Metal‐Mediated Nitrogen Doping of Carbon Supports Boosts Hydrogen Production from Ammonia
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.
Authors
- Diego Gianolio (ORCID: https://orcid.org/0000-0002-0708-4492)
- Ben Young (ORCID: https://orcid.org/0000-0001-6451-9360)
- David M. Grant (ORCID: https://orcid.org/0000-0002-6786-7720)
- Luke L. Keenan (ORCID: https://orcid.org/0000-0001-9892-7864)
- Min Zhu (ORCID: https://orcid.org/0000-0003-0023-3747)
- Emerson C. Kohlrausch (ORCID: https://orcid.org/0000-0001-5767-2076)
- Donato Decarolis (ORCID: https://orcid.org/0000-0001-5512-7090)
- Y Chen
- Andreas Weilhard (ORCID: https://orcid.org/0000-0002-0904-5788)
- T Lee
- Mohsen Danaie (ORCID: https://orcid.org/0000-0002-9325-7571)
- Alberto Roldán (ORCID: https://orcid.org/0000-0003-0353-9004)
- Thomas Liddy
- M. Schuster (ORCID: https://orcid.org/0000-0003-3399-7372)
- Graham J. Hutchings
- David A. Duncan
- Gazi N. Aliev
- Andrei N. Khlobystov
- Siqi Wang
- Wolfgang Theis
- Jesum Alves Fernandes
Institutions
- Engineering and Physical Sciences Research Council (GB)
- University of Nottingham (GB)
- Diamond Light Source (GB)
- Research Complex at Harwell (GB)
- Johnson Matthey (United Kingdom) (GB)
- Cardiff University (GB)
- University of Birmingham (GB)
- Cranfield University (GB)
- Cardiff Metropolitan University (GB)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-12-21
- DOI
- https://doi.org/10.1002/anie.202522937
- Citations
- 1
- Primary Topic
- Ammonia Synthesis and Nitrogen Reduction
- Type
- article
- Field-Weighted Citation Impact
- 0.39
Funders
- Engineering and Physical Sciences Research Council