Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Tang, Michael T.; Liu, Xinyan; Ji, Yongfei; Norskov, Jens K.; Chan, Karen

doi:10.1021/acs.jpcc.0c08310

Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Journal Article · Tue Dec 15 00:00:00 EST 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c08310· OSTI ID:1767971

^[1]; Liu, Xinyan ^[2]; ^[3]; ^[4]; ^[4]

Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Guangzhou Univ. (China)
Technical Univ. of Denmark, Lyngby (Denmark)

Despite the apparent simplicity of the hydrogen evolution reaction (HER) and the decades of research into it, controversy remains in the literature regarding the identity of the active site and the competition between the Heyrovsky and Tafel steps. In this work, we use charge-extrapolated ab initio simulations with explicit water in conjunction with mean-field microkinetic modeling to explore the mechanism for HER on both close-packed (111) and stepped (211) transition metals. First, we show that atop H*, beyond a monolayer of hollow H*, is unlikely to play a role in the HER mechanism, given its very positive adsorption energies. The energetics suggests the Volmer–Heyrovsky mechanism to predominate on fcc transition metals under typical operating conditions. Here, we evaluate our theoretical results vs several experimental observations. We show that the Volmer–Heyrovsky mechanism predicts an activity volcano with its peak at a H* binding ΔG_H* ≈ 0 eV, consistent with experiment. In contrast, the Volmer–Tafel volcano shows a broad rate plateau between ΔG_H* ≈ 0 eV and ΔG_H* ≈ – 0.4 eV. We find our theoretical Tafel slopes to be consistent with experimental ones on a range of transition metals. We show that, in line with experimental observations, the introduction of a CO(g) atmosphere shifts the strong binding metals toward the weak binding leg. Our study suggests that the simple thermodynamic approach to HER activity still holds, even when a detailed kinetic picture is considered.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0004993

OSTI ID:: 1767971

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 51 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

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