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Title: Crystallographic Facet Dependence of the Hydrogen Evolution Reaction on CoPS: Theory and Experiments

Abstract

Cobalt phosphosulfide (CoPS) has recently emerged as a promising earth-abundant electrocatalyst for the hydrogen evolution reaction (HER). Nonetheless, the influence of crystallographic surface on the HER activity of CoPS and other nonmetallic electrocatalysts remains an important open question in the design of high-performance catalysts. Herein, the HER activities of the (100) and (111) facets of CoPS single crystals were studied using complementary experimental and computational approaches. Natural (111) and polished (100) facets of CoPS single crystals were selectively exposed to reveal that the HER behaviors on these two facets are quite different, with current density-potential curves crossing near 0.35 V vs RHE. Computational analysis can explain this phenomenon in terms of strongly differing H atom adsorption free energies and H-H recombination barriers on the facets, in conjunction with a simple kinetic model. At low potential (0-0.35 V), H adsorption (Volmer step) is rate limiting due to the endergonic adsorption on the (111) facet vs exergonic adsorption on the (100) facet, yielding a faster HER rate for the latter. However, at high potential (>0.35 V), H 2 recombination/desorption becomes limiting and thus the (111) facet, with lower associated barriers, shows better HER activity. Explicit consideration of both steps and their interplaymore » allows for a comprehensive description of the overpotential-dependence of the HER activity. This integrated study yields additional insight into the factors which govern the facet-dependence of catalytic activity on nonmetallic electrocatalysts and can further improve the design of advanced nanostructured HER catalysts.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [2]; ORCiD logo [2]
  1. Department of Chemistry, University of Wisconsin−Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States, Department of Applied Physics, Nanjing University of Science and Technology, Nanjing 210094, P. R. China
  2. Department of Chemistry, University of Wisconsin−Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States
  3. Department of Applied Physics, Nanjing University of Science and Technology, Nanjing 210094, P. R. China
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1416850
Alternate Identifier(s):
OSTI ID: 1508323
Grant/Contract Number:  
FG02-09ER46664; SC0002162
Resource Type:
Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis Journal Volume: 8 Journal Issue: 2; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CoPS; crystallographic facet dependence; DFT calculations; electrocatalyst; electrocatalytic properties; hydrogen evolution reaction (HER); theoretical insights

Citation Formats

Wu, Tao, Stone, Michael L., Shearer, Melinda J., Stolt, Matthew J., Guzei, Ilia A., Hamers, Robert J., Lu, Ruifeng, Deng, Kaiming, Jin, Song, and Schmidt, J. R. Crystallographic Facet Dependence of the Hydrogen Evolution Reaction on CoPS: Theory and Experiments. United States: N. p., 2018. Web. doi:10.1021/acscatal.7b03167.
Wu, Tao, Stone, Michael L., Shearer, Melinda J., Stolt, Matthew J., Guzei, Ilia A., Hamers, Robert J., Lu, Ruifeng, Deng, Kaiming, Jin, Song, & Schmidt, J. R. Crystallographic Facet Dependence of the Hydrogen Evolution Reaction on CoPS: Theory and Experiments. United States. doi:10.1021/acscatal.7b03167.
Wu, Tao, Stone, Michael L., Shearer, Melinda J., Stolt, Matthew J., Guzei, Ilia A., Hamers, Robert J., Lu, Ruifeng, Deng, Kaiming, Jin, Song, and Schmidt, J. R. Fri . "Crystallographic Facet Dependence of the Hydrogen Evolution Reaction on CoPS: Theory and Experiments". United States. doi:10.1021/acscatal.7b03167.
@article{osti_1416850,
title = {Crystallographic Facet Dependence of the Hydrogen Evolution Reaction on CoPS: Theory and Experiments},
author = {Wu, Tao and Stone, Michael L. and Shearer, Melinda J. and Stolt, Matthew J. and Guzei, Ilia A. and Hamers, Robert J. and Lu, Ruifeng and Deng, Kaiming and Jin, Song and Schmidt, J. R.},
abstractNote = {Cobalt phosphosulfide (CoPS) has recently emerged as a promising earth-abundant electrocatalyst for the hydrogen evolution reaction (HER). Nonetheless, the influence of crystallographic surface on the HER activity of CoPS and other nonmetallic electrocatalysts remains an important open question in the design of high-performance catalysts. Herein, the HER activities of the (100) and (111) facets of CoPS single crystals were studied using complementary experimental and computational approaches. Natural (111) and polished (100) facets of CoPS single crystals were selectively exposed to reveal that the HER behaviors on these two facets are quite different, with current density-potential curves crossing near 0.35 V vs RHE. Computational analysis can explain this phenomenon in terms of strongly differing H atom adsorption free energies and H-H recombination barriers on the facets, in conjunction with a simple kinetic model. At low potential (0-0.35 V), H adsorption (Volmer step) is rate limiting due to the endergonic adsorption on the (111) facet vs exergonic adsorption on the (100) facet, yielding a faster HER rate for the latter. However, at high potential (>0.35 V), H2 recombination/desorption becomes limiting and thus the (111) facet, with lower associated barriers, shows better HER activity. Explicit consideration of both steps and their interplay allows for a comprehensive description of the overpotential-dependence of the HER activity. This integrated study yields additional insight into the factors which govern the facet-dependence of catalytic activity on nonmetallic electrocatalysts and can further improve the design of advanced nanostructured HER catalysts.},
doi = {10.1021/acscatal.7b03167},
journal = {ACS Catalysis},
number = 2,
volume = 8,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acscatal.7b03167

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Cited by: 9 works
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Figures / Tables:

Figure 1. Figure 1.: (a) Photograph of a representative CoPS single crystal. (b) XRD patterns for the as-grown single crystal of CoPS with the (111) facet (top), a single crystal with a cut and polished (100) facet (middle), in comparison with the standard PXRD pattern of the cubic pyrite phase CoPS (simulatedmore » from ICSD #62414). (c) and (d) optical images of the as-grown (111) and cut and polished (100) facets, respectively. (e) EDS spectra for the as-grown (111) and cut and polished (100) facets. Note, all data shown in b−e were taken on the same two single crystals.« less

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Works referencing / citing this record:

CCDC 1564316: Experimental Crystal Structure Determination
dataset, January 2018


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.