Comprehensive Phase Diagrams of MoS2 Edge Sites Using Dispersion-Corrected DFT Free Energy Calculations

Andrew S. Rosen, Justin M Notestein*, Randall Q Snurr

*Corresponding author for this work

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

A comprehensive set of surface phase diagrams addressing the catalytically relevant edges of the (100) surface of MoS2 catalysts is developed using dispersion-corrected density functional theory and ab initio thermodynamic modeling. The results of the temperature-dependent, free energy-based thermodynamic model are presented over the full range of catalytically relevant temperatures and pressures, in addition to S- and H-coverages ranging from 0 to 100%. The results of this work allow for a full thermodynamic analysis to be performed at the conditions relevant to any promising reaction involving MoS2, ranging from hydrodesulfurization to dehydrogenation to electrocatalysis. Several methodological recommendations are discussed and implemented with the goal of improving the accuracy of the surface phase diagrams at minimal computational expense. A library of the most stable S- and H-adsorption modes is also developed so that linear scaling relationships can be used to correlate thermodynamic stability with kinetic activity. Applying the results to C-H bond activation of methane with a S2 oxidant, we predict S-coverages near 100% on the Mo- and S-edges to be thermodynamically favored and S monomers on edge sites with high S-coverages to be kinetically favorable. For H-abstraction on surface S atoms, the Mo-edge is also predicted to be more active than the S-edge.

Original languageEnglish (US)
Pages (from-to)15318-15329
Number of pages12
JournalJournal of Physical Chemistry C
Volume122
Issue number27
DOIs
StatePublished - Jul 12 2018

Fingerprint

Discrete Fourier transforms
Free energy
Phase diagrams
free energy
phase diagrams
Thermodynamics
thermodynamics
Electrocatalysis
Hydrodesulfurization
Methane
Dehydrogenation
Oxidants
Density functional theory
dehydrogenation
Thermodynamic stability
recommendations
Monomers
Chemical activation
Adsorption
methane

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

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title = "Comprehensive Phase Diagrams of MoS2 Edge Sites Using Dispersion-Corrected DFT Free Energy Calculations",
abstract = "A comprehensive set of surface phase diagrams addressing the catalytically relevant edges of the (100) surface of MoS2 catalysts is developed using dispersion-corrected density functional theory and ab initio thermodynamic modeling. The results of the temperature-dependent, free energy-based thermodynamic model are presented over the full range of catalytically relevant temperatures and pressures, in addition to S- and H-coverages ranging from 0 to 100{\%}. The results of this work allow for a full thermodynamic analysis to be performed at the conditions relevant to any promising reaction involving MoS2, ranging from hydrodesulfurization to dehydrogenation to electrocatalysis. Several methodological recommendations are discussed and implemented with the goal of improving the accuracy of the surface phase diagrams at minimal computational expense. A library of the most stable S- and H-adsorption modes is also developed so that linear scaling relationships can be used to correlate thermodynamic stability with kinetic activity. Applying the results to C-H bond activation of methane with a S2 oxidant, we predict S-coverages near 100{\%} on the Mo- and S-edges to be thermodynamically favored and S monomers on edge sites with high S-coverages to be kinetically favorable. For H-abstraction on surface S atoms, the Mo-edge is also predicted to be more active than the S-edge.",
author = "Rosen, {Andrew S.} and Notestein, {Justin M} and Snurr, {Randall Q}",
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Comprehensive Phase Diagrams of MoS2 Edge Sites Using Dispersion-Corrected DFT Free Energy Calculations. / Rosen, Andrew S.; Notestein, Justin M; Snurr, Randall Q.

In: Journal of Physical Chemistry C, Vol. 122, No. 27, 12.07.2018, p. 15318-15329.

Research output: Contribution to journalArticle

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AB - A comprehensive set of surface phase diagrams addressing the catalytically relevant edges of the (100) surface of MoS2 catalysts is developed using dispersion-corrected density functional theory and ab initio thermodynamic modeling. The results of the temperature-dependent, free energy-based thermodynamic model are presented over the full range of catalytically relevant temperatures and pressures, in addition to S- and H-coverages ranging from 0 to 100%. The results of this work allow for a full thermodynamic analysis to be performed at the conditions relevant to any promising reaction involving MoS2, ranging from hydrodesulfurization to dehydrogenation to electrocatalysis. Several methodological recommendations are discussed and implemented with the goal of improving the accuracy of the surface phase diagrams at minimal computational expense. A library of the most stable S- and H-adsorption modes is also developed so that linear scaling relationships can be used to correlate thermodynamic stability with kinetic activity. Applying the results to C-H bond activation of methane with a S2 oxidant, we predict S-coverages near 100% on the Mo- and S-edges to be thermodynamically favored and S monomers on edge sites with high S-coverages to be kinetically favorable. For H-abstraction on surface S atoms, the Mo-edge is also predicted to be more active than the S-edge.

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