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Title: Methoxy Formation Induced Defects on MoS2

Abstract

Here, we find that exposure of the MoS2 basal plane to methanol leads to the formation of adsorbed methoxy and coincides with sulfur vacancy generation. The conversion of methanol to methoxy on MoS2 is temperature dependent. Density functional theory simulations and experiment indicate that the methoxy moieties are bound to molybdenum, not sulfur, while some adsorbed methanol is readily desorbed near or slightly above room temperature. Our calculations also suggest that the dissociation of methanol via O–H bond scission occurs at the defect site (sulfur vacancy), followed subsequently by formation of a weakly bound H2S species that promptly desorbs from the surface with creation of new sulfur vacancy. Photoluminescence and scanning tunneling microscopy show clear evidence of the sulfur vacancy creation on the MoS2 surface, after exposure to methanol.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [3]; ORCiD logo [4];  [5]; ORCiD logo [5];  [6]; ORCiD logo [1]
  1. Univ. of Nebraska, Lincoln, NE (United States)
  2. Univ. of Nebraska, Lincoln, NE (United States); Daegu Univ., Gyeongsan (Korea)
  3. Univ. of Central Florida, Orlando, FL (United States)
  4. Univ. of Central Florida, Orlando, FL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  5. Univ. of California, Riverside, CA (United States)
  6. Univ. of Central Florida, Orlando, FL (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of Central Florida, Orlando, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1543647
Grant/Contract Number:  
FG02-07ER15842
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 18; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; science & technology - other topics; materials science; Syngas; MoS2 catalysis; defect creation; density functional theory; methoxy

Citation Formats

Evans, Prescott E., Jeong, Hae Kyung, Hooshmand, Zahra, Le, Duy, Rawal, Takat B., Naghibi Alvillar, Sahar, Bartels, Ludwig, Rahman, Talat S., and Dowben, Peter A. Methoxy Formation Induced Defects on MoS2. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b02053.
Evans, Prescott E., Jeong, Hae Kyung, Hooshmand, Zahra, Le, Duy, Rawal, Takat B., Naghibi Alvillar, Sahar, Bartels, Ludwig, Rahman, Talat S., & Dowben, Peter A. Methoxy Formation Induced Defects on MoS2. United States. https://doi.org/10.1021/acs.jpcc.8b02053
Evans, Prescott E., Jeong, Hae Kyung, Hooshmand, Zahra, Le, Duy, Rawal, Takat B., Naghibi Alvillar, Sahar, Bartels, Ludwig, Rahman, Talat S., and Dowben, Peter A. Tue . "Methoxy Formation Induced Defects on MoS2". United States. https://doi.org/10.1021/acs.jpcc.8b02053. https://www.osti.gov/servlets/purl/1543647.
@article{osti_1543647,
title = {Methoxy Formation Induced Defects on MoS2},
author = {Evans, Prescott E. and Jeong, Hae Kyung and Hooshmand, Zahra and Le, Duy and Rawal, Takat B. and Naghibi Alvillar, Sahar and Bartels, Ludwig and Rahman, Talat S. and Dowben, Peter A.},
abstractNote = {Here, we find that exposure of the MoS2 basal plane to methanol leads to the formation of adsorbed methoxy and coincides with sulfur vacancy generation. The conversion of methanol to methoxy on MoS2 is temperature dependent. Density functional theory simulations and experiment indicate that the methoxy moieties are bound to molybdenum, not sulfur, while some adsorbed methanol is readily desorbed near or slightly above room temperature. Our calculations also suggest that the dissociation of methanol via O–H bond scission occurs at the defect site (sulfur vacancy), followed subsequently by formation of a weakly bound H2S species that promptly desorbs from the surface with creation of new sulfur vacancy. Photoluminescence and scanning tunneling microscopy show clear evidence of the sulfur vacancy creation on the MoS2 surface, after exposure to methanol.},
doi = {10.1021/acs.jpcc.8b02053},
journal = {Journal of Physical Chemistry. C},
number = 18,
volume = 122,
place = {United States},
year = {2018},
month = {4}
}

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