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

Journal Article · · Journal of Physical Chemistry. C
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Northwestern University, Evanston, IL (United States); DOE/OSTI
  2. Northwestern University, Evanston, IL (United States)
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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, here 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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States); University of Minnesota, Minneapolis, MN (United States); Northwestern University, Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Air Force Office of Scientific Research (AFOSR); National Defense Science and Engineering Graduate (NDSEG)
Grant/Contract Number:
SC0012702; AC02-05CH11231
OSTI ID:
1539257
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 27 Vol. 122; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (1)

Surface Morphology and Sulfur Reduction Pathways of MoS2 Mo Edges of the Monolayer and (100) and (103) Surfaces by Molecular Hydrogen: A DFT Study journal February 2019

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