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Toward alcohol synthesis from CO hydrogenation on Cu(111)-supported MoS 2 – predictions from DFT+KMC

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0047835· OSTI ID:1849713
 [1];  [2];  [3];  [2]
  1. Univ. of Central Florida, Orlando, FL (United States). Dept. of Physics; Univ. of Central Florida, Orlando, FL (United States)
  2. Univ. of Central Florida, Orlando, FL (United States). Dept. of Physics; Univ. of Central Florida, Orlando, FL (United States). Renewable Energy and Chemical Transformations Cluster
  3. Univ. of Central Florida, Orlando, FL (United States). Dept. of Physics
+ Show Author Affiliations
In the quest for cheap and efficient catalysts for alcohol synthesis from syngas, a material of interest is single-layer MoS2 owing to its low cost, abundancy, and flexible structure. Because of the inertness of its basal plane, however, it is essential to find ways that make it catalytically active. Herein, by means of density functional theory based calculations of reaction pathways and activation energy barriers and accompanying kinetic Monte Carlo simulations, we show that while S vacancy row structures activate the MoS2 basal plane, further enhancement of chemical activity and selectivity can be achieved by interfacing the MoS2 layer with a metallic support. When defect-laden MoS2 is grown on Cu(111), there is not only an increase in the active region (surface area of active sites) but also charge transfer from Cu to MoS2, resulting in a shift of the Fermi level such that the frontier states (d orbitals of the exposed Mo atoms) appear close to it, making the MoS2/Cu(111) system ready for catalytic activity. Finally, our calculated thermodynamics of reaction pathways lead to the conclusion that the Cu(111) substrate promotes both methanol and ethanol as the products, while kinetic Monte Carlo simulations suggest a high selectivity toward the formation of ethanol.
Research Organization:
Univ. of Central Florida, Orlando, FL (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
FG02-07ER15842
OSTI ID:
1849713
Alternate ID(s):
OSTI ID: 1781211
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 154; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

2D materials
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
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activation energies
catalysts and catalysis
density functional theory
hybrid materials
hydrogenation process
physics
reaction mechanisms
syngas
thermodynamics