Methoxy Formation Induced Defects on MoS2

Evans, Prescott E.; Jeong, Hae Kyung; Hooshmand, Zahra; Le, Duy; Rawal, Takat B.; Naghibi Alvillar, Sahar; Bartels, Ludwig; Rahman, Talat S.; Dowben, Peter A.

doi:10.1021/acs.jpcc.8b02053

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:

Evans, Prescott E. ^[1];

^[2]; Hooshmand, Zahra ^[3];

^[3];

^[4]; Naghibi Alvillar, Sahar ^[5];

^[5]; Rahman, Talat S. ^[6];

^[1]

Univ. of Nebraska, Lincoln, NE (United States)
Univ. of Nebraska, Lincoln, NE (United States); Daegu Univ., Gyeongsan (Korea)
Univ. of Central Florida, Orlando, FL (United States)
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)
Univ. of California, Riverside, CA (United States)
Univ. of Central Florida, Orlando, FL (United States); Univ. of California, Berkeley, CA (United States)

Publication Date:: 2018-04-10

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.

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                    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

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                    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.

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@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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Title: Methoxy Formation Induced Defects on MoS2

Abstract

Citation Formats

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Density Functional Theory Study of CO Hydrogenation on a MoS 2 Surface journal, March 2009

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Effects of potassium doping on CO hydrogenation over MoS2 catalysts: A first-principles investigation journal, July 2014

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Controlled argon beam-induced desulfurization of monolayer molybdenum disulfide journal, May 2013

A direct comparison of CVD-grown and exfoliated MoS 2 using optical spectroscopy journal, May 2014

X-ray photoelectron spectroscopy study of the interaction of alcohols with oxide surfaces journal, January 1985

An ESCA study of the termination of the passivation of elemental metals journal, August 1978

Photo/Electrochemical Applications of Metal Sulfide/TiO 2 Heterostructures journal, November 2019

Title: Methoxy Formation Induced Defects on MoS₂

Single-Layer MoS ₂ with Sulfur Vacancies: Structure and Catalytic Application
journal, March 2014

Alcohols as alternative fuels: An overview
journal, July 2011

Density Functional Theory Study of CO Hydrogenation on a MoS ₂ Surface
journal, March 2009

CO hydrogenation reaction on sulfided molybdenum catalysts
journal, October 2009

Effects of potassium doping on CO hydrogenation over MoS2 catalysts: A first-principles investigation
journal, July 2014

Kinetic Analysis of Mixed Alcohol Synthesis from Syngas over K/MoS ₂ Catalyst
journal, December 1997

Density functional theory study on water–gas-shift reaction over molybdenum disulfide
journal, August 2009

Mixed alcohol synthesis from carbon monoxide and dihydrogen over potassium-promoted molybdenum carbide catalysts
journal, August 1991

Room-temperature oxidation of K2CO3/MoS2 catalysts and its effects on alcohol synthesis from CO and H2
journal, December 1992

Structure and Distribution of Alkali Promoter in K/MoS2 Catalysts and Their Effects on Alcohol Synthesis from Syngas
journal, August 1993

Dispersion of alkali on the surface of Co-MoS2/clay catalyst: a comparison of K and Cs as a promoter for synthesis of alcohol
journal, July 2003

Synthesis of higher alcohols from syngas over alkali promoted MoS2 catalysts supported on multi-walled carbon nanotubes
journal, August 2009

A DFT study on the adsorption and dissociation of methanol over MoS2 surface
journal, February 2011

Methanol and Water Dissociation on TiO ₂ (110): The Role of Surface Oxygen
journal, October 2008

Chemistry of and on TiO2-anatase surfaces by DFT calculations: a partial review
journal, December 2006

Methanol Adsorption and Dissociation on TiO ₂ (110) from First Principles Calculations
journal, July 2007

Steps on rutile TiO $_{2}$ (110): Active sites for water and methanol dissociation
journal, November 2011

Imaging Adsorbate O−H Bond Cleavage: Methanol on TiO ₂ (110)
journal, April 2006

Experimental Investigation of the Interaction of Water and Methanol with Anatase−TiO ₂ (101)
journal, March 2003

A Mechanistic Study of Methanol Decomposition over Cu/SiO2, ZrO2/SiO2, and Cu/ZrO2/SiO2
journal, June 1999

Reactions of methanol on TiO2(001) single crystal surfaces
journal, December 1989

Different binding sites for methanol dehydrogenation and deoxygenation on stoichiometric and defective TiO2(110) surfaces
journal, October 2003

The chemistry of methanol on the TiO2(110) surface: the influence of vacancies and coadsorbed species
journal, January 1999

Defects Engineered Monolayer MoS ₂ for Improved Hydrogen Evolution Reaction
journal, January 2016

Selective Adsorption of Thiol Molecules at Sulfur Vacancies on MoS ₂ (0001), Followed by Vacancy Repair via S–C Dissociation
journal, October 2012

Chemical and Electronic Repair Mechanism of Defects in MoS ₂ Monolayers
journal, September 2017

Facile growth of monolayer MoS2 film areas on SiO2
journal, May 2013

The nonmetal to metal transition with alkali doping of films of molecular icosahedra
journal, January 1997

Surface-induced spin state locking of the [Fe(H ₂ B(pz) ₂ ) ₂ (bipy)] spin crossover complex
journal, April 2016

Graphene-like Boron–Carbon–Nitrogen Monolayers
journal, February 2017

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Projector augmented-wave method
journal, December 1994

Generalized Gradient Approximation Made Simple
journal, October 1996

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Methanol decomposition on single crystal Cu ₂ O
journal, May 1990

Dehydrogenation of methanol on Cu ₂ O(100) and (111)
journal, June 2017

Adsorption and Reaction of Methanol on Clean and Oxygen Precovered Cu(111)
journal, August 2004

Methanol on Anatase TiO ₂ (101): Mechanistic Insights into Photocatalysis
journal, September 2017

Applications of ESCA to polymer chemistry. XVII. Systematic investigation of the core levels of simple homopolymers
journal, April 1978

XPS, UPS and thermal desorption studies of alcohol adsorption on Cu(110)
journal, May 1980

Surface Chemistry of Cu in the Presence of CO ₂ and H ₂ O
journal, September 2008

Atomically Thin ${MoS}_{2}$ A New Direct-Gap Semiconductor
journal, September 2010

Emerging Photoluminescence in Monolayer MoS₂
journal, April 2010

Controlled argon beam-induced desulfurization of monolayer molybdenum disulfide
journal, May 2013

A direct comparison of CVD-grown and exfoliated MoS ₂ using optical spectroscopy
journal, May 2014

X-ray photoelectron spectroscopy study of the interaction of alcohols with oxide surfaces
journal, January 1985

An ESCA study of the termination of the passivation of elemental metals
journal, August 1978

Photo/Electrochemical Applications of Metal Sulfide/TiO ₂ Heterostructures
journal, November 2019