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Title: CO, CO2, and H2 Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon and Metal Sites

Abstract

A systematic study on the adsorption of atomic and molecular hydrogen and carbon oxides on cubic (001) and hexagonal (0001) WC surfaces by periodical density functional theory is reported. Calculations have been performed by employing the Perdew–Burke–Ernzerhof exchange correlation functional with van der Waals corrections to account for the dispersive force term. In addition, dipole corrections were applied for W- and C-terminated hexagonal WC(0001) surfaces. Good agreement is found between calculated and reported data for representative bulk properties. Regarding surface properties, our results indicate that atomic hydrogen adsorbs quite strongly while H2 does, in general, dissociatively on the studied surfaces, with very small energy barriers (<0.35 eV) for the cleavage of the H–H bonds. The C sites of the carbide play an essential role in the binding of H atoms and the cleavage of H–H bonds. Studies examining the interaction of tungsten carbide with CO and CO2 also evidence the importance of C sites. The reactivity of C- and W-terminated (0001) hexagonal WC surfaces significantly differs. Atomic hydrogen, carbon monoxide, and CO2 are more stable on a C- than on a W-terminated surface, and only this latter termination is able to cleave spontaneously a C–O bond of the CO2 molecule.more » This difference in reactivity may open a number of possibilities for fine-tuning the selectivity of the resulting material or designing compounds catalytically active for specific reactions by carefully adjusting the proportion of C, W, and mixed terminations during the synthesis procedure.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]
  1. National Univ. of Colombia, Medellín (Colombia). Faculty of Mines. Dept. of Materials and Minerals. Research Group on Catalysis and Nanomaterials; Univ. of Medellín (Colombia). Faculty of Basic Sciences
  2. Univ. of Medellín (Colombia). Faculty of Basic Sciences
  3. National Univ. of Colombia, Medellín (Colombia). Faculty of Mines. Dept. of Materials and Minerals. Research Group on Catalysis and Nanomaterials
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States); National Univ. of Colombia, Medellín (Colombia); Univ. of Medellín (Colombia)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Univ. of Colombia (Colombia)
OSTI Identifier:
1514379
Report Number(s):
BNL-211686-2019-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 14; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Koverga, Andrey A., Flórez, Elizabeth, Dorkis, Ludovic, and Rodriguez, José A. CO, CO2, and H2 Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon and Metal Sites. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.8b11840.
Koverga, Andrey A., Flórez, Elizabeth, Dorkis, Ludovic, & Rodriguez, José A. CO, CO2, and H2 Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon and Metal Sites. United States. https://doi.org/10.1021/acs.jpcc.8b11840
Koverga, Andrey A., Flórez, Elizabeth, Dorkis, Ludovic, and Rodriguez, José A. Fri . "CO, CO2, and H2 Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon and Metal Sites". United States. https://doi.org/10.1021/acs.jpcc.8b11840. https://www.osti.gov/servlets/purl/1514379.
@article{osti_1514379,
title = {CO, CO2, and H2 Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon and Metal Sites},
author = {Koverga, Andrey A. and Flórez, Elizabeth and Dorkis, Ludovic and Rodriguez, José A.},
abstractNote = {A systematic study on the adsorption of atomic and molecular hydrogen and carbon oxides on cubic (001) and hexagonal (0001) WC surfaces by periodical density functional theory is reported. Calculations have been performed by employing the Perdew–Burke–Ernzerhof exchange correlation functional with van der Waals corrections to account for the dispersive force term. In addition, dipole corrections were applied for W- and C-terminated hexagonal WC(0001) surfaces. Good agreement is found between calculated and reported data for representative bulk properties. Regarding surface properties, our results indicate that atomic hydrogen adsorbs quite strongly while H2 does, in general, dissociatively on the studied surfaces, with very small energy barriers (<0.35 eV) for the cleavage of the H–H bonds. The C sites of the carbide play an essential role in the binding of H atoms and the cleavage of H–H bonds. Studies examining the interaction of tungsten carbide with CO and CO2 also evidence the importance of C sites. The reactivity of C- and W-terminated (0001) hexagonal WC surfaces significantly differs. Atomic hydrogen, carbon monoxide, and CO2 are more stable on a C- than on a W-terminated surface, and only this latter termination is able to cleave spontaneously a C–O bond of the CO2 molecule. This difference in reactivity may open a number of possibilities for fine-tuning the selectivity of the resulting material or designing compounds catalytically active for specific reactions by carefully adjusting the proportion of C, W, and mixed terminations during the synthesis procedure.},
doi = {10.1021/acs.jpcc.8b11840},
journal = {Journal of Physical Chemistry. C},
number = 14,
volume = 123,
place = {United States},
year = {Fri Mar 15 00:00:00 EDT 2019},
month = {Fri Mar 15 00:00:00 EDT 2019}
}

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Works referenced in this record:

Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis
journal, August 1973


Molybdenum carbide catalysts 3. Turnover rates for the hydrogenolysis of n-butane
journal, September 1990


Catalysis by Molybdenum Carbide in Activation of C-C, C-O and C-H bonds
journal, November 1990


Selective chemisorption of carbon monoxide and hydrogen over supported molybdenum carbide catalysts
journal, January 1992

  • Lee, Jae Sung; Lee, Kyung Hee; Lee, Jeong Yong
  • The Journal of Physical Chemistry, Vol. 96, Issue 1
  • DOI: 10.1021/j100180a067

Electronic and structural properties of transition-metal carbide and nitride surfaces
journal, January 1995


New Catalysts for the Conversion of Methane to Synthesis Gas: Molybdenum and Tungsten Carbide
journal, November 1998

  • Claridge, John B.; York, Andrew P. E.; Brungs, Attila J.
  • Journal of Catalysis, Vol. 180, Issue 1
  • DOI: 10.1006/jcat.1998.2260

Characterization of Molybdenum Carbides for Methane Reforming by TPR, XRD, and XPS
journal, September 2001

  • Oshikawa, Katsuhiko; Nagai, Masatoshi; Omi, Shinzo
  • The Journal of Physical Chemistry B, Vol. 105, Issue 38
  • DOI: 10.1021/jp0111867

Surface Chemistry of Transition Metal Carbides
journal, January 2005

  • Hwu, Henry H.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 105, Issue 1
  • DOI: 10.1021/cr0204606

Water-Gas-Shift Reaction on Molybdenum Carbide Surfaces:  Essential Role of the Oxycarbide
journal, October 2006

  • Liu, Ping; Rodriguez, José A.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp0621629

Catalyst size matters: Tuning the molecular mechanism of the water–gas shift reaction on titanium carbide based compounds
journal, November 2008


High Activity Carbide Supported Catalysts for Water Gas Shift
journal, March 2011

  • Schweitzer, Neil M.; Schaidle, Joshua A.; Ezekoye, Obiefune K.
  • Journal of the American Chemical Society, Vol. 133, Issue 8
  • DOI: 10.1021/ja110705a

Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO
journal, May 2014

  • Porosoff, Marc D.; Yang, Xiaofang; Boscoboinik, J. Anibal
  • Angewandte Chemie International Edition, Vol. 53, Issue 26
  • DOI: 10.1002/anie.201404109

Cubic Carbides
journal, April 1966


High Surface Area Nanoparticulate Transition Metal Carbides Prepared by Alkalide Reduction
journal, October 2002

  • Nelson, Jennifer A.; Wagner, Michael J.
  • Chemistry of Materials, Vol. 14, Issue 10
  • DOI: 10.1021/cm020675w

Engineering Non-sintered, Metal-Terminated Tungsten Carbide Nanoparticles for Catalysis
journal, April 2014

  • Hunt, Sean T.; Nimmanwudipong, Tarit; Román-Leshkov, Yuriy
  • Angewandte Chemie International Edition
  • DOI: 10.1002/anie.201400294

Hydrogen evolution reaction (HER) at thin film and bulk TiC electrodes
journal, December 2007


Trends in the Hydrogen Evolution Activity of Metal Carbide Catalysts
journal, March 2014

  • Michalsky, Ronald; Zhang, Yin-Jia; Peterson, Andrew A.
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs500056u

The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo 2 C(001) surfaces
journal, January 2014

  • Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 28
  • DOI: 10.1039/c4cp01943a

The decomposition of ethanol over Mo2C/carbon catalysts
journal, July 2007


Identifying trends and descriptors for selective CO 2 conversion to CO over transition metal carbides
journal, January 2015

  • Porosoff, Marc D.; Kattel, Shyam; Li, Wenhui
  • Chemical Communications, Vol. 51, Issue 32
  • DOI: 10.1039/c5cc01545f

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 effect of the method of preparation on the catalytic activity of tungsten carbide for hydrogen evolution
journal, January 1980


Tungsten carbide cathodes for electrolysis of sulphuric acid solutions
journal, January 1983


WC as a non-platinum hydrogen evolution electrocatalyst for high temperature PEM water electrolysers
journal, December 2012

  • Nikiforov, A. V.; Petrushina, I. M.; Christensen, E.
  • International Journal of Hydrogen Energy, Vol. 37, Issue 24
  • DOI: 10.1016/j.ijhydene.2012.09.112

Adsorption and reaction of CO and H 2 O on WC(0001) surface: A first-principles investigation
journal, January 2018


Density functional study of H2O adsorption and dissociation on WC(0001)
journal, July 2014


Interactions between hydrogen and tungsten carbide: a first principles study
journal, January 2014

  • Xi, Yongjie; Huang, Liang; Forrey, Robert C.
  • RSC Adv., Vol. 4, Issue 75
  • DOI: 10.1039/c4ra06225f

Interactions of H with tungsten carbide surfaces: An ab initio study
journal, January 2007


Hydrogen adsorption on model tungsten carbide surfaces
journal, August 2009


Dissociative Hydrogen Adsorption on the Hexagonal Mo 2 C Phase at High Coverage
journal, April 2014

  • Wang, Tao; Li, Yong-Wang; Wang, Jianguo
  • The Journal of Physical Chemistry C, Vol. 118, Issue 15
  • DOI: 10.1021/jp501471u

Adsorption and dissociation of molecular hydrogen on orthorhombic β-Mo2C and cubic δ-MoC (001) surfaces
journal, February 2017


High-precision sampling for Brillouin-zone integration in metals
journal, August 1989


Structure and stability of β-Mo2C bulk and surfaces: A density functional theory study
journal, March 2009


Catalytic Activity and Product Selectivity Trends for Carbon Dioxide Electroreduction on Transition Metal-Coated Tungsten Carbides
journal, September 2017

  • Wannakao, Sippakorn; Artrith, Nongnuch; Limtrakul, Jumras
  • The Journal of Physical Chemistry C, Vol. 121, Issue 37
  • DOI: 10.1021/acs.jpcc.7b05741

Accurate description of van der Waals complexes by density functional theory including empirical corrections
journal, January 2004

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 25, Issue 12
  • DOI: 10.1002/jcc.20078

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


An off-lattice model for Br electrodeposition on Au(100): from DFT to experiment
journal, August 2004


Density Functional Theory study of electric field effects on CO and OH adsorption and co-adsorption on gold surfaces
journal, July 2013


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

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

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

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1323224

Theoretical study of the stability of cubic WC
journal, September 1988


Structural and electronic properties of WC
journal, November 1988

  • Liu, Amy Y.; Wentzcovitch, Renata M.; Cohen, Marvin L.
  • Physical Review B, Vol. 38, Issue 14
  • DOI: 10.1103/physrevb.38.9483

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

Theoretical study on the electronic properties and stabilities of low-index surfaces of WC polymorphs
journal, January 2011


Theoretical study on the stability, elasticity, hardness and electronic structures of W–C binary compounds
journal, July 2010


Trends in the chemical properties of early transition metal carbide surfaces: A density functional study
journal, July 2005


The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis
journal, May 2004


Trends in the Exchange Current for Hydrogen Evolution
journal, January 2005

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of The Electrochemical Society, Vol. 152, Issue 3
  • DOI: 10.1149/1.1856988

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

  • Senanayake, Sanjaya D.; Ramírez, Pedro J.; Waluyo, Iradwikanari
  • The Journal of Physical Chemistry C, Vol. 120, Issue 3
  • DOI: 10.1021/acs.jpcc.5b12012

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


Comparison of Tungsten and Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Oleic Acid
journal, November 2013

  • Hollak, Stefan A. W.; Gosselink, Robert W.; van Es, Daan S.
  • ACS Catalysis, Vol. 3, Issue 12
  • DOI: 10.1021/cs400744y

Analysis of the electrocatalytic activity of α-molybdenum carbide thin porous electrodes toward the hydrogen evolution reaction
journal, December 2016


Effect of transition metals in the hydrogen evolution electrocatalytic activity of molybdenum carbide
journal, July 2017


Comparison of electrochemical stability of transition metal carbides (WC, W2C, Mo2C) over a wide pH range
journal, March 2012


Multiple Phases of Molybdenum Carbide as Electrocatalysts for the Hydrogen Evolution Reaction
journal, May 2014

  • Wan, Cheng; Regmi, Yagya N.; Leonard, Brian M.
  • Angewandte Chemie International Edition, Vol. 53, Issue 25
  • DOI: 10.1002/anie.201402998

CO adsorption on close-packed transition and noble metal surfaces: trends from ab initio calculations
journal, February 2004

  • Gajdo, Marek; Eichler, Andreas; Hafner, Jürgen
  • Journal of Physics: Condensed Matter, Vol. 16, Issue 8
  • DOI: 10.1088/0953-8984/16/8/001

Size Dependence of the Adsorption Energy of CO on Metal Nanoparticles: A DFT Search for the Minimum Value
journal, January 2012

  • Yudanov, Ilya V.; Genest, Alexander; Schauermann, Swetlana
  • Nano Letters, Vol. 12, Issue 4
  • DOI: 10.1021/nl300515z

Surface structure and energetics of oxygen and CO adsorption on α-Mo2C(0001)
journal, December 2005


Catalytic Properties of Molybdenum Carbide, Nitride and Phosphide: A Theoretical Study
journal, December 2003


Density Functional Theory of Water−Gas Shift Reaction on Molybdenum Carbide
journal, November 2005

  • Tominaga, Hiroyuki; Nagai, Masatoshi
  • The Journal of Physical Chemistry B, Vol. 109, Issue 43
  • DOI: 10.1021/jp053706u

Adsorption, Dissociation, and Hydrogenation of CO 2 on WC(0001) and WC-Co Alloy Surfaces Investigated with Theoretical Calculations
journal, June 2012

  • Wu, Shiuan-Yau; Ho, Jia-Jen
  • The Journal of Physical Chemistry C, Vol. 116, Issue 24
  • DOI: 10.1021/jp302901r

Works referencing / citing this record:

Binding and activation of ethylene on tungsten carbide and platinum surfaces
journal, January 2019

  • Jimenez-Orozco, Carlos; Flórez, Elizabeth; Montoya, Alejandro
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 31
  • DOI: 10.1039/c9cp03214b

Assessing the usefulness of transition metal carbides for hydrogenation reactions
journal, January 2019

  • Prats, Hector; Piñero, Juan José; Viñes, Francesc
  • Chemical Communications, Vol. 55, Issue 85
  • DOI: 10.1039/c9cc06084g

Activation of Gold on Metal Carbides: Novel Catalysts for C1 Chemistry
journal, January 2020