Revealing the activity of Co3Mo3N and Co3Mo3N0.5 as electrocatalysts for the hydrogen evolution reaction

Sun, Y., Wang, L., Guselnikova, O., Semyonov, O., Fraser, J., Zhou, Y., López, N. and Ganin, A. Y. (2022) Revealing the activity of Co3Mo3N and Co3Mo3N0.5 as electrocatalysts for the hydrogen evolution reaction. Journal of Materials Chemistry A, 10(2), pp. 855-861. (doi: 10.1039/D1TA08389A)

Abstract

The hydrogen evolution reaction (HER) from water is governed by electrocatalysts used. Multiple factors such as crystal structure, composition and morphology dictate the final catalytic performance. However, as multicomponent materials are developed to replace noble metals in the HER, it has become increasingly difficult to identify intrinsically active materials. Hence, there is an imperative for phase-pure catalysts to be synthetized and tested without obscuring contributions from impurities or substrates. Herein, we demonstrate that phase-pure, unsupported Co3Mo3N achieves a competitively low overpotential (OVP) of 108 ± 8 mV at 10 mA cm‒2 in 0.5 M H2SO4. Density functional theory (DFT) reveals weakly binding metal sites as the catalytic centres for the HER in the nitride. Remarkably, the N-deficient Co3Mo3N0.5 shows similar electrochemical properties but has limited chemical stability under cathodic bias. Thus, even though nitrogen sites play only a minor role in catalytic performance, their occupancy is crucial for the stability of nitride catalysts in the corrosive electrolyte. The composite of Co3Mo3N on Ni-foam sustains 10 ± 0.7 mA cm‒2 at applied potential of just 20 mV over extended time, highlighting the utility of nitrides for future design of stable and active HER catalytic systems.

• Item Type: Articles
• Additional Information: A.Y.G. acknowledges the University of Glasgow and EPSRC (EP/N509668/1) for supporting this work. Y.S. thanks China Scholarship Council for providing him with the scholarship. Y.Z. acknowledges the support of the Basic and Applied Research Project (No. 202102020495) of Guangzhou. L.W., Y.Z. and N.L. appreciate the National Super-Computer Center in Guangzhou (China) and the Barcelona Supercomputing Center (Spain) for providing computational resource. O.G. and O.S. acknowledge the support from the Tomsk Polytechnic University Enhancement programme.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sun, Youyi and Ganin, Dr Alexey and Fraser, Mr James
• Authors: Sun, Y., Wang, L., Guselnikova, O., Semyonov, O., Fraser, J., Zhou, Y., López, N., and Ganin, A. Y.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of Materials Chemistry A
• Publisher: Royal Society of Chemistry
• ISSN: 2050-7488
• ISSN (Online): 2050-7496
• Published Online: 13 December 2021
• Copyright Holders: Copyright © 2021 The Royal Society of Chemistry
• First Published: First published in Journal of Materials Chemistry A 10(2): 855-861
• Publisher Policy: Reproduced under a Creative Commons License

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
172865		EPSRC DTP 16/17 and 17/18	Mary Beth Kneafsey	Engineering and Physical Sciences Research Council (EPSRC)	EP/N509668/1	Research and Innovation Services