms of the power density and energy density.

  8. Synthesis of an excellent electrocatalyst for oxygen reduction reaction with supercritical fluid: Graphene cellular monolith with ultrafine and highly dispersive multimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yazhou; Cheng, Xiaonong; Yen, Clive H.; Wai, Chien M.; Wang, Chongmin; Yang, Juan; Lin, Yuehe

    2017-04-01

    Graphene cellular monolith (GCM) can be used as an excellent support for nanoparticles in widespread applications. However, it's still a great challenge to deposit the desirable nanoparticles in GCM that have small size, controllable structure, composition, and high dispersion using the current methods. Here we demonstrate a green, efficient and large-scale method to address this challenge using supercritical fluid (SCF). By this superior method, graphene hydrogel can be transferred into GCM while being deposited with ultrafine and highly dispersive nanoparticles. Specifically, the bimetallic PtFe/GCM and the trimetallic PtFeCo/GCM catalysts are successfully synthesized, and their electrocatalytic performances toward oxygen reduction reaction (ORR) are also studied. The resultant PtFe/GCM shows the significant enhancement in ORR activity, including a factor of 8.47 enhancement in mass activity (0.72 A mgPt-1), and a factor of 7.67 enhancement in specific activity (0.92 mA cm-2), comparing with those of the commercial Pt/C catalyst (0.085 A mgPt-1, 0.12 mA cm-2). Importantly, by introducing the Co, the trimetallic PtFeCo/GCM exhibits the further improved ORR activities (1.28 A mgPt-1, 1.80 mA cm-2). The high ORR activity is probably attributed to the alloying structure, ultrafine size, highly dispersive, well-defined, and a better interface with 3D porous graphene support.

  9. Atomic-Level Co3O4 Layer Stabilized by Metallic Cobalt Nanoparticles: A Highly Active and Stable Electrocatalyst for Oxygen Reduction.

    Science.gov (United States)

    Liu, Min; Liu, Jingjun; Li, Zhilin; Wang, Feng

    2018-02-28

    Developing atomic-level transition oxides may be one of the most promising ways for providing ultrahigh electrocatalytic performance for oxygen reduction reaction (ORR), compared with their bulk counterparts. In this article, we developed a set of atomically thick Co 3 O 4 layers covered on Co nanoparticles through partial reduction of Co 3 O 4 nanoparticles using melamine as a reductive additive at an elevated temperature. Compared with the original Co 3 O 4 nanoparticles, the synthesized Co 3 O 4 with a thickness of 1.1 nm exhibits remarkably enhanced ORR activity and durability, which are even higher than those obtained by a commercial Pt/C in an alkaline environment. The superior activity can be attributed to the unique physical and chemical structures of the atomic-level oxide featuring the narrowed band gap and decreased work function, caused by the escaped lattice oxygen and the enriched coordination-unsaturated Co 2+ in this atomic layer. Besides, the outstanding durability of the catalyst can result from the chemically epitaxial deposition of the Co 3 O 4 on the cobalt surface. Therefore, the proposed synthetic strategy may offer a smart way to develop other atomic-level transition metals with high electrocatalytic activity and stability for energy conversion and storage devices.

  10. Photoassisted oxygen reduction reaction on mpg-C3N4: The effects of elements doping on the performance of ORR

    Science.gov (United States)

    He, Qiuchen; Zhou, Feng; Zhan, Su; Huang, Naibao; Tian, Yu

    2018-02-01

    The oxygen reduction reaction (ORR) is a crux step in the fuel cells, which is limited to the catalysts. Low-cost nonmetal inorganic catalysts were considered to be the best prospect that may replace platinum. Graphitic carbon nitride (g-C3N4), which has wide prospect in photocatalysis, was found with the activity of ORR. In calculation work, we used the elements of the VIA family (O, S, and Se) to dope g-C3N4 and investigated the electronic properties and the ability of O2 adsorption in details based on the first principle. The result suggested that the performance of ORR of g-C3N4 may be enhanced by O doping, which can uplift the Fermi level of g-C3N4 and weaken the OH- absorption ability to enhance the O2 adsorption ability. After that, we synthetised O/g-C3N4 and S/g-C3N4 to test their ORR performance. According to the result, O doping can significantly enhance the performance of ORR of g-C3N4 which correspond with the calculation result. Then, the photo-assistant method was used to further enhance the ORR of g-C3N4 which was caused by the transition of the photo-induced electrons of g-C3N4 from VB to CB.

  11. Surface Modification of Multi-Walled Carbon Nanotubes via Hemoglobin-Derived Iron and Nitrogen-Rich Carbon Nanolayers for the Electrocatalysis of Oxygen Reduction

    Directory of Open Access Journals (Sweden)

    Wensheng Li

    2017-05-01

    Full Text Available The great challenge of boosting the oxygen reduction reaction (ORR activity of non-noble-metal electrocatalysts is how to achieve effective exposure and full utilization of nitrogen-rich active sites. To realize the goals of high utilization of active sites and fast electron transport, here we report a new strategy for synthesis of an iron and nitrogen co-doped carbon nanolayers-wrapped multi-walled carbon nanotubes as ORR electrocatalyst (N-C@CNT-Fe via using partially carbonized hemoglobin as a single-source precursor. The onset and half-wave potentials for ORR of N-C@CNT-Fe are only 45 and 54 mV lower than those on a commercial Pt/C (20 wt.% Pt catalyst, respectively. Besides, this catalyst prepared in this work has been confirmed to follow a four-electron reaction mechanism in ORR process, and also displays ultra-high electrochemical cycling stability in both acidic and alkaline electrolytes. The enhancement of ORR activity can be not only attributed to full exposure and utilization of active site structures, but also can be resulted from the improvement of electrical conductivity owing to the introduction of CNT support. The analysis of X-ray photoelectric spectroscopy shows that both Fe–N and graphitic-N species may be the ORR active site structures of the prepared catalyst. Our study can provide a valuable idea for effective improvement of the electrocatalytic activity of non-noble-metal ORR catalysts.

  12. Synergistic interaction and controllable active sites of nitrogen and sulfur co-doping into mesoporous carbon sphere for high performance oxygen reduction electrocatalysts

    Science.gov (United States)

    Oh, Taeseob; Kim, Myeongjin; Park, Dabin; Kim, Jooheon

    2018-05-01

    Nitrogen and sulfur co-doped mesoporous carbon sphere (NSMCS) was prepared as a metal-free catalyst by an economical and facile pyrolysis process. The mesoporous carbon spheres were derived from sodium carboxymethyl cellulose as the carbon source and the nitrogen and sulfur dopants were derived from urea and p-benzenedithiol, respectively. The doping level and chemical states of nitrogen and sulfur in the prepared NSMCS can be easily adjusted by controlling the pyrolysis temperature. The NSMCS pyrolyzed at 900 °C (NSMCS-900) exhibited higher oxygen reduction reaction activity than the mesoporous carbon sphere doped solely with nitrogen or sulfur, due to the synergistic effect of co-doping. Among all the NSMCS samples, NSMCS-900 exhibited excellent ORR catalytic activity owing to the presence of a highly active site, consisting of pyridinic N, graphitic N, and thiophene S. Remarkably, the NSMCS-900 catalyst was comparable with commercial Pt/C, in terms of the onset and the half-wave potentials and showed better durability than Pt/C for ORR in an alkaline electrolyte. The approach demonstrated in this work could be used to prepare promising metal-free electrocatalysts for application in energy conversion and storage.

  13. Synthesis of Pt nanoparticles as catalysts of oxygen reduction with microbubble-assisted low-voltage and low-frequency solution plasma processing

    Science.gov (United States)

    Horiguchi, Genki; Chikaoka, Yu; Shiroishi, Hidenobu; Kosaka, Shinpei; Saito, Morihiro; Kameta, Naohiro; Matsuda, Naoki

    2018-04-01

    In the preparation of metallic nanoparticles by conventional solution plasma (SP) techniques, unstable plasma emission becomes an issue when the voltage and frequency of the waves applied between two electrodes placed in solution are lowered to avoid the boiling of the solution. In this study, we confirm that, in the presence of microbubbles, plasma is generated stably at low voltage (440 V) and low frequency (50-100 Hz) and small-size (≤10 nm) Pt nanoparticles (PtNPs) are synthesized in succession using a flow cell. The smallest PtNPs, ∼3.3 nm in diameter, are obtained using half-wave rectification, a tungsten wire anode, and a platinum wire cathode. The PtNPs are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimeter-differential thermal analysis. The oxygen reduction reaction (ORR) is investigated in 0.1 M HClO4 solution on carbon-supported PtNPs using a rotating ring-disk electrode. The catalytic activities per initial electrochemical active surface area of the carbon-supported PtNPs synthesized employing the low-voltage, low-frequency (LVLF)-SP technique is higher than that of the commercially available 20 wt% Pt on Vulcan XC-72R. These results indicate that the LVLF-SP technique is a promising approach to producing carbon-supported PtNPs that catalyze ORR with low energy consumption.

  14. Electrodeposited ultrafine NbOx, ZrOx, and TaO x nanoparticles on carbon black supports for oxygen reduction electrocatalysts in acidic media

    KAUST Repository

    Seo, Jeongsuk; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2013-01-01

    A remarkable electrocatalytic activity was obtained for the oxygen reduction reaction (ORR) in acidic solutions on ultrafine nano-oxide catalysts based on group IV or V elements. By potentiostatic electrodepostion in nonaqueous solutions at 298 K followed by heat treatment in H2 gas, highly dispersed fine nanoparticles of NbOx, ZrOx, and TaOx with sizes of less than 5 nm were prepared and deposited on carbon black (CB) loaded electrodes. These oxide nanoparticles showed high catalytic activities with high onset potentials of 0.96 VRHE (NbOx), 1.02 VRHE (ZrOx), and 0.93 V RHE (TaOx) for the ORR. Owing to the high chemical stability of group IV and V oxides, the catalysts were very stable during the ORR in acidic solutions. Surface characterization and chemical identification were performed using scanning transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). All results clearly indicate the formation of nano-oxide electrocatalysts that show an outstanding ORR performance, whereas the bulk oxides are not active because of the absence of electronic conductivity. The present work demonstrates potential candidates for highly stable, non-noble-metal cathode catalysts for polymer electrolyte fuel cells (PEFCs), where the catalysts are exposed to highly acidic and oxidizing conditions. © 2013 American Chemical Society.

  15. From two-dimension to one-dimension: the curvature effect of silicon-doped graphene and carbon nanotubes for oxygen reduction reaction.

    Science.gov (United States)

    Zhang, Peng; Hou, Xiuli; Mi, Jianli; He, Yanqiong; Lin, Lin; Jiang, Qing; Dong, Mingdong

    2014-09-07

    For the goal of practical industrial development of fuel cells, inexpensive, sustainable, and highly efficient electrocatalysts for oxygen reduction reactions (ORR) are highly desirable alternatives to platinum (Pt) and other rare metals. In this work, based on density functional theory, silicon (Si)-doped carbon nanotubes (CNTs) and graphene as metal-free, low cost, and high-performance electrocatalysts for ORR are studied systematically. It is found that the curvature effect plays an important role in the adsorption and reduction of oxygen. The adsorption of O2 becomes weaker as the curvature varies from positive values (outside CNTs) to negative values (inside CNTs). The free energy change of the rate-determining step of ORR on the concave inner surface of Si-doped CNTs is smaller than that on the counterpart of Si-doped graphene, while that on the convex outer surface of Si-doped CNTs is larger than that on Si-doped graphene. Uncovering this new ORR mechanism on silicon-doped carbon electrodes is significant as the same principle could be applied to the development of various other metal-free efficient ORR catalysts for fuel cell applications.

  16. AN INVESTIGATION ON THE EFFECT OF FUNCTIONALISED GRAPHENE COMPOSITED WITH NCNT AND FE-NCNT ON THE OXYGEN REDUCTION REACTION VIA PHYSICAL MIXING METHOD

    Directory of Open Access Journals (Sweden)

    CHONG W.Z.

    2016-02-01

    Full Text Available Oxygen reduction reaction plays a major role in fuel cell applications to generate electricity by an electrochemical reaction. In this study, functionalised graphene composited with Fe-NCNT or NCNT were investigated on its ORR activity using a physical mixing method. Initially, functionalised graphene was produced via oxidation of graphene. NCNT and Fe-NCNT was obtained from the previously prepared samples using chemical vapour deposition technique and electrochemical reduction method for Fe-NCNT. The physical mixing between functionalised graphene and NCNT or Fe-NCNT was performed using sonication with the presence of pyrrole to produce the desired nanocatalyst. The surface morphologies and microstructures of the synthesised nanocatalysts were studied using field emission scanning electron microscopy. Surface chemical functionality of the nanocatalysts was investigated using X-ray photoelectron microscopy. Meanwhile, the ORR performance of nanocatalysts in a half cell were investigated using cyclic voltammetry techniques in both alkaline and acidic electrolytes. From this study, agglomeration of functionalised graphene (f-graphene was observed on the Fe-NCNTs indicating a hindrance in transfer of electrons within the catalyst surface. NCNT/f-graphene showed to contain higher percentage of pyridinic-N which claimed to have favored the catalytic activity compared to Fe-NCNT/f-graphene. Likewise, a higher onset potential was recorded for NCNT/f-graphene which indicated a higher ORR activity than the Fe-NCNT/f-graphene.

  17. A Nanopore-Structured Nitrogen-Doped Biocarbon Electrocatalyst for Oxygen Reduction from Two-Step Carbonization of Lemna minor Biomass

    Science.gov (United States)

    Guo, Chaozhong; Li, Zhongbin; Niu, Lidan; Liao, Wenli; Sun, Lingtao; Wen, Bixia; Nie, Yunqing; Cheng, Jing; Chen, Changguo

    2016-05-01

    So far, the development of highly active and stable carbon-based electrocatalysts for oxygen reduction reaction (ORR) to replace commercial Pt/C catalyst is a hot topic. In this study, a new nanoporous nitrogen-doped carbon material was facilely designed by two-step pyrolysis of the renewable Lemna minor enriched in crude protein under a nitrogen atmosphere. Electrochemical measurements show that the onset potential for ORR on this carbon material is around 0.93 V (versus reversible hydrogen electrode), slightly lower than that on the Pt/C catalyst, but its cycling stability is higher compared to the Pt/C catalyst in an alkaline medium. Besides, the ORR at this catalyst approaches to a four-electron transfer pathway. The obtained ORR performance can be basically attributed to the formation of high contents of pyridinic and graphitic nitrogen atoms inside this catalyst. Thus, this work opens up the path in the ORR catalysis for the design of nitrogen-doped carbon materials utilizing aquatic plants as starting precursors.

  18. A Platinum Monolayer Core-Shell Catalyst with a Ternary Alloy Nanoparticle Core and Enhanced Stability for the Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Haoxiong Nan

    2015-01-01

    Full Text Available We synthesize a platinum monolayer core-shell catalyst with a ternary alloy nanoparticle core of Pd, Ir, and Ni. A Pt monolayer is deposited on carbon-supported PdIrNi nanoparticles using an underpotential deposition method, in which a copper monolayer is applied to the ternary nanoparticles; this is followed by the galvanic displacement of Cu with Pt to generate a Pt monolayer on the surface of the core. The core-shell Pd1Ir1Ni2@Pt/C catalyst exhibits excellent oxygen reduction reaction activity, yielding a mass activity significantly higher than that of Pt monolayer catalysts containing PdIr or PdNi nanoparticles as cores and four times higher than that of a commercial Pt/C electrocatalyst. In 0.1 M HClO4, the half-wave potential reaches 0.91 V, about 30 mV higher than that of Pt/C. We verify the structure and composition of the carbon-supported PdIrNi nanoparticles using X-ray powder diffraction, X-ray photoelectron spectroscopy, thermogravimetry, transmission electron microscopy, and energy dispersive X-ray spectrometry, and we perform a stability test that confirms the excellent stability of our core-shell catalyst. We suggest that the porous structure resulting from the dissolution of Ni in the alloy nanoparticles may be the main reason for the catalyst’s enhanced performance.

  19. 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

  20. 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.

  1. 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.

  2. Bubble dynamic templated deposition of three-dimensional palladium nanostructure catalysts: Approach to oxygen reduction using macro-, micro-, and nano-architectures on electrode surfaces

    International Nuclear Information System (INIS)

    Yang Guimei; Chen Xing; Li Jie; Guo Zheng; Liu Jinhuai; Huang Xingjiu

    2011-01-01

    Highlights: → We synthesize the Pd nanostructures by bubbles dynamic templated. → We obtain Pd nanobuds and Pd nanodendrites by changing the reaction precursor. → We obtain Pd macroelectrode voltammertric behavior using small amount of Pd materials. → We proved a ECE process. → The Pd nanostructures/GCE for O 2 reduction is a 2-step 4-electron process. - Abstract: Three-dimensional (3D) palladium (Pd) nanostructures (that is, nano-buds or nano-dendrites) are fabricated by bubble dynamic templated deposition of Pd onto a glassy carbon electrode (GCE). The morphology can be tailored by changing the precursor concentration and reaction time. Scanning electron microscopy images reveal that nano-buds or nano-dendrites consist of nanoparticles of 40-70 nm in diameter. The electrochemical reduction of oxygen is reported at such kinds of 3D nanostructure electrodes in aqueous solution. Data were collected using cyclic voltammetry. We demonstrate the Pd macroelectrode behavior of Pd nanostructure modified electrode by exploiting the diffusion model of macro-, micro-, and nano-architectures. In contrast to bare GCE, a significant positive shift and splitting of the oxygen reduction peak (vs Ag/AgCl/saturated KCl) at Pd nanostructure modified GCE was observed.

  3. Refining cocoon to prepare (N, S, and Fe) ternary-doped porous carbon aerogel as efficient catalyst for the oxygen reduction reaction in alkaline medium

    Science.gov (United States)

    Li, Changqing; Sun, Fengzhan; Lin, Yuqing

    2018-04-01

    Various advanced sulfur doped Fe-N-C non-noble metal catalysts of oxygen reduction reaction (ORR) have been recently designed and reported with excellent catalytic activity. Herein, we refined cocoon with several steps to form silk fibroin solution, treated with iron salt to prepare an easy available, heteroatom (N, S, and Fe) ternary-doped, porous carbon aerogel (HDCA). Heteroatom existed in organic compounds in silk fibroin endow active site for ORR of the resultant carbon frameworks. Moreover, the amino acids presented in silk fibroin acted as ligands, functioning with Fe ions to form FeNx coordination compounds, which also served as active sites towards ORR. The synthesized HDCA electrocatalysts, especially HDCA-800 (obtained at 800 °C) displayed excellent catalytic activity with onsets, half-wave potential of 0.94 V, 0.79 V and higher limited current density of 3.80 mA cm-2 through a near four-electron reduction pathway with an average electron transferred number of 3.86, making them promising alternatives for state-of-the-art ORR electrocatalysts in fuel cell field. The porous structure with synergistic effect of N and S heteroatom doping has been proposed to play a key role in facilitating the desired ORR reaction.

  4. A quasi-direct methanol fuel cell system based on blend polymer membrane electrolytes

    DEFF Research Database (Denmark)

    Li, Qingfeng; Hjuler, Hans Aage; Hasiotis, C.

    2002-01-01

    , compared to less than 100 ppm CO for the Nafion-based technology at 80degrees C. The high CO tolerance makes it possible to use the reformed hydrogen directly from a simple methanol reformer without further CO removal. That both the fuel cell and the methanol reformer operate at temperatures around 200......On the basis of blend polymer electrolytes of polybenzimidazole and sulfonated polysulfone, a polymer electrolyte membrane fuel cell was developed with an operational temperature up to 200degrees C. Due to the high operational temperature, the fuel cell can tolerate 1.0-3.0 vol % CO in the fuel...

  5. Methanol adsorption on Pt(111)

    International Nuclear Information System (INIS)

    Melo, A.V.; Chottiner, G.S.; Hoffman, R.W.; O'Grady, W.E.

    1984-12-01

    High resolution electron energy loss spectroscopy has been used to study the decomposition of methanol on a Pt(111) surface. Several intermediate states in the decomposition are identified by quenching the sample when reactions occur. At 100 K a set of peaks at 800, 1040, 1350, and 2890 cm -1 indicates the presence of a multilayer molecularly adsorbed methanol. As the sample is warmed to 130 K peaks develop at 1700 and 2780 cm -1 , suggesting the formation of formaldehyde on the surface. With further heating, peaks grow at 1820 and 2560 cm -1 due to the formation of a formyl species during the decomposition of methanol over Pt(111). Further heating leads to the final conversion of the surface species to adsorbed CO and carbonaceous residues

  6. Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)-electrodes: Effects of the heteroatomic junction on the reaction paths

    Science.gov (United States)

    Schulte, E.; Belletti, G.; Arce, M.; Quaino, P.

    2018-05-01

    The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the Osbnd O bond breaking in O2∗ and OOH∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O2∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The Osbnd O scission of the OOH∗ was found to be a barrierless process in Ausbnd Pt systems and nearly barrierless in all Ausbnd Pd systems, implying that the reduction ofO2 in these systems proceeds via the full reduction of O2 to H2O , avoiding H2O2 formation.

  7. Controlling the Interfacial Environment in the Electrosynthesis of MnOx Nanostructures for High-Performance Oxygen Reduction/Evolution Electrocatalysis.

    Science.gov (United States)

    Hosseini-Benhangi, Pooya; Kung, Chun Haow; Alfantazi, Akram; Gyenge, Elöd L

    2017-08-16

    High-performance, nonprecious metal bifunctional electrocatalysts for the oxygen reduction and evolution reactions (ORR and OER, respectively) are of great importance for rechargeable metal-air batteries and regenerative fuel cells. A comprehensive study based on statistical design of experiments is presented to investigate and optimize the surfactant-assisted structure and the resultant bifunctional ORR/OER activity of anodically deposited manganese oxide (MnO x ) catalysts. Three classes of surfactants are studied: anionic (sodium dodecyl sulfate, SDS), non-ionic (t-octylphenoxypolyethoxyethanol, Triton X-100), and cationic (cetyltrimethylammonium bromide, CTAB). The adsorption of surfactants has two main effects: increased deposition current density due to higher Mn 2+ and Mn 3+ concentrations at the outer Helmholtz plane (Frumkin effect on the electrodeposition kinetics) and templating of the MnO x nanostructure. CTAB produces MnO x with nanoneedle (1D) morphology, whereas nanospherical- and nanopetal-like morphologies are obtained with SDS and Triton, respectively. The bifunctional performance is assessed based on three criteria: OER/ORR onset potential window (defined at 2 and -2 mA cm -2 ) and separately the ORR and OER mass activities. The best compromise among these three criteria is obtained either with Triton X-100 deposited catalyst composed of MnOOH and Mn 3 O 4 or SDS deposited catalyst containing a combination of α- and β-MnO 2 , MnOOH, and Mn 3 O 4 .The interaction effects among the deposition variables (surfactant type and concentration, anode potential, Mn 2+ concentration, and temperature) reveal the optimal strategy for high-activity bifunctional MnO x catalyst synthesis. Mass activities for OER and ORR up to 49 A g -1 (at 1556 mV RHE ) and -1.36 A g -1 (at 656 mV RHE ) are obtained, respectively.

  8. Self-assembled dopamine nanolayers wrapped carbon nanotubes as carbon-carbon bi-functional nanocatalyst for highly efficient oxygen reduction reaction and antiviral drug monitoring

    Science.gov (United States)

    Khalafallah, Diab; Akhtar, Naeem; Alothman, Othman Y.; Fouad, H.; Abdelrazek khalil, Khalil

    2017-09-01

    Oxygen reduction reaction (ORR) catalysts are the heart of eco-friendly energy resources particularly low temperature fuel cells. Although valuable efforts have been devoted to synthesize high performance catalysts for ORR, considerable challenges are extremely desirable in the development of energy technologies. Herein, we report a simple self-polymerization method to build a thin film of dopamine along the tubular nanostructures of multi-walled carbon nanotubes (CNT) in a weak alkaline solution. The dopamine@CNT hybrid (denoted as DA@CNT) reveals an enhanced electrocatalytic activity towards ORR with highly positive onset potential and cathodic current as a result of their outstanding features of longitudinal mesoporous structure, high surface area, and ornamentation of DA layers with nitrogen moieties, which enable fast electron transport and fully exposed electroactive sites. Impressively, the as-obtained hybrid afford remarkable electrochemical durability for prolonged test time of 60,000 s compared to benchmark Pt/C (20 wt%) catalyst. Furthermore, the developed DA@CNT electrode was successfully applied to access the quality of antiviral drug named Valacyclovir (VCR). The DA@CNT electrode shows enhanced sensing performance in terms of large linear range (3-75 nM), low limit of detection (2.55 nM) than CNT based electrode, indicating the effectiveness of the DA coating. Interestingly, the synergetic effect of nanostructured DA and CNT can significantly boost the electronic configuration and exposure level of active species for ORR and biomolecule recognition. Therefore, the existing carbon-based porous electrocatalyst may find numerous translational applications as attractive alternative to noble metals in polymer electrolyte membrane fuel cells and quality control assessment of pharmaceutical and therapeutic drugs.

  9. Nitrogen and sulfur co-doped porous carbon – is an efficient electrocatalyst as platinum or a hoax for oxygen reduction reaction in acidic environment PEM fuel cell?

    International Nuclear Information System (INIS)

    Sahoo, Madhumita; Ramaprabhu, S.

    2017-01-01

    Non-precious, heteroatom doped carbon is reported to replace commercial Pt/C in both alkaline and acidic half-cell rotating disc electrode study; however the real world full cell measurements with the metal-free electrocatalysts overcoming the practical troubles in acidic environment proton exchange membrane fuel cell (PEMFC) are almost negligible to confirm the claim. Nitrogen and sulfur co-doped porous carbon (DPC) was synthesized in a one step, high yield process from single source ionic liquid precursor using eutectic salt as porogens to achieve porosity. Structural characterization confirms 7.03% nitrogen and 1.68% sulfur doping into the high surface area, porous carbon structure. As the cathode oxygen reduction reaction (ORR) catalyst, metal-free DPC and Pt nanoparticles decorated DPC (Pt/DPC) shows stable and high exchange current density by four electron transfer pathway in acidic half–cell liquid environment due to the synergistic effect of nitrogen and sulfur doping and porous nature of DPC. In an actual solid state full cell measurement, Pt/DPC shows higher performance comparable to commercial Pt/C; however DPC failed to reciprocate the half-cell performance due to blockage of active sites in the membrane electrode assembly fabrication process. - Highlights: • Synthesis of N and S co-doped porous carbon (DPC) in simple one-pot technique. • High surface area DPC shows comparable activity for ORR in half-cell acidic PEMFC study. • Real-world performance of DPC gives 20 mW/cm 2 peak power density at 60 °C. • Homogeneous Pt nanoparticles decorated DPC (Pt/DPC) outperforms commercial Pt/C. • Pt/DPC shows maximum power density of 718 mW/cm 2 with lower 0.3 mg/cm 2 total Pt loading.

  10. Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Lewera, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw (Poland); Inukai, J. [Clean Energy Research Center, University of Yamanashi, 7-32 Miyamae-cho, Kofu 400-0006 (Japan); Zhou, W.P. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Cao, D. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Duong, H.T. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Alonso-Vante, N. [Laboratory of Electrocatalysis, UMR-CNRS 6503, University of Poitiers, F-86022 Poitiers (France)]. E-mail: Nicolas.Alonso.Vante@univ-poitiers.fr; Wieckowski, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)]. E-mail: andrzej@scs.uiuc.edu

    2007-05-10

    Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO{sub 2} or SO {sub x} forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples.

  11. Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

    International Nuclear Information System (INIS)

    Lewera, A.; Inukai, J.; Zhou, W.P.; Cao, D.; Duong, H.T.; Alonso-Vante, N.; Wieckowski, A.

    2007-01-01

    Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO 2 or SO x forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples

  12. Study of the oxygen reduction reaction using Pt-Rare earths (La, Ce, Er) electrocatalysts for application of PEM fuel cells

    International Nuclear Information System (INIS)

    Gomes, Thiago Bueno

    2013-01-01

    The complexity of the oxygen reduction reaction (ORR) and its potential losses make it responsible for the most part of efficiency losses at the Fuel Cells. For this reaction the electrocatalyst witch is most appropriated and shows better performance is platinum, a noble metal that elevates the cost, raising barriers for Fuel Cells technology to enter the market. First this work focuses on reducing the amount of platinum used in the cathode, by being replaced by rare earths. The most common methods of synthesis involves a large amount of steps and this work proposed to prepare the electrocatalyst through a simpler way that would not take so many steps and time to be done. Using an ultrasound mixer the electrocatalyst was prepared mixing platinum supported on carbon black and the rare earths lanthanum, cerium and erbium oxides to be applied in a half-cell study of the ORR. The Koutecky-Levich plots shows that among the electrocatalysts prepared the Pt80Ce20/C had the catalytic activity close to the commercial BASF platinum on carbon black, suggesting that the reaction was taken by the 4-electron path. As found in some works in literature, among the rare earth used to study the ORR, cerium is the one witch shows the better performance because it is able to store and provide oxygen. This feature is of great interest for the ORR because this reaction is first order to the oxygen concentration. Results show that is possible to reduce the amount of platinum maintaining the same electrocatalyst activity. (author)

  13. Oxygen reduction activities compared in rotating-disk electrode and proton exchange membrane fuel cells for highly active Fe-N-C catalysts

    International Nuclear Information System (INIS)

    Jaouen, F.; Goellner, V.; Lefèvre, M.; Herranz, J.; Proietti, E.; Dodelet, J.P.

    2013-01-01

    In the past three years, two novel synthesis methods for non-precious metal catalysts resulting in a breakthrough of their activity and performance at the cathode of the proton-exchange membrane fuel cell (PEMFC) have been reported by the group of Prof. Dodelet. While the activity of these novel Fe-based catalysts for the oxygen reduction reaction is very high in PEMFC, our preliminary activity measurements with the rotating disk electrode (RDE) technique on one of them showed an activity being a factor 30–100 lower than the one measured in PEMFC at 80 °C. The present work explains to a large extent this huge difference. Two Fe-N-C catalysts synthesized via our novel approaches and one Fe-N-C catalyst synthesized via our classical approach were investigated in RDE and PEMFC. In both systems, the effect of the ink formulation (Nafion-to-catalyst ratio) was investigated. Optimization of the RDE ink formulation explains a factor between 5 and 10 in the two-decade gap mentioned above. Then, the effect of temperature in the RDE system was investigated. An increase from 20 to 80 °C was found to result in a theoretical maximum twofold increase in activity. However, in practice, decreased O 2 solubility with increased temperature cancels this effect. After taking into account these two parameters, a difference in ORR activity between RDE and PEMFC of ca a factor five still remained for one of the two novel Fe-N-C catalysts investigated here. The lower initial activity measured in RDE for this catalyst is shown to be due to the fast adsorption of anions (HSO 4 − ) from the liquid H 2 SO 4 electrolyte on protonated nitrogen atoms (NH + ) found on its surface. The phenomenon of anion adsorption and associated decreased ORR activity also applies to the other novel Fe-N-C catalyst, but is slower and does not immediately occur in RDE.

  14. Intercalation assembly of Li{sub 3}VO{sub 4} nanoribbons/graphene sandwich-structured composites with enhanced oxygen reduction catalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Huang, K.; Ling, Q.N.; Huang, C.H.; Bi, K. [State Key Laboratory of Information Photonics and Optical Communications & School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Wang, W.J.; Yang, T.Z. [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Lu, Y.K. [School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083 (China); Liu, J., E-mail: liujun4982004@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083 (China); Zhang, R.; Fan, D.Y.; Wang, Y.G. [State Key Laboratory of Information Photonics and Optical Communications & School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Lei, Ming, E-mail: mlei@bupt.edu.cn [State Key Laboratory of Information Photonics and Optical Communications & School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China)

    2015-10-15

    Novel sandwich-like nanocomposites of alternative stacked ultrathin Li{sub 3}VO{sub 4} nanoribbons and graphene sheets (LVO-G) were successfully developed by a facile intercalation assembly method with a post heating treatment. The characterization results demonstrate that the average size of the Li{sub 3}VO{sub 4} nanoribbons with a non-layered crystal structure is a few micrometers in length, 50–100 nm in width and a few atomic layers in height. The addition of graphene sheets can modify the preferred orientation of the Li{sub 3}VO{sub 4} nanoribbons from (110) to (011) plane and restrict the growth of impurity phase at the same time. In addition, EIS analysis has also verified the reduced resistance and thus the enhance conductivity of LVO-G nanocomposites compared with bare Li{sub 3}VO{sub 4} nanoribbons. What's more, the electrocatalytic performances of these novel LVO-G nanocomposites for oxygen reduction reaction (ORR) in alkaline solution are further investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test. It is found that the enhanced activity and stability of LVO-G can be attributed to the synergistic effect between the Li{sub 3}VO{sub 4} nanoribbons and graphene sheets with a larger reduction current density and a smaller onset potential value for LVO-G25 compared with LVO-G50 due to the change of components. - Highlights: • Novel sandwich-structured LVO-G by a facile intercalation assembly method. • Addition of G sheets can modify the preferred orientation of Li{sub 3}VO{sub 4} nanoribbon. • Enhanced ORR activity and stability due to synergistic effect are demonstrated.

  15. 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.

  16. Improved Oxygen Reduction Activity and Durability of Dealloyed PtCox Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects

    Science.gov (United States)

    Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M.; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E.; Mukerjee, Sanjeev

    2015-01-01

    The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo3/HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt–Pt and Pt–Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling. PMID:26413384

  17. In situ formation of a 3D core-shell and triple-conducting oxygen reduction reaction electrode for proton-conducting SOFCs

    Science.gov (United States)

    Zhang, Zhenbao; Wang, Jian; Chen, Yubo; Tan, Shaozao; Shao, Zongping; Chen, Dengjie

    2018-05-01

    BaZrxCeyY1-x-yO3-δ are recognized proton-conducting electrolyte materials for proton-conducting solid oxide fuel cells (H+-SOFCs) below 650 °C. Here Co cations are incorporated into the BaZr0.4Ce0.4Y0.2O3-δ (BZCY) scaffold to generate a 3D core-shell and triple-conducting (H+/O2-/e-) electrode in situ via infiltrating and reactive sintering. The core is the bulk BZCY scaffold, while the shell is composed of the cubic Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ, cubic spinel Co3O4 and cubic fluorite (Ce, Zr, Y)O2. The obtained electrode exhibits an excellent compatibility with the BZCY electrolyte, and performs well in yielding a low and stable polarization resistance for oxygen reduction reaction for intermediate-temperature H+-SOFCs. In particular, it achieves polarization resistances as low as 0.094 and 0.198 Ω cm2 at 650 and 600 °C in wet air (3% H2O) when the sintering temperature for the electrode is 900 °C. In addition, a symmetrical cell also exhibits operation stability of 70 h at 650 °C. Furthermore, a fuel cell assembled with the 3D core-shell and triple-conducting electrode delivers a peak power density of ∼330 mW cm-2 at 650 °C. The substantially improved electrochemical performance and high stability are ascribed to the unique core-shell structure and the formation of Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ in the shell.

  18. Re-examination of the Pt Particle Size Effect on the Oxygen Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion

    International Nuclear Information System (INIS)

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-01-01

    Highlights: • Pt particle size effect on ORR was re-evaluated for Pt/C catalysts. • Nafion-free activity of Pt/C catalysts was evaluated using thin-film RDE methods. • Ultrathin-uniform catalyst layers were employed to obtain accurate activity values. • Specific activity increased steeply from 2 to 10 nm and less steeply at over 10 nm. • Re-evaluated effect agrees with a particle model assuming terrace active sites. - Abstract: The platinum ‘particle size effect’ on the oxygen reduction reaction (ORR) has been re-evaluated using commercial Pt/C catalysts (2–10 nm Pt particle) and polycrystalline Pt (poly-Pt) in 0.1 M HClO 4 with a rotating disk electrode method. Nafion-free catalyst layers were employed to obtain specific activities (SA) that were not perturbed (suppressed) by sulfonate anion adsorption/blocking. By using ultrathin uniform catalyst layers, O 2 diffusion limitation was minimized as confirmed from the high SAs of our supported catalysts that were comparable to unsupported sputtered Pt having controlled sizes. The specific activity (SA) steeply increased for the particle sizes in the range ∼2–10 nm (0.8–1.8 mA/cm 2 Pt at 0.9 V vs. RHE) and plateaued over ∼10 nm to 2.7 mA/cm 2 Pt for bulk poly-Pt. On the basis of the activity trend for the range of particle sizes studied, it appears that the effect of carbon support on activity is negligible. The experimental results and the concomitant profile of SA vs. particle size was found to be in an agreement to a truncated octahedral particle model that assumes active terrace sites.

  19. Metal-organic framework derived Fe/Fe3C@N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions.

    Science.gov (United States)

    Song, Chunsen; Wu, Shikui; Shen, Xiaoping; Miao, Xuli; Ji, Zhenyuan; Yuan, Aihua; Xu, Keqiang; Liu, Miaomiao; Xie, Xulan; Kong, Lirong; Zhu, Guoxing; Ali Shah, Sayyar

    2018-08-15

    The development of simple and cost-effective synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is critical to renewable energy technologies. Herein, we report an interesting bifunctional HER and ORR electrocatalyst of Fe/Fe 3 C@N-doped-carbon porous hierarchical polyhedrons (Fe/Fe 3 C@N-C) by a simple metal-organic framework precursor route. The Fe/Fe 3 C@N-C polyhedrons consisting of Fe and Fe 3 C nanocrystals enveloped by N-doped carbon shells and accompanying with some carbon nanotubes on the surface were prepared by thermal annealing of Zn 3 [Fe(CN) 6 ] 2 ·xH 2 O polyhedral particles in nitrogen atmosphere. This material exhibits a large specific surface area of 182.5 m 2  g -1 and excellent ferromagnetic property. Electrochemical tests indicate that the Fe/Fe 3 C@N-C hybrid has apparent HER activity with a relatively low overpotential of 236 mV at the current density of 10 mA cm -2 and a small Tafel slope of 59.6 mV decade -1 . Meanwhile, this material exhibits excellent catalytic activity toward ORR with an onset potential (0.936 V vs. RHE) and half-wave potential (0.804 V vs. RHE) in 0.1 M KOH, which is comparable to commercial 20 wt% Pt/C (0.975 V and 0.820 V), and shows even better stability than the Pt/C. This work provides a new insight to developing multi-functional materials for renewable energy application. Copyright © 2018 Elsevier Inc. All rights reserved.

  20. Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol

    DEFF Research Database (Denmark)

    Alberico, E.; Nielsen, Martin

    2015-01-01

    The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous...