Metal‐Mediated Nitrogen Doping of Carbon Supports Boosts Hydrogen Production from Ammonia

Liddy, Thomas J., Young, Benjamin J., Kohlrausch, Emerson C., Weilhard, Andreas, Aliev, Gazi N., Chen, Yifan, Schuster, Manfred E., Danaie, Mohsen, Keenan, Luke L., Decarolis, Donato, Gianolio, Diego, Wang, Siqi, Zhu, Mingming, Hutchings, Graham J. ORCID: https://orcid.org/0000-0001-8885-1560, Grant, David M., Theis, Wolfgang, Lee, Tien‐Lin, Duncan, David A., Roldan, Alberto ORCID: https://orcid.org/0000-0003-0353-9004, Khlobystov, Andrei N. and Alves Fernandes, Jesum 2025. Metal‐Mediated Nitrogen Doping of Carbon Supports Boosts Hydrogen Production from Ammonia. Angewandte Chemie International Edition , e22937. 10.1002/anie.202522937

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Abstract

Ammonia is an attractive hydrogen carrier, yet its practical use is limited by the need for efficient catalytic decomposition. We demonstrate that in‐situ N‐doping of Ru nanoparticles and graphitized carbon nanofiber supports during reaction produces a sharp increase in hydrogen production during the first 40 h, followed by stable activity. Spectroscopic and microscopic analyses, together with density functional theory simulations, reveal that Ru nitridation is rapid and support‐independent, resulting in a mechanistic shift from the traditional Langmuir–Hinshelwood to a Mars–van Krevelen pathway, further confirmed by isotopic labelling experiments. In contrast, the progressive nitridation of the carbon support, observed via X‐ray photoelectron spectroscopy, modulates the electronic environment of Ru and functions as a dynamic nitrogen reservoir that enables reversible N atoms exchange with the Ru particles, facilitating N desorption from the Ru surface and thereby governing the catalytic activity enhancement. These new findings provide new mechanistic insight into ammonia decomposition and establish progressive nitrogen doping of carbon supports as a strategy for designing efficient metal‐based catalysts for hydrogen production.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Schools > Chemistry Research Institutes & Centres > Cardiff Catalysis Institute (CCI)
Additional Information:	License information from Publisher: LICENSE 1: URL: http://creativecommons.org/licenses/by/4.0/
Publisher:	Wiley
ISSN:	1433-7851
Date of First Compliant Deposit:	5 January 2026
Date of Acceptance:	15 December 2025
Last Modified:	05 Jan 2026 16:45
URI:	https://orca.cardiff.ac.uk/id/eprint/183562

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