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Reaction Mechanism and Strategy for Optimizing the Hydrogen Evolution Reaction on Single-Layer 1T′ WSe₂ and WTe₂ Based on Grand Canonical Potential Kinetics

Song, Jie and Kwon, Soonho and Hossain, Md Delowar and Chen, Sheng and Li, Zhenyu and Goddard, William A. (2021) Reaction Mechanism and Strategy for Optimizing the Hydrogen Evolution Reaction on Single-Layer 1T′ WSe₂ and WTe₂ Based on Grand Canonical Potential Kinetics. ACS Applied Materials & Interfaces, 13 (46). pp. 55611-55620. ISSN 1944-8252. doi:10.1021/acsami.1c14234.

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Transition-metal dichalcogenides (TMDs) in the 1T′ phase are known high-performance catalysts for hydrogen evolution reaction (HER). Many experimental and some theoretical studies report that vacant sites play an important role in the HER on the basal plane. To provide benchmark calculations for comparison directly with future experiments on TMDs to obtain a validated detailed understanding that can be used to optimize the performance and material, we apply a recently developed grand canonical potential kinetics (GCP-K) formulation to predict the HER at vacant sites on the basal plane of the 1T′ structure of WSe₂ and WTe₂. The accuracy of GCP-K has recently been validated for single-crystal nanoparticles. Using the GCP-K formulation, we find that the transition-state structures and the concentrations of the four intermediates (0−3 H at the selenium or tellurium vacancy) change continuously as a function of the applied potential. The onset potential (at 10 mA/cm⁻²) is −0.53 V for WSe₂ (experiment is −0.51 V) and −0.51 V for WTe₂ (experiment is −0.57 V). We find multistep reaction mechanisms for H₂ evolution from Volmer−Volmer−Tafel (VVT) to Volmer−Heyrovsky (VH) depending on the applied potential, leading to an unusual non-monotonic change in current density with the applied potential. For example, our detailed understanding of thereaction mechanism suggests a strategy to improve the catalytic performance significantly by alternating the applied potential periodically.

Item Type:Article
Related URLs:
URLURL TypeDescription
Song, Jie0000-0002-3936-8983
Kwon, Soonho0000-0002-9225-3018
Hossain, Md Delowar0000-0003-3440-8306
Li, Zhenyu0000-0003-2112-9834
Goddard, William A.0000-0003-0097-5716
Additional Information:© 2021 American Chemical Society. Received 27 July 2021. Accepted 29 October 2021. Published online 15 November 2021. This material is based on works performed by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. This work is also supported by the National Natural Science Foundation of China (21825302). This work uses the resources of the National Energy Research Scientific Computing center (NERSC). The authors declare no competing financial interest.
Group:Liquid Sunlight Alliance
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0021266
National Natural Science Foundation of China21825302
National Energy Research Scientific Computing Center (NERSC)UNSPECIFIED
Subject Keywords:density functional theory; grand canonical potential kinetics; hydrogen evolution reaction; transition-metal dichalcogenides; WSe2; WTe2; 1T′ structure; reaction mechanisms
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Issue or Number:46
Record Number:CaltechAUTHORS:20211115-181201722
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Official Citation:Reaction Mechanism and Strategy for Optimizing the Hydrogen Evolution Reaction on Single-Layer 1T′ WSe2 and WTe2 Based on Grand Canonical Potential Kinetics. Jie Song, Soonho Kwon, Md Delowar Hossain, Sheng Chen, Zhenyu Li, and William A. Goddard. ACS Applied Materials & Interfaces 2021 13 (46), 55611-55620; DOI: 10.1021/acsami.1c14234
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:111871
Deposited By: Donna Wrublewski
Deposited On:15 Nov 2021 19:02
Last Modified:07 Dec 2021 21:46

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