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Title: The conversion of CO2 to methanol on orthorhombic β-Mo2C and Cu/β-Mo2C catalysts: Mechanism for admetal induced change in the selectivity and activity

Journal Article · · Catalysis Science and Technology
DOI:https://doi.org/10.1039/c5cy02143j· OSTI ID:1351739
 [1];  [2];  [2];  [3];  [1];  [3];  [1];  [3]
  1. Univ. de Barcelona, Barcelona (Spain)
  2. Univ. Central de Venezuela, Caracas (Venezuela)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
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Here, the conversion of CO2 into methanol catalyzed by β-Mo2C and Cu/β-Mo2C surfaces has been investigated by means of a combined experimental and theoretical study. Experiments have shown the direct activation and dissociation of the CO2 molecule on bare β-Mo2C, whereas on Cu/β-Mo2C, CO2 must be assisted by hydrogen for its conversion. Methane and CO are the main products on the clean surface and methanol production is lower. However, the deposition of Cu clusters avoids methane formation and increases methanol production even above that corresponding to a model of the technical catalyst. DFT calculations on surface models of both possible C- and Mo-terminations corroborate the experimental observations. Calculations for the clean Mo-terminated surface reveal the existence of two possible routes for methane production (C + 4H → CH4; CH3O + 3H → CH4 + H2O) which are competitive with methanol synthesis, displaying slightly lower energy barriers. On the other hand, a model for Cu deposited clusters on the Mo-terminated surface points towards a new route for methanol and CO production avoiding methane formation. The new route is a direct consequence of the generation of a Mo2C–Cu interface. The present experimental and theoretical results entail the interesting catalytic properties of Mo2C as an active support of metallic nanoparticles, and also illustrate how the deposition of a metal can drastically change the activity and selectivity of a carbide substrate for CO2 hydrogenation.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704
OSTI ID:
1351739
Report Number(s):
BNL-113746-2017-JA; CSTAGD; R&D Project: CO040; KC0302010
Journal Information:
Catalysis Science and Technology, Vol. 6, Issue 18; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 81 works
Citation information provided by
Web of Science

References (53)

Hydrogenation of CO 2 to Methanol on CeO x /Cu(111) and ZnO/Cu(111) Catalysts: Role of the Metal–Oxide Interface and Importance of Ce 3+ Sites journal January 2016
Scanning Tunneling Microscopy Study of Formate Species Synthesized from CO 2 Hydrogenation and Prepared by Adsorption of Formic Acid over Cu(111) journal February 2000
Brønsted–Evans–Polanyi Relationship for Transition Metal Carbide and Transition Metal Oxide Surfaces journal February 2013
Fundamentals of Methanol Synthesis on Metal Carbide Based Catalysts: Activation of CO2 and H2 journal December 2014
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO journal May 2014
A surface science investigation of the water-gas shift reaction on Cu(111) journal March 1987
Establishing the Accuracy of Broadly Used Density Functionals in Describing Bulk Properties of Transition Metals journal February 2013
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts journal March 2015
Synthesis of α-MoC1-x and β-MoCy Catalysts for CO2 Hydrogenation by Thermal Carburization of Mo-oxide in Hydrocarbon and Hydrogen Mixtures journal June 2014
High Activity Carbide Supported Catalysts for Water Gas Shift journal March 2011
Is the observed hydrogenation of formate the rate-limiting step in methanol synthesis? journal January 1995
Hydrogenation of CO 2 to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO 2 journal October 2015
Bulk Properties of Transition Metals: A Challenge for the Design of Universal Density Functionals journal August 2014
Structure and electronic properties of Cu nanoclusters supported on Mo 2 C(001) and MoC(001) surfaces journal September 2015
Desulfurization Reactions on Ni 2 P(001) and α-Mo 2 C(001) Surfaces:  Complex Role of P and C Sites journal March 2005
CO adsorption on Cu(111) and Cu(001) surfaces: Improving site preference in DFT calculations journal October 2005
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Elementary steps of syngas reactions on Mo2C(001): Adsorption thermochemistry and bond dissociation journal June 2012
Water-Gas-Shift Reaction on Molybdenum Carbide Surfaces:  Essential Role of the Oxycarbide journal October 2006
Conversion of CO 2 to Dimethylether and Methanol over Hybrid Catalysts journal July 1992
Adsorption and Reaction of CO 2 on Mo 2 C Catalyst journal September 2002
The Carburization of Transition Metal Molybdates (MxMoO4, M = Cu, Ni or Co) and the Generation of Highly Active Metal/Carbide Catalysts for CO2 Hydrogenation journal May 2015
CO2 hydrogenation on Au/TiC, Cu/TiC, and Ni/TiC catalysts: Production of CO, methanol, and methane journal November 2013
CO 2 Activation and Methanol Synthesis on Novel Au/TiC and Cu/TiC Catalysts journal August 2012
Modern Global Climate Change journal December 2003
Generalized thermodynamic analysis of methanol synthesis: Effect of feed composition journal June 2015
Atomic and electronic structure of molybdenum carbide phases: bulk and low Miller-index surfaces journal January 2013
Carbon Dioxide Conversion to Methanol over Size-Selected Cu 4 Clusters at Low Pressures journal July 2015
Engineering Transition-Metal-Coated Tungsten Carbides for Efficient and Selective Electrochemical Reduction of CO 2 to Methane journal July 2015
Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis journal September 2012
High Coverage CO Adsorption and Dissociation on the Orthorhombic Mo 2 C(100) Surface journal January 2014
How to make the most of carbon dioxide journal October 2015
Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄) journal January 2010
Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation journal February 2011
Structural Influences on Adsorption Energy. III. CO on Cu(100) journal March 1972
Identifying trends and descriptors for selective CO 2 conversion to CO over transition metal carbides journal January 2015
Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions journal January 2012
The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo 2 C(001) surfaces journal January 2014
Surface characterization of α-Mo2C (0001) journal May 1999
Generalized Gradient Approximation Made Simple journal October 1996
Projector augmented-wave method journal December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Special points for Brillouin-zone integrations journal June 1976
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
New Synthetic Routes to More Active Cu/ZnO Catalysts Used for Methanol Synthesis journal January 2004
Methane capture at room temperature: adsorption on cubic δ-MoC and orthorhombic β-Mo 2 C molybdenum carbide (001) surfaces journal January 2015
A theoretical study of dioxymethylene, proposed as intermediate in the oxidation of formaldehyde to formate over copper journal February 2000
A DFT study of dioxymethylene adsorption on the copper (111) surface journal November 1999
Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2 journal January 1994
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO journal May 2014
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
CO adsorption on Cu(111) and Cu(001) surfaces: improving site preference in DFT calculations text January 2004

Cited By (11)

A review of the catalytic hydrogenation of carbon dioxide into value-added hydrocarbons journal January 2017
Potassium-Promoted Molybdenum Carbide as a Highly Active and Selective Catalyst for CO 2 Conversion to CO journal May 2017
Ab initio investigation of the atomistic descriptors in the activation of small molecules on 3 d transition-metal 13-atom clusters: The example of H 2 , CO, H 2 O, and CO 2 journal December 2019
Edge Segregated Polymorphism in 2D Molybdenum Carbide journal February 2019
Surface and Interface Engineering: Molybdenum Carbide–Based Nanomaterials for Electrochemical Energy Conversion journal September 2019
Highly active Au/δ-MoC and Au/β-Mo 2 C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance journal January 2017
Porous MoxCy/SiO2 Material for CO2 Hydrogenation journal August 2019
Aluminum complexes with new non-symmetric ferrocenyl amidine ligands and their application in CO 2 transformation into cyclic carbonates journal January 2020
Cu-Mo2C/MCM-41: An Efficient Catalyst for the Selective Synthesis of Methanol from CO2 journal May 2016
Bridging Mo 2 C–C and highly dispersed copper by incorporating N-functional groups to greatly enhance the catalytic activity and durability for carbon dioxide hydrogenation journal January 2018
New Set of Multicomponent Crystals as Efficient Heterogeneous Catalysts for the Synthesis of Cyclic Carbonates journal March 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 activation
CO2 hydrogenation
methanol
methane
reverse water-gas shift reaction
metal carbides
copper