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Title: Mechanism of Hydrogen Evolution Reaction on 1T-MoS 2 from First Principles

Abstract

The 1T phase of transition-metal dichalcogenides (TMDs) has been shown in recent experiments to display excellent catalytic activity for hydrogen evolution reaction (HER), but the catalytic mechanism has not been elucidated so far. Herein, using 1T MoS 2 as the prototypical TMD material, we studied the HER activity on its basal plane from periodic density functional theory (DFT) calculations. Compared to the nonreactive basal plane of 2H phase MoS 2, the catalytic activity of the basal plane of 1T phase MoS 2 mainly arises from its affinity for binding H at the surface S sites. Using the binding free energy (ΔG H) of H as the descriptor, we found that the optimum evolution of H2 will proceed at surface H coverage of 12.5% ~ 25%. Within this coverage, we viewed the reaction energy and barrier for the three elementary steps of the HER process. The Volmer step was found to be facile, whereas the subsequent Heyrovsky reaction is kinetically more favorable than the Tafel reaction. Our results suggest that at low overpotential, HER can take place readily on the basal plane of 1T MoS 2 via the Volmer–Heyrovsky mechanism. Moreover, we screened the dopants for the HER activity and foundmore » that substitutional doping of the Mo atom by metals such as Mn, Cr, Cu, Ni, and Fe can make 1T MoS 2 a better HER catalyst.« less

Authors:
 [1];  [1]
  1. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1485139
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 8; 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; 1T MoS2; hydrogen evolution reaction; catalytic activity; basal plane; Volmer−Heyrovsky mechanism; substitutional doping

Citation Formats

Tang, Qing, and Jiang, De-en. Mechanism of Hydrogen Evolution Reaction on 1T-MoS2 from First Principles. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b01211.
Tang, Qing, & Jiang, De-en. Mechanism of Hydrogen Evolution Reaction on 1T-MoS2 from First Principles. United States. doi:10.1021/acscatal.6b01211.
Tang, Qing, and Jiang, De-en. Mon . "Mechanism of Hydrogen Evolution Reaction on 1T-MoS2 from First Principles". United States. doi:10.1021/acscatal.6b01211. https://www.osti.gov/servlets/purl/1485139.
@article{osti_1485139,
title = {Mechanism of Hydrogen Evolution Reaction on 1T-MoS2 from First Principles},
author = {Tang, Qing and Jiang, De-en},
abstractNote = {The 1T phase of transition-metal dichalcogenides (TMDs) has been shown in recent experiments to display excellent catalytic activity for hydrogen evolution reaction (HER), but the catalytic mechanism has not been elucidated so far. Herein, using 1T MoS2 as the prototypical TMD material, we studied the HER activity on its basal plane from periodic density functional theory (DFT) calculations. Compared to the nonreactive basal plane of 2H phase MoS2, the catalytic activity of the basal plane of 1T phase MoS2 mainly arises from its affinity for binding H at the surface S sites. Using the binding free energy (ΔGH) of H as the descriptor, we found that the optimum evolution of H2 will proceed at surface H coverage of 12.5% ~ 25%. Within this coverage, we viewed the reaction energy and barrier for the three elementary steps of the HER process. The Volmer step was found to be facile, whereas the subsequent Heyrovsky reaction is kinetically more favorable than the Tafel reaction. Our results suggest that at low overpotential, HER can take place readily on the basal plane of 1T MoS2 via the Volmer–Heyrovsky mechanism. Moreover, we screened the dopants for the HER activity and found that substitutional doping of the Mo atom by metals such as Mn, Cr, Cu, Ni, and Fe can make 1T MoS2 a better HER catalyst.},
doi = {10.1021/acscatal.6b01211},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 8,
volume = 6,
place = {United States},
year = {2016},
month = {6}
}

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Works referencing / citing this record:

The Role of Supported Atomically Distributed Metal Species in Electrochemistry and How to Create Them
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  • Cheng, Yuwen; Wang, Lijuan; Song, Yan
  • Journal of Materials Chemistry A, Vol. 7, Issue 26
  • DOI: 10.1039/c9ta03859k

MoS2 Coexisting in 1T and 2H Phases Synthesized by Common Hydrothermal Method for Hydrogen Evolution Reaction
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Unravelling the synergy effects of defect-rich 1T-MoS 2 /carbon nanotubes for the hydrogen evolution reaction by experimental and calculational studies
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  • Jayabal, Subramaniam; Saranya, Govindarajan; Liu, Yongqiang
  • Sustainable Energy & Fuels, Vol. 3, Issue 8
  • DOI: 10.1039/c9se00244h

Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers
journal, January 2017


The Role of Supported Atomically Distributed Metal Species in Electrochemistry and How to Create Them
journal, May 2019

  • Ding, Yuxiao; Schlögl, Robert; Heumann, Saskia
  • ChemElectroChem, Vol. 6, Issue 15
  • DOI: 10.1002/celc.201900598

Unravelling the synergy effects of defect-rich 1T-MoS 2 /carbon nanotubes for the hydrogen evolution reaction by experimental and calculational studies
journal, January 2019

  • Jayabal, Subramaniam; Saranya, Govindarajan; Liu, Yongqiang
  • Sustainable Energy & Fuels, Vol. 3, Issue 8
  • DOI: 10.1039/c9se00244h

Deep insights into the exfoliation properties of MAX to MXenes and the hydrogen evolution performances of 2D MXenes
journal, January 2019

  • Cheng, Yuwen; Wang, Lijuan; Song, Yan
  • Journal of Materials Chemistry A, Vol. 7, Issue 26
  • DOI: 10.1039/c9ta03859k

MoS2 Coexisting in 1T and 2H Phases Synthesized by Common Hydrothermal Method for Hydrogen Evolution Reaction
journal, June 2019


Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers
journal, January 2017