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

Title: Systematic theoretical study of ethylene adsorption on δ-MoC(001), TiC(001), and ZrC(001) surfaces

Abstract

A systematic study of ethylene adsorption over δ-MoC(001), TiC(001), and ZrC(001) surfaces was conducted by means of calculations based on periodic density functional theory. The structure and electronic properties of each carbide pristine surface had a strong influence in the bonding of ethylene. It was found that the metal and carbon sites of the carbide could participate in the adsorption process. As a consequence of this, very different bonding mechanisms were seen on δ-MoC(001) and TiC(001). The bonding of the molecule on the TMC(001) systems showed only minor similarities to the type of bonding found on a typical metal like Pt(111). In general, the ethylene binding energy follow the trend in stability: ZrC(001) < TiC(001) < δ-MoC(001) < Pt(111). The van der Waals correction to the energy produces large binding energy values, modifies the stability orders and drives the ethylene closer to the surface but the adsorbate geometry parameters remain unchanged. Ethylene was activated on clearly defined binding geometries, changing its hybridization from sp2 to sp3 with an elongation (0.16–0.31 Å) of the C=C bond. As a result, on the basis of this theoretical study, δ-MoC(001) is proposed as a potential catalyst for the hydrogenation of olefins, whereas TiC(001) couldmore » be useful for their hydrogenolysis.« less

Authors:
 [1];  [2];  [1];  [3];  [3]
  1. Univ. de Antioquia UdeA, Medellin (Columbia)
  2. Univ. de Medellin, Medellin (Columbia)
  3. 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:
1326743
Report Number(s):
BNL-112634-2016-JA
Journal ID: ISSN 1932-7447; R&D Project: CO027; KC0302010
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 25; 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

Jimenez-Orozco, Carlos, Florez, Elizabeth, Moreno, Andres, Liu, Ping, and Rodriguez, José A. Systematic theoretical study of ethylene adsorption on δ-MoC(001), TiC(001), and ZrC(001) surfaces. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jpcc.6b03106.
Jimenez-Orozco, Carlos, Florez, Elizabeth, Moreno, Andres, Liu, Ping, & Rodriguez, José A. Systematic theoretical study of ethylene adsorption on δ-MoC(001), TiC(001), and ZrC(001) surfaces. United States. https://doi.org/10.1021/acs.jpcc.6b03106
Jimenez-Orozco, Carlos, Florez, Elizabeth, Moreno, Andres, Liu, Ping, and Rodriguez, José A. Tue . "Systematic theoretical study of ethylene adsorption on δ-MoC(001), TiC(001), and ZrC(001) surfaces". United States. https://doi.org/10.1021/acs.jpcc.6b03106. https://www.osti.gov/servlets/purl/1326743.
@article{osti_1326743,
title = {Systematic theoretical study of ethylene adsorption on δ-MoC(001), TiC(001), and ZrC(001) surfaces},
author = {Jimenez-Orozco, Carlos and Florez, Elizabeth and Moreno, Andres and Liu, Ping and Rodriguez, José A.},
abstractNote = {A systematic study of ethylene adsorption over δ-MoC(001), TiC(001), and ZrC(001) surfaces was conducted by means of calculations based on periodic density functional theory. The structure and electronic properties of each carbide pristine surface had a strong influence in the bonding of ethylene. It was found that the metal and carbon sites of the carbide could participate in the adsorption process. As a consequence of this, very different bonding mechanisms were seen on δ-MoC(001) and TiC(001). The bonding of the molecule on the TMC(001) systems showed only minor similarities to the type of bonding found on a typical metal like Pt(111). In general, the ethylene binding energy follow the trend in stability: ZrC(001) < TiC(001) < δ-MoC(001) < Pt(111). The van der Waals correction to the energy produces large binding energy values, modifies the stability orders and drives the ethylene closer to the surface but the adsorbate geometry parameters remain unchanged. Ethylene was activated on clearly defined binding geometries, changing its hybridization from sp2 to sp3 with an elongation (0.16–0.31 Å) of the C=C bond. As a result, on the basis of this theoretical study, δ-MoC(001) is proposed as a potential catalyst for the hydrogenation of olefins, whereas TiC(001) could be useful for their hydrogenolysis.},
doi = {10.1021/acs.jpcc.6b03106},
journal = {Journal of Physical Chemistry. C},
number = 25,
volume = 120,
place = {United States},
year = {2016},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrogenation with molybdenum carbide
journal, March 1998


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


Metal Carbides as Alternative Electrocatalyst Supports
journal, April 2013

  • Liu, Ying; Kelly, Thomas G.; Chen, Jingguang G.
  • ACS Catalysis, Vol. 3, Issue 6
  • DOI: 10.1021/cs4001249

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

Fundamentals of Methanol Synthesis on Metal Carbide Based Catalysts: Activation of CO2 and H2
journal, December 2014

  • Posada-Pérez, Sergio; Viñes, Francesc; Rodriguez, José A.
  • Topics in Catalysis, Vol. 58, Issue 2-3
  • DOI: 10.1007/s11244-014-0355-8

Desulfurization of Thiophene on Au/TiC(001): Au−C Interactions and Charge Polarization
journal, June 2009

  • Rodriguez, José A.; Liu, Ping; Takahashi, Yoshiro
  • Journal of the American Chemical Society, Vol. 131, Issue 24
  • DOI: 10.1021/ja901522a

Benzene adsorption on Mo2C: A theoretical and experimental study
journal, May 2010


Toluene hydrogenation at low temperature using a molybdenum carbide catalyst
journal, February 2011

  • Frauwallner, María-Laura; López-Linares, Francisco; Lara-Romero, J.
  • Applied Catalysis A: General, Vol. 394, Issue 1-2
  • DOI: 10.1016/j.apcata.2010.12.024

A comparative study of ring opening of naphthalene, tetralin and decalin over Mo2C/HY and Pd/HY catalysts
journal, June 2011


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

Steam Reforming on Transition-Metal Carbides from Density-Functional Theory
journal, April 2012


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

  • Rodriguez, José A.; Ramírez, Pedro J.; Asara, Gian Giacomo
  • Angewandte Chemie International Edition, Vol. 53, Issue 42
  • DOI: 10.1002/anie.201407208

Reaction of Ethylene with Clean and Carbide-Modified Mo(110):  Converting Surface Reactivities of Molybdenum to Pt-Group Metals
journal, January 1996

  • Frühberger, B.; Chen, J. G.
  • Journal of the American Chemical Society, Vol. 118, Issue 46
  • DOI: 10.1021/ja960656l

Tungsten and Tungsten Carbide Supported on Activated Carbon:  Surface Structures and Performance for Ethylene Hydrogenation
journal, March 2001

  • Moreno-Castilla, C.; Alvarez-Merino, M. A.; Carrasco-Marín, F.
  • Langmuir, Vol. 17, Issue 5
  • DOI: 10.1021/la001367k

In-situ carbonization synthesis and ethylene hydrogenation activity of ordered mesoporous tungsten carbide
journal, August 2011


A systematic density functional theory study of the electronic structure of bulk and (001) surface of transition-metals carbides
journal, May 2005

  • Viñes, F.; Sousa, C.; Liu, P.
  • The Journal of Chemical Physics, Vol. 122, Issue 17
  • DOI: 10.1063/1.1888370

A Systematic Density Functional Study of Molecular Oxygen Adsorption and Dissociation on the (001) Surface of Group IV−VI Transition Metal Carbides
journal, November 2007

  • Viñes, F.; Sousa, C.; Illas, F.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 45
  • DOI: 10.1021/jp0754987

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

First principles methods using CASTEP
journal, January 2005

  • Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J.
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6
  • DOI: 10.1524/zkri.220.5.567.65075

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

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

The Infra‐Red Absorption Spectra of Ethylene and Tetra‐Deutero‐Ethylene under High Resolution
journal, February 1942

  • Gallaway, W. S.; Barker, E. F.
  • The Journal of Chemical Physics, Vol. 10, Issue 2
  • DOI: 10.1063/1.1723676

Carbon–Carbon and Carbon–Hydrogen Distances in Simple Polyatomic Molecules
journal, January 1955

  • Herzberg, G.; Stoicheff, B. P.
  • Nature, Vol. 175, Issue 4445
  • DOI: 10.1038/175079a0

On the dissociation of molecular hydrogen by Au supported on transition metal carbides: choice of the most active support
journal, January 2011

  • Florez, Elizabeth; Gomez, Tatiana; Rodriguez, José A.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 15
  • DOI: 10.1039/c0cp02882g

Beneficial compressive strain for oxygen reduction reaction on Pt (111) surface
journal, September 2014

  • Kattel, Shyam; Wang, Guofeng
  • The Journal of Chemical Physics, Vol. 141, Issue 12
  • DOI: 10.1063/1.4896604

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

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009


Adsorption of Simple Alkenes on Pt(111) and Pt−Sn Surface Alloys: Bond Strength versus Heat of Adsorption
journal, August 2008

  • Becker, Conrad; Haubrich, Jan; Wandelt, Klaus
  • The Journal of Physical Chemistry C, Vol. 112, Issue 38
  • DOI: 10.1021/jp805089z

Molecular modeling of ethylene decomposition on platinum surfaces
journal, August 1993


Density Functional Theory (DFT) Studies of C1and C2Hydrocarbons Species on Pt Clusters
journal, December 1998

  • Watwe, R. M.; Spiewak, B. E.; Cortright, R. D.
  • Journal of Catalysis, Vol. 180, Issue 2
  • DOI: 10.1006/jcat.1998.2288

Decomposition of ethylene on transition metal surfaces M(111). A comparative DFT study of model reactions for M=Pd, Pt, Rh, Ni
journal, June 2011

  • Basaran, Duygu; Aleksandrov, Hristiyan A.; Chen, Zhao-Xu
  • Journal of Molecular Catalysis A: Chemical, Vol. 344, Issue 1-2
  • DOI: 10.1016/j.molcata.2011.04.019

The chemisorption and dissociation of ethylene on Pt{111} from first principles
journal, March 1999

  • Ge, Q.; King, D. A.
  • The Journal of Chemical Physics, Vol. 110, Issue 10
  • DOI: 10.1063/1.478356

Low temperature adsorption of ethylene and butadiene on platinum and palladium surfaces: A theoretical study of the di?/? competition
journal, January 1991

  • Sautet, Philippe; Paul, Jean -Francois
  • Catalysis Letters, Vol. 9, Issue 3-4
  • DOI: 10.1007/BF00773183

Microcalorimetric Studies of H2, C2H4, and C2H2Adsorption on Pt Powder
journal, June 1998

  • Spiewak, B. E.; Cortright, R. D.; Dumesic, J. A.
  • Journal of Catalysis, Vol. 176, Issue 2
  • DOI: 10.1006/jcat.1998.2047

Assessing the importance of Van der Waals interactions on the adsorption of azobenzene on the rutile TiO2(110) surface
journal, August 2012


Metal-Olefin and -Acetylene Bonding in Complexes
journal, July 1972

  • Hartley, Frank R.
  • Angewandte Chemie International Edition in English, Vol. 11, Issue 7
  • DOI: 10.1002/anie.197205961

Theoretical study of the binding of ethylene to second-row transition metal atoms
journal, November 1992

  • Blomberg, Margareta R. A.; Siegbahn, Per E. M.; Svensson, Mats
  • The Journal of Physical Chemistry, Vol. 96, Issue 24
  • DOI: 10.1021/j100203a040

Hydrogenation Reactions on Au/TiC(001): Effects of AuC Interactions on the Dissociation of H2
journal, July 2010


Novel Au–TiC catalysts for CO oxidation and desulfurization processes
journal, May 2011


Microkinetic Modeling and Reduced Rate Expressions of Ethylene Hydrogenation and Ethane Hydrogenolysis on Platinum
journal, January 2011

  • Salciccioli, M.; Chen, Y.; Vlachos, D. G.
  • Industrial & Engineering Chemistry Research, Vol. 50, Issue 1
  • DOI: 10.1021/ie100364a

Metal carbides and nitrides as potential catalysts for hydroprocessing
journal, February 2003


Hydrogenation and ring opening of naphthalene on bulk and supported Mo2C catalysts
journal, May 2007


Theory of phase stabilities and bonding mechanisms in stoichiometric and substoichiometric molybdenum carbide
journal, October 1999

  • Hugosson, Håkan W.; Eriksson, Olle; Nordström, Lars
  • Journal of Applied Physics, Vol. 86, Issue 7
  • DOI: 10.1063/1.371284

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

Molybdenum carbide catalysed hydrogen production from formic acid – A density functional theory study
journal, January 2014


Synthesis of nanocrystalline molybdenum carbide materials and their characterization
journal, July 2015


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

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

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


Cu-Mo2C/MCM-41: An Efficient Catalyst for the Selective Synthesis of Methanol from CO2
journal, May 2016


    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