Mixed Close-Packed Cobalt Molybdenum Nitrides as Non-noble Metal Electrocatalysts for the Hydrogen Evolution Reaction
Abstract
A two-step solid-state reaction for preparing cobalt molybdenum nitride with a nanoscale morphology has been used to produce a highly active and stable electrocatalyst for the hydrogen evolution reaction (HER) under acidic conditions that achieves an iR-corrected current density of 10 mA cm(-2) at -0.20 V vs RHE at low catalyst loadings of 0.24 mg/cm(2) in rotating disk experiments under a H2 atmosphere. Neutron powder diffraction and pair distribution function (PDF) studies have been used to overcome the insensitivity of X-ray diffraction data to different transition-metal nitride structural polytypes and show that this cobalt molybdenum nitride crystallizes in space group P63/mmc with lattice parameters of a = 2.85176(2) Å and c = 10.9862(3) Å and a formula of Co0.6Mo1.4N2. This space group results from the four-layered stacking sequence of a mixed close-packed structure with alternating layers of transition metals in octahedral and trigonal prismatic coordination and is a structure type for which HER activity has not previously been reported. Based on the accurate bond distances obtained from time-of-flight neutron diffraction data, it is determined that the octahedral sites contain a mixture of divalent Co and trivalent Mo, while the trigonal prismatic sites contain Mo in a higher oxidation state. X-ray photoelectron spectroscopy (XPS) studies confirm that at the sample surface nitrogen is present and N-H moieties are abundant.
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Bimetallic nitrides show bifunctional catalytic activities because the coordination of two metal species could provide both-way rich active sites and improved electronic conductivity.
“Compared with single-metal nitrides, bimetallic nitrides show bifunctional catalytic activities because the coordination of two metal species could provide both-way rich active sites and improved electronic conductivity, which result in enhanced water-splitting performance.21−23”
From Electronic Structure Tuning in Ni<sub>3</sub>FeN/r-GO Aerogel toward Bifunctional Electrocatalyst for Overall Water Splitting (2018) · cites this paper as [21]
Single-metal nitrides have not been reported to be bifunctional.
“However, single-metal nitrides have not been reported to be bifunctional.”
From Electronic Structure Tuning in Ni<sub>3</sub>FeN/r-GO Aerogel toward Bifunctional Electrocatalyst for Overall Water Splitting (2018) · cites this paper as [21]
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- Authors
- Cao, B., Veith, G. M., Neuefeind, J. C., Adzic, R. R., & Khalifah, P. G.
- Affiliations
- Brookhaven National Laboratory (US)
- Oak Ridge National Laboratory (US)
- Chemistry Department, Brookhaven National Laboratory, Upton, New York 11793, United States
- Corresponding author
- Khalifah, Peter G.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2013-12-11
- Volume
- 135
- Issue
- 51
- Pages
- 19186-19192
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2320339889
- Cited by
- 998
- References
- 2
- Citations by year
- 2026: 20 · 2025: 47 · 2024: 59 · 2023: 50 · 2022: 63 · 2021: 78 · 2020: 101 · 2019: 104 · 2018: 133 · 2017: 111 · 2016: 102 · 2015: 82 · 2014: 48
- FWCI
- 28.13
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Materials Science › Materials Chemistry › Hydrogen Storage and Materials
- Physical Sciences › Chemical Engineering › Catalysis › Ammonia Synthesis and Nitrogen Reduction
- Keywords
- cobalt molybdenum nitride, hydrogen evolution reaction, non-noble metal electrocatalysts, acidic electrocatalysis, P6_3/mmc space group, crystal structure determination, bond lengths, oxidation state distribution, solid-state synthesis, nanocatalysts
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