Insights into the Hydrogen Evolution Reaction on 2D Transition-Metal Dichalcogenides

Wang, Zhenbin; Tang, Michael T.; Cao, Ang; Chan, Karen; Nørskov, Jens K.

doi:10.1021/acs.jpcc.1c10436

Title: Insights into the Hydrogen Evolution Reaction on 2D Transition-Metal Dichalcogenides

Journal Article · Fri Mar 11 00:00:00 EST 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c10436· OSTI ID:1888249

^[1];

^[2]; Cao, Ang ^[1];

^[1]; Nørskov, Jens K. ^[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

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Toyota Research Institute

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1888249

Journal Information:: Journal of Physical Chemistry. C, Vol. 126, Issue 11; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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