Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

Matanovic, Ivana; Garzon, Fernando H.

doi:10.1039/C8CP01643G

Title: Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

Journal Article · 26 April 2018 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/C8CP01643G · OSTI ID:1440453

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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)

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.

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Research Organization:: Los Alamos National Laboratory (LANL)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

Grant/Contract Number:: AC52-06NA25396; AC02-05CH11231

OSTI ID:: 1440453

Report Number(s):: LA-UR-18-21724

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 21 Vol. 20; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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