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High entropy spinel oxide for efficient electrochemical oxidation of ammonia

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Abstract

Ammonia has emerged as a promising energy carrier owing to its carbon neutral content and low expense in long-range transportation. Therefore, development of a specific pathway to release the energy stored in ammonia is therefore in urgent demand. Electrochemical oxidation provides a convenient and reliable route to attain efficient utilization of ammonia. Here, we report that the high entropy (Mn, Fe, Co, Ni, Cu)3O4 oxides can achieve high electrocatalytic activity for ammonia oxidation reaction (AOR) in non-aqueous solutions. The AOR onset overpotential of (Mn, Fe, Co, Ni, Cu)3O4 is 0.70 V, which is nearly 0.2 V lower than that of their most active single metal cation counterpart. The mass spectroscopy study reveals that (Mn, Fe, Co, Ni, Cu)3O4 preferentially oxidizes ammonia to environmentally friendly diatomic nitrogen with a Faradic efficiency of over 85%. The X-ray photoelectron spectroscopy (XPS) result indicates that the balancing metal d-band of Mn and Cu cations helps retain a long-lasting electrocatalytic activity. Overall, this work introduces a new family of earth-abundant transition metal high entropy oxide electrocatalysts for AOR, thus heralding a new paradigm of catalyst design for enabling ammonia as an energy carrier.

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Acknowledgements

This research is partially supported by the Energy Research Seed Grant from Duke Energy Initiative, the National Science Foundation (Nos. CHE-1565657 and CHE-1954838) and the Army Research Office (W911NFN-18-2-004). S. H. and P. N. are both supported by fellowships from Department of Chemistry at Duke University. This work was performed in part at the Duke University Shared Materials Instrumentation Facility (SMIF), a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), which is supported by the National Science Foundation (award number ECCS-2025064) as part of the National Nanotechnology Coordinated Infrastructure (NNCI).

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Authors and Affiliations

  1. Department of Chemistry, Duke University, Durham, NC, 27708, USA

    Shi He, Vasishta Somayaji, Mengdi Wang, Seung-Hoon Lee, Zhijia Geng, Siyuan Zhu, Peter Novello & Jie Liu

  2. U.S. Army Research Office, P.O. Box 12211, Research Triangle Park, NC, 27709, USA

    Chakrapani V. Varanasi

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  1. Shi He
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  2. Vasishta Somayaji
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He, S., Somayaji, V., Wang, M. et al. High entropy spinel oxide for efficient electrochemical oxidation of ammonia. Nano Res. 15, 4785–4791 (2022). https://doi.org/10.1007/s12274-021-3665-8

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