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Title: 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 » (as was originally postulated for δ-MoN).« less

Authors:
 [1];  [2];  [3];  [1]
  1. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. 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}
}

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Works referenced in this record:

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journal, October 2004


Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs
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Mixed Close-Packed Cobalt Molybdenum Nitrides as Non-noble Metal Electrocatalysts for the Hydrogen Evolution Reaction
journal, December 2013


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journal, May 2009


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journal, April 1997


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journal, August 2012


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journal, February 2013


Works referencing / citing this record:

Phase Stability and Compressibility of 3R-MoN2 at High Pressure
journal, July 2019


Emerging new generation electrocatalysts for the oxygen reduction reaction
journal, January 2016


Recent advances in nanostructured metal nitrides for water splitting
journal, January 2018


Recent advancements in Pt-nanostructure-based electrocatalysts for the oxygen reduction reaction
journal, January 2019


Geometries, electronic properties and stability of molybdenum and tungsten nitrides low-index surfaces
journal, September 2018


Earth-Abundant Nanomaterials for Oxygen Reduction
journal, December 2015


Synergism of molybdenum nitride and palladium for high-efficiency formic acid electrooxidation
journal, January 2018


The Electrocatalytic Stability Investigation of a Proton Manager MOF for the Oxygen Reduction Reaction in Acidic Media
journal, November 2018


Molecular titanium nitrides: nucleophiles unleashed
journal, January 2017


Dual-Functional N Dopants in Edges and Basal Plane of MoS 2 Nanosheets Toward Efficient and Durable Hydrogen Evolution
journal, December 2016


Transition-metal-oxide-based catalysts for the oxygen reduction reaction
journal, January 2018


Defect Engineering of Molybdenum-Based Materials for Electrocatalysis
journal, November 2020