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), 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 allowsmore »
- Authors:
-
- 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
- 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
- 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:
- Journal Article: 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. https://doi.org/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. 2018.
"Crystallographic Facet Dependence of the Hydrogen Evolution Reaction on CoPS: Theory and Experiments". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1416850},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 2,
volume = 8,
place = {United States},
year = {Fri Jan 12 00:00:00 EST 2018},
month = {Fri Jan 12 00:00:00 EST 2018}
}
Web of Science
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