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Title: Binding and activation of ethylene on tungsten carbide and platinum surfaces

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/C9CP03214B · OSTI ID:1546046

In this paper, density functional calculations were used to evaluate the ability of cubic and hexagonal phases of tungsten carbide to bind ethylene, as a model compound of unsaturated hydrocarbons, since its adsorption is the first step in important catalytic processes. The calculations give the following trend in stability: α-WC(0001)-C > α-WC(0001)-W > Pt(111) > γ-WC(001), with the binding energy varying in the range of -0.72 to -2.91 eV. The sub-surface layers play a crucial role in the binding, favoring a charge reorganization at extended ranges (above 6 Å) from bulk towards the surface, however, the electronic structure of the surface was modified only in the topmost layer. The surface sites for geometric C2H4 activation were identified, leading to a surface distortion due to an upwards shifting of surface atoms in the range 0.13–0.61 Å observed in Pt(111), α-WC(0001)-C, and γ-WC(001), with distortion energies of 0.13, 0.15 and 0.61 eV, respectively. The activation of C2H4 on tungsten carbides was compared with other transition metal carbide surfaces, which leads to a general classification of the elongation of carbon–carbon bond into a set of only three groups. If the interest is to activate ethylene C=C bond, the surface sites and the binding modes should be those of the groups II and III. The infrared spectra show mainly four useful signals as a fingerprint to support and complement future experiments. The results of this work indicate that the α-WC-W surface could be directly responsible for the catalytic performance, while the binding of olefins on α-WC-C could cause surface poisoning. The metastable γ-WC(001) surface could be a promising system as compared to the known α-WC(0001) surface, but challenges arise regarding its synthesis, stability and catalytic performance. Finally, these results pave the way to address further experimental and theoretical studies focused on the hydrogenation of ethylene and more complex unsaturated hydrocarbons.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE
Grant/Contract Number:
SC0012704
OSTI ID:
1546046
Alternate ID(s):
OSTI ID: 1545402
Report Number(s):
BNL-211916-2019-JAAM; PPCPFQ
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 21, Issue 31; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

References (40)

Water-Gas-Shift Reaction on Molybdenum Carbide Surfaces:  Essential Role of the Oxycarbide journal October 2006
Density functional study of H2O adsorption and dissociation on WC(0001) journal July 2014
A Au monolayer on WC(0001) with unexpected high activity towards CO oxidation journal January 2018
Surface science and catalysis of ethylene hydrogenation journal January 1995
Interactions between hydrogen and tungsten carbide: a first principles study journal January 2014
Theoretical study of the stability of cubic WC journal September 1988
A systematic density functional theory study of the electronic structure of bulk and (001) surface of transition-metals carbides journal May 2005
Acetylene and Ethylene Adsorption on a β-Mo 2 C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions journal September 2017
Kinetics and thermodynamics of H 2 O dissociation and CO oxidation on the Pt/WC (0001) surface: A density functional theory study journal February 2017
DFT study of platinum and palladium overlayers on tungsten carbide: Structure and electrocatalytic activity toward hydrogen oxidation/evolution reaction journal April 2013
Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrogenation with molybdenum carbide journal March 1998
Adsorption and reaction of CO and H 2 O on WC(0001) surface: A first-principles investigation journal January 2018
Special points for Brillouin-zone integrations journal June 1976
Adsorption of Hexacyclic C 6 H 6 , C 6 H 8 , C 6 H 10 , and C 6 H 12 on a Mo-Terminated α-Mo 2 C (0001) Surface journal March 2013
Tungsten and Tungsten Carbide Supported on Activated Carbon:  Surface Structures and Performance for Ethylene Hydrogenation journal March 2001
Structural studies of WC(0001) and the adsorption of benzene journal November 1998
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
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
Hydrogenation and ring opening of naphthalene on bulk and supported Mo2C catalysts journal May 2007
Ethylene hydrogenation catalysis on Pt(111) single-crystal surfaces studied by using mass spectrometry and in situ infrared absorption spectroscopy journal October 2016
Ethylene Hydrogenation on Pt(111) Monitored in Situ at High Pressures Using Sum Frequency Generation journal January 1996
Control of the catalytic activity of tungsten carbides I. Preparation of highly dispersed tungsten carbides journal June 1986
Catalysis by transition metal carbides IV. Mechanism of ethylene hydrogenation and the nature of active sites on tantalum monocarbide journal January 1982
Surface Chemistry of Transition Metal Carbides journal January 2005
A fast and robust algorithm for Bader decomposition of charge density journal June 2006
Selective catalytic behaviour of tungsten carbide in the liquid-phase hydrogenation of organic compounds journal January 1973
A theoretical understanding on the CO-tolerance mechanism of the WC(0001) supported Pt monolayer: Some improvement strategies journal December 2016
CO, CO 2 , and H 2 Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon and Metal Sites journal March 2019
Improved grid-based algorithm for Bader charge allocation journal January 2007
About one stable and three metastable eutectic microconstituents in the Fe–W–C system journal July 2008
Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis journal August 1973
Is platinum necessary for efficient hydrogen evolution? – DFT study of metal monolayers on tungsten carbide journal December 2013
Benzene adsorption on Mo2C: A theoretical and experimental study journal May 2010
Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces journal June 2016
Catalytic activities of TiC, WC, and TaC for hydrogenation of ethylene journal October 1979
Electron spectroscopic study of the interaction of WC(0001) with different adsorbates (C6H6, CO and NO) journal March 1998
Synthesis of nanocrystalline molybdenum carbide materials and their characterization journal July 2015
Surface Chemistry of Transition Metal Carbides journal April 2005
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021

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