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Title: CO, CO 2, and H 2 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 H 2 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 CO 2 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 CO 2 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 ofmore » the CO 2 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.« 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 Lab. (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) (SC-22); 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:
Journal Article: 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. doi: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. doi: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},
issn = {1932-7447},
number = 14,
volume = 123,
place = {United States},
year = {2019},
month = {3}
}

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