A Physical Model for Understanding the Activation of MoS2 Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction

Liu, Mingjie; Wu, Qin; Hybertsen, M. S.

doi:10.26434/chemrxiv.11916168

Title: A Physical Model for Understanding the Activation of MoS₂ Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction

Abstract

All the DFT calculations are done with the Vienna Ab Initio Simulation Package (VASP) using the projector augmented wave method. The Bayesian error estimation exchange-correlation functionals (BEEF) with van der Waals interactions are employed. A plane-wave cutoff energy of 400 eV is used together with PAW-PBE potentials where semi core p states are treated as valence. All the calculations allow for spin-polarization. The structures are relaxed until the force is converged to < 0.01 eV/Å. The lattice parameter of MoS₂ unit cell, optimized with this functional, is 3.19 Å. A (4×4) supercell is used to model all the transition metal doped MoS₂ systems studied here, including those with S vacancies. For calculations in the initial dopant structure exploration, the Brillouin zone is sampled with a 3x3x1 Monkhorst-Pack k-point mesh. A 6×6×1 Monkhorst-Pack k-point mesh is used for the H binding energy and density of states calculations. In all calculations, the vacuum layer is set as 15 Å to eliminate periodic interaction perpendicular to the basal plane.

Authors:

Liu, Mingjie ^[1];

^[1]; Hybertsen, M. S. ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Publication Date:: Mon Feb 03 00:00:00 EST 2020

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

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

OSTI Identifier:: 1631928

Report Number(s):: BNL-215970-2020-JAAM
Journal ID: ISSN 1089-5639

Grant/Contract Number:: SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 124; Journal Issue: 4; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats


                    Liu, Mingjie, Wu, Qin, and Hybertsen, M. S. A Physical Model for Understanding the Activation of MoS2 Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction.  United States: N. p., 2020. 
Web.  doi:10.26434/chemrxiv.11916168.

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                    Liu, Mingjie, Wu, Qin, & Hybertsen, M. S. A Physical Model for Understanding the Activation of MoS2 Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction.  United States.  https://doi.org/10.26434/chemrxiv.11916168

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                    Liu, Mingjie, Wu, Qin, and Hybertsen, M. S. Mon .  
"A Physical Model for Understanding the Activation of MoS2 Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction".  United States.  https://doi.org/10.26434/chemrxiv.11916168.  https://www.osti.gov/servlets/purl/1631928.

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@article{osti_1631928,

  title        = {A Physical Model for Understanding the Activation of MoS2 Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction},

  author       = {Liu, Mingjie and Wu, Qin and Hybertsen, M. S.},

  abstractNote = {All the DFT calculations are done with the Vienna Ab Initio Simulation Package (VASP) using the projector augmented wave method. The Bayesian error estimation exchange-correlation functionals (BEEF) with van der Waals interactions are employed. A plane-wave cutoff energy of 400 eV is used together with PAW-PBE potentials where semi core p states are treated as valence. All the calculations allow for spin-polarization. The structures are relaxed until the force is converged to < 0.01 eV/Å. The lattice parameter of MoS2 unit cell, optimized with this functional, is 3.19 Å. A (4×4) supercell is used to model all the transition metal doped MoS2 systems studied here, including those with S vacancies. For calculations in the initial dopant structure exploration, the Brillouin zone is sampled with a 3x3x1 Monkhorst-Pack k-point mesh. A 6×6×1 Monkhorst-Pack k-point mesh is used for the H binding energy and density of states calculations. In all calculations, the vacuum layer is set as 15 Å to eliminate periodic interaction perpendicular to the basal plane.},

  doi          = {10.26434/chemrxiv.11916168},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 4,

  volume       = 124,

  place        = {United States},

  year         = {Mon Feb 03 00:00:00 EST 2020},

  month        = {Mon Feb 03 00:00:00 EST 2020}

}

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Figures / Tables:

Figure 1: Physical model for H-S bond formation: (1) an electronic promotion process that pushes an electron from the full valence shell of S to neighboring metal atoms; (2) H binding to fill the partially open valence shell of the S site.

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Title: A Physical Model for Understanding the Activation of MoS2 Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction

Abstract

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Figures / Tables:

Title: A Physical Model for Understanding the Activation of MoS₂ Basal-plane Sulfur Atoms for the Hydrogen Evolution Reaction