Insights into the Hydrogen Evolution Reaction on 2D Transition-Metal Dichalcogenides
Abstract
Understanding hydrogen evolution reaction (HER) behaviors over two-dimensional transition-metal dichalcogenides (2D-TMDs) is critical for the development of nonprecious HER electrocatalysts with better activity. Here, in this work, by combining density functional theory calculations with microkinetic modeling, we thoroughly investigated the HER mechanism on 2D-TMDs. We find an important dependence of simulated cell size on the calculated hydrogen adsorption energy and the activation barrier for MoS2. Distinct from previous “H migration” mechanisms proposed for the Heyrovsky reaction, the rate-determining step for MoS2, we propose that the Mo site only serves as the stabilized transition state rather than H adsorption. In comparison to transition-metal electrocatalysts, we find that the activation barrier of the Heyrovsky reaction on 2D-TMDs scales with the hydrogen adsorption energy exactly as for transition metals except that all activation energies are displaced upward by ca. 0.4 eV. This higher Heyrovsky activation barrier is responsible for the substantially lower activity of 2D-TMDs. We further show that this higher activation barrier stems from the more positively charged adsorbed hydrogen on the chalcogenides interacting repulsively with the incoming proton. Based on these insights, we discuss potential strategies for the design of nonprecious HER catalysts with activity comparable to Pt.
- Authors:
-
[1];
[2];
[1];
- Technical Univ. of Denmark, Lyngby (Denmark)
- Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Toyota Research Institute
- OSTI Identifier:
- 1888249
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 126; Journal Issue: 11; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; activation energy; adsorption; catalysts; evolution reactions; hydrogen
Citation Formats
Wang, Zhenbin, Tang, Michael T., Cao, Ang, Chan, Karen, and Nørskov, Jens K. Insights into the Hydrogen Evolution Reaction on 2D Transition-Metal Dichalcogenides. United States: N. p., 2022.
Web. doi:10.1021/acs.jpcc.1c10436.
Wang, Zhenbin, Tang, Michael T., Cao, Ang, Chan, Karen, & Nørskov, Jens K. Insights into the Hydrogen Evolution Reaction on 2D Transition-Metal Dichalcogenides. United States. https://doi.org/10.1021/acs.jpcc.1c10436
Wang, Zhenbin, Tang, Michael T., Cao, Ang, Chan, Karen, and Nørskov, Jens K. Fri .
"Insights into the Hydrogen Evolution Reaction on 2D Transition-Metal Dichalcogenides". United States. https://doi.org/10.1021/acs.jpcc.1c10436. https://www.osti.gov/servlets/purl/1888249.
@article{osti_1888249,
title = {Insights into the Hydrogen Evolution Reaction on 2D Transition-Metal Dichalcogenides},
author = {Wang, Zhenbin and Tang, Michael T. and Cao, Ang and Chan, Karen and Nørskov, Jens K.},
abstractNote = {Understanding hydrogen evolution reaction (HER) behaviors over two-dimensional transition-metal dichalcogenides (2D-TMDs) is critical for the development of nonprecious HER electrocatalysts with better activity. Here, in this work, by combining density functional theory calculations with microkinetic modeling, we thoroughly investigated the HER mechanism on 2D-TMDs. We find an important dependence of simulated cell size on the calculated hydrogen adsorption energy and the activation barrier for MoS2. Distinct from previous “H migration” mechanisms proposed for the Heyrovsky reaction, the rate-determining step for MoS2, we propose that the Mo site only serves as the stabilized transition state rather than H adsorption. In comparison to transition-metal electrocatalysts, we find that the activation barrier of the Heyrovsky reaction on 2D-TMDs scales with the hydrogen adsorption energy exactly as for transition metals except that all activation energies are displaced upward by ca. 0.4 eV. This higher Heyrovsky activation barrier is responsible for the substantially lower activity of 2D-TMDs. We further show that this higher activation barrier stems from the more positively charged adsorbed hydrogen on the chalcogenides interacting repulsively with the incoming proton. Based on these insights, we discuss potential strategies for the design of nonprecious HER catalysts with activity comparable to Pt.},
doi = {10.1021/acs.jpcc.1c10436},
journal = {Journal of Physical Chemistry. C},
number = 11,
volume = 126,
place = {United States},
year = {Fri Mar 11 00:00:00 EST 2022},
month = {Fri Mar 11 00:00:00 EST 2022}
}
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