Active site switching on high entropy phosphides as bifunctional oxygen electrocatalysts for rechargeable/robust Zn-air battery
He R, Wang S, Yang L, Horta S, Ding Y, Di C, Zhang X, Xu Y, Ibáñez M, Zhou Y, Mebs S, Dau H, Hausmann JN, Huo W, Menezes PW, Cabot A. 2024. Active site switching on high entropy phosphides as bifunctional oxygen electrocatalysts for rechargeable/robust Zn-air battery. Energy and Environmental Science.
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Journal Article
| Epub ahead of print
| English
Scopus indexed
Author
He, Ren;
Wang, Shiqi;
Yang, Linlin;
Horta, SharonaISTA;
Ding, Yang;
Di, Chong;
Zhang, Xuesong;
Xu, Ying;
Ibáñez , MariaISTA 
;
Zhou, Yingtang;
Mebs, Stefan;
Dau, Holger
All
;
Zhou, Yingtang;
Mebs, Stefan;
Dau, Holger
All
Department
Abstract
High-entropy materials (HEMs) offer a quasi-continuous spectrum of active sites and have generated great expectations in fields such as electrocatalysis and energy storage. Despite their potential, the complex composition and associated surface phenomena of HEMs pose challenges to their rational design and development. In this context, we have synthesized FeCoNiPdWP high entropy phosphide (HEP) nanoparticles using a low-temperature colloidal method, and explored their application as bifunctional electrocatalysts for the oxygen evolution and reduction reactions (OER/ORR). Our analysis provides a detailed understanding of the individual roles and transformations of each element during OER/ORR operation. Notably, the HEPs exhibit an exceptionally low OER overpotential of 227 mV at 10 mA cm−2, attributed to the reconstructed HEP surface into a FeCoNiPdW high entropy oxyhydroxide with high oxidation states of Fe, Co, and Ni serving as the active sites. Additionally, Pd and W play crucial roles in modulating the electronic structure to optimize the adsorption energy of oxygen intermediates. For the ORR, Pd emerges as the most active component. In the reconstructed catalyst, the strong d–d orbital coupling of especially Pd, Co, and W fine-tunes ORR electron transfer pathways, delivering an ORR half-wave potential of 0.81 V with a pure four-electron reduction mechanism. The practicality of these HEPs catalysts is showcased through the assembly of aqueous zinc–air batteries. These batteries demonstrate a superior specific capacity of 886 mA h gZn−1 and maintain excellent stability over more than 700 hours of continuous operation. Overall, this study not only elucidates the role of each element in HEMs but also establishes a foundational framework for the design and development of next-generation bifunctional oxygen catalysts, broadening the potential applications of these complex materials in advanced energy systems.
Publishing Year
Date Published
2024-08-22
Journal Title
Energy and Environmental Science
Publisher
Royal Society of Chemistry
Acknowledgement
This work was financially supported by the SyDEC at project from the Spanish MCIN/AEI/FEDER (PID2022-136883OB-C22) and Generalitat de Catalunya 2021SGR01581. J. N. H. and P. W. M. acknowledge support from the German Federal Ministry of Education and Research in the framework of the project “Catlab” (03EW0015A/B). L. Yang thanks the China Scholarship Council (CSC) for the scholarship support (202008130132). This work was supported by the European Union Horizon 2020 research and innovation program (No. 857470) and the European Regional Development Fund via the Foundation for Polish Science International Research Agenda PLUS program (No. MAB PLUS/2018/8). The publication was created within the framework of the project of the Minister of Science and Higher Education, Poland “Support for the activities of Centres of Excellence established in Poland under Horizon 2020” under contract no. MEiN/2023/DIR/3795. H. D. and S. M. thank the German Federal Ministry of Education and Research (BMBF) for supporting the Live-XAS project (05K22KE1) and the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) for support under Germany's Excellence Strategy – EXC 2008/1 – 390540038 – UniSysCat. The authors thank the Helmholtz-Zentrum Berlin (HZB) for beamtime allocation at the KMC-3 synchrotron beamline of the BESSY synchrotron in Berlin-Adlershof and Dr Ivo Zizak as well as Dr Michael Haumann for technical support.
ISSN
eISSN
IST-REx-ID
Cite this
He R, Wang S, Yang L, et al. Active site switching on high entropy phosphides as bifunctional oxygen electrocatalysts for rechargeable/robust Zn-air battery. Energy and Environmental Science. 2024. doi:10.1039/d4ee01912a
He, R., Wang, S., Yang, L., Horta, S., Ding, Y., Di, C., … Cabot, A. (2024). Active site switching on high entropy phosphides as bifunctional oxygen electrocatalysts for rechargeable/robust Zn-air battery. Energy and Environmental Science. Royal Society of Chemistry. https://doi.org/10.1039/d4ee01912a
He, Ren, Shiqi Wang, Linlin Yang, Sharona Horta, Yang Ding, Chong Di, Xuesong Zhang, et al. “Active Site Switching on High Entropy Phosphides as Bifunctional Oxygen Electrocatalysts for Rechargeable/Robust Zn-Air Battery.” Energy and Environmental Science. Royal Society of Chemistry, 2024. https://doi.org/10.1039/d4ee01912a.
R. He et al., “Active site switching on high entropy phosphides as bifunctional oxygen electrocatalysts for rechargeable/robust Zn-air battery,” Energy and Environmental Science. Royal Society of Chemistry, 2024.
He R, Wang S, Yang L, Horta S, Ding Y, Di C, Zhang X, Xu Y, Ibáñez M, Zhou Y, Mebs S, Dau H, Hausmann JN, Huo W, Menezes PW, Cabot A. 2024. Active site switching on high entropy phosphides as bifunctional oxygen electrocatalysts for rechargeable/robust Zn-air battery. Energy and Environmental Science.
He, Ren, et al. “Active Site Switching on High Entropy Phosphides as Bifunctional Oxygen Electrocatalysts for Rechargeable/Robust Zn-Air Battery.” Energy and Environmental Science, Royal Society of Chemistry, 2024, doi:10.1039/d4ee01912a.
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