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Title: Boosting the activity of transition metal carbides towards methane activation by nanostructuring

Abstract

The interaction of methane with pristine surfaces of bulk MoC and Mo2C is known to be weak. In contrast, a series of X-ray photoelectron spectroscopy (XPS) experiments, combined with thermal desorption mass spectroscopy (TDS), for MoCy (y = 0.5–1.3) nanoparticles supported on Au(111)—which is completely inert towards CH4—show that these systems adsorb and dissociate CH4 at room temperature and low CH4 partial pressure. This industrially-relevant finding has been further investigated with accurate density functional theory (DFT) based calculations on a variety of MoCy supported model systems. The DFT calculations reveal that the MoCy/Au(111) systems can feature low C–H bond scission energy barriers, smaller than the CH4 adsorption energy. Our theoretical results for bulk surfaces of Mo2C and MoC show that a simple Brønsted–Evans–Polanyi (BEP) relationship holds for C–H bond scission on these systems. However, this is not the case for methane activation on the MoCy nanoparticles as a consequence of their unique electronic and chemical properties. Finally, the discovery that supported molybdenum carbide nanoparticles are able to activate methane at room temperature paves the road towards the design of a new family of active carbide catalysts for methane activation and valorisation, with important implications in climate change mitigation and carbonmore » cycle closure.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [4]
  1. Univ. of Barcelona (Spain)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Central Univ. of Venezuela, Caracas (Venezuela)
  3. Central Univ. of Venezuela, Caracas (Venezuela)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1609096
Alternate Identifier(s):
OSTI ID: 1605958
Report Number(s):
BNL-213806-2020-JAAM
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 22; Journal Issue: 13; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; methane; metal carbides; gold

Citation Formats

Figueras, Marc, Gutiérrez, Ramón A., Prats, Hector, Viñes, Francesc, Ramírez, Pedro J., Illas, Francesc, and Rodriguez, José A. Boosting the activity of transition metal carbides towards methane activation by nanostructuring. United States: N. p., 2020. Web. doi:10.1039/D0CP00228C.
Figueras, Marc, Gutiérrez, Ramón A., Prats, Hector, Viñes, Francesc, Ramírez, Pedro J., Illas, Francesc, & Rodriguez, José A. Boosting the activity of transition metal carbides towards methane activation by nanostructuring. United States. doi:https://doi.org/10.1039/D0CP00228C
Figueras, Marc, Gutiérrez, Ramón A., Prats, Hector, Viñes, Francesc, Ramírez, Pedro J., Illas, Francesc, and Rodriguez, José A. Fri . "Boosting the activity of transition metal carbides towards methane activation by nanostructuring". United States. doi:https://doi.org/10.1039/D0CP00228C. https://www.osti.gov/servlets/purl/1609096.
@article{osti_1609096,
title = {Boosting the activity of transition metal carbides towards methane activation by nanostructuring},
author = {Figueras, Marc and Gutiérrez, Ramón A. and Prats, Hector and Viñes, Francesc and Ramírez, Pedro J. and Illas, Francesc and Rodriguez, José A.},
abstractNote = {The interaction of methane with pristine surfaces of bulk MoC and Mo2C is known to be weak. In contrast, a series of X-ray photoelectron spectroscopy (XPS) experiments, combined with thermal desorption mass spectroscopy (TDS), for MoCy (y = 0.5–1.3) nanoparticles supported on Au(111)—which is completely inert towards CH4—show that these systems adsorb and dissociate CH4 at room temperature and low CH4 partial pressure. This industrially-relevant finding has been further investigated with accurate density functional theory (DFT) based calculations on a variety of MoCy supported model systems. The DFT calculations reveal that the MoCy/Au(111) systems can feature low C–H bond scission energy barriers, smaller than the CH4 adsorption energy. Our theoretical results for bulk surfaces of Mo2C and MoC show that a simple Brønsted–Evans–Polanyi (BEP) relationship holds for C–H bond scission on these systems. However, this is not the case for methane activation on the MoCy nanoparticles as a consequence of their unique electronic and chemical properties. Finally, the discovery that supported molybdenum carbide nanoparticles are able to activate methane at room temperature paves the road towards the design of a new family of active carbide catalysts for methane activation and valorisation, with important implications in climate change mitigation and carbon cycle closure.},
doi = {10.1039/D0CP00228C},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 13,
volume = 22,
place = {United States},
year = {2020},
month = {3}
}

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Works referenced in this record:

Methane activation: the past and future
journal, January 2014

  • Tang, Pei; Zhu, Qingjun; Wu, Zhaoxuan
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE00604F

Luftchemie und Klima
journal, June 2007

  • Feichter, Johann; Schurath, Ulrich; Zellner, Reinhard
  • Chemie in unserer Zeit, Vol. 41, Issue 3
  • DOI: 10.1002/ciuz.200700423

Economic carbon cycle feedbacks may offset additional warming from natural feedbacks
journal, December 2018

  • Woodard, Dawn L.; Davis, Steven J.; Randerson, James T.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 3
  • DOI: 10.1073/pnas.1805187115

Controlled Oxidation of Hydrocarbons by the Membrane-Bound Methane Monooxygenase: The Case for a Tricopper Cluster
journal, August 2008

  • Chan, Sunney I.; Yu, Steve S. -F.
  • Accounts of Chemical Research, Vol. 41, Issue 8
  • DOI: 10.1021/ar700277n

Misconceptions and challenges in methane-to-methanol over transition-metal-exchanged zeolites
journal, May 2019


Single Step Oxidation of Methane to Methanol–Towards Better Understanding
journal, January 2013


Room Temperature Methane Capture and Activation by Ni Clusters Supported on TiC(001): Effects of Metal–Carbide Interactions on the Cleavage of the C–H Bond
journal, March 2019

  • Prats, Hèctor; Gutiérrez, Ramón A.; Piñero, Juan José
  • Journal of the American Chemical Society, Vol. 141, Issue 13
  • DOI: 10.1021/jacs.8b13552

Nonoxidative Activation of Methane
journal, January 2003

  • Choudhary, Tushar V.; Aksoylu, Erhan; Wayne Goodman, D.
  • Catalysis Reviews, Vol. 45, Issue 1
  • DOI: 10.1081/CR-120017010

Kinetics of the activated dissociative adsorption of methane on the low index planes of nickel single crystal surfaces
journal, August 1987

  • Beebe, Thomas P.; Goodman, D. Wayne; Kay, Bruce D.
  • The Journal of Chemical Physics, Vol. 87, Issue 4
  • DOI: 10.1063/1.453162

Methane Activation by Platinum: Critical Role of Edge and Corner Sites of Metal Nanoparticles
journal, April 2010

  • Viñes, Francesc; Lykhach, Yaroslava; Staudt, Thorsten
  • Chemistry - A European Journal, Vol. 16, Issue 22
  • DOI: 10.1002/chem.201000296

Dry Reforming of Methane on a Highly-Active Ni-CeO 2 Catalyst: Effects of Metal-Support Interactions on C−H Bond Breaking
journal, May 2016

  • Liu, Zongyuan; Grinter, David C.; Lustemberg, Pablo G.
  • Angewandte Chemie International Edition, Vol. 55, Issue 26
  • DOI: 10.1002/anie.201602489

Methane Activation by Iron-Carbide Cluster Anions FeC 6
journal, June 2015


Conversion of methane to benzene over Mo2C and Mo2C/ZSM-5 catalysts
journal, January 1996

  • Solymosi, F.; Sz�ke, A.; Cser�nyi, J.
  • Catalysis Letters, Vol. 39, Issue 3-4
  • DOI: 10.1007/BF00805576

Impact of the presence of Mo carbide species prepared ex situ in Mo/HZSM-5 on the catalytic properties in methane aromatization
journal, May 2018


Methane capture at room temperature: adsorption on cubic δ-MoC and orthorhombic β-Mo 2 C molybdenum carbide (001) surfaces
journal, January 2015

  • Posada-Pérez, Sergio; dos Santos Politi, José Roberto; Viñes, Francesc
  • RSC Advances, Vol. 5, Issue 43
  • DOI: 10.1039/C4RA17225F

CH4 dissociation and C C coupling on Mo-terminated MoC surfaces: A DFT study
journal, January 2020


Methane Conversion to Aromatics on Mo/H-ZSM5:  Structure of Molybdenum Species in Working Catalysts
journal, January 2001

  • Ding, Weiping; Li, Senzi; D. Meitzner, George
  • The Journal of Physical Chemistry B, Vol. 105, Issue 2
  • DOI: 10.1021/jp0030692

Characterization of Molybdenum Carbide Nanoparticles Formed on Au(111) Using Reactive-Layer Assisted Deposition
journal, January 2005

  • Horn, Jillian M.; Song, Zhen; Potapenko, Denis V.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 1
  • DOI: 10.1021/jp044837i

Acid and Basic Catalysis.
journal, October 1928


Inertia and driving force of chemical reactions
journal, January 1938


Preparation and Structural Characterization of RuS 2 Nanoislands on Au(111)
journal, July 2004

  • Cai, Tanhong; Song, Zhen; Rodriguez, Jose A.
  • Journal of the American Chemical Society, Vol. 126, Issue 29
  • DOI: 10.1021/ja047634g

Inverse oxide/metal catalysts: A versatile approach for activity tests and mechanistic studies
journal, February 2010


Inverse Oxide/Metal Catalysts in Fundamental Studies and Practical Applications: A Perspective of Recent Developments
journal, June 2016

  • Rodriguez, José A.; Liu, Ping; Graciani, Jesús
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
  • DOI: 10.1021/acs.jpclett.6b00499

Growth and structural studies of In/Au(111) alloys and InO x /Au(111) inverse oxide/metal model catalysts
journal, February 2020

  • Kang, Jindong; Mahapatra, Mausumi; Rui, Ning
  • The Journal of Chemical Physics, Vol. 152, Issue 5
  • DOI: 10.1063/1.5139237

A Novel Growth Mode of Mo on Au (111) from a Mo(CO) 6 Precursor:  An STM Study
journal, January 2003

  • Song, Zhen; Cai, Tanhong; Rodriguez, Jose A.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 4
  • DOI: 10.1021/jp0270405

Molecular Level Study of the Formation and the Spread of MoO 3 on Au (111) by Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy
journal, July 2003

  • Song, Zhen; Cai, Tanhong; Chang, Zhipeng
  • Journal of the American Chemical Society, Vol. 125, Issue 26
  • DOI: 10.1021/ja034862m

The molybdenum–carbon interface: formation and electronic structure of the carbide layer
journal, November 2000


Chemistry of thiophene on Mo(110), MoCx and MoSx surfaces: photoemission studies
journal, June 2000


Surface characterization of α-Mo2C (0001)
journal, May 1999


Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO 2 : The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability
journal, June 2016

  • Posada-Pérez, Sergio; Ramírez, Pedro J.; Evans, Jaime
  • Journal of the American Chemical Society, Vol. 138, Issue 26
  • DOI: 10.1021/jacs.6b04529

The interaction of oxygen with TiC(001): Photoemission and first-principles studies
journal, January 2004

  • Rodriguez, J. A.; Liu, P.; Dvorak, J.
  • The Journal of Chemical Physics, Vol. 121, Issue 1
  • DOI: 10.1063/1.1755669

Detailed spectroscopic studies of oxygen on metal carbide surfaces
journal, September 1998


Substrate-Dependent Reactivity of Water on Metal Carbide Surfaces
journal, December 1999

  • Didziulis, Stephen V.; Frantz, Peter; Perry, Scott S.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 50
  • DOI: 10.1021/jp9923668

High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level
journal, March 2009

  • Park, J. B.; Graciani, J.; Evans, J.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 13
  • DOI: 10.1073/pnas.0812604106

Water–gas shift activity of Au and Cu nanoparticles supported on molybdenum oxides
journal, February 2008


Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄)
journal, January 2010

  • Yang, Yixiong; Evans, Jaime; Rodriguez, Jose A.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 33
  • DOI: 10.1039/c001484b

CO2 hydrogenation on Au/TiC, Cu/TiC, and Ni/TiC catalysts: Production of CO, methanol, and methane
journal, November 2013


Low-energy nanoscale clusters of (TiC) n n = 6, 12: a structural and energetic comparison with MgO
journal, January 2013

  • Lamiel-Garcia, Oriol; Bromley, Stefan T.; Illas, Francesc
  • Theoretical Chemistry Accounts, Vol. 132, Issue 3
  • DOI: 10.1007/s00214-012-1312-x

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Atomic and electronic structure of molybdenum carbide phases: bulk and low Miller-index surfaces
journal, January 2013

  • Politi, José Roberto dos Santos; Viñes, Francesc; Rodriguez, Jose A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 30
  • DOI: 10.1039/c3cp51389k

Jacob’s Ladder as Sketched by Escher: Assessing the Performance of Broadly Used Density Functionals on Transition Metal Surface Properties
journal, December 2017

  • Vega, Lorena; Ruvireta, Judit; Viñes, Francesc
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 1
  • DOI: 10.1021/acs.jctc.7b01047

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

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Improved initial guess for minimum energy path calculations
journal, June 2014

  • Smidstrup, Søren; Pedersen, Andreas; Stokbro, Kurt
  • The Journal of Chemical Physics, Vol. 140, Issue 21
  • DOI: 10.1063/1.4878664

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Theoretical Investigation of Methane Oxidation on Pd(111) and Other Metallic Surfaces
journal, June 2018

  • Yoo, Jong Suk; Schumann, Julia; Studt, Felix
  • The Journal of Physical Chemistry C, Vol. 122, Issue 28
  • DOI: 10.1021/acs.jpcc.8b02142

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