Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Catalytic C2H2 synthesis via low temperature CO hydrogenation on defect-rich 2D-MoS 2 and 2D-MoS2 decorated with Mo clusters

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5129712· OSTI ID:1800398
 [1];  [2];  [2];  [3];  [2];  [2];  [2];  [3];  [2];  [3]
  1. Univ. of Central Florida, Orlando, FL (United States); OSTI
  2. Univ. of Central Florida, Orlando, FL (United States)
  3. Univ. of Central Florida, Orlando, FL (United States). Renewable Energy and Chemical Transformations Cluster
+ Show Author Affiliations
Rational design of novel catalytic materials used to synthesize storable fuels via the CO hydrogenation reaction has recently received considerable attention. In this work, defect poor and defect rich 2D-MoS2 as well as 2D-MoS2 decorated with Mo clusters are employed as catalysts for the generation of acetylene (C2H2) via the CO hydrogenation reaction. Temperature programmed desorption is used to study the interaction of CO and H2 molecules with the MoS2 surface as well as the formation of reaction products. The experiments indicate the presence of four CO adsorption sites below room temperature and a competitive adsorption between the CO and H2 molecules. The investigations show that CO hydrogenation is not possible on defect poor MoS2 at low temperatures. However, on defect rich 2D-MoS2, small amounts of C2H2 are produced, which desorb from the surface at temperatures between 170 K and 250 K. A similar C2H2 signal is detected from defect poor 2D-MoS2 decorated with Mo clusters, which indicates that low coordinated Mo atoms on 2D-MoS2 are responsible for the formation of C2H2. Density functional theory investigations are performed to explore possible adsorption sites of CO and understand the formation mechanism of C2H2 on MoS2 and Mo7/MoS2. The theoretical investigation indicates a strong binding of C2H2 on the Mo sites of MoS2 preventing the direct desorption of C2H2 at low temperatures as observed experimentally. Instead, the theoretical results suggest that the experimental data are consistent with a mechanism in which CHO radical dimers lead to the formation of C2H2 that presents an exothermic desorption.
Research Organization:
University of Central Florida, Orlando, FL (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
FG02-07ER15842
OSTI ID:
1800398
Alternate ID(s):
OSTI ID: 1600052
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 152; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (54)

An MoS x Structure with High Affinity for Adsorbate Interaction journal September 2012
Ni/ADM: a high activity and selectivity to C2+OH catalyst for catalytic conversion of synthesis gas to C1-C5 mixed alcohols journal March 2005
The rise of two-dimensional MoS2 for catalysis journal July 2018
Direct vibrational detection of surface reaction channels leading to CO dissociation and to its inhibition on Mo(110) journal February 1991
Methane conversion and Fischer?Tropsch catalysis over MoS2: Predictions and interpretations from molecular orbital theory journal September 1989
Carbon monoxide adsorption kinetics on molybdenum (100) journal March 1973
Dissociation of CO on Mo(100) journal October 1976
Adsorption of carbon monoxide on the molybdenum (100) surface journal September 1978
CO adsorption studies on pure and Ni-covered Cu(111) surfaces journal November 1986
Chemical evidence for the dissociation of CO on Mo(100) journal November 1980
Role of alkali promoters in K/MoS2 catalysts for CO-H2 reactions journal March 1994
Sulfide catalyst for methanol synthesis, its reactivity and characterization. II. Reduction properties in relation to catalytic properties journal June 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Influence of MoS2 catalyst morphology on the hydrodeoxygenation of phenols journal March 2008
Unsupported MoS2 and CoMoS2 catalysts for hydrodeoxygenation of phenol journal September 2012
Quantum-chemical-based microkinetics simulations of syngas conversion over MoS2(1 0 0) surface journal April 2019
Gold atoms and clusters on MgO(100) films; an EPR and IRAS study journal June 2009
CO dissociation on Mo(110) studied by high-resolution core-level spectroscopy journal October 2001
Effect of cobalt promoter on Co–Mo–K/C catalysts used for mixed alcohol synthesis journal October 2001
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
Nonmetal to Metal Transition and Ultrafast Charge Carrier Dynamics of Zn Clusters on p-Si(100) by fs-XUV Photoemission Spectroscopy journal June 2018
Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS 2 Catalysts journal June 2013
Theoretical Study of the MoS 2 (100) Surface:  A Chemical Potential Analysis of Sulfur and Hydrogen Coverage. 2. Effect of the Total Pressure on Surface Stability journal June 2002
Density Functional Theory Study of CO Adsorption on Molybdenum Sulfide journal February 2005
Density Functional Theory Study of Triangular Molybdenum Sulfide Nanocluster and CO Adsorption on It journal July 2005
Density Functional Theory Study of CO Adsorption and Dissociation on Molybdenum(100)
  • Scheijen, Freek J. E.; Niemantsverdriet, J. W. (Hans); Ferré, Daniel Curulla
  • The Journal of Physical Chemistry C, Vol. 111, Issue 36 https://doi.org/10.1021/jp072673a
journal September 2007
Single-Layer MoS 2 with Sulfur Vacancies: Structure and Catalytic Application journal March 2014
Density Functional Theory Study of CO Hydrogenation on a MoS 2 Surface journal March 2009
Adsorption and Dissociation of CO on Body-Centered Cubic Transition Metals and Alloys: Effect of Coverage and Scaling Relations
  • Scheijen, Freek J. E.; Ferré, Daniel Curulla; Niemantsverdriet, J. W. (Hans)
  • The Journal of Physical Chemistry C, Vol. 113, Issue 25 https://doi.org/10.1021/jp811130k
journal May 2009
Methanol Synthesis from H 2 and CO 2 on a Mo 6 S 8 Cluster: A Density Functional Study † journal March 2010
Toward the Growth of an Aligned Single-Layer MoS 2 Film journal September 2011
Ambipolar MoS 2 Thin Flake Transistors journal February 2012
Integrated Circuits Based on Bilayer MoS2 Transistors journal January 2012
Emerging Photoluminescence in Monolayer MoS2 journal April 2010
Single-Layer MoS2 Phototransistors journal December 2011
Integrated Circuits and Logic Operations Based on Single-Layer MoS 2 journal November 2011
Few-Layer MoS 2 : A Promising Layered Semiconductor journal April 2014
The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets journal April 2013
Single-layer MoS2 transistors journal January 2011
Ultrasensitive photodetectors based on monolayer MoS2 journal June 2013
Synthesis of wafer-scale uniform molybdenum disulfide films with control over the layer number using a gas phase sulfur precursor journal January 2014
Mechanism of coverage dependent CO adsorption and dissociation on the Mo(100) surface journal January 2017
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
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
MoS 2 -supported gold nanoparticle for CO hydrogenation journal September 2017
Mirror twin grain boundaries in molybdenum dichalcogenides journal November 2018
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Single layer MoS 2 on the Cu(111) surface: First-principles electronic structure calculations journal February 2012
Atomically Thin MoS2 A New Direct-Gap Semiconductor journal September 2010
Generalized Gradient Approximation Made Simple journal October 1996
Crossover from Three-Dimensional to Two-Dimensional Geometries of Au Nanostructures on Thin MgO(001) Films: A Confirmation of Theoretical Predictions journal May 2007
Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts journal July 2007

Similar Records

MoS2-supported Au31 for CO hydrogenation: A first-principle study
Journal Article · Thu Apr 30 20:00:00 EDT 2020 · Journal of Vacuum Science and Technology A · OSTI ID:1800399
A Single Layer of MoS2 Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate
Journal Article · Tue Feb 19 19:00:00 EST 2019 · Journal of Physical Chemistry. C · OSTI ID:1530185

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Auger electron spectroscopy
Catalysts and Catalysis
Chemistry
Crystal structure
Density functional theory
Hydrogenation process
Physics
Surface and interface chemistry
Temperature programmed desorption