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Sample records for effective electrocatalyst activity

  1. Understanding the Effects of Surface Chemistry and Microstructure on the Activity and Stability of Pt Electrocatalysts on Non-Carbon Supports

    Energy Technology Data Exchange (ETDEWEB)

    Mustain, William [Univ. of Conneticut, Storrs, CT (United States)

    2015-02-12

    The objective of this project is to elucidate the effects of the chemical composition and microstructure of the electrocatalyst support on the activity, stability and utilization of supported Pt clusters.

  2. Nanostructured electrocatalysts with tunable activity and selectivity

    Science.gov (United States)

    Mistry, Hemma; Varela, Ana Sofia; Kühl, Stefanie; Strasser, Peter; Cuenya, Beatriz Roldan

    2016-04-01

    The field of electrocatalysis has undergone tremendous advancement in the past few decades, in part owing to improvements in catalyst design at the nanoscale. These developments have been crucial for the realization of and improvement in alternative energy technologies based on electrochemical reactions such as fuel cells. Through the development of novel synthesis methods, characterization techniques and theoretical methods, rationally designed nanoscale electrocatalysts with tunable activity and selectivity have been achieved. This Review explores how nanostructures can be used to control electrochemical reactivity, focusing on three model reactions: O2 electroreduction, CO2 electroreduction and ethanol electrooxidation. The mechanisms behind nanoscale control of reactivity are discussed, such as the presence of low-coordinated sites or facets, strain, ligand effects and bifunctional effects in multimetallic materials. In particular, studies of how particle size, shape and composition in nanostructures can be used to tune reactivity are highlighted.

  3. Recent advances in platinum monolayer electrocatalysts for oxygen reduction reaction: Scale-up synthesis, structure and activity of Pt shells on Pd cores

    Energy Technology Data Exchange (ETDEWEB)

    Sasaki, K., E-mail: ksasaki@bnl.go [Brookhaven National Laboratory, Chemistry Department, Upton, NY 11973 (United States); Wang, J.X. [Brookhaven National Laboratory, Chemistry Department, Upton, NY 11973 (United States); Naohara, H. [Toyota Motor Corporation, Susono 410-1193 (Japan); Marinkovic, N. [University of Delaware, Department of Chemical Engineering, Newark, DE 19716 (United States); More, K. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Inada, H. [Hitachi High Technologies America, Pleasanton, CA 94588 (United States); Adzic, R.R., E-mail: adzic@bnl.go [Brookhaven National Laboratory, Chemistry Department, Upton, NY 11973 (United States)

    2010-03-01

    We have established a scale-up synthesis method to produce gram-quantities of Pt monolayer electrocatalysts. The core-shell structure of the Pt/Pd/C electrocatalyst has been verified using the HAADF-STEM Z-contrast images, STEM/EELS, and STEM/EDS line profile analysis. The atomic structure of this electrocatalyst and formation of a Pt monolayer on Pd nanoparticle surfaces were examined using in situ EXAFS. The Pt mass activity of the Pt/Pd/C electrocatalyst for ORR is considerably higher than that of commercial Pt/C electrocatalysts. The results with Pt monolayer electrocatalysts may significantly impact science of electrocatalysis and fuel-cell technology, as they have demonstrated an exceptionally effective way of using Pt that can resolve problems of other approaches, including electrocatalysts' inadequate activity and high Pt content.

  4. Recent advances in platinum monolayer electrocatalysts for oxygen reduction reaction: Scale-up synthesis, structure and activity of Pt shells on Pd cores

    International Nuclear Information System (INIS)

    Sasaki, K.; Wang, J.X.; Naohara, H.; Marinkovic, N.; More, K.; Inada, H.; Adzic, R.R.

    2010-01-01

    We have established a scale-up synthesis method to produce gram-quantities of Pt monolayer electrocatalysts. The core-shell structure of the Pt/Pd/C electrocatalyst has been verified using the HAADF-STEM Z-contrast images, STEM/EELS, and STEM/EDS line profile analysis. The atomic structure of this electrocatalyst and formation of a Pt monolayer on Pd nanoparticle surfaces were examined using in situ EXAFS. The Pt mass activity of the Pt/Pd/C electrocatalyst for ORR is considerably higher than that of commercial Pt/C electrocatalysts. The results with Pt monolayer electrocatalysts may significantly impact science of electrocatalysis and fuel-cell technology, as they have demonstrated an exceptionally effective way of using Pt that can resolve problems of other approaches, including electrocatalysts' inadequate activity and high Pt content.

  5. The effect of low platinum loading on the efficiency of PEMFC’s electrocatalysts supported on TiO2–Nb, and SnO2–Nb: An experimental comparison between active and stable conditions

    International Nuclear Information System (INIS)

    Shahgaldi, Samaneh; Hamelin, Jean

    2015-01-01

    Highlights: • SnO 2 –Nb, and TiO 2 –Nb thin films synthesized via sputtering. • SnO 2 –Nb, and TiO 2 –Nb thin films applied as a Pt support in PEMFC. • Low amount of Pt sputtered on supports as catalyst in cathode side. • Fabricate a single cell and plot I–V curves. - Abstract: Electrocatalyst supports have been demonstrated to strongly influence the cost, performance and durability of PEMFC systems, which have been among the heated research topics in the course of the past decades. However, the present support materials used in fuel cell stack are not adequately durable for commercialization. Development of active electrocatalyst with cost effectiveness and high durability is one of the main challenges. In this paper, titania and tin oxide nanoparticles doped nobidium were selected as thermo chemically stable and carbonless electrocatalyst supports. Low Pt loading (0.05 mg/cm 2 ) is deposited on supports through sputtering method, and the structure, the distribution of nanoparticles, and the electrical resistivity were systematically analyzed. To make the studies of oxygen reduction reaction activity, catalytic stability and performance of PEMFC more precise, rotation disk electrode (RDE), cyclic voltammetry (CV), and single cell test were utilized. The data analysis of this study highlighted that SnO 2 –Nb–Pt depicted higher stability and better fuel cell performance in comparison with TiO 2 –Nb–Pt

  6. Atomically Monodisperse Nickel Nanoclusters as Highly Active Electrocatalysts for Water Oxidation

    KAUST Repository

    Joya, Khurram

    2016-04-08

    Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 and initiate the oxygen evolution at an amazingly low overpotential of ~1.51 V (vs RHE; η ≈ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm–2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec–1 is observed using Ni4(PET)8. These results are comparable to the state-of-the art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm–2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.

  7. Highly ordered Pd nanowire arrays as effective electrocatalysts for ethanol oxidation in direct alcohol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Xu, C.W. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Wang, H. [Departement of Applied Chemistry, Dongguan University of Technology, Dongguan 523106 (China); Shen, P.K. [School of Physics and Engineering, Sun Yet-Sen University, Guangzhou 510275 (China); Jiang, S.P.

    2007-12-03

    Pd nanowire arrays (NWAs) with high electrochemically active surface area are successfully fabricated using anodized aluminum oxide electrodeposition. The electrocatalytic activity and stability of the Pd NWAs for ethanol electrooxidation are not only significantly higher that of conventional Pd film electrodes, but also higher than that of well-established commercial PtRu/C electrocatalysts. The Pd NWAs show great potential as electrocatalysts for ethanol electrooxidation in alkaline media in direct ethanol fuel cells. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  8. Iron Is the Active Site in Nickel/Iron Water Oxidation Electrocatalysts

    Directory of Open Access Journals (Sweden)

    Bryan M. Hunter

    2018-04-01

    Full Text Available Efficient catalysis of the oxygen-evolution half-reaction (OER is a pivotal requirement for the development of practical solar-driven water splitting devices. Heterogeneous OER electrocatalysts containing first-row transition metal oxides and hydroxides have attracted considerable recent interest, owing in part to the high abundance and low cost of starting materials. Among the best performing OER electrocatalysts are mixed Fe/Ni layered double hydroxides (LDH. A review of the available experimental data leads to the conclusion that iron is the active site for [NiFe]-LDH-catalyzed alkaline water oxidation.

  9. Electrochemical investigation of surface area effects on PVD Al-Ni as electrocatalyst for alkaline water electrolysis

    DEFF Research Database (Denmark)

    Kjartansdóttir, Cecilía Kristín; Caspersen, Michael; Egelund, Sune Daaskov

    2014-01-01

    , additional 40mV are gained. For the OER, smaller roughness values were observed with the same activity trend as for the HER. The electrocatalyst are however found not to be stable in the anodic environment during electrolysis. The corrosion mechanism of a skeletal nickel electrocatalyst during the OER...

  10. 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.

  11. Correlating microstructure and activity for polysulfide reduction and oxidation at WS2 electrocatalysts

    DEFF Research Database (Denmark)

    Stephens, Ifan E.L.; Ducati, Caterina; Fray, Derek J.

    2013-01-01

    The polysulfide reduction and oxidation activity of WS2 electrocatalysts was studied. This was undertaken with a specific view to improve the efficiency of the polysulfide-bromine redox flow battery, for large scale energy storage. Using data from the literature, it is estimated that the catalysts.......47 and 1 M NaOH, simulating the operating conditions of a half-charged polysulfide-bromine redox flow battery. The catalyst activity increased in the following order: IF-WS2

  12. Platinum monolayer electrocatalysts for oxygen reduction: effect of substrates, and long-term stability

    Directory of Open Access Journals (Sweden)

    J. ZHANG

    2005-03-01

    Full Text Available We describe a novel concept for a Ptmonolayer electrocatalyst and present the results of our electrochemical, X-ray absorption spectroscopy, and scanning tunneling microscopy studies. The electrocatalysts were prepared by a new method for depositing Pt monolayers involving the galvanic displacement by Pt of an underpotentially deposited Cu monolayer on substrates of Au (111, Ir(111, Pd(111, Rh(111 and Ru(0001 single crylstals, and Pd nanoparticles. The kinetics of O2 reduction showed significant enhancement with Pt monolayers on Pd(111 and Pd nanoparticle surfaces in comparisonwith the reaction on Pt(111 and Pt nanoparticles, respectively. This increase in catalytic activity is attributed partly to the decreased formation of PtOH, as shown by in situ X-ray absorption spectroscopy. The results illustrate that placing a Pt monolayer on a suitable substrate of metal nanoparticles is an attractive way of designing better O2 reduction electrocatalysts with very low Pt contents.

  13. Enhanced methanol electro-oxidation activity of Pt/MWCNTs electro-catalyst using manganese oxide deposited on MWCNTs

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Khodadadi, Abbas Ali; Mortazavi, Yadollah; Rashidi, Alimorad; Choolaei, Mohammadmehdi

    2014-01-01

    Highlights: • Promoting effects of manganese oxide (MnO x ) on methanol electro-oxidation over Pt/MWCNTs are studied. • 3.3 times higher activity and improved stability are observed on Pt/MnO x -MWCNTs in MOR. • Both hydrogen spill over and bi-functional mechanism are facilitated in presence of MnO x . • MnO x significantly enhances electrochemical active surface area and dispersion of Pt nanoparticles. • Proton conductivity of electrocatalyst layer is improved upon MnO x incorporation. - Abstract: Electro-oxidation of methanol on platinum nanoparticles supported on a nanocomposite of manganese oxide (MnO x ) and multi-wall carbon nanotubes (MWCNTs) is investigated. The morphology, structure, and chemical composition of the electro-catalysts are characterized by TEM, XRD, EDS, TGA, and H 2 -TPR. The electro-catalytic properties of electrodes are examined by cyclic voltammetry, CO-stripping, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Compared to Pt/MWCNTs, the Pt/MnO x -MWCNTs electro-catalyst exhibits about 3.3 times higher forward peak current density, during cyclic voltammetry, and 4.6 times higher exchange current density in methanol electro-oxidation reaction. In addition, deposition of manganese oxide onto MWCNTs dramatically increases the electrochemical active surface area from 29.7 for Pt/MWCNTs to 89.4 m 2 g −1 Pt for Pt/MnO x -MWCNTs. The results of long-term cyclic voltammetry show superior stability of Pt nanoparticles upon addition of manganese oxide to the support. Furthermore, the kinetics of formation of the chemisorbed OH groups improves upon manganese oxide incorporation. This leads to a lower onset potential of CO ads oxidation on Pt/MnO x -MWCNTs than on Pt/MWCNTs

  14. The influence of copper in dealloyed binary platinum–copper electrocatalysts on methanol electroxidation catalytic activities

    Energy Technology Data Exchange (ETDEWEB)

    Poochai, Chatwarin [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Veerasai, Waret, E-mail: waret.vee@mahidol.ac.th [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Somsook, Ekasith [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Dangtip, Somsak [Department of Physics, and NANOTEC COE at Mahidol University, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand)

    2015-08-01

    In this study, we prepared and characterized carbon paper-supported dealloyed binary Pt–Cu core–shell electrocatalysts (denoted as Pt{sub x}Cu{sub (100−x)/}CP) by cyclic co-electrodeposition and selective copper dealloying in an acidic medium, and we investigated the effect of the copper content in the samples on the catalytic activities toward methanol electroxidation reaction (MOR). X-ray photo-emission spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) indicated that the structure of dealloyed binary Pt–Cu catalysts possessed a Pt-rich shell and a Cu rich core. X-ray absorption near edge spectroscopy (XANES) displayed that the oxidation states of Pt and Cu were zero and one, respectively, implying the formation of metallic Pt and Cu{sub 2}O, respectively. X-ray diffraction spectroscopy (XRD) confirmed that Cu was inserted into a face-centered cubic Pt structure forming Pt–Cu alloys. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) displayed a cubic shape of Pt/CP and a spherical shape of Pt{sub x}Cu{sub (100−x)/}CP with several hundred nanometer sizes of agglomeration that depended on the Cu content. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy were performed to confirm that the sample of Pt{sub 70}Cu{sub 30}/CP exhibited the best catalytic activities in terms of the specific current, current density, catalytic poisoning tolerance, and stability. - Graphical abstract: Display Omitted - Highlights: • Binary electrocatalysts of Pt{sub x}Cu{sub (100−x)}/CP were prepared by cyclic co-electrodeposition and selective copper dealloying. • The structures of Pt{sub x}Cu{sub (100−x)}/CP were a Pt rich shell and a Cu rich core. • The Pt{sub 70}Cu{sub 30}/CP was the excellent catalytic activity towards methanol electrooxidation and CO{sub ads} tolerance.

  15. 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.

  16. PtPb nanoparticle electrocatalysts: control of activity through synthetic methods

    International Nuclear Information System (INIS)

    Ghosh, Tanushree; Matsumoto, Futoshi; McInnis, Jennifer; Weiss, Marilyn; Abruna, Hector D.; DiSalvo, Francis J.

    2009-01-01

    Solution phase synthesis of intermetallic nanoparticles without using surfactants (for catalytic applications) and subsequent control of size distribution remains a challenge: of growing interest, but not widely explored yet. To understand the questions in the syntheses of Pt containing intermetallic nanoparticles (as electrocatalysts for direct fuel cells) by using sodium naphthalide as the reducing agent, the effects of the Pt precursors' organic ligands were investigated. PtPb syntheses were studied as the model case. In particular, methods that lead to nanoparticles that are independent single crystals are desirable. Platinum acetylacetonate, which is soluble in many organic solvents, has ligands that may interfere less with nanoparticle growth and ordering. Interesting trends, contrary to expectations, were observed when precursors were injected into a reducing agent solution at high temperatures. The presence of acetylacetonate, from the precursor, on the nanoparticles was confirmed by ATR, while SEM imaging showed evidence of morphological changes in the nanoparticles with increasing reaction temperature. A definite relationship between domain size and extent of observed residue (organic material and sodium) present on the particles could be established. By varying post-reaction solvent removal techniques, room temperature crystallization of PtPb nanoparticles was also achieved. Electrochemical activity of the nanoparticles was also much higher than that of nanoparticles synthesized by previous reaction schemes using sodium naphthalide as the reducing agent. Along with the above mentioned techniques, BET, TEM, CBED, SAED, and XRD were used as characterization tools for the prepared nanoparticles.

  17. Relationships between structure and activity of carbon as a multifunctional support for electrocatalysts.

    Science.gov (United States)

    Stevanović, Sanja I; Panić, Vladimir V; Dekanski, Aleksandar B; Tripković, Amalija V; Jovanović, Vladislava M

    2012-07-14

    We report on new insights into the relationships between structure and activity of glassy carbon (GC), as a model material for electrocatalyst support, during its anodization in acid solution. Our investigation strongly confirms the role of CFGs in promotion of Pt activity by the "spill-over" effect related to CO(ads) for methanol electrooxidation (MEO) on a carbon-supported Pt catalyst. Combined analysis of voltammetric and impedance behaviour as well as changes in GC surface morphology induced by intensification of anodizing conditions reveal an intrinsic influence of the carbon functionalization and the structure of a graphene oxide (GO) layer on the electrical and electrocatalytic properties of activated GC. Although GO continuously grows during anodization, it structurally changes from being a graphite inter-layer within graphite ribbons toward a continuous GO surface layer that deteriorates the native structure of GC. As a consequence of the increased distance between GO-spaced graphite layers, the GC conductivity decreases until the case of profound GO exfoliation under drastic anodizing conditions. This exposes the native, yet abundantly functionalized, GC texture. While GC capacitance continuously increases with intensification of anodizing conditions, the surface nano-roughness and GO resistance reach the highest values at modest anodizing conditions, and then decrease upon drastic anodization due to the onset of GO exfoliation. We found for the first time that the activity of a GC-supported Pt catalyst in MEO, as one of the promising half-reactions in polymer electrolyte fuel cells, strictly follows the changes in GC nano-roughness and GO-induced GC resistance. The highest GC/Pt MEO activity is reached when optimal distance between graphite layers and optimal degree of GC functionalization bring the highest amount of CFGs into intimate contact with the Pt surface. This confirms the promoting role of CFGs in MEO catalysis.

  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. Monodispersed porous flowerlike PtAu nanocrystals as effective electrocatalysts for ethanol oxidation

    Science.gov (United States)

    Li, Shumin; Xu, Hui; Xiong, Zhiping; Zhang, Ke; Wang, Caiqin; Yan, Bo; Guo, Jun; Du, Yukou

    2017-11-01

    Designing and tuning the bimetallic nanoparticles with desirable morphology and structure can embody them with greatly enhanced electrocatalytic activity and stability towards liquid fuel oxidation. We herein reported a facile one-pot method for the controlled synthesis of monodispersed binary PtAu nanoflowers with abundant exposed surface area. Owing to its fantastic structure, synergistic and electronic effect, such as-prepared PtAu nanoflowers exhibited outstandingly high electrocatalytic activity with the mass activity of 6482 mA mg-1 towards ethanol oxidation, which is 28.3 times higher than that of commercial Pt/C (227 mA mg-1). More interesting, the present PtAu nanoflower catalysts are more stable for the ethanol oxidation reaction in the alkaline with lower current density decay and retained a much higher current density after successive CVs of 500 cycles than that of commercial Pt/C. This work may open a new way for maximizing the catalytic performance of electrocatalysts towards ethanol oxidation by synthesizing shape-controlled alloy nanoparticles with more surface active sites to enhance the performances of direct fuel cells reaction, chemical conversion, and beyond.

  20. An in situ vapour phase hydrothermal surface doping approach for fabrication of high performance Co3O4 electrocatalysts with an exceptionally high S-doped active surface.

    Science.gov (United States)

    Tan, Zhijin; Liu, Porun; Zhang, Haimin; Wang, Yun; Al-Mamun, Mohammad; Yang, Hua Gui; Wang, Dan; Tang, Zhiyong; Zhao, Huijun

    2015-04-04

    A facile in situ vapour phase hydrothermal (VPH) surface doping approach has been developed for fabrication of high performance S-doped Co3O4 electrocatalysts with an unprecedentedly high surface S content (>47%). The demonstrated VPH doping approach could be useful for enrichment of surface active sites for other metal oxide electrocatalysts.

  1. Highly Active PdNi/RGO/Polyoxometalate Nanocomposite Electrocatalyst for Alcohol Oxidation.

    Science.gov (United States)

    Hu, Jing; Wu, Xiaofeng; Zhang, Qingfan; Gao, Mingyan; Qiu, Haifang; Huang, Keke; Feng, Shouhua; Wang, Tingting; Yang, Ying; Liu, Zhelin; Zhao, Bo

    2018-02-27

    A PdNi/RGO/polyoxometalate nanocomposite has been successfully synthesized by a simple wet-chemical method. Characterizations such as transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction analysis, and X-ray photoelectron spectroscopy are employed to verify the morphology, structure, and elemental composition of the as-prepared nanocomposite. Inspired by the fast-developing fuel cells, the electrochemical catalytic performance of the nanocomposite toward methanol and ethanol oxidation in alkaline media is further tested. Notably, the nanocomposite exhibits excellent catalytic activity and long-term stability toward alcohol electrooxidation compared with the PdNi/RGO and commercial Pd/C catalyst. Furthermore, the electrochemical results reveal that the prepared nanocomposite is attractive as a promising electrocatalyst for direct alcohol fuel cells, in which the phosphotungstic acid plays a crucial role in enhancing the electrocatalytic activities of the catalyst.

  2. Electrocatalysts using porous polymers and method of preparation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Di-Jia; Yuan, Shengwen; Goenaga, Gabriel A.

    2016-08-02

    A method of producing an electrocatalyst article using porous polymers. The method creates a porous polymer designed to receive transition metal groups disposed at ligation sites and activating the transition metals to form an electrocatalyst which can be used in a fuel cell. Electrocatalysts prepared by this method are also provided. A fuel cell which includes the electrocatalyst is also provided.

  3. Electrocatalysts using porous polymers and method of preparation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Di-Jia; Yuan, Shengwen; Goenaga, Gabriel A.

    2015-04-21

    A method of producing an electrocatalyst article using porous polymers. The method creates a porous polymer designed to receive transition metal groups disposed at ligation sites and activating the transition metals to form an electrocatalyst which can be used in a fuel cell. Electrocatalysts prepared by this method are also provided. A fuel cell which includes the electrocatalyst is also provided.

  4. Effect of Pt:Sn atomic ratio on the preparation of PtSn/C electrocatalysts using electron beam irradiation

    International Nuclear Information System (INIS)

    Silva, Dionisio F.; Oliveira Neto, Almir; Pino, Eddy S.; Linardi, Marcelo; Spinace, Estevam V.

    2009-01-01

    PtSn/C electrocatalysts were prepared with Pt:Sn atomic ratios of 3:1, 1:1 and 1:3 in water/2-propanol using electron beam irradiation. The obtained materials were characterized by EDX, XRD and cyclic voltammetry. The ethanol electro-oxidation was studied by chronoamperometry. The XRD diffractograms of the PtSn/C electrocatalysts showed typical face-centered cubic (fcc) structure of platinum and the presence of a SnO 2 phase (cassiterite). The mean crystallite sizes of Pt fcc phase was in the range of 3.0-3.5 nm. The PtSn/C electrocatalysts were active for ethanol electro-oxidation at room temperature and the material prepared with Pt:Sn atomic ratio of 1:1 showed the best activity. (author)

  5. Effect of Pt:Sn atomic ratio on the preparation of PtSn/C electrocatalysts using electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Dionisio F.; Oliveira Neto, Almir; Pino, Eddy S.; Linardi, Marcelo; Spinace, Estevam V., E-mail: dfsilva@ipen.b, E-mail: espinace@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2009-07-01

    PtSn/C electrocatalysts were prepared with Pt:Sn atomic ratios of 3:1, 1:1 and 1:3 in water/2-propanol using electron beam irradiation. The obtained materials were characterized by EDX, XRD and cyclic voltammetry. The ethanol electro-oxidation was studied by chronoamperometry. The XRD diffractograms of the PtSn/C electrocatalysts showed typical face-centered cubic (fcc) structure of platinum and the presence of a SnO{sub 2} phase (cassiterite). The mean crystallite sizes of Pt fcc phase was in the range of 3.0-3.5 nm. The PtSn/C electrocatalysts were active for ethanol electro-oxidation at room temperature and the material prepared with Pt:Sn atomic ratio of 1:1 showed the best activity. (author)

  6. Investigating the effects of proton exchange membrane fuel cell conditions on carbon supported platinum electrocatalyst composition and performance

    Energy Technology Data Exchange (ETDEWEB)

    Patel, Anant; Artyushkova, Kateryna; Atanassov, Plamen; Colbow, Vesna; Dutta, Monica; Harvey, Davie; Wessel, Silvia

    2011-12-01

    Changes that carbon-supported platinum electrocatalysts undergo in a proton exchange membrane fuel cell environment were simulated by ex situ heat treatment of catalyst powder samples at 150 C and 100% relative humidity. In order to study modifications that are introduced to chemistry, morphology, and performance of electrocatalysts, XPS, HREELS and three-electrode rotating disk electrode experiments were performed. Before heat treatment, graphitic content varied by 20% among samples with different types of carbon supports, with distinct differences between bulk and surface compositions within each sample. Following the aging protocol, the bulk and surface chemistry of the samples were similar, with graphite content increasing or remaining constant and Pt-carbide decreasing for all samples. From the correlation of changes in chemical composition and losses in performance of the electrocatalysts, we conclude that relative distribution of Pt particles on graphitic and amorphous carbon is as important for electrocatalytic activity as the absolute amount of graphitic carbon present

  7. Investigating the effects of proton exchange membrane fuel cell conditions on carbon supported platinum electrocatalyst composition and performance

    Energy Technology Data Exchange (ETDEWEB)

    A. Patel; K. Artyushkova; P. Atanassov; V. Colbow; M. Dutta; D. Harvey; S. Wessel

    2012-04-30

    Changes that carbon-supported platinum electrocatalysts undergo in a proton exchange membrane fuel cell environment were simulated by ex situ heat treatment of catalyst powder samples at 150 C and 100% relative humidity. In order to study modifications that are introduced to chemistry, morphology, and performance of electrocatalysts, XPS, HREELS and three-electrode rotating disk electrode experiments were performed. Before heat treatment, graphitic content varied by 20% among samples with different types of carbon supports, with distinct differences between bulk and surface compositions within each sample. Following the aging protocol, the bulk and surface chemistry of the samples were similar, with graphite content increasing or remaining constant and Pt-carbide decreasing for all samples. From the correlation of changes in chemical composition and losses in performance of the electrocatalysts, we conclude that relative distribution of Pt particles on graphitic and amorphous carbon is as important for electrocatalytic activity as the absolute amount of graphitic carbon present

  8. WS{sub 2} nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Han, Guan-Qun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Yan-Ru; Hu, Wen-Hui [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2015-11-01

    WS{sub 2} nanosheets (WS{sub 2} NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS{sub 2} (E-WS{sub 2}). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS{sub 2} consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS{sub 2}, with a low overpotential of 80 mV and high current density (10 mA cm{sup −2}, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS{sub 2} for HER. • E-WS{sub 2} shows the better electrocatalytic activity than bulk WS{sub 2}. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

  9. WS_2 nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Han, Guan-Qun; Liu, Yan-Ru; Hu, Wen-Hui; Dong, Bin; Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi; Liu, Chen-Guang

    2015-01-01

    WS_2 nanosheets (WS_2 NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS_2 (E-WS_2). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS_2 consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS_2, with a low overpotential of 80 mV and high current density (10 mA cm"−"2, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS_2 for HER. • E-WS_2 shows the better electrocatalytic activity than bulk WS_2. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

  10. Co-catalytic effect of nickel in Pt-Ru/C and Pt-Sn/C electrocatalysts for ethanol electrooxidation

    OpenAIRE

    Ribadeneira, R. E.; Hoyos, B. A.

    2010-01-01

    In the present study, we examined the effect of adding nickel to Pt-Ru and Pt-Sn catalysts for ethanol electrooxidation. The alcohol-reduction process with ethylene glycol was used to prepare ten electrocatalysts. These were microchemically and physically characterized by EDX and XRD analysis. The electrocatalysts were evaluated at mini-electrodes with cyclic voltammetry at 25 and 50 °C in sulfuric acid and ethanol solutions, and as anodes in fuel cell tests. Nickel addition to Pt-Ru mixtures...

  11. Effects of microstructure and composition of anode Pt based electrocatalysts on performance of direct alcohol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, L.; Li, H.; Yan, S.; Sun, G. [Dalian Inst. of Chemical Physics, Dalian (China). Direct Alcohol Fuel Cell Lab; Xin, Q. [Dalian Inst. of Chemical Physics, Dalian (China). Direct Alcohol Fuel Cell Lab; Dalian Inst. of Chemical Physics, Dalian (China). State Key Laboratory of Catalysis

    2008-07-01

    This paper reported on a study in which platinum (Pt)-based electrocatalysts were synthesized and characterized by XRD, TEM and EDS. The focus of the study was on the relationship between the microstructure and components of PtRu and PtSn catalysts and the performance of direct alcohol fuel cells (DAFCs). All of the Pt-based electrocatalysts were prepared by a modified polyol method. XRD patterns of the 2 catalysts showed that both catalysts have an fcc pattern of Pt. This was also confirmed by the shift of diffraction peaks of Pt in both catalysts. Electrochemical measurements were carried out using an EG and G model 273A potentiostat/galvanostat and a three-electrode test cell at room temperature. Membrane electrode assemblies (MEAs) were fabricated with a pair of stainless steel plates with parallel flow-fields. The MEAs were activated by 1 M methanol/ethanol at 75 degrees C for 3 hours before all the data were collected. The study showed that PtRu is active to methanol electrooxidation while PtSn is active to ethanol electrooxidation. Based on the above experimental analysis, it was determined that the dilatation of Pt lattice parameter is favourable for ethanol adsorption, while the suitable contract of Pt lattice parameter is favorable for methanol electrooxidation. Since Pt is more electronegative than Sn, the partial electrons of Sn atom could be transferred to Pt atom leading to filling of Pt d band. Although Ru is as electronegative as Pt, the electric effect of Pt and Ru may not be as pronounced. 4 refs., 4 figs.

  12. Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells.

    Science.gov (United States)

    Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

    2016-02-15

    In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

  13. Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells

    Science.gov (United States)

    Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

    2016-02-01

    In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

  14. Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

    2017-06-28

    Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

  15. Pt-Richcore/Sn-Richsubsurface/Ptskin Nanocubes As Highly Active and Stable Electrocatalysts for the Ethanol Oxidation Reaction.

    Science.gov (United States)

    Rizo, Rubén; Arán-Ais, Rosa M; Padgett, Elliot; Muller, David A; Lázaro, Ma Jesús; Solla-Gullón, José; Feliu, Juan M; Pastor, Elena; Abruña, Héctor D

    2018-03-14

    Direct ethanol fuel cells are one of the most promising electrochemical energy conversion devices for portable, mobile and stationary power applications. However, more efficient and stable and less expensive electrocatalysts are still required. Interestingly, the electrochemical performance of the electrocatalysts toward the ethanol oxidation reaction can be remarkably enhanced by exploiting the benefits of structural and compositional sensitivity and control. Here, we describe the synthesis, characterization, and electrochemical behavior of cubic Pt-Sn nanoparticles. The electrochemical activity of the cubic Pt-Sn nanoparticles was found to be about three times higher than that obtained with unshaped Pt-Sn nanoparticles and six times higher than that of Pt nanocubes. In addition, stability tests indicated the electrocatalyst preserves its morphology and remains well-dispersed on the carbon support after 5000 potential cycles, while a cubic (pure) Pt catalyst exhibited severe agglomeration of the nanoparticles after a similar stability testing protocol. A detailed analysis of the elemental distribution in the nanoparticles by STEM-EELS indicated that Sn dissolves from the outer part of the shell after potential cycling, forming a ∼0.5 nm Pt skin. This particular atomic composition profile having a Pt-rich core, a Sn-rich subsurface layer, and a Pt-skin surface structure is responsible for the high activity and stability.

  16. Nano-Pt/C electrocatalysts: synthesis and activity for alcohol oxidation

    International Nuclear Information System (INIS)

    Huong Nguyen, Thi Giang; Anh Pham, Thi Van; Phuong, Thi Xuan; Binh Lam, Thi Xuan; Tran, Van Man; Thoa Nguyen, Thi Phuong

    2013-01-01

    Nano-sized platinum electrocatalysts on a carbon support (Pt/C) have been synthesized by the polyol reduction method under microwave irradiation using ethylene glycol (EG) as the reductant and carbon vulcan XC-72R as the support material. The physical characteristics of the Pt/C materials were analyzed using transmission electron microscopy and Brunauer–Emmet–Teller nitrogen adsorption theory. The glycerol and EG electro-oxidation in alkaline media on the Pt/C catalysts was investigated with cyclic voltammetry and chronoamperometry. The particle size of Pt on carbon was about 3.0 nm. The catalytic activity for the alcohol electro-oxidation of Pt/C materials synthesized in various pH values (7.9–9.5) was found to be significantly higher than that of commercial Pt/C (Aldrich Sigma, 10 wt% Pt/activated carbon). The Pt/C catalyst synthesized in pH 9.5 showed the best electrochemical behavior. At all the synthesized Pt/C electrodes, compared with glycerol, the oxidation rate of EG was about ten times higher. (paper)

  17. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jaramillo, Thomas F. [Stanford Univ., CA (United States). Dept. of Chemical Engineering. Shriram Center

    2016-04-20

    IrO3/IrOx catalyst significantly outperforms rutile IrO2 and RuO2, the only other OER catalysts to have reasonable stability and activity in acidic electrolyte, and in fact demonstrates the best activity for any known OER catalyst measured in either acidic or in alkaline electrolyte. For alkaline conditions we have demonstrated that the combined effect of cerium as a dopant and gold as a metal support, significantly enhances the OER activity of electrodeposited NiOx films. This NiCeOx-Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts reported to date (Nature Energy, accepted 2016). These studies of new catalysts for the OER, both in acid and in base, are fundamental to enabling new technologies of interest for the DOE, including the production of sustainable fuels and chemicals. ORR: One method to significantly reduce the Pt loading in fuel cell devices is to increase the ORR activity of Pt based systems. To this end we have synthesized a high surface area supported meso-structured PtxNi alloy thin film with a double gyroid morphology that both exhibits high activity and stability for the ORR (submitted, 2016). We have furthermore developed a Ru-core, Pt-shell system that improves the per Pt site activity by more than a factor of 2 (ChemElectroChem, 2014). Further refinement, optimizing Pt-shell thickness and reducing particle sintering during processing, enabled us to obtain a mass activity that is 2 times higher than commercial Pt/C from TKK. These are important contributions to the DOE goal of reducing Pt loading since an improved understanding of how to increase mass activity and stability helps enable low Pt content fuel cells.

  18. 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.

  19. Atomically Monodisperse Nickel Nanoclusters as Highly Active Electrocatalysts for Water Oxidation

    KAUST Repository

    Joya, Khurram; Sinatra, Lutfan; AbdulHalim, Lina G.; Joshi, Chakra Prasad; Hedhili, Mohamed N.; Bakr, Osman; Hussain, Irshad

    2016-01-01

    are comparable to the state-of-the art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm–2 demonstrates the long-term stability

  20. 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.

  1. 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.

  2. Highly Stable and Active Pt/Nb-TiO2 Carbon-Free Electrocatalyst for Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Shuhui Sun

    2012-01-01

    Full Text Available The current materials used in proton exchange membrane fuel cells (PEMFCs are not sufficiently durable for commercial deployment. One of the major challenges lies in the development of an inexpensive, efficient, and highly durable and active electrocatalyst. Here a new type of carbon-free Pt/Nb-TiO2 electrocatalyst has been reported. Mesoporous Nb-TiO2 hollow spheres were synthesized by the sol-gel method using polystyrene (PS sphere templates. Pt nanoparticles (NPs were then deposited onto mesoporous Nb-TiO2 hollow spheres via a simple wet-chemical route in aqueous solution, without the need for surfactants or potentiostats. The growth densities of Pt NPs on Nb-TiO2 supports could be easily modulated by simply adjusting the experimental parameters. Electrochemical studies of Pt/Nb-TiO2 show much enhanced activity and stability than commercial E-TEK Pt/C catalyst. PtNP/Nb-TiO2 is a promising new cathode catalyst for PEMFC applications.

  3. Surface-oxidized cobalt phosphide used as high efficient electrocatalyst in activated carbon air-cathode microbial fuel cell

    Science.gov (United States)

    Yang, Tingting; Wang, Zhong; Li, Kexun; Liu, Yi; Liu, Di; Wang, Junjie

    2017-09-01

    Herein, we report a simplistic method to fabricate the surface-oxidized cobalt phosphide (CoP) nanocrystals (NCs), which is used as electrocatalyst for oxygen reduction reaction (ORR) in microbial fuel cell (MFC) for the first time. The corallite-like CoP NCs are successfully prepared by a hydrothermal reaction following a phosphating treatment in N2 atmosphere. When used as an ORR catalyst, cobalt phosphide shows comparable onset potential, inferior resistance, as well as a small Tafel slope with long-term stability in neutral media. The maximum power density of MFC embellished with 10% CoP reached 1914.4 ± 59.7 mW m-2, which is 108.5% higher than the control. The four-electron pathway, observed by the RDE, plays a crucial role in electrochemical catalytic activity. In addition, material characterizations indicate that the surface oxide layer (CoOx) around the metallic CoP core is important and beneficial for ORR. Accordingly, it can be expected that the as-synthesized CoP will be a promising candidate of the non-precious metal ORR electrocatalysts for electrochemical energy applications.

  4. Further insights into the durability of Pt3Co/C electrocatalysts: Formation of “hollow” Pt nanoparticles induced by the Kirkendall effect

    International Nuclear Information System (INIS)

    Dubau, L.; Durst, J.; Maillard, F.; Guétaz, L.; Chatenet, M.; André, J.; Rossinot, E.

    2011-01-01

    Highlights: ► Pt 3 Co/C electrocatalysts for the oxygen reduction reaction. ► During operation in a PEMFC, Co atoms are depleted from the mother electrocatalyst. ► The structure of the Pt–Co/C electrocatalysts in the long-term is determined by a balance between Co surface segregation and formation of oxygenated species from water. ► The presence of Co atoms in the subsurface region severely depreciates the oxygen reduction reaction activity. ► “Hollow” Pt nanoparticles have been detected for the first time in a PEMFC. - Abstract: This paper provides further insights into the degradation mechanisms of nanometer-sized Pt 3 Co/C particles under various proton-exchange membrane fuel cell (PEMFC) operating conditions. We confirm that Co atoms are continuously depleted from the mother Pt 3 Co/C electrocatalyst because they can diffuse from the bulk to the surface of the material. The structure of the Pt–Co/C nanoparticles in the long-term is determined by a balance between Co surface segregation and formation of oxygenated species from water splitting. When the PEMFC is operated at high current density (low cathode potential, below the onset of surface oxide formation from water), a steady-state is reached between the rate of Co dissolution at the surface and Co surface segregation. Consequently, Co and Pt atoms remain homogeneously distributed within the Pt–Co/C particles and the thickness of the Pt-shell is maintained to a small value not detectable by atomic-resolution high-angle annular dark-field scanning transmission electron microscopy. When the PEMFC is operated at low current density (high cathode potential), the formation of surface oxides from water and the resulting “place-exchange” mechanism enhance the rate of diffusion of Co atoms to the surface. Consequently, the fresh Pt 3 Co/C particles form core/shell particles with thick Pt-shells and Co content < 5 at% and, ultimately, “hollow” Pt nanoparticles (Kirkendall effect). To the

  5. 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.

  6. 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...

  7. A facile lyophilization synthesis of MoS{sub 2} QDs@graphene as a highly active electrocatalyst for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenzhu; Li, Feng; Wang, Xiang; Tang, Yu; Yang, Yuanyuan; Gao, Wenbin [State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Gansu Provincial Engineering Laboratory for Chemical Catalysis, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Li, Rong, E-mail: liyirong@lzu.edu.cn [State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Gansu Provincial Engineering Laboratory for Chemical Catalysis, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    2017-04-15

    Highlights: • The target catalyst was prepared by a facile and novel lyophilization method. • The HER activity of various morphologies of MoS{sub 2}-based catalysts were studied. • The catalyst owns superior dispersion, large active sites and high conductivity. • The catalyst exhibits superior HER activity and long-term stability. - Abstract: The development of robust, active and nonprecious electrocatalysts for hydrogen evolution reaction is quite urgent but still challenging. Here MoS{sub 2} QDs@Graphene is prepared via a facile lyophilization method, which leads to a better dispersion of MoS{sub 2} QDs on the graphene and optimizes the electronic mobility between the MoS{sub 2} layers. Impressively, the electrocatalyst MoS{sub 2} QDs@Graphene demonstrates the remarkable activity for HER in 0.5 M H{sub 2}SO{sub 4} solution, with a current density of 10 mA cm{sup −2} at a low overpotential of 140 mV and strong stability in acid condition. The achieved excellent performance is attributed to its morphology with large amount of active sites fabricated by the lyophilization method. This new method opens new pathway for the fabrication of non-precious metal electrocatalysts achieving high activity.

  8. Achieving high-powered Zn/air fuel cell through N and S co-doped hierarchically porous carbons with tunable active-sites as oxygen electrocatalysts

    Science.gov (United States)

    Tang, Qiaowei; Wang, Luming; Wu, Mingjie; Xu, Nengneng; Jiang, Lei; Qiao, Jinli

    2017-10-01

    Electrochemical reduction of oxygen is the heart of the next-generation energy technologies to fuel cells and metal-air batteries, of which the reference catalysts suffer from two critical bottlenecks lying in their insufficient electroactivities and unclear active site structures. Herein, we introduce the effectively hierarchically porous carbons (HPCs) as the active-sites enriched platform for oxygen electroreduction. Three quaternized copolymers (PUB, PAADDA and PICP) with different chemical structures are used to pursue Fe/N/S-tailored ORR electrocatalysts. The most efficient one prepared by PAADDA gives the onset potential of 0.94 V and a half-wave potential of 0.85 V in basic solution, as well as superb electroactivities of low H2O2% and high electron transfer number in both alkaline and acidic medium. Surprisingly, they all display high discharge power density as applied to Zn-air fuel cells, and the HPCs-PAADDA catalyst thrillingly reaches 516.3 mW cm-2 when catalyst loading is optimized to 5.0 mg cm-2. The results elucidate that the polymer with long aliphatic chain is propitious to trap metals to create active sites and enwrap silica template to construct uniform pore structure. Only two kinds of nitrogen configuration (pyridinic-N and graphitic-N) are found with distinct structure in these HPCs, which happens to be active sites.

  9. Highly active dealloyed Cu@Pt core-shell electrocatalyst towards 2-propanol electrooxidation in acidic solution

    Energy Technology Data Exchange (ETDEWEB)

    Poochai, Chatwarin, E-mail: p_chatwarin@yahoo.com

    2017-02-28

    Highlights: • This is the first report on electrooxidation of 2-propanol in acidic media on dealloyed Cu@Pt/CP core-shell electrocatalyst. • The dealloyed Cu@Pt/CP is prepared using cyclic co-electrodeposition and selective Cu dealloying (CCEd-sCuD). • The structure of dealloyed Cu@Pt/CP is core-shell structure with Cu-rich core and Pt-rich surface. • The dealloyed Cu@Pt/CP shows high activity and great stability towards 2-propanol electrooxidation in acidic media. - Abstract: Dealloyed Cu@Pt core-shell electrocatalyst was fabricated by cyclic co-electrodeposition and selective Cu dealloying (CCEd-sCuD) on carbon paper (CP), namely Cu@Pt/CP. The Cu@Pt/CP exhibited a core-shell structure comprising with a Cu-rich core and a Pt-rich shell. The crystalline phases of Pt/CP and Cu@Pt/CP were a face-centered cubic (fcc). The compressive lattice strain approximately 0.85% was found in the Cu@Pt/CP owing to a lattice mismatch between a core and a shell region. In the core-region, Cu was formed Pt-Cu alloy as major and copper oxide and also metallic copper as minor. The morphology and grain size of the Cu@Pt/CP displayed a porous spherical shape with 100 nm in diameter, while those of Pt/CP seemed to be a cubic shape with smaller diameter of 40 nm. In electrochemical and catalytic activity, the surface of Cu@Pt/CP had a larger electrochemical active surface area (ECSA) than that of Pt/CP due to a porous formation caused by Cu dealloying. It is not surprising that the Cu@Pt/CP showed higher catalytic activity and greater stability towards 0.5 M 2-propanol electrooxidation in 0.5 M H{sub 2}SO{sub 4} in terms of peak current density (j{sub p}), peak potential (E{sub p}), onset potential (E{sub onset}), diffusion coefficient (D), and charge transfer resistance (R{sub ct}) which were caused by electronic structure modification, higher compressive lattice strain, and larger ECSA, compared with Pt/CP.

  10. Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting

    Science.gov (United States)

    Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias; Cheng, Xi; Kim, Bae-Jung; Durst, Julien; Bozza, Francesco; Graule, Thomas; Schäublin, Robin; Wiles, Luke; Pertoso, Morgan; Danilovic, Nemanja; Ayers, Katherine E.; Schmidt, Thomas J.

    2017-09-01

    The growing need to store increasing amounts of renewable energy has recently triggered substantial R&D efforts towards efficient and stable water electrolysis technologies. The oxygen evolution reaction (OER) occurring at the electrolyser anode is central to the development of a clean, reliable and emission-free hydrogen economy. The development of robust and highly active anode materials for OER is therefore a great challenge and has been the main focus of research. Among potential candidates, perovskites have emerged as promising OER electrocatalysts. In this study, by combining a scalable cutting-edge synthesis method with time-resolved X-ray absorption spectroscopy measurements, we were able to capture the dynamic local electronic and geometric structure during realistic operando conditions for highly active OER perovskite nanocatalysts. Ba0.5Sr0.5Co0.8Fe0.2O3-δ as nano-powder displays unique features that allow a dynamic self-reconstruction of the material’s surface during OER, that is, the growth of a self-assembled metal oxy(hydroxide) active layer. Therefore, besides showing outstanding performance at both the laboratory and industrial scale, we provide a fundamental understanding of the operando OER mechanism for highly active perovskite catalysts. This understanding significantly differs from design principles based on ex situ characterization techniques.

  11. Facile solvothermal synthesis of highly active and robust Pd1.87Cu0.11Sn electrocatalyst towards direct ethanol fuel cell applications

    Science.gov (United States)

    Jana, Rajkumar; Dhiman, Shikha; Peter, Sebastian C.

    2016-08-01

    Ordered intermetallic Pd1.87Cu0.11Sn ternary electrocatalyst has been synthesized by sodium borohydride reduction of precursor salts Pd(acac)2, CuCl2.2H2O and SnCl2 using one-pot solvothermal synthesis method at 220 °C with a reaction time of 24 h. To the best of our knowledge, here for the first time we report surfactant free synthesis of a novel ordered intermetallic ternary Pd1.87Cu0.11Sn nanoparticles. The ordered structure of the catalyst has been confirmed by powder x-ray diffraction, transmission electron microscopy (TEM). Composition and morphology of the nanoparticles have been confirmed through field emission scanning electron microscopy, energy-dispersive spectrometry and TEM. The electrocatalytic activity and stability of the ternary electrocatalyst towards ethanol oxidation in alkaline medium was investigated by cyclic voltammetry and chronoamperometry techniques. The catalyst is proved to be highly efficient and stable upto 500th cycle and even better than commercially available Pd/C (20 wt%) electrocatalysts. The specific and mass activity of the as synthesized ternary catalyst are found to be ∼4.76 and ∼2.9 times better than that of commercial Pd/C. The enhanced activity and stability of the ordered ternary Pd1.87Cu0.11Sn catalyst can make it as a promising candidate for the alkaline direct ethanol fuel cell application.

  12. Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electrooxidation

    International Nuclear Information System (INIS)

    Crisafulli, Rudy

    2013-01-01

    PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H 2 PtCl 6 .6H 2 O, SnCl 2 .2H 2 O and CuCl 2 .2H 2 O as metal sources, NaBH 4 and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, Xray diffraction, transmission electron microscopy, line scan energy dispersive Xray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic effluents were analysed by gas chromatography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the assynthesized electrocatalysts were in the range of PtSnCu/C (50:40:10) AR/ED > PtSnCu/C (50:10:40) BR/CD. PtSn/C (50:50) BR/CD, PtSnCu/C (50:10:40) BR/CD, PtSnCu/C (50:40:10) AR/CD electrocatalysts and Pt/C BASF, PtSn/C (75:25) BASF commercial electrocatalysts were tested in single Direct Ethanol Fuel Cell. The results showed the following performance for ethanol electro-oxidation: PtSn/C (50:50) BR/CD > PtSnCu/C (50:40:10) AR/CD > PtSnCu/C > PtSn/C (75:25) BASF > PtSnCu/C (50:10:40) BR/CD > Pt/C BASF. (author)

  13. 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.

  14. NiCo2S4 nanowires array as an efficient bifunctional electrocatalyst for full water splitting with superior activity

    Science.gov (United States)

    Liu, Danni; Lu, Qun; Luo, Yonglan; Sun, Xuping; Asiri, Abdullah M.

    2015-09-01

    The present communication reports the topotactic conversion of NiCo2O4 nanowires array on carbon cloth (NiCo2O4 NA/CC) into NiCo2S4 NA/CC, which is used as an efficient bifunctional electrocatalyst for water splitting with good durability and superior activity in 1.0 M KOH. This NiCo2S4 NA/CC electrode produces 100 mA cm-2 at an overpotential of 305 mV for hydrogen evolution and 100 mA cm-2 at an overpotential of 340 mV for oxygen evolution. To afford a 10 mA cm-2 water-splitting current, the alkaline water electrolyzer made from NiCo2S4 NA/CC needs a cell voltage of 1.68 V, which is 300 mV less than that for NiCo2O4 NA/CC, and has good stability.The present communication reports the topotactic conversion of NiCo2O4 nanowires array on carbon cloth (NiCo2O4 NA/CC) into NiCo2S4 NA/CC, which is used as an efficient bifunctional electrocatalyst for water splitting with good durability and superior activity in 1.0 M KOH. This NiCo2S4 NA/CC electrode produces 100 mA cm-2 at an overpotential of 305 mV for hydrogen evolution and 100 mA cm-2 at an overpotential of 340 mV for oxygen evolution. To afford a 10 mA cm-2 water-splitting current, the alkaline water electrolyzer made from NiCo2S4 NA/CC needs a cell voltage of 1.68 V, which is 300 mV less than that for NiCo2O4 NA/CC, and has good stability. Electronic supplementary information (ESI) available: Experimental section and ESI Figures. See DOI: 10.1039/c5nr04064g

  15. Effect of copper oxide electrocatalyst on CO2 reduction using Co3O4 as anode

    Directory of Open Access Journals (Sweden)

    V.S.K. Yadav

    2016-09-01

    Full Text Available The reduction of carbon dioxide (CO2 to products electrochemically (RCPE in 0.5 M NaHCO3 and Na2CO3 liquid phase electrolyte solutions was investigated. Cobalt oxide (Co3O4 as anode and cuprous oxide (Cu2O as the cathode were considered, respectively. The impacts of applied potential with time of reaction during reduction of CO2 to products were studied. The anode and cathode were prepared by depositing electrocatalysts on the graphite plate. Ultra-fast liquid chromatography (UFLC was used to analyze the products obtained from the reduction of CO2. The feasible way of reduction by applying voltages with current densities was clearly correlated. The results illustrate the capability of electrocatalyst successfully to remove atmospheric CO2 in the form of valuable chemicals. Maximum Faradaic efficiency of ethanol was 98.1% at 2 V and for formic acid (36.6% at 1.5 V was observed in NaHCO3. On the other hand, in Na2CO3 electrolyte solution maximum efficiency for ethanol was 55.21% at 1.5 V and 25.1% for formic acid at 2 V. In both electrolytes other end products like methanol, propanol, formaldehyde and acetic acid were formed at various applied voltage and output current densities.

  16. 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.

  17. Develop high activity, low cost non-PGM fuel cell electrocatalyst and stable supports

    Energy Technology Data Exchange (ETDEWEB)

    Colon-Mercado, H. R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL; Garcia-Diaz, B. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL; Gaillard, J. B. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL

    2016-09-28

    A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFC. Iron based functionalities have been engineered into Metallic Organic Framework (MOF) catalysts to evaluate their impact on activity for the ORR. A series of FePhen@MOF catalysts have been synthesized with varying [Fe] to investigate the effect on electrochemical and electrocatalytic properties. The magnitude of the FeII/III redox couple and the electrochemical surface area are analyzed to determine if there is a correlation between [Fe] and the ORR onset potential and/or the relative number of active sites.

  18. 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.

  19. Electrochemical probing into the active sites of graphitic-layer encapsulated iron oxygen reduction reaction electrocatalysts

    DEFF Research Database (Denmark)

    Zhong, Lijie; Jensen, Jens Oluf; Cleemann, Lars Nilausen

    2018-01-01

    is still unclear compared with the well-recognized surface coordinated FeNx/C structure. Using the strong complexing effect of the iron component with anions, cyanide (CN−) in alkaline and thiocyanate (SCN−) in acidic media, the metal containing active sites are electrochemically probed. Three...

  20. Bridgehead isomer effects in bis(phosphido)-bridged diiron hexacarbonyl proton reduction electrocatalysts.

    Science.gov (United States)

    Rahaman, Ahibur; Gimbert-Suriñach, Carolina; Ficks, Arne; Ball, Graham E; Bhadbhade, Mohan; Haukka, Matti; Higham, Lee; Nordlander, Ebbe; Colbran, Stephen B

    2017-03-07

    The influence of the substitution, orientation and structure of the phosphido bridges in [Fe 2 (CO) 6 (μ-PR 2 ) 2 ] electrocatalysts of proton reduction has been studied. The isomers e,a-[Fe 2 (CO) 6 {μ-P(Ar)H} 2 ] (1a(Ar): Ar = Ph, 2'-methoxy-1,1'-binaphthyl (bn')), e,e-[Fe 2 (CO) 6 {μ-P(Ar)H} 2 ] (1b(Ar): Ar = Ph, bn') were isolated from reactions of iron pentacarbonyl and the corresponding primary phosphine, syntheses that also afforded the phosphinidene-capped tri-iron clusters, [Fe 3 (CO) 9 (μ-CO)(μ 3 -Pbn')] (2) and [Fe 3 (CO) 9 (μ 3 -PAr) 2 ] (3(Ar), Ar = Ph, bn'). A ferrocenyl (Fc)-substituted dimer [Fe 2 (CO) 6 {μ:μ'-1,2-(P(CH 2 Fc)CH 2 ) 2 C 6 H 4 }] (4), in which the two phosphido bridges are linked by an o-xylyl group, was also prepared. The molecular structures of complexes 1a(Ph), 1b(Ph), 1b(bn'), 2 and 4 were established by X-ray crystallography. All complexes have been examined as electrocatalysts for proton reduction using p-toluene sulfonic acid in tetrahydrofuran. Cyclic voltammograms of the dimers with acid exhibit two catalysis waves for proton reduction. The first wave, which appears at the potential of the primary reduction, reaches maximum current (turnover) at moderate acid concentrations and is rapidly overtaken by the second wave, which appears at more negative potential. Both of these reductive waves show an initial first order dependence on acid. The electrochemistry and electrocatalyses of the [Fe 2 (CO) 6 (μ-PR 2 ) 2 ] dimers show subtle variations with the nature of the bridging phosphido group(s), including the orientation of bridgehead hydrogen atoms.

  1. Effects of the Electrodeposition Time in the Synthesis of Carbon-Supported Pt(Cu and Pt-Ru(Cu Core-Shell Electrocatalysts for Polymer Electrolye Fuel Cells

    Directory of Open Access Journals (Sweden)

    Griselda Caballero-Manrique

    2016-08-01

    Full Text Available Pt(Cu/C and Pt-Ru(Cu/C electrocatalysts with core-shell structure supported on Vulcan Carbon XC72R have been synthesized by potentiostatic deposition of Cu nanoparticles on the support, galvanic exchange with Pt and spontaneous deposition of Ru species. The duration of the electrodeposition time of the different species has been modified and the obtained electrocatalysts have been characterized using electrochemical and structural techniques. The High Resolution Transmission Electron Microscopy (HRTEM, Fast Fourier Transform (FFT and Energy Dispersive X-ray (EDX microanalyses allowed the determining of the effects of the electrodeposition time on the nanoparticle size and composition. The best conditions identified from Cyclic Voltammetry (CV corresponded to onset potentials for CO and methanol oxidation on Pt-Ru(Cu/C of 0.41 and 0.32 V vs. the Reversible Hydrogen Electrode (RHE, respectively, which were smaller by about 0.05 V than those determined for Ru-decorated commercial Pt/C. The CO oxidation peak potentials were about 0.1 V smaller when compared to commercial Pt/C and Pt-Ru/C. The positive effect of Cu was related to its electronic effect on the Pt shells and also to the generation of new active sites for CO oxidation. The synthesis conditions to obtain the best performance for CO and methanol oxidation on the core-shell Pt-Ru(Cu/C electrocatalysts were identified. When compared to previous results in literature for methanol, ethanol and formic acid oxidation on Pt(Cu/C catalysts, the present results suggest an additional positive effect of the deposited Ru species due to the introduction of the bifunctional mechanism for CO oxidation.

  2. 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.

  3. Comparison of different promotion effect of PtRu/C and PtSn/C electrocatalysts for ethanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huanqiao; Cao, Lei [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Graduate School of the Chinese Academy Sciences, Beijing 100039 (China); Sun, Gongquan; Jiang, Luhua [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Xin, Qin [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

    2007-08-01

    Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90 C. (author)

  4. Comparison of different promotion effect of PtRu/C and PtSn/C electrocatalysts for ethanol electro-oxidation

    International Nuclear Information System (INIS)

    Li, Huanqiao; Sun, Gongquan; Cao, Lei; Jiang, Luhua; Xin, Qin

    2007-01-01

    Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90 o C

  5. 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

  6. 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.

  7. Electrocatalysts for fuel cells

    International Nuclear Information System (INIS)

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

    2008-01-01

    It was investigated the oxygen reduction reaction (fundamental reaction in fuel cells) on electrocatalysts of Pt, Co, Ni and their alloys CoNi, PtCo, PtNi, PtCoNi in H 2 SO 4 0.5 M and KOH 0.5 M as electrolyte. The electrocatalysts were synthesized using mechanical alloying processes and chemical vapor deposition. The electrocatalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray spectroscopy. The evaluation was performed using electrocatalytic technique of rotating disk electrode and kinetic parameters were determined for each electro catalyst. We report the performance of all synthesized electrocatalysts in acid and alkaline means. (Author)

  8. High stability and high activity Pd/ITO-CNTs electrocatalyst for direct formic acid fuel cell

    International Nuclear Information System (INIS)

    Qu, Wei-Li; Gu, Da-Ming; Wang, Zhen-Bo; Zhang, Jing-Jia

    2014-01-01

    Graphical abstract: The addition of ITO in Pd/CNTs catalyst significantly improves the activity and stability of catalyst for formic acid electrooxidation due to excellent stability and high electrical conductivity of ITO, and metal-support interaction between Pd nanoparticles and ITO. - Highlights: • Pd catalyst with ITO and CNTs as a mixture support for DFAFC was first prepared by microwave-assisted polyol process. • The activity and stability of Pd/ITO-CNTs catalyst is significantly higher than those of Pd/CNTs. • When ITO content is 50% of ITO/CNTs support mass, Pd/ITO-CNTs exhibits the best performance. - Abstract: Indium tin oxide (ITO) and carbon nanotube hybrid has been explored as a support for Pd catalyst. Pd/ITO-CNTs catalysts with different ITO contents were prepared by the microwave-assisted polyol process. The as-prepared Pd/ITO-CNTs catalysts were characterized by X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), and electrochemical measurements in this work. The TEM results show that Pd particle size distribution in the Pd/ITO-CNTs catalyst is more uniform than that in Pd/CNTs, indicating that the ITO can promote the dispersion of Pd nanoparticles. It is found that there is metal-support interaction between Pd nanoparticles and ITO in the Pd/ITO-CNTs catalyst through XPS test. The results of electrochemical tests prove that the Pd/ITO-CNTs catalysts exhibit higher electro-catalytic activity and stability than Pd/CNTs toward formic acid electrooxidation. When the ITO content is 50% of ITO-CNTs support mass, the Pd/ITO-CNTs catalyst has the best catalytic performance for formic acid electrooxidation. The peak current density of formic acid electrooxidation on the Pd/ITO-CNTs50% electrode is 1.53 times as high as that on Pd/CNTs, 2.31 times higher than that on Pd/ITO. The results of aging

  9. CaCu3Ti4O12: A Bifunctional Perovskite Electrocatalyst for Oxygen Evolution and Reduction Reaction in Alkaline Medium

    International Nuclear Information System (INIS)

    Kushwaha, H.S.; Halder, Aditi; Thomas, P.; Vaish, Rahul

    2017-01-01

    Highlights: •A cost effective double perovskite CaCu 3 Ti 4 O 12 have been synthesized using oxalate precursor method. •CCTO electrocatalyst exhibit enhanced bifunctional electrocatalytic activities. •CCTO electrocatalyst have lower overpotential and higher mass activity as compared to noble metal oxide and well-known perovskite catalysts. •Electrochemical impedance spectroscopy investigations of oxygen reactions on perovskite surfaces. -- Abstract: Perovskite oxides are prominent materials as the bifunctional electrocatalysts for both oxygen reduction/evolution reactions (ORR/OER) for the electrochemical energy conversion and storage using regenerative fuel cells and rechargeable metal-air batteries. In this work, a quadruple perovskite CaCu 3 Ti 4 O 12 has been synthesized oxalate precursor route. X-ray diffraction pattern shows phase purity of the synthesized electrocatalyst. The synthesized CCTO electrocatalyst have crystallite size of 26 nm. Electrochemical investigations reveal that CCTO exhibit efficient catalytic activity. More interestingly, an extremely high OER activity is observed for CCTO electrocatalysts which is found superior than similar class of perovskites. Additionally, CCTO shows efficient ORR activity with an onset potential of 0.83 V which is better than that of Pt/C catalyst (≈0.94 V). These results demonstrate the significant potential of CCTO perovskite as a bifunctional electrode material for alkaline fuel cells and metal-air batteries.

  10. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction

    DEFF Research Database (Denmark)

    Escribano, Maria Escudero; Malacrida, Paolo; Hansen, Martin Hangaard

    2016-01-01

    is lanthanum, cerium, samarium, gadolinium, terbium, dysprosium, thulium, or calcium. The materials are among the most active polycrystalline Pt-based catalysts reported, presenting activity enhancement by a factor of 3 to 6 over Pt. The active phase consists of a Pt overlayer formed by acid leaching. The ORR...

  11. Mesoporous Ruthenium/Ruthenium Oxide Thin Films: Active Electrocatalysts for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Kibsgaard, Jakob; Hellstern, Thomas R.; Choi, Shin-Jung

    2017-01-01

    We report the first synthesis of a fully contiguous large area supported thin film of highly ordered mesoporous Ru and RuO2 and investigate the electrocatalytic properties towards the oxygen evolution reaction (OER). We find that the nanoscale porous network of these catalysts provides significant...... enhancements in geometric OER activity without any loss in specific activity. This work demonstrates a strategy for engineering materials at the nanoscale that can simultaneously decrease precious metal loading and increase electrode activity....

  12. 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.

  13. Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts

    DEFF Research Database (Denmark)

    Verdaguer Casadevall, Arnau; Li, Christina W.; Johansson, Tobias Peter

    2015-01-01

    CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H-2 reduction of Cu2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Tem...

  14. Activity and Stability of RuOx Based Electrocatalysts for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Paoli, Elisa Antares

    . By coupling Electrochemical Quartz Crystal Microbalance (EQCM) measurements with Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) analyses of the electrolyte, we emphasize the importance of monitoring the mass loss. Finally, the thesis focuses on improving the stability of ruthenium dioxide under OER...... results show that an improvement of stability can be obtained, slightly decreasing the activity as well. Unfortunately, a drastic enhancement, as hoped, was not detected. Instead the results serve as a starting point from which the strategy and method for stability improvements can be further developed....... activity on oxides and studies on well-defined surfaces are required. Notably, industrial applications demand maximized surface-to-bulk ratio, hence fabrication of catalysts in nanoparticulate form. In this perspective, this project aimed at investigating well-defined mass-selected ruthenium and ruthenium...

  15. Graphene decorated with Pd nanoparticles via electrostatic self-assembly: A highly active alcohol oxidation electrocatalyst

    International Nuclear Information System (INIS)

    Guo, Shujing; Li, Shuwen; Hu, Tengyue; Gou, Galian; Ren, Ren; Huang, Jingwei; Xie, Miao; Jin, Jun; Ma, Jiantai

    2013-01-01

    Graphical abstract: Novel perylene-connected ionic liquids (PTCDI-ILs) have been successfully synthesized in a convenient approach and used as linkers for three-component Pd/PTCDI-ILs/GS heterostructure when non-covalently attached on graphene. The obtained nano-hybrids represented high electrochemical surface area and enhanced electrocatalytic activity for DAFCs in alkaline media. -- Highlights: • A novel preparation of three-component Pd/ionic liquids/graphene heterostructure has been constructed. • The Pd-based nano-catalysts have relatively low price and higher resistance to CO poisoning when compared with Pt-based catalysts. • The nano-catalysts represent high electrochemical surface area and enhanced electrocatalytic activity for DAFCs in alkaline media. -- Abstract: Graphene nanosheets (GS) are non-covalently functionalized with novel N,N-bis-(n-butylimidazolium bromide salt)-3,4,9,10-perylene tetracarboxylic acid diimide (PTCDI-ILs) via the π–π stacking, and then employed as the support of Pd nanoparticles. The negatively charged Pd precursors are adsorbed on positively charged imidazolium ring moiety of PTCDI-ILs wrapping GS surface via electrostatic self-assembly and then in situ reduced by NaBH 4 . X-ray diffraction and transmission electron microscope images reveal that Pd nanoparticles with an average size of 2.7 nm are uniformly dispersed on GS surface. The Pd/PTCDI-ILs/GS exhibits unexpectedly high activity toward alcohol oxidation reaction, which can be attributed to the large electrochemical surface area of Pd nanoparticles. It also shows enhanced electrochemical stability due to the structural integrity of PTCDI-ILs/GS. This provides a facile approach to synthesize GS-based nanoelectrocatalysts

  16. Electrocatalysts and their Supporting Materials for Proton Exchange Membrane Fuel Cells: Activity and Durability Studies

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna

    of methanol electro-oxidation for ALD deposited Pt films on Si(100) and Pt-Si alloys on Si(100). ALD deposited Pt films on Si(100) were subsequently annealed at various temperatures to obtain Pt-Si alloy film on Si(100). Obtained alloys were subsequently characterised as potentially highly active methanol...... in oxygen reduction, carbon monoxide and methanol electro-oxidation reactions were explored. Employed catalysts were characterized electrochemically and physiochemically using techniques such as: cyclic voltammetry, rotating disk electrode technique, SEM, TEM, EDS, XPS, TGA/DTA, Raman, XRD, FTIR-IR among...... to long-term durability procedures. A significant part of the PhD study involved development of electrochemical instrumentation and techniques, such as: RDE and set-up, oxygen reduction, methanol and CO electrooxidation, long-term durability procedures, etc. The techniques employed by the author were self...

  17. Synthesis, characterization and catalytic activity toward methanol oxidation of electrocatalyst Pt4+-NH2-MCM-41

    International Nuclear Information System (INIS)

    Zheng Huajun; Chen Zuo; Wang Limin; Ma Chun’an

    2012-01-01

    Highlights: ► It was first confirmed that the Pt 4+ exhibited a good electro-catalytic property for methanol oxidation. ► The Pt 4+ perfectly distributed on a mesoporous molecular sieve matrix synthesis by a facile method. ► The good performance of catalyst resistance to poisoning because of a homogeneous distribution of Pt 4+ and large specific surface area. - Abstract: Mesoporous material with functional group (Pt 4+ -NH 2 -MCM-41) was prepared by grafting aminopropyl group and adsorbing platinum ions on the surface of the commercial molecular sieve (MCM-41). The characterization carried out by X-ray photoelectron spectroscopy, X-ray diffraction, and N 2 adsorption–desorption measurement pointed out that Pt was adsorbed on the NH 2 -MCM-41 surface as the oxidation state (Pt 4+ ) and the surface area of Pt 4+ -NH 2 -MCM-41 was up to 564 m 2 /g. Transmission electron microscopy and elemental mapping indicated a homogeneous distribution of Pt 4+ throughout all surface of the mesoporous materials. Electro-catalytic properties of methanol oxidation on the Pt 4+ -NH 2 -MCM-41 electrode were investigated with electrochemical methods. The results showed that the Pt 4+ -NH 2 -MCM-41 electrode exhibited catalytic activity in the methanol electro-oxidation with the apparent activation energy being 49.29 kJ/mol, and the control step of methanol electro-oxidation was the mass transfer process. It is first proved that platinum ions had good electro-catalytic property for methanol oxidation and provided a new idea for developing electrode materials in future.

  18. Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2.

    Science.gov (United States)

    Kowal, A; Li, M; Shao, M; Sasaki, K; Vukmirovic, M B; Zhang, J; Marinkovic, N S; Liu, P; Frenkel, A I; Adzic, R R

    2009-04-01

    Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol's slow, inefficient oxidation even at the best electrocatalysts. We synthesized a ternary PtRhSnO(2)/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C-C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO(2), which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst's activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt-Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C-C bond splitting in other catalytic processes.

  19. Porous Co3O4 nanorods anchored on graphene nanosheets as an effective electrocatalysts for aprotic Li-O2 batteries

    Science.gov (United States)

    Yuan, Mengwei; Yang, Yan; Nan, Caiyun; Sun, Genban; Li, Huifeng; Ma, Shulan

    2018-06-01

    The large over-potential during the battery operation is a great obstacle for the application of Li-O2 batteries. The porous structure and electrical conductivity of the electrocatalysts are significant for the electrocatalytic performance of Li-O2 batteries. In this work, a porous Co3O4/GN nanocomposite (Co3O4 nanorods anchored on graphene nanosheets) is prepared via a facile hydrothermal method assisted with heat treatment. The unique structure of Co3O4/GN endows efficient electrocatalystic activity for Li-O2 batteries. In comparison to the Co3O4, the Co3O4/GN demonstrates a better cycle performance showing more than 40 cycles with a 1500 mAh g-1 capacity limit strategy at a current density of 300 mA g-1, and a reduced over-potential of 110 mV at high current density (1200 mA g-1). The Co3O4/GN also displays a high initial specific capacity (7600 mAh g-1) and a good reversibility in full cycle with a coulombic efficiency of 99.8% in the first cycle. The impressed cyclability, specific capacity, rate performance, and low over-potentials indicate that the as-prepared Co3O4/GN nanocomposite is a promising catalyst candidate for reversible Li-O2 batteries.

  20. Semiconductor-Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting.

    Science.gov (United States)

    Nellist, Michael R; Laskowski, Forrest A L; Lin, Fuding; Mills, Thomas J; Boettcher, Shannon W

    2016-04-19

    semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

  1. Pd-NiO decorated multiwalled carbon nanotubes supported on reduced graphene oxide as an efficient electrocatalyst for ethanol oxidation in alkaline medium

    Science.gov (United States)

    Rajesh, Dhanushkotti; Indra Neel, Pulidindi; Pandurangan, Arumugam; Mahendiran, Chinnathambi

    2018-06-01

    The synthesis of Pd-NiO nanoparticles decorated multiwalled carbon nanotubes (MWCNTs) on reduced graphene oxide (rGO) for ethanol electrooxidation is reported. NiO nanoparticles (NPs) were deposited on functionalized MWCNTs by wet impregnation method. Pd nanoparticles were formed on NiO-MWCNTs by the addition of PdCl2 and its reduction using NaBH4. The Pd-NiO/MWCNTs nanocomposite then deposited on rGO support using ultrasound irradiation which led to the formation of the Pd-NiO/MWCNTs/rGO electrocatalyst. The prepared electrocatalysts were characterized by XRD, SEM, HR-TEM and XPS analysis. Electrochemical measurements demonstrate that as synthesized Pd-NiO/MWCNTs/rGO electrocatalyst exhibit higher catalytic activity (90.89 mA/cm2) than either Pd/MWCNTs/rGO (43.05 mA/cm2) or Pd/C (28.0 mA/cm2) commercial catalyst. Chronoamperometry study of Pd-NiO/MWCNTs/rGO electrocatalyst showed long-term electrochemical stability. The enhanced catalytic activity of Pd-NiO/MWCNTs/rGO electrocatalyst for electrooxidation of ethanol can be attributed to the synergistic effect between Pd & NiO active sites.

  2. Two-Dimensional Material Molybdenum Disulfides as Electrocatalysts for Hydrogen Evolution

    Directory of Open Access Journals (Sweden)

    Lei Yang

    2017-09-01

    Full Text Available Recently, transition metal dichalcogenides (TMDs, represented by MoS2, have been proven to be a fascinating new class of electrocatalysts in hydrogen evolution reaction (HER. The rich chemical activities, combined with several strategies to regulate its morphologies and electronic properties, make MoS2 very attractive for understanding the fundamentals of electrocatalysis. In this review, recent developments in using MoS2 as electrocatalysts for the HER with high activity are presented. The effects of edges on HER activities of MoS2 are briefly discussed. Then we demonstrate strategies to further enhance the catalytic performance of MoS2 by improving its conductivity or engineering its structure. Finally, the key challenges to the industrial application of MoS2 in electrocatalytic hydrogen evolution are also pointed out.

  3. 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.

  4. Electrocatalysts for hydrogen energy

    CERN Document Server

    Losiewicz, Bozena

    2015-01-01

    This special topic volume deals with the development of novel solid state electrocatalysts of a high performance to enhance the rates of the hydrogen or oxygen evolution. It contains a description of various types of metals, alloys and composites which have been obtained using electrodeposition in aqueous solutions that has been identified to be a technologically feasible and economically superior technique for the production of the porous electrodes. The goal was to produce papers that would be useful to both the novice and the expert in hydrogen technologies. This volume is intended to be us

  5. Rapid synthesis of platinum-ruthenium bimetallic nanoparticles dispersed on carbon support as improved electrocatalysts for ethanol oxidation.

    Science.gov (United States)

    Gu, Zhulan; Li, Shumin; Xiong, Zhiping; Xu, Hui; Gao, Fei; Du, Yukou

    2018-07-01

    Bimetallic nanocatalysts with small particle size benefit from markedly enhanced electrocatalytic activity and stability during small molecule oxidation. Herein, we report a facile method to synthesize binary Pt-Ru nanoparticles dispersed on a carbon support at an optimum temperature. Because of its monodispersed nanostructure, synergistic effects were observed between Pt and Ru and the PtRu/C electrocatalysts showed remarkably enhanced electrocatalytic activity towards ethanol oxidation. The peak current density of the Pt 1 Ru 1 /C electrocatalyst is 3731 mA mg -1 , which is 9.3 times higher than that of commercial Pt/C (401 mA mg -1 ). Furthermore, the synthesized Pt 1 Ru 1 /C catalyst exhibited higher stability during ethanol oxidation in an alkaline medium and maintained a significantly higher current density after successive cyclic voltammograms (CVs) of 500 cycles than commercial Pt/C. Our work highlights the significance of the reaction temperature during electrocatalyst synthesis, leading to enhanced catalytic performance towards ethanol oxidation. The Pt 1 Ru 1 /C electrocatalyst has great potential for application in direct ethanol fuel cells. Copyright © 2018 Elsevier Inc. All rights reserved.

  6. 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)

  7. Preparation and characterization of electrocatalysts based on palladium for electro-oxidation of alcohols in alkaline medium

    International Nuclear Information System (INIS)

    Brandalise, Michele

    2012-01-01

    In this study Pd/C, Au/C, PdAu/C, PdAuPt/C, PdAuBi/C and PdAuIr/C electrocatalysts were prepared by the sodium borohydride reduction method for the electrochemical oxidation of methanol, ethanol and ethylene glycol. This methodology consists in mix an alkaline solution of sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. The electrocatalysts were characterized by energy dispersive X-ray (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry. The electrochemical oxidation of the alcohols was studied by chronoamperometry using a thin porous coating technique. The mechanism of ethanol electro-oxidation was studied by Fourier Transformed Infrared (FTIR) in situ. The most effective electrocatalysts were tested in alkaline single cells directly fed with methanol, ethanol or ethylene glycol. Preliminary studies showed that the most suitable atomic composition for preparing the ternary catalysts is 50:45:05. Electrochemical data in alkaline medium show that the electrocatalysts PdAuPt/C (50:45:05) showed the better activity for methanol electro oxidation, while PdAuIr/C was the most active for ethanol oxidation and PdAuBi/C (50:45:05) was the most effective for ethylene glycol oxidation in alkaline medium. These results show that the addition of gold in the composition of electrocatalysts increases their catalytic activities. The spectroelectrochemical FTIR in situ data permitted to conclude that C-C bond is not broken and the acetate is formed. (author)

  8. Characteristics of NixFe1−xOy Electrocatalyst on Hematite as Photoanode for Solar Hydrogen Production

    Directory of Open Access Journals (Sweden)

    Chih-Ping Yen

    2017-11-01

    Full Text Available The use of hematite as the photoanode for photoelectrochemical hydrogen production by solar energy has been actively studied due to its abundance, stability, and adequate optical properties. Deposition of an electrocatalyst overlayer on the hematite may increase kinetics and lower the onset potential for water splitting. NixFe1−xOy is one of the most effective electrocatalysts reported for this purpose. However, the condition and results of the previous reports vary significantly, and a comprehensive model for NixFe1−xOy/hematite is lacking. Here, we report a simple and novel chemical bath deposition method for depositing low-onset-potential NixFe1−xOy electrocatalyst on hematite. With a Ni percentage of 80% and an immersion time of 2 min, the as-prepared NixFe1−xOy overlayer raised the photovoltage from 0.2 V to 0.7 V, leading to a cathodic shift of the onset potential by 400 mV, while maintaining the same level of current density. The dependence of the electrochemical and photoelectrochemical characteristics of the photoanode on the condition of the electrocatalyst was studied systematically and explained based on energy level diagrams and kinetics.

  9. High index surfaces of Au-nanocrystals supported on one-dimensional MoO3-nanorod as a bi-functional electrocatalyst for ethanol oxidation and oxygen reduction

    International Nuclear Information System (INIS)

    Karuppasamy, L.; Chen, C.Y.; Anandan, S.; Wu, J.J.

    2017-01-01

    Highlights: •Synthesis of a new class of Au nanocrystals enclosed with high index surface supported on MoO 3 nanorods by ultrasonic probe method. •The role of supporting materials reduces the loading of Au and acts as a co-catalyst. •The as prepared electrocatalyst exhibits enhanced catalytic activity and stability towards both EOR and ORR. -- Abstract: The design of highly active electrocatalyst for ethanol electrooxidation (EOR) and oxygen reduction reaction (ORR) is of great significance for the improvement of efficient direct ethanol fuel cells (DEFCs). Therefore, creating high index facets nanocrystals with abundant catalytic active sites of stepped atoms is an effective way to enhance the electrocatalytic performance. In this article, we prepared the high index surface structures of Au nanocrystals supported on one-dimensional (1-D) MoO 3 nanorods by using two steps ultrasonic probe irradiation method. The size and physical properties of as electrocatalysts were studied by using field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and x-ray diffraction (XRD) instrumentation. Besides, the catalytic activity of as Au-MoO 3 electrocatalyst was determined by using cyclic voltammetry (CV), chronoamperometric (CA), electrochemical impedance spectroscopy (EIS), CO-stripping, and linear sweep voltammetry-rotating disk electrode (LSV-RDE). As a consequence, the Au-MoO 3 nanocomposites has been considered as an effective electrocatalyst for both ethanol oxidation and oxygen reduction reaction.

  10. Palladium-based electrocatalysts for ethanol oxidation reaction in DEFC

    International Nuclear Information System (INIS)

    Moraes, L.P.R. de; Elsheikh, A.; Silva, E. L. da; Radtke, C.; Amico, S.C.; Malfatti, C.F.

    2014-01-01

    Direct ethanol fuel cells require the use of electrocatalysts to promote bond cleavage of the ethanol molecule in an efficient way. Currently, most electrocatalysts contain platinum, which enables improved catalytic activity and stability in acidic media. However platinum presents high cost and low availability. Based on that, novel catalysts have been developed, such as those based on palladium and its alloys, which have attained excellent results in the oxidation of ethanol in alkaline media. In this work, Pd, PdSn and PdNiSn catalysts supported on Vulcan XC72R carbon were synthesized via impregnation/reduction. The electrocatalysts were characterized by RBS, XRD and cyclic voltammetry. The X-ray diffraction results showed the formation of an alloy and not the deposition of isolated elements. The synthesized catalysts displayed good catalytic activity, as observed by cyclic voltammetry, being the best electrochemical performance achieved by the ternary alloy. (author)

  11. Nitrogen and sulfur dual-doped chitin-derived carbon/graphene composites as effective metal-free electrocatalysts for dye sensitized solar cells

    Science.gov (United States)

    Di, Yi; Xiao, Zhanhai; Yan, Xiaoshuang; Ru, Geying; Chen, Bing; Feng, Jiwen

    2018-05-01

    The photovoltaic performance of dye-sensitized solar cell (DSSC) is strongly influenced by the electrocatalytic ability of its counter electrode (CE) materials. To obtain the affordable and high-performance electrocatalysts, the N/S dual-doped chitin-derived carbon materials SCCh were manufactured via in-situ S-doped method in the annealing process, where richer active sites are created compared to the pristine chitin-derived carbon matrix CCh, thus enhancing the intrinsic catalytic activity of carbon materials. When SCCh is incorporated with graphene, the yielded composites hold a further boosted catalytic activity due to facilitating the electronic fast transfer. The DSSC assembled with the optimizing rGO-SCCh-3 composite CE shows a favourable power conversion efficiency of 6.36%, which is comparable with that of the Pt-sputtering electrode (6.30%), indicate of the outstanding I3- reduction ability of the composite material. The electrochemical characterizations demonstrate that the low charge transfer resistance and excellent electrocatalytic activity all contribute to the superior photovoltaic performance. More importantly, the composite CE exhibits good electrochemical stability in the practical operation. In consideration of the low cost and the simple preparation procedure, the present metal-free carbonaceous composites could be used as a promising counter electrode material in future large scale production of DSSCs.

  12. Rare earth metal oxides as BH4-tolerance cathode electrocatalysts for direct borohydride fuel cells

    Institute of Scientific and Technical Information of China (English)

    NI Xuemin; WANG Yadong; GUO Feng; YAO Pei; PAN Mu

    2012-01-01

    Rare earth metal oxides (REMO) as cathode electrocatalysts in direct borohydride fuel cell (DBFC) were investigated.The REMO electrocatalysts tested showed favorable activity to the oxygen electro-reduction reaction and strong tolerance to the attack of BH4- in alkaline electrolytes.The simple membraneless DBFCs using REMO as cathode electrocatalyst and using hydrogen storage alloy as anodic electrocatalyst exhibited an open circuit of about 1 V and peak power of above 60 mW/cm2.The DBFC using Sm2O3 as cathode electrocatalyst showed a relatively better performance.The maximal power density of 76.2 mW/cm2 was obtained at the cell voltage of 0.52 V.

  13. High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jaemin [Department; Shih, Pei-Chieh [Department; Tsao, Kai-Chieh [Department; Pan, Yung-Tin [Department; Yin, Xi [Department; Sun, Cheng-Jun [X-ray; Yang, Hong [Department

    2017-08-17

    Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap between Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.

  14. Influence of method of preparation of Pt Ru/C electrocatalysts on the catalytic activity for the ethanol oxidation reaction in acidic medium; Influencia do metodo de preparacao de eletrocatalisadores PtRu/C sobre a atividade catalitica frente a reacao de oxidacao de etanol em meio acido

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Walber dos Santos; Silva, Uriel Lean Valente; Souza, Jose Pio Iudice de, E-mail: jpio@ufpa.br [Universidade Federal do Para, (UFPA), Belem, PA (Brazil). Instituto de Ciencias Exatas e Naturais. Faculdade de Quimica

    2013-09-01

    In this work the influence of variations in the borohydrate reduction method on the properties of Pt Ru/C electrocatalysts was investigated. The electrocatalysts were prepared using 1:1 ; 2:1; 5:1; 50:1 and 250:1 molar ratios of NaBH{sub 4} to metals. The reduction was also performed by dripping or by fast addition of the solution. The results showed that Pt Ru nanoparticles obtained by fast addition had the smallest crystallite sizes. It was also noted that the catalytic activity increased as the borohydrate:metal molar ratio increased. The Pt Ru/C electrocatalysts (50:1) obtained by fast addition presented the best catalytic activity for ethanol electro-oxidation. (author)

  15. Palladium-based electrocatalysts for ethanol oxidation reaction in alkaline direct ethanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, Leticia Poras Reis de; Amico, Sandro Campos; Malfatti, Celia de Fraga, E-mail: leticiamoraes@usp.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre (Brazil); Matos, Bruno R.; Santiago, Elisabete Inacio; Fonseca, Fabio Coral [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2016-07-01

    Full text: Direct ethanol fuel cells require adequate electrocatalysts to promote the carbon carbon cleavage of ethanol molecule. Typical electrocatalysts are based on platinum, which have shown improved activity in acidic media. However, Pt-based catalysts have high cost and are easily deactivated by CO poisoning. Therefore, novel catalysts have been developed, and among then, palladium-based materials have shown promising results for the oxidation of ethanol in alkaline media. The present study reports on the performance of alkaline direct ethanol fuel cell (ADEFC) by using carbon-supported Pd, PdSn, PdNi, and PdNiSn produced by impregnation-reduction of the metallic precursors. The effect of chemical functionalization by acid treatment of the carbon support (Vulcan) was investigated. The electrocatalysts were studied by thermogravimetric analysis (TGA), X-rays diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV), and ADEFC tests. TGA measurements of functionalized Vulcan evidenced the characteristic weight losses attributed to the presence of surface functional groups due to the acid treatment. A high degree of alloying between Pd and Sn was inferred from XRD data, whereas in both PdNi and PdNiSn, Ni occurs mostly segregated in the oxide form. TEM analyses indicated agglomeration of Pd and PdSn particles, whereas a more uniform particle distribution was observed for PdNi and PdNiSn samples. CV curves showed that the peak potential for the oxidation of ethanol shifts towards negative values for all samples supported on functionalized Vulcan indicating that ethanol oxidation is facilitated. Microstructural and electrochemical features were confirmed by ADEFC tests, which revealed that the highest open circuit voltage and maximum power density were achieved for PdNiSn electrocatalysts supported on functionalized Vulcan with uniform particle distribution and improved triple phase boundaries. (author)

  16. Palladium-based electrocatalysts for ethanol oxidation reaction in alkaline direct ethanol fuel cell

    International Nuclear Information System (INIS)

    Moraes, Leticia Poras Reis de; Amico, Sandro Campos; Malfatti, Celia de Fraga; Matos, Bruno R.; Santiago, Elisabete Inacio; Fonseca, Fabio Coral

    2016-01-01

    Full text: Direct ethanol fuel cells require adequate electrocatalysts to promote the carbon carbon cleavage of ethanol molecule. Typical electrocatalysts are based on platinum, which have shown improved activity in acidic media. However, Pt-based catalysts have high cost and are easily deactivated by CO poisoning. Therefore, novel catalysts have been developed, and among then, palladium-based materials have shown promising results for the oxidation of ethanol in alkaline media. The present study reports on the performance of alkaline direct ethanol fuel cell (ADEFC) by using carbon-supported Pd, PdSn, PdNi, and PdNiSn produced by impregnation-reduction of the metallic precursors. The effect of chemical functionalization by acid treatment of the carbon support (Vulcan) was investigated. The electrocatalysts were studied by thermogravimetric analysis (TGA), X-rays diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV), and ADEFC tests. TGA measurements of functionalized Vulcan evidenced the characteristic weight losses attributed to the presence of surface functional groups due to the acid treatment. A high degree of alloying between Pd and Sn was inferred from XRD data, whereas in both PdNi and PdNiSn, Ni occurs mostly segregated in the oxide form. TEM analyses indicated agglomeration of Pd and PdSn particles, whereas a more uniform particle distribution was observed for PdNi and PdNiSn samples. CV curves showed that the peak potential for the oxidation of ethanol shifts towards negative values for all samples supported on functionalized Vulcan indicating that ethanol oxidation is facilitated. Microstructural and electrochemical features were confirmed by ADEFC tests, which revealed that the highest open circuit voltage and maximum power density were achieved for PdNiSn electrocatalysts supported on functionalized Vulcan with uniform particle distribution and improved triple phase boundaries. (author)

  17. Stable and efficient nitrogen-containing-carbon based electrocatalysts for reactions in energy conversion systems.

    Science.gov (United States)

    Wang, Sicong; Teng, Zhenyuan; Wang, Chengyin; Wang, Guoxiu

    2018-05-17

    High activity and stability are crucial for practical electrocatalysts used for reactions in fuel cells, metal-air batteries and water electrolysis including ORR, HER, OER and oxidation reactions of formic acid and alcohols. N-C based electrocatalysts have shown promising prospects for catalyzing these reactions, however, there is no systematic review for strategies toward engineering active and stable N-C based electrocatalysts reported by far. Herein, a comprehensive comparison of recently reported N-C based electrocatalysts regarding both electrocatalytic activity and long-term stability is presented. In the first part of this review, relationships between electrocatalytic reactions and element selections for modifying N-C based materials are discussed. Afterwards, synthesis methods for N-C based electrocatalysts are summarized, and synthetic strategies for highly stable N-C based electrocatalysts are presented. Multiple tables containing data on crucial parameters for both electrocatalytic activity and stability are displayed in this review. Finally, constructing M-Nx moieties is proposed as the most promising engineering strategy for stable N-C based electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Pr0.6Sr0.4CoO3-δ electrocatalyst for solid oxide fuel cell cathode introduced via infiltration

    International Nuclear Information System (INIS)

    Lee, Shiwoo; Miller, Nicholas; Staruch, Margo; Gerdes, Kirk; Jain, Menka; Manivannan, Ayyakkannu

    2011-01-01

    Highlights: → High electrocatalytic activity of Sr-doped PrCoO 3 for oxygen reduction reaction has been demonstrated. → 35-38% of power density enhancement has been achieved for a commercial cell by introducing Sr-doped PrCoO 3 via infiltration. → Fuel cells modified with nano-sized electrocatalyst have shown relatively stable performance for 200 h. → Reliable performance comparison has been realized by utilizing a parallel cell testing system. - Abstract: Effects of infiltrated Pr 0.6 Sr 0.4 CoO 3-δ (PSCo) electrocatalyst on SOFC cathode performance have been studied. Nano-sized particulate catalysts, deposited on surfaces of a composite cathode of Sm 2 O 3 doped CeO 2 (SDC) and La 1-x Sr x Co 1-y Fe y O 3-δ (LSCF), are assumed to effectively widen active sites, or triple phase boundaries, for the oxygen reduction reaction. Area specific resistance of commercially available cells has been decreased by 36-40% with the addition of 23 wt% PSCo electrocatalyst on cathode. Analysis of the impedance spectra demonstrates that PSCo electrocatalyst plays a significant role in dissociation of oxygen molecules and adsorption of oxygen atoms into the cathode. A total of 200 h operation of the cells demonstrated that catalytic activity of PSCo has not been significantly degraded. Simultaneous operations of multiple cells using a parallel-cell testing system have made it possible to compare the performance of several cells with high reliability.

  19. 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

  20. Preparation and characterization of Pt–CeO{sub 2}/C and Pt–TiO{sub 2}/C electrocatalysts with improved electrocatalytic activity for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-03-30

    Graphical abstract: - Highlights: • Adding TiO{sub 2} or CeO{sub 2} to Pt/C reduced its Pt particle size. • Methanol oxidation current density decreased as Pt–CeO{sub 2}/C > Pt–TiO{sub 2}/C > Pt/C. • Decreased R{sub ct} values were observed at Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C. - Abstract: Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C electrocatalysts were synthesized by solid state reaction of TiO{sub 2}/C and CeO{sub 2}/C powders using intermittent microwave heating, followed by chemical reduction of platinum ions using mixed reducing agents of ethylene glycol and sodium borohydride. The crystal structure, surface morphology and chemical composition of prepared electrocatalysts were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX). The phase angle values of different Pt diffraction planes in Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C were shifted in the positive direction relative to those in Pt/C. Pt particles with diameter values of 3.06 and 2.78 nm were formed in Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C, respectively. The electrochemical performance of prepared electrocatalysts was examined using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Pt–CeO{sub 2}/C showed an enhanced oxidation current density when compared to Pt/C. Long time oxidation test at Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C revealed their improved stability. Lower charge transfer resistance values were estimated at Pt–metal oxide/C electrocatalysts.

  1. Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Jennifer N. [Univ. of California, San Diego, CA (United States); Wang, Joseph [Univ. of California, San Diego, CA (United States)

    2014-08-31

    controlled, the nanocrystals boast a defined shape, morphology, orientation and size and are synthesized at benign reaction conditions. Adapting the methods of biomineralization towards the synthesis of platinum nanocrystals will allow effective control at a molecular level of the synthesis of highly active metal electrocatalysts, with readily tailored properties, through tuning of the biochemical inputs. The proposed research will incorporate many facets of biomineralization by: (1) isolating peptides that selectively bind particular crystal faces of platinum (2) isolating peptides that promote the nucleation and growth of particular nanocrystal morphologies (3) using two-dimensional DNA scaffolds to control the spatial orientation and density of the platinum nucleating peptides, and (4) combining bio-templating and soluble peptides to control crystal nucleation, orientation, and morphology. The resulting platinum nanocrystals will be evaluated for their electrocatalytic behavior (on common carbon supports) to determine their optimal size, morphology and crystal structure. We expect that such rational biochemical design will lead to highly uniform and efficient platinum nanocrystal catalysts for fuel cell applications.

  2. SiO2 decoration dramatically enhanced the stability of PtRu electrocatalysts with undetectable deterioration in fuel cell performance

    Science.gov (United States)

    Yu, Xinxin; Xu, Zejun; Yang, Zehui; Xu, Sen; Zhang, Quan; Ling, Ying; Zhang, Yunfeng; Cai, Weiwei

    2018-06-01

    Prevention of Ru dissolution is essential for steady CO tolerance of anodic electrocatalysts in direct methanol fuel cells. Here, we demonstrate a facile way to stabilize Ru atoms by decorating commercial CB/PtRu with SiO2, which shows a six-fold higher stability and similar activity toward a methanol oxidation reaction leading to no discernible degradation in fuel cell performance compared to commercial CB/PtRu electrocatalysts. The higher stability and stable CO tolerance of SiO2-decorated electrocatalysts originate from the SiO2 coating, since Ru atoms are partially ionized during SiO2 decorating, resulting in difficulties in dissolution; while, in the case of commercial CB/PtRu, the dissolved Ru offers active sites for Pt coalescences and CO species resulting in the rapid decay of the electrochemical surface area and fuel cell performance. To the best of our knowledge, this is the first study about the stabilization of Ru atoms by SiO2. The highest stability is obtained for a PtRu electrocatalyst with negligible effect on the electrochemical properties.

  3. Investigation of methanol oxidation on a highly active and stable Pt–Sn electrocatalyst supported on carbon–polyaniline composite for application in a passive direct methanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Amani, Mitra [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Kazemeini, Mohammad [Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Hamedanian, Mahboobeh [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Pahlavanzadeh, Hassan [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Gharibi, Hussein, E-mail: h.gharibi@utah.edu [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Department of Material Science & Engineering, 122 S Campus Drive, University of Utah, Salt Lake City, UT 84112 (United States)

    2015-08-15

    Highlights: • PtSn/C-PANI performed superior in the MOR compared with a commercial PtRu/C. • Catalytic activity of PtRu/C was highly reduced during the accelerated durability test. • Anode of the PtSn/C-PANI in a passive DMFC lowered methanol crossover by 30%. - Abstract: Polyaniline fiber (PANI) was synthesized and utilized to fabricate a vulcan–polyaniline (C-PANI) composite. Pt/C-PANI and PtSn/C-PANI electro-catalysts with different Pt:Sn atomic ratios were prepared by the impregnation method. These electro-catalysts, along with commercial PtRu/C (Electrochem), were characterized with respect to their structural and electrochemical properties in methanol oxidation reaction (MOR). PtSn(70:30)/C-PANI showed excellent performance in MOR, the obtained maximum current density being about 40% and 50% higher than that for PtRu/C and Pt/C-PANI, respectively. It was also found that the CO tolerance and stability of PtSn(70:30)/C-PANI was considerably higher than that of PtRu/C. Finally, the performance of these two materials was compared in a passive direct methanol fuel cell (DMFC). The DMFC test results demonstrated that the membrane electrode assembly (MEA) prepared using PtSn(70:30)/C-PANI anode catalyst performed more satisfactorily in terms of maximum power density and lower methanol crossover.

  4. Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics

    Science.gov (United States)

    Zhang, Jian; Wang, Tao; Liu, Pan; Liao, Zhongquan; Liu, Shaohua; Zhuang, Xiaodong; Chen, Mingwei; Zschech, Ehrenfried; Feng, Xinliang

    2017-05-01

    Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm-2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers.

  5. Influence of Support Material of PtSnNiGa/C Electrocatalysts for Ethanol Oxidation

    Directory of Open Access Journals (Sweden)

    Deise M Santos

    2017-07-01

    Full Text Available Ethanol is a promising alternative source for fuel cells due to its low toxicity and high power density. However, the cleavage of the C-C bond, CO poisoning, and low electrocatalyst stability are still considered crucial issues. To overcome this limitation, binary, ternary and quaternary electrocatalysts have been investigated along with new carbon supports. This paper presents a physicochemical and electrochemical investigation of quaternary PtSnNiGa/C electrocatalysts supported on Vulcan XC72 and Printex-L6 carbons and also a carbon produced by natural gas pyrolysis in an Argon plasma torch (Black Plasma. The electrochemical characterization was performed through cyclic voltammetry, chronoamperometry, chronopotentiometry and electrochemical impedance spectroscopy in the presence of ethanol 1.0 mol L-1. Energy dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy and transmission electron microscopy were also carried out for physicochemical characterization. The electrochemical results show that the quaternary electrocatalysts supported on Vulcan XC72 and Printex-L6 carbons display a high current normalized by Pt mass and are more stable than the electrocatalyst supported on Black Plasma. In addition, the quaternary electrocatalysts with reduced Pt loading display better electrocatalytic activity towards the EOR compared to high Pt loading electrocatalysts. DOI: http://dx.doi.org/10.17807/orbital.v9i3.949 

  6. Facile synthesis of highly active PdAu nanowire networks as self-supported electrocatalyst for ethanol electrooxidation.

    Science.gov (United States)

    Hong, Wei; Wang, Jin; Wang, Erkang

    2014-06-25

    In recent years, direct ethanol fuel cells (DEFCs) are attracting increasing attention owing to their wide applications. However, a significant challenge in the development of DEFC technology is the urgent need for highly active anode catalysts for the ethanol oxidation reaction. In this work, a facile and reproducible method for the high-yield synthesis of PdAu nanowire networks is demonstrated. The whole synthetic process is very simple, just mixing Na2PdCl4, HAuCl4, and KBr in an aqueous solution and using polyvinylpyrrolidone as a protective reagent while sodium borohydride as a reductant. The whole synthetic process can be simply performed at room temperature and completed in 30 min, which can greatly simplify the synthetic process and lower the preparation cost. Electrochemical catalytic measurement results prove that the as-prepared catalysts exhibit dramatically enhanced electrocatalytic activity for ethanol electrooxidation in alkaline solution. The facile synthetic process and excellent catalytic performance of the as-prepared catalysts demonstrate that they can be used as a promising catalyst for DEFCs.

  7. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    International Nuclear Information System (INIS)

    Wang, C.-H.; Shih, H.-C.; Tsai, Y.-T.; Du, H.-Y.; Chen, L.-C.; Chen, K.-H.

    2006-01-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN x NTs) directly grown on the carbon cloth have been investigated. The CN x NTs directly grown on the carbon cloth (CN x NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN x NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN x NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN x NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications

  8. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    Energy Technology Data Exchange (ETDEWEB)

    Wang, C.-H. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Shih, H.-C. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Tsai, Y.-T. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Du, H.-Y. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Chen, L.-C. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China); Chen, K.-H. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China) and Institue of Atomic and Molecular Science, Academia Sinica, Taipei, Taiwan (China)]. E-mail: chenkh@pub.iams.sinica.edu.tw

    2006-12-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN {sub x} NTs) directly grown on the carbon cloth have been investigated. The CN {sub x} NTs directly grown on the carbon cloth (CN {sub x} NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN {sub x} NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN {sub x} NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN {sub x} NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications.

  9. Metal-Organic Frameworks as Highly Active Electrocatalysts for High-Energy Density, Aqueous Zinc-Polyiodide Redox Flow Batteries.

    Science.gov (United States)

    Li, Bin; Liu, Jian; Nie, Zimin; Wang, Wei; Reed, David; Liu, Jun; McGrail, Pete; Sprenkle, Vincent

    2016-07-13

    The new aqueous zinc-polyiodide redox flow battery (RFB) system with highly soluble active materials as well as ambipolar and bifunctional designs demonstrated significantly enhanced energy density, which shows great potential to reduce RFB cost. However, the poor kinetic reversibility and electrochemical activity of the redox reaction of I3(-)/I(-) couples on graphite felts (GFs) electrode can result in low energy efficiency. Two nanoporous metal-organic frameworks (MOFs), MIL-125-NH2 and UiO-66-CH3, that have high surface areas when introduced to GF surfaces accelerated the I3(-)/I(-) redox reaction. The flow cell with MOF-modified GFs serving as a positive electrode showed higher energy efficiency than the pristine GFs; increases of about 6.4% and 2.7% occurred at the current density of 30 mA/cm(2) for MIL-125-NH2 and UiO-66-CH3, respectively. Moreover, UiO-66-CH3 is more promising due to its excellent chemical stability in the weakly acidic electrolyte. This letter highlights a way for MOFs to be used in the field of RFBs.

  10. CoP/WS2 nanoflake heterostructures as efficient electrocatalysts for significant improvement in hydrogen evolution activity

    Science.gov (United States)

    Chen, Yajie; Kang, Chuanhong; Wang, Ruihong; Ren, Zhiyu; Fu, Huiying; Xiao, Yuting; Tian, Guohui

    2018-06-01

    The CoP/WS2 nanoflake composites were synthesized via the sulfuration and subsequent phosphidation using the pre-prepared WO2.72 nanowires as precursors. Originally, WO2.72 nanowires were prepared and followed by sulfuration to obtain WS2 nanoflakes. The as-prepared WS2 nanoflakes were used as substrates, on which the Co3O4 nanoparticles were uniformly anchored to construct the Co3O4/WS2 nanoflakes. Finally, the Co3O4/WS2 composites were subjected to phosphidation and in-situ converted into CoP/WS2 nanoflakes. Because of the dual functionalities of both CoP and WS2, the abundant interfaces as well as their synergy, the CoP/WS2 nanoflakes exhibited much higher electrocatalytic activity, smaller overpotential (-81 mV), lower Tafel slope (62 mV decade-1), and higher stability toward hydrogen-evolution reaction than those for the single CoP and WS2.

  11. Hierarchical cobalt poly-phosphide hollow spheres as highly active and stable electrocatalysts for hydrogen evolution over a wide pH range

    Science.gov (United States)

    Wu, Tianli; Pi, Mingyu; Wang, Xiaodeng; Guo, Weimeng; Zhang, Dingke; Chen, Shijian

    2018-01-01

    Exploring highly-efficient and low-cost non-noble metal electrocatalyst toward the hydrogen evolution reaction (HER) is highly desired for renewable energy system but remains challenging. In this work, three dimensional hierarchical porous cobalt poly-phosphide hollow spheres (CoP3 HSs) were prepared by topotactic phosphidation of the cobalt-based precursor via vacuum encapsulation technique. As a porous HER cathode, the CoP3 HSs delivers remarkable electrocatalytic performance over the wide pH range. It needs overpotentials of -69 mV and -118 mV with a small Tafel slope of 51 mV dec-1 to obtain current densities of 10 mA cm-2 and 50 mA cm-2, respectively, and maintains its electrocatalytic performance over 30 h in acidic solution. In addition, CoP3 also exhibit superior electrocatalytic performance and stability under neutral and alkaline conditions for the HER. Both experimental measurements and density functional theory (DFT) calculations are performed to explore the mechanism behind the excellent HER performance. The results of our study make the porous CoP3 HSs as a promising electrocatalyst for practical applications toward energy conversion system and present a new way for designing and fabricating HER electrodes through high degree of phosphorization and nano-porous architecture.

  12. Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap

    Directory of Open Access Journals (Sweden)

    Ramesh Karunagaran

    2018-01-01

    Full Text Available Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF and carbon microspheres (N-CMS synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism.

  13. Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap.

    Science.gov (United States)

    Karunagaran, Ramesh; Coghlan, Campbell; Shearer, Cameron; Tran, Diana; Gulati, Karan; Tung, Tran Thanh; Doonan, Christian; Losic, Dusan

    2018-01-28

    Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas) into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR) in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF) and carbon microspheres (N-CMS) synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism.

  14. Perovskites As Electrocatalysts for Alkaline Water Electrolysis

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey Valerievich; De La Osa Puebla, Ana Raquel; Jensen, Jens Oluf

    2014-01-01

    such as X-ray diffraction, electrical conductivity, scanning electron microscopy (SEM), energy dispersive microscopy (EDX) and rotating disk electrode. The perovskites tested in this work were both produced by a ball-milling technique and by an auto-combustion synthesis, which appeared to be a fast...... and robust method for synthesis of perovskites with various chemical compositions1. The electrochemical performance of the materials was tested through pellet pressing of the perovskite powders. This involved in some case a time consuming preparation process. Furthermore the technique should show...... the adequate reproducibility.2 In this work we show the development of the method, which was further used to compare the activity of various electrocatalysts (Figures 1,2). The electrocatalytic activity of all prepared perovskites was tested in 1M KOH at 80 °C, using an ink consisting of potassium exchanged...

  15. Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electrooxidation; Preparacao de eletrocatalisadores PtSnCu/C e PtSn/C e ativacao por processos de dealloying para aplicacao na oxidacao eletroquuimica do etanol

    Energy Technology Data Exchange (ETDEWEB)

    Crisafulli, Rudy

    2013-06-01

    PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H{sub 2}PtCl{sub 6}.6H{sub 2}O, SnCl{sub 2}.2H{sub 2}O and CuCl{sub 2}.2H{sub 2}O as metal sources, NaBH{sub 4} and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, Xray diffraction, transmission electron microscopy, line scan energy dispersive Xray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic effluents were analysed by gas chromatography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the assynthesized electrocatalysts were in the range of <=2 nm to 3 nm and after dealloying there were no significant variations in sizes. The energy dispersive Xray analysis of the as-synthesized electrocatalysts showed a Pt:Sn and Pt:Sn:Cu atomic ratios similar to the nominal values. After chemical and electrochemical dealloying of the electrocatalysts the ranged Pt:Sn and Pt:Sn:Cu atomic ratios showed that Cu and Sn atoms were removed. However, chemical dealloying process proved to be more efficient for removing Cu and electrochemical dealloying for removing Sn. The line scan energy dispersive X-ray analysis showed that acid and electrochemical treatments were efficient to dealloying Cu and/or Sn superficial atoms of

  16. In situ growth of well-ordered NiFe-MOF-74 on Ni foam by Fe2+ induction as an efficient and stable electrocatalyst for water oxidation.

    Science.gov (United States)

    Xing, Jiale; Guo, Kailu; Zou, Zehua; Cai, Minmin; Du, Jing; Xu, Cailing

    2018-06-06

    Well-ordered NiFe-MOF-74 is in situ grown on Ni foam by the induction of Fe2+ and directly used as an OER electrocatalyst. Benefited from the intrinsic open porous structure of MOF-74, the in situ formed MOF arrays and the synergistic effect of Ni and Fe, outstanding water oxidation activity is obtained in alkaline electrolytes with an overpotential of 223 mV at 10 mA cm-2.

  17. Non-platinum electrocatalysts for PEM fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Lee, K.; Zhang, L.; Shi, Z.; Hui, R.; Zhang, J. [National Research Council of Canada, Vancouver, BC (Canada). Inst. For Fuel Cell Innovation

    2008-07-01

    High cost, low reliability and durability are the main barriers preventing widespread commercialization of fuel cells. In particular, the platinum (Pt)-based electrocatalysts used in proton exchange membrane (PEM) fuel cells, including direct methanol fuel cells (DMFCs) are major contributors to the high cost of PEM fuel cells. The Institute for Fuel Cell Innovation at the National Research Council of Canada has developed several new non-Pt electrocatalysts for PEM fuel cell applications. This paper presented the research results on these catalysts, including transition metal macrocycles, chalcogenides, and Ir- or Pd-based alloys. It also described catalyst structure modes via theoretical density functional theory (DFT) calculations. Research activities on these electrocatalysts was summarized in terms of catalytic activity and the oxygen reduction reaction (ORR). Typical catalysts such as cobalt(Co)-polypyrrole (PPy) and the chalcogenides show promising results in terms of catalytic activity and a 4-electron reaction mechanism. Efforts are underway to modify both catalyst structure and synthesis methods in order to further improve catalyst performance. 4 refs., 2 figs.

  18. Nanostructured electrocatalyst for fuel cells : silica templated synthesis of Pt/C composites.

    Energy Technology Data Exchange (ETDEWEB)

    Stechel, Ellen Beth; Switzer, Elise E.; Fujimoto, Cy H.; Atanassov, Plamen Borissov; Cornelius, Christopher James; Hibbs, Michael R.

    2007-09-01

    Platinum-based electrocatalysts are currently required for state-of-the-art fuel cells and represent a significant portion of the overall fuel cell cost. If fuel cell technology is to become competitive with other energy conversion technologies, improve the utilization of precious metal catalysts is essential. A primary focus of this work is on creating enhanced nanostructured materials which improve precious-metal utilization. The goal is to engineer superior electrocatalytic materials through the synthesis, development and investigation of novel templated open frame structures synthesized in an aerosol-based approach. Bulk templating methods for both Pt/C and Pt-Ru composites are evaluated in this study and are found to be limited due to the fact that the nanostructure is not maintained throughout the entire sample. Therefore, an accurate examination of structural effects was previously impossible. An aerosol-based templating method of synthesizing nanostructured Pt-Ru electrocatalysts has been developed wherein the effects of structure can be related to electrocatalytic performance. The aerosol-based templating method developed in this work is extremely versatile as it can be conveniently modified to synthesize alternative materials for other systems. The synthesis method was able to be extended to nanostructured Pt-Sn for ethanol oxidation in alkaline media. Nanostructured Pt-Sn electrocatalysts were evaluated in a unique approach tailored to electrocatalytic studies in alkaline media. At low temperatures, nanostructured Pt-Sn electrocatalysts were found to have significantly higher ethanol oxidation activity than a comparable nanostructured Pt catalyst. At higher temperatures, the oxygen-containing species contribution likely provided by Sn is insignificant due to a more oxidized Pt surface. The importance of the surface coverage of oxygen-containing species in the reaction mechanism is established in these studies. The investigations in this work present

  19. Development of nanosized electrocatalysts for direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Mohamedi, M. [Institut National de la Recherche Scientifique, Varennes, PQ (Canada). Centre de l' Energie, Materiaux et Telecommunications

    2008-07-01

    Fuel cells have been touted as a promising power supply for automotive, portable or stationary use. Although methanol is a strong contender as an alternative fuel, the extensive use of this toxic compound is not practical due to environmental hazards. Ethanol is a good substitute because it has a very positive environmental, health, and safety footprint with no major uncertainties or hazards. Ethanol is a hydrogen-rich liquid which has more energy density than methanol. The C-C bond has a determining effect on fuel cell efficiency and the theoretical energy yield. Therefore, a good electrocatalyst towards the complete oxidation of ethanol must activate the C-C bond breaking while avoiding the poisoning of the catalytic surface by carbon monoxide species that occurs with methanol oxidation. The objective of this study was to develop new catalyst nanoparticles of well-controlled shape, size, and composition with excellent stability and better electrocatalytic activity. This paper described the recent achievements regarding the development of a series of PtxSn100-x catalysts prepared by pulsed laser deposition (PLD). It reported on the effect of several deposition parameters on the structure and properties of the deposited catalysts. It also described how these deposition conditions affect the electrocatalytic response of the resulting materials toward ethanol oxidation. Some interesting periodic oscillations were observed at some catalysts during ethanol electrooxidation. 7 refs., 1 fig.

  20. Preparation of Pt Ru/C electrocatalysts using gamma radiation for application as anode in direct methanol fuel cell

    International Nuclear Information System (INIS)

    Spinace, Estevam V.; Silva, Dionisio F. da; Cruz, Victor A. da; Oliveira Neto, Almir; Machado, Luci D.B.; Pino, Eddy S.; Linardi, Marcelo

    2005-01-01

    PtRu nanoparticles supported on carbon (PtRu/C electrocatalysts) were prepared submitting a water/2-propanol mixture containing the metal ions and the carbon support to gamma radiation. The water/2-propanol (v/v) and the total dose (kGy) were studied. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The methanol electro-oxidation was studied by cyclic voltammetry using the thin porous coating. In the studied conditions, the electrocatalytic activity of the prepared electrocatalysts depend on the water/2-propanol ratio used in the reaction medium. (author)

  1. 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

  2. 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....

  3. Preparation and characterization of electrocatalysts based on palladium for electro-oxidation of alcohols in alkaline medium; Preparacao e caracterizacao de eletrocatalisadores a base de paladio para oxidacao eletroquimica de alcoois em meio alcalino

    Energy Technology Data Exchange (ETDEWEB)

    Brandalise, Michele

    2012-07-01

    In this study Pd/C, Au/C, PdAu/C, PdAuPt/C, PdAuBi/C and PdAuIr/C electrocatalysts were prepared by the sodium borohydride reduction method for the electrochemical oxidation of methanol, ethanol and ethylene glycol. This methodology consists in mix an alkaline solution of sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. The electrocatalysts were characterized by energy dispersive X-ray (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry. The electrochemical oxidation of the alcohols was studied by chronoamperometry using a thin porous coating technique. The mechanism of ethanol electro-oxidation was studied by Fourier Transformed Infrared (FTIR) in situ. The most effective electrocatalysts were tested in alkaline single cells directly fed with methanol, ethanol or ethylene glycol. Preliminary studies showed that the most suitable atomic composition for preparing the ternary catalysts is 50:45:05. Electrochemical data in alkaline medium show that the electrocatalysts PdAuPt/C (50:45:05) showed the better activity for methanol electro oxidation, while PdAuIr/C was the most active for ethanol oxidation and PdAuBi/C (50:45:05) was the most effective for ethylene glycol oxidation in alkaline medium. These results show that the addition of gold in the composition of electrocatalysts increases their catalytic activities. The spectroelectrochemical FTIR in situ data permitted to conclude that C-C bond is not broken and the acetate is formed. (author)

  4. Silver decorated beta-manganese oxide nanorods as an effective cathode electrocatalyst for rechargeable lithium–oxygen battery

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zheng [Center for Fuel Cell Innovation, State Key Laboratory of Material Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Research Center for Engineering Technology of Polymeric Composites of Shanxi Province, School of Materials Science and Engineering, North University of China, TaiYuan 030051 (China); Zhang, Ming; Cheng, Junfang [Center for Fuel Cell Innovation, State Key Laboratory of Material Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Gong, Yingpeng, E-mail: ypgong@hust.edu.cn [Center for Fuel Cell Innovation, State Key Laboratory of Material Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Li, Xi, E-mail: lixi@hust.edu.cn [School of Automation, Huazhong University of Science and Technology, Wuhan 430074 (China); Chi, Bo; Pu, Jian; Jian, Li [Center for Fuel Cell Innovation, State Key Laboratory of Material Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2015-03-25

    Highlights: • Ag/β-MnO{sub 2} was prepared by in-situ composite technique using polymeric additives. • Ag/β-MnO{sub 2} can effectively improve the discharge capacity and the cycle life. • Li{sub 2}O is the main discharge product and no Li{sub 2}CO{sub 3} is formed. - Abstract: In this paper, Ag nanoparticles decorated β-MnO{sub 2} nanorods are studied as cathode catalyst for rechargeable lithium–oxygen battery (LOB). β-MnO{sub 2} nanorods are prepared using a simple hydrothermal method based on MnO{sub 4}{sup −} and the decoration of Ag nanoparticles is performed by in-situ composite technique in the presence of polymeric additives. The as-prepared materials are characterized by XRD, TEM, XPS, BET and Raman spectrum. Electrochemical charging and discharging capacity of β-MnO{sub 2} and Ag/β-MnO{sub 2} electrodes are investigated at the current density of 0.02 mA cm{sup −2} in the voltage window of 2.0–4.0 V. LOB with Ag/β-MnO{sub 2} electrode shows an initial discharge capacity of 873 mA hg{sup −1}{sub (electrode)}, with reversible charge capacity of 811 mA hg{sup −1}{sub (electrode)} while battery with only β-MnO{sub 2} has discharge capacity of 541 mA hg{sup −1}{sub (electrode)} and charge capacity of 445 mA hg{sup −1}{sub (electrode)}. Ag/β-MnO{sub 2} nanocomposite electrode shows good rate capability and cycle stability. After 10 cycles, the capacity of 742 mA hg{sup −1}{sub (electrode)} is still retained at the current density of 0.02 mA cm{sup −2} while only 219 mA hg{sup −1}{sub (electrode)} is retained at 0.5 mA cm{sup −2}. The capacity retention rate is 84.9% and 70.2% at 0.02 and 0.5 mA cm{sup −2}, respectively. During discharging, Li{sub 2}O is the main discharge product and no Li{sub 2}CO{sub 3} is formed. The results show that the electrochemical performance of β-MnO{sub 2} is greatly enhanced when Ag nanoparticles are introduced. And it is highly effective for decreasing the charging potential close to the

  5. Toward highly stable electrocatalysts via nanoparticle pore confinement.

    Science.gov (United States)

    Galeano, Carolina; Meier, Josef C; Peinecke, Volker; Bongard, Hans; Katsounaros, Ioannis; Topalov, Angel A; Lu, Anhui; Mayrhofer, Karl J J; Schüth, Ferdi

    2012-12-19

    The durability of electrode materials is a limiting parameter for many electrochemical energy conversion systems. In particular, electrocatalysts for the essential oxygen reduction reaction (ORR) present some of the most challenging instability issues shortening their practical lifetime. Here, we report a mesostructured graphitic carbon support, Hollow Graphitic Spheres (HGS) with a specific surface area exceeding 1000 m(2) g(-1) and precisely controlled pore structure, that was specifically developed to overcome the long-term catalyst degradation, while still sustaining high activity. The synthetic pathway leads to platinum nanoparticles of approximately 3 to 4 nm size encapsulated in the HGS pore structure that are stable at 850 °C and, more importantly, during simulated accelerated electrochemical aging. Moreover, the high stability of the cathode electrocatalyst is also retained in a fully assembled polymer electrolyte membrane fuel cell (PEMFC). Identical location scanning and scanning transmission electron microscopy (IL-SEM and IL-STEM) conclusively proved that during electrochemical cycling the encapsulation significantly suppresses detachment and agglomeration of Pt nanoparticles, two of the major degradation mechanisms in fuel cell catalysts of this particle size. Thus, beyond providing an improved electrocatalyst, this study describes the blueprint for targeted improvement of fuel cell catalysts by design of the carbon support.

  6. 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.

  7. Carbon-Supported PtRuMo Electrocatalysts for Direct Alcohol Fuel Cells

    Directory of Open Access Journals (Sweden)

    José L.G. Fierro

    2013-10-01

    Full Text Available The review article discusses the current status and recent findings of our investigations on the synthesis and characterization of carbon-supported PtRuMo electrocatalysts for direct alcohol fuel cells. In particular, the effect of the carbon support and the composition on the structure, stability and the activity of the PtRuMo nanoparticles for the electrooxidation of CO, methanol and ethanol have been studied. Different physicochemical techniques have been employed for the analysis of the catalysts structures: X-ray analytical methods (XRD, XPS, TXRF, thermogravimetry (TGA and transmission electron microscopy (TEM, as well as a number of electrochemical techniques like CO adsorption studies, current-time curves and cyclic voltammetry measurements. Furthermore, spectroscopic methods adapted to the electrochemical systems for in situ studies, such as Fourier transform infrared spectroscopy (FTIRS and differential electrochemical mass spectrometry (DEMS, have been used to evaluate the oxidation process of CO, methanol and ethanol over the carbon-supported PtRuMo electrocatalysts.

  8. Controlling electrodeposited ultrathin amorphous Fe hydroxides film on V-doped nickel sulfide nanowires as efficient electrocatalyst for water oxidation

    Science.gov (United States)

    Shang, Xiao; Yan, Kai-Li; Lu, Shan-Shan; Dong, Bin; Gao, Wen-Kun; Chi, Jing-Qi; Liu, Zi-Zhang; Chai, Yong-Ming; Liu, Chen-Guang

    2017-09-01

    Developing cost-effective electrocatalysts with both high activity and stability remains challenging for oxygen evolution reaction (OER) in water electrolysis. Herein, based on V-doped nickel sulfide nanowire on nickel foam (NiVS/NF), we further conduct controllable electrodeposition of Fe hydroxides film on NiVS/NF (eFe/NiVS/NF) to further improve OER performance and stability. For comparison, ultrafast chemical deposition of Fe hydroxides on NiVS/NF (uFe/NiVS/NF) is also utilized. V-doping of NiVS/NF may introduce more active sites for OER, and nanowire structure can expose abundant active sites and facilitate mass transport. Both of the two depositions generate amorphous Fe hydroxides film covering on the surface of nanowires and lead to enhanced OER activities. Furthermore, electrodeposition strategy realizes uniform Fe hydroxides film on eFe/NiVS/NF confirmed by superior OER activity of eFe/NiVS/NF than uFe/NiVS/NF with relatively enhanced stability. The OER activity of eFe/NiVS/NF depends on various electrodepositon time, and the optimal time (15 s) is obtained with maximum OER activity. Therefore, the controllable electrodeposition of Fe may provide an efficient and simple strategy to enhance the OER properties of electrocatalysts.

  9. Evaluation of the Optimum Composition of Low-Temperature Fuel Cell Electrocatalysts for Methanol Oxidation by Combinatorial Screening.

    Science.gov (United States)

    Antolini, Ermete

    2017-02-13

    Combinatorial chemistry and high-throughput screening represent an innovative and rapid tool to prepare and evaluate a large number of new materials, saving time and expense for research and development. Considering that the activity and selectivity of catalysts depend on complex kinetic phenomena, making their development largely empirical in practice, they are prime candidates for combinatorial discovery and optimization. This review presents an overview of recent results of combinatorial screening of low-temperature fuel cell electrocatalysts for methanol oxidation. Optimum catalyst compositions obtained by combinatorial screening were compared with those of bulk catalysts, and the effect of the library geometry on the screening of catalyst composition is highlighted.

  10. 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

  11. 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.

  12. Design of oxide electrocatalysts for efficient conversion of CO2 into liquid fuels

    DEFF Research Database (Denmark)

    Bhowmik, Arghya

    catalyst development have obtained limited success due to adsorbate scaling relations on metallic surfaces. Preliminary experimental results indicate rutile oxide catalysts are active at very low overpotential, although the scientific understanding is missing. This thesis aims at delivering knowledge....... It is concluded that under experimental condition, CO* coverage is necessary for methanol evolution from RuO2 electrocatalyst, but very high coverage lead to evolution of formic acid and hydrogen together. Building on the understanding of descriptors for CO2RR activity and CO* spectator effects, a new method...... metal atom composition as well as different CO* coverages is done. It is identified that monolayer or lesser amount of iridium oxide on RuO2 catalyst can have a methanol onset potential of -0.2 V below RHE. This is attributed to a combination of ligand effect and adsorbate interaction. Through...

  13. Electrochemical evaluation of electrocatalysts for fuel cell applications : a practical approach

    Energy Technology Data Exchange (ETDEWEB)

    Atwan, M.H. [General Motors R and D Technical Center, Warren, MI (United States); Gyenge, E.L. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Northwood, D.O. [Windsor Univ., ON (Canada). Dept. of Mechanical, Automotive and Materials Engineering

    2010-07-01

    Various electrochemical techniques were used to investigate supported nano-size electrocatalysts during the oxidation of a specific fuel for fuel cell applications. Cyclic voltammetry (CV) on static and dynamic rotating disc electrodes (RDE) and fuel cell station tests demonstrated that the most active catalyst showed the most negative oxidation peak potential. A Tafel equation indicated that a low anodic/cathodic overpotential was a clear indication of higher catalytic activity. The lower overpotential was achieved for a specific current load by ensuring a low Tafel slope and as high an exchange current density as possible. The RDE and fuel cell station tests showed that the best performance was recorded for electrocatalysts with the Tafel slope values and exchange current densities that gave rise to the lowest overpotential. The study demonstrated that RDE and CV can be used to reliably assess electrocatalysts prior to full fuel cell testing. 52 refs., 3 tabs., 6 figs.

  14. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.

    Science.gov (United States)

    McCrory, Charles C L; Jung, Suho; Peters, Jonas C; Jaramillo, Thomas F

    2013-11-13

    Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.

  15. Pt-Ru nanoparticles supported on functionalized carbon as electrocatalysts for the methanol oxidation

    International Nuclear Information System (INIS)

    Salgado, J.R.C.; Fernandes, J.C.S.; Botelho do Rego, A.M.; Ferraria, A.M.; Duarte, R.G.; Ferreira, M.G.S.

    2011-01-01

    Highlights: → The functionalized carbon using acid solutions contains surface oxygenated groups. → Uniform dispersion of PtRu nanoparticles on the carbon surface was achieved. → Physical analysis showed the formation of PtRu alloy catalysts on functionalized carbon. → PtRu alloy catalysts on functionalized carbon enhanced the methanol oxidation rate. - Abstract: Platinum-ruthenium alloy electrocatalysts, for methanol oxidation reaction, were prepared on carbons thermally treated in helium atmosphere or chemically functionalized in H 2 O 2 , or in HNO 3 + H 2 SO 4 or in HNO 3 solutions. The functionalized carbon that is produced using acid solutions contains more surface oxygenated functional groups than carbon treated with H 2 O 2 solution or HeTT. The XRD/HR-TEM analysis have showed the existence of a higher alloying degree for Pt-Ru electrocatalysts supported on functionalized carbon, which present superior electrocatalytic performance, assessed by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy, as compared to electrocatalysts on unfunctionalized carbon. It also was found that Pt-Ru alloy electrocatalysts on functionalized carbon improve the reaction rate compared to Pt-Ru on carbons treated with H 2 O 2 solution and thermally. A mechanism is discussed, where oxygenated groups generated from acid functionalization of carbon and adsorbed on Pt-Ru electrocatalysts are considered to enhance the electrocatalytic activity of the methanol oxidation reaction.

  16. Preparation and characterization of PT-rare earth/C electrocatalysts for PEM fuel cells

    International Nuclear Information System (INIS)

    Santoro, Thais Aranha de Barros

    2009-01-01

    Pt-rare earth/C electrocatalysts (rare earth = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Lu) were prepared (20 wt.% and Pt-to-RE atomic ratio of 50:50) by an alcohol reduction process using H 2 PtCl 6 .6H 2 O (Aldrich) and rare earth (III) chlorides (Aldrich) as metal sources, ethylene glycol as solvent and reducing agent, and Vulcan XC72 as support. The electrocatalysts were characterized by Energy Dispersive X-ray Spectroscopy (EDX), X-Ray Diffractometry (XRD) and Transmission Electron Microscopy (TEM). The energy dispersive x-ray spectroscopy analysis showed that the Pt-Rare Earth atomic ratios obtained for all electrocatalysts were similar to those used in the preparations. In all diffractograms, it was observed a broad peak at about 25 degree which was associated to the Vulcan XC72 support material and four peaks at approximately 28=40 degree, 47 degree, 67 degree and 82 degree, which were associated to the (111), (200), (220), (311), and (222) planes, respectively, of the face-centered cubic (fcc) structure characteristic of platinum and platinum alloys. For the Pt-Rare Earth/C electrocatalysts, it was also observed peaks related to the rare earth oxides on the X ray diffractograms. PtLa/C electrocatalysts were prepared at different atomic ratio. Transmission electronic microscopy micrographs of electrocatalysts showed a reasonable distribution of the Pt particles on the carbon support with some agglomerations, which is in agreement with x-ray diffractometry result. The performance for CO, methanol and ethanol oxidation was investigated by cyclic voltammetry, chronoamperometry and Fourier transform infrared spectroscopy spectroscopy. The electrocatalytic activity of the Pt-Rare Earth/C electro catalyst, specially PtLa/C, were higher than that of the Pt/C electrocatalyst. Fourier transform infrared spectroscopy studies for ethanol oxidation on Pt-Rare Earth/C electrocatalyst showed that acetaldehyde and acetic acid were the main products. The PtLa/C (30

  17. Ternary mixed metal Fe-doped NiCo2O4 nanowires as efficient electrocatalysts for oxygen evolution reaction

    Science.gov (United States)

    Yan, Kai-Li; Shang, Xiao; Li, Zhen; Dong, Bin; Li, Xiao; Gao, Wen-Kun; Chi, Jing-Qi; Chai, Yong-Ming; Liu, Chen-Guang

    2017-09-01

    Designing mixed metal oxides with unique nanostructures as efficient electrocatalysts for water electrolysis has been an attractive approach for the storage of renewable energies. The ternary mixed metal spinel oxides FexNi1-xCo2O4 (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, 1) have been synthesized by a facile hydrothermal approach and calcination treatment using nickel foam as substrate. Fe/Ni ratios have been proved to affect the nanostructures of FexNi1-xCo2O, which imply different intrinsic activity for oxygen evolution reaction (OER). SEM images show that Fe0.5Ni0.5Co2O4 has the uniform nanowires morphology with about 30 nm of the diameter and 200-300 nm of the length. The OER measurements show that Fe0.5Ni0.5Co2O4 exhibits the better electrocatalytic performances with lower overpotential of 350 mV at J = 10 mA cm-2. In addition, the smaller Tafel slope of 27 mV dec-1 than other samples with different Fe/Ni ratios for Fe0.5Ni0.5Co2O4 is obtained. The improved OER activity of Fe0.5Ni0.5Co2O4 may be attributed to the synergistic effects from ternary mixed metals especially Fe-doping and the uniform nanowires supported on NF. Therefore, synthesizing Fe-doped multi-metal oxides with novel nanostructures may be a promising strategy for excellent OER electrocatalysts and it also provides a facile way for the fabrication of high-activity ternary mixed metal oxides electrocatalysts.

  18. Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Xiao-Ping; Dai, Hong-Bin, E-mail: mshbdai@scut.edu.cn; Wu, Lin-Song; Wang, Ping, E-mail: mspwang@scut.edu.cn

    2017-07-01

    Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N{sub 2}H{sub 4} electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N{sub 2}H{sub 4} as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

  19. Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

    International Nuclear Information System (INIS)

    Wen, Xiao-Ping; Dai, Hong-Bin; Wu, Lin-Song; Wang, Ping

    2017-01-01

    Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N_2H_4 electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N_2H_4 as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

  20. Pt-Ru/CeO2/carbon nanotube nanocomposites: an efficient electrocatalyst for direct methanol fuel cells.

    Science.gov (United States)

    Sun, Zhenyu; Wang, Xiang; Liu, Zhimin; Zhang, Hongye; Yu, Ping; Mao, Lanqun

    2010-07-20

    Pt-Ru/CeO(2)/multiwalled carbon nanotube (MWNT) electrocatalysts were prepared using a rapid sonication-facilitated deposition method and were characterized by X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and voltammetry. Morphological characterization by TEM revealed that CeO(2) nanoparticles (NPs) were in intimate contact with Pt-Ru NPs, and both were highly dispersed on the exteriors of nanotubes with a small size and a very narrow size distribution. Compared with the Pt-Ru/MWNT and Pt/MWNT electrocatalysts, the as-prepared Pt-Ru/CeO(2)/MWNT exhibited a significantly improved electrochemically active surface area (ECSA) and a remarkably enhanced activity toward methanol oxidation. The effects of the Pt-Ru loading and the Pt-to-Ru molar ratio on the electrocatalytic activity of Pt-Ru/CeO(2)/MWNT for methanol oxidation were investigated. We found that a maximum activity toward methanol oxidation reached at the 10 wt % of Pt-Ru loading and 1:1 of Pt-to-Ru ratio. Moreover, the role of CeO(2) in the catalysts for the enhancement of methanol oxidation was discussed in terms of both bifunctional mechanism and electronic effects.

  1. 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.

  2. MnO2/MCMB electrocatalyst for all solid-state alkaline zinc-air cells

    International Nuclear Information System (INIS)

    Zhang, G.Q.; Zhang, X.G.

    2004-01-01

    Nanostructured MnO 2 /mesocarbon microbeads (MCMB) composite has been prepared successfully for use in zinc-air cell as electrocatalyst for oxygen reaction. The scanning electron microscope (SEM) images showed that the MnO 2 nanorods were formed and covered on the surface of MCMB in bird's nest morphology. X-ray diffraction (XRD) pattern indicated that the MnO 2 has the hollandite structure with a composition approximating KMn 8 O 16 . By the cathodic polarization curve tests, the nanostructured material demonstrated excellent electrocatalytic activity as a kind of oxygen electrode electrocatalyst compared with electrolytic MnO 2 . An all solid-state zinc-air cell has been fabricated with this material as electrocatalyst for oxygen electrode and potassium salt of cross-linked poly(acrylic acid) as an alkaline polymer gel electrolyte. The cell has good discharge characteristics at room temperature

  3. Carbon supported nanoparticles Pt Ru (Pt Ru/C electrocatalysts) prepared using electron beam irradiation; Preparacao de nanoparticulas de PtRu suportadas em carbono (eletrocatalisadores PtRu/C) utilizando feixe de eletrons

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Dionisio F. da; Oliveira Neto, Almir; Pino, Eddy S.; Linardi, Marcelo; Spinace, Estevam V. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Programa de Celulas a Combustivel], e-mail: espinace@ipen.br, e-mail: dfsilva@ipen.br

    2006-07-01

    Carbon-supported Pt Ru (electrocatalysts PtRu/C nanoparticles) were prepared submitting a water/ethylene glycol mixture containing Pt(IV) and Ru(III) ions and the carbon support to electron beam irradiation. The PtRu/C electrocatalysts were characterized by EDX, XRD and cyclic voltammetry and tested for methanol electro-oxidation aiming fuel cell application. The obtained PtRu/C electrocatalysts were more active for methanol electro-oxidation than the commercial PtRu/C ETEK electrocatalyst at ambient temperature. (author)

  4. Evaluation of Pd Nanoparticle-Decorated CeO2-MWCNT Nanocomposite as an Electrocatalyst for Formic Acid Fuel Cells

    Science.gov (United States)

    Saleem, Junaid; Safdar Hossain, SK.; Al-Ahmed, Amir; Rahman, Ateequr; McKay, Gordon; Hossain, Mohammed M.

    2018-04-01

    In this work, CeO2-modified Pd/CeO2-carbon nanotube (CNT) electrocatalyst for the electro-oxidation of formic acid has been investigated. The support CNT was first modified with different amounts (5-30 wt.%) of CeO2 using a precipitation-deposition method. The electrocatalysts were developed by dispersing Pd on the CeO2-CNT supports using the borohydride reduction method. The synthesized electrocatalysts were analyzed for composition, morphology and electronic structure using x-ray diffraction (XRD), scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) techniques. The formation of Pd nanoparticles on the CeO2-CNT support was confirmed using TEM. The activity of Pd/CeO2-CNT and of Pd-CNT samples upon oxidation of formic acid was evaluated by using carbon monoxide stripping voltammetry, cyclic voltammetry, and chronoamperometry. The addition of moderate amounts of cerium oxide (up to 10 wt.%) significantly improved the activity of Pd/CeO2-CNT compared to the unmodified Pd-CNT. Pd/10 wt.% CeO2-CNT showed a current density of 2 A mg-1, which is ten times higher than that of the unmodified Pd-CNT (0.2 A mg-1). Similarly, the power density obtained for Pd/10 wt.% CeO2-CNT in an air-breathing formic acid fuel cell was 6.8 mW/cm2 which is two times higher than Pd-CNT (3.2 mW/cm2), thus exhibiting the promotional effects of CeO2 to Pd/CeO2-CNT. A plausible justification for the improved catalytic performance and stability is provided in the light of the physical characterization results.

  5. Ethanol Electro-oxidation on Novel Electrocatalyst PtVSnO2/C in Acidic Media

    International Nuclear Information System (INIS)

    Jin, Biyao; Sun, Hongyan; Huang, Minghui; Zhao, Lianhua

    2014-01-01

    Graphical abstract: - Highlights: • Novel electrocatalyst PtVSnO 2 /C is synthesized by a modified Bönnemann method. • Adding Sn and V changes the geometric and electronic structure of Pt. • PtVSnO 2 /C improved catalytic activity and the ability of resisting CO poisoning. - Abstract: A novel carbon-supported Pt-V-SnO 2 catalyst is prepared by a modified Bönnemann method. Pt/C, PtV/C, and PtSnO 2 /C are used for comparative analysis to study PtVSnO 2 /C in terms of its structure and electrocatalytic activity for the ethanol oxidation reaction (EOR). Characterization of its structural properties by X-ray diffraction (XRD) and transmission electron microscopy (TEM) is described. It is shown that the Pt lattice parameter decreases with the addition of V but increases with the addition of Sn in the PtVSn/C catalyst. TEM analysis reveals that the prepared catalyst particles are in the nanosize range (2-4 nm). EDS confirms the atomic compositions of the synthesized catalysts to be similar to the nominal values. The electrocatalytic activities are characterized by cyclic voltammetry (CV) and amperometric i-t curve measurement (i-t) techniques. The incorporation of a small amount of V in the PtSnO 2 /C electrocatalyst leads to higher activity for the ethanol oxidation reaction at room temperature. According to the Arrhenius equation, the apparent activation energy of PtVSnO 2 /C (3:1:3) for EOR is the lowest among the studied catalysts, which may be attributed to a synergistic effect between Sn and V

  6. Gently reduced graphene oxide incorporated into cobalt oxalate rods as bifunctional oxygen electrocatalyst

    International Nuclear Information System (INIS)

    Phihusut, Doungkamon; Ocon, Joey D.; Jeong, Beomgyun; Kim, Jin Won; Lee, Jae Kwang; Lee, Jaeyoung

    2014-01-01

    Graphical abstract: - Abstract: Water-oxygen electrochemistry is at the heart of key renewable energy technologies (fuel cells, electrolyzers, and metal-air batteries) due to the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Although much effort has been devoted to the development of improved bifunctional electrocatalysts, an inexpensive, highly active oxygen electrocatalyst, however, remains to be a challenge. In this paper, we present a facile and robust method to create gently reduced graphene oxide incorporated into cobalt oxalate microstructures (CoC 2 O 4 /gRGO) and demonstrate its excellent and stable electrocatalytic activity in both OER and ORR, arising from the inherent properties of the components and their physicochemical interaction. Our synthesis technique also explores a single pot method to partially reduce graphene oxide and form CoC 2 O 4 structures while maintaining the solution processability of reduced graphene oxide. While the OER activity of CoC 2 O 4 /gRGO is exclusively due to CoC 2 O 4 , which transformed into OER-active Co species, the combination with gRGO significantly improves OER stability. On the other hand, CoC 2 O 4 /gRGO exhibits synergistic effect towards ORR, via a quasi-four-electron pathway, leading to a slightly higher ORR limiting current than Pt/C. Remarkably, gRGO offers dual functionality, contributing to ORR activity via the N-functional groups and also enhancing OER stability through the gRGO coating around CoC 2 O 4 structures. Our results suggest a new class of metal-carbon composite that has the potential to be alternative bifunctional catalysts for regenerative fuel cells and metal-air batteries

  7. Raman Spectroscopy and Electrochemical Investigations of Pt Electrocatalyst Supported on Carbon Prepared through Plasma Pyrolysis of Natural Gas

    Directory of Open Access Journals (Sweden)

    Tereza Cristina Santos Evangelista

    2015-01-01

    Full Text Available Physicochemical and electrochemical characterisations of Pt-based electrocatalysts supported on carbon (Vulcan carbon, C1, and carbon produced by plasma pyrolysis of natural gas, C2 toward ethanol electrooxidation were investigated. The Pt20/C180 and Pt20/C280 electrocatalysts were prepared by thermal decomposition of polymeric precursors at 350°C. The electrochemical and physicochemical characterisations of the electrocatalysts were performed by means of X-ray diffraction (XRD, transmission electron microscope (TEM, Raman scattering, cyclic voltammetry, and chronoamperometry tests. The XRD results show that the Pt-based electrocatalysts present platinum metallic which is face-centered cubic structure. The results indicate that the Pt20/C180 electrocatalyst has a smaller particle size (10.1–6.9 nm compared with the Pt20/C280 electrocatalyst; however, the Pt20/C280 particle sizes are similar (12.8–10.4 nm and almost independent of the reflection planes, which suggests that the Pt crystallites grow with a radial shape. Raman results reveal that both Vulcan carbon and plasma carbon are graphite-like materials consisting mostly of sp2 carbon. Cyclic voltammetry and chronoamperometry data obtained in this study indicate that the deposition of Pt on plasma carbon increases its electrocatalytic activity toward ethanol oxidation reaction.

  8. CuZn Alloy- Based Electrocatalyst for CO2 Reduction

    KAUST Repository

    Alazmi, Amira

    2014-06-01

    ABSTRACT CuZn Alloy- Based Electrocatalyst for CO2 Reduction Amira Alazmi Carbon dioxide (CO2) is one of the major greenhouse gases and its emission is a significant threat to global economy and sustainability. Efficient CO2 conversion leads to utilization of CO2 as a carbon feedstock, but activating the most stable carbon-based molecule, CO2, is a challenging task. Electrochemical conversion of CO2 is considered to be the beneficial approach to generate carbon-containing fuels directly from CO2, especially when the electronic energy is derived from renewable energies, such as solar, wind, geo-thermal and tidal. To achieve this goal, the development of an efficient electrocatalyst for CO2 reduction is essential. In this thesis, studies on CuZn alloys with heat treatments at different temperatures have been evaluated as electrocatalysts for CO2 reduction. It was found that the catalytic activity of these electrodes was strongly dependent on the thermal oxidation temperature before their use for electrochemical measurements. The polycrystalline CuZn electrode without thermal treatment shows the Faradaic efficiency for CO formation of only 30% at applied potential ~−1.0 V vs. RHE with current density of ~−2.55 mA cm−2. In contrast, the reduction of oxide-based CuZn alloy electrode exhibits 65% Faradaic efficiency for CO at lower applied potential about −1.0 V vs. RHE with current density of −2.55 mA cm−2. Furthermore, stable activity was achieved over several hours of the reduction reaction at the modified electrodes. Based on electrokinetic studies, this improvement could be attributed to further stabilization of the CO2•− on the oxide-based Cu-Zn alloy surface.

  9. Engineering Platinum Alloy Electrocatalysts in Nanoscale for PEMFC Application

    Energy Technology Data Exchange (ETDEWEB)

    He, Ting [Idaho National Laboratory

    2016-03-01

    Fuel cells are expected to be a key next-generation energy source used for vehicles and homes, offering high energy conversion efficiency and minimal pollutant emissions. However, due to large overpotentials on anode and cathode, the efficiency is still much lower than theoretically predicted. During the past decades, considerable efforts have been made to investigate synergy effect of platinum alloyed with base metals. But, engineering the alloy particles in nanoscale has been a challenge. Most important challenges in developing nanostructured materials are the abilities to control size, monodispersity, microcomposition, and even morphology or self-assembly capability, so called Nanomaterials-by-Design, which requires interdisciplinary collaborations among computational modeling, chemical synthesis, nanoscale characterization as well as manufacturing processing. Electrocatalysts, particularly fuel cell catalysts, are dramatically different from heterogeneous catalysts because the surface area in micropores cannot be electrochemically controlled on the same time scale as more transport accessible surfaces. Therefore, electrocatalytic architectures need minimal microporous surface area while maximizing surfaces accessible through mesopores or macropores, and to "pin" the most active, highest performance physicochemical state of the materials even when exposed to thermodynamic forces, which would otherwise drive restructuring, crystallization, or densification of the nanoscale materials. In this presentation, results of engineering nanoscale platinum alloy particles down to 2 ~ 4 nm will be discussed. Based on nature of alloyed base metals, various synthesis technologies have been studied and developed to achieve capabilities of controlling particle size and particle microcomposition, namely, core-shell synthesis, microemulsion technique, thermal decomposition process, surface organometallic chemical method, etc. The results show that by careful engineering the

  10. Preparation of PtRu/C anode electrocatalysts using gamma radiation for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Silva, Dionisio Fortunato da

    2006-01-01

    Pt Ru/C (carbon-supported Pt Ru nanoparticles) anode electrocatalysts were prepared using radiolytic process (gamma radiation) and tested for methanol electro-oxidation. In this process, water/2-propanol and water/ethylene glycol solutions containing the metallic ions and the carbon support were submitted to gamma radiation under stirring. The water/alcohol ratio (v/v) and the total dose (kGy) were studied. A nominal Pt Ru atomic ratio of 50:50 were used in all experiments. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV). The electro-oxidation of methanol was studied by cyclic voltammetry using the thin porous coating technique. The electrocatalysts prepared in water/2-propanol showed crystallite size in the range of 3-5 nm and Pt Ru atomic ratio of 50:50. The electrocatalysts prepared in water/ethylene glycol showed crystallite size (2-3 nm) smaller than the ones obtained in water/2-propanol, however, the Pt Ru atomic ratios obtained were approximately 80:20, showing that only part of ruthenium ions were reduced. For methanol oxidation the electrocatalytic activity depends on the water/2-propanol and water/ethylene glycol ratio used in the reaction medium. The electrocatalysts prepared in water/2-propanol showed inferior performance to the ones prepared in water/ethylene glycol, which showed similar or superior performances (amperes per gram of platinum) to the commercial electrocatalyst from E-TEK. (author)

  11. 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.

  12. A Pt-Co3O4-CD electrocatalyst with enhanced electrocatalytic performance and resistance to CO poisoning achieved by carbon dots and Co3O4 for direct methanol fuel cells.

    Science.gov (United States)

    Sun, Yue; Zhou, Yunjie; Zhu, Cheng; Hu, Lulu; Han, Mumei; Wang, Aoqi; Huang, Hui; Liu, Yang; Kang, Zhenhui

    2017-05-04

    Highly efficient electrocatalysts remain huge challenges in direct methanol fuel cells (DMFCs). Here, a Pt-Co 3 O 4 -CDs/C composite was fabricated as an anode electrocatalyst with low Pt content (12 wt%) by using carbon dots (CDs) and Co 3 O 4 nanoparticles as building blocks. The Pt-Co 3 O 4 -CDs/C composite catalyst shows a significantly enhanced electrocatalytic activity (1393.3 mA mg -1 Pt), durability (over 4000 s) and CO-poisoning tolerance. The superior catalytic activity should be attributed to the synergistic effect of CDs, Pt and Co 3 O 4 . Furthermore, the Pt-Co 3 O 4 -CDs/C catalyst was integrated into a single cell, which exhibits a maximum power density of 45.6 mW cm -2 , 1.7 times the cell based on the commercial 20 wt% Pt/C catalyst.

  13. Activity, Performance, and Durability for the Reduction of Oxygen in PEM Fuel Cells, of Fe/N/C Electrocatalysts Obtained from the Pyrolysis of Metal-Organic-Framework and Iron Porphyrin Precursors

    International Nuclear Information System (INIS)

    Yang, Lijun; Larouche, Nicholas; Chenitz, Régis; Zhang, Gaixia; Lefèvre, Michel; Dodelet, Jean-Pol

    2015-01-01

    Graphical abstract: TOC After a first decay common to all electrocatalysts, only NC Por-0.8 -1150 Ar + NH3 shows an improvement in durability attributable to a decrease in water flooding its catalytic sites, particularly those located in micropores. - Abstract: Fe/N/C type catalysts have been produced by ballmilling ZIF-8 (a metal-organic-framework) and a chloroiron-tetramethoxyporphyrin (ClFeTMPP). The resulting material was first pyrolyzed in Ar at temperatures ranging from 850 to 1150 °C, then in NH 3 at 950 °C in order to produce two series of catalysts: the Ar and the Ar + NH 3 ones. They were labeled NC Por-x-T Ar or NC Por-x-T Ar + NH 3 , where x is the nominal Fe loading in wt% and T is the temperature of the first pyrolysis in Ar. At 80 °C in H 2 /O 2 fuel cell, the most active and performing catalyst is NC Por-0.8-1050 Ar + NH 3 . All NC Por-0.8-T Ar + NH 3 catalysts with T comprised between 850 and 1050 °C display the same instability behavior. The only catalyst showing an improvement in durability is NC Por-0.8-1150 Ar + NH 3 . It is proposed that the drastic change in durability upon increasing the first pyrolysis temperature, from 1050 to 1150 °C in Ar, is attributable to an important decrease in the heteroatom content (a drop of 32% for both N and O atoms) of the catalyst upon graphitization, reducing the hydrophilic character of its carbonaceous support and decreasing the possibility of water flooding its catalytic sites, particularly the sites located in micropores

  14. Metal- and Carbon-Based Materials as Heterogeneous Electrocatalysts for CO₂ Reduction.

    Science.gov (United States)

    Khan, Azam; Ullah, Haseeb; Nasir, Jamal Abdul; Shuda, Suzanne; Chen, Wei; Khan, M Abdullah

    2018-05-01

    Climate change caused by continuous rising level of CO2 and the depletion of fossil fuels reserves has made it highly desirable to electrochemically convert CO2 into fuels and commodity chemicals. Implementing this approach will close the carbon cycle by recycling CO2 providing a sustainable way to store energy in the chemical bonds of portable molecular fuels. In order to make the process commercially viable, the challenge of slow kinetics of CO2 electroreduction and low energy efficiency of the process need to be addressed. To this end, this review summarizes the progress made in the past few years in the development of heterogeneous electrocatalysts with a focus on nanostructured material for CO2 reduction to CO, HCOOH/HCOO-, CH2O, CH4, H2C2O4/HC2O-4, C2H4, CH3OH, CH3CH2OH, etc. The electrocatalysts presented here are classified into metals, metal alloys, metal oxides, metal chalcogenides and carbon based materials on the basis of their elemental composition, whose performance is discussed in light of catalyst activity, product selectivity, Faradaic efficiency (FE), catalytic durability and in selected cases mechanism of CO2 electroreduction. The effect of particle size, morphology and solution-electrolyte type and composition on the catalyst property/activity is also discussed and finally some strategies are proposed for the development of CO2 electroreduction catalysts. The aim of this article is to review the recent advances in the field of CO2 electroreduction in order to further facilitate research and development in this area.

  15. Advancing semiconductor-electrocatalyst systems: application of surface transformation films and nanosphere lithography.

    Science.gov (United States)

    Brinkert, Katharina; Richter, Matthias H; Akay, Ömer; Giersig, Michael; Fountaine, Katherine T; Lewerenz, Hans-Joachim

    2018-05-24

    Photoelectrochemical (PEC) cells offer the possibility of carbon-neutral solar fuel production through artificial photosynthesis. The pursued design involves technologically advanced III-V semiconductor absorbers coupled via an interfacial film to an electrocatalyst layer. These systems have been prepared by in situ surface transformations in electrochemical environments. High activity nanostructured electrocatalysts are required for an efficiently operating cell, optimized in their optical and electrical properties. We demonstrate that shadow nanosphere lithography (SNL) is an auspicious tool to systematically create three-dimensional electrocatalyst nanostructures on the semiconductor photoelectrode through controlling their morphology and optical properties. First results are demonstrated by means of the photoelectrochemical production of hydrogen on p-type InP photocathodes where hitherto applied photoelectrodeposition and SNL-deposited Rh electrocatalysts are compared based on their J-V and spectroscopic behavior. We show that smaller polystyrene particle masks achieve higher defect nanostructures of rhodium on the photoelectrode which leads to a higher catalytic activity and larger short circuit currents. Structural analyses including HRSEM and the analysis of the photoelectrode surface composition by using photoelectron spectroscopy support and complement the photoelectrochemical observations. The optical performance is further compared to theoretical models of the nanostructured photoelectrodes on light scattering and propagation.

  16. 3D structured Mo-doped Ni3S2 nanosheets as efficient dual-electrocatalyst for overall water splitting

    Science.gov (United States)

    Wu, Chengrong; Liu, Bitao; Wang, Jun; Su, Yongyao; Yan, Hengqing; Ng, Chuntan; Li, Cheng; Wei, Jumeng

    2018-05-01

    Searching for a cost-effective, high efficient and stable bifunctional electrocatalyst for overall water-splitting is critical to renewable energy systems. In this study, three-dimensional (3D) curved nanosheets of Mo-doped Ni3S2 grown on nickel foam were successfully synthesized via a one-step hydrothermal process. The hydrogen-evolution reaction (HER) and the oxygen-evolution reaction (OER) in alkaline environment of this 3D catalyst are investigated in detail. The results show that it possesses lower overpotential, high current densities and small Tafel slopes both in OER and HER. For HER, the catalysts show excellent electrochemical performance, demonstrating a low over-potential of 212 mV at 10 mA cm-2 with a large decrease of 127 mV compared to the undoped Ni3S2. And it also shows a lower overpotential of 260 mV at 10 mA cm-2 which decreases 30 mV for OER. In addition, it is only need 1.67 V for the overall water splitting at 10 mA cm-2 which is 70 mV. It found that the Mo element would change the morphology of Ni3S2 and induce much more active sites for HER and OER. The as-prepared Mo-doped Ni3S2 bi-functional electrocatalyst could act as the promising electrode materials for water splitting.

  17. Engineering the Activity and Stability of Pt-Alloy Cathode Fuel-Cell Electrocatalysts by Tuning the Pt-Pt Distance

    DEFF Research Database (Denmark)

    Escribano, Maria Escudero; Malacrida, Paolo; Vej-Hansen, Ulrik Grønbjerg

    2014-01-01

    for enhancing the cathode activity is to alloy Pt with transition metals [1-2]. However, alloys of Pt and late transition metals are typically unstable under fuel-cell conditions. Herein, we present experimental and theoretical studies showing the trends in activity and stability of novel cathode catalysts...

  18. Nanostructured carbon-supported Pd electrocatalysts for ethanol oxidation: synthesis and characterization

    International Nuclear Information System (INIS)

    Gacutan, E M; Tongol, B J; Climaco, M I; Telan, G J; Malijan, F; Hsu, H Y; Garcia, J; Fulo, H

    2012-01-01

    The need to lower the construction cost of fuel cells calls for the development of non-Pt based electrocatalysts. Among others, Pd has emerged as a promising alternative to Pt for fuel cell catalysis. This research aims to investigate the synthesis and characterization of nanostructured Pd-based catalysts dispersed on carbon support as anode materials in direct ethanol fuel cells. For the preparation of the first Pd-based electrocatalyst, palladium nanoparticles (NPs) were synthesized via oleylamine (OAm)-mediated synthesis and precursor method with a mean particle size of 3.63 ± 0.59 nm as revealed by transmission electron microscopy (TEM). Carbon black was used as a supporting matrix for the OAm-capped Pd NPs. Thermal annealing and acetic acid washing were used to remove the OAm capping agent. To evaluate the electrocatalytic activity of the prepared electrocatalyst towards ethanol oxidation, cyclic voltammetry (CV) studies were performed using 1.0 M ethanol in basic medium. The CV data revealed the highest peak current density of 11.05 mA cm −2 for the acetic acid-washed Pd/C electrocatalyst. Meanwhile, the fabrication of the second Pd-based electrocatalyst was done by functionalization of the carbon black support using 3:1 (v/v) H 2 SO 4 :HNO 3 . The metal oxide, NiO, was deposited using precipitation method while polyol method was used for the deposition of Pd NPs. X-ray diffraction (XRD) analysis revealed that the estimated particle size of the synthesized catalysts was at around 9.0–15.0 nm. CV results demonstrated a 36.7% increase in the catalytic activity of Pd–NiO/C (functionalized) catalyst towards ethanol oxidation compared to the non-functionalized catalyst. (paper)

  19. Nanostructured carbon-supported Pd electrocatalysts for ethanol oxidation: synthesis and characterization

    Science.gov (United States)

    Gacutan, E. M.; Climaco, M. I.; Telan, G. J.; Malijan, F.; Hsu, H. Y.; Garcia, J.; Fulo, H.; Tongol, B. J.

    2012-12-01

    The need to lower the construction cost of fuel cells calls for the development of non-Pt based electrocatalysts. Among others, Pd has emerged as a promising alternative to Pt for fuel cell catalysis. This research aims to investigate the synthesis and characterization of nanostructured Pd-based catalysts dispersed on carbon support as anode materials in direct ethanol fuel cells. For the preparation of the first Pd-based electrocatalyst, palladium nanoparticles (NPs) were synthesized via oleylamine (OAm)-mediated synthesis and precursor method with a mean particle size of 3.63 ± 0.59 nm as revealed by transmission electron microscopy (TEM). Carbon black was used as a supporting matrix for the OAm-capped Pd NPs. Thermal annealing and acetic acid washing were used to remove the OAm capping agent. To evaluate the electrocatalytic activity of the prepared electrocatalyst towards ethanol oxidation, cyclic voltammetry (CV) studies were performed using 1.0 M ethanol in basic medium. The CV data revealed the highest peak current density of 11.05 mA cm-2 for the acetic acid-washed Pd/C electrocatalyst. Meanwhile, the fabrication of the second Pd-based electrocatalyst was done by functionalization of the carbon black support using 3:1 (v/v) H2SO4:HNO3. The metal oxide, NiO, was deposited using precipitation method while polyol method was used for the deposition of Pd NPs. X-ray diffraction (XRD) analysis revealed that the estimated particle size of the synthesized catalysts was at around 9.0-15.0 nm. CV results demonstrated a 36.7% increase in the catalytic activity of Pd-NiO/C (functionalized) catalyst towards ethanol oxidation compared to the non-functionalized catalyst.

  20. Electrocatalyst advances for hydrogen oxidation in phosphoric acid fuel cells

    Science.gov (United States)

    Stonehart, P.

    1984-01-01

    The important considerations that presently exist for achieving commercial acceptance of fuel cells are centered on cost (which translates to efficiency) and lifetime. This paper addresses the questions of electrocatalyst utilization within porous electrode structures and the preparation of low-cost noble metal electrocatalyst combinations with extreme dispersions of the metal. Now that electrocatalyst particles can be prepared with dimensions of 10 A, either singly or in alloy combinations, a very large percentage of the noble metal atoms in a crystallite are available for reaction. The cost savings for such electrocatalysts in the present commercially driven environment are considerable.

  1. Study of Catalysts and Electrocatalysts for NO{sub x} Removal in Combustion Gases ELECTRONOX Project Final Report; Estudio de Catalizadores y Electrocatalizadores para la Eliminacion de NO{sub x} en Gases de Combustion. Informe Final Proyecto ELECTRONOX

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz Martinez, E; Marono Bujan, M; Sanchez-Hervas, J M

    2009-12-11

    The final aim of the ELECTRONOX project was to develop new methodologies and technologies for NO{sub x} removal. To fulfil this objective, studies of selective catalytic reduction of NO{sub x} with hydrocarbons, both conventional and with electrochemical promotion, have been undertaken at pilot plant level, using appropriate catalyst/electrocatalysts configurations and in conditions similar to those required in their possible practical application. None of the catalysts/electrocatalysts studied is active and stable enough, under realistic conditions, to consider its possible industrial application, because the value of NO{sub x} conversion achieved by selective catalytic reduction with hydrocarbons, both conventional and with electrochemical promotion, decreases in presence of the different inhibitors and poisons present in the combustion gas, while the promotional effect on the catalytic activity and selectivity is more pronounced. In addition, the catalysts/electrocatalysts suffer from different deactivation processes, such as: sulphur poisoning, carbon deposition and sintering. However, the developed electrochemical catalyst looks promising for NO{sub x} removal in combustion gases, because it can be promoted under realistic operating conditions. (Author) 23 refs.

  2. Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Hsu, Ryan S; Higgins, Drew; Chen Zhongwei

    2010-01-01

    Novel tin-oxide (SnO 2 )-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO 2 -coated SWNT (SnO 2 -SWNT) bundles were synthesized by a simple chemical-solution route. SnO 2 -SWNT bundles supporting Pt (Pt/SnO 2 -SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO 2 -SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO 2 loading of Pt/SnO 2 -SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

  3. Design Principles for Covalent Organic Frameworks as Efficient Electrocatalysts in Clean Energy Conversion and Green Oxidizer Production.

    Science.gov (United States)

    Lin, Chun-Yu; Zhang, Lipeng; Zhao, Zhenghang; Xia, Zhenhai

    2017-05-01

    Covalent organic frameworks (COFs), an emerging class of framework materials linked by covalent bonds, hold potential for various applications such as efficient electrocatalysts, photovoltaics, and sensors. To rationally design COF-based electrocatalysts for oxygen reduction and evolution reactions in fuel cells and metal-air batteries, activity descriptors, derived from orbital energy and bonding structures, are identified with the first-principle calculations for the COFs, which correlate COF structures with their catalytic activities. The calculations also predict that alkaline-earth metal-porphyrin COFs could catalyze the direct production of H 2 O 2 , a green oxidizer and an energy carrier. These predictions are supported by experimental data, and the design principles derived from the descriptors provide an approach for rational design of new electrocatalysts for both clean energy conversion and green oxidizer production. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells.

    Science.gov (United States)

    Hsu, Ryan S; Higgins, Drew; Chen, Zhongwei

    2010-04-23

    Novel tin-oxide (SnO(2))-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO(2)-coated SWNT (SnO(2)-SWNT) bundles were synthesized by a simple chemical-solution route. SnO(2)-SWNT bundles supporting Pt (Pt/SnO(2)-SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO(2)-SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO(2) loading of Pt/SnO(2)-SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

  5. 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...

  6. A highly active PtCu3 intermetallic core-shell, multilayered Pt-skin, carbon embedded electrocatalyst produced by a scale-up sol-gel synthesis.

    Science.gov (United States)

    Bele, M; Jovanovič, P; Pavlišič, A; Jozinović, B; Zorko, M; Rečnik, A; Chernyshova, E; Hočevar, S; Hodnik, N; Gaberšček, M

    2014-11-07

    We present a novel, scaled-up sol-gel synthesis which enables one to produce 20 g batches of highly active and stable carbon supported PtCu3 nanoparticles as cathode materials for low temperature fuel cell application. We confirm the presence of an ordered intermetallic phase underneath a multilayered Pt-skin together with firm embedment of nanoparticles in the carbon matrix.

  7. Atomic resolution structural insights into PdPt nanoparticle–carbon interactions for the design of highly active and stable electrocatalysts

    International Nuclear Information System (INIS)

    Slanac, Daniel A.; Li Lin; Mayoral, Alvaro; Yacaman, Miguel José; Manthiram, Arumugam; Stevenson, Keith J.; Johnston, Keith P.

    2012-01-01

    Graphical abstract: - Abstract: Interfacial interactions between sub-4 nm metal alloy nanoparticles and carbon supports, although not well understood at the atomic level, may be expected to have a profound influence on catalytic properties. Pd 3 Pt 2 alloy particles comprised of a disordered surface layer over a corrugated crystalline core are shown to exhibit strong interfacial interactions with a ∼20–50 nm spherical carbon support, as characterized by probe aberration corrected scanning transmission electron microscopy (pcSTEM). The disordered shells were formed from defects introduced by Pd during arrested growth synthesis of the alloy nanoparticles. The chemical and morphological changes in the catalyst, before and after cyclic stability testing (1000 cycles, 0.5–1.2 V), were probed with cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and pcSTEM. The strong metal–support interaction, along with the uniform alloy structure raised the mass activity by a factor of 1.8 versus pure Pt. The metal–support interactions also mitigated nanoparticle coalescence, dissolution, and ripening, resulting in only a 20% loss in mass activity (versus 60% for pure Pt on carbon) after the cyclic stability test. The design of alloy structure, guided by insight from atomic scale pcSTEM, for enhanced catalytic activity and stability, resulting from strong wetting with a deformable disordered shell, has the potential to be a general paradigm for improving catalytic performance.

  8. 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.

  9. Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Santos, Mauro Coelho dos

    2015-01-01

    Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm -2 and 31 mW.cm -2 for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

  10. Ethanol electro-oxidation in alkaline medium using Pd/c and PdRh/C electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Silva, Dionisio Furtunato da; Geraldes, Adriana Napoleao; Pino, Eddy Segura; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Linardi, Marcelo

    2013-01-01

    In this study, carbon-supported Pd (Pd/C) and bimetallic PdRh (Pd:Rh 90:10 atomic ratio) (PdRh/C) electrocatalysts were prepared using electron beam irradiation. The morphology and composition of the obtained materials were characterized by Cyclic voltammetry (VC), Chronoamperometry (CA), Energy dispersive X-ray (EDX), X-ray Diffraction (XRD) and Thermo-gravimetric analysis (TGA). The catalytic activities of the electrocatalysts toward the ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC), in a range temperature of 50 to 85 deg C. The best performances were obtained at 85 deg C (25 mW.cm -2 ) and 75 deg C (38 mW.cm -2 ) for Pd/C and PdRh/C electrocatalysts, respectively. The XRD of the PdRh/C electrocatalyst showed the presence of Pd-rich (fcc) phase. CV and CA experiments showed that PdRh/C electrocatalyst demonstrated superior activity toward ethanol electro-oxidation at room temperature, compared to Pd/C electrocatalyst. (author)

  11. Ethanol electro-oxidation in alkaline medium using Pd/c and PdRh/C electrocatalysts prepared by electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Dionisio Furtunato da; Geraldes, Adriana Napoleao; Pino, Eddy Segura; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Linardi, Marcelo, E-mail: dfsilva@ipen.br, E-mail: drinager@ig.com.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2013-07-01

    In this study, carbon-supported Pd (Pd/C) and bimetallic PdRh (Pd:Rh 90:10 atomic ratio) (PdRh/C) electrocatalysts were prepared using electron beam irradiation. The morphology and composition of the obtained materials were characterized by Cyclic voltammetry (VC), Chronoamperometry (CA), Energy dispersive X-ray (EDX), X-ray Diffraction (XRD) and Thermo-gravimetric analysis (TGA). The catalytic activities of the electrocatalysts toward the ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC), in a range temperature of 50 to 85 deg C. The best performances were obtained at 85 deg C (25 mW.cm{sup -2}) and 75 deg C (38 mW.cm{sup -2}) for Pd/C and PdRh/C electrocatalysts, respectively. The XRD of the PdRh/C electrocatalyst showed the presence of Pd-rich (fcc) phase. CV and CA experiments showed that PdRh/C electrocatalyst demonstrated superior activity toward ethanol electro-oxidation at room temperature, compared to Pd/C electrocatalyst. (author)

  12. Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: drinager@ig.com.br, E-mail: dfsilva@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Santos, Mauro Coelho dos [Universidade Federal do ABC (LEMN/CCNH/UFABC), Santo Andre, SP (Brazil)

    2015-07-01

    Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm{sup -2} and 31 mW.cm{sup -2} for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

  13. 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.

  14. Hierarchically structured graphene-carbon nanotube-cobalt hybrid electrocatalyst for seawater battery

    Science.gov (United States)

    Suh, Dong Hoon; Park, Sul Ki; Nakhanivej, Puritut; Kim, Youngsik; Hwang, Soo Min; Park, Ho Seok

    2017-12-01

    The design of cost-effective and highly active catalysts is a critical challenge. Inspired by the strong points of stability and conductivity of carbon nanotubes (CNTs), high catalytic activity of Co nanoparticles, and rapid ion diffusion and large accessible area of three-dimensional (3D) graphene, we demonstrate a novel strategy to construct a hierarchical hybrid structure consisting of Co/CoOx nanoparticles-incorporated CNT branches onto the 3D reduced graphene oxide (rGO) architecture. The surface-modified 3D rGO by steam activation process has a large surface area and abundant defect sites, which serve as active sites to uniformly grow Co/CoOx nanoparticles. Furthermore, the CNTs preserve their performance stably by encapsulating Co nanoparticles, while the uniformly decorated Co/CoOx nanoparticles exhibit superior electrocatalytic activity toward oxygen evolution/reduction reaction due to highly exposed active sites. Employing the hybrid particle electrocatalyst, the seawater battery operates stably at 0.01 mA cm-2 during 50 cycles, owing to the good electrocatalytic ability.

  15. A Permselective CeOx Coating Improves the Stability of Oxygen Evolution Electrocatalysts

    KAUST Repository

    Obata, Keisuke

    2017-12-05

    Highly active NiFeOx electrocatalysts for the oxygen evolution reaction (OER) suffer gradual deactivation with time due to the loss of Fe species from the active sites into solution during catalysis. Here, we describe the anodic deposition of a CeOx layer that prevents the loss of such Fe species from the OER catalysts, achieving a highly stable performance. The CeOx layer does not affect the OER activity of the catalyst underneath but exhibits unique permselectivity, allowing the permeation of OH- and O2 through while preventing the diffusion of redox ions through the layer to function as a selective O2-evolving electrode. The use of such permselective protective layer provides a new strategy for improving the durability of electrocatalysts.

  16. A Permselective CeOx Coating Improves the Stability of Oxygen Evolution Electrocatalysts

    KAUST Repository

    Obata, Keisuke; Takanabe, Kazuhiro

    2017-01-01

    Highly active NiFeOx electrocatalysts for the oxygen evolution reaction (OER) suffer gradual deactivation with time due to the loss of Fe species from the active sites into solution during catalysis. Here, we describe the anodic deposition of a CeOx layer that prevents the loss of such Fe species from the OER catalysts, achieving a highly stable performance. The CeOx layer does not affect the OER activity of the catalyst underneath but exhibits unique permselectivity, allowing the permeation of OH- and O2 through while preventing the diffusion of redox ions through the layer to function as a selective O2-evolving electrode. The use of such permselective protective layer provides a new strategy for improving the durability of electrocatalysts.

  17. A permselective CeO{sub x} coating to improve the stability of oxygen evolution electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Obata, Keisuke; Takanabe, Kazuhiro [King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC) and Physical Sciences and Engineering Division PSE, Thuwal (Saudi Arabia)

    2018-02-05

    Highly active NiFeO{sub x} electrocatalysts for the oxygen evolution reaction (OER) suffer gradual deactivation with time owing to the loss of Fe species from the active sites into solution during catalysis. The anodic deposition of a CeO{sub x} layer prevents the loss of such Fe species from the OER catalysts, achieving a highly stable performance. The CeO{sub x} layer does not affect the OER activity of the catalyst underneath but exhibits unique permselectivity, allowing the permeation of OH{sup -} and O{sub 2} through while preventing the diffusion of redox ions through the layer to function as a selective O{sub 2}-evolving electrode. The use of such a permselective protective layer provides a new strategy for improving the durability of electrocatalysts. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

    2018-05-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

  19. 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.

  20. Glycerol electro-oxidation in alkaline medium using Pd/C and PdSn/C electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Geraldes, Adriana Napoleao; Silva, Dionisio Fortunato da; Pino, Eddy Segura; Spinace, Estevan Vitorio; Oliveira Neto, Almir; Linardi, Marcelo; Santos, Mauro Coelhos dos

    2013-01-01

    Carbon-supported metal nanoparticles were prepared for fuel cell applications by radiation-induced reduction of metal ions precursors. Pd/C and PdSn/C electrocatalysts (Pd:Sn atomic ratio 90:10), prepared by using electron beam irradiation, were tested for glycerol electro-oxidation in single alkaline direct glycerol fuel cell (ADGFC). EDX analysis showed that the Pd:Sn atomic ratio is very similar to the nominal one. X-ray diffractograms of PdSn/C electrocatalyst showed the presence of Pd (fcc) phase. Cyclic voltammetry (CV) indicated that Pd/C and PdSn/C electrocatalysts have good activity for glycerol electro-oxidation, at room temperature. Experiments with single ADGFC were carried out from 60 to 90 deg C, using Pd/C and PdSn/C electrocatalysts and glycerol 2.0 mol.L -1 , as fuel. The best performance was obtained at 85 deg C, for both electrocatalysts. The Pd/C and PdSn/C electrocatalysts showed similar performance (34 mW cm -2 ), at 85 deg C. (author)

  1. Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

    Science.gov (United States)

    Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

    2015-10-01

    Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.; Vörös, Márton; Galli, Giulia; Stahl, Shannon S.; Hammes-Schiffer, Sharon

    2017-03-06

    NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni2+ to Ni3+, followed by oxidation to a mixed Ni3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.

  3. Ancient Chemistry "Pharaoh's Snakes" for Efficient Fe-/N-Doped Carbon Electrocatalysts.

    Science.gov (United States)

    Ren, Guangyuan; Gao, Liangliang; Teng, Chao; Li, Yunan; Yang, Hequn; Shui, Jianglan; Lu, Xianyong; Zhu, Ying; Dai, Liming

    2018-04-04

    The method of fabricating nonprecious metal electrocatalysts with high activity and durability through a facile and eco-friendly procedure is of great significance to the development of low-cost fuel cells and metal-air batteries. Herein, we present that an ancient chemical reaction of "Pharaoh's snakes" can be a fast and convenient technique to prepare Fe-/N-doped carbon (Fe/N-C) nanosheet/nanotube electrocatalysts with sugar, soda, melamine, and iron nitrate as precursors. The resultant Fe/N-C catalyst has a hierarchically porous structure, a large surface area, and uniformly distributed active sites. The catalyst shows high electrocatalytic activities toward both the oxygen reduction reaction with a half-wave potential of 0.90 V (vs reversible hydrogen electrode) better than that of Pt/C and the oxygen evolution reaction with an overpotential of 0.46 V at the current density of 10 mA cm -2 comparable to that of RuO 2 . The activity and stability of the catalyst are also evaluated in primary and rechargeable Zn-air batteries. In both conditions, three-dimensional Fe/N-C exhibited performances superior to Pt/C. Our work demonstrates a success of utilizing an ancient science to make a state-of-the-art electrocatalyst.

  4. Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

    2015-01-01

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO x /MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO x addition. • Bi-functional mechanism is facilitated in presence of CoO x . - Abstract: The electro-catalytic behavior of Pt-CoO x /MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH 4  as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO x , Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO ads on Pt active sites by the participation of CoO x . Compared to Pt/MWCNTs, Pt-CoO x /MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO x /MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups

  5. Modified Carbon Nanomaterials as Active Electrocatalysts

    OpenAIRE

    Tavakkoli, Mohammad

    2017-01-01

    Water splitting (WS) has attracted increasing attention for producing highly pure hydrogen and oxygen. WS is also a promising technique to store intermittent electrical energy from renewable resources such as solar and wind energy in the form of H2 fuel. WS consists of two half-reactions: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). For HER, efficient non-precious catalysts are required to replace the rare and expensive Pt-based catalysts. For OER, more efficient low...

  6. Use of Dendrimers during the Synthesis of Pt-Ru Electrocatalysts for PEM Fuel Cells: Effects on the Physical and Electrochemical Properties

    Directory of Open Access Journals (Sweden)

    J. C. Calderón

    2011-01-01

    Full Text Available In this work, Pt-Ru catalysts were synthesized by a novel methodology which includes the use as encapsulating molecules of dendrimers of different generation: zero (DN-0, one (DN-1, two (DN-2, and three (DN-3. Synthesized catalysts were heat-treated at 350°C, and the effects of this treatment was established from the physical (X-ray dispersive energy (XDE and X-ray diffraction (XRD and electrochemical characterization (cyclic voltammetry and chronoamperometry. Results showed that the heat-treatment benefits the catalytic properties of synthesized materials in terms of CO and methanol electrochemical oxidation. The curves for CO stripping were more defined for heat-treated catalysts, and methanol oxidation current densities were higher for these materials. These changes are principally explained from the removal of organic residues remaining on the surface of the Pt-Ru nanoparticles after the synthesis procedure. After the activation of the catalysts by heating at 350°C, the real importance of the use of these encapsulating molecules and the effect of the generation of the dendrimer become visible. From these results, it can be concluded that synthesized catalysts are good catalytic anodes for direct methanol fuel cells (DMFCs.

  7. 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.

  8. Electrodeposition of a Pt-PrO{sub 2-x} electrocatalyst on diamond electrodes for the oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Liang; Hu, Jingping; Foord, John S. [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA (United Kingdom)

    2012-09-15

    The electrodeposition of Pt-PrO{sub 2-x} nanostructures on boron-doped diamond electrodes was explored by decorating platinum nanoparticles with praseodymium oxide, for application as an electrocatalyst in the electrooxidation of methanol in direct methanol fuel cells. A high loading of platinum with good stability was deposited by adopting a two-stage protocol, which involved a stepped potential route and a chronoamperometric approach. Praseodymium oxide was then coated on the platinum particles from solutions containing praseodymium nitrate and hydrogen peroxide. The porous microstructure of the resulting catalyst was characterized by X-ray photoelectron spectroscopy and scanning electron microscope, along with electrochemical measurement. The addition of praseodymium oxide to the Pt resulted in a higher catalytic activity profile for methanol oxidation along with an improved resistance to poisoning effects caused by incompletely oxidized carbonaceous species. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Enhanced Hydrogen Evolution Reactions on Nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS) Electrocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Digraskar, Renuka V.; Mulik, Balaji B. [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India); Walke, Pravin S. [National Centre for Nanosciences and Nanotechnology, University of Mumbai, Mumbai 400098, MH (India); Ghule, Anil V. [Department of Chemistry, Shivaji University, Kolhapur, 416004, MH (India); Sathe, Bhaskar R., E-mail: bhaskarsathe@gmail.com [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India)

    2017-08-01

    Graphical abstract: CZTS nano-electrocatalyst (2.6 ± 0.4 nm) for HER is synthesized by one step sonochemical method with uniform size distribution, which shows promisingly lower onset potential with higher current density and longer stability. - Highlights: • The nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS; ∼3 nm) based electrocatalytic systems were developed by facile sonochemical method. • The novel Cu{sub 2}ZnSnS{sub 4} based nanoclustered cathode improves the electrocatalytic performance toward hydrogen generation reaction (HER). • The electrocatalytic result exhibits lower Tafel slope, higher exchange current density, excellent current stability and lower charge transfer resistance. • The high activity due to synergetic effect of Cu, Zn, Sn and S from their internal cooperative supports. - Abstract: A novel and facile one-step sonochemical method is used to synthesize Cu{sub 2}ZnSnS{sub 4} (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer−Emmett−Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density −130 mA/cm{sup 2}, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm{sup 2}, excellent

  10. High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Haohong; Li, Dongguo; Tang, Yan; He, Yang; Ji, Shufang; Wang, Rongyue; Lv, Haifeng; Lopes, Pietro P.; Paulikas, Arvydas P.; Li, Haoyi; Mao, Scott X.; Wang, Chongmin; Markovic, Nenad M.; Li, Jun; Stamenkovic, Vojislav R.; Li, Yadong

    2017-04-05

    Search for active, stable and cost-efficient electrocatalysts for hydrogen production via water splitting could make substantial impact to the energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high surface area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) compared to Rh/C and Pt/C catalysts. The atomic structure of the rhodium phosphide nanocubes was directly observed by annular dark-field scanning transmission electron microscopy (ADF-STEM), which revealed phosphorous-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorous plays crucial role in determining the robust catalyst properties.

  11. High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Haohong [Department; Chemistry; Li, Dongguo [Materials; Tang, Yan [Department; amp, Molecular; He, Yang [Department; Ji, Shufang [Department; Wang, Rongyue [Materials; Lv, Haifeng [Materials; Lopes, Pietro P. [Materials; Paulikas, Arvydas P. [Materials; Li, Haoyi [Department; amp, Molecular; Mao, Scott X. [Department; Wang, Chongmin [Environmental; Markovic, Nenad M. [Materials; Li, Jun [Department; amp, Molecular; Stamenkovic, Vojislav R. [Materials; Li, Yadong [Department

    2017-04-05

    The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.

  12. Electrocatalysts with platinum, cobalt and nickel preparations by mechanical alloyed and CVD for the reaction of oxygen reduction; Electrocatalizadores a base de platino, cobalto y niquel preparados por aleado mecanico y CVD para la reaccion de reduccion de oxigeno

    Energy Technology Data Exchange (ETDEWEB)

    Garcia C, M A [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)

    2008-07-01

    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{sub 2}SO{sub 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{sub 2}O{sub 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

  13. 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.

  14. Hollow TiO2@Co9S8 Core-Branch Arrays as Bifunctional Electrocatalysts for Efficient Oxygen/Hydrogen Production.

    Science.gov (United States)

    Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang; Wang, Yadong; Wang, Xiuli; Lu, Xihong; Xia, Xinhui; Tu, Jiangping

    2018-03-01

    Designing ever more efficient and cost-effective bifunctional electrocatalysts for oxygen/hydrogen evolution reactions (OER/HER) is greatly vital and challenging. Here, a new type of binder-free hollow TiO 2 @Co 9 S 8 core-branch arrays is developed as highly active OER and HER electrocatalysts for stable overall water splitting. Hollow core-branch arrays of TiO 2 @Co 9 S 8 are readily realized by the rational combination of crosslinked Co 9 S 8 nanoflakes on TiO 2 core via a facile and powerful sulfurization strategy. Arising from larger active surface area, richer/shorter transfer channels for ions/electrons, and reinforced structural stability, the as-obtained TiO 2 @Co 9 S 8 core-branch arrays show noticeable exceptional electrocatalytic performance, with low overpotentials of 240 and 139 mV at 10 mA cm -2 as well as low Tafel slopes of 55 and 65 mV Dec -1 for OER and HER in alkaline medium, respectively. Impressively, the electrolysis cell based on the TiO 2 @Co 9 S 8 arrays as both cathode and anode exhibits a remarkably low water splitting voltage of 1.56 V at 10 mA cm -2 and long-term durability with no decay after 10 d. The versatile fabrication protocol and smart branch-core design provide a new way to construct other advanced metal sulfides for energy conversion and storage.

  15. 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.

  16. Low Pt content of carbon supported Pt-Ni-TiO2 nanotube electrocatalysts for direct methanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Q.Z; Wu, X.; Ma, Z.F. [Shanghai Jiao Tong Univ., Shanghai, (China). Dept. of Chemical Engineering

    2008-07-01

    Interest in titanium oxide (TiO2) nanomaterial is growing due to their special characteristics for optics, catalysis, and photoelectricity conversion. In this study, the anatase/rutile crystalline of TiO2 nanoparticles was synthesized by co-deposition. TiO2 nanotubes were then obtained by microwave irradiations. This paper described the mechanism to fabricate TiO2 nanotubes. The conditions for preparing TiO2 nanotubes by microwave irradiation were optimized. Electrocatalysts were then prepared on the basis of the synthesized TiO2 nanotube. Their performances were investigated by the electro-oxidation of methanol. When Pt electrocatalysts were doped with a certain content of TiO2 nanotubes, they had more electrocatalytic activity for methanol electro-oxidation, particularly if the second transition metal, such as Ni, was added into the electrocatalyst. The electrocatalysts contained 5 and 10 wt per cent of Pt and Ni respectively. The 10 wt per cent TiO2 nanotubes showed better activities than any other catalysts for methanol electro-oxidation. According to XRD and TEM results, the size of nanoparticles of Pt became smaller after adding TiO2 nanotubes into the catalysts. It was concluded that here might be some interactions between Pt, Ni, and TiO2 nanotubes.

  17. Homogeneously Dispersed Co9S8 Anchored on Nitrogen and Sulfur Co-Doped Carbon Derived from Soybean as Bifunctional Oxygen Electrocatalysts and Supercapacitors.

    Science.gov (United States)

    Xiao, Zhen; Xiao, Guozheng; Shi, Minhao; Zhu, Ying

    2018-05-16

    Developing low-cost and highly active multifunctional electrocatalysts to replace noble metal catalysts is crucial for the commercialization of future clean energy technology. Herein, homogeneous Co 9 S 8 nanoparticles anchored on nitrogen and sulfur co-doped porous carbon nanomaterials (CoS@NSCs) are fabricated by pyrolysis of natural soybean treated with cobalt nitrate. The unique porous structures of the soybean are utilized to provide space for the oxidation and complexation reactions for cobalt compounds, thus leading to in situ generation of homogenously dispersed cobalt sulfide nanoparticles that anchored on the N,S co-doped carbon framework. Because of the coupling effect of cobalt sulfide and doping heteroatoms, CoS@NSC-800 not only displays excellent electrocatalytic performances with low overpotential and high current density toward both oxygen reduction reaction and oxygen evolution reaction comparable to the commercial Pt/C catalyst and IrO 2 catalyst, but also might be a promising candidate for high-performance supercapacitors. The method for the preparation of the multifunctional hybrids is simple but effective for the formation of uniformly distributed metal sulfide nanoparticles anchored on carbon materials, therefore providing a new perspective for the design and synthesis of multifunctional electrocatalysts for electrochemical energy conversion and storage at a large scale.

  18. Ethanol Oxidation Reaction Using PtSn/C+Ce/C Electrocatalysts: Aspects of Ceria Contribution

    International Nuclear Information System (INIS)

    De Souza, R.F.B.; Silva, J.C.M.; Assumpção, M.H.M.T.; Neto, A.O.; Santos, M.C.

    2014-01-01

    The ethanol oxidation reaction (EOR) was investigated using PtSn/C + Ce/C electrocatalysts in different mass ratios (58:42, 53:47, and 42:58) prepared using the polymeric precursor method. Transmission electron microscopy (TEM) experiments showed particles sizes in the range of 3 to 7 nm. Changes in the net parameters observed for Pt suggest the incorporation of Sn into the Pt crystalline network with the formation of an alloy mixture with the SnO 2 phase. Among the PtSn/C + Ce/C catalysts investigated, the 53:47 composition showed the highest activity towards the EOR. In this case, the j versus t curves obtained in the presence of ethanol in acidic media exhibited a current density 90% higher than that observed with the commercial PtSn/C (ETEK). Correspondingly, during the experiments performed on single direct ethanol fuel cells, the maximum power density obtained using PtSn/C + Ce/C (53:47) as the anode was approximately 60% higher than that obtained using the commercial catalyst. FTIR data showed that the observed behavior for ethanol oxidation may be explained in terms of a synergic effect of bifunctional mechanism with electronic effects, in addition to a chemical effect of ceria that provides oxygen-containing species to oxidize acetaldehyde to acetic acid

  19. Characterization of Pt-Pd/C Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    S. S. Mahapatra

    2011-01-01

    Full Text Available The Pt-Pd/C electrocatalyst was synthesized on graphite substrate by the electrochemical codeposition technique. The physicochemical characterization of the catalyst was done by SEM, XRD, and EDX. The electrochemical characterization of the Pt-Pd/C catalyst for methanol electro-oxidation was studied over a range of NaOH and methanol concentrations using cyclic voltammetry, quasisteady-state polarization, chronoamperometry, and electrochemical impedance spectroscopy. The activity of methanol oxidation increased with pH due to better OH species coverage on the electrode surface. At methanol concentration (>1.0 M, there is no change in the oxidation peak current density because of excess methanol at the electrode surface and/or depletion of OH− at the electrode surface. The Pt-Pd/C catalyst shows good stability and the low value of Tafel slope and charge transfer resistance. The enhanced electrocatalytic activity of the electrodes is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption, and ad-atom contribution on the alloyed surface.

  20. 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.

  1. ETEM Studies of Electrodes and Electro-catalysts

    DEFF Research Database (Denmark)

    Jooss, Christian; Mildner, Stephanie; Beleggia, Marco

    2016-01-01

    Environmental TEM is an excellent tool for gaining insight into the atomic and electronic structure of electro-catalysts under operating conditions. Several electrochemical reactions such as oxidation/reduction processes of electrodes, heterogeneous gas phase catalysis of water splitting...

  2. Electrocatalysts for fuel cells; Electrocatalizadores para celdas de combustible

    Energy Technology Data Exchange (ETDEWEB)

    Garcia C, M. A.; Fernandez V, S. M. [ININ, Depto. de Quimica, Apdo. Postal 18-1027, Col. Escandon, Mexico 11801, D. F. (Mexico); Vargas G, J. R. [IPN, Depto. de Ingenieria Metalurgica, Mexico 07300, D. F. (Mexico)

    2008-07-01

    It was investigated the oxygen reduction reaction (fundamental reaction in fuel cells) on electrocatalysts of Pt, Co, Ni and their alloys CoNi, PtCo, PtNi, PtCoNi in H{sub 2}SO{sub 4} 0.5 M and KOH 0.5 M as electrolyte. The electrocatalysts were synthesized using mechanical alloying processes and chemical vapor deposition. The electrocatalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray spectroscopy. The evaluation was performed using electrocatalytic technique of rotating disk electrode and kinetic parameters were determined for each electro catalyst. We report the performance of all synthesized electrocatalysts in acid and alkaline means. (Author)

  3. Development of efficient electrocatalysts via molecular hybridization of NiMn layered double hydroxide nanosheets and graphene

    Science.gov (United States)

    Ma, Wei; Ma, Renzhi; Wu, Jinghua; Sun, Pengzhan; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

    2016-05-01

    Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade, which is much superior to as-exfoliated nanosheets. The analyses of electrochemical activity surface area (ECSA) and impedance spectra clearly indicated that the superlattice structure was ideal in facilitating the migration/transfer of the charge and reactants, revealing the electrochemical energetics and mechanism behind the synergistic effect arising from molecular hybridization. The proof of concept toward total water splitting using the newly developed hybrid electrocatalyst was demonstrated by an electrolysis cell powered by a single AA battery.Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade

  4. How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

    Science.gov (United States)

    Bachmeier, Andreas; Wang, Vincent C C; Woolerton, Thomas W; Bell, Sophie; Fontecilla-Camps, Juan C; Can, Mehmet; Ragsdale, Stephen W; Chaudhary, Yatendra S; Armstrong, Fraser A

    2013-10-09

    The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.

  5. Preparation of PtRu/C and PtSn/C electrocatalysts using electron beam irradiation for direct and ethanol fuel cell

    International Nuclear Information System (INIS)

    Silva, Dionisio Furtunato da

    2009-01-01

    PtRu/C and PtSn/C electrocatalysts were prepared using electron beam irradiation. The metal ions were dissolved in water/2-propanol and water/ethylene glycol solutions and the carbon support was added. The resulting mixtures were irradiated under stirring. The effect of water/ethylene glycol and water/2-propanol (v/v) ratio, Pt:Ru and Pt:Sn atomic ratios, the irradiation time and dose rate were studied. The obtained materials were characterized by Energy dispersive analysis of X-rays (EDX), X-ray diffraction (XRD), cyclic voltammetry (CV) and Moessbauer spectroscopy. The electro-oxidation of methanol and ethanol were studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. The electrocatalysts were also tested on the Direct Methanol and Ethanol Fuel Cells. PtRu/C electrocatalysts prepared in water/ethylene glycol showed Pt:Ru atomic ratios different from the nominal ones. The results suggested that part of the Ru(III) ions were not reduced. The obtained materials showed the face-centered cubic (fcc) structure of Pt and Pt alloys with crystallite sizes of 2-3 nm. PtRu/C electrocatalysts prepared in water/2-propanol showed Pt:Ru atomic ratios similar to the nominal ones. The obtained materials also showed the fcc structure of platinum and platinum alloys with crystallite sizes of 3-4 nm. PtSn/C electrocatalysts prepared in water/ethylene glycol and water/2-propanol showed Pt:Sn atomic ratios similar to the nominal ones. The obtained materials showed the platinum (fcc) phase with crystallite sizes in the range of 2 - 4 nm and a SnO 2 (cassiterite) phase. The obtained PtRu/C and PtSn/C electrocatalysts showed similar or superior performance for methanol and ethanol electro-oxidation compared to commercial PtRu/C (E-TEK) and PtSn/C (BASF) electrocatalysts. (author)

  6. Highly efficient and stable MoP-RGO nanoparticles as electrocatalysts for hydrogen evolution

    International Nuclear Information System (INIS)

    Wu, Zexing; Wang, Jie; Zhu, Jing; Guo, Junpo; Xiao, Weiping; Xuan, Cuijuan; Lei, Wen; Wang, Deli

    2017-01-01

    Graphical abstract: Graphene supported MoP (MoP-RGO) was synthesized through a facile solvothermal reaction followed by high-temperature phosphating treatment method. The material exhibits an outstanding HER performance in both acid and alkaline media. RGO act as a substrate which can not only avoid the nanoparticles aggregation, but also facilitate the electron transfer during the electrocatalytic process. - Abstract: Electrochemical splitting of water to obtain hydrogen plays a vital role in high energy density devices, especially for fuel cells. In this work, reduced graphene oxide supported molybdenum phosphide nanoparticles (MoP-RGO) were prepared via a facile solvothermal reaction followed by high-temperature phosphating treatment. The electrochemical measurement results indicate that the MoP-RGO nanocomposite obtained at 900 °C exhibits excellent electrocatalytic activity for hydrogen evolution reaction (HER) with overpotentials of 117 mV and 150 mV at a current density of 10 mA cm"−"2 in acid and alkaline media, respectively. Furthermore, the instability of the catalyst in basic medium was systemically investigated. This work provides a facile strategy for the synthesis of cost-effective carbon supported metal phosphide as HER electrocatalyst.

  7. Nitrogen Doped Graphene Supported Pt Nanoflowers as Electrocatalysts for Oxidation of Formaldehyde.

    Science.gov (United States)

    Xie, Aijuan; Zhou, Wenting; Luo, Shiping; Chen, Yu; Zhou, Xiaoqing; Chao, Yao

    2017-02-01

    A facile Pt nanoflowers/nitrogen-doped graphene (PtNFs/NG) electrocatalyst was prepared via depositing Pt nanoflowers (PtNFs) onto the nitrogen-doped graphene (NG) matrix with urea as the nitrogen source and PtNFs/NG modified glassy carbon electrode (GCE) was prepared by electro-chemical method. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscope, X-ray photoelectron spectroscopy (XPS) and Scanning electron microscope (SEM) were used to characterize the resulting composites. Also oxidation of formaldehyde on the resulting PtNFs/NG modified electrode was investigated. The influence of deposition time, electrodeposition potential and formaldehyde concentration on electrooxidation of formaldehyde was detected, the experimental results indicate the high performance of PtNFs/NG catalyst for formaldehyde oxidation is at electrodeposition time of 300 s with the applied potential of −0.3 V. Electrochemical process, electrocatalytic stability and chronoamperometry were also inspected, it was indicated that formalde-hyde oxidation reaction on the PtNFs/NG electrode is diffusion-controlled and PtNFs/NG exhibits a high catalytic activity, stability as well as excellent poisoning-tolerance towards formaldehyde oxidation, which is attributed to the synergistic effect of PtNFs and NG. It turns out that PtNFs/NG can be used in direct liquid-feed fuel cells as a promising alternative catalyst.

  8. Electro-catalysts for hydrogen production from ethanol for use in SOFC anodes

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Marcos Aurelio da; Paz Fiuza, Raigenis da; Guedes, Bruna C.; Pontes, Luiz A.; Boaventura, Jaime Soares [UFBA, Salvador, Bahia (Brazil). Energy and Materials Science Group

    2010-07-01

    Nickel and cobalt catalysts, supported on YSZ, were prepared by wet impregnation, with and without citric acid; the metal load was 10 and 35% by weight. The catalyst composition was studied by XRF, XPS and SEM-EDS. At low metal concentration, the results of these techniques presented comparables figures; at high concentration, SEM-EDS suggested a non-uniform distribution. The analysis showed that the solids were mixed oxides and formed an alloy after reduction. The surface passivation was possible under controlled conditions. The catalytic test with the steam reforming of ethanol indicated that the metal load had almost no effect on the catalytic activity, but decreased its selectivity. Afterwards, a unitary SOFC was prepared with deposition of the cathode layer. AFM and EIS were used for the characterization of SOFC components. They showed that the electro-catalyst surface was almost all covered with the metal phase, including the large pore walls of the anode. The YSZ phase dominates the material conductance of the complete SOFC assembly (anode/electrolyte/cathode). The unitary SOFC was tested with hydrogen, gaseous ethanol or natural gas; the SOFC operating with ethanol and hydrogen fuel presented virtually no over-potential. (orig.)

  9. Palladium-based electrocatalysts for ethanol oxidation reaction in DEFC; Eletrocatalisadores de paladio para reacao de oxidacao do etanol em DEFC

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, L.P.R. de; Elsheikh, A.; Silva, E. L. da; Radtke, C.; Amico, S.C.; Malfatti, C.F., E-mail: leticiaprm@gmail.com [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil)

    2014-07-01

    Direct ethanol fuel cells require the use of electrocatalysts to promote bond cleavage of the ethanol molecule in an efficient way. Currently, most electrocatalysts contain platinum, which enables improved catalytic activity and stability in acidic media. However platinum presents high cost and low availability. Based on that, novel catalysts have been developed, such as those based on palladium and its alloys, which have attained excellent results in the oxidation of ethanol in alkaline media. In this work, Pd, PdSn and PdNiSn catalysts supported on Vulcan XC72R carbon were synthesized via impregnation/reduction. The electrocatalysts were characterized by RBS, XRD and cyclic voltammetry. The X-ray diffraction results showed the formation of an alloy and not the deposition of isolated elements. The synthesized catalysts displayed good catalytic activity, as observed by cyclic voltammetry, being the best electrochemical performance achieved by the ternary alloy. (author)

  10. Platinum Monolayer Electrocatalysts for Anodic Oxidation of Alcohols.

    Science.gov (United States)

    Li, Meng; Liu, Ping; Adzic, Radoslav R

    2012-12-06

    The slow, incomplete oxidation of methanol and ethanol on platinum-based anodes as well as the high price and limited reserves of Pt has hampered the practical application of direct alcohol fuel cells. We describe the electrocatalysts consisting of one Pt monolayer (one atom thick layer) placed on extended or nanoparticle surfaces having the activity and selectivity for the oxidation of alcohol molecules that can be controlled with platinum-support interaction. The suitably expanded Pt monolayer (i.e., Pt/Au(111)) exhibits a factor of 7 activity increase in catalyzing methanol electrooxidation relative to Pt(111). Sizable enhancement is also observed for ethanol electrooxidation. Furthermore, a correlation between substrate-induced lateral strain in a Pt monolayer and its activity/selectivity is established and rationalized by experimental and theoretical studies. The knowledge we gained with single-crystal model catalysts was successfully applied in designing real nanocatalysts. These findings for alcohols are likely to be applicable for the oxidation of other classes of organic molecules.

  11. Fuel cell: new electrocatalysts for SOFC (Solid Oxide Fuel Cells) anodes and regulation between cell performance and catalytic activity; Celula a combustivel: novos eletrocatalisadores para anodos de SOFC (Celulas a Combustivel de Oxido Solido) e correlacao entre desempenho da celula e atividade catalitica

    Energy Technology Data Exchange (ETDEWEB)

    Boaventura, Jaime S.; Aguiar, Aurinete B.; Brandao, Soraia T. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil); Frank, Maria Helena Troise; Campos, Michel F. [PETROBRAS, Rio de Janeiro, RJ (Brazil)

    2004-07-01

    Electro-catalysts were prepared using new routes. Chemical Ultrasound Deposition (CUD) method: aqueous solution of nickel nitrate and citric acid was ultrasound vaporized and deposited on heated Ytria-stabilized Zirconia (YSZ). Resin impregnation (IPR) method: nickel oxide and YSZ were mixed, added to phenolic resins, precipitated in acidic water and milled. Wet impregnation method (IMP) was used for comparison: YSZ and an aqueous solution of nickel nitrate and citric acid were mixed, followed by evaporation, drying and calcination. The catalysts were evaluated for methane steam reforming in a quartz reactor. The reactions were conducted for one hour with no significant catalytic activity loss. In reactions with 100 mg of catalyst and a mixture consisting of methane and steam (3:1), IPR catalyst showed activity higher and better stability than those by IMP. On other tests, the reform was conducted with 100 mg of catalyst and methane to steam of 10. The IPR catalyst activity was so high that the reaction approached equilibrium conditions. Anode/electrolyte/cathode units (A/E/C) were prepared with the above catalysts as follows: the anode was a catalyst porous layer; the electrolyte an YSZ dense layer; and the cathode an LSM porous layer; graphite powder formed the material porosity. The two first layers, in powder form, were put in a stainless steel cast, pressed to 4000 bars and sinterized. The cathode layer was subsequently added using tape-casting techniques followed by sintering. A/E/C units showed 40% linear contraction and porosity higher than 20%. For fuel cell tests, A/E/C was mounted in alumina plates with platinum current collectors. Unitary SOF cells were loaded with hydrogen diluted in nitrogen showing opened circuit voltage from circa 700 mV, for the CUD anode, to 350 mV, for the IPR anode. The unitary SOFC was loaded with methane for 15 minutes or longer, with no noticeable voltage loss. At 1300 K the SOFC made with IPR or IMP catalysts showed opened

  12. Boosting the Performance of the Nickel Anode in the Oxygen Evolution Reaction by Simple Electrochemical Activation

    KAUST Repository

    Shinagawa, Tatsuya; Ng, Marcus Tze-Kiat; Takanabe, Kazuhiro

    2017-01-01

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement

  13. Review of low pressure plasma processing of proton exchange membrane fuel cell electrocatalysts

    OpenAIRE

    Brault , Pascal

    2016-01-01

    Review article; International audience; The present review is describing recent advances in plasma deposition and treatment of low temperature proton exchange membrane fuel cells electrocatalysts. Interest of plasma processing for growth of platinum based, non-precious and metal free electrocatalysts is highlighted. Electrocatalysts properties are tentatively correlated to plasma parameters.

  14. Nitrogen-doped micropore-dominant carbon derived from waste pine cone as a promising metal-free electrocatalyst for aqueous zinc/air batteries

    Science.gov (United States)

    Lei, Xiaoke; Wang, Mengran; Lai, Yanqing; Hu, Langtao; Wang, Hao; Fang, Zhao; Li, Jie; Fang, Jing

    2017-10-01

    The exploitation for highly effective and low-cost metal-free catalysts with facile and environmental friendly method for oxygen reduction reaction is still a great challenge. To find an effective method for catalyst synthesis, in this manuscript, waste biomass pine cone is employed as raw material and nitrogen-doped micropore-dominant carbon material with excellent ORR catalytic activity is successfully synthesized. The as-prepared N-doped micropore-dominant carbon possesses a high surface area of 1556 m2 g-1. In addition, this carbon electrocatalyst loaded electrode exhibits a high discharge voltage 1.07 V at the current density of 50 mA cm-2, which can be ascribed to the rich micropores and high content of pyridinic N of the prepared carbon, indicative of great potential in the application of zinc/air batteries.

  15. Highly efficient and durable TiN nanofiber electrocatalyst supports.

    Science.gov (United States)

    Kim, Hyun; Cho, Min Kyung; Kwon, Jeong An; Jeong, Yeon Hun; Lee, Kyung Jin; Kim, Na Young; Kim, Min Jung; Yoo, Sung Jong; Jang, Jong Hyun; Kim, Hyoung-Juhn; Nam, Suk Woo; Lim, Dong-Hee; Cho, EunAe; Lee, Kwan-Young; Kim, Jin Young

    2015-11-28

    To date, carbon-based materials including various carbon nanostructured materials have been extensively used as an electrocatalyst support for proton exchange membrane fuel cell (PEMFC) applications due to their practical nature. However, carbon dissolution or corrosion caused by high electrode potential in the presence of O2 and/or water has been identified as one of the main failure modes for the device operation. Here, we report the first TiN nanofiber (TNF)-based nonwoven structured materials to be constructed via electrospinning and subsequent two-step thermal treatment processes as a support for the PEMFC catalyst. Pt catalyst nanoparticles (NPs) deposited on the TNFs (Pt/TNFs) were electrochemically characterized with respect to oxygen reduction reaction (ORR) activity and durability in an acidic medium. From the electrochemical tests, the TNF-supported Pt catalyst was better and more stable in terms of its catalytic performance compared to a commercially available carbon-supported Pt catalyst. For example, the initial oxygen reduction performance was comparable for both cases, while the Pt/TNF showed much higher durability from an accelerated degradation test (ADT) configuration. It is understood that the improved catalytic roles of TNFs on the supported Pt NPs for ORR are due to the high electrical conductivity arising from the extended connectivity, high inertness to the electrochemical environment and strong catalyst-support interactions.

  16. Robust Platinum-Based Electrocatalysts for Fuel Cell Applications

    Science.gov (United States)

    Coleman, Eric James

    Polymer electrolyte fuel cells (PEMFCs) are energy conversion devices that exploit the energetics of the reaction between hydrogen fuel and O 2 to generate electricity with water as the only byproduct. PEMFCs have attracted substantial attention due to their high conversion efficiency, high energy density, and low carbon footprint. However, PEMFC performance is hindered by the high activation barrier and slow reaction rates at the cathode where O2 undergoes an overall 4-electron reduction to water. The most efficient oxygen reduction reaction (ORR) catalyst materials to date are Pt group metals due to their high catalytic activity and stability in a wide range of operating conditions. Before fuel cells can become economically viable, efforts must be taken to decrease Pt content while maintaining a high level of ORR activity. This work describes the design and synthesis of a Pt-Cu electrocatalyst with ORR activity exceeding that of polycrystalline Pt. Production of this novel catalyst is quite simple and begins with synthesis of a porous Cu substrate, formed by etching Al from a Cu-Al alloy. The porous Cu substrate is then coated with a Pt layer via a spontaneous electrochemical process known as galvanic replacement. The Pt layer enhances the ORR activity (as measured by a rotating ring-disk electrode (RRDE)) and acts as a barrier towards corrosion of the Cu understructure. Growth of the Pt layer can be manipulated by time, temperature, concentration of Pt precursor, and convection rate during galvanic replacement. Data from analytical and electrochemical techniques confirm multiple Pt loadings have been achieved via the galvanic replacement process. The boost in ORR activity for the PtCu catalyst was determined to be a result of its lower affinity towards (site-blocking) OH adsorption. A unique catalyst degradation study explains the mechanism of initial catalyst ORR deactivation for both monometallic and bimetallic Pt-based catalysts. Finally, a rigorous and

  17. Chemometric study of the effects of PtRu:BH4-molar ratio and solvent used in the preparation of PtRu/C electrocatalysts for for direct methanol fuel cell anodes

    Energy Technology Data Exchange (ETDEWEB)

    Polanco, N.S.O.; Neto, A.O.; Spinace, E.V. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Tusi, M.M. [Universidade Regional Integrada do Alto Uruguai e das Missoes (URI), Santiago, RS (Brazil); Brandalise, M. [Instituto Federal Fluminense (IFF), Campos dos Goyracazes, RJ (Brazil)

    2014-07-01

    PtRu/C electrocatalysts were prepared by borohydride reduction method and a chemometric study was performed to evaluate the influence of the solvent (water and isopropyl alcohol) and amount of reducing agent (PtRu:BH4- molar ratios of 5 and 15) in maximum power density. In borohydride reduction method, a solution containing sodium hydroxide and sodium borohydride (NaBH4) is added to a mixture containing water, isopropyl alcohol, metallic precursors and the carbon support Vulcan XC72. The obtained materials were characterized by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Membrane Electrode Assemblies (MEA's) were produced and tests in single direct methanol fuel cells were performed. The amount of sodium borohydride used in the reduction showed more influence on the maximum power density than the change of solvent of the reaction. (author)

  18. 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.

  19. 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.

  20. 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.

  1. Enhanced methanol electro-oxidation reaction on Pt-CoO{sub x}/MWCNTs hybrid electro-catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Nouralishahi, Amideddin, E-mail: Nouralishahi@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Caspian Faculty of Engineering, University of Tehran, P.O. Box 43841-119, Rezvanshahr (Iran, Islamic Republic of); Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Rashidi, Ali Morad, E-mail: Rashidiam@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: Mortazav@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Khodadadi, Abbas Ali, E-mail: Khodadad@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Choolaei, Mohammadmehdi, E-mail: Choolaeimm@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of)

    2015-04-30

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO{sub x}/MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO{sub x} addition. • Bi-functional mechanism is facilitated in presence of CoO{sub x}. - Abstract: The electro-catalytic behavior of Pt-CoO{sub x}/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH{sub 4} as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO{sub x}, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO{sub ads} on Pt active sites by the participation of CoO{sub x}. Compared to Pt/MWCNTs, Pt-CoO{sub x}/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO{sub x}/MWCNTs, at small overpotentials. However, at higher overpotentials, the

  2. Synthesis and characterization of PtRuMo/C nanoparticle electrocatalyst for direct ethanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhen-Bo; Yin, Ge-Ping [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Lin, Yong-Ge [Department of Chemistry, University of Puerto Rico, Rio Piedras Campus, San Juan, PR 00931 (United States)

    2007-07-10

    This research aims at enhancement of the performance of anodic catalysts for the direct ethanol fuel cell (DEFC). Two distinct DEFC nanoparticle electrocatalysts, PtRuMo/C and PtRu/C, were prepared and characterized, and one glassy carbon working electrode for each was employed to evaluate the catalytic performance. The cyclic-voltammetric, chronoamperometric, and amperometric current-time measurements were done in the solution 0.5 mol L{sup -1} CH{sub 3}CH{sub 2}OH and 0.5 mol L{sup -1} H{sub 2}SO{sub 4}. The composition, particle sizes, lattice parameters, morphology, and the oxidation states of the metals on nanoparticle catalyst surfaces were determined by energy dispersive analysis of X-ray (EDAX), X-ray diffraction (XRD), transmission electron micrographs (TEM) and X-ray photoelectron spectrometer (XPS), respectively. The results of XRD analysis showed that both PtRuMo/C and PtRu/C had a face-centered cubic (fcc) structure with smaller lattice parameters than that of pure platinum. The typical particle sizes were only about 2.5 nm. Both electrodes showed essentially the same onset potential as shown in the CV for ethanol electrooxidation. Despite their comparable active specific areas, PtRuMo/C was superior to PtRu/C in respect of the catalytic activity, durability and CO-tolerance. The effect of Mo in the PtRuMo/C nanoparticle catalyst was illustrated with a bifunctional mechanism, hydrogen-spillover effect and the modification on the Pt electronic states. (author)

  3. Carbon supported ultrafine gold phosphorus nanoparticles as highly efficient electrocatalyst for alkaline ethanol oxidation reaction

    International Nuclear Information System (INIS)

    Li, Tongfei; Fu, Gengtao; Su, Jiahui; Wang, Yi; Lv, Yinjie; Zou, Xiuyong; Zhu, Xiaoshu; Xu, Lin; Sun, Dongmei; Tang, Yawen

    2017-01-01

    Graphical abstract: We develop a new kind of carbon supported gold-phosphorus (Au-P/C) electrocatalyst by a facile and novel phosphorus reduction method, and demonstrate the Au-P/C is a highly active and stable electrocatalyst for the ethanol oxidation reaction. - Highlights: • Au-P/C catalyst is synthesized by a facile and novel white-phosphorus reduce method. • AuP particles with ultrafine particle-size are uniformly dispersed on carbon support. • Au-P/C catalyst exhibits much higher content of P 0 than reported metal/P catalysts. • Au-P/C catalysts show excellent catalytic properties for ethanol oxidation reaction. - Abstract: Herein, we develop a new kind of carbon supported gold-phosphorus (Au-P/C) electrocatalyst for the alkaline ethanol oxidation reaction (EOR). The Au-P/C catalysts with different Au/P ratio (i.e., AuP/C, Au 3 P 2 /C and Au 4 P 3 /C) can be obtained by a facile and novel hot-reflux method with white phosphorus (P 4 ) as reductant and ethanol as solvent. The crystal structure, composition and particle-size of the Au-P/C catalysts are investigated by X-ray diffraction (XRD), Energy Dispersive Spectrometer (EDS), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), etc. The results demonstrate that Au-P/C catalysts present an alloy phase with the high content of P, ultrafine particle-size and high dispersity on carbon support, which results in excellent electrocatalytic activity and stability towards the EOR compared with that of the free-phosphorus Au/C catalyst. In addition, among the various Au-P/C catalysts with different Au/P ratio, the AuP/C sample exhibits the best electrocatalytic performance in comparison with other Au 3 P 2 /C and Au 4 P 3 /C samples.

  4. Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte.

    Science.gov (United States)

    Wang, Nan; Li, Ligui; Zhao, Dengke; Kang, Xiongwu; Tang, Zhenghua; Chen, Shaowei

    2017-09-01

    Nitrogen and sulfur-codoped graphene composites with Co 9 S 8 (NS/rGO-Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO 2 catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only -0.193 V to reach 10 mA cm -2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half-wave potential in ORR and the potential to reach 10 mA cm -2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm -2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S-codoped rGO, and Co 9 S 8 nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Rational geometrical engineering of palladium sulfide multi-arm nanostructures as a superior bi-functional electrocatalyst.

    Science.gov (United States)

    Nandan, R; Nanda, K K

    2017-08-31

    Geometrical tunability offers sharp edges and an open-armed structure accompanied with a high electrochemical active surface area to ensure the efficient and effective utilization of materials by exposing the electrochemical active sites for facile accessibility of reactant species. Herein, we report a one-step, single-pot, surfactant-free, electroless, and economic route to synthesize palladium sulfide nanostructures with different geometries at mild temperatures and their catalytic properties towards the oxygen reduction reaction (ORR) and methanol electro-oxidation (MOR). For ORR, the positive on-set, half wave potentials, smaller Tafel slope, high electrochemical active surface area, large roughness factor, and better cyclic stability of the proposed nanostructures as compared to those of the commercial state-of-the-art Pt-C/PdS catalysts suggest their superiority in an alkaline medium. In addition, high mass activity (J f ∼ 715 mA mg -1 ), in comparison with that of the commercial state-of-the-art Pt-C/PdS catalysts (J f ∼ 138/41 mA mg -1 , respectively), and high J f /J b (1.52) along with the superior operational stability of the multi-arm palladium sulfide nanostructures towards MOR advocates the bi-functional behavior of the catalyst and its potential as a promising Pt-free anode/cathode electrocatalyst in fuel cells.

  6. 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.

  7. 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.

  8. Graphitized nanodiamond supporting PtNi alloy as stable anodic and cathodic electrocatalysts for direct methanol fuel cell

    International Nuclear Information System (INIS)

    Wang, Yongjiao; Zang, Jianbing; Dong, Liang; Pan, Hong; Yuan, Yungang; Wang, Yanhui

    2013-01-01

    Highlights: • The graphitized nanodiamond (GND) showed a higher oxidation-resistance than XC-72. • The PtNi/GND electrocatalytic exhibited greater stability than PtNi/XC-72. • The PtNi/GND had a better catalytic activity for MOR and ORR than Pt/GND. -- Abstract: Surface graphitized nanodiamond (GND) with a diamond core covered by a graphitic carbon shell was prepared by annealing ND at the temperature of 1300 °C in a vacuum of 10 −3 Pa. PtNi electrocatalysts were prepared by a microwave heating polyol method using the prepared GND as a support. The composition and morphology of the PtNi electrocatalysts supported on GND (PtNi/GND) were characterized by X-ray diffraction, transmission electron microscopy and energy dispersion spectra. The results showed that nano-scaled PtNi alloy particles with an atomic ratio of approximately 1:1 were uniformly deposited on the GND through co-reduction process. The electrocatalytic activities of the PtNi/GND electrocatalysts for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) were investigated by cyclic voltammetry, chronoamperometry and linear sweep voltammetry. The PtNi/GND exhibited better electrocatalytic activities than the Pt/GND either for MOR and ORR. In comparison with traditional carbon support Vulcan XC-72, GND showed higher oxidation-resistance, and consequently led to greater stability for the PtNi/GND than PtNi/XC-72

  9. 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.

  10. Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

    Science.gov (United States)

    Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

    2016-01-01

    Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles. PMID:27650532

  11. When NiO@Ni Meets WS2 Nanosheet Array: A Highly Efficient and Ultrastable Electrocatalyst for Overall Water Splitting.

    Science.gov (United States)

    Wang, Dewen; Li, Qun; Han, Ce; Xing, Zhicai; Yang, Xiurong

    2018-01-24

    The development of low-cost, high-efficiency, and stable bifunctional electrocatalysts toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of paramount importance for large-scale water splitting. Here, we develop a new strategy for the first design and synthesis of a NiO@Ni decorated WS 2 nanosheet array on carbon cloth (NiO@Ni/WS 2 /CC) composite. This composite serves as a unique three-dimensional (3D) synergistic electrocatalyst that not only combines the intrinsic properties of individual NiO@Ni and WS 2 , but also exhibits significantly improved HER and OER activities when compared to that of pure NiO@Ni and WS 2 . This electrocatalyst possesses Pt-like activity for HER and exhibits better OER performance than that for commercial RuO 2 , as well as demonstrating superior long-term durability in alkaline media. Furthermore, it enables an alkaline electrolyzer with a current density of 10 mA cm -2 at a cell voltage as 1.42 V, which is the lowest one among all reported values to date. The excellent performance is mainly attributed to the unique 3D configuration and multicomponent synergies among NiO, Ni, and WS 2 . Our findings provide a new idea to design advanced bifunctional catalysts for water splitting.

  12. When NiO@Ni Meets WS2 Nanosheet Array: A Highly Efficient and Ultrastable Electrocatalyst for Overall Water Splitting

    Directory of Open Access Journals (Sweden)

    Dewen Wang

    2017-12-01

    Full Text Available The development of low-cost, high-efficiency, and stable bifunctional electrocatalysts toward the hydrogen evolution reaction (HER and oxygen evolution reaction (OER is of paramount importance for large-scale water splitting. Here, we develop a new strategy for the first design and synthesis of a NiO@Ni decorated WS2 nanosheet array on carbon cloth (NiO@Ni/WS2/CC composite. This composite serves as a unique three-dimensional (3D synergistic electrocatalyst that not only combines the intrinsic properties of individual NiO@Ni and WS2, but also exhibits significantly improved HER and OER activities when compared to that of pure NiO@Ni and WS2. This electrocatalyst possesses Pt-like activity for HER and exhibits better OER performance than that for commercial RuO2, as well as demonstrating superior long-term durability in alkaline media. Furthermore, it enables an alkaline electrolyzer with a current density of 10 mA cm–2 at a cell voltage as 1.42 V, which is the lowest one among all reported values to date. The excellent performance is mainly attributed to the unique 3D configuration and multicomponent synergies among NiO, Ni, and WS2. Our findings provide a new idea to design advanced bifunctional catalysts for water splitting.

  13. Evaluation of Pt−Au/MWCNT (Multiwalled Carbon Nanotubes) electrocatalyst performance as cathode of a proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Beltrán-Gastélum, M.; Salazar-Gastélum, M.I.; Félix-Navarro, R.M.; Pérez-Sicairos, S.; Reynoso-Soto, E.A.; Lin, S.W.; Flores-Hernández, J.R.; Romero-Castañón, T.; Albarrán-Sánchez, I.L.; Paraguay-Delgado, F.

    2016-01-01

    A comparative study between Pt−Au/MWCNT and Pt/C (commercial) as cathodic electrocatalyst of H_2/O_2 fuel cell is performed. Pt−Au/MWCNT is synthesized using the reverse microemulsion method and this procedure is scaled-up in order to prepare membrane-electrode assemblies for fuel cells with an active area of 9 cm"2. Those electrocatalysts are characterized by both physicochemical techniques and electrochemical measurements to evaluate their catalytic activity for ORR (Oxygen Reduction Reaction). In the half-cell study, Pt−Au/MWCNT show higher kinetic current density as cathodic electrocatalyst compared with Pt/C. Likewise, in a fuel cell hardware the maximum power density is significantly higher for Pt−Au/MWCNT cathode (625 mW cm"−"2 at 0.426 V) when compared with Pt/C anode (355 mW cm"−"2 at 0.499 V). - Highlights: • Pt−Au/MWCNT was synthesized by reverse microemulsión method. • Pt−Au/MWCNT and Pt/C were characterized by microscopic and spectroscopic techniques. • Both materials were studied as catalysts for ORR by electrochemical techniques. • Catalysts were used to prepare MEA's, the performance in fuel cell was evaluated. • Maximum power densities were 625 mW cm"−"2 for Pt−Au/MWCNT and 355 mW cm"−"2 for Pt/C.

  14. 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

  15. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    Science.gov (United States)

    Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

    2009-12-15

    The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

  16. CuZn Alloy- Based Electrocatalyst for CO2 Reduction

    KAUST Repository

    Alazmi, Amira

    2014-01-01

    , especially when the electronic energy is derived from renewable energies, such as solar, wind, geo-thermal and tidal. To achieve this goal, the development of an efficient electrocatalyst for CO2 reduction is essential. In this thesis, studies on CuZn alloys

  17. 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.

  18. Evaluation of the performance degradation at PAFC investigation of dealloying process of electrocatalysts with in-situ XRD

    Energy Technology Data Exchange (ETDEWEB)

    Nakajima, Noriyuki; Uchida, Hiroyuki; Watanabe, Masahiro [Yamanashi Univ., Kofu (Japan)] [and others

    1996-12-31

    As a complementary research project to the demonstration project of 5MW and 1 MW PAFC plants, the mechanism and rate of deterioration of the cells and stacks have been studied from 1995 FY, with the objective of establishing an estimation method for the service life-time of the cell stacks. This work has been performed in the Basic Research Project, as part of that project on PAFC`s, selecting four subjects (Electrocatalysts degradation, Electrolyte fill-level, Cell material corrosion, Electrolyte loss) as the essential factors relating to the life-time. In this study, the effect of temperature and potential on the dealloying process of electrocatalysts was examined in H{sub 3}PO{sub 4} electrolyte with X-ray diffraction measurement.

  19. 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.

  20. Symmetrical synergy of hybrid Co9S8-MoSx electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng

    2017-01-07

    There exists a strong demand to replace expensive noble metal catalysts with efficient and earth-abundant catalysts for hydrogen evolution reaction (HER). Recently the Co- and Mo-based sulfides such as CoS2, Co9S8, and MoSx have been considered as several promising HER candidates. Here, a highly active and stable hybrid electrocatalyst 3D flower-like hierarchical Co9S8 nanosheets incorporated with MoSx has been developed via a one-step sulfurization method. Since the amounts of Co9S8 and MoSx are easily adjustable, we verify that small amounts of MoSx promotes the HER activity of Co9S8, and vise versa. In other words, we validate that symmetric synergy for HER in the Co- and Mo-based sulfide hybrid catalysts, a long-standing question requiring clear experimental proofs. Meanwhile, the best electrocatalyst Co9S8-30@MoSx/CC in this study exhibits excellent HER performance with an overpotential of −98 mV at −10 mA/cm2, a small Tafel slope of 64.8 mV/dec, and prominent electrochemical stability.

  1. Symmetrical synergy of hybrid CoS2-WS2 electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng; Yang, Xiulin; Li, Henan; Hedhili, Mohamed N.; Huang, Kuo-Wei; Li, Lain-Jong; Zhang, Wenjing

    2017-01-01

    A highly active and stable hybrid electrocatalyst 3D hierarchical CoS2 nanosheets incorporated with WS2 (CoS2@WS2) has been developed via a one-step sulfurization method for the first time, where the contents of WS2 can be adjusted easily. We first prove the addition of small amounts of WS2 enhances the hydrogen evolution reaction (HER) performance of CoS2, and vise versa. In other words, we validated the symmetric synergy for HER between the Co- and W-based sulfide hybrid catalysts. In addition, we confirmed that the formation of nanointerfaces of Co-S-W between CoS2 and WS2 was responsible for the excellent HER activity (an overpotential of -97.2 mV at -10 mA/cm2, a small Tafel slope of 66.0 mV/dec, and prominent electrochemical stability) of hybrid electrocatalyst CoS2@WS2.

  2. Symmetrical synergy of hybrid CoS2-WS2 electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng

    2017-06-05

    A highly active and stable hybrid electrocatalyst 3D hierarchical CoS2 nanosheets incorporated with WS2 (CoS2@WS2) has been developed via a one-step sulfurization method for the first time, where the contents of WS2 can be adjusted easily. We first prove the addition of small amounts of WS2 enhances the hydrogen evolution reaction (HER) performance of CoS2, and vise versa. In other words, we validated the symmetric synergy for HER between the Co- and W-based sulfide hybrid catalysts. In addition, we confirmed that the formation of nanointerfaces of Co-S-W between CoS2 and WS2 was responsible for the excellent HER activity (an overpotential of -97.2 mV at -10 mA/cm2, a small Tafel slope of 66.0 mV/dec, and prominent electrochemical stability) of hybrid electrocatalyst CoS2@WS2.

  3. An electrochemical impedance spectroscopy study of polymer electrolyte membrane fuel cells electrocatalyst single wall carbon nanohorns-supported.

    Science.gov (United States)

    Brandão, Lúcia; Boaventura, Marta; Passeira, Carolina; Gattia, Daniele Mirabile; Marazzi, Renzo; Antisari, Marco Vittori; Mendes, Adélio

    2011-10-01

    Electrochemical impedance spectroscopy (EIS) was used to study the polymer electrolyte membrane fuel cells (PEMFC) performance when using single wall carbon nanohorns (SWNH) to support Pt nanoparticles. Additionally, as-prepared and oxidized SWNH Pt-supports were compared with conventional carbon black. Two different oxidizing treatments were considered: oxygen flow at 500 degrees C and reflux in an acid solution at 85 degrees C. Both oxidizing treatments increased SWNH surface area; oxygen treatment increased surface area 4 times while acid treatment increased 2.6 times. The increase in surface area should be related to the opening access to the inner tube of SWNH. Acid treatment of SWNH increased chemical fragility and decreased electrocatalyst load in comparison with as-prepared SWNH. On the other hand, the oxygen treated SWNH sample allowed to obtain the highest electrocatalyst load. The use of as-prepared and oxygen treated SWNH showed in both cases catalytic activities 60% higher than using conventional carbon black as electrocatalyst support in PEMFC. Moreover, EIS analysis indicated that the major improvement in performance is related to the cathode kinetics in the as-prepared SWNH sample, while concerning the oxidized SWNH sample, the improvements are related to the electrokinetics in both anode and cathode electrodes. These improvements should be related with differences in the hydrophobic character between SWNH and carbon black.

  4. Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: making ir capable of splitting C-C bond.

    Science.gov (United States)

    Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, Nebojsa S; More, Karren; Adzic, Radoslav R

    2013-01-09

    Splitting the C-C bond is the main obstacle to electrooxidation of ethanol (EOR) to CO(2). We recently demonstrated that the ternary PtRhSnO(2) electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article, we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We characterized and compared the properties of several carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO(2) NP core decorated with multimetallic nanoislands (MM' = PtIr, PtRh, IrRh, PtIrRh) prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM'/SnO(2) NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity toward CO(2) formation of several of these MM'/SnO(2)/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO(2)/C catalysts. We demonstrate that the PtIr/SnO(2)/C catalyst with high Ir content shows outstanding catalytic properties with the most negative EOR onset potential and reasonably good selectivity toward ethanol complete oxidation to CO(2).

  5. Investigation of nano Pt and Pt-based alloys electrocatalysts for direct methanol fuel cells and their properties

    Directory of Open Access Journals (Sweden)

    Chunguang Suo

    2014-03-01

    Full Text Available The electrocatalysts used in micro direct methanol fuel cell (μDMFC, such as Pt/C and Pt alloy/C, prepared by liquid-phase NaBH4 reduction method have been investigated. XC-72 (Cobalt corp. Company, U.S.A is chosen as the activated carrier for the electrocatalysts to keep the catalysts powder in the range of several nanometers. The XRD, SEM, EDX analyses indicated that the catalysts had small particle size in several nanometers, in excellent dispersed phase and the molar ratio of the precious metals was found to be optimal. The performances of the DMFCs using cathodic catalyst with Pt percentage of 30wt% and different anodic catalysts (Pt-Ru, Pt-Ru-Mo were tested. The polarization curves and power density curves of the cells were measured to determine the optimal alloy composition and condition for the electrocatalysts. The results showed that the micro direct methanol fuel cell with 30wt% Pt/C as the cathodic catalyst and n(Pt:n(Ru:n(Mo = 3:2:2 PtRuMo/C as the anodic catalyst at room temperature using 2.0mol/L methanol solution has the best performances.

  6. Preparation of Pt Au/C and Pt Au Bi/C electrocatalysts using electron beam irradiation for ethanol electro-oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Silva, Dionisio F.; Geraldes, Adriana N.; Cardoso, Elisangela S.Z.; Gomes, Thiago B.; Linardi, Marcelo; Oliveira Neto, Almir; Spinace, Estevam V.

    2011-01-01

    Pt Au/C (50:50) and PtAuBi/C electrocatalysts with Pt:Au:Bi atomic ratios of 50:40:10, 50:30:20 and 50:10:40 were prepared in water/2-propanol using electron beam irradiation. The materials were characterized by X-ray diffraction (XRD) and the electro-oxidation of ethanol was studied by chronoamperometry at room temperature. The X-ray diffraction measurements for all electrocatalysts prepared showed four peaks, which are associated with the planes of the face-centered cubic (fcc) structure characteristic of Pt and Pt alloys. For PtAuBi/C it was also observed the presence of a mixture of BiPt alloys and bismuth phases. The average crystallite sizes for Pt/C, PtAu/C, PtAuBi/C (50:40:10), PtAuBi/C (50:30:20) and PtAuBi/C (50:10:40) were in the range of 2.0 - 4.0 nm. The activity of the electrocatalysts for ethanol oxidation in alkaline medium showed that PtAuBi/C (50:40:10) had a higher performance for ethanol oxidation compared to others electrocatalysts prepared. (author)

  7. Ni3S2 nanowires grown on nickel foam as an efficient bifunctional electrocatalyst for water splitting with greatly practical prospects

    Science.gov (United States)

    Zhang, Dawei; Li, Jingwei; Luo, Jiaxian; Xu, Peiman; Wei, Licheng; Zhou, Dan; Xu, Weiming; Yuan, Dingsheng

    2018-06-01

    It is essential to synthesize low-cost, earth-abundant bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) for water electrolysis. Herein, we present a one-step sulfurization method to fabricate Ni3S2 nanowires directly grown on Ni foam (Ni3S2 NWs/Ni) as such an electrocatalyst. This synthetic strategy has several advantages including facile preparation, low cost and can even be expanded to large-scale preparation for practical applications. The as-synthesized Ni3S2 NWs/Ni exhibits a low overpotential of 81 and 317 mV to render a current density of 10 mA cm‑2 for the HER and OER, respectively, in 1.0 mol l‑1 KOH solution. The Ni3S2 NWs/Ni was integrated to be the cathode and the anode in the alkaline electrolyzer for overall water splitting with a current density of 10 mA cm‑2 afforded at a cell voltage of 1.63 V. More importantly, this electrolyzer maintained its electrocatalytic activity even after continual water splitting for 30 h. Owing to its simple synthesis process, the earth-abundant electrocatalyst and high performance, this versatile Ni3S2 NWs/Ni electrode will become a promising electrocatalyst for water splitting.

  8. Preparation of Pt Au/C and Pt Au Bi/C electrocatalysts using electron beam irradiation for ethanol electro-oxidation in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Dionisio F.; Geraldes, Adriana N.; Cardoso, Elisangela S.Z.; Gomes, Thiago B.; Linardi, Marcelo; Oliveira Neto, Almir; Spinace, Estevam V., E-mail: dfsilva@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2011-07-01

    Pt Au/C (50:50) and PtAuBi/C electrocatalysts with Pt:Au:Bi atomic ratios of 50:40:10, 50:30:20 and 50:10:40 were prepared in water/2-propanol using electron beam irradiation. The materials were characterized by X-ray diffraction (XRD) and the electro-oxidation of ethanol was studied by chronoamperometry at room temperature. The X-ray diffraction measurements for all electrocatalysts prepared showed four peaks, which are associated with the planes of the face-centered cubic (fcc) structure characteristic of Pt and Pt alloys. For PtAuBi/C it was also observed the presence of a mixture of BiPt alloys and bismuth phases. The average crystallite sizes for Pt/C, PtAu/C, PtAuBi/C (50:40:10), PtAuBi/C (50:30:20) and PtAuBi/C (50:10:40) were in the range of 2.0 - 4.0 nm. The activity of the electrocatalysts for ethanol oxidation in alkaline medium showed that PtAuBi/C (50:40:10) had a higher performance for ethanol oxidation compared to others electrocatalysts prepared. (author)

  9. Control of Architecture in Rhombic Dodecahedral Pt–Ni Nanoframe Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Becknell, Nigel [Department; Materials; Son, Yoonkook [Department; Kim, Dohyung [Department; Li, Dongguo [Materials; Yu, Yi [Department; Niu, Zhiqiang [Department; Lei, Teng [Department; Sneed, Brian T. [Center; More, Karren L. [Center; Markovic, Nenad M. [Materials; Stamenkovic, Vojislav R. [Materials; Yang, Peidong [Department; Materials; Department; Kavli Energy NanoSciences Institute, Berkeley, California 94720, United States

    2017-08-08

    Platinum-based alloys are known to demonstrate advanced properties in electrochemical reactions that are relevant for proton exchange membrane fuel cells and electrolyzers. Further development of Pt alloy electrocatalysts relies on the design of architectures with highly active surfaces and optimized utilization of the expensive elpment, Pt. Here, we show that the three-dimensional Pt anisotropy of Pt-Ni rhombic dodecahedra can be tuned by controlling the ratio between Pt and Ni precursors such that either a completely hollow nanoframe or a new architecture, the excavated nanoframe, can be obtained. The excavated nanoframe showed similar to 10 times higher specific and similar to 6 times higher mass activity for the oxygen reduction reaction than Pt/C, and twice the mass activity of the hollow nanoframe. The high activity is attributed to enhanced Ni content in the near-surface region and the extended two-dimensional sheet structure within the nanoframe that minimizes the number of buried Pt sites.

  10. 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)

  11. Synthesis and electrochemical characterization of highly tolerant Pd electrocatalysts as cathodes in direct ethylene glycol fuel cells (DEGFC)

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez Varela, F.J.; Fraire Luna, S. [Cinvestav, Unidad Saltillo, Ramos Arizpe, Coahuila (Mexico)] e-mail: javier.varela@cinvestav.edu.mx; Savadogo, O. [Laboratoire d' Electrochimie et de Materiaux Energetiques, Ecole Polytechnique de Montreal, Montreal, QC (Canada)

    2009-09-15

    Highly selective Pd electrocatalysts were synthesized by the formic acid method and evaluated as cathodes for DEGFC applications. In rotating disc measurements in acid medium, the Pd/C cathode showed important catalytic activity for the Oxygen Reduction Reaction (ORR). In the presence of ethylene glycol (EG, C{sub 2}H{sub 6}O{sub 2}), Pd/C exhibited an excellent electrochemical behavior and full tolerance to the organic molecule. No current density peaks associated to the EG oxidation reaction emerged and the shift in onset potential for the ORR (Eonset) toward more negative potentials was negligible on this cathode. Moreover, the evaluation of Pd/C in a DEGFC operating at 80 degrees Celsius demonstrated its high performance as cathode. As a comparison, commercial Pt/C was tested under the same conditions showing a limited selectivity for the ORR. The detrimental effect of EG on the Pt electrocatalysts resulted in high intensity current density peaks due to the oxidation of EG and a significant shift in Eonset. Given these results, it is expected that highly efficient Pd-based cathodes can find application in DEGFCs. [Spanish] Se sintetizaron electrocatalizadores altamente selectivos mediante el metodo de acido formico y se evaluaron como catodos en aplicaciones de CCGED. En mediciones de disco rotatorio en medio acido, el catodo Pd/C mostro importante actividad catalitica en la reaccion de reduccion de oxigeno (RRO). En la presencia de glicol de etileno (GE, C{sub 2}H{sub 6}O{sub 2}), Pd/C exhibio un excelente comportamiento electromecanico y tolerancia total a la molecula organica. No surgieron picos de densidad de corriente asociados con la reaccion de oxidacion de GE y el corrimiento en el potencial de inicio para la RRO (Einicio) hacia potenciales mas negativos fue despreciable en este catodo. Como comparacion, se probo un Pt/C bajo las mismas condiciones y se observo una selectividad limitada para el RRO. El efecto perjudicial de GE en el electrocatalizador

  12. Proton Exchange Membrane Fuel Cell With Enhanced Durability Using Fluorinated Carbon As Electrocatalyst

    Directory of Open Access Journals (Sweden)

    Ahmad Yasser

    2017-01-01

    Full Text Available This study evaluates the fluorination of a carbon aerogel and its effects on the durability of the resulting electrocatalyst for Proton Exchange Membrane Fuel Cell (PEMFC. Fluorine has been introduced before or after platinum deposition. The different electrocatalysts are physico-chemically and electrochemically characterized, and the results discussed by comparison with commercial Pt/XC72 from E-Tek. The results demonstrate that the level of fluorination of the carbon aerogel can be controlled. The fluorination modifies the texture of the carbons by increasing the pore size and decreasing the specific surface area, but the textures remain appropriate for PEMFC applications. Two fluorination sites are observed, leading to both high covalent C-F bond and weakened ones, the quantity of which depends on whether the treatment is done before or after platinum deposition. The order of the different treatments is very important. The presence of platinum contributes to the fluorination mechanism, but leads to amorphous platinum rather inactive towards the Oxygen Reduction Reaction. Finally, a better durability was demonstrated for the fluorinated then platinized catalyst compared both to the same but not fluorinated catalyst and to the reference commercial material (based on the loss of the electrochemical real surface area after accelerated stress tests.

  13. Optimizing Carbonaceous Nanostructure Composition as a Substrate to Grow Co Electrocatalysts

    Directory of Open Access Journals (Sweden)

    M Pourreza

    2018-02-01

    Full Text Available Global warming and other adverse environmental effects of fossil fuels have forced humans to consider clean and renewable energy resources. In this context, hydrogen production from water splitting reaction is a key approach. In order to reduce required overpotential for water oxidation reaction, it is necessary to use low cost and earth abundant electrocatalysts like Co, Cu, Fe, Mn, Ni and Zn nanostructures. Herein, cobalt nanostructures on steel-mesh substrate were applied. Electrochemical method was used for growth of Co nanoflakes because of its simplicity and scalability for commercial approach. On the other hand, using carbonaceous support layers including nanomaterials such as graphene and carbon nanotubes, can reduce overpotential and increase efficiency of the electrocatalyst.  According to the results, 40 wt% of graphene oxide and 60 wt% of carbon nanotubes in prepared carbon paste led to better growth for cobalt oxide nanoflakes. For the mentioned layer, cobalt was detected in metallic crystalline phase and the overpotential and electrical resistance measured 305 mV and 20 Ω, respectively.

  14. In Situ Synthesis and Characterization of Polyethyleneimine-Modified Carbon Nanotubes Supported PtRu Electrocatalyst for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Xi Geng

    2015-01-01

    Full Text Available PtRu bimetallic nanoparticles were successfully synthesized on polyethyleneimine- (PEI- functionalized multiwalled carbon nanotubes (MWCNTs via an effective and facile polyol reduction approach. Noncovalent surface modification of MWCNTs with PEI was confirmed by FTIR and zeta potential measurements. The morphology, crystalline structure, and composition of the hybrid material were characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray powder diffraction (XRD, and energy dispersive X-ray spectroscopy (EDX, respectively. According to SEM and TEM observations, PtRu nanoparticles with narrow size distribution were homogeneously deposited on PEI-MWCNTs. Cyclic voltammetry tests demonstrated that the as-prepared PtRu/PEI-MWCNTs nanocomposite had a large electrochemical surface area and exhibited enhanced electrocatalytic activity towards methanol oxidation in comparison with oxidized MWCNTs as catalyst support. PEI-functionalized CNTs, as useful building blocks for the assembly of Pt-based electrocatalyst, may have great potential for applications such as direct methanol fuel cell (DMFC.

  15. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    International Nuclear Information System (INIS)

    Kepenienė, V.; Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J.; Vaitkus, R.; Norkus, E.

    2016-01-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  16. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Kepenienė, V., E-mail: virginalisk@gmail.com [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Vaitkus, R. [Faculty of Chemistry, Vilnius University, Vilnius LT 03225 (Lithuania); Norkus, E. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania)

    2016-03-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  17. Covalent Organic Framework Electrocatalysts for Clean Energy Conversion.

    Science.gov (United States)

    Lin, Chun-Yu; Zhang, Detao; Zhao, Zhenghang; Xia, Zhenhai

    2018-02-01

    Covalent organic frameworks (COFs) are promising for catalysis, sensing, gas storage, adsorption, optoelectricity, etc. owning to the unprecedented combination of large surface area, high crystallinity, tunable pore size, and unique molecular architecture. Although COFs are in their initial research stage, progress has been made in the design and synthesis of COF-based electrocatalysis for the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, and CO 2 reduction in energy conversion and fuel generation. Design principles are also established for some of the COF materials toward rational design and rapid screening of the best electrocatalysts for a specific application. Herein, the recent advances in the design and synthesis of COF-based catalysts for clean energy conversion and storage are presented. Future research directions and perspectives are also being discussed for the development of efficient COF-based electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  19. Selenide-Based Electrocatalysts and Scaffolds for Water Oxidation Applications

    KAUST Repository

    Xia, Chuan

    2015-11-05

    Selenide-based electrocatalysts and scaffolds on carbon cloth are successfully fabricated and demonstrated for enhanced water oxidation applications. A max­imum current density of 97.5 mA cm−2 at an overpotential of a mere 300 mV and a small Tafel slope of 77 mV dec−1 are achieved, suggesting the potential of these materials to serve as advanced oxygen evolution reaction catalysts.

  20. Preparation of supported electrocatalyst comprising multiwalled carbon nanotubes

    Science.gov (United States)

    Wu, Gang; Zelenay, Piotr

    2013-08-27

    A process for preparing a durable non-precious metal oxygen reduction electrocatalyst involves heat treatment of a ball-milled mixture of polyaniline and multiwalled carbon nanotubes in the presence of a Fe species. The catalyst is more durable than catalysts that use carbon black supports. Performance degradation was minimal or absent after 500 hours of operation at constant cell voltage of 0.40 V.

  1. Selenide-Based Electrocatalysts and Scaffolds for Water Oxidation Applications

    KAUST Repository

    Xia, Chuan; Jiang, Qiu; Zhao, Chao; Hedhili, Mohamed N.; Alshareef, Husam N.

    2015-01-01

    Selenide-based electrocatalysts and scaffolds on carbon cloth are successfully fabricated and demonstrated for enhanced water oxidation applications. A max­imum current density of 97.5 mA cm−2 at an overpotential of a mere 300 mV and a small Tafel slope of 77 mV dec−1 are achieved, suggesting the potential of these materials to serve as advanced oxygen evolution reaction catalysts.

  2. Nitrogen: Unraveling the Secret to Stable Carbon-Supported Pt-Alloy Electrocatalysts

    Science.gov (United States)

    2013-10-01

    release; distribution is unlimited. Nitrogen: unraveling the secret to stable carbon-supported Pt- alloy electrocatalysts The views, opinions and/or...Nitrogen: unraveling the secret to stable carbon-supported Pt-alloy electrocatalysts Report Title Nitrogen functionalities significantly improve...design and optimization of next generation high performance catalyst materials. Nitrogen: unraveling the secret to stable carbon-supported Pt-alloy

  3. 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.

  4. 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.

  5. Silicon Nano wires with MoS_x and Pt as Electrocatalysts for Hydrogen Evolution Reaction

    International Nuclear Information System (INIS)

    Hsieh, S.H.; Ho, S.T.; Chen, W.J.

    2016-01-01

    A convenient method was used for synthesizing Pt-nanoparticle//silicon nano wires nano composites. Obtained Pt-/silicon nano wires electrocatalysts were characterized by transmission electron microscopy (TEM). The hydrogen evolution reaction efficiency of the Pt-/silicon nano wire nano composite catalysts was assessed by examining polarization and electrolysis measurements under solar light irradiations. The electrochemical characterizations demonstrate that Pt-/silicon nano wire electrodes exhibited an excellent catalytic activity for hydrogen evolution reaction in an acidic electrolyte. The hydrogen production capability of Pt-/silicon nano wires is also comparable to /silicon nano wires and Pt/silicon nano wires. Electrochemical impedance spectroscopy experiments suggest that the enhanced performance of Pt-/silicon nano wires can be attributed to the fast electron transfer between Pt-/silicon nano wire electrodes and electrolyte interfaces.

  6. High-throughput synthesis of mixed-metal electrocatalysts for CO{sub 2} reduction

    Energy Technology Data Exchange (ETDEWEB)

    He, Jingfu; Dettelbach, Kevan E.; Li, Tengfei [Department of Chemistry, The University of British Columbia, Vancouver, BC (Canada); Salvatore, Danielle A. [Department of Chemical and Biological Engineering, The University of British Columbia, Vancouver, BC (Canada); Berlinguette, Curtis P. [Department of Chemistry, The University of British Columbia, Vancouver, BC (Canada); Department of Chemical and Biological Engineering, The University of British Columbia, Vancouver, BC (Canada)

    2017-05-22

    The utilization of CO{sub 2} as a feedstock requires fundamental breakthroughs in catalyst design. The efficiencies and activities of pure metal electrodes towards the CO{sub 2} reduction reaction are established, but the corresponding data on mixed-metal systems are not as well developed. In this study we show that the near-infrared driven decomposition (NIRDD) of solution-deposited films of metal salts and subsequent electrochemical reduction offers the unique opportunity to form an array of mixed-metal electrocatalyst coatings with excellent control of the metal stoichiometries. This synthetic method enabled us to develop an empirical structure-property correlation to help inform the development of optimized CO{sub 2} catalyst compositions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. High-throughput synthesis of mixed-metal electrocatalysts for CO2 reduction

    International Nuclear Information System (INIS)

    He, Jingfu; Dettelbach, Kevan E.; Li, Tengfei; Salvatore, Danielle A.; Berlinguette, Curtis P.

    2017-01-01

    The utilization of CO 2 as a feedstock requires fundamental breakthroughs in catalyst design. The efficiencies and activities of pure metal electrodes towards the CO 2 reduction reaction are established, but the corresponding data on mixed-metal systems are not as well developed. In this study we show that the near-infrared driven decomposition (NIRDD) of solution-deposited films of metal salts and subsequent electrochemical reduction offers the unique opportunity to form an array of mixed-metal electrocatalyst coatings with excellent control of the metal stoichiometries. This synthetic method enabled us to develop an empirical structure-property correlation to help inform the development of optimized CO 2 catalyst compositions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Ethanol oxidation on a nichrome-supported spherical platinum microparticle electrocatalyst prepared by electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhen-Hui; Li, Jing; Dong, Xiaoya; Wang, Dong; Chen, Tiwei; Qiao, Haiyan; Huang, Aiping [College of Chemistry and Environmental Science, Henan Key Laboratory for Environmental Pollution Control, Henan Normal University, Jianshe Road, Xinxiang 453007 (China)

    2008-11-15

    A novel electrode was rapidly prepared by depositing microparticle platinum onto a nichrome substrate in dilute chloroplatinic acid solution by cyclic voltammetry. The SEM results revealed that the deposits were composed of spherical Pt microparticles. Cyclic voltammetry and chronoamperometry were used for the characterization of the electrodes. Results of the electrochemical measurements showed that the spherical Pt microparticle electrodes retained the properties of metal platinum, increased the catalytic activity and promoted the electrocatalytic oxidation of ethanol. Moreover, the deposited Pt microparticles improved the electrochemical properties of the support material and reduced the dosage of noble metal platinum remarkably. The cost could be reduced dramatically by decreasing the contents of platinum. The spherical Pt microparticles deposited on the nichrome supports are likely a potential electrocatalyst for ethanol electrooxidation. (author)

  9. Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

    Science.gov (United States)

    Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Watt, Gerald D.; Chu, Sang-Hyon; Park, Yeonjoon; Thibeault, Sheila

    2004-01-01

    Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

  10. Theoretical studies of Pt-Ti nanoparticles for potential use as PEMFC electrocatalysts.

    Science.gov (United States)

    Jennings, Paul C; Pollet, Bruno G; Johnston, Roy L

    2012-03-07

    A theoretical investigation is presented of alloying platinum with titanium to form binary Pt-Ti nanoalloys as an alternative to the expensive pure platinum catalysts commonly used for Proton Exchange Membrane Fuel Cell cathode electrocatalysts. Density Functional Theory calculations are performed to investigate compositional effects on structural properties as well as Oxygen Reduction Reaction kinetics and poisoning effects. High symmetry A(32)-B(6) clusters are studied to investigate structural properties. From these structures binding energies of hydroxyl and carbon monoxide are studied on a range of sites on the surface of the clusters. Promising results are obtained suggesting that the bimetallic Pt-Ti nanoalloys may exhibit enhanced properties compared to pure platinum catalysts.

  11. Facile one-pot synthesis of CoS{sub 2}-MoS{sub 2}/CNTs as efficient electrocatalyst for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yan-Ru; Hu, Wen-Hui; Li, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Shang, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Han, Guan-Qun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Yun-Qi, E-mail: liuyq@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2016-10-30

    Highlights: • Ternary hybrid CoS{sub 2}-MoS{sub 2}/CNTs electrocatalysts have been prepared. • CNTs as support may provide good conductivity and low the agglomeration of MoS{sub 2}. • CoS{sub 2} with intrinsic metallic conductivity may enhance the activity for HER. • Ternary CoS{sub 2}-MoS{sub 2}/CNTs have the better activity and stability for HER. - Abstract: Ternary hybrid cobalt disulfide-molybdenum disulfides supported on carbon nanotubes (CoS{sub 2}-MoS{sub 2}/CNTs) electrocatalysts have been prepared via a simple hydrothermal method. CNTs as support may provide good conductivity and low the agglomeration of layered MoS{sub 2} structure. CoS{sub 2} with intrinsic metallic conductivity may enhance the activity of the ternary hybrid electrocatalysts for hydrogen evolution reaction (HER). X-ray diffraction (XRD) data confirm the formation of ternary hybrid nanocomposites composed of CNTs, CoS{sub 2} and amorphous MoS{sub 2}. Scanning electron microscopy (SEM) images show that strong combination between MoS{sub 2}, CNTs and regular orthohexagonal CoS{sub 2} has been obtained. The dispersion of each component is good and no obvious agglomeration can be observed. It is found that compared with CoS{sub 2}/CNTs and MoS{sub 2}/CNTs, the ternary CoS{sub 2}-MoS{sub 2}/CNTs have the better activity for HER with a low onset potential of 70 mV (vs. RHE) and a small Talel slope of 67 mV dec{sup −1}, and are extremely stable after 1000 cycles. In addition, the optimal doping ratio of Co to Mo is 2:1, which have better HER activity. It is proved that the introduction of carbon materials and Co atoms could improve the performances of MoS{sub 2}-based electrocatalysts for HER.

  12. Facile one-pot synthesis of CoS_2-MoS_2/CNTs as efficient electrocatalyst for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Liu, Yan-Ru; Hu, Wen-Hui; Li, Xiao; Dong, Bin; Shang, Xiao; Han, Guan-Qun; Chai, Yong-Ming; Liu, Yun-Qi; Liu, Chen-Guang

    2016-01-01

    Highlights: • Ternary hybrid CoS_2-MoS_2/CNTs electrocatalysts have been prepared. • CNTs as support may provide good conductivity and low the agglomeration of MoS_2. • CoS_2 with intrinsic metallic conductivity may enhance the activity for HER. • Ternary CoS_2-MoS_2/CNTs have the better activity and stability for HER. - Abstract: Ternary hybrid cobalt disulfide-molybdenum disulfides supported on carbon nanotubes (CoS_2-MoS_2/CNTs) electrocatalysts have been prepared via a simple hydrothermal method. CNTs as support may provide good conductivity and low the agglomeration of layered MoS_2 structure. CoS_2 with intrinsic metallic conductivity may enhance the activity of the ternary hybrid electrocatalysts for hydrogen evolution reaction (HER). X-ray diffraction (XRD) data confirm the formation of ternary hybrid nanocomposites composed of CNTs, CoS_2 and amorphous MoS_2. Scanning electron microscopy (SEM) images show that strong combination between MoS_2, CNTs and regular orthohexagonal CoS_2 has been obtained. The dispersion of each component is good and no obvious agglomeration can be observed. It is found that compared with CoS_2/CNTs and MoS_2/CNTs, the ternary CoS_2-MoS_2/CNTs have the better activity for HER with a low onset potential of 70 mV (vs. RHE) and a small Talel slope of 67 mV dec"−"1, and are extremely stable after 1000 cycles. In addition, the optimal doping ratio of Co to Mo is 2:1, which have better HER activity. It is proved that the introduction of carbon materials and Co atoms could improve the performances of MoS_2-based electrocatalysts for HER.

  13. Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cullen, David A [ORNL

    2016-01-01

    Late transition metal nanocrystals find applications in heterogeneous catalysis such as plasmon-enhanced catalysis and as electrode materials for fuel cells, a zero-emission and sustainable energy technology. Their commercial viability for automotive transportation has steadily increased in recent years, almost exclusively due to the discovery of more efficient bimetallic nanocatalysts for the oxygen reduction reaction (ORR) at the cathode. Despite improvements to catalyst design, achieving high activity while maintaining durability is essential to further enhance their performance for this and other important applications in catalysis. Electronic effects arising from the generation of metal-metal interfaces, from plasmonic metals, and from lattice distortions, can vastly improve sorption properties at catalytic surfaces, while increasing durability.[1] Multimetallic lattice-strained nanoparticles are thus an interesting opportunity for fundamental research.[2,3] A colloidal synthesis approach is demonstrated to produce AuPd alloy and Pd@Au core-shell nanoicosahedra as catalysts for electro-oxidations. The nanoparticles are characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and large solid angle energy dispersive X-ray spectroscopy (EDS) on an FEI Talos 4-detector STEM/EDS system. Figure 1 shows bright-field (BF) and high-angle annular dark-field (HAADF) ac-STEM images of the alloy and core-shell nanoicosahedra together with EDS line-scans and elemental maps. These structures are unique in that the presence of twin boundaries, alloying, and core-shell morphology could create highly strained surfaces and interfaces. The shell thickness of the core-shell structures observed in HAADF-STEM images is tuned by adjusting the ratio between metal precursors (Figure 2a-f) to produce shells ranging from a few to several monolayers. Specific activity was measured in ethanol electro-oxidation to examine the effect of shell thickness on

  14. MoSx-coated NbS2 nanoflakes growth on glass carbon: an advanced electrocatalyst for the hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng; Lin, Shi-Hsin; Yang, Xiulin; Li, Henan; Hedhili, Mohamed N.; Li, Lain-Jong; Zhang, Wenjing; Shi, Yumeng

    2018-01-01

    Recent experimental and theoretical studies have demonstrated that two-dimensional (2D) transition metal dichalcogenide (TMDC) nanoflakes are one of the most promising candidates for non-noblemetal electrocatalysts for hydrogen evolution reaction (HER). However, it is still demanding to optimize their conductivity and enrich active sites for the high efficient electrochemical performance. Herein, we report a chemical vapor deposition (CVD) and thermal annealing two-step strategy to controllably synthesize hybrid electrocatalysts consisting of metallic NbS2 nanoflake backbones and highly catalytic active MoSx nanocrystalline shell on polished commercial glass carbon (GC). In addition, the amounts of MoSx in the hybrids can be easily adjusted, we first demonstrate that small amount of MoSx obviously promotes the HER activity of 2D NbS2 nanoflakes, which is in good consistence with the density functional theory (DFT) calculation results. Meanwhile, the optimized MoSx@NbS2/GC electrocatalyst displays a superior HER activity with an overpotential of -164 mV at -10 mA/cm2, a small Tafel slope of 43.2 mV/dec, and prominent electrochemical stability. This study provides a new path for enhancing the HER performance of 2D TMDC nanoflakes.

  15. 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.

  16. MoSx-coated NbS2 nanoflakes growth on glass carbon: an advanced electrocatalyst for the hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng

    2018-01-19

    Recent experimental and theoretical studies have demonstrated that two-dimensional (2D) transition metal dichalcogenide (TMDC) nanoflakes are one of the most promising candidates for non-noblemetal electrocatalysts for hydrogen evolution reaction (HER). However, it is still demanding to optimize their conductivity and enrich active sites for the high efficient electrochemical performance. Herein, we report a chemical vapor deposition (CVD) and thermal annealing two-step strategy to controllably synthesize hybrid electrocatalysts consisting of metallic NbS2 nanoflake backbones and highly catalytic active MoSx nanocrystalline shell on polished commercial glass carbon (GC). In addition, the amounts of MoSx in the hybrids can be easily adjusted, we first demonstrate that small amount of MoSx obviously promotes the HER activity of 2D NbS2 nanoflakes, which is in good consistence with the density functional theory (DFT) calculation results. Meanwhile, the optimized MoSx@NbS2/GC electrocatalyst displays a superior HER activity with an overpotential of -164 mV at -10 mA/cm2, a small Tafel slope of 43.2 mV/dec, and prominent electrochemical stability. This study provides a new path for enhancing the HER performance of 2D TMDC nanoflakes.

  17. Ternary CoS{sub 2}/MoS{sub 2}/RGO electrocatalyst with CoMoS phase for efficient hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yan-Ru; Shang, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Gao, Wen-Kun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Chi, Jing-Qi; Li, Xiao; Yan, Kai-Li; Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Yun-Qi, E-mail: liuyq@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2017-08-01

    Highlights: • Ternary CoS{sub 2}/MoS{sub 2}/RGO with CoMoS phase as electrocatalyst for HER was prepared. • CoMoS phase have the metallic nature and highly intrinsic activity for HER. • RGO support ensures good distribution of CoMoS phase and enhances the conductivity. • The introduction of CoMoS and RGO may be a novel strategy for efficient HER of MoS{sub 2}. - Abstract: CoMoS phase with metallic character plays crucial role on enhancing the activity of MoS{sub 2} electrocatalysts for hydrogen evolution reaction (HER). However, only Co atoms located in the edges of MoS{sub 2} can create CoMoS phase, so it is a challenge to obtain CoMoS phase with homogeneous distribution limited by the layered MoS{sub 2} and doping method of Co. Herein, we reported a simple one-pot hydrothermal method to prepare novel ternary CoS{sub 2}/MoS{sub 2}/RGO with CoMoS phase for HER using reduced graphene oxide (RGO) as support. XPS proves the formation of CoMoS phase, implying the enhanced activity for HER. RGO support ensures the well distribution of CoMoS phase and enhances the conductivity of CoS{sub 2}/MoS{sub 2}/RGO. Compared to CoS{sub 2}/RGO, MoS{sub 2}/RGO and CoS{sub 2}/MoS{sub 2}, the obtained CoS{sub 2}/MoS{sub 2}/RGO shows superior activity for HER with an onset overpotential of −80 mV (vs. RHE), small Tafel slope of 56 mV dec{sup −1}, high exchange current density of 11.4 μA cm{sup −2} and rigid electrochemical durability. The enhanced performances for HER may be ascribed to the formation of CoMoS phase with high activity and the existence of RGO support with good electrical conductivitys in ternary CoS{sub 2}/MoS{sub 2}/RGO. Therefore, the introduction of CoMoS phase and RGO into MoS{sub 2} could effectively enhance electrocatalytic properties for HER.

  18. Preparation of PtRu/C anode electrocatalysts using gamma radiation for methanol electro-oxidation; Preparacao de eletrocatalisadores PtRu/C utilizando radiacao gama para aplicacao como anodo na oxidacao direta de metanol

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Dionisio Fortunato da

    2006-07-01

    Pt Ru/C (carbon-supported Pt Ru nanoparticles) anode electrocatalysts were prepared using radiolytic process (gamma radiation) and tested for methanol electro-oxidation. In this process, water/2-propanol and water/ethylene glycol solutions containing the metallic ions and the carbon support were submitted to gamma radiation under stirring. The water/alcohol ratio (v/v) and the total dose (kGy) were studied. A nominal Pt Ru atomic ratio of 50:50 were used in all experiments. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV). The electro-oxidation of methanol was studied by cyclic voltammetry using the thin porous coating technique. The electrocatalysts prepared in water/2-propanol showed crystallite size in the range of 3-5 nm and Pt Ru atomic ratio of 50:50. The electrocatalysts prepared in water/ethylene glycol showed crystallite size (2-3 nm) smaller than the ones obtained in water/2-propanol, however, the Pt Ru atomic ratios obtained were approximately 80:20, showing that only part of ruthenium ions were reduced. For methanol oxidation the electrocatalytic activity depends on the water/2-propanol and water/ethylene glycol ratio used in the reaction medium. The electrocatalysts prepared in water/2-propanol showed inferior performance to the ones prepared in water/ethylene glycol, which showed similar or superior performances (amperes per gram of platinum) to the commercial electrocatalyst from E-TEK. (author)

  19. Performance PtSnRh electrocatalysts supported on carbon-Sb2O5.SbO2 for the electro-oxidation of ethanol, prepared by an alcohol-reduction process

    International Nuclear Information System (INIS)

    Castro, Jose Carlos

    2013-01-01

    PtSnRh electrocatalysts supported on carbon-Sb 2 O 5 .SnO 2 , with metal loading of 20 wt%, were prepared by an alcohol-reduction process, using H 2 PtCl 6 .6H 2 O (Aldrich), RhCl 3 .xH 2 O (Aldrich) and SnCl 2 .2H 2 O (Aldrich), as source of metals; Sb 2 O 5 .SnO 2 (ATO) and carbon Vulcan XC72, as support; and ethylene glycol as reducing agent. The electrocatalysts obtained were characterized physically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The diffractograms showed which PtSnRh/C-ATO electrocatalysts had FCC structure of Pt and Pt alloys, besides several peaks associated with SnO 2 and ATO. The average sizes of crystallites were between 2 and 4 nm. TEM micrographs showed a good distribution of the nanoparticles on the support. The average sizes of particles were between 2 and 3 nm, with good agreement for the average size of the crystallites. The performances of the electrocatalysts were analyzed by electrochemical techniques and in real conditions of operation using single direct ethanol fuel cell. In the chronoamperometry at 50 deg C, the electrocatalysts with carbon (85 wt%) and ATO (15 wt%) support, showed the best activity, and the atomic proportions which achieved the best results were PtSnRh(70:25:05) e (90:05:05). PtSnRh(70:25:05)/85C+15ATO electrocatalysts showed the best performance in a direct ethanol fuel cell. (author)

  20. A novel IrNi@PdIr/C core-shell electrocatalyst with enhanced activity and durability for the hydrogen oxidation reaction in alkaline anion exchange membrane fuel cells.

    Science.gov (United States)

    Qin, Bowen; Yu, Hongmei; Jia, Jia; Jun, Chi; Gao, Xueqiang; Yao, Dewei; Sun, Xinye; Song, Wei; Yi, Baolian; Shao, Zhigang

    2018-03-08

    Herein, a novel non-platinum core-shell catalyst, namely, IrNi@PdIr/C was prepared via a galvanic replacement reaction; it exhibits enhanced hydrogen oxidation activity and excellent stability under alkaline conditions. Electrochemical experiments demonstrated that the mass and specific activities at 50 mV of IrNi@PdIr/C are 2.1 and 2.2 times that of commercial Pt/C in 0.1 M KOH at 298 K, respectively. Moreover, accelerated degradation tests have shown that the electrochemically active surface area (ECSA) of IrNi@PdIr/C reduces by only 5.1%, which is almost 4 times less than that of commercial Pt/C and the mass activity at 50 mV of IrNi@PdIr/C after 2000 potential cycles is still 1.8 times higher than that of aged Pt/C. XRD and XPS analysis suggest that the enhanced HOR activity is attributed to the weakening of the hydrogen binding to the PdIr overlayers induced by the IrNi core. The better stability to potential cycling can be associated with the PdIr shell, which inhibits oxide formation. These results suggest that IrNi@PdIr/C is a promising non-platinum anode catalyst for alkaline anion exchange membrane fuel cells.

  1. Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2016-02-28

    Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

  2. Hollow Au@Pd and Au@Pt core-shell nanoparticles as electrocatalysts for ethanol oxidation reactions

    KAUST Repository

    Song, Hyon Min

    2012-09-27

    Hybrid alloys among gold, palladium and platinum become a new category of catalysts primarily due to their enhanced catalytic effects. Enhancement means not only their effectiveness, but also their uniqueness as catalysts for the reactions that individual metals may not catalyze. Here, preparation of hollow Au@Pd and Au@Pt core-shell nanoparticles (NPs) and their use as electrocatalysts are reported. Galvanic displacement with Ag NPs is used to obtain hollow NPs, and higher reduction potential of Au compared to Ag, Pd, and Pt helps to produce hollow Au cores first, followed by Pd or Pt shell growth. Continuous and highly crystalline shell growth was observed in Au@Pd core-shell NPs, but the sporadic and porous-like structure was observed in Au@Pt core-shell NPs. Along with hollow core-shell NPs, hollow porous Pt and hollow Au NPs are also prepared from Ag seed NPs. Twin boundaries which are typically observed in large size (>20 nm) Au NPs were not observed in hollow Au NPs. This absence is believed to be due to the role of the hollows, which significantly reduce the strain energy of edges where the two lattice planes meet. In ethanol oxidation reactions in alkaline medium, hollow Au@Pd core-shell NPs show highest current density in forward scan. Hollow Au@Pt core-shell NPs maintain better catalytic activities than metallic Pt, which is thought to be due to the better crystallinity of Pt shells as well as the alloy effect of Au cores. © 2012 The Royal Society of Chemistry.

  3. Nano-electrochemical deposition of fuel cells electrocatalysts

    CSIR Research Space (South Africa)

    Mathe

    2008-11-01

    Full Text Available stream_source_info Mathe_2008.pdf.txt stream_content_type text/plain stream_size 34594 Content-Encoding UTF-8 stream_name Mathe_2008.pdf.txt Content-Type text/plain; charset=UTF-8 1 Nano-electrochemical deposition... of fuel cells electrocatalysts MK MATHE a,*, TS MKWIZU a,b, I CUKROWSKI b * ,aCSIR Materials Science and Manufacturing, Energy and Processes, PO Box 395, Pretoria, 0001 bDepartment of Chemistry, University of Pretoria, Pretoria, 0002 Email: kmathe...

  4. 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.

  5. The Study on the Performance of Carbon Supported PtSnM (M = W, Pd, and Ni) Ternary Electro-Catalysts for Ethanol Electro-Oxidation Reaction.

    Science.gov (United States)

    Noh, Chang Soo; Heo, Dong Hyun; Lee, Ki Rak; Jeon, Min Ku; Sohn, Jung Min

    2016-05-01

    PtSn/C and Pt5Sn4M/C (M = W, Pd, Ni) electrocatalysts were prepared by impregnation method using NaBH4 as a reducing agent. Chemical composition, crystalline size, and alloy formation were determined by EDX, XRD and TEM. The average particle sizes of the synthesized catalysts were approximately 3.64-4.95 nm. The electro-chemical properties were measured by CO stripping, cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. The maximum specific activity of the electro-catalysts for ethanol electro-oxidation was 406.08 mA m(-2) in Pt5Sn4Pd/C. The poisoning rate of the Pt5Sn4Pd/C (0.0017% s(-1)) was 4.5 times lower than that of the PtSn/C (0.0076% s(-1)).

  6. Pt and PtRu nanoparticles supported on N-doped carbons as electrocatalysts for methanol electro oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Viviane Santos; Silva, Julio Cesar Martins; Oliveira Neto, Almir; Spinace, Estevam Vitorio, E-mail: viviane_sp_saopaulo@yahoo.com.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2016-07-01

    Full text: Methanol is a liquid transportation fuel that can be produced from fossil or renewable resources. Fuel cells employing methanol directly as fuel (Direct Methanol Fuel Cell - DMFC) are very attractive as power source for portable, mobile and stationary applications [1]. PtRu/C electrocatalyst has been considered the best electrocatalyst for methanol electro-oxidation, however, its performance is strongly dependent on the method of preparation and on the characteristics of the carbon support. N-doped carbons with different N contents (1, 2 and 5 wt%) were prepared by thermal treatment of carbon with urea at 800 deg C. Pt and PtRu nanoparticles were supported on N-doped carbons by coreduction of Pt(IV) and Ru(III) ions using an alcohol-reduction process [2]. The obtained materials were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction, Transmission electron microscopy and Cyclic Voltammetry. Pt and PtRu nanoparticles supported on N-doped carbons showed superior performance for methanol electro-oxidation when compared to the materials supported on non-modified carbon and to Pt/C and PtRu/C commercial electrocatalysts. Pt/C and PtRu/C prepared with the carbon modified with 2.5 wt% of N content showed the best activities. (author) [1] Y. Zhou, K. Neyerlin, T.S. Olson, S. Pylypenko, J. Bult, H.N. Dinh, T. Gennett, Z. Shao and R. O'Hayre, Energy Environ. Sci. 3, 1437 (2010); [2] E.V. Spinace, A.Oliveira Neto, T.R.R. Vasconcellos, M. Linardi, J. Power Sources 137, 17 (2004)

  7. Effects of Activating Schoolyards

    DEFF Research Database (Denmark)

    Pawlowski, Charlotte Skau; Schipperijn, Jasper; Andersen, Henriette Bondo

    schools. Two gender-segregated focus groups at each school, including in total 57 fourth to eight graders (28 girls), were conducted. The focus groups included go-along interviews in the schoolyard, and a post-it note activity. The data was collected between April and June 2016 (six months after...... as positive for their schoolyard as it provided more variation in play facilities and improved the appearance. However, at most schools the children experienced that the renewed schoolyards were dominated by the youngest children (under 10-year-old). To minimise crowding some schools had formally restricted...... access to the renovated areas for older children and allowed them to leave the school area during recess. Furthermore, most of the children felt that the renewed schoolyard areas were far from their classrooms. CONCLUSIONS: Renewing the schoolyard is not enough to stimulate physical activity. Schools...

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. The Fundamental Role of Nano-Scale Oxide Films in the Oxidation of Hydrogen and the Reduction of Oxygen on Noble Metal Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Digby Macdonald

    2005-04-15

    The derivation of successful fuel cell technologies requires the development of more effective, cheaper, and poison-resistant electrocatalysts for both the anode (H{sub 2} oxidation in the presence of small amounts of CO from the reforming of carbonaceous fuels) and the cathode (reduction of oxygen in the presence of carried-over fuel). The proposed work is tightly focused on one specific aspect of electrocatalysis; the fundamental role(s) played by nanoscale (1-2 nm thick) oxide (''passive'') films that form on the electrocatalyst surfaces above substrate-dependent, critical potentials, on charge transfer reactions, particularly at elevated temperatures (25 C < T < 200 C). Once the role(s) of these films is (are) adequately understood, we will then use this information to specify, at the molecular level, optimal properties of the passive layer for the efficient electrocatalysis of the oxygen reduction reaction.

  13. Radiolytic Preparation of Electrocatalysts with Pt-Co and Pt-Sn Nanoparticles for a Proton Exchange Membrane Fuel Cell

    Directory of Open Access Journals (Sweden)

    Sang Kyum Kim

    2014-01-01

    Full Text Available Nanosized Pt-Sn/VC and Pt-Co/VC electrocatalysts were prepared by a one-step radiation-induced reduction (30 kGy process using distilled water as the solvent and Vulcan XC72 as the supporting material. While the Pt-Co/VC electrodes were compared with Pt/VC (40 wt%, HiSpec 4000, in terms of their electrocatalytic activity towards the oxidation of H2, the Pt-Co/VC electrodes were evaluated in terms of their activity towards the hydrogen oxidation reaction (HOR and compared with Pt/VC (40 wt%, HiSpec 4000, Pt-Co/VC, and Pt-Sn/VC in a single cell. Additionally, the prepared electrocatalyst samples (Pt-Co/VC and Pt-Sn/VC were characterized by transmission electron microscopy (TEM, scanning electron microscope (SEM, thermogravimetric analysis (TGA, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, electrochemical surface area (ECSA, and fuel cell polarization performance.

  14. Preparation and electrochemistry of graphene nanosheets–multiwalled carbon nanotubes hybrid nanomaterials as Pd electrocatalyst support for formic acid oxidation

    International Nuclear Information System (INIS)

    Yang Sudong; Shen Chengmin; Lu Xiangjun; Tong Hao; Zhu Jiajia; Zhang Xiaogang; Gao Hongjun

    2012-01-01

    Highlights: ► Graphene nanosheets–MWCNTs (GNS–CNTs) composites as Pd electrocatalysts support were synthesized by in situ reduction method. ► The direct electrooxidation of HCOOH is improved on the GNS–CNTs based catalyst. ► Both activity and durability of GNS–CNTs based catalyst are improved greatly. ► Pd/GNS–CNTs catalysts exhibit excellent performance when the mass ratio of GO to CNTs is 5:1. - Abstract: Graphene nanosheets–MWCNTs (GNS–CNTs) composites were synthesized by in situ reduction method, and then palladium nanoparticles (NPs) were supported on the GNS–CNTs by a microwave-assisted polyol process. Microstructure measurements showed that the graphene nanosheets and the CNTs formed a uniform nanocomposite with CNTs absorbed on the graphene nanosheets surface and/or filled between the graphene nanosheets. Compared to Pd/Vulcan XC-72R carbon, Pd/GNS, or Pd/CNTs catalysts, the Pd/GNS–CNTs catalysts exhibit excellent electrocatalytic activity and stability for formic acid electro-oxidation when the mass ratio of GO to CNTs is 5:1. The superior performance of Pd/GNS–CNTs catalysts may arise from large surface area utilization for NPs and enhanced electronic conductivity of the supports. Therefore, the GNS–CNTs composite should be a promising carbon material for application as electrocatalyst support in fuel cells.

  15. 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)

  16. 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

  17. 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.

  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. Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

    Science.gov (United States)

    Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

    2017-09-19

    As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

  20. Study of fluorine doped (Nb,Ir)O_2 solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

    International Nuclear Information System (INIS)

    Kadakia, Karan Sandeep; Jampani, Prashanth H.; Velikokhatnyi, Oleg I.; Datta, Moni Kanchan; Patel, Prasad; Chung, Sung Jae; Park, Sung Kyoo; Poston, James A.; Manivannan, Ayyakkannu; Kumta, Prashant N.

    2016-01-01

    Graphical abstract: High surface area (∼300 m"2/g) nanostructured powders of nominal composition (Nb_1_−_xIr_x)O_2 and (Nb_1_−_xIr_x)O_2:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb_1_−_xIr_x)O_2 with an optimal composition (Nb_0_._7_5Ir_0_._2_5)O_2:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO_2 and nanostructured in-house chemically synthesized IrO_2. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb_1_−_xIr_x)O_2:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb_0_._7_5Ir_0_._2_5)O_2:10F exhibits superior electrochemical activity than pure IrO_2. • Stability of the (Nb,Ir)O_2:10F nanomaterials is comparable to pure (Nb,Ir)O_2. • High surface area F doped (Nb,Ir)O_2 are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m"2/g) nanostructured powders of (Nb_1_−_xIr_x)O_2 and (Nb_1_−_xIr_x)O_2:10F (∼100 m"2/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb_2O_5 and 10 wt.% F doped Nb_2O_5 powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O_2 and 10 wt.% F doped (Nb,Ir)O_2 [(NbIr)O_2:10F] electro-catalysts by soaking in IrCl_4 followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb_0_._7_5Ir_0_._2_5)O_2:10F with ∼75 at.% reduction in noble metal content exhibited comparable OER activity to commercial hydrated IrO_2 and nanostructured in-house chemically synthesized IrO_2

  1. Study of fluorine doped (Nb,Ir)O{sub 2} solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kadakia, Karan Sandeep [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Jampani, Prashanth H., E-mail: pjampani@pitt.edu [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Velikokhatnyi, Oleg I.; Datta, Moni Kanchan [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Patel, Prasad [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Chung, Sung Jae [Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Park, Sung Kyoo [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Poston, James A.; Manivannan, Ayyakkannu [US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Kumta, Prashant N. [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Department of Oral Biology, School of Dental Medicine, University of Pittsburgh, PA 15217 (United States)

    2016-10-15

    Graphical abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of nominal composition (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb{sub 1−x}Ir{sub x})O{sub 2} with an optimal composition (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO{sub 2} and nanostructured in-house chemically synthesized IrO{sub 2}. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F exhibits superior electrochemical activity than pure IrO{sub 2}. • Stability of the (Nb,Ir)O{sub 2}:10F nanomaterials is comparable to pure (Nb,Ir)O{sub 2}. • High surface area F doped (Nb,Ir)O{sub 2} are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F (∼100 m{sup 2}/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb{sub 2}O{sub 5} and 10 wt.% F doped Nb{sub 2}O{sub 5} powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O{sub 2} and 10 wt.% F doped (Nb,Ir)O{sub 2} [(NbIr)O{sub 2}:10F] electro-catalysts by soaking in IrCl{sub 4} followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb{sub 0.75}Ir

  2. Carbon-Nanotubes-Supported Pd Nanoparticles for Alcohol Oxidations in Fuel Cells: Effect of Number of Nanotube Walls on Activity.

    Science.gov (United States)

    Zhang, Jin; Lu, Shanfu; Xiang, Yan; Shen, Pei Kang; Liu, Jian; Jiang, San Ping

    2015-09-07

    Carbon nanotubes (CNTs) are well known electrocatalyst supports due to their high electrical conductivity, structural stability, and high surface area. Here, we demonstrate that the number of inner tubes or walls of CNTs also have a significant promotion effect on the activity of supported Pd nanoparticles (NPs) for alcohol oxidation reactions of direct alcohol fuel cells (DAFCs). Pd NPs with similar particle size (2.1-2.8 nm) were uniformly assembled on CNTs with different number of walls. The results indicate that Pd NPs supported on triple-walled CNTs (TWNTs) have the highest mass activity and stability for methanol, ethanol, and ethylene glycol oxidation reactions, as compared to Pd NPs supported on single-walled and multi-walled CNTs. Such a specific promotion effect of TWNTs on the electrocatalytic activity of Pd NPs is not related to the contribution of metal impurities in CNTs, oxygen-functional groups of CNTs or surface area of CNTs and Pd NPs. A facile charge transfer mechanism via electron tunneling between the outer wall and inner tubes of CNTs under electrochemical driving force is proposed for the significant promotion effect of TWNTs for the alcohol oxidation reactions in alkaline solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Performance and selectivity of PtxSn/C electro-catalysts for ethanol oxidation prepared by reduction with different formic acid concentrations

    International Nuclear Information System (INIS)

    Zignani, Sabrina C.; Baglio, Vincenzo; Linares, José J.; Monforte, Giuseppe; Gonzalez, Ernesto R.; Aricò, Antonino S.

    2012-01-01

    Carbon supported Pt–Sn catalysts were prepared by reduction of Pt and Sn precursors with formic acid and characterized in terms of structure, morphology and surface properties. The electrocatalytic activity for ethanol oxidation was studied in a direct ethanol fuel cell (DEFC) at 70 °C and 90 °C. Electrochemical and physico-chemical data indicated that a proper balance of Pt and Sn species in the near surface region was necessary to maximize the reaction rate. The best atomic surface composition, in terms of electrochemical performance, was Pt:Sn 65:35 corresponding to a bulk composition 75:25 namely Pt 3 Sn 1 /C. The reaction products of ethanol electro-oxidation in single cell and their distribution as a function of the nature of catalyst were determined. Essentially, acetaldehyde and acetic acid were detected as the main reaction products; whereas, a lower content of CO 2 was formed. The selectivity toward acetic acid vs. acetaldehyde increased with the increase of the Sn content and decreased by decreasing the concentration of the reducing agent used in the catalyst preparation. According to the recent literature, these results have been interpreted on the basis of ethanol adsorption characteristics and ligand effects occurring for Sn-rich electrocatalysts.

  4. Hybrid NiCoOx adjacent to Pd nanoparticles as a synergistic electrocatalyst for ethanol oxidation

    Science.gov (United States)

    Wang, Wei; Yang, Yan; Liu, Yanqin; Zhang, Zhe; Dong, Wenkui; Lei, Ziqiang

    2015-01-01

    To improve the electrocatalytic activity of Pd for ethanol oxidation, hybrid NiCoOx adjacent to Pd catalyst (Pd-NiCoOx/C) is successfully synthesized. Physical characterization shows NiCoOx is closely adjacent to Pd nanoparticles in Pd-NiCoOx/C catalyst, which leads to Strong Metal-Support Interactions (SMSI) between the NiCoOx and Pd nanoparticles, in favor of the electrocatalytic properties. The Pd-NiCoOx/C catalyst is estimated to own larger electrochemically active surface area than Pd/C and Pd-NiO/C catalysts. Moreover, compared to Pd/C catalyst, the onset potential of Pd-NiCoOx/C catalyst is negative 40 mV for ethanol oxidation. Noticeably, the current density of Pd-NiCoOx/C catalyst is 2.05 and 1.43 times higher contrasted to Pd/C and Pd-NiO/C catalysts accordingly. Importantly, the Pd-NiCoOx/C catalyst exhibits better stability during ethanol oxidation, which is a promising electrocatalyst for application in direct alkaline alcohol fuel cells.

  5. 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

  6. Halloysite-derived nitrogen doped carbon electrocatalysts for anion exchange membrane fuel cells

    Science.gov (United States)

    Lu, Yaxiang; Wang, Lianqin; Preuß, Kathrin; Qiao, Mo; Titirici, Maria-Magdalena; Varcoe, John; Cai, Qiong

    2017-12-01

    Developing the low-cost, highly active carbonaceous materials for oxygen reduction reaction (ORR) catalysts has been a high-priority research direction for durable fuel cells. In this paper, two novel N-doped carbonaceous materials with flaky and rod-like morphology using the natural halloysite as template are obtained from urea nitrogen source as well as glucose (denoted as GU) and furfural (denoted as FU) carbon precursors, respectively, which can be directly applied as metal-free electrocatalysts for ORR in alkaline electrolyte. Importantly, compared with a benchmark Pt/C (20wt%) catalyst, the as-prepared carbon catalysts demonstrate higher retention in diffusion limiting current density (after 3000 cycles) and enhanced methanol tolerances with only 50-60mV negative shift in half-wave potentials. In addition, electrocatalytic activity, durability and methanol tolerant capability of the two N-doped carbon catalysts are systematically evaluated, and the underneath reasons of the outperformance of rod-like catalysts over the flaky are revealed. At last, the produced carbonaceous catalysts are also used as cathodes in the single cell H2/O2 anion exchange membrane fuel cell (AEMFC), in which the rod-like FU delivers a peak power density as high as 703 mW cm-2 (vs. 1106 mW cm-2 with a Pt/C benchmark cathode catalyst).

  7. 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).

  8. PdCu alloy nanoparticle-decorated copper nanotubes as enhanced electrocatalysts: DFT prediction validated by experiment

    Science.gov (United States)

    Wu, Dengfeng; Xu, Haoxiang; Cao, Dapeng; Fisher, Adrian; Gao, Yi; Cheng, Daojian

    2016-12-01

    In order to combine the advantages of both 0D and 1D nanostructured materials into a single catalyst, density functional theory (DFT) calculations have been used to study the PdCu alloy NP-decorated Cu nanotubes (PdCu@CuNTs). These present a significant improvement of the electrocatalytic activity of formic acid oxidation (FAO). Motivated by our theoretical work, we adopted the seed-mediated growth method to successfully synthesize the nanostructured PdCu@CuNTs. The new catalysts triple the catalytic activity for FAO, compared with commercial Pd/C. In summary, our work provides a new strategy for the DFT prediction and experimental synthesis of novel metal NP-decorated 1D nanostructures as electrocatalysts for fuel cells.

  9. 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.

  10. Substrate selection for fundamental studies of electrocatalysts and photoelectrodes: inert potential windows in acidic, neutral, and basic electrolyte.

    Directory of Open Access Journals (Sweden)

    Jesse D Benck

    Full Text Available The selection of an appropriate substrate is an important initial step for many studies of electrochemically active materials. In order to help researchers with the substrate selection process, we employ a consistent experimental methodology to evaluate the electrochemical reactivity and stability of seven potential substrate materials for electrocatalyst and photoelectrode evaluation. Using cyclic voltammetry with a progressively increased scan range, we characterize three transparent conducting oxides (indium tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide and four opaque conductors (gold, stainless steel 304, glassy carbon, and highly oriented pyrolytic graphite in three different electrolytes (sulfuric acid, sodium acetate, and sodium hydroxide. We determine the inert potential window for each substrate/electrolyte combination and make recommendations about which materials may be most suitable for application under different experimental conditions. Furthermore, the testing methodology provides a framework for other researchers to evaluate and report the baseline activity of other substrates of interest to the broader community.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-15

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

  12. Highly acid-durable carbon coated Co3O4 nanoarrays as efficient oxygen evolution electrocatalysts

    KAUST Repository

    Yang, Xiulin; Li, Henan; Lu, Ang-Yu; Min, Shixiong; Idriss, Zacharie; Hedhili, Mohamed N.; Huang, Kuo-Wei; Idriss, Hicham; Li, Lain-Jong

    2016-01-01

    Most oxygen evolution reaction (OER) electrocatalysts are not stable in corrosive acids. Even the expensive RuO2 or IrO2, the most acid-resistant oxides, can be dissolved at an oxidative potential. Herein, we realize that the failures of OER catalysts are mostly caused by the weak interface between catalysts and the substrates. Hence, the study of the interface structure between catalysts and substrates is critical. In this work, we observe that the cheap OER catalysts Co3O4 can be more durable than the state-of-the-art RuO2 if the interface quality is good enough. The Co3O4 nanosheets deposited on carbon paper (Co3O4/CP) is prepared by electroplating of Co-species and followed by a two-step calcination process. The 1st step occurs in vacuum in order to maintain the surface integrity of the carbon paper and converts Co-species to Co(II)O. The 2nd step is a calcination in ambient conditions which enables the complete transformation of Co(II)O to Co3O4 without degrading the mechanical strength of the Co3O4-CP interface. Equally important, an in situ formation of a layer of amorphous carbon on top of Co3O4 further enhances the OER catalyst stability. Therefore, these key advances make the Co3O4 catalyst highly active toward the OER in 0.5 M H2SO4 with a small overpotential (370 mV), to reach 10 mA/cm2. The observed long lifetime for 86.8 h at a constant current density of 100 mA/cm2, is among the best of the reported in literature so far, even longer than the state-of-art RuO2 on CP. Overall, our study provides a new insight and methodology for the construction of a high-performance and high stability OER electrocatalysts in corrosive acidic environments.

  13. Nickel-based anodic electrocatalysts for fuel cells and water splitting

    Science.gov (United States)

    Chen, Dayi

    Our world is facing an energy crisis, so people are trying to harvest and utilize energy more efficiently. One of the promising ways to harvest energy is via solar water splitting to convert solar energy to chemical energy stored in hydrogen. Another of the options to utilize energy more efficiently is to use fuel cells as power sources instead of combustion engines. Catalysts are needed to reduce the energy barriers of the reactions happening at the electrode surfaces of the water-splitting cells and fuel cells. Nickel-based catalysts happen to be important nonprecious electrocatalysts for both of the anodic reactions in alkaline media. In alcohol fuel cells, nickel-based catalysts catalyze alcohol oxidation. In water splitting cells, they catalyze water oxidation, i.e., oxygen evolution. The two reactions occur in a similar potential range when catalyzed by nickel-based catalysts. Higher output current density, lower oxidation potential, and complete substrate oxidation are preferred for the anode in the applications. In this dissertation, the catalytic properties of nickel-based electrocatalysts in alkaline medium for fuel oxidation and oxygen evolution are explored. By changing the nickel precursor solubility, nickel complex nanoparticles with tunable sizes on electrode surfaces were synthesized. Higher methanol oxidation current density is achieved with smaller nickel complex nanoparticles. DNA aggregates were used as a polymer scaffold to load nickel ion centers and thus can oxidize methanol completely at a potential about 0.1 V lower than simple nickel electrodes, and the methanol oxidation pathway is changed. Nickel-based catalysts also have electrocatalytic activity towards a wide range of substrates. Experiments show that methanol, ethanol, glycerol and glucose can be deeply oxidized and carbon-carbon bonds can be broken during the oxidation. However, when comparing methanol oxidation reaction to oxygen evolution reaction catalyzed by current nickel

  14. Highly acid-durable carbon coated Co3O4 nanoarrays as efficient oxygen evolution electrocatalysts

    KAUST Repository

    Yang, Xiulin

    2016-04-21

    Most oxygen evolution reaction (OER) electrocatalysts are not stable in corrosive acids. Even the expensive RuO2 or IrO2, the most acid-resistant oxides, can be dissolved at an oxidative potential. Herein, we realize that the failures of OER catalysts are mostly caused by the weak interface between catalysts and the substrates. Hence, the study of the interface structure between catalysts and substrates is critical. In this work, we observe that the cheap OER catalysts Co3O4 can be more durable than the state-of-the-art RuO2 if the interface quality is good enough. The Co3O4 nanosheets deposited on carbon paper (Co3O4/CP) is prepared by electroplating of Co-species and followed by a two-step calcination process. The 1st step occurs in vacuum in order to maintain the surface integrity of the carbon paper and converts Co-species to Co(II)O. The 2nd step is a calcination in ambient conditions which enables the complete transformation of Co(II)O to Co3O4 without degrading the mechanical strength of the Co3O4-CP interface. Equally important, an in situ formation of a layer of amorphous carbon on top of Co3O4 further enhances the OER catalyst stability. Therefore, these key advances make the Co3O4 catalyst highly active toward the OER in 0.5 M H2SO4 with a small overpotential (370 mV), to reach 10 mA/cm2. The observed long lifetime for 86.8 h at a constant current density of 100 mA/cm2, is among the best of the reported in literature so far, even longer than the state-of-art RuO2 on CP. Overall, our study provides a new insight and methodology for the construction of a high-performance and high stability OER electrocatalysts in corrosive acidic environments.

  15. Combined Photoemission Spectroscopy and Electrochemical Study of a Mixture of (Oxy)carbides as Potential Innovative Supports and Electrocatalysts.

    Science.gov (United States)

    Calvillo, Laura; Valero-Vidal, Carlos; Agnoli, Stefano; Sezen, Hikmet; Rüdiger, Celine; Kunze-Liebhäuser, Julia; Granozzi, Gaetano

    2016-08-03

    Active and stable non-noble metal materials, able to substitute Pt as catalyst or to reduce the Pt amount, are vitally important for the extended commercialization of energy conversion technologies, such as fuel cells and electrolyzers. Here, we report a fundamental study of nonstoichiometric tungsten carbide (WxC) and its interaction with titanium oxycarbide (TiOxCy) under electrochemical working conditions. In particular, the electrochemical activity and stability of the WxC/TiOxCy system toward the ethanol electrooxidation reaction (EOR) and hydrogen evolution reaction (HER) are investigated. The chemical changes caused by the applied potential are established by combining photoemission spectroscopy and electrochemistry. WxC is not active toward the ethanol electrooxidation reaction at room temperature but it is highly stable under these conditions thanks to the formation of a passive thin film on the surface, consisting mainly of WO2 and W2O5, which prevents the full oxidation of WxC. In addition, WxC is able to adsorb ethanol, forming ethoxy groups on the surface, which constitutes the first step for the ethanol oxidation. The interaction between WxC and TiOxCy plays an important role in the electrochemical stability of WxC since specific orientations of the substrate are able to stabilize WxC and prevent its corrosion. The beneficial interaction with the substrate and the specific surface chemistry makes tungsten carbide a good electrocatalyst support or cocatalyst for direct ethanol fuel cells. However, WxC is active toward the HER and chemically stable under hydrogen reduction conditions, since no changes in the chemical composition or dissolution of the film are observed. This makes tungsten carbide a good candidate as electrocatalyst support or cocatalyst for the electrochemical production of hydrogen.

  16. 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.

  17. Perovskite oxides La0.4Sr0.6CoxMn1-xO3 (x = 0, 0.2, 0.4 as an effective electrocatalyst for lithium—air batteries

    Directory of Open Access Journals (Sweden)

    Yajun Zhao

    2018-01-01

    Full Text Available Co-doped perovskite oxide La0.4Sr0.6CoxMn1-xO3 (x = 0, 0.2, 0.4 composites are prepared by sol–gel method utilizing citric acid as chelating agent. These composites show good catalytic activities when tested as catalysts rechargeable lithium—air batteries. In particular, the La0.4Sr0.6Co0.4Mn0.6O3 shows a lower potential gap. When these samples are tested as catalysts for Li—air batteries at a current density of 100 mA g−1, the discharge capacities with different La0.4Sr0.6CoxMn1-xO3 (x = 0, 0.2, 0.4 catalysts are 5819, 6420, and 7227 mA h g−1, respectively. In addition, under a capacity limitation of 1000 mA h g−1, the cell using La0.4Sr0.6Co0.4Mn0.6O3 as catalyst shows good cycling stability up to 46 cycles. The good electrochemical performance suggests that suitable doping of Co in Mn site of La0.4Sr0.6MnO3 could be a promising route to improve the catalytic activity.

  18. 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.

  19. 3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports.

    Science.gov (United States)

    Sneed, Brian T; Cullen, David A; Reeves, Kimberly S; Dyck, Ondrej E; Langlois, David A; Mukundan, Rangachary; Borup, Rodney L; More, Karren L

    2017-09-06

    Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of the cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Furthermore, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.

  20. Synthesis of grape-like carbon nanospheres and their application as photocatalyst and electrocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Mahajan, Mani, E-mail: manimahajan86@gmail.com; Singla, Gourav, E-mail: gsinghla@gmail.com; Singh, K., E-mail: kusingh@thapar.edu; Pandey, O.P., E-mail: oppandey@thapar.edu

    2015-12-15

    Carbon nanospheres of grape-like structure (CNS) with diameter ranging from 40 to 50 nm and wall thickness of 6–8 nm were synthesized by solvothermal route. The phase structure, morphology, microstructure, thermal stability, disorder and optical properties of synthesized CNS were investigated by various characterization techniques. The possible formation and growth mechanism for CNS were discussed on the basis of the in-build reaction conditions. The degradation study of organic pollutants (methylene blue) in UV light in the presence of synthesized CNS was done. The stability of the CNS in electrochemical performance was also discussed at the different potential window and compared its electrocatalytic activity with platinum supported on CNS which shows the better response for oxygen reduction reactions (ORR) at an optimized potential window (–0.2 to 1.0 V vs SCE). - Graphical abstract: A representative synthesis mechanism of carbon nano sphere (CNS) showing spherical morphology with its photo as well as electrocatalyst properties. - Highlights: • Carbon nanospheres (CNS) have been synthesized using in situ chemical-reduction route. • The bare CNS shows good luminescence and photocatalytic applications. • The Pt/CNS shows better electrochemical performance than the reported Pt/C.

  1. Nanostructured Carbon Materials as Supports in the Preparation of Direct Methanol Fuel Cell Electrocatalysts

    Directory of Open Access Journals (Sweden)

    María Jesús Lázaro

    2013-08-01

    Full Text Available Different advanced nanostructured carbon materials, such as carbon nanocoils, carbon nanofibers, graphitized ordered mesoporous carbons and carbon xerogels, presenting interesting features such as high electrical conductivity and extensively developed porous structure were synthesized and used as supports in the preparation of electrocatalysts for direct methanol fuel cells (DMFCs. The main advantage of these supports is that their physical properties and surface chemistry can be tailored to adapt the carbonaceous material to the catalytic requirements. Moreover, all of them present a highly mesoporous structure, diminishing diffusion problems, and both graphitic character and surface area can be conveniently modified. In the present work, the influence of the particular features of each material on the catalytic activity and stability was analyzed. Results have been compared with those obtained for commercial catalysts supported on Vulcan XC-72R, Pt/C and PtRu/C (ETEK. Both a highly ordered graphitic and mesopore-enriched structure of these advanced nanostructured materials resulted in an improved electrochemical performance in comparison to the commercial catalysts assayed, both towards CO and alcohol oxidation.

  2. Plasma nitriding induced growth of Pt-nanowire arrays as high performance electrocatalysts for fuel cells

    Science.gov (United States)

    Du, Shangfeng; Lin, Kaijie; Malladi, Sairam K.; Lu, Yaxiang; Sun, Shuhui; Xu, Qiang; Steinberger-Wilckens, Robert; Dong, Hanshan

    2014-09-01

    In this work, we demonstrate an innovative approach, combing a novel active screen plasma (ASP) technique with green chemical synthesis, for a direct fabrication of uniform Pt nanowire arrays on large-area supports. The ASP treatment enables in-situ N-doping and surface modification to the support surface, significantly promoting the uniform growth of tiny Pt nuclei which directs the growth of ultrathin single-crystal Pt nanowire (2.5-3 nm in diameter) arrays, forming a three-dimensional (3D) nano-architecture. Pt nanowire arrays in-situ grown on the large-area gas diffusion layer (GDL) (5 cm2) can be directly used as the catalyst electrode in fuel cells. The unique design brings in an extremely thin electrocatalyst layer, facilitating the charge transfer and mass transfer properties, leading to over two times higher power density than the conventional Pt nanoparticle catalyst electrode in real fuel cell environment. Due to the similar challenges faced with other nanostructures and the high availability of ASP for other material surfaces, this work will provide valuable insights and guidance towards the development of other new nano-architectures for various practical applications.

  3. Aligned carbon nanotube array functionalization for enhanced atomic layer deposition of platinum electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dameron, Arrelaine A., E-mail: arrelaine.dameron@nrel.gov [National Renewable Energy Laboratory, 1617 Cole Blvd Golden, Golden, CO 80401 (United States); Pylypenko, Svitlana; Bult, Justin B.; Neyerlin, K.C.; Engtrakul, Chaiwat; Bochert, Christopher; Leong, G. Jeremy; Frisco, Sarah L.; Simpson, Lin; Dinh, Huyen N.; Pivovar, Bryan [National Renewable Energy Laboratory, 1617 Cole Blvd Golden, Golden, CO 80401 (United States)

    2012-04-15

    Uniform metal deposition onto high surface area supports is a key challenge of developing successful efficient catalyst materials. Atomic layer deposition (ALD) circumvents permeation difficulties, but relies on gas-surface reactions to initiate growth. Our work demonstrates that modified surfaces within vertically aligned carbon nanotube (CNT) arrays, from plasma and molecular precursor treatments, can lead to improved catalyst deposition. Gas phase functionalization influences the number of ALD nucleation sites and the onset of ALD growth and, in turn, affects the uniformity of the coating along the length of the CNTs within the aligned arrays. The induced chemical changes for each functionalization route are identified by X-ray photoelectron and Raman spectroscopies. The most effective functionalization routes increase the prevalence of oxygen moieties at defect sites on the carbon surfaces. The striking effects of the functionalization are demonstrated with ALD Pt growth as a function of surface treatment and ALD cycles examined by electron microscopy of the arrays and the individual CNTs. Finally, we demonstrate applicability of these materials as fuel cell electrocatalysts and show that surface functionalization affects their performance towards oxygen reduction reaction.

  4. Sonochemical synthesis of a PdAg/C electrocatalyst for oxygen reduction reaction; Sintesis sonoquimica de un electrocatalizador de PdAg/C para la reaccion de reduccion de oxigeno

    Energy Technology Data Exchange (ETDEWEB)

    Godinez-Garcia, A.; Perez-Robles, J.F. [Centro de Investigacion y de Estudios Avanzados del IPN. Santiago de Queretaro, Queretaro (Mexico)]. E-mail: jperez@qro.cinvestav.mx; Solorza-Feria, O. [CINVESTAV-IPN, Mexico, D.F. (Mexico)

    2009-09-15

    The synthesis and characterization of nanocatalysts for fuel cells has been a primary line of research for the purpose of obtaining less expensive electrocatalysts with better activity. A large variety of methods exist to synthesize useful nanoparticles as electrocatalysts. Each method generates particles with a different surface morphology and, therefore, the catalytic activity usually varies depending on which is used in the synthesis. In this work, PdAg/C electrocatalysts are synthesized with high-intensity ultrasonic irradiation and compared to those obtained using a conventional method such as reduction by NaBH{sub 4}. The study of this technique is of interest because it produces highly dispersed carbon-supported nanoparticles with very clean surfaces. Each electrocatalyst was evaluated for its oxygen reduction reaction (ORR) in acid medium with cyclic voltamperometry (CV) and rotating disc electrode (RDE). The electrocatalyst was characterized with x-ray diffraction and transmission electron microscopy (TEM). The physical characterization reveals that the electrocatalyst is composed of nanometric bimetallic aggregates. An important characteristic of the PdAg/C alloy obtained using ultrasound is better activity than that obtained by reduction with NaBH{sub 4}. [Spanish] La sintesis y caracterizacion de nanocatalizadores para celdas de combustible ha sido una de las principales lineas de investigacion, con el objetivo de obtener electrocatalizadores mas baratos y con una mejor actividad. Existen una gran variedad de metodos para sintetizar nanoparticulas utiles como electrocatalizadores, cada metodo genera particulas con una morfologia superficial diferente por lo que la actividad catalitica suele variar dependiendo de cual se utilice en la sintesis. En este trabajo se sintetizan electrocatalizadores de PdAg/C con irradiacion ultrasonica de alta intensidad y se comparan con las obtenidas con un metodo convencional como es la reduccion por NaBH{sub 4}. Esta

  5. First report of vertically aligned (Sn,Ir)O2:F solid solution nanotubes: Highly efficient and robust oxygen evolution electrocatalysts for proton exchange membrane based water electrolysis

    Science.gov (United States)

    Ghadge, Shrinath Dattatray; Patel, Prasad P.; Datta, Moni K.; Velikokhatnyi, Oleg I.; Shanthi, Pavithra M.; Kumta, Prashant N.

    2018-07-01

    One dimensional (1D) vertically aligned nanotubes (VANTs) of (Sn0.8Ir0.2)O2:10F are synthesized for the first time by a sacrificial template assisted approach. The aim is to enhance the electrocatalytic activity of F doped (Sn,Ir)O2 solid solution electrocatalyst for oxygen evolution reaction (OER) in proton exchange membrane (PEM) based water electrolysis by generating (Sn0.8Ir0.2)O2:10F nanotubes (NTs). The 1D vertical channels and the high electrochemically active surface area (ECSA ∼38.46 m2g-1) provide for facile electron transport. This results in low surface charge transfer resistance (4.2 Ω cm2), low Tafel slope (58.8 mV dec-1) and excellent electrochemical OER performance with ∼2.3 and ∼2.6 fold higher electrocatalytic activity than 2D thin films of (Sn0.8Ir0.2)O2:10F and benchmark IrO2 electrocatalysts, respectively. Furthermore, (Sn0.8Ir0.2)O2:10F NTs exhibit excellent mass activity (21.67 A g-1), specific activity (0.0056 mAcm-2) and TOF (0.016 s-1), which is ∼2-2.6 fold higher than thin film electrocatalysts at an overpotential of 270 mV, with a total mass loading of 0.3 mg cm-2. In addition, (Sn0.8Ir0.2)O2:10F NTs demonstrate remarkable electrochemical durability - comparable to thin films of (Sn0.8Ir0.2)O2:10F and pure IrO2, operated under identical testing conditions in PEM water electrolysis. These results therefore indicate promise of (Sn0.8Ir0.2)O2:10F NTs as OER electrocatalysts for efficient and sustainable hydrogen production.

  6. 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.

  7. 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.

  8. 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.

  9. Structure-activity relationship of surfactant for preparing DMFC anodic catalyst

    International Nuclear Information System (INIS)

    Su Yi; Xue Xinzhong; Xu Weilin; Liu Changpeng; Xing Wei; Zhou Xiaochun; Tian Tian; Lu Tianhong

    2006-01-01

    Three kinds of surfactants as stabilizer were applied to the preparation of electrocatalysts for direct methanol fuel cell (DMFC). The catalysts have been characterized by examining their catalytic activities, morphologies and particle sizes by means of cyclic voltammetry, chronoamperometry, X-ray diffraction and transmission electron microscopy (TEM). It is found that the surfactants with different structures have a significantly influence on the catalyst shape and activity. The catalysts prepared with non-ionic surfactants as the stabilizer show higher activity for direct oxidation of methanol. The structure-activity relationship (SAR) analysis has been explored and the effect of hydrophile-lipophile balance (HLB value) has also been discussed

  10. 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

  11. Amorphous nickel/cobalt tungsten sulfide electrocatalysts for high-efficiency hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Lun [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Wu, Xinglong, E-mail: hkxlwu@nju.edu.cn [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Department of Physics, NingBo University, NingBo 315001 (China); Zhu, Xiaoshu [Center for Analysis and Testing, Nanjing Normal University, Nanjing 210093 (China); He, Chengyu; Meng, Ming; Gan, Zhixing [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Chu, Paul K. [Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China)

    2015-06-30

    Graphical abstract: - Highlights: • Amorphous nickel/cobalt tungsten sulfides were synthesized by a thermolytic process. • Amorphous NiWS and CoWS could realize hydrogen evolution efficiently. • Ni/Co promotion and annealing alter the porous structure and chemical bonding states. • Active sites on the surface of amorphous WS{sub x} are increased with Ni or Co doping. • Amorphous NiWS and CoWS have immense potentials in water splitting devices. - Abstract: The hydrogen evolution reaction (HER), an appealing solution for future energy supply, requires efficient and inexpensive electrocatalysts with abundant active surface sites. Although crystalline MoS{sub 2} and WS{sub 2} are promising candidates, their activity is dominated by edge sites. Amorphous tungsten sulfide prepared so far lacks the required active sites and its application has thus been hampered. In this work, nickel and cobalt incorporated amorphous tungsten sulfide synthesized by a thermolytic process is demonstrated to enhance the HER efficiency dramatically. The amorphous nickel tungsten sulfide (amorphous NiWS) annealed at 210 °C delivers the best HER performance in this system boasting a Tafel slope of 55 mV per decade and current density of 8.6 mA cm{sup −2} at 250 mV overpotential in a sustained test for 24 h. The introduction of Ni or Co into the catalyst and subsequent thermal treatment alters the porous structure and chemical bonding states thereby increasing the density of active sites on the surface.

  12. Investigation of Novel Electrocatalysts for Metal Supported Solid Oxide Fuel Cells - Ru:GDC

    DEFF Research Database (Denmark)

    Sudireddy, Bhaskar Reddy; Nielsen, Jimmi; Thydén, Karl Tor Sune

    2015-01-01

    Even though solid oxide fuel cells (SOFCs) have a high potential with respect to efficiency and fuel flexibility they are not yet competitive in terms of cost and durability with conventional chemical energy conversion technologies. The potential cost reduction can be achieved through...... in tolerating the vibrations, transient loads, thermal and redox cycling [1-2]. The DTU MS-SOFC design based on ferritic stainless steel requires incorporation of electrocatalyst into the anode functional layer by infiltration methods [3]. Previously, the preferred electrocatalyst has been gadolinium doped...... and microstructure of the infiltrated electrocatalyst layer was characterized using high-resolution electron microscopy. The electrochemical characterization involved polarization curves and electrochemical impedance spectroscopy (EIS) in the temperature range of 650-750ºC. The polarization curve for Ru...

  13. Seawater splitting for high-efficiency hydrogen evolution by alloyed PtNix electrocatalysts

    Science.gov (United States)

    Zheng, Jingjing

    2017-08-01

    Robust electrocatalyst is a prerequisite to realize high-efficiency hydrogen evolution by water splitting. Expensive platinum (Pt) is a preferred electrode catalyst for state-of-the-art hydrogen evolution reaction (HER). We present here a category of alloyed PtNix electrocatalysts by a facile green chemical reduction method, which are used to catalyze HER during seawater splitting. The catalytic performances are optimized by tuning stoichiometric Pt/Ni ratio, yielding a maximized catalytic behavior for PtNi5 electrode. The minimized onset potential is as low as -0.38 V and the corresponding Tafel slope is 119 mV dec-1. Moreover, the launched alloy electrodes have remarkable stability at -1.2 V over 12 h. The high efficiency as well as good durability demonstrates the PtNix electrocatalysts to be promising in practical applications.

  14. Tuning of CO2 Reduction Selectivity on Metal Electrocatalysts.

    Science.gov (United States)

    Wang, Yuhang; Liu, Junlang; Wang, Yifei; Al-Enizi, Abdullah M; Zheng, Gengfeng

    2017-11-01

    Climate change, caused by heavy CO 2 emissions, is driving new demands to alleviate the rising concentration of atmospheric CO 2 levels. Enlightened by the photosynthesis of green plants, photo(electro)chemical catalysis of CO 2 reduction, also known as artificial photosynthesis, is emerged as a promising candidate to address these demands and is widely investigated during the past decade. Among various artificial photosynthetic systems, solar-driven electrochemical CO 2 reduction is widely recognized to possess high efficiencies and potentials for practical application. The efficient and selective electroreduction of CO 2 is the key to the overall solar-to-chemical efficiency of artificial photosynthesis. Recent studies show that various metallic materials possess the capability to play as electrocatalysts for CO 2 reduction. In order to achieve high selectivity for CO 2 reduction products, various efforts are made including studies on electrolytes, crystal facets, oxide-derived catalysts, electronic and geometric structures, nanostructures, and mesoscale phenomena. In this Review, these methods for tuning the selectivity of CO 2 electrochemical reduction of metallic catalysts are summarized. The challenges and perspectives in this field are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ni-based electrocatalyst for water oxidation developed In-situ in a HCO3 -/CO2 system at near-neutral pH

    KAUST Repository

    Joya, Khurram Saleem

    2014-03-10

    Electrochemically generated NiOx nanoworms from a neutral bicarbonate system split water into dioxygen and protons with tremendous efficiency and stability. The NiOx electrocatalyst follows a pH-potential dependence, revealing a PCET (proton coupled electron transfer) mechanism of one electron and one proton oxidation. It does not require proton abstracting phosphate or borate buffers for electrogeneration and catalysis, and shows promising activity for anodic oxidation of water in phosphate, borate, and carbonate buffers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Ni-based electrocatalyst for water oxidation developed In-situ in a HCO3 -/CO2 system at near-neutral pH

    KAUST Repository

    Joya, Khurram Saleem; Joya, Yasir F.; De Groot, Huub J M

    2014-01-01

    Electrochemically generated NiOx nanoworms from a neutral bicarbonate system split water into dioxygen and protons with tremendous efficiency and stability. The NiOx electrocatalyst follows a pH-potential dependence, revealing a PCET (proton coupled electron transfer) mechanism of one electron and one proton oxidation. It does not require proton abstracting phosphate or borate buffers for electrogeneration and catalysis, and shows promising activity for anodic oxidation of water in phosphate, borate, and carbonate buffers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. Oxide (CeO{sub 2}, NiO, Co{sub 3}O{sub 4} and Mn{sub 3}O{sub 4})-promoted Pd/C electrocatalysts for alcohol electrooxidation in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Changwei; Tian, Zhiqun; Jiang, San Ping [School of Mechanical and Aerospace Engineering, Nanyang Technological University (Singapore); Shen, Peikang [School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

    2008-01-01

    This study investigated Pt/C, Pd/C and oxide (CeO{sub 2}, NiO, Co{sub 3}O{sub 4} and Mn{sub 3}O{sub 4})-promoted Pd/C for electrooxidation reactions of methanol, ethanol, ethylene glycol and glycerol in alkaline media. The results show that Pd/C electrocatalysts alone have low activity and very poor stability for the alcohol electrooxidation. However, addition of oxides like CeO{sub 2}, NiO, Co{sub 3}O{sub 4} and Mn{sub 3}O{sub 4} significantly promotes catalytic activity and stability of the Pd/C electrocatalysts for the alcohol electrooxidation. The Pd-Co{sub 3}O{sub 4} (2:1, w:w)/C shows the highest activity for the electrooxidation of methanol, EG and glycerol while the most active catalyst for the ethanol electrooxidation is Pd-NiO (6:1, w:w)/C. On the other hand, Pd-Mn{sub 3}O{sub 4}/C shows significantly better performance stability than other oxide-promoted Pd/C for the alcohol electrooxidation. The poor stability of the Pd-Co{sub 3}O{sub 4}/C electrocatalysts is most likely related to the limited solubility of cobalt oxides in alkaline solutions. (author)

  19. Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Geraldes, Adriana Napoleão; Furtunato da Silva, Dionisio; Pino, Eddy Segura; Martins da Silva, Júlio César; Brambilla de Souza, Rodrigo Fernando; Hammer, Peter; Spinacé, Estevam Vitório; Neto, Almir Oliveira; Linardi, Marcelo; Coelho dos Santos, Mauro

    2013-01-01

    Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd:Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3–5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd:Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 90 °C, and the best performance of 44 mW cm −2 in 2.0 mol L −1 ethanol was obtained at 85 °C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support

  20. Performance of a PEM water electrolyser using a TaC-supported iridium oxide electrocatalyst

    DEFF Research Database (Denmark)

    Polonský, J.; Mazúr, P.; Paidar, M.

    2014-01-01

    by dispersing the precious metal compound onto a catalyst support. Electrocatalysts with 50, 70 and 90 wt.% of IrO2 on a TaC support were tested in a laboratory PEM water electrolyser and compared with pure IrO2. The temperature was set at 90, 110, 120 and 130 °C respectively and the cell voltage was varied......Polymer electrolyte membrane (PEM) water electrolysis is an attractive way of producing carbon-free hydrogen. One of the drawbacks of this method is the need for precious metal-based electrocatalysts. This calls for a highly efficient utilization of the precious metal, which can be obtained...

  1. A DFT-based genetic algorithm search for AuCu nanoalloy electrocatalysts for CO2 reduction

    DEFF Research Database (Denmark)

    Lysgaard, Steen; Mýrdal, Jón Steinar Garðarsson; Hansen, Heine Anton

    2015-01-01

    Using a DFT-based genetic algorithm (GA) approach, we have determined the most stable structure and stoichiometry of a 309-atom icosahedral AuCu nanoalloy, for potential use as an electrocatalyst for CO2 reduction. The identified core–shell nano-particle consists of a copper core interspersed....... This shows that the mixed Cu135@Au174 core–shell nanoalloy has a similar adsorption energy, for the most favorable site, as a pure gold nano-particle. Cu, however, has the effect of stabilizing the icosahedral structure because Au particles are easily distorted when adding adsorbates....... that it is possible to use the LCAO mode to obtain a realistic estimate of the molecular chemisorption energy for systems where the computation in normal grid mode is not computationally feasible. These corrections are employed when calculating adsorption energies on the Cu, Au and most stable mixed particles...

  2. 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.

  3. 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.

  4. Carbon-supported iron complexes as electrocatalysts for the cogeneration of hydroxylamine and electricity in a NO-H2 fuel cell: A combined electrochemical and density functional theory study

    Science.gov (United States)

    Sheng, Xia; Alvarez-Gallego, Yolanda; Dominguez-Benetton, Xochitl; Baert, Kitty; Hubin, Annick; Zhao, Hailiang; Mihaylov, Tzvetan T.; Pierloot, Kristine; Vankelecom, Ivo F. J.; Pescarmona, Paolo P.

    2018-06-01

    Carbon-supported iron complexes were investigated as electrocatalysts for the reduction of nitric oxide (NO) in a H2-NO fuel cell conceived for the production of hydroxylamine (NH2OH) with concomitant generation of electricity. Two types of iron complexes with tetradentate ligands, namely bis(salicylidene)ethylenediimine (Salen) and phthalocyanine (Pc), supported on activated carbon or graphite were prepared and evaluated as electrocatalysts, either without further treatment or after pyrolysis at 700 °C. The performance in the reduction of NO of gas diffusion cathodes based on these electrocatalysts was investigated in an electrochemical half cell (3-electrode configuration) using linear sweep voltammetry (LSV). The most promising electrocatalysts were studied further by chronoamperometric experiments in a H2-NO fuel cell, which allowed comparison in terms of power output and hydroxylamine production. Depending on the concentration of the NO feed (6 or 18%), the best electrocatalytic performance was delivered either by FePc or FeSalen. The gas diffusion electrode based on FeSalen supported on activated carbon with 0.3 wt% Fe-loading provided the highest current density (86 A/m2) and the best current efficiency (43%) towards the desired NH2OH when operating at the higher NO concentration (18%). Moreover, FeSalen offers the advantage of being cheaper than FePc. The experimental work was complemented by density functional theory (DFT) calculations, which allowed to shed more light on the reaction mechanism for the reduction of nitric oxide at the atomistic level.

  5. Ru-decorated Pt surfaces as model fuel cell electrocatalysts for CO electrooxidation.

    Science.gov (United States)

    Maillard, F; Lu, G-Q; Wieckowski, A; Stimming, U

    2005-09-01

    This feature article concerns Pt surfaces modified (decorated) by ruthenium as model fuel cell electrocatalysts for electrooxidation processes. This work reveals the role of ruthenium promoters in enhancing electrocatalytic activity toward organic fuels for fuel cells, and it particularly concerns the methanol decomposition product, surface CO. A special focus is on surface mobility of the CO as it is catalytically oxidized to CO(2). Different methods used to prepare Ru-decorated Pt single crystal surfaces as well as Ru-decorated Pt nanoparticles are reviewed, and the methods of characterization and testing of their activity are discussed. The focus is on the origin of peak splitting involved in the voltammetric electrooxidation of CO on Ru-decorated Pt surfaces, and on the interpretative consequences of the splitting for single crystal and nanoparticle Pt/Ru bimetallic surfaces. Apparently, screening through the literature allows formulating several models of the CO stripping reaction, and the validity of these models is discussed. Major efforts are made in this article to compare the results reported by the Urbana-Champaign group and the Munich group, but also by other groups. As electrocatalysis is progressively more and more driven by theory, our review of the experimental findings may serve to summarize the state of the art and clarify the roads ahead. Future studies will deal with highly dispersed and reactive nanoscale surfaces and other more advanced catalytic materials for fuel cell catalysis and related energy applications. It is expected that the metal/metal and metal/substrate interactions will be increasingly investigated on atomic and electronic levels, with likewise increasing participation of theory, and the structure and reactivity of various monolayer catalytic systems involving more than two metals (that is ternary and quaternary systems) will be interrogated.

  6. Stability of CoP x Electrocatalysts in Continuous and Interrupted Acidic Electrolysis of Water.

    Science.gov (United States)

    Goryachev, Andrey; Gao, Lu; Zhang, Yue; Rohling, Roderigh Y; Vervuurt, René H J; Bol, Ageeth A; Hofmann, Jan P; Hensen, Emiel J M

    2018-04-11

    Cobalt phosphides are an emerging earth-abundant alternative to platinum-group-metal-based electrocatalysts for the hydrogen evolution reaction (HER). Yet, their stability is inferior to platinum and compromises the large-scale applicability of CoP x in water electrolyzers. In the present study, we employed flat, thin CoP x electrodes prepared through the thermal phosphidation (PH 3 ) of Co 3 O 4 films made by plasma-enhanced atomic layer deposition to evaluate their stability in acidic water electrolysis by using a multi-technique approach. The films were found to be composed of two phases: CoP in the bulk and a P-rich surface CoP x (P/Co>1). Their performance was evaluated in the HER and the exchange current density was determined to be j 0 =-8.9 ⋅ 10 -5  A/cm 2 . The apparent activation energy of HER on CoP x ( E a =81±15 kJ/mol) was determined for the first time. Dissolution of the material in 0.5 M H 2 SO 4 was observed, regardless of the constantly applied cathodic potential, pointing towards a chemical instead of an electrochemical origin of the observed cathodic instability. The current density and HER faradaic efficiency (FE) were found to be stable during chronoamperometric treatment, as the chemical composition of the HER-active phase remained unchanged. On the contrary, a dynamic potential change performed in a repeated way facilitated dissolution of the film, yielding its complete degradation within 5 h. There, the FE was also found to be changing. An oxidative route of CoP x dissolution has also been proposed.

  7. Highly cost-effective and sulfur/coking resistant VOx-grafted TiO2 nanoparticles as an efficient anode catalyst for direct conversion of dry sour methane in solid oxide fuel cells

    NARCIS (Netherlands)

    Garcia, A.; Yan, N.; Vincent, A.; Singh, A.; Hill, J.M.; Chuang, K. T.; Luo, J.L.

    2015-01-01

    In this work, we show that grafted metal oxide can be a highly cost-effective and active anode for solid oxide fuel cells for sour methane conversion. The developed electro-catalyst was composed of vanadium oxide grafted TiO2 nanoparticles (VOx/TiO2) infiltrated into a porous La0.4Sr0.5Ba0.1TiO3+δ

  8. Tantalum carbide as a novel support material for anode electrocatalysts in polymer electrolyte membrane water electrolysers

    DEFF Research Database (Denmark)

    Polonský, Jakub; Petrushina, Irina; Christensen, Erik

    2012-01-01

    Iridium oxide (IrO2) currently represents a state of the art electrocatalyst for anodic oxygen evolution. Since iridium is both expensive and scarce, the future practical application of this process makes it essential to reduce IrO2 loading on the anodes of PEM water electrolysers. In the present...

  9. WC as a non-platinum hydrogen evolution electrocatalyst for high temperature PEM water electrolysers

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Petrushina, Irina; Christensen, Erik

    2012-01-01

    Tungsten carbide (WC) nanopowder was tested as a non-platinum cathode electrocatalyst for polymer electrolyte membrane (PEM) water electrolysers, operating at elevated temperatures. It was prepared in thermal plasma reactor with confined plasma jet from WO3 precursor in combination with CH4...

  10. Immobilization of molecular cobalt electrocatalyst by hydrophobic interaction with hematite photoanode for highly stable oxygen evolution

    KAUST Repository

    Joya, Khurram

    2015-07-15

    A unique modification of a hematite photoanode with perfluorinated Co-phthalocyanine (CoFPc) by strong binding associated with hydrophobic interaction is demonstrated. The resultant molecular electrocatalyst – hematite photoanode hybrid material showed significant onset shift and high stability for photoelectrochemical oxidation evolution reaction (OER).

  11. A highly durable fuel cell electrocatalyst based on double-polymer-coated carbon nanotubes.

    Science.gov (United States)

    Berber, Mohamed R; Hafez, Inas H; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

    2015-11-23

    Driven by the demand for the commercialization of fuel cell (FC) technology, we describe the design and fabrication of a highly durable FC electrocatalyst based on double-polymer-coated carbon nanotubes for use in polymer electrolyte membrane fuel cells. The fabricated electrocatalyst is composed of Pt-deposited polybenzimidazole-coated carbon nanotubes, which are further coated with Nafion. By using this electrocatalyst, a high FC performance with a power density of 375 mW/cm(2) (at 70 ˚C, 50% relative humidity using air (cathode)/H2(anode)) was obtained, and a remarkable durability of 500,000 accelerated potential cycles was recorded with only a 5% loss of the initial FC potential and 20% loss of the maximum power density, which were far superior properties compared to those of the membrane electrode assembly prepared using carbon black in place of the carbon nanotubes. The present study indicates that the prepared highly durable fuel cell electrocatalyst is a promising material for the next generation of PEMFCs.

  12. Benchmarking Pt-based electrocatalysts for low temperature fuel cell reactions with the rotating disk electrode

    DEFF Research Database (Denmark)

    Pedersen, Christoffer Mølleskov; Escribano, Maria Escudero; Velazquez-Palenzuela, Amado Andres

    2015-01-01

    We present up-to-date benchmarking methods for testing electrocatalysts for polymer exchange membrane fuel cells (PEMFC), using the rotating disk electrode (RDE) method. We focus on the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) in the presence of CO. We have chosen...

  13. Immobilization of molecular cobalt electrocatalyst by hydrophobic interaction with hematite photoanode for highly stable oxygen evolution

    KAUST Repository

    Joya, Khurram; Morlanes, Natalia; Maloney, Edward; Rodionov, Valentin; Takanabe, Kazuhiro

    2015-01-01

    A unique modification of a hematite photoanode with perfluorinated Co-phthalocyanine (CoFPc) by strong binding associated with hydrophobic interaction is demonstrated. The resultant molecular electrocatalyst – hematite photoanode hybrid material showed significant onset shift and high stability for photoelectrochemical oxidation evolution reaction (OER).

  14. PEM-fuel cells for mobile application. Sub task: development of electrocatalysts. Final report; PEM-Brennstoffzelle fuer mobile Anwendung. Teilprojekt: Katalysatorenentwicklung. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Starz, K A

    1999-01-01

    PEM fuel cells are gaining increasing importance for use in automotive application. The goal of the research program reported here was to develop the basic technology and components for PEMFC stacks for use in transport applications. The sub-task of Degussa was to develop improved electrocatalysts for PEMFC single cells and stacks. The technical objectives of the research project were met. Electrocatalysts, characterized by a high Pt-dispersion, high surface area and excellent activity, were developed. With this material, considerable progress was made to reduce the total platinum loading of PEMFC cells and stacks to about 0,5 mgPt/cm{sup 2}. With this value, the goal of the program (<0,8 mg/cm{sup 2}) was significantly surpassed. Additionally, higher power densities of >0.4 W/cm{sup 2} were achieved at Degussa for hydrogen/air and reformate/air operation of the PEMFC. A CO-tolerant anode electrocatalyst, exhibiting a CO-tolerance of up to 100 ppm CO, enables the operation of PEMFC stacks with on-board generated methanol reformate. The performance of the new electrocatalyst materials was verified by DaimlerChrysler in a PEMFC demonstration stack at the end of the program. (orig.) [Deutsch] PEM-Brennstoffzellen gewinnen fuer die mobile Anwendung immer mehr an Bedeutung. Im Rahmen des hier beschriebenen Leitprojektes sollten die Basistechnologien fuer den Einsatz der PEM-Brennstoffzelle im mobilen Bereich (Elektrotraktion) entwickelt werden. Das Teilprojekt der Degussa befasst sich mit der Entwicklung von verbesserten Elektrokatalysatoren fuer PEM-Brennstoffzellenstacks. Die technischen Arbeitsziele des Vorhabens wurden erreicht. So konnten Elektrokatalysatoren bereitgestellt werden, die sich durch eine hohe Pt-Dispersion, eine grosse Pt-Oberflaeche sowie eine sehr gute Aktivitaet auszeichnen. Mit diesen Elektrokatalysatoren gelang es, die Platinbeladung der PEM-Elektroden (Anode und Kathode) erheblich abzusenken. Mit einer Gesamtplatinbeladung von 0,5 mg/cm{sup 2

  15. A facile approach to prepare crumpled CoTMPyP/electrochemically reduced graphene oxide nanohybrid as an efficient electrocatalyst for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Juanjuan, E-mail: majj0518@hotmail.com [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Liu, Lin; Chen, Qian; Yang, Min [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Wang, Danping [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Tong, Zhiwei [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Chen, Zhong, E-mail: aszchen@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore)

    2017-03-31

    Highlights: • Crumpled CoTMPyP/ERGO hybrid was successfully prepared by a facile two-step process. • CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. • CoTMPyP/ERGO hybrid film shows good electrocatalytic activity and stability for HER. - Abstract: Elaborate design and synthesis of efficient and stable non-Pt electrocatalysts for some renewable energy related conversion/storage processes are one of the major goals of sustainable chemistry. Herein, we report a facile method to fabricate Co porphyrin functionalized electrochemically reduced graphene oxide (CoTMPyP/ERGO) thin film by direct assembly of oppositely charged tetrakis(N-methylpyridyl) porphyrinato cobalt (CoTMPyP) and GO nanosheets under mild conditions followed by an electrochemical reduction procedure. STEM analysis confirms that CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. The electrochemical properties of CoTMPyP/ERGO were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy. The results demonstrate that CoTMPyP/ERGO nanohybrid film can serve as excellent electrocatalyst for hydrogen evolution in alkaline solution with high activity and stability. The intimate contact and efficient electron transfer between CoTMPyP and ERGO, as well as the crumpled structure, contribute to the improvement of the electrocatalytic performance.

  16. Facile synthesis of pyrite-type binary nickel iron diselenides as efficient electrocatalyst for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Jing-Qi; Shang, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liang, Fei [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Li, Xiao; Liu, Yan-Ru; Yan, Kai-Li [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Gao, Wen-Kun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2017-04-15

    Highlights: • Binary pyrite-type Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC was prepared by a facile two-step process. • The effect of Ni/Fe (Ni{sub x}Fe{sub 1-x}Se{sub 2} x = 0, 0.2, 0.5, 0.8, 1) on OER was investigated. • Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC (x = 0.5) possesses the better electrocatalytic activity for OER. • The enhanced activity may be attributed to binary Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} and CFC support. - Abstract: Pyrite-type binary nickel iron diselenides (Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}) supported on carbon fiber cloth (CFC) as electrocatalysts for oxygen evolution reaction (OER) have been prepared by a facile two-step process. Firstly, binary Ni{sub 0.5}Fe{sub 0.5} hydroxide nanosheets have been electrodeposited on CFC. Secondly, a solvothermal selenization process has been used to convert Ni{sub 0.5}Fe{sub 0.5}/CFC into Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC. XRD shows that Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} on CFC has the typically octahedral crystalline. XPS proves the existence and valence of Ni, Fe and Se. SEM images show that Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} has novel pyrite-type octahedral morphology with uniform size and good dispersion on the surface of CFC. SEM elemental mapping images confirm the good distribution of Ni, Fe, Se element on CFC. TEM and SAED provide the clear diffraction rings of octahedral Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}, which is consistent with the results of XRD. Furtherly, the effect of different ratio of Ni/Fe (Ni{sub x}Fe{sub 1-x}Se{sub 2} x = 0, 0.2, 0.5, 0.8, 1) on OER performances has been systematically investigated. The electrochemical measurements results show that Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC (x = 0.5) possesses the better electrocatalytic activity with the lower overpotential, Tafel slope and long-term stability than other samples. The enhanced activity of Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC may be attributed to the intrinsic activity of binary Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} and faster electron

  17. TCNQ-induced in-situ electrochemical deposition for the synthesis of silver nanodendrites as efficient bifunctional electrocatalysts

    International Nuclear Information System (INIS)

    Chen, Zhengyan; Li, Congling; Ni, Yangyang; Kong, Fantao; Zhang, Yongbo; Kong, Aiguo; Shan, Yongkui

    2017-01-01

    Graphical abstract: Silver nanodendrites with superior electrocatalytic activity for oxygen reduction reaction (ORR) and hydrogen peroxide detection were synthesized by electrodeposition method using organic semiconductor 7,7,8,8-tetracyanoquinodimethane (TCNQ) as the inducer. - Highlights: • AgNDs were obtained by electrodepositing route under the induction of TCNQ. • The AgNDs-TCNQ/GCE showed superior activity comparable to Pt/C for ORR. • The AgNDs-TCNQ/GCE exhibited highly catalytic activity toward H_2O_2 detection. • A novel pathway for synthesizing bifunctional Ag-based electrocatalyst. - Abstract: Sliver (Ag) nanodendrites (AgNDs) directly growing on the glassy carbon electrode (GCE) were obtained by an in-situ electrodepositing route under the induction of organic semiconductor 7,7,8,8-tetracyanoquinodimethane (TCNQ). The morphology of the Ag nanostructures can be controlled by the electrodepositing time, applied potentials, and the concentrations of Ag ions. The AgNDs/TCNQ/GCE obtained at the optimized conditions displays the oxygen reduction reaction (ORR) onset potential of 0.98 V, which is the same as that over Pt/C-JM catalyst (0.98 V). It demonstrated that AgNDs possessed the highest electrocatalytic activity for ORR among the various Ag-based electrocatalysts reported in literature in alkaline electrolyte. At the same time, the performance of AgNDs/TCNQ/GCE toward hydrogen peroxide detection was investigated in a range of the concentration from 10 μM to 17 mM. It also showed the higher catalytic activity for hydrogen peroxide reduction reaction with the hydrogen peroxide detection limit reaching 0.47 μM level. The Tafel polarization curve, electrochemically active surface area, and the electrochemical impedance were measured to understand and explore the catalytic behavior of the prepared AgNDs/TCNQ/GCE. The enhanced performance of AgNDs for ORR and hydrogen peroxide detection can be ascribed to the special tree-like morphology with highly

  18. A Roadmap for Achieving Sustainable Energy Conversion and Storage: Graphene-Based Composites Used Both as an Electrocatalyst for Oxygen Reduction Reactions and an Electrode Material for a Supercapacitor

    Directory of Open Access Journals (Sweden)

    Peipei Huo

    2018-01-01

    Full Text Available Based on its unique features including 2D planar geometry, high specific surface area and electron conductivity, graphene has been intensively studied as oxygen reduction reaction (ORR electrocatalyst and supercapacitor material. On the one hand, graphene possesses standalone electrocatalytic activity. It can also provide a good support for combining with other materials to generate graphene-based electrocatalysts, where the catalyst-support structure improves the stability and performance of electrocatalysts for ORR. On the other hand, graphene itself and its derivatives demonstrate a promising electrochemical capability as supercapacitors including electric double-layer capacitors (EDLCs and pseudosupercapacitors. A hybrid supercapacitor (HS is underlined and the advantages are elaborated. Graphene endows many materials that are capable of faradaic redox reactions with an outstanding pseudocapacitance behavior. In addition, the characteristics of graphene-based composite are also utilized in many respects to provide a porous 3D structure, formulate a novel supercapacitor with innovative design, and construct a flexible and tailorable device. In this review, we will present an overview of the use of graphene-based composites for sustainable energy conversion and storage.

  19. A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2to CO

    KAUST Repository

    Rasul, Shahid; Anjum, Dalaver H.; Jedidi, Abdesslem; Minenkov, Yury; Cavallo, Luigi; Takanabe, Kazuhiro

    2014-01-01

    The challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy-efficient, and non-precious-metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous

  20. Characterization of a titanium-promoted supported platinum electrocatalyst

    International Nuclear Information System (INIS)

    Beard, B.C.; Ross, P.N. Jr.

    1986-01-01

    X-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and extended x-ray adsorption fine structure (EXAFS) were used for the characte3rization of a highly dispersed Ti[promoted Pt electrocatalyst. This bimetallic catalyst was prepared by addition of TiCl/sub 4/ to a methanol-water solution containing Pt on carbon black catalyst in suspension. Following filtration and air drying (300 0 C), heat-treatments up to 1200 0 C under flowing helium were performed to promote the formation of Pt-Ti alloy phases. XPS indicated the development of a peak at a binding energy of 454.9 eV (assigned to Ti in Pt/sub 3/Ti), which increased in area with heat-treatment such that after the 1200 0 C heat-treatment ≅ 50% of the Ti was converted to the intermetallic phase, Pt/sub 3/Ti. The Pt (4f, 7/2) photoelectron line shifted (+0.3 eV) to 71.2 eV following the 1200 0 C heat-treatment, identical to the Pt(4f, 7/2) binding energy for bulk Pt/sub 3/Ti. XRD showed only fcc reflections, indicating the excess Ti present as TiO/sub 2/ was x-ray amorphous. Prior to heat-treatment of the Ti impregnated catalyst, the fcc reflections indicated a lattice parameter of 3.927 A, identical to that for pure Pt. As heat-treatment temperature increased the lattice parameter decreased to 3.906A, the value for bulk Pt/sub 3/Ti. Particle size estimates indicated a progressive increase in the crystallite size of Pt alloy phase with temperature to a final size of Β150A at 1200 0 C. Definitive proof of an ordered Pt/sub 3/Ti phase was the presence of superlattice diffraction lines from materials heated above 900 0 C. EXAFS of these catalysts confirmed the conversion of an initial Pt-TiO/sub 2/ mixture to Pt/sub 3/Ti at 900 0 -1200 0 C heat-treatment temperatures

  1. Effectiveness of Nigerian Bamboo Activated with Different Activating ...

    African Journals Online (AJOL)

    The effectiveness of Nigerian Bamboo activated with different activating agents on the adsorption of BTX was investigated. A series of activated carbons was prepared from Nigerian bamboo, carbonized at 400oC – 500oC and impregnated with different concentrations of four acids at 800oC in a muffle furnace for 2 hours.

  2. Mn-doped NiP2 nanosheets as an efficient electrocatalyst for enhanced hydrogen evolution reaction at all pH values

    Science.gov (United States)

    Wang, Xiaodeng; Zhou, Hongpeng; Zhang, Dingke; Pi, Mingyu; Feng, Jiajia; Chen, Shijian

    2018-05-01

    Developing stable and high-efficiency hydrogen generation electrocatalysts, particularly for the cathode hydrogen evolution reaction (HER), is an urgent challenge in energy conversion technologies. In this work, we have successfully synthesized Mn-doped NiP2 nanosheets on carbon cloth (Mn-NiP2 NSs/CC), which behaves as a higher efficient three dimensional HER electrocatalyst with better stability at all pH values than pure NiP2. Electrochemical tests demonstrate that the catalytic activity of NiP2 is enhanced by Mn doping. In 0.5 M H2SO4, this Mn-NiP2 NSs/CC catalyst drives 10 mA cm-2 at an overpotential of 69 mV, which is 20 mV smaller than pure NiP2. To achieve the same current density, it demands overpotentials of 97 and 107 mV in 1.0 M KOH and phosphate-buffered saline (PBS), respectively. Compared with pure NiP2, higher HER electrocatalytic performance for Mn-NiP2 NSs/CC can be attributed to its lower thermo-neutral hydrogen adsorption free energy, which is supported by density functional theory calculations.

  3. 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

  4. Performance PtSnRh electrocatalysts supported on carbon-Sb{sub 2}O{sub 5}.SbO{sub 2} for the electro-oxidation of ethanol, prepared by an alcohol-reduction process; Desempenho de eletrocatalisadores PtSnRh suportados em carbono-Sb{sub 2}O{sub 5}.SnO{sub 2} para a oxidacao eletroquimica do etanol, preparados pelo metodo de reducao por alcool

    Energy Technology Data Exchange (ETDEWEB)

    Castro, Jose Carlos

    2013-07-01

    PtSnRh electrocatalysts supported on carbon-Sb{sub 2}O{sub 5}.SnO{sub 2}, with metal loading of 20 wt%, were prepared by an alcohol-reduction process, using H{sub 2}PtCl{sub 6}.6H{sub 2}O (Aldrich), RhCl{sub 3}.xH{sub 2}O (Aldrich) and SnCl{sub 2}.2H{sub 2}O (Aldrich), as source of metals; Sb{sub 2}O{sub 5}.SnO{sub 2} (ATO) and carbon Vulcan XC72, as support; and ethylene glycol as reducing agent. The electrocatalysts obtained were characterized physically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The diffractograms showed which PtSnRh/C-ATO electrocatalysts had FCC structure of Pt and Pt alloys, besides several peaks associated with SnO{sub 2} and ATO. The average sizes of crystallites were between 2 and 4 nm. TEM micrographs showed a good distribution of the nanoparticles on the support. The average sizes of particles were between 2 and 3 nm, with good agreement for the average size of the crystallites. The performances of the electrocatalysts were analyzed by electrochemical techniques and in real conditions of operation using single direct ethanol fuel cell. In the chronoamperometry at 50 deg C, the electrocatalysts with carbon (85 wt%) and ATO (15 wt%) support, showed the best activity, and the atomic proportions which achieved the best results were PtSnRh(70:25:05) e (90:05:05). PtSnRh(70:25:05)/85C+15ATO electrocatalysts showed the best performance in a direct ethanol fuel cell. (author)

  5. Study of the oxygen reduction reaction using Pt-Rare earths (La, Ce, Er) electrocatalysts for application of PEM fuel cells; Estudo da reacao de reducao do oxigenio utilizando eletrocatalisadores a base de Pt-terras raras (La, Ce, Er) para aplicacao em celulas a combustivel tipo PEM

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Thiago Bueno

    2013-07-01

    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)

  6. 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.

  7. How bimetallic electrocatalysts does work for reactions involved in fuel cells? Example of ethanol oxidation and comparison to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Leger, J.-M.; Rousseau, S.; Coutanceau, C.; Hahn, F.; Lamy, C. [UMR 6503, Electrocatalysis Group, CNRS - University of Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex (France)

    2005-09-05

    Carbon-supported Pt-based nanosized electrocatalysts can be synthesized for methanol and ethanol electrooxidation. The electrocatalytic activity of Pt can be greatly enhanced by using Pt-Ru/C for methanol oxidation or Pt-Sn/C for ethanol oxidation. In situ IR reflectance spectroscopy is a convenient tool to better understand the importance of the different adsorption steps involved in the mechanisms of electrooxidation. With Pt/C, it appears clearly that linearly adsorbed CO is the poisoning species formed during methanol and ethanol oxidation. In the case of methanol, even with Pt-Ru/C (the most active catalyst), adsorbed CO is also a reactive intermediate. The enhancement of activity observed in such a case is due to the possibility to activate water at lower potentials in the presence of Ru. With Pt-Sn/C, the mechanism of the electrooxidation of ethanol is strongly modified. If at low potentials, poisoning with adsorbed CO still exists (as with Pt/C), the oxidation of ethanol at potentials greater than 0.4 V versus RHE occurs through an adsorbed acetyl species which can lead to the formation of acetaldehyde and acetic acid as final products in addition to carbon dioxide. (author)

  8. 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.

  9. K{sub 1.33}Mn{sub 8}O{sub 16} as an electrocatalyst and a cathode

    Energy Technology Data Exchange (ETDEWEB)

    Jalili, Seifollah, E-mail: sjalili@kntu.ac.ir [Department of Chemistry, K. N. Toosi University of Technology, P.O. Box 15875-4416, Tehran (Iran, Islamic Republic of); Computational Physical Sciences Research Laboratory, School of Nano-Science, Institute for Research in Fundamental Sciences (IPM), P.O. Box 19395-5531, Tehran (Iran, Islamic Republic of); Moharramzadeh Goliaei, Elham [Department of Chemistry, K. N. Toosi University of Technology, P.O. Box 15875-4416, Tehran (Iran, Islamic Republic of); Schofield, Jeremy [Chemical Physics Theory Group, Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, Ontario, Canada M5S 3H6 (Canada)

    2017-02-15

    Density functional theory (DFT) calculations are carried out to investigate the electronic, magnetic and thermoelectric properties of bulk and nanosheet K{sub 1.33}Mn{sub 8}O{sub 16} materials. The catalytic activity and cathodic performance of bulk and nanosheet structures are examined using the Tran-Blaha modified Becke-Johnson (TB-mBJ) exchange potential. Electronic structure calculations reveal an anti-ferromagnetic ground state, with a TB-mMBJ band gap in bulk K{sub 1.33}Mn{sub 8}O{sub 16} that is in agreement with experimental results. Density of state plots indicate a partial reduction of Mn{sup 4+} ions to Mn{sup 3+}, without any obvious sign of Jahn-Teller distortion. Moreover, use of the O p-band center as a descriptor of catalytic activity suggests that the nanosheet has enhanced catalytic activity compared to the bulk structure. Thermoelectric parameters such as the Seebeck coefficient, electrical conductivity, and thermal conductivity are also calculated, and it is found that the Seebeck coefficients decrease with increasing temperature. High Seebeck coefficients for both spin-up and spin-down states are found in the nanosheet relative to their value in the bulk K{sub 1.33}Mn{sub 8}O{sub 16} structure, whereas the electrical and thermal conductivity are reduced relative to the bulk. In addition, figures of merit values are calculated as a function of the chemical potential and it is found that the nanosheet has a figure of merit of ~1 at room temperature, compared to 0.5 for the bulk material. All results suggest that K{sub 1.33}Mn{sub 8}O{sub 16} nanosheets can be used both as a material in waste heat recovery and as an electrocatalyst in fuel cells and batteries. - Graphical abstract: K{sub 1.33}Mn{sub 8}O{sub 16}: bulk and nanosheet. - Highlights: • Electronic properties of bulk and nanosheet forms of K{sub 1.33}Mn{sub 8}O{sub 16} have been studied. • The K{sub 1.33}Mn{sub 8}O{sub 16} nanosheet is a semiconductor while the bulk is a metal. • K

  10. The Solid-Phase Synthesis of an Fe-N-C Electrocatalyst for High-Power Proton-Exchange Membrane Fuel Cells.

    Science.gov (United States)

    Liu, Qingtao; Liu, Xiaofang; Zheng, Lirong; Shui, Jianglan

    2018-01-26

    The environmentally friendly synthesis of highly active Fe-N-C electrocatalysts for proton-exchange membrane fuel cells (PEMFCs) is desirable but remains challenging. A simple and scalable method is presented to fabricate Fe II -doped ZIF-8, which can be further pyrolyzed into Fe-N-C with 3 wt % of Fe exclusively in Fe-N 4 active moieties. Significantly, this Fe-N-C derived acidic PEMFC exhibits an unprecedented current density of 1.65 A cm -2 at 0.6 V and the highest power density of 1.14 W cm -2 compared with previously reported NPMCs. The excellent PEMFC performance can be attributed to the densely and atomically dispersed Fe-N 4 active moieties on the small and uniform catalyst nanoparticles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Metal-Carbon-CNF Composites Obtained by Catalytic Pyrolysis of Urban Plastic Residues as Electro-Catalysts for the Reduction of CO2

    Directory of Open Access Journals (Sweden)

    Jesica Castelo-Quibén

    2018-05-01

    Full Text Available Metal–carbon–carbon nanofibers composites obtained by catalytic pyrolysis of urban plastic residues have been prepared using Fe, Co or Ni as pyrolitic catalysts. The composite materials have been fully characterized from a textural and chemical point of view. The proportion of carbon nanofibers and the final content of carbon phases depend on the used pyrolitic metal with Ni being the most active pyrolitic catalysts. The composites show the electro-catalyst activity in the CO2 reduction to hydrocarbons, favoring all the formation of C1 to C4 hydrocarbons. The tendency of this activity is in accordance with the apparent faradaic efficiencies and the linear sweep voltammetries. The cobalt-based composite shows high selectivity to C3 hydrocarbons within this group of compounds.

  12. Highly efficient transition metal and nitrogen co-doped carbide-derived carbon electrocatalysts for anion exchange membrane fuel cells

    Science.gov (United States)

    Ratso, Sander; Kruusenberg, Ivar; Käärik, Maike; Kook, Mati; Puust, Laurits; Saar, Rando; Leis, Jaan; Tammeveski, Kaido

    2018-01-01

    The search for an efficient electrocatalyst for oxygen reduction reaction (ORR) to replace platinum in fuel cell cathode materials is one of the hottest topics in electrocatalysis. Among the many non-noble metal catalysts, metal/nitrogen/carbon composites made by pyrolysis of cheap materials are the most promising with control over the porosity and final structure of the catalyst a crucial point. In this work we show a method of producing a highly active ORR catalyst in alkaline media with a controllable porous structure using titanium carbide derived carbon as a base structure and dicyandiamide along with FeCl3 or CoCl2 as the dopants. The resulting transition metal-nitrogen co-doped carbide derived carbon (M/N/CDC) catalyst is highly efficient for ORR electrocatalysis with the activity in 0.1 M KOH approaching that of commercial 46.1 wt.% Pt/C. The catalyst materials are also investigated by scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy to characterise the changes in morphology and composition causing the raise in electrochemical activity. MEA performance of M/N/CDC cathode materials in H2/O2 alkaline membrane fuel cell is tested with the highest power density reached being 80 mW cm-2 compared to 90 mW cm-2 for Pt/C.

  13. Activating wearables : the Butterfly Effect

    NARCIS (Netherlands)

    2015-01-01

    In this demo we show an active garment to support people in matters of emotion regulation and interactions with other people. This demonstrator shows the marriage of ‘hard’ technology and ‘soft’ textiles in a subtle moving wearable product.

  14. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

    Science.gov (United States)

    Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, ChandraSekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

    2016-01-01

    Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts. PMID:27958290

  15. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

    Science.gov (United States)

    Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, Chandrasekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

    2016-12-01

    Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

  16. High activity of cubic PtRh alloys supported on graphene towards ethanol electrooxidation.

    Science.gov (United States)

    Rao, Lu; Jiang, Yan-Xia; Zhang, Bin-Wei; Cai, Yuan-Rong; Sun, Shi-Gang

    2014-07-21

    Cubic PtRh alloys supported on graphene (PtxRhy/GN) with different atomic ratio of Pt and Rh were directly synthesized for the first time using the modified polyol method with Br(-) for the shape-directing agents. The process didn't use surface-capping agents such as PVP that easily occupy the active sites of electrocatalysts and are difficult to remove. Graphene is the key factor for cubic shape besides Br(-) and keeping catalysts high-dispersed. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to characterize the structure and morphology of these electrocatalysts. The results showed that they were composed of homogeneous cubic PtRh alloys. Traditional electrochemical methods, such as cyclic voltammetry and chronoamperometry, were used to investigate the electrocatalytic properties of PtxRhy/GN towards ethanol electrooxidation. It can be seen that PtxRhy/GN with all atomic ratios exhibited high catalytic activity, and the most active one has a composition with Pt : Rh = 9 : 1 atomic ratio. Electrochemical in situ FTIR spectroscopy was used to evaluate the cleavage of C-C bond in ethanol at room temperature in acidic solutions, the results illustrated that Rh in an alloy can promote the split of C-C bond in ethanol, and the alloy catalyst with atomic ratio Pt : Rh = 1 : 1 showed obviously better performance for the C-C bond breaking in ethanol and higher selectivity for the enhanced activity of ethanol complete oxidation to CO2 than alloys with other ratios of Pt and Rh. The investigation indicates that high activity of PtxRhy/GN electrocatalyst towards ethanol oxidation is due to the specific shape of alloys and the synergistic effect of two metal elements as well as graphene support.

  17. Recent progress in electrocatalysts with mesoporous structures for application in polymer electrolyte membrane fuel cells

    OpenAIRE

    Xing, Wei; Wu, Zucheng; Tao, Shanwen

    2016-01-01

    Recently mesoporous materials have drawn great attention in fuel cell related applications, such as preparation of polymer electrolyte membranes and catalysts, hydrogen storage and purification. In this mini-review, we focus on recent developments in mesoporous electrocatalysts for polymer electrolyte membrane fuel cells, including metallic and metal-free catalysts for use as either anode or cathode catalysts. Mesoporous Pt-based metals have been synthesized as anode catalysts with improved a...

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  19. MOF-derived Co-doped nickel selenide/C electrocatalysts supported on Ni foam for overall water splitting

    KAUST Repository

    Ming, Fangwang

    2016-09-01

    It is of prime importance to develop dual-functional electrocatalysts with good activity for overall water splitting, which remains a great challenge. Herein, we report the synthesis of a Co-doped nickel selenide (a mixture of NiSe and NiSe)/C hybrid nanostructure supported on Ni foam using a metal-organic framework as the precursor. The resulting catalyst exhibits excellent catalytic activity toward the oxygen evolution reaction (OER), which only requires an overpotential of 275 mV to drive a current density of 30 mA cm. This overpotential is much lower than those reported for precious metal free OER catalysts. The hybrid is also capable of catalyzing the hydrogen evolution reaction (HER) efficiently. A current density of -10 mA cm can be achieved at 90 mV. In addition, such a hybrid nanostructure can achieve 10 and 30 mA cm at potentials of 1.6 and 1.71 V, respectively, along with good durability when functioning as both the cathode and the anode for overall water splitting in basic media.

  20. MOF-derived Co-doped nickel selenide/C electrocatalysts supported on Ni foam for overall water splitting

    KAUST Repository

    Ming, Fangwang; Liang, Hanfeng; Shi, Huanhuan; Xu, Xun; Mei, Gui; Wang, Zhoucheng

    2016-01-01

    It is of prime importance to develop dual-functional electrocatalysts with good activity for overall water splitting, which remains a great challenge. Herein, we report the synthesis of a Co-doped nickel selenide (a mixture of NiSe and NiSe)/C hybrid nanostructure supported on Ni foam using a metal-organic framework as the precursor. The resulting catalyst exhibits excellent catalytic activity toward the oxygen evolution reaction (OER), which only requires an overpotential of 275 mV to drive a current density of 30 mA cm. This overpotential is much lower than those reported for precious metal free OER catalysts. The hybrid is also capable of catalyzing the hydrogen evolution reaction (HER) efficiently. A current density of -10 mA cm can be achieved at 90 mV. In addition, such a hybrid nanostructure can achieve 10 and 30 mA cm at potentials of 1.6 and 1.71 V, respectively, along with good durability when functioning as both the cathode and the anode for overall water splitting in basic media.

  1. [Effect of Kaixinsan on monoamine oxidase activity].

    Science.gov (United States)

    Wang, Shi; Dong, Xian-Zhe; Tan, Xiao; Wang, Yu-Ning; Liu, Ping

    2016-05-01

    To observe the effect of antidepressant medicine prescription, Kaixinsan (KXS) on monoamine oxidase (MAO) activity, and explore the mechanism of KXS in elevating the levels of monoamine neurotransmitter from the perspective of metabolism, in vitro enzyme reaction system and C6 neuroglial cells, the effect of KXS at different concentrations on MAO-A and MAO-B activity was observed. In animal studies, the effect of KXS at different concentrations on MAO-A and MAO-B activities of brain mitochondrialin normal rats and solitary chronic unpredictable moderate stress (CMS) model rats after intragastric administration for 1, 2, 3 weeks. Results showed that 10 g•L⁻¹ KXS could significantly reduce the activity of MAO-A and MAO-B in enzyme reaction system; and in C6 cells, KXS within 0.625-10 g•L⁻¹ concentration range had no significant effect on the activity of MAO-A, but had obvious inhibitory effect on the activity of MAO-B in a dose dependent manner. KXS had no significant effect on the activity of MAO-A and MAO-B in brains of normal rats after action for 1, 2, 3 weeks. After 2 and 3 weeks treatment with 338 mg•kg⁻¹ dose KXS, MAO-A activity in the brain of CMS rats was decreased as compared with the model group (PMAO-B activity after 1, 2, 3 weeks of treatment. The results indicated that KXS had certain effect on in vitro MAO-A and MAO-B activity, had no effect on brain MAO-A and MAO-B activity in vivo in normal rats, and had certain inhibitory effect on MAO-A activity in brains of CMS rats. Copyright© by the Chinese Pharmaceutical Association.

  2. 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)

  3. Ir4+-Doped NiFe LDH to expedite hydrogen evolution kinetics as a Pt-like electrocatalyst for water splitting.

    Science.gov (United States)

    Chen, Qian-Qian; Hou, Chun-Chao; Wang, Chuan-Jun; Yang, Xiao; Shi, Rui; Chen, Yong

    2018-06-06

    NiFe-layered double hydroxide (NiFe LDH) is a state-of-the-art oxygen evolution reaction (OER) electrocatalyst, yet it suffers from rather poor catalytic activity for the hydrogen evolution reaction (HER) due to its extremely sluggish water dissociation kinetics, severely restricting its application in overall water splitting. Herein, we report a novel strategy to expedite the HER kinetics of NiFe LDH by an Ir4+-doping strategy to accelerate the water dissociation process (Volmer step), and thus this catalyst exhibits superior and robust catalytic activity for finally oriented overall water splitting in 1 M KOH requiring only a low initial voltage of 1.41 V delivering at 20 mA cm-2 for more than 50 h.

  4. Effectiveness of worksite physical activity counseling

    NARCIS (Netherlands)

    Proper, K.I.

    2003-01-01

    The aim of this thesis was to describe the effectiveness of a particular worksite physical activity intervention involving individual counseling of workers. First, a summary of the existing literature is given as to the effectiveness of worksite physical activity programs. A strong evidence was

  5. Tuning crystal phase of NiS_x through electro-oxidized nickel foam: A novel route for preparing efficient electrocatalysts for oxygen evolution reaction

    International Nuclear Information System (INIS)

    Li, Xiao; Shang, Xiao; Rao, Yi; Dong, Bin; Han, Guan-Qun; Hu, Wen-Hui; Liu, Yan-Ru; Yan, Kai-Li; Chi, Jing-Qi; Chai, Yong-Ming; Liu, Chen-Guang

    2017-01-01

    Highlights: • Electro-oxidized nickel foam as a support has been used to prepare NiS_x phases. • Ni(OH)_2 layer on electro-oxidized NF is responsible for the growth of β-NiS. • NiS_x/NF(Ox) composed of β-NiS and Ni_3S_2 has enhanced electrocatalytic activity. • The growth mechanisms of mixed NiS_x phases of NiS_x/NF(Ox) have been discussed. - Abstract: A facile solvothermal sulfurization using electro-oxidized nickel foam (NF(Ox)) as support has been applied to prepare NiS_x/NF(Ox) electrocatalyst with highly efficient activity for oxygen evolution reaction (OER). XRD patterns confirm the composition of NiS_x/NF(Ox): two kinds of crystal phase including β-NiS and Ni_3S_2. While using bare NF as support under identical conditions, only Ni_3S_2 phase can be detected. SEM images reveal two kinds of morphologies of NiS_x/NF(Ox) including pyramids structure of β-NiS and nanorod-like structure of Ni_3S_2, which implies the tuning effect of electro-pretreatment of NF on the selective preparation of NiS_x crystal phase. It can be speculated that Ni(OH)_2 layer derived from electro-oxidized NF is responsible for the growth of β-NiS while metallic Ni is transformed into Ni_2S_3 during sulfurization. Electrochemical measurements for OER indicate the enhanced electrocatalytic activity of NiS_x/NF(Ox) with a small overpotential of 72 mV to reach 10 mA cm"−"2 compared with Ni_3S_2/NF, which may be ascribed to the improved electron-transfer kinetics relating to the unique atomic configurations and crystalline structures of β-NiS. The electro-oxidation pretreatment of nickel foam provides a simple and convenient method by tuning different NiS_x crystal phases for preparing excellent OER eletrocatalysts.

  6. Tuning crystal phase of NiS{sub x} through electro-oxidized nickel foam: A novel route for preparing efficient electrocatalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao; Shang, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Rao, Yi [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580, PR China (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580, PR China (China); Han, Guan-Qun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580, PR China (China); Hu, Wen-Hui; Liu, Yan-Ru; Yan, Kai-Li; Chi, Jing-Qi; Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2017-02-28

    Highlights: • Electro-oxidized nickel foam as a support has been used to prepare NiS{sub x} phases. • Ni(OH){sub 2} layer on electro-oxidized NF is responsible for the growth of β-NiS. • NiS{sub x}/NF(Ox) composed of β-NiS and Ni{sub 3}S{sub 2} has enhanced electrocatalytic activity. • The growth mechanisms of mixed NiS{sub x} phases of NiS{sub x}/NF(Ox) have been discussed. - Abstract: A facile solvothermal sulfurization using electro-oxidized nickel foam (NF(Ox)) as support has been applied to prepare NiS{sub x}/NF(Ox) electrocatalyst with highly efficient activity for oxygen evolution reaction (OER). XRD patterns confirm the composition of NiS{sub x}/NF(Ox): two kinds of crystal phase including β-NiS and Ni{sub 3}S{sub 2}. While using bare NF as support under identical conditions, only Ni{sub 3}S{sub 2} phase can be detected. SEM images reveal two kinds of morphologies of NiS{sub x}/NF(Ox) including pyramids structure of β-NiS and nanorod-like structure of Ni{sub 3}S{sub 2}, which implies the tuning effect of electro-pretreatment of NF on the selective preparation of NiS{sub x} crystal phase. It can be speculated that Ni(OH){sub 2} layer derived from electro-oxidized NF is responsible for the growth of β-NiS while metallic Ni is transformed into Ni{sub 2}S{sub 3} during sulfurization. Electrochemical measurements for OER indicate the enhanced electrocatalytic activity of NiS{sub x}/NF(Ox) with a small overpotential of 72 mV to reach 10 mA cm{sup −2} compared with Ni{sub 3}S{sub 2}/NF, which may be ascribed to the improved electron-transfer kinetics relating to the unique atomic configurations and crystalline structures of β-NiS. The electro-oxidation pretreatment of nickel foam provides a simple and convenient method by tuning different NiS{sub x} crystal phases for preparing excellent OER eletrocatalysts.

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

    KAUST Repository

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2016-12-14

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

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

    KAUST Repository

    Zheng, Yao

    2016-11-28

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

  10. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

    Science.gov (United States)

    Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

    2016-05-17

    Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±δ/La1-xSrxCoO3-δ oxide thin films, and

  11. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions

    KAUST Repository

    Feng, Zhenxing

    2016-05-05

    Conspectus Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal–air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1–xSrxCoO3−δ and (La1–ySry)2CoO4±δ/La1–xSrxCoO3

  12. Development and Study of Tantalum and Niobium Carbides as Electrocatalyst Supports for the Oxygen Electrode for PEM Water Electrolysis at Elevated Temperatures

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Petrushina, Irina; Prag, Carsten Brorson

    2013-01-01

    Polymer electrolyte membrane (PEM) water electrolysis is a prospective method of producing hydrogen. We focused on one of its issues – the lack of a suitable support material for the anode electrocatalyst. TaC and NbC were studied as possible electrocatalyst supports for the PEM water electrolysis...

  13. Molybdenum sulphides on carbon supports as electrocatalysts for hydrogen evolution in acidic industrial wastewater

    International Nuclear Information System (INIS)

    Kokko, M.; Bayerköhler, F.; Erben, J.; Zengerle, R.; Kurz, Ph.; Kerzenmacher, S.

    2017-01-01

    Highlights: • MoS_x is an efficient and durable catalyst for H_2 evolution in acidic wastewater. • MoS_x outperformed Pt as H_2-catalyst in long term in acidic wastewater. • Improved activity over time was likely due to changes in MoS_x structure. - Abstract: Microbial electrolysis cells (MECs) are an attractive future alternative technology to generate renewable hydrogen and simultaneously treat wastewaters. The thermodynamics of hydrogen evolution in MECs can be greatly improved by operating the cathode at acidic pH in combination with a neutral pH microbial anode. This can easily be achieved with acidic industrial wastewaters that have to be neutralised before discharge. For the hydrogen evolution reaction (HER) in acidic wastewater, efficient and inexpensive catalysts are required that are compatible with the often complex chemical composition of wastewaters. In this study, molybdenum sulphides (MoS_x) on different carbon supports were successfully used for hydrogen evolution in different acidic media. At first, the cathodes were screened by linear sweep voltammetry in sulphuric acid (pH 0) or phosphate buffer (pH 2.2). After this, the overpotentials for H_2 production of the best cathodes and their long term performances (⩾1 week) were determined in acidic industrial wastewater (pH 2.4) obtained from a plant mainly producing cellulose acetate. For the most promising MoS_x cathodes, the overpotentials for HER (at 3 mA cm"−"2) were only ∼40 mV higher than for a platinum electrode. Most importantly, the catalytic efficiency of the MoS_x electrodes improved in the wastewater over time (7–17 days), while Pt electrodes were found to be slowly deactivated. Thus, MoS_x emerges as an affordable, efficient and especially durable electrocatalyst for HER in real acidic wastewaters and this could be an important contribution to take energy production from wastewaters in the form of hydrogen towards practical applications.

  14. Hierarchically scaffolded CoP/CoP2 nanoparticles: controllable synthesis and their application as a well-matched bifunctional electrocatalyst for overall water splitting.

    Science.gov (United States)

    Li, Wan; Zhang, Shilin; Fan, Qining; Zhang, Fazhi; Xu, Sailong

    2017-05-04

    Transition metal phosphide (TMP) nanostructures have stimulated increasing interest for use in water splitting owing to their abundant natural sources and high activity for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Typically, the preparation of hierarchical TMPs involves the utilization of expensive or dangerous phosphorus sources, and, in particular, the understanding of topotactic transformations of the precursors to crystalline phases-which could be utilized to enhance electrocatalytic performance-remains very limited. We, herein, report a controllable preparation of CoP/CoP 2 nanoparticles well dispersed in flower-like Al 2 O 3 scaffolds (f-CoP/CoP 2 /Al 2 O 3 ) as a bifunctional electrocatalyst for the HER and OER via the phosphorization of a flower-like CoAl layered double hydroxide precursor. Characterization by in situ X-ray diffraction (XRD) monitored the topotactic transformation underlying the controllable formation of CoP/CoP 2 via tuning the phosphorization time. Electrocatalytic tests showed that an f-CoP/CoP 2 /Al 2 O 3 electrode exhibited a lower onset potential and higher electrocatalytic activity for the HER and OER in the same alkaline electrolyte than electrodes of flower-like and powdered CoP/Al 2 O 3 . The enhanced electrochemical performance was experimentally supported by measuring the electrochemically active surface area. The f-CoP/CoP 2 /Al 2 O 3 composite further generated a current density of 10 mA cm -2 at 1.65 V when used as a bifunctional catalyst for overall water splitting. Our results demonstrate that the preparation route based on the LDH precursor may provide an alternative for investigating diverse TMPs as bifunctional electrocatalysts for water splitting.

  15. Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O{sub 2} fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Palma, Livia M.; Almeida, Thiago S.; Andrade, Adalgisa R. de, E-mail: ardandra@ffclrp.usp.br [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, Ribeirao Preto, SP (Brazil)

    2012-03-15

    This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L{sup -1}H{sub 2}SO{sub 4}), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt{sub 64}Sn{sub 15}Ru{sub 13}Ni{sub 8}/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt{sub 64}Sn{sub 15}Ru{sub 13}Ni{sub 8}/C catalyst displayed the best performance for DEFC. (author)

  16. Silver decorated LaMnO3 nanorod/graphene composite electrocatalysts as reversible metal-air battery electrodes

    Science.gov (United States)

    Hu, Jie; Liu, Qiunan; Shi, Lina; Shi, Ziwei; Huang, Hao

    2017-04-01

    Perovskite LaMnO3 nanorod/reduced graphene oxides (LMO-NR/RGO) decorated with Ag nanoparticles are studied as a bifunctional catalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. LMO-NR/RGO composites are synthesized by using cetyltrimethyl ammonium bromide (CTAB) as template via a simple hydrothermal reaction followed by heat treatment; overlaying of Ag nanoparticles is obtained through a traditional silver mirror reaction. Electron microscopy reveals that LMO-NR is embedded between the sheets of RGO, and the material is homogeneously overlaid with Ag nanoparticles. The unique composite morphology of Ag/LMO-NR/RGO not only enhances the electron transport property by increasing conductivity but also facilitates the diffusion of electrolytes and oxygen. As confirmed by electrochemical testing, Ag/LMO-NR/RGO exhibits very strong synergy with Ag nanoparticles, LMO-NR, and RGO, and the catalytic activities of Ag/LMO-NR/RGO during ORR and OER are significantly improved. With the novel catalyst, the homemade zinc-air battery can be reversibly charged and discharged and display a stable cycle performance, indicating the great potential of this composite as an efficient bifunctional electrocatalyst for metal-air batteries.

  17. Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O2 fuel cell

    International Nuclear Information System (INIS)

    Palma, Livia M.; Almeida, Thiago S.; Andrade, Adalgisa R. de

    2012-01-01

    This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L -1 H 2 SO 4 ), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt 64 Sn 15 Ru 13 Ni 8 /C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt 64 Sn 15 Ru 13 Ni 8 /C catalyst displayed the best performance for DEFC. (author)

  18. Controlled synthesis of Pt/CS/PW12-GNs composite as an anodic electrocatalyst for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Li, Zhongshui; Lei, Fengling; Ye, Lingting; Zhang, Xiaofeng; Lin, Shen

    2015-01-01

    Controlled assembly in aqueous solution was used to synthesize the well-organized Pt/CS/PW 12 -GNs composite. By the aid of linear cationic polysaccharide chitosan, 2-D distribution worm-like Pt nanoparticles with their length and width of 15–20 and 3–4 nm, respectively, were formed on the surface of CS/PW 12 -GNs using HCOOH as a reducing agent at room temperature. The introduction of CS leads to well dispersion of worm-like Pt nanoparticles, the electroactivity of H 3 PW 12 O 40 (PW 12 ) alleviates CO poisoning toward Pt particles, and graphene nanosheets (GNs) ensure excellent electrical conductivity of the composites. The combined action among different components results in significantly enhanced catalytic activity of Pt/CS/PW 12 -GNs toward methanol oxidation and better tolerance of CO. The as-synthesized Pt/CS/PW 12 -GNs exhibit the forward peak current density of 445 mA mg −1 , which is much higher than that (220 mA mg −1 ) for Pt/C-JM (the commercially available Johnson Matthey Hispec4000 catalyst, simplified as Pt/C-JM) and some recently reported Pt/graphene-based nanomaterials. The construction of 2-D distribution worm-like Pt nanoparticles and facile wet chemical synthesis strategy provide a promising way to develop superior performance electrocatalysts for direct methanol fuel cells applications

  19. Exclusive Hydrogen Generation by Electrocatalysts Coated with an Amorphous Chromium-Based Layer Achieving Efficient Overall Water Splitting

    KAUST Repository

    Qureshi, Muhammad

    2017-08-08

    Successful conversion of renewable energy to useful chemicals requires efficient devices that can electrocatalyze or photocatalyze redox reactions, e.g., overall water splitting. Excellent electrocatalysts for the hydrogen evolution reaction (HER), such as Pt, can also cause other side-reactions, including the water-forming back-reaction from H2 and O2 products. A Cr-based amorphous layer coated on catalysts can work as a successful surface modifier that avoids the back-reaction, but its capabilities and limitations toward other species have not been studied. Herein, we investigated the Cr-based layer on Pt from perspectives of both electrocatalysis and photocatalysis using redox-active molecules/ions (O2, ferricyanide, IO3–, S2O82–, H2O2, and CO gas). Our systematic study revealed that utilization of the Cr-based layer realized an exclusive cathodic reaction only to HER, even in the presence of the aforementioned reactive species, suggesting that Cr-based layers work as membranes, as well as corrosion and poison inhibition layers. However, the Cr-based layer experienced self-oxidation and dissolved into the aqueous phase when a strong oxidizing agent or low pH was present. Presented herein are fundamental and critical aspects of the Cr-based modifier, which is essential for the successful and practical development of solar fuel production systems.

  20. Controlled synthesis of Pt/CS/PW{sub 12}-GNs composite as an anodic electrocatalyst for direct methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhongshui; Lei, Fengling; Ye, Lingting; Zhang, Xiaofeng; Lin, Shen, E-mail: shenlin@fjnu.edu.cn [Fujian Normal University, College of Chemistry & Chemical Engineering (China)

    2015-04-15

    Controlled assembly in aqueous solution was used to synthesize the well-organized Pt/CS/PW{sub 12}-GNs composite. By the aid of linear cationic polysaccharide chitosan, 2-D distribution worm-like Pt nanoparticles with their length and width of 15–20 and 3–4 nm, respectively, were formed on the surface of CS/PW{sub 12}-GNs using HCOOH as a reducing agent at room temperature. The introduction of CS leads to well dispersion of worm-like Pt nanoparticles, the electroactivity of H{sub 3}PW{sub 12}O{sub 40} (PW{sub 12}) alleviates CO poisoning toward Pt particles, and graphene nanosheets (GNs) ensure excellent electrical conductivity of the composites. The combined action among different components results in significantly enhanced catalytic activity of Pt/CS/PW{sub 12}-GNs toward methanol oxidation and better tolerance of CO. The as-synthesized Pt/CS/PW{sub 12}-GNs exhibit the forward peak current density of 445 mA mg{sup −1}, which is much higher than that (220 mA mg{sup −1}) for Pt/C-JM (the commercially available Johnson Matthey Hispec4000 catalyst, simplified as Pt/C-JM) and some recently reported Pt/graphene-based nanomaterials. The construction of 2-D distribution worm-like Pt nanoparticles and facile wet chemical synthesis strategy provide a promising way to develop superior performance electrocatalysts for direct methanol fuel cells applications.

  1. Exclusive Hydrogen Generation by Electrocatalysts Coated with an Amorphous Chromium-Based Layer Achieving Efficient Overall Water Splitting

    KAUST Repository

    Qureshi, Muhammad; Shinagawa, Tatsuya; Tsiapis, Nikolaos; Takanabe, Kazuhiro

    2017-01-01

    Successful conversion of renewable energy to useful chemicals requires efficient devices that can electrocatalyze or photocatalyze redox reactions, e.g., overall water splitting. Excellent electrocatalysts for the hydrogen evolution reaction (HER), such as Pt, can also cause other side-reactions, including the water-forming back-reaction from H2 and O2 products. A Cr-based amorphous layer coated on catalysts can work as a successful surface modifier that avoids the back-reaction, but its capabilities and limitations toward other species have not been studied. Herein, we investigated the Cr-based layer on Pt from perspectives of both electrocatalysis and photocatalysis using redox-active molecules/ions (O2, ferricyanide, IO3–, S2O82–, H2O2, and CO gas). Our systematic study revealed that utilization of the Cr-based layer realized an exclusive cathodic reaction only to HER, even in the presence of the aforementioned reactive species, suggesting that Cr-based layers work as membranes, as well as corrosion and poison inhibition layers. However, the Cr-based layer experienced self-oxidation and dissolved into the aqueous phase when a strong oxidizing agent or low pH was present. Presented herein are fundamental and critical aspects of the Cr-based modifier, which is essential for the successful and practical development of solar fuel production systems.

  2. One-Pot and Facile Fabrication of Hierarchical Branched Pt-Cu Nanoparticles as Excellent Electrocatalysts for Direct Methanol Fuel Cells.

    Science.gov (United States)

    Cao, Yanqin; Yang, Yong; Shan, Yufeng; Huang, Zhengren

    2016-03-09

    Hierarchical branched nanoparticles are one promising nanostructure with three-dimensional open porous structure composed of integrated branches for superior catalysis. We have successfully synthesized Pt-Cu hierarchical branched nanoparticles (HBNDs) with small size of about 30 nm and composed of integrated ultrathin branches by using a modified polyol process with introduction of poly(vinylpyrrolidone) and HCl. This strategy is expected to be a general strategy to prepare various metallic nanostructures for catalysis. Because of the special open porous structure, the as-prepared Pt-Cu HBNDs exhibit greatly enhanced specific activity toward the methanol oxidation reaction as much as 2.5 and 1.7 times compared with that of the commercial Pt-Ru and Pt-Ru/C catalysts, respectively. Therefore, they are potentially applicable as electrocatalysts for direct methanol fuel cells.

  3. 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.

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

    International Nuclear Information System (INIS)

    Lee, Eungje; Murthy, Arun; Manthiram, Arumugam

    2011-01-01

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

  5. 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.

  6. Surface-Tuned Co3O4 Nanoparticles Dispersed on Nitrogen-Doped Graphene as an Efficient Cathode Electrocatalyst for Mechanical Rechargeable Zinc-Air Battery Application.

    Science.gov (United States)

    Singh, Santosh K; Dhavale, Vishal M; Kurungot, Sreekumar

    2015-09-30

    The most vital component of the fuel cells and metal-air batteries is the electrocatalyst, which can facilitate the oxygen reduction reaction (ORR) at a significantly reduced overpotential. The present work deals with the development of surface-tuned cobalt oxide (Co3O4) nanoparticles dispersed on nitrogen-doped graphene as a potential ORR electrocatalyst possessing some unique advantages. The thermally reduced nitrogen-doped graphene (NGr) was decorated with three different morphologies of Co3O4 nanoparticles, viz., cubic, blunt edged cubic, and spherical, by using a simple hydrothermal method. We found that the spherical Co3O4 nanoparticle supported NGr catalyst (Co3O4-SP/NGr-24h) has acquired a significant activity makeover to display the ORR activity closely matching with the state-of-the-art Pt supported carbon (PtC) catalyst in alkaline medium. Subsequently, the Co3O4-SP/NGr-24h catalyst has been utilized as the air electrode in a Zn-air battery, which was found to show comparable performance to the system derived from PtC. Co3O4-SP/NGr-24h catalyst has shown several hours of flat discharge profile at the discharge rates of 10, 20, and 50 mA/cm(2) with a specific capacity and energy density of ~590 mAh/g-Zn and ~840 Wh/kg-Zn, respectively, in the primary Zn-air battery system. In conjunction, Co3O4-SP/NGr-24h has outperformed as an air electrode in mechanical rechargeable Zn-air battery as well, which has shown consistent flat discharge profile with minimal voltage loss at a discharge rate of 50 mA/cm(2). The present results, thus demonstrate that the proper combination of the tuned morphology of Co3O4 with NGr will be a promising and inexpensive material for efficient and ecofriendly cathodes for Zn-air batteries.

  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. Facile fabrication of palladium-ionic liquids-nitrogen-doped graphene nanocomposites as enhanced electro-catalyst for ethanol oxidation

    Science.gov (United States)

    Li, Shuwen; Yang, Honglei; Ren, Ren; Ma, Jianxin; Jin, Jun; Ma, Jiantai

    2015-10-01

    The palladium-ionic liquids-nitrogen-doped graphene nanocomposites are facile fabricated as enhanced electro-catalyst for ethanol oxidation. First, the ionic liquids functionalized nitrogen-doping graphene nanosheets (PDIL-NGS) with few layers is synthesized through a facile and effective one-pot hydrothermal method with graphene oxide as raw material, urea as reducing-doping agents and ionic liquids (ILs) derived from 3,4,9,10-perylene tetracarboxylic acid as functional molecules. The results of systematic characterization reveal that the PDIL molecules not only can functionalize NGS by π-π stacking with no affecting the nitrogen doping but also prevent the agglomeration of NGS. More importantly, the processing performance and the property of electron transfer are remarkably enhanced duo to introducing a large number of ILs groups. Then, the enhanced electrocatalytic Pd nanoparticles are successfully anchored on PDIL-NGS by a facile and surfactant-free synthetic technique. As an anode catalyst, the novel catalyst exhibits better kinetics, more superior electrocatalytic performance, higher tolerance and electrochemical stability than the other catalysts toward ethanol electrooxidation, owing to the role of PDIL molecules. Therefore, the new catalyst is believed to have the potential use for direct alcohol fuel cells in the future and the functionalized NGS is promising useful materials applied in other fields.

  9. Photoelectrochemical Water Oxidation by GaAs Nanowire Arrays Protected with Atomic Layer Deposited NiO x Electrocatalysts

    Science.gov (United States)

    Zeng, Joy; Xu, Xiaoqing; Parameshwaran, Vijay; Baker, Jon; Bent, Stacey; Wong, H.-S. Philip; Clemens, Bruce

    2018-02-01

    Photoelectrochemical (PEC) hydrogen production makes possible the direct conversion of solar energy into chemical fuel. In this work, PEC photoanodes consisting of GaAs nanowire (NW) arrays were fabricated, characterized, and then demonstrated for the oxygen evolution reaction (OER). Uniform and periodic GaAs nanowire arrays were grown on a heavily n-doped GaAs substrates by metal-organic chemical vapor deposition selective area growth. The nanowire arrays were characterized using cyclic voltammetry and impedance spectroscopy in a non-aqueous electrochemical system using ferrocene/ferrocenium (Fc/Fc+) as a redox couple, and a maximum oxidation photocurrent of 11.1 mA/cm2 was measured. GaAs NW arrays with a 36 nm layer of nickel oxide (NiO x ) synthesized by atomic layer deposition were then used as photoanodes to drive the OER. In addition to acting as an electrocatalyst, the NiO x layer served to protect the GaAs NWs from oxidative corrosion. Using this strategy, GaAs NW photoanodes were successfully used for the oxygen evolution reaction. This is the first demonstration of GaAs NW arrays for effective OER, and the fabrication and protection strategy developed in this work can be extended to study any other nanostructured semiconductor materials systems for electrochemical solar energy conversion.

  10. Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

    Science.gov (United States)

    Navaee, Aso; Salimi, Abdollah

    2018-05-01

    Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

  11. The performance and degradation of Pt electrocatalysts on novel carbon carriers for PEMFC applications

    Energy Technology Data Exchange (ETDEWEB)

    Mamat, M.S.; Grant, D.M.; Walker, G.S. [Energy and Sustainability Research Division, Faculty of Engineering, University of Nottingham, Nottingham NG7 2RD (United Kingdom); Grigoriev, S.A.; Dzhus, K.A. [Hydrogen Energy and Plasma Technology Institute, Russian Research Center ' ' Kurchatov Institute' ' , Kurchatov sq. 1, 123182 Moscow (Russian Federation)

    2010-07-15

    Electrocatalyst stability is an important factor influencing the performance of polymer electrolyte membrane (PEM) fuel cells and is essential in maintaining the cell output. The aim of this work was to elucidate factors which influence the stability of platinum supported onto graphitic nanofibres (Pt/GNFs) and to compare the performance of these materials with the commonly used Pt/Vulcan electrocatalyst. Platinum nanoparticles (average diameter of 6.9 nm) were supported on GNFs which were prepared by chemical vapour deposition over an unsupported nickel oxide (NiO) catalyst precursor. The performance of Pt/GNFs based electrodes were studied by cyclic voltammetry and a single-cell fuel cell test and were compared with a commercially available carbon nanostructure, Vulcan XC-72, which was also impregnated with Pt nanoparticles. Characterisation of the pre- and post-operation of the Pt/GNFs by XRD and TEM showed that structural changes of the Pt had occurred during testing. It was found that the average diameter of each grain and the degree of agglomeration among particles was increased, creating elongated clusters of Pt along the carbon fibre. Analysis of electrocatalyst post-operation also identified that the sulphate from the Nafion membrane was reacting with the Pt surface forming platinum sulphide (PtS). These phases were confirmed by the presence of low intensity, but sharp XRD peaks, attributed to a few large diameter particles (49 nm). These two factors resulted in current density dropping from 0.2 A/cm{sup 2} to 0.1 A/cm{sup 2} (at 0.70 V) over a 25 h test period. (author)

  12. Mace-like hierarchical MoS2/NiCo2S4 composites supported by carbon fiber paper: An efficient electrocatalyst for the hydrogen evolution reaction

    Science.gov (United States)

    Sun, Lan; Wang, Tao; Zhang, Long; Sun, Yunjin; Xu, Kewei; Dai, Zhengfei; Ma, Fei

    2018-02-01

    The rational design and preparation of earth-abundant, stable and efficient electrocatalysts for hydrogen production is currently the subject in extensive scientific and technological researches toward the future of a clean-energy society. Herein, a mace-like MoS2/NiCo2S4 hierarchical structure is designed and synthesized on carbon fiber paper via a facile hydrothermal method, and evaluated as electrocatalyst for hydrogen evolution reaction. In the MoS2/NiCo2S4/carbon fiber paper hierarchical structures, MoS2 nanosheets are dispersively distributed on the surface of NiCo2S4 nanowires, which provides an enlarged surface area, abundant interfaces and catalytic active sites. As for hydrogen evolution reaction, such MoS2/NiCo2S4/carbon fiber paper heterostructures give rise to a hydrogen evolution reaction catalytic current density of 10 mA cm-2 with a lower overpotential of 139 mV and a smaller Tafel slope of 37 mV·dec-1 than those of MoS2/carbon fiber paper and NiCo2S4/carbon fiber paper counterparts, exhibiting a prominent electrocatalytic performance. Moreover, the electrocatalytic properties change little after 5000 CV cycles and continual electrolysis for 12 h without obvious decay, respectively, demonstrating high durability and stability. The excellent hydrogen evolution reaction performances endow the hierarchical configuration MoS2/NiCo2S4/carbon fiber paper with promising alternative in HER and other related renewable energy fields.

  13. 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.

  14. Silver decorated LaMnO_3 nanorod/graphene composite electrocatalysts as reversible metal-air battery electrodes

    International Nuclear Information System (INIS)

    Hu, Jie; Liu, Qiunan; Shi, Lina; Shi, Ziwei; Huang, Hao

    2017-01-01

    Graphical abstract: Silver decorated LaMnO_3 nanorod/reduced graphene oxide composite possess excellent bifunctional electrocatalytic activity and good electrochemical stability in alkaline medium. - Highlights: • Silver decorated LaMnO_3 nanorod/graphene composite were synthesized for the first time. • The ORR and OER of composite in alkaline medium were evaluated. • This composite as an efficient bifunctional catalyst has a good cycle performance. - Abstract: Perovskite LaMnO_3 nanorod/reduced graphene oxides (LMO-NR/RGO) decorated with Ag nanoparticles are studied as a bifunctional catalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. LMO-NR/RGO composites are synthesized by using cetyltrimethyl ammonium bromide (CTAB) as template via a simple hydrothermal reaction followed by heat treatment; overlaying of Ag nanoparticles is obtained through a traditional silver mirror reaction. Electron microscopy reveals that LMO-NR is embedded between the sheets of RGO, and the material is homogeneously overlaid with Ag nanoparticles. The unique composite morphology of Ag/LMO-NR/RGO not only enhances the electron transport property by increasing conductivity but also facilitates the diffusion of electrolytes and oxygen. As confirmed by electrochemical testing, Ag/LMO-NR/RGO exhibits very strong synergy with Ag nanoparticles, LMO-NR, and RGO, and the catalytic activities of Ag/LMO-NR/RGO during ORR and OER are significantly improved. With the novel catalyst, the homemade zinc-air battery can be reversibly charged and discharged and display a stable cycle performance, indicating the great potential of this composite as an efficient bifunctional electrocatalyst for metal-air batteries.

  15. Silver decorated LaMnO{sub 3} nanorod/graphene composite electrocatalysts as reversible metal-air battery electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Jie [State Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao, 066004 (China); Hebei Key Laboratory of Applied Chemistry, Department of Environment and Chemistry, Yanshan University, Qinhuangdao, 066004 (China); Liu, Qiunan; Shi, Lina; Shi, Ziwei [Hebei Key Laboratory of Applied Chemistry, Department of Environment and Chemistry, Yanshan University, Qinhuangdao, 066004 (China); Huang, Hao, E-mail: huanghao@ysu.edu.cn [State Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao, 066004 (China); Henan Huanghe Whirlwind Co. Ltd., Changge, 461500 (China)

    2017-04-30

    Graphical abstract: Silver decorated LaMnO{sub 3} nanorod/reduced graphene oxide composite possess excellent bifunctional electrocatalytic activity and good electrochemical stability in alkaline medium. - Highlights: • Silver decorated LaMnO{sub 3} nanorod/graphene composite were synthesized for the first time. • The ORR and OER of composite in alkaline medium were evaluated. • This composite as an efficient bifunctional catalyst has a good cycle performance. - Abstract: Perovskite LaMnO{sub 3} nanorod/reduced graphene oxides (LMO-NR/RGO) decorated with Ag nanoparticles are studied as a bifunctional catalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. LMO-NR/RGO composites are synthesized by using cetyltrimethyl ammonium bromide (CTAB) as template via a simple hydrothermal reaction followed by heat treatment; overlaying of Ag nanoparticles is obtained through a traditional silver mirror reaction. Electron microscopy reveals that LMO-NR is embedded between the sheets of RGO, and the material is homogeneously overlaid with Ag nanoparticles. The unique composite morphology of Ag/LMO-NR/RGO not only enhances the electron transport property by increasing conductivity but also facilitates the diffusion of electrolytes and oxygen. As confirmed by electrochemical testing, Ag/LMO-NR/RGO exhibits very strong synergy with Ag nanoparticles, LMO-NR, and RGO, and the catalytic activities of Ag/LMO-NR/RGO during ORR and OER are significantly improved. With the novel catalyst, the homemade zinc-air battery can be reversibly charged and discharged and display a stable cycle performance, indicating the great potential of this composite as an efficient bifunctional electrocatalyst for metal-air batteries.

  16. Effect of losartan on human platelet activation.

    Science.gov (United States)

    Guerra-Cuesta, J I; Montón, M; Rodríguez-Feo, J A; Jiménez, A M; González-Fernández, F; Rico, L A; García, R; Gómez, J; Farré, J; Casado, S; López-Farré, A

    1999-03-01

    Previous studies have demonstrated that losartan can block the thromboxane A2 receptor on the vascular wall. The aim of the present study was to assess the effect of losartan on human platelet activation. Platelets were obtained from 15 healthy men, aged 26-40 years. Platelet activation was measured by changes in the light transmission of platelet-rich plasma stimulated by the thromboxane A2 analog U46619 (5 x 10(-6) mol/l) or ADP (10(-5) mol/l). U46619-stimulated platelet aggregation was significantly inhibited by losartan in a dose-dependent manner. Only a high dose of EXP 3174 (5 x 10(-5) mol/l), the in vivo active metabolite of losartan, was able to attenuate U46619-induced platelet activation. Captopril, an angiotensin I converting inhibitor, failed to modify U46619-induced platelet aggregation. Furthermore, the binding of [3H]-U46619 to platelets was competitively inhibited by losartan, whereas only a high dose of EXP 3174 reduced the binding of [3H]-U46619. Captopril failed to modify the binding of [3H]-U46619 to platelets. Losartan also reduced the platelet activation induced by ADP (10(-5) mol/l), a platelet agonist partially dependent on thromboxane A2. In addition, when thromboxane A2 generation was blocked by aspirin, ADP-induced platelet aggregation was inhibited to a similar degree to the inhibition induced by losartan. Exogenous angiotensin II did not elicit any modification of either U46619- or ADP-stimulated platelet aggregation. Losartan decreased platelet aggregation by a thromboxane A2-dependent mechanism. EXP 3174 was less potent than losartan in reducing thromboxane A2-dependent platelet activation. Captopril and exogenous angiotensin II had no effect on human platelet activation. These results suggest that losartan reduced thromboxane A2-dependent platelet activation independently of its effect on angiotensin II.

  17. Development of Refractory Ceramics for The Oxygen Evolution Reaction (OER) Electrocatalyst Support for Water Electrolysis at elevated temperatures

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Prag, Carsten Brorson; Polonsky, J.

    2012-01-01

    Commercial TaC and Si3N4 powders were tested as possible electrocatalyst support materials for the Oxygen Evolution Reaction (OER) for PEM water electrolysers, operating at elevated temperatures. TaC and Si3N4 were characterised by thermogravimmetric and differential thermal analysis...

  18. 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...

  19. Microwave-irradiation polyol synthesis of PVP-protected Pt–Ni electrocatalysts for methanol oxidation reaction

    CSIR Research Space (South Africa)

    Mathe, Ntombizodwa R

    2017-01-01

    Full Text Available ://doi.org/10.1007/s12678-017-0441-3 Microwave-Irradiation Polyol Synthesis of PVP-Protected Pt–Ni Electrocatalysts for Methanol Oxidation Reaction Ntombizodwa R. Mathe Manfred R. Scriba Rirhandzu S. Rikhotso Neil J. Coville ABSTRACT: Bimetallic Pt...

  20. Hollow Au@Pd and Au@Pt core-shell nanoparticles as electrocatalysts for ethanol oxidation reactions

    KAUST Repository

    Song, Hyon Min; Anjum, Dalaver H.; Sougrat, Rachid; Hedhili, Mohamed N.; Khashab, Niveen M.

    2012-01-01

    that individual metals may not catalyze. Here, preparation of hollow Au@Pd and Au@Pt core-shell nanoparticles (NPs) and their use as electrocatalysts are reported. Galvanic displacement with Ag NPs is used to obtain hollow NPs, and higher reduction potential of Au

  1. Combinatorial investigation of Pt-Ru-Sn alloys as an anode electrocatalysts for direct alcohol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Chu, Young Hwan [Department of New Energy.Resource Engineering, College of Science and Engineering, Sangji University, 124, Sangjidae-gil, Wonju-si, Gangwon-Do 220-702 (Korea); Shul, Yong Gun [Department of Chemical and Biomolecular Engineering, Yonsei University, 134, Shinchon-Dong, Seodaemun-Gu, Seoul 120-749 (Korea)

    2010-10-15

    Low-temperature direct alcohol fuel cells fed with different kinds of alcohol (methanol, ethanol and 2-propanol) have been investigated by employing ternary electrocatalysts (Pt-Ru-Sn) as anode catalysts. Combinatorial chemistry has been applied to screen the 66-PtRuSn-anode arrays at the same time to reduce cost, time, and effort when we select the optimum composition of electrocatalysts for DAFCs (Direct Alcohol Fuel Cells). PtRuSn (80:20:0) showed the lowest onset potential for methanol electro-oxidation, PtRuSn (50:0:50) for ethanol, and PtRuSn (20:70:10) for 2-propanol in CV results respectively, and single cell performance test indicated that Ru is more suitable for direct methanol fuel cell system, Sn for direct ethanol fuel cell system, and 2-propanol could be applied as fuel with low platinum composition anode electrocatalyst. The single cell performance results and electrochemical results (CV) were well matched with the combinatorial electrochemical results. As a result, we could verify the availability of combinatorial chemistry by comparing the results of each extreme electrocatalysts compositions as follows: PtRuSn (80:20:0) for methanol, PtRuSn (50:0:50) for ethanol and PtRuSn (20:70:10) for 2-propanol. (author)

  2. Selective and efficient reduction of carbon dioxide to carbon monoxide on oxide-derived nanostructured silver electrocatalysts

    NARCIS (Netherlands)

    Ma, Ming; Trześniewski, Bartek J.; Xie, Jie; Smith, Wilson A.

    2016-01-01

    In this work, the selective electrocatalytic reduction of carbon dioxide to carbon monoxide on oxide-derived silver electrocatalysts is presented. By a simple synthesis technique, the overall high faradaic efficiency for CO production on the oxide-derived Ag was shifted by more than 400 mV towards a

  3. A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

    Science.gov (United States)

    Feng, Yan; Liu, Hui; Yang, Jun

    2017-06-01

    Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

  4. Non-precious electrocatalysts for polymer electrolyte fuel cell cathode

    Energy Technology Data Exchange (ETDEWEB)

    Wu, G.; Chung, H.T.; Zelenay, P. [Los Alamos National Laboratory, Los Alamos, NM (United States). Materials Physics and Applications

    2009-07-01

    This study investigated the feasibility of reducing the high cost of polymer electrolyte fuel cell stacks by using non-precious catalysts for the oxygen reduction reaction (ORR). Most research interest has focused on ORR catalysts based on heat-treated precursors of transition metals, nitrogen and carbon. While initial ORR activity of such catalysts has improved in recent years, it is not sufficient for automotive use. The long-term stability of these catalysts is also insufficient. The activity and durability of the catalysts must be improved significantly in order to overcome these limitations. In addition, innovative electrode structures must be developed to allow for operation with thick catalyst layers. The ORR reaction mechanism must also be well understood in terms of the active reaction site. This presentation summarized non-precious ORR catalysis research at Los Alamos, with particular focus on catalysts obtained by heat treatment of polymers (such as polyaniline) on high-surface-area carbon in the presence of transition metals, cobalt and iron. These heat-treated catalysts achieve respectable ORR activity and improved stability in both aqueous and polymer electrolytes. Electrochemical and non-electrochemical techniques such as XPS, XANES and XAFS were used to examine the source of ORR activity of these heat-treated catalysts.

  5. Development of new electrocatalysts for proton exchange membrane fuel cells

    International Nuclear Information System (INIS)

    Franco, Egberto Gomes

    2005-01-01

    In this work the colloidal method was chosen to perform the catalysts. This method produces nano catalysts well dispersed in the carbon support. The catalyst systems were performed with platinum, ruthenium, molybdenum, nickel, dysprosium, terbium, samarium and uranium. The method chosen to synthesize catalysts produced binary' and ternary systems with a good distribution of the nano crystals. The quaternary systems performed in this work shows a crystallite size 2 to 3 times greater than the binary and ternary ones. This could indicate that some modifications in the method should be done to improve the electrocatalytic activity of the quaternary systems. The characterization of the catalysts were performed by the following techniques; X-ray fluorescence analysis, X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy, high resolution transmission electron microscopy, scanning electron microscopy, cyclic voltammetry and polarization curves. The PtRuMo system was identified as the most electro active system by cyclic voltammetry in order to oxidize methanol and ethanol. The PtRuDy system shows a good electrochemical activity to ethanol oxidation, but after the use of ethanol the catalyst lost 42 % of the activity when operating with hydrogen and oxygen. The binary system Pt U presents some promising results, this system start the oxidation of CO in 5 mV vs RHE. Besides this fact, when operating with ethanol the Pt U system shows no degradation of the catalytic activity. (author)

  6. Proliferative Activity and Neuroprotective Effect of Ligustrazene ...

    African Journals Online (AJOL)

    Proliferative Activity and Neuroprotective Effect of. Ligustrazene Derivative by Irritation of Vascular. Endothelial Growth Factor Expression in Middle Cerebral. Artery Occlusion Rats. Zhang Huazheng1, Wang Penglong2, Ren Liwei1, Wang Xiaobo2, Li Guoliang2,. Wang Mina1, Chu Fuhao2, Gong Yan2, Xu Bing2, Bi Siling1, ...

  7. Effectiveness of physical activity intervention at workplace

    Directory of Open Access Journals (Sweden)

    Marzena Malińska

    2017-04-01

    Full Text Available A physical activity is a key factor contributing to the improvement and maintenance of one’s general health. Although this issue is by no means limited to the workplace, it is precisely the work environment that can provide the basis for keeping and reinforcing more health-conscious attitudes and lifestyles, including programs promoting a physical activity. The paper presents an analysis of the literature on the effectiveness of physical activity intervention at the workplace. Particular attention is paid to the impact of the physical activity programs on musculoskeletal disorders, absenteeism, work ability, physical capacity and body weight of the participants. Given a marginal extent of programs of this kind in Poland, the authors’ intention was to show the benefits resulting from implementation of and participation in such initiatives. Med Pr 2017;68(2:277–301

  8. [Effectiveness of physical activity intervention at workplace].

    Science.gov (United States)

    Malińska, Marzena

    2017-03-24

    A physical activity is a key factor contributing to the improvement and maintenance of one's general health. Although this issue is by no means limited to the workplace, it is precisely the work environment that can provide the basis for keeping and reinforcing more health-conscious attitudes and lifestyles, including programs promoting a physical activity. The paper presents an analysis of the literature on the effectiveness of physical activity intervention at the workplace. Particular attention is paid to the impact of the physical activity programs on musculoskeletal disorders, absenteeism, work ability, physical capacity and body weight of the participants. Given a marginal extent of programs of this kind in Poland, the authors' intention was to show the benefits resulting from implementation of and participation in such initiatives. Med Pr 2017;68(2):277-301. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

  9. Pt, PtCo and PtNi electrocatalysts prepared with mechanical alloying for oxygen reduction reaction in alkaline medium; Electrocatalizadores de Pt, PtCo y PtNi preparados por aleado mecanico para la reaccion de reduccion de oxigeno en medio alcalino

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Contreras, M.A.; Fernandez-Valverde, S.M. [Instituto Nacional de Investigaciones Nucleares, Ocoyoacac, Estado de Mexico (Mexico)]. E-mail: miguel.garcia@inin.gob.mx; Vargas-Garcia, J.R. [ESIQIE-IPN, Mexico D.F. (Mexico

    2009-09-15

    Pt, PtCo and PtNi electrocatalysts were prepared using mechanical alloying and their electrocatalytic activity was investigated for oxygen reduction reaction (ORR) in KOH 0.5 M using cyclic voltametry and rotary disc electrode (RDE) techniques. The electrocatalysts were characterized using x-ray diffraction, sweep electron microscopy, dispersive x-ray transmission and chemical analysis. The physical characterization indicated that all the electrocatalysts are alloys formed by agglomerated particles composed of nanocrystals. The chemical analysis showed the presence of iron in the alloys. For the electrocatalytic evaluation, polarization curves and Koutecky-Levich and Tafel graphs were obtained to determine the kinetic parameters of the electrocatalysts in the study. With the same experimental conditions, the PtCo presented better electrocatalytic performance with a higher exchange current density. [Spanish] Se prepararon electrocatalizadores de Pt, PtCo y PtNi por aleado mecanico y se investigo su actividad electrocatalitica para la reaccion de reduccion de oxigeno (RRO) en KOH 0.5 M utilizando las tecnicas de Voltametria ciclica y Electrodo de Disco Rotatorio. Los electrocatalizadores se caracterizaron por difraccion de rayos X, Microscopia electronica de Barrido, de Transmision y analisis quimico por dispersion de rayos X. La caracterizacion fisica indico que todos los electrocatalizadores son aleaciones formadas de particulas aglomeradas, compuestas de nanocristales. El analisis quimico mostro la presencia de hierro en las aleaciones. Para la evaluacion electrocatalitica se obtuvieron curvas de polarizacion, graficas de Koutecky-Levich y de Tafel para determinar los parametros cineticos de los electrocatalizadores en estudio. En las mismas condiciones experimentales, el PtCo presento el mejor desempeno electrocatalitico con la densidad de corriente de intercambio mas alta.

  10. Pd nanowire arrays as electrocatalysts for ethanol electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hong; Cheng, Faliang [Dongguan University of Technology, Dongguan 523106 (China); Xu, Changwei; Jiang, Sanping [School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798 (Singapore)

    2007-05-15

    Highly ordered Pd nanowire arrays were prepared by template-electrodeposition method using anodic aluminum oxide template. The Pd nanowire arrays, in this paper, have high electrochemical active surface and show excellent catalytic properties for ethanol electrooxidation in alkaline media. The activity of Pd nanowire arrays for ethanol oxidation is not only higher that of Pd film, but also higher than that of commercial E-TEK PtRu(2:1 by weight)/C. The micrometer sized pores and channels in nanowire arrays act as structure units. They make liquid fuel diffuse into and products diffuse out of the catalysts layer much easier, therefore, the utilization efficiency of catalysts gets higher. Pd nanowire arrays are stable catalysts for ethanol oxidation. The nanowire arrays may be a great potential in direct ethanol fuel cells and ethanol sensors. (author)

  11. Design of Pd/PANI/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation.

    Science.gov (United States)

    Wang, An-Liang; Xu, Han; Feng, Jin-Xian; Ding, Liang-Xin; Tong, Ye-Xiang; Li, Gao-Ren

    2013-07-24

    Low cost, high activity, and long-term durability are the main requirements for commercializing fuel cell electrocatalysts. Despite tremendous efforts, developing non-Pt anode electrocatalysts with high activity and long-term durability at low cost remains a significant technical challenge. Here we report a new type of hybrid Pd/PANI/Pd sandwich-structured nanotube array (SNTA) to exploit shape effects and synergistic effects of Pd-PANI composites for the oxidation of small organic molecules for direct alcohol fuel cells. These synthesized Pd/PANI/Pd SNTAs exhibit significantly improved electrocatalytic activity and durability compared with Pd NTAs and commercial Pd/C catalysts. The unique SNTAs provide fast transport and short diffusion paths for electroactive species and high utilization rate of catalysts. Besides the merits of nanotube arrays, the improved electrocatalytic activity and durability are especially attributed to the special Pd/PANI/Pd sandwich-like nanostructures, which results in electron delocalization between Pd d orbitals and PANI π-conjugated ligands and in electron transfer from Pd to PANI.

  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. 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.

  14. Effective diffusion of confined active Brownian swimmers

    Science.gov (United States)

    Sandoval, Mario; Dagdug, Leonardo

    2014-11-01

    We find theoretically the effect of confinement and thermal fluctuations, on the diffusivity of a spherical active swimmer moving inside a two-dimensional narrow cavity of general shape. The explicit formulas for the effective diffusion coefficient of a swimmer moving inside two particular cavities are presented. We also compare our analytical results with Brownian Dynamics simulations and we obtain excellent agreement. L.D. thanks Consejo Nacional de Ciencia y Tecnologia (CONACyT) Mexico, for partial support by Grant No. 176452. M. S. thanks CONACyT and Programa de Mejoramiento de Profesorado (PROMEP) for partially funding this work under Grant No. 103.5/13/6732.

  15. Regulatory Effects of Fisetin on Microglial Activation

    OpenAIRE

    Chuang, Jing-Yuan; Chang, Pei-Chun; Shen, Yi-Chun; Lin, Chingju; Tsai, Cheng-Fang; Chen, Jia-Hong; Yeh, Wei-Lan; Wu, Ling-Hsuan; Lin, Hsiao-Yun; Liu, Yu-Shu; Lu, Dah-Yuu

    2014-01-01

    Increasing evidence suggests that inflammatory processes in the central nervous system that are mediated by microglial activation play a key role in neurodegeneration. Fisetin, a plant flavonol commonly found in fruits and vegetables, is frequently added to nutritional supplements due to its antioxidant properties. In the present study, treatment with fisetin inhibited microglial cell migration and ROS (reactive oxygen species) production. Treatment with fisetin also effectively inhibited LPS...

  16. Effective dose to radon considering people's activities

    International Nuclear Information System (INIS)

    Shimo, M.; Seki, K.; Kikuchi, I.

    1992-01-01

    The tidal volume was estimated for evaluating the effective dose due to radon concentration in the atmosphere. In this study regional population was separated to vocation and non-vocation. The occupancy time and the breathing rate for both vocation and non-vocation groups were estimated, and the annual tidal volume for both groups were calculated. Human actions were separated to 18 activities in the process for estimating the breathing rate. It was clear that the breathing rate depended on human activity and that the human activity changed with its age, so the breathing rate varied with age. Finally the effective doses due to radon and radon progeny indoors and outdoors were evaluated. The maximum annual effective dose was estimated to be 1.2 mSv, minimum 0.2 mSv, and mean 0.51 mSv for vocation. For non-vocation, the male maximum value 0.43 mSv was obtained at the 16 age and the minimum 0.12 mSv at the 70 age, whereas female maximum 0.26 mSv was obtained at the 12 age and the minimum 0.11 mSv at the 70 age. In addition in this study objective areas are Aichi, Gifu, and Mie prefectures for vocation and only Aichi prefecture for non-vocation. (author)

  17. Physical activity effects on bone metabolism.

    Science.gov (United States)

    Smith, E L; Gilligan, C

    1991-01-01

    The incidence of osteoporotic fractures rises exponentially with age and is increasing faster than the demographic increase in the aging population. Physical activity has great potential to reduce the risk for osteoporotic fractures. Three independent but interactive factors contribute to the risk of fractures: bone strength, the risk of falling, and the effectiveness of neuromuscular response that protects the skeleton from injury. Exercise can reduce fracture risk not only by preventing bone loss, but by decreasing the risk of falling and the force of impact by improving strength, flexibility, balance, and reaction time. Extreme inactivity causes rapid bone loss of up to 40%, while athletic activity results in bone hypertrophy of up to 40%. Exercise intervention programs have reduced bone loss or increased bone mass in both men and women of various ages and initial bone status. These benefits have been shown for arm bone mineral content, total body calcium, spine, calcium bone index, tibia, and calcaneus. In both middle-aged and elderly women, physical activity intervention reduced bone loss or increased bone mass. The mechanisms for maintenance of skeletal integrity rely on a cellular response to hormonal and mechanical load stimuli. Studies in animal models show that training affects cellular activity. In osteoporotics, cellular erosion is increased and mineral apposition rate (MAR) decreased compared with normal age-matched controls. In contrast to this, sows trained on a treadmill 20 min per day for 20 weeks had greater active periosteal surface, periosteal MAR, and osteonal MAR than untrained sows.

  18. Hydrogen evolution by a metal-free electrocatalyst

    KAUST Repository

    Zheng, Yao

    2014-04-28

    Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics. © 2014 Macmillan Publishers Limited. All rights reserved.

  19. Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Raugei, Simone [Center for Molecular Electrocatalysis,; Helm, Monte L. [Center for Molecular Electrocatalysis,; Hammes-Schiffer, Sharon [Department of Chemistry, University of Illinois at Urbana—Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, United States; Appel, Aaron M. [Center for Molecular Electrocatalysis,; O’Hagan, Molly [Center for Molecular Electrocatalysis,; Wiedner, Eric S. [Center for Molecular Electrocatalysis,; Bullock, R. Morris [Center for Molecular Electrocatalysis,

    2015-11-25

    Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for H2 production and oxidation based on earth-abundant metals. Our work seeks to address fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy-efficient catalysts. Proton-transfer reactions can be rate-limiting and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2, although generally at higher overpotentials. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, these iron complexes had a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently intramolecular proton movement was slow. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle because optimization of a specific catalytic step can negatively influence another step and not necessarily lead to a better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free-energy change of each catalytic step, yielding a nearly flat free-energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates.

  20. Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Raugei, Simone; Helm, Monte L.; Hammes-Schiffer, Sharon; Appel, Aaron M.; O’Hagan, Molly; Wiedner, Eric S.; Bullock, R. Morris

    2016-01-19

    Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for H2 production and oxidation based on earth-abundant metals. Our work seeks to address fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy-efficient catalysts. Proton-transfer reactions can be rate-limiting and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2, although generally at higher overpotentials. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, these iron complexes had a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently intramolecular proton movement was slow. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle because optimization of a specific catalytic step can negatively influence another step and not necessarily lead to a better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free-energy change of each catalytic step, yielding a nearly flat free-energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates.

  1. Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

    Science.gov (United States)

    Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

    2018-01-01

    Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

  2. PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: brandalise@usp.br, E-mail: mmtusi@usp.br, E-mail: rmpiasen@ipen.br, E-mail: ovcorrea@ipen.br, E-mail: mlinardi@ipen.br, E-mail: espinace@ipen.br, E-mail: aolivei@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2009-07-01

    PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H{sub 2}PtCl{sub 6.6}H{sub 2}O, RuCl{sub 3.x}H{sub 2}O and Bi(NO{sub 3}){sub 3.5}H{sub 2}O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

  3. PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

    International Nuclear Information System (INIS)

    Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir

    2009-01-01

    PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H 2 PtCl 6.6 H 2 O, RuCl 3.x H 2 O and Bi(NO 3 ) 3.5 H 2 O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-30

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

  5. Pd-Pt alloys nanowires as support-less electrocatalyst with high synergistic enhancement in efficiency for methanol oxidation in acidic medium.

    Science.gov (United States)

    Rana, Moumita; Patil, Pramod K; Chhetri, Manjeet; Dileep, K; Datta, Ranjan; Gautam, Ujjal K

    2016-02-01

    In a facile approach, Pd73Pt27 alloy nanowires (NWs) with large aspect ratios were synthesized in high yield by using sacrificial templates. Unlike majority of processes, our synthesis was carried out in aqueous solution with no intermittent separating stages for the products, while maintaining the NW morphology up to ∼30% of Pt. Upon evaporation of their dispersion, the NWs transform into a stable porous membrane due to self-entanglement and can be directly lifted and employed for electrocatalytic applications without external catalyst supports. We show that the NW membranes exhibit efficient electrocatalytic performance for methanol oxidation reaction (MOR) with 10 times higher mass activity and 4.4 times higher specific activity in acidic media as compared to commercial Pt catalysts. The membrane electrocatalysts is robust and exhibited very good stability with retention of ∼70% mass-activity after 4000 potential cycles. Since Pd was found to be inert towards MOR in acidic medium, our investigation provides a direct estimate of synergistic enhancement of efficiency. Over 10 times increment of mass activity appears to be significantly higher than previous investigations in various other reaction media. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Effects of composition on structure and activity of PtRu/C catalysts.

    Science.gov (United States)

    Wiltshire, Richard J K; King, Colin R; Rose, Abigail; Wells, Peter P; Davies, Hazel; Hogarth, Martin P; Thompsett, David; Theobald, Brian; Mosselmans, Fredrick W; Roberts, Mark; Russell, Andrea E

    2009-04-07

    A series of carbon supported PtRu bimetallic catalysts with varying Pt:Ru ratio were prepared and characterised using ex situ and in situ XRD, in situ EXAFS at 0 V vs. RHE, ex situ XPS and monolayer CO stripping voltammetry. Although the catalysts were found to be well mixed/alloyed, with no evidence of unalloyed Ru (oxides) present, the surfaces of the electrocatalyst nanoparticles were found to be enriched with Pt compared to the nominal bulk composition. The methanol oxidation activities of the catalysts were determined in 1.0 mol dm(-3) H2SO4. In agreement with published studies of polycrystalline bulk PtRu alloys the catalyst with a 0.6 surface fraction of Pt was found to give the best methanol oxidation activity at 30 degrees C. However, at 80 degrees C a greater surface fraction of Ru could be tolerated, with some activity at low current densities found for a Pt surface fraction as low as 0.2. The results support the conclusion that a limited amount of methanol dehydrogenation occurs at Ru sites or Ru dominated surface ensembles at 80 degrees C.

  7. Electro-oxidation of methanol and ethanol using PtRu/C, PtSn/C and PtSnRu/C electrocatalysts prepared by an alcohol-reduction process

    Energy Technology Data Exchange (ETDEWEB)

    Neto, Almir Oliveira; Dias, Ricardo R.; Tusi, Marcelo M.; Linardi, Marcelo; Spinace, Estevam V. [Instituto de Pesquisas Energeticas e Nucleares, IPEN-CNEN/SP, Av. Prof. Lineu Prestes 2242, Cidade Universitaria, CEP 05508-900 Sao Paulo, SP (Brazil)

    2007-03-30

    PtRu/C, PtSn/C and PtSnRu/C electrocatalysts were prepared by the alcohol reduction process using ethylene glycol as the solvent and reduction agent and Vulcan Carbon XC72 as the support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electrochemical oxidation of methanol and ethanol were studied by chronoamperometry using a thin porous coating technique. The PtSn/C electrocatalyst prepared by this methodology showed superior performance compared to the PtRu/C and PtSnRu/C electrocatalysts for methanol and ethanol oxidation at room temperature. (author)

  8. Electro-oxidation of methanol and ethanol using PtRu/C, PtSn/C and PtSnRu/C electrocatalysts prepared by an alcohol-reduction process

    Science.gov (United States)

    Neto, Almir Oliveira; Dias, Ricardo R.; Tusi, Marcelo M.; Linardi, Marcelo; Spinacé, Estevam V.

    PtRu/C, PtSn/C and PtSnRu/C electrocatalysts were prepared by the alcohol reduction process using ethylene glycol as the solvent and reduction agent and Vulcan Carbon XC72 as the support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electrochemical oxidation of methanol and ethanol were studied by chronoamperometry using a thin porous coating technique. The PtSn/C electrocatalyst prepared by this methodology showed superior performance compared to the PtRu/C and PtSnRu/C electrocatalysts for methanol and ethanol oxidation at room temperature.

  9. 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.

  10. Confinement dependence of electro-catalysts for hydrogen evolution from water splitting

    Directory of Open Access Journals (Sweden)

    Mikaela Lindgren

    2014-02-01

    Full Text Available Density functional theory is utilized to articulate a particular generic deconstruction of the electrode/electro-catalyst assembly for the cathode process during water splitting. A computational model was designed to determine how alloying elements control the fraction of H2 released during zirconium oxidation by water relative to the amount of hydrogen picked up by the corroding alloy. This model is utilized to determine the efficiencies of transition metals decorated with hydroxide interfaces in facilitating the electro-catalytic hydrogen evolution reaction. A computational strategy is developed to select an electro-catalyst for hydrogen evolution (HE, where the choice of a transition metal catalyst is guided by the confining environment. The latter may be recast into a nominal pressure experienced by the evolving H2 molecule. We arrived at a novel perspective on the uniqueness of oxide supported atomic Pt as a HE catalyst under ambient conditions.

  11. 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.

  12. Editors' Choice Growth of Layered WS2Electrocatalysts for Highly Efficient Hydrogen Production Reaction

    KAUST Repository

    Alsabban, Merfat M.

    2016-08-18

    Seeking more economical alternative electrocatalysts without sacrificing much in performance to replace precious metal Pt is one of the major research topics in hydrogen evolution reactions (HER). Tungsten disulfide (WS2) has been recognized as a promising substitute for Pt owing to its high efficiency and low-cost. Since most existing works adopt solution-synthesized WS2 crystallites for HER, direct growth of WS2 layered materials on conducting substrates should offer new opportunities. The growth of WS2 by the thermolysis of ammonium tetrathiotungstate (NH4)(2)WS4 was examined under various gaseous environments. Structural analysis and electrochemical studies show that the H2S environment leads to the WS2 catalysts with superior HER performance with an extremely low overpotential (eta(10) = 184 mV). (C) The Author(s) 2016. Published by ECS. All rights reserved.

  13. Editors' Choice Growth of Layered WS2Electrocatalysts for Highly Efficient Hydrogen Production Reaction

    KAUST Repository

    Alsabban, Merfat M.; Min, Shixiong; Hedhili, Mohamed N.; Ming, Jun; Li, Lain-Jong; Huang, Kuo-Wei

    2016-01-01

    Seeking more economical alternative electrocatalysts without sacrificing much in performance to replace precious metal Pt is one of the major research topics in hydrogen evolution reactions (HER). Tungsten disulfide (WS2) has been recognized as a promising substitute for Pt owing to its high efficiency and low-cost. Since most existing works adopt solution-synthesized WS2 crystallites for HER, direct growth of WS2 layered materials on conducting substrates should offer new opportunities. The growth of WS2 by the thermolysis of ammonium tetrathiotungstate (NH4)(2)WS4 was examined under various gaseous environments. Structural analysis and electrochemical studies show that the H2S environment leads to the WS2 catalysts with superior HER performance with an extremely low overpotential (eta(10) = 184 mV). (C) The Author(s) 2016. Published by ECS. All rights reserved.

  14. Toward High-Performance and Low-Cost Hydrogen Evolution Reaction Electrocatalysts: Nanostructuring Cobalt Phosphide (CoP) Particles on Carbon Fiber Paper.

    Science.gov (United States)

    Yu, Shu Hearn; Chua, Daniel H C

    2018-05-02

    In this communication, we facily fabricated nanostructured CoP particles (150 to 200 nm) on carbon fiber paper (CFP) for hydrogen evolution reaction (HER) by a simple two-step process via a green route. In the first step, crystalline Co 3 O 4 nanocubes (150-200 nm) were loaded on CFP through a hydrothermal process at low temperature (120 °C). Interestingly, crystalline Co 3 O 4 nanocubes with a size 150-200 nm exhibited different growth mechanisms in contrast to the crystalline Co 3 O 4 nanocubes with a size <100 nm reported earlier. In the second step, these crystalline Co 3 O 4 nanocubes were converted to catalytically active CoP particles through chemical vapor deposition (CVD) phosphorization (denoted as CoP/CFP-H). Remarkably, CoP/CFP-H exhibited a low Tafel slope of 49.7 mV/dec and only required overpotentials of 128.1, 144.4, and 190.8 mV to drive geometric current densities of -10, -20, and -100 mA cm -2 , respectively. Besides, the CoP/CFP-H also demonstrated an excellent durability in an acidic environment under 2000 sweeps at a high scan rate (100 mV s -1 ) and a 24 h chronopotentiometry testing. For comparison, CoP was also fabricated through the electrodeposition method, followed by CVD phosphorization (denoted as CoP/CFP-E). It was found that the latter had exhibited inferior activity compared to CoP/CFP-H. The good performances of CoP/CFP-H are essentially due to the rational designs of electrode: (i) the applications of highly HER active CoP electrocatalyst, (ii) the intimate contact of nanostructured CoP on carbon fibers, and (iii) the large electrochemical surface area at electrocatalyst/electrolyte interface due to the large retaining of particles features after phosphorization. Notably, the intermediate Co 3 O 4 /CFP can serve as a platform to develop other cobalt-based functional materials.

  15. [Effect of physical activity on functional performance].

    Science.gov (United States)

    Nikolaus, T

    2001-02-01

    Epidemiological studies clearly show a connection between physical activity and the occurrence of disabilities in old age. Physical exercise is possible and useful at every age. Numerous intervention trials have shown that training of endurance, strength and coordination has positive effects on the cardiovascular system, the lung, the musculo-skeletal system, metabolism and the immune system in elderly people. Even very frail elderly people can increase their muscle strength and functional capabilities by strength training. Group sessions may improve social interactions and additionally increase the quality of life.

  16. 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.

  17. 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.

  18. Physical activity and its effects on reproduction.

    Science.gov (United States)

    Redman, Leanne M

    2006-05-01

    The reproductive system is tightly coupled with energy balance, and thereby changes in the status of energy balance through changes in physical activity can impact on the reproductive system. In light of the new physical activity for health recommendations, it is therefore important to understand the inherent effects, both positive and negative, of physical activity on the reproductive system. At both extremes of the energy spectrum, disorders of chronic energy excess and energy deficiency are characterized by a wide range of reproductive disorders, including menstrual irregularity, anovulation, polycystic ovarian syndrome, and infertility in women, and erectile dysfunction and altered spermatogenesis in men. Although laboratory research indicates that individuals may be able to prevent or reverse reproductive disruptions, either by increasing energy expenditure in cases of energy excess or by dietary reform in cases of energy deficits, there is an acute need for applied research to confirm this idea and to identify mechanisms by which the availability of energy per se regulates reproductive function in humans.

  19. Regulatory effects of fisetin on microglial activation.

    Science.gov (United States)

    Chuang, Jing-Yuan; Chang, Pei-Chun; Shen, Yi-Chun; Lin, Chingju; Tsai, Cheng-Fang; Chen, Jia-Hong; Yeh, Wei-Lan; Wu, Ling-Hsuan; Lin, Hsiao-Yun; Liu, Yu-Shu; Lu, Dah-Yuu

    2014-06-26

    Increasing evidence suggests that inflammatory processes in the central nervous system that are mediated by microglial activation play a key role in neurodegeneration. Fisetin, a plant flavonol commonly found in fruits and vegetables, is frequently added to nutritional supplements due to its antioxidant properties. In the present study, treatment with fisetin inhibited microglial cell migration and ROS (reactive oxygen species) production. Treatment with fisetin also effectively inhibited LPS plus IFN-γ-induced nitric oxide (NO) production, and inducible nitric oxide synthase (iNOS) expression in microglial cells. Furthermore, fisetin also reduced expressions of iNOS and NO by stimulation of peptidoglycan, the major component of the Gram-positive bacterium cell wall. Fisetin also inhibited the enhancement of LPS/IFN-γ- or peptidoglycan-induced inflammatory mediator IL (interlukin)-1 β expression. Besides the antioxidative and anti-inflammatory effects of fisetin, our study also elucidates the manner in fisetin-induced an endogenous anti-oxidative enzyme HO (heme oxygenase)-1 expression. Moreover, the regulatory molecular mechanism of fisetin-induced HO-1 expression operates through the PI-3 kinase/AKT and p38 signaling pathways in microglia. Notably, fisetin also significantly attenuated inflammation-related microglial activation and coordination deficit in mice in vivo. These findings suggest that fisetin may be a candidate agent for the development of therapies for inflammation-related neurodegenerative diseases.

  20. Regulatory Effects of Fisetin on Microglial Activation

    Directory of Open Access Journals (Sweden)

    Jing-Yuan Chuang

    2014-06-01

    Full Text Available Increasing evidence suggests that inflammatory processes in the central nervous system that are mediated by microglial activation play a key role in neurodegeneration. Fisetin, a plant flavonol commonly found in fruits and vegetables, is frequently added to nutritional supplements due to its antioxidant properties. In the present study, treatment with fisetin inhibited microglial cell migration and ROS (reactive oxygen species production. Treatment with fisetin also effectively inhibited LPS plus IFN-γ-induced nitric oxide (NO production, and inducible nitric oxide synthase (iNOS expression in microglial cells. Furthermore, fisetin also reduced expressions of iNOS and NO by stimulation of peptidoglycan, the major component of the Gram-positive bacterium cell wall. Fisetin also inhibited the enhancement of LPS/IFN-γ- or peptidoglycan-induced inflammatory mediator IL (interlukin-1 β expression. Besides the antioxidative and anti-inflammatory effects of fisetin, our study also elucidates the manner in fisetin-induced an endogenous anti-oxidative enzyme HO (heme oxygenase-1 expression. Moreover, the regulatory molecular mechanism of fisetin-induced HO-1 expression operates through the PI-3 kinase/AKT and p38 signaling pathways in microglia. Notably, fisetin also significantly attenuated inflammation-related microglial activation and coordination deficit in mice in vivo. These findings suggest that fisetin may be a candidate agent for the development of therapies for inflammation-related neurodegenerative diseases.

  1. A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2to CO

    KAUST Repository

    Rasul, Shahid

    2014-12-23

    The challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy-efficient, and non-precious-metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous CO2 conversion. A non-noble metal electrocatalyst based on a copper-indium (Cu-In) alloy that selectively converts CO2 to CO with a low overpotential is reported. The electrochemical deposition of In on rough Cu surfaces led to Cu-In alloy surfaces. DFT calculations showed that the In preferentially located on the edge sites rather than on the corner or flat sites and that the d-electron nature of Cu remained almost intact, but adsorption properties of neighboring Cu was perturbed by the presence of In. This preparation of non-noble metal alloy electrodes for the reduction of CO2 provides guidelines for further improving electrocatalysis.

  2. Sonochemical synthesis and characterization of Pt/CNT, Pt/TiO2, and Pt/CNT/TiO2 electrocatalysts for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Bedolla-Valdez, Z.I.; Verde-Gómez, Y.; Valenzuela-Muñiz, A.M.; Gochi-Ponce, Y.; Oropeza-Guzmán, M.T.; Berhault, Gilles; Alonso-Núñez, G.

    2015-01-01

    Highlights: • Pt/CNT/TiO 2 electrocatalyst was successfully prepared by the sonochemical method. • The electrocatalyst Pt/CNT/TiO 2 was synthesized without heat treatments, additives or surfactants. • The TiO 2 -Pt interaction improves the CO-tolerance of Pt/CNT/TiO 2 , as well as the electrocatalyst stability. • Low amount of multi-walled carbon nanotubes increases the current density of Pt/CNT/TiO 2 significantly compared to Pt/TiO 2 . - Abstract: Pt electrocatalyst supported on composite formed of multi-walled carbon nanotubes and titanium oxide (CNT/TiO 2 ) was successfully synthesized by a sonochemical method without heat treatments, surfactants or additives. This electrocatalyst could be used for direct methanol fuel cells (DMFC) applications. For comparison, Pt/CNT and Pt/TiO 2 electrocatalysts were prepared as reference samples. Structural properties and morphology of the synthesized materials were examined by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and their specific surface areas were determined by the Brunauer-Emmett-Teller method. The Pt and acid-treated CNT contents were analyzed by inductively coupled plasma atomic emission spectroscopy and thermogravimetric analysis, respectively. The electrochemical properties of the synthesized electrocatalysts were evaluated by cyclic voltammetry (CV) and chronoamperometry in a three-electrode cell at room temperature. The evaluation performed using electrochemical techniques suggests that TiO 2 promotes the CO-tolerance due to TiO 2 -Pt interaction. The CV tests demonstrated that 6 wt.% of acid-treated CNT increases significantly the current density when Pt selectively interacts with TiO 2 .

  3. Evaluation of colloidal Pd and Pd-alloys as anode electrocatalysts for direct borohydride fuel cells applications

    Energy Technology Data Exchange (ETDEWEB)

    Atwan, M.H. [General Motors R and D Technical Center, Warren, MI (United States); Gyenge, E.L. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Northwood, D.O. [Windsor Univ., ON (Canada). Dept. of Mechanical, Automotive and Materials Engineering

    2010-07-01

    An evaluation was conducted to assess the use of colloidal palladium (Pd) and Pd alloys as anode electrocatalysts for direct borohydride fuel cell applications. A modified Bonneman method was used to investigate borohydride oxidation on supported Pd and Pd-alloy nano-electrocatalysts. Cyclic voltammetry (CV), rotating disk electrode (RDE) voltammetry, and single fuel cell test stations were used to determine Tafel slopes, exchange current densities, oxidation peak potentials, and fuel cell performance. The study also investigated the influence of temperature and oxidant flow and fuel flow rates on fuel cell performance. The study showed that the current density of the fuel cell increased with increases in temperature for all the investigated Pd electrocatalysts. However, the increase in current density was not as high as expected when fuel flow rates were increased. A current density of 50 mA cm{sup -2} was observed at 298 K with a Pd-Ir anode catalyst operating at a cell voltage of 0.5 V. 28 refs., 1 tab., 15 figs.

  4. Electrochemical oxidation of ethanol using PtRh/C electrocatalysts in alkaline medium and synthesized by sodium borohydride and alcohol reduction

    International Nuclear Information System (INIS)

    Fontes, Eric Hossein

    2017-01-01

    PtRh/C were prepared by the following atomic proportions: (100,0), (0,100), (90,10), (70,30) and (50,50). The methods employed in the synthesis of these materials were reduction by sodium borohydride and reduction by alcohol. The metal salts used were H 2 PtCl 6 3•6H 2 0 and (RhNO 3 ) 3 , the support used was Carbon black XC72 and the bulk metal composition was 20% and 80% of support. The electrocatalysts were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction and Transmission electron microscopy. The ethanol electrochemical oxidation mechanism was investigated by in situ Fourier Transform Infrared Spectroscopy couple to an Attenuated Total Reflection technique. The electrocatalytic activity were evaluated by Cyclic Voltammetry, Linear Sweep Voltammetry and Chronoamperometry techniques. The Fuel Cells tests were made in a single direct alcohol fuel cell with alkaline membrane. The working electrodes were prepared by a thin porous coating technique. X-ray diffraction allowed to verify metallic alloys, segregate phases and to calculate the percentage of metallic alloys. It was else possible to identify crystallographic phases. Infrared Spectroscopy allowed to verify that the electrochemical oxidation of ethanol was carried out by an incomplete mechanism. PtRh(70:30)/C prepared by sodium borohydride produced large amounts of carbon dioxide and acetaldehyde. Rh/C showed electrocatalytic activity when compared with other materials studied.

  5. Metal ion effects on enolase activity

    International Nuclear Information System (INIS)

    Lee, M.E.; Nowak, T.

    1986-01-01

    Most metal binding studies with yeast enolase suggest that two metals per monomer are required for catalytic activity. The functions of metal I and metal II have not been unequivocally defined. In a series of kinetic experiments where the concentration of MgII is kept constant at subsaturating levels (1mM), the addition of MnII or of ZnII gives a hyperbolic decrease in activity. The final velocity of these mixed metal systems is the same velocity obtained with either only MnII or ZnII respectively. The concentration of MnII (40 μM) or of Zn (2μM) which gives half maximal effect in the presence of (1mM) MgII is approximately the same as the Km' value for MnII (9μM) or ZnII (3μM) respectively. Direct binding of MnII to enolase in the absence and presence of MgII shows that MnII and MgII compete for the same metal site on enolase. In the presence of 2-phosphoglycerate (2-PGA) and MgII, only a single site is occupied by MnII. Results suggest MnII at site I and MgII at site II. PRR and high resolution 1 H and 31 P NMR studies of enzyme-ligand complexes containing MnII and MgII and MnII are consistent with this model. 31 P measurements allow a measure of the equilibrium constant (0.36) for enolase. Saturation transfer measurements yield net rate constants (k/sub f/ = 0.49s -1 ; k/sub r/ = 1.3s -1 ) for the overall reaction. These values are smaller than k/sub cat/ (38s -1 ) measured under analogous conditions. The cation at site I appears to determine catalytic activity

  6. Radiation effects on active pixel sensors (APS)

    International Nuclear Information System (INIS)

    Cohen, M.; David, J.P.

    1999-01-01

    Active pixel sensor (APS) is a new generation of image sensors which presents several advantages relatively to charge coupled devices (CCDs) particularly for space applications (APS requires only 1 voltage to operate which reduces considerably current consumption). Irradiation was performed using 60 Co gamma radiation at room temperature and at a dose rate of 150 Gy(Si)/h. 2 types of APS have been tested: photodiode-APS and photoMOS-APS. The results show that photoMOS-APS is more sensitive to radiation effects than photodiode-APS. Important parameters of image sensors like dark currents increase sharply with dose levels. Nevertheless photodiode-APS sensitivity is one hundred time lower than photoMOS-APS sensitivity

  7. Hierarchical Pd-Sn alloy nanosheet dendrites: an economical and highly active catalyst for ethanol electrooxidation.

    Science.gov (United States)

    Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

    2013-01-01

    Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.

  8. 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.

  9. Harvesting a 3D N-Doped Carbon Network from Waste Bean Dregs by Ionothermal Carbonization as an Electrocatalyst for an Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Yimai Chen

    2017-11-01

    Full Text Available Three-dimensional nitrogen-doped carbon (3D-NCN has been synthesized via the ionothermal carbonization method using waste soybean dregs (SD as the precursor. N2 adsorption/desorption isotherms show that the as-prepared 3D-NCN formed a hierarchically porous structure with a specific BET surface area of 1093.4 m2 g−1 and a total pore volume of 1.77 cm3 g−1. The TEM images clearly show that graphene-like carbon sheets were formed on the edge of the networks. The characterization of the samples collected at different temperature indicated that salt melt plays the key role in the formation of the network structure and rich pores. When 3D-NCN is as electrocatalyst for ORR, it shows an onset potential of 0.945 V with a more positive half-wave potential (0.846 V, which is comparable to that of commercial Pt/C. In addition, the long-term cycle results show that the onset potential and half-wave potential only negatively shifted by 6 mV and 8 mV after 10,000 cycles respectively, which are smaller than those values of commercial Pt/C. Due to its high ORR activity, durability, and low-cost, producing 3D-NCN from SD in molten salt medium provides a promising approach to replace the Pt-based catalysts for use in fuel cells.

  10. Single-Crystalline Ultrathin Nickel Nanosheets Array from In Situ Topotactic Reduction for Active and Stable Electrocatalysis.

    Science.gov (United States)

    Kuang, Yun; Feng, Guang; Li, Pengsong; Bi, Yongmin; Li, Yaping; Sun, Xiaoming

    2016-01-11

    Simultaneously synthesizing and structuring atomically thick or ultrathin 2D non-precious metal nanocrystal may offer a new class of materials to replace the state-of-art noble-metal electrocatalysts; however, the synthetic strategy is the bottleneck which should be urgently solved. Here we report the synthesis of an ultrathin nickel nanosheet array (Ni-NSA) through in situ topotactic reduction from Ni(OH)2 array precursors. The Ni nanosheets showed a single-crystalline lamellar structure with only ten atomic layers in thickness and an exposed (111) facet. Combined with a superaerophobic (low bubble adhesive) arrayed structure the Ni-NSAs exhibited a dramatic enhancement on both activity and stability towards the hydrazine-oxidation reaction (HzOR) relative to platinum. Furthermore, the partial oxidization of Ni-NSAs in ambient atmosphere resulted in effective water-splitting electrocatalysts for the hydrogen-evolution reaction (HER). © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

  11. Influence of different carbon nanostructures on the electrocatalytic activity and stability of Pt supported electrocatalysts

    DEFF Research Database (Denmark)

    Stamatin, Serban Nicolae; Borghei, Maryam; Andersen, Shuang Ma

    2014-01-01

    Commercially available graphitized carbon nanofibers and multi-walled carbon nanotubes, two carbon materials with very different structure, have been functionalized in a nitric–sulfuric acid mixture. Further on, the materials have been platinized by a microwave assisted polyol method. The relative...

  12. Activity and stability studies of platinized multi-walled carbon nanotubes as fuel cell electrocatalysts

    DEFF Research Database (Denmark)

    Stamatin, Serban Nicolae; Borghei, Maryam; Dhiman, Rajnish

    2015-01-01

    A non-covalent functionalization for multi-walled carbon nanotubes has been used as an alternative to the damaging acid treatment. Platinum nanoparticles with similar particle size distribution have been deposited on the surface modified multi-walled carbon nanotubes. The interaction between...

  13. [Effect of physical activity on longevity].

    Science.gov (United States)

    Wilczek, Mateusz M; Krupienicz, Andrzej

    2016-11-25

    Multiple population studies have reported a positive correlation between higher levels of physical activity (PA) and longer lifespan. It has been generally accepted that it occurs due to PA having a direct effect on longevity. However, this idea is negated by experiments on animal models and an observational study on a twin cohort published recently by Karvinen et al. This unique study includes a pairwise comparison of monozygotic twins discordant for PA, therefore eliminating any influence of genetic factors on both mortality and tendency to take up exercise. The intriguing lack of differences in lifespan in such pairs implies that PA is not an important life prolonging factor. This discovery casts doubt on the validity of PA recommendations found in numerous medical guidelines. Nevertheless, the mentioned results apply only to the plain PA - longevity relation. They do not consider health benefits of PA, for which solid evidence exists. In particular, PA clearly reduces the risk of obesity-related diseases. This may indirectly yet significantly affect the length and quality of life, even if the direct relationship between PA and lifespan will be proven false in further research. © 2016 MEDPRESS.

  14. Accuracy in activation analysis: count rate effects

    International Nuclear Information System (INIS)

    Lindstrom, R.M.; Fleming, R.F.

    1980-01-01

    The accuracy inherent in activation analysis is ultimately limited by the uncertainty of counting statistics. When careful attention is paid to detail, several workers have shown that all systematic errors can be reduced to an insignificant fraction of the total uncertainty, even when the statistical limit is well below one percent. A matter of particular importance is the reduction of errors due to high counting rate. The loss of counts due to random coincidence (pulse pileup) in the amplifier and to digitization time in the ADC may be treated as a series combination of extending and non-extending dead times, respectively. The two effects are experimentally distinct. Live timer circuits in commercial multi-channel analyzers compensate properly for ADC dead time for long-lived sources, but not for pileup. Several satisfactory solutions are available, including pileup rejection and dead time correction circuits, loss-free ADCs, and computed corrections in a calibrated system. These methods are sufficiently reliable and well understood that a decaying source can be measured routinely with acceptably small errors at a dead time as high as 20 percent

  15. Hematopoiesis-activating effects of androgen (fluoxymesterone)

    International Nuclear Information System (INIS)

    Shirakura, Takuo; Inoue, Tatsu; Maekawa, Tadashi.

    1978-01-01

    Hematopoiesis-activating effect of fluoxymesterone (FMT) (androgen preparation) on hematopoietic hematoblast was evaluated. The results were as follows. (1) To C 3 H/He strain male mice, 2 mg/day of FMT was injected into each femoral muscle alternatively. On the 5th day of the first injection, radioactive iron was injected intraperitoneally; after 48 hrs, blood was collected for examining the incorporation rate of 59 Fe. The results showed significant increase. (2) After 4 mg of FMT was injected once into the femoral muscle, spleen colony-forming cells (CFU-S) of the mouse femur were examined. Calculation of either of surface colonies and microscopic colonies showed absolute increase of the number of CFU-S in the femoral marrow. The microscopic colonies were classified into three colony types of erythrocytes, granulocytes, and megakaryocytes on the basis of histology of the cellular component; and changes were evaluated in each type of the colonies. This evaluation clarified that an increase in colonies which appeared 24 hrs after the injection of the hormon was due to an increase in the erythrocyte and megakaryocyte colonies and that which appeared 48 hrs after the injection was due to an increase in granulocyte colonies. (Ueda, J.)

  16. Compton effect thermally activated depolarization dosimeter

    Science.gov (United States)

    Moran, Paul R.

    1978-01-01