skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Highly active Au/δ-MoC and Cu/δ-MoC catalysts for the conversion of CO2: The metal/C ratio as a key factor defining activity, selectivity, and stability

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b04529· OSTI ID:1326741
 [1];  [2];  [2];  [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)
+ Show Author Affiliations

The ever growing increase of CO2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO2 activation and conversion toward valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO2 to CO with some subsequent selective hydrogenation toward methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo2C and Au/δ-MoC catalysts provides evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO2 conversion. Here, a control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.

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:
1326741
Report Number(s):
BNL-112632-2016-JA; R&D Project: CP027; KC0302010
Journal Information:
Journal of the American Chemical Society, Vol. 138, Issue 26; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 124 works
Citation information provided by
Web of Science

References (59)

Generalized Gradient Approximation Made Simple journal October 1996
New Catalysts for the Conversion of Methane to Synthesis Gas: Molybdenum and Tungsten Carbide journal November 1998
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
Projector augmented-wave method journal December 1994
Kinetic Monte Carlo simulations of the water gas shift reaction on Cu(1 1 1) from density functional theory based calculations journal January 2016
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO journal May 2014
Catalytic reduction of CO 2 by H 2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities journal January 2016
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts journal March 2015
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Effects of carbon on the stability and chemical performance of transition metal carbides: A density functional study journal March 2004
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
Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes journal January 2013
Mitigation of CO2 by Chemical Conversion:  Plausible Chemical Reactions and Promising Products journal March 1996
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
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO 2 Hydrogenation journal March 2016
Hydrogen production in the decomposition and steam reforming of methanol on Mo2C/carbon catalysts journal July 2007
Effect of interparticle interaction on the low temperature oxidation of CO over size-selected Au nanocatalysts supported on ultrathin TiC films journal February 2007
Computational Identification of Descriptors for Selectivity in Syngas Reactions on a Mo 2 C Catalyst journal August 2015
Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions journal January 2012
Water-Gas-Shift Reaction on Molybdenum Carbide Surfaces:  Essential Role of the Oxycarbide journal October 2006
Desulfurization of Thiophene on Au/TiC(001): Au−C Interactions and Charge Polarization journal June 2009
Role of Au−C Interactions on the Catalytic Activity of Au Nanoparticles Supported on TiC(001) toward Molecular Oxygen Dissociation journal March 2010
Carbon Dioxide Hydrogenation to Formic Acid by Using a Heterogeneous Gold Catalyst journal November 2011
A perspective on the properties and surface reactivities of carbides and nitrides of titanium and vanadium journal January 2013
Hydrogenation of CO on molybdenum and cobalt molybdenum carbides journal May 2012
Carbon Dioxide Reforming of Methane To Produce Synthesis Gas over Metal-Supported Catalysts:  State of the Art journal January 1996
Production of CO-Free H2 by Formic Acid Decomposition over Mo2C/Carbon Catalysts journal June 2010
Fundamental Concepts in Heterogeneous Catalysis book January 2014
Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity journal July 1996
Charge Polarization at a Au-TiC Interface and the Generation of Highly Active and Selective Catalysts for the Low-Temperature Water-Gas Shift Reaction journal September 2014
Characterization of Molybdenum Carbides for Methane Reforming by TPR, XRD, and XPS journal September 2001
Special points for Brillouin-zone integrations journal June 1976
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
Mechanism of the Surface Hydrogen Induced Conversion of CO 2 to Methanol at Cu(111) Step Sites journal January 2016
Carbide and Nitride Overlayers on Early Transition Metal Surfaces:  Preparation, Characterization, and Reactivities journal January 1996
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
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
Interaction of SO2 with Cu/TiC(001) and Au/TiC(001): Toward a new family of DeSOx catalysts journal April 2011
Catalyst size matters: Tuning the molecular mechanism of the water–gas shift reaction on titanium carbide based compounds journal November 2008
Recent Advances in Catalysts for Methanol Synthesis via Hydrogenation of CO and CO 2 journal December 2003
Surface Chemistry of Transition Metal Carbides journal January 2005
Dissociation of SO 2 on Au/TiC(001): Effects of Au-C Interactions and Charge Polarization journal August 2008
The selectivity and activity of catalyst for CO hydrogenation to methanol and hydrocarbon: A comparative study on Cu, Co and Ni surfaces journal March 2016
Transition metal carbides as novel materials for CO 2 capture, storage, and activation journal January 2016
Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis journal August 1973
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
Preparation and catalytic properties of transition metal carbides and nitrides journal June 1992
Mechanism of the Water Gas Shift Reaction on Pt:  First Principles, Experiments, and Microkinetic Modeling journal March 2008
Methane as raw material in synthetic chemistry: the final frontier journal January 2013
Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation journal February 2011
Carbon Dioxide as Chemical Feedstock book January 2010
Climate Change 2013 – The Physical Science Basis book March 2014

Cited By (11)

Facile synthesis of high surface area molybdenum carbide nanoparticles journal December 2018
CO2 hydrogenation to high-value products via heterogeneous catalysis journal December 2019
A perovskite oxide LaCoO 3 cocatalyst for efficient photocatalytic reduction of CO 2 with visible light journal January 2018
Visualizing Formation of Tungsten Carbide Model Catalyst and its Interaction with Oxygen journal December 2019
Surface and Interface Engineering: Molybdenum Carbide–Based Nanomaterials for Electrochemical Energy Conversion journal September 2019
Activation of Gold on Metal Carbides: Novel Catalysts for C1 Chemistry journal January 2020
Porous MoxCy/SiO2 Material for CO2 Hydrogenation journal August 2019
CO 2 abatement using two-dimensional MXene carbides journal January 2018
Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts journal March 2017
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
Assembly of hollow mesoporous nanoarchitectures composed of ultrafine Mo 2 C nanoparticles on N-doped carbon nanosheets for efficient electrocatalytic reduction of oxygen journal January 2017

Similar Records

Highly active Au/δ-MoC and Au/β-Mo2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance
Journal Article · Mon May 08 00:00:00 EDT 2017 · Catalysis Science and Technology · OSTI ID:1326741
+5 more
Activation of Gold on Metal Carbides: Novel Catalysts for C1 Chemistry
Journal Article · Wed Jan 08 00:00:00 EST 2020 · Frontiers in Chemistry · OSTI ID:1326741
Acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces: A comprehensive periodic DFT study
Journal Article · Tue Dec 06 00:00:00 EST 2016 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1326741
+2 more

Related Subjects

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