Molybdenum nitrides as oxygen reduction reaction catalysts: Structural and electrochemical studies
Abstract
Monometallic (δ-MoN, Mo5N6, and Mo2N) and bimetallic molybdenum nitrides (Co0.6Mo1.4N2) were investigated as electrocatalysts for the oxygen reduction reaction (ORR), which is a key half-reaction in hydrogen fuel cells. Monometallic hexagonal molybdenum nitrides are found to exhibit improved activities over rock salt type molybdenum nitride (γ-Mo2N), suggesting that improvements are due to either the higher molybdenum valence or a more favorable coordination environment in the hexagonal structures. Further enhancements in activity were found for hexagonal bimetallic cobalt molybdenum nitride (Co0.6Mo1.4N2), resulting in a modest onset potential of 0.713 V versus reversible hydrogen electrode (RHE). Co0.6Mo1.4N2 exhibits good stability in acidic environments, and in the potential range lower than 0.5 V versus RHE, the ORR appears to proceed via a four-electron mechanism based on the analysis of rotating disc electrode results. A redetermination of the structures of the binary molybdenum nitrides was carried out using neutron diffraction data, which is far more sensitive to nitrogen site positions than X-ray diffraction data. In conclusion, the revised monometallic hexagonal nitride structures all share many common features with the Co0.6Mo1.4N2 structure, which has alternating layers of cations in octahedral and trigonal prismatic coordination, and are thus not limited to only trigonal prismatic Mo environmentsmore »
- Authors:
-
- Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1330514
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 5; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Cao, Bingfei, Neuefeind, Joerg C., Adzic, Radoslav R., and Khalifah, Peter G. Molybdenum nitrides as oxygen reduction reaction catalysts: Structural and electrochemical studies. United States: N. p., 2015.
Web. doi:10.1021/ic5024778.
Cao, Bingfei, Neuefeind, Joerg C., Adzic, Radoslav R., & Khalifah, Peter G. Molybdenum nitrides as oxygen reduction reaction catalysts: Structural and electrochemical studies. United States. https://doi.org/10.1021/ic5024778
Cao, Bingfei, Neuefeind, Joerg C., Adzic, Radoslav R., and Khalifah, Peter G. 2015.
"Molybdenum nitrides as oxygen reduction reaction catalysts: Structural and electrochemical studies". United States. https://doi.org/10.1021/ic5024778. https://www.osti.gov/servlets/purl/1330514.
@article{osti_1330514,
title = {Molybdenum nitrides as oxygen reduction reaction catalysts: Structural and electrochemical studies},
author = {Cao, Bingfei and Neuefeind, Joerg C. and Adzic, Radoslav R. and Khalifah, Peter G.},
abstractNote = {Monometallic (δ-MoN, Mo5N6, and Mo2N) and bimetallic molybdenum nitrides (Co0.6Mo1.4N2) were investigated as electrocatalysts for the oxygen reduction reaction (ORR), which is a key half-reaction in hydrogen fuel cells. Monometallic hexagonal molybdenum nitrides are found to exhibit improved activities over rock salt type molybdenum nitride (γ-Mo2N), suggesting that improvements are due to either the higher molybdenum valence or a more favorable coordination environment in the hexagonal structures. Further enhancements in activity were found for hexagonal bimetallic cobalt molybdenum nitride (Co0.6Mo1.4N2), resulting in a modest onset potential of 0.713 V versus reversible hydrogen electrode (RHE). Co0.6Mo1.4N2 exhibits good stability in acidic environments, and in the potential range lower than 0.5 V versus RHE, the ORR appears to proceed via a four-electron mechanism based on the analysis of rotating disc electrode results. A redetermination of the structures of the binary molybdenum nitrides was carried out using neutron diffraction data, which is far more sensitive to nitrogen site positions than X-ray diffraction data. In conclusion, the revised monometallic hexagonal nitride structures all share many common features with the Co0.6Mo1.4N2 structure, which has alternating layers of cations in octahedral and trigonal prismatic coordination, and are thus not limited to only trigonal prismatic Mo environments (as was originally postulated for δ-MoN).},
doi = {10.1021/ic5024778},
url = {https://www.osti.gov/biblio/1330514},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 5,
volume = 54,
place = {United States},
year = {Mon Feb 09 00:00:00 EST 2015},
month = {Mon Feb 09 00:00:00 EST 2015}
}
Web of Science
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