Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study
Abstract
We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate for the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.
- Authors:
-
[1];
[2]
- Univ. of New Mexico, Albuquerque, NM (United States). Chemical and Biological Engineering Dept. Center for Micro-Engineered Materials; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Univ. of New Mexico, Albuquerque, NM (United States). Chemical and Biological Engineering Dept. Center for Micro-Engineered Materials; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1440453
- Alternate Identifier(s):
- OSTI ID: 1437516
- Report Number(s):
- LA-UR-18-21724
Journal ID: ISSN 1463-9076
- Grant/Contract Number:
- AC52-06NA25396; AR 1261-4005; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 20; Journal Issue: 21; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Material Science
Citation Formats
Matanovic, Ivana, and Garzon, Fernando H. Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study. United States: N. p., 2018.
Web. doi:10.1039/C8CP01643G.
Matanovic, Ivana, & Garzon, Fernando H. Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study. United States. https://doi.org/10.1039/C8CP01643G
Matanovic, Ivana, and Garzon, Fernando H. Thu .
"Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study". United States. https://doi.org/10.1039/C8CP01643G. https://www.osti.gov/servlets/purl/1440453.
@article{osti_1440453,
title = {Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study},
author = {Matanovic, Ivana and Garzon, Fernando H.},
abstractNote = {We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate for the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.},
doi = {10.1039/C8CP01643G},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 21,
volume = 20,
place = {United States},
year = {Thu Apr 26 00:00:00 EDT 2018},
month = {Thu Apr 26 00:00:00 EDT 2018}
}
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