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Title: Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [1]; ORCiD logo [1]
  1. Center for Renewable Carbon, University of Tennessee, Knoxville Tennessee 37996 USA
  2. Bredesen Center for Interdisciplinary Research and Education, Knoxville Tennessee 37996 USA, Oak Ridge National Laboratory, Oak Ridge Tennessee 37831 USA
  3. Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville Tennessee 37996 USA
  4. Department of Chemistry and Vanderbilt Institute of Nanoscale Science and Engineering, Vanderbilt University, Nashville Tennessee 37240 USA
  5. Chemical and Biomolecular Engineering, Vanderbilt University, Nashville TN 37235 USA
  6. Oak Ridge National Laboratory, Oak Ridge Tennessee 37831 USA, Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville Tennessee 37996 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400596
Grant/Contract Number:
NE0000693 12-3528
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 9; Journal Issue: 6; Related Information: CHORUS Timestamp: 2017-10-20 15:16:30; Journal ID: ISSN 1867-3880
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Regmi, Yagya N., Roy, Asa, Goenaga, Gabriel A., McBride, James R., Rogers, Bridget. R., Zawodzinski, Jr., Thomas A., Labbé, Nicole, and Chmely, Stephen C.. Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide. Germany: N. p., 2017. Web. doi:10.1002/cctc.201601477.
Regmi, Yagya N., Roy, Asa, Goenaga, Gabriel A., McBride, James R., Rogers, Bridget. R., Zawodzinski, Jr., Thomas A., Labbé, Nicole, & Chmely, Stephen C.. Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide. Germany. doi:10.1002/cctc.201601477.
Regmi, Yagya N., Roy, Asa, Goenaga, Gabriel A., McBride, James R., Rogers, Bridget. R., Zawodzinski, Jr., Thomas A., Labbé, Nicole, and Chmely, Stephen C.. Tue . "Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide". Germany. doi:10.1002/cctc.201601477.
@article{osti_1400596,
title = {Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide},
author = {Regmi, Yagya N. and Roy, Asa and Goenaga, Gabriel A. and McBride, James R. and Rogers, Bridget. R. and Zawodzinski, Jr., Thomas A. and Labbé, Nicole and Chmely, Stephen C.},
abstractNote = {},
doi = {10.1002/cctc.201601477},
journal = {ChemCatChem},
number = 6,
volume = 9,
place = {Germany},
year = {Tue Feb 14 00:00:00 EST 2017},
month = {Tue Feb 14 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/cctc.201601477

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

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  • Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte.more » Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.« less
  • Graphical abstract: Both Mo{sub 2}C and Mo{sub 2}N can be transformed to MoP, whereas the reverse changes are inviable, which is used to develop a promising and practical pathway for preparing MoP nanoparticles. Highlights: {yields} Mo carbide, nitride and phosphide are prepared. {yields} The structural stability increases in the order of Mo{sub 2}N < Mo{sub 2}C < MoP. {yields} Both Mo{sub 2}C and Mo{sub 2}N can be transformed to MoP, whereas the reverse changes are inviable. {yields} This study develops a promising and practical pathway for preparing MoP nanoparticles. -- Abstract: The structural stability and transformations of Mo carbide, nitridemore » and phosphide were investigated under various atmosphere conditions by X-ray diffraction (XRD). The results indicated that the order of structural stability of these Mo-based compounds was as follows: Mo{sub 2}N < Mo{sub 2}C < MoP. Both Mo{sub 2}C and Mo{sub 2}N can be transformed to MoP, whereas the reverse transformations did not occur. Noticeably, compared with those Mo sources containing oxygen, the use of Mo{sub 2}C/Mo{sub 2}N as Mo-source can produce finely dispersed MoP nanoparticles by the temperature-programmed reaction (TPR) method. The result was probably due to the fact that lower-levels H{sub 2}O generated during synthesis process can avoid strong hydrothermal sintering. The influence of formation energy had been considered and was found to relate to the structural stability and transformations of these Mo-based compounds.« less
  • The electrocatalytic activities of high surface area tungsten carbides for H/sub 2/ oxidation in acid electrolytes were studied and found to be dependent on the methods of preparation of the carbides. Auger electron spectroscopy and x-ray photoemission spectroscopy were used to determine how the surface compositions and chemical states of surface atoms varied with methods of preparation. Bulk crystallographic structures were determined using x-ray diffraction. Low temperature (700/sup 0/C) carburization of tungstic acid was found to deposit or cause the accumulation of an inert carbon layer over the tungsten carbide. This phenomenon could be minimized by mixing the tungstic acidmore » with 10 w/o NH/sub 4/Cl. The most active carbide was slightly carbon deficient at both the surface and in the bulk, with the carbon deficiency probably replaced by oxygen. This active surface was most easily prepared by carburizing amorphous, white, tungstic acid hydrate. Oxygen substitution for carbon probably occurs during an intermediate state of carbon dissolution in the reduced tungsten metal and is aided by the defect structure in the tungstic acid. The increased activity of the oxygen substituted carbide is due to a reduced interaction of the surface with the electrolyte, resulting from covalent tungsten-oxygen bonding. The absolute activity of active tungsten carbide for the oxidation of pure H/sub 2/ at 25/sup 0/C is four orders of magnitude lower than that for Pt.« less
  • Graphical abstract: The electrocatalytic activity of tungsten carbide and titania nanocomposite is related to the structure, crystal phase and chemical components of the nanocomposite, and is also affected by the property of electrolyte. A synergistic effect exists between tungsten carbide and titania of the composite. Highlights: {yields} Electrocatalytic activity of tungsten carbide and titania nanocomposite with core-shell structure. {yields} Activity is related to the structure, crystal phase and chemical component of the nanocomposite. {yields} The property of electrolyte affects the electrocatalytic activity. {yields} A synergistic effect exists between tungsten carbide and titania of the composite. -- Abstract: Tungsten carbide andmore » titania nanocomposite was prepared by combining a reduced-carbonized approach with a mechanochemical approach. The samples were characterized by X-ray diffraction, transmission electron microscope under scanning mode and X-ray energy dispersion spectrum. The results show that the crystal phases of the samples are composed of anatase, rutile, nonstoichiometry titanium oxide, monotungsten carbide, bitungsten carbide and nonstoichiometry tungsten carbide, and they can be controlled by adjusting the parameters of the reduced-carbonized approach; tungsten carbide particles decorate on the surface of titania support, the diameter of tungsten carbide particle is smaller than 20 nm and that of titania is around 100 nm; the chemical components of the samples are Ti, O, W and C. The electrocatalytic activity of the samples was measured by a cyclic voltammetry with three electrodes. The results indicate that the electrocatalytic activities of the samples are related to their crystal phases and the property of electrolyte in aqueous solution. A synergistic effect between titania and tungsten carbide is reported for the first time.« less
  • The ability to harness the metal-metal and metal-oxygen coordination structures of nanoalloy catalysts is critical for catalyzing the oxygen reduction reaction because such a detailed atomic-scale structure dictates the surface binding site and strength for molecular oxygen and oxygenated intermediate species in the electrocatalytic process. This report describes the results of an investigation of the metal-metal and metal-oxygen coordination structures of ternary nanoalloys and their manipulation to enhance the electrocatalytic activity for oxygen reduction reaction. The basic hypothesis is that such atomic-scale structure can be manipulated by oxidative-reductive thermal treatment to influence the binding site and strength of molecular oxygenmore » and oxygenated species on the nanoalloy surface. The results have revealed remarkable increases in both mass activity and specific activity for the catalysts processed by the oxidative-reductive treatment over those treated under non-reactive or low-degree oxidative atmospheres before the reductive treatment. In comparison with non-reactive-reductive treatment, an increased degree of heteroatomic alloying among the three metal components in the ternary catalysts and a decreased percentage of oxides (NiO and CoO) have been revealed by X-ray absorption fine structure spectroscopy for the catalysts treated by the oxidative-reductive treatment. An enrichment of surface Pt has also been detected by x-ray photoelectron spectroscopy for such catalysts. A combination of the increase in the heteroatomic alloying, the decrease in metal oxides, and the enrichment of surface Pt by the oxidative-reductive thermal treatment has therefore been concluded to be responsible for the enhanced electrocatalytic activity. The demonstration of this new approach to manipulating the metal-metal and metal-oxygen coordination structures forms the basis for an effective strategy in engineering ternary nanoalloy catalysts, and has provided new insights into the role of such structures in the enhancement of the electrocatalytic activity.« less