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Cooperative spin alignment enhances dimerization in the electrochemical ammonia oxidation reaction

Nature Chemistry (2025)Cite this article

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Abstract

Ammonia has recently attracted growing attention as a promising hydrogen carrier because it can be liquefied and stored in bulk under mild conditions. To fully harness its potential, more efforts are needed to elucidate and control the mechanisms of its decomposition. Here we show that intermediate dimerization processes proceed through a cooperative spin alignment effect between intermediates and can be promoted by the magnetic ordering rearrangement of magnetic substrates. We explored a series of Co/Pt magnetic thin-film catalysts as model materials to investigate spin-sensitive NHx dimerization and eventual enhancement on catalytic activity. Through in situ spectroscopic analysis and theoretical verification, we demonstrate that coupling of N–NH with aligned net magnetic moments is the most favourable with the lowest energy barriers. This provides a precedent for understanding spin kinetics to help improve the catalytic efficiency of electrochemical ammonia decomposition.

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Fig. 1: Identification of magnetization-enhanced AOR in experimental manifestations.
Fig. 2: sXAS diagnosis of spin-sensitive intermediate species.
Fig. 3: Theoretical calculation and verification.
Fig. 4: Magnetic domain structure of Co/Pt thin films and magnetization enhancement mechanism.

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Acknowledgements

This research is supported by the National Research Foundation, Singapore, and A*STAR (Agency for Science, Technology and Research) under its LCER Phase 2 Programme Hydrogen & Emerging Technologies FI, Directed Hydrogen Programme (award number U2305D4003 to Z.J.X.) and the National Research Foundation under its Frontier Competitive Research Programme (NRF-F-CRP-2024-0008 to Z.J.X.). The synchrotron radiation experiments were performed at the Soft X-ray Spectroscopy Beamline at the Australian Synchrotron, with the support of the Singapore-International Synchrotron Access Programme (SG-ISAP) by the National Synchrotron Programme, Singapore to S.Z., T.W. and X.L. We thank the National Nature Science Foundation of China for support (grant number 52072060 to T.L.). S.Z. gratefully acknowledges support from Q. Chen via the National Natural Science Foundation of China (grant number 52125604).

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Author notes

  1. These authors contributed equally: Siyuan Zhu, Qian Wu.

Authors and Affiliations

  1. School of Energy Storage Science and Engineering, North China University of Technology, Beijing, China

    Siyuan Zhu

  2. School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore

    Siyuan Zhu, Qian Wu, Chencheng Dai, Anke Yu, Tianze Wu, Xiaoning Li & Zhichuan J. Xu

  3. Beijing National Laboratory for Molecular Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Xiao Ren

  4. Australian Synchrotron, Clayton, Victoria, Australia

    Anton Tadich

  5. National Engineering Research Center of Electromagnetic Radiation Control Materials, University of Electronic Science and Technology of China, Chengdu, China

    Dengfu Deng & Tao Liu

  6. Faculty of Materials and Manufacturing, Beijing University of Technology, Key Lab of Advanced Functional Materials, Ministry of Education, Beijing, China

    Qiong Wu & Ming Yue

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Contributions

Z.J.X. conceived the study and supervised the project. S.Z. designed and performed experiments. S.Z., A.Y., T.W., Q.W. and Z.J.X. analysed and interpreted data. X.R., D.D., T.L., Q.W. and M.Y. fabricated the thin films and performed thin-film characterization. Z.J.X. and S.Z. proposed the mechanism. Q.W. performed the theoretical calculations. S.Z., T.W., X.L. and A.T. performed the sXAS experiments. S.Z., C.D. and Z.J.X. wrote and edited the paper. All authors reviewed and edited the paper.

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Correspondence to Zhichuan J. Xu.

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Nature Chemistry thanks Leanne Chen, Ping Xu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Zhu, S., Wu, Q., Dai, C. et al. Cooperative spin alignment enhances dimerization in the electrochemical ammonia oxidation reaction. Nat. Chem. (2025). https://doi.org/10.1038/s41557-025-01900-1

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