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Electronic modulation of Ni2P through anion and cation substitution toward highly efficient oxygen evolution

通过阴、 阳离子取代调控Ni2P的电子结构用于高效氧析出反应

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Abstract

Rationally designed oxygen evolution reaction (OER) catalysts with structural and compositional superiorities are essential for energy-related electrocatalytic techniques. Transition-metal phosphides have been used as promising electrocatalysts for OER. Incorporating heteroatoms into the lattice can induce lattice distortion and redistribution of electron density, consequently modifying the electronic structure and improving catalytic performance. Herein, Fe- and S-substituted Ni2P uniformly dispersed throughout porous carbon substrate (Ni—Fe—P—S@C) was rationally designed through transformation from the pre-synthesized NiFe-metal organic frameworks (NiFe-MOFs) by partial sulfurization and subsequent phosphorization process. Experimental results and density functional theory calculations showed that Fe and S incorporation could modulate the electronic structure of Ni2P and alter the adsorption free energies of reaction intermediates, contributing to admirable electrocatalytic activity and stability toward OER. Notably, the in-situ formed partially oxidized surface was vital to further improve the local environment. This proposed cation- and anion-substitution strategy will bring new inspiration to boost the electrocatalytic performance of transition-metal-based electrocatalysts for energy conversion applications.

摘要

合理设计具有结构和组分优势的氧析出反应(OER)催化剂对电催化能源转换技术至关重要. 过渡金属磷化物是较有前景的OER催化剂. 将杂原子引入过渡金属磷化物的晶格可以引起晶格畸变和电子密度的重新分布, 从而改变电子结构, 提高催化性能. 在此基础上, 本文通过部分硫化和随后的磷化过程, 将预先合成的镍铁金属有机框架(NiFe-MOFs)转化为均匀分散在多孔碳基底上的Fe和S取代的Ni2P(Ni–Fe–P–S@C). 实验结果和密度泛函理论计算表明, Fe和S的掺入可以调节Ni2P的电子结构, 改变反应中间体的吸附自由能, 使得Ni–Fe–P–S@C 具有良好的OER催化活性和稳定性. 值得注意的是, 原位形成的部分氧化的表面对改善局部环境并进一步提升催化活性至关重要. 本文提出的阴、阳离子取代策略为提高过渡金属基催化剂的电催化性能带来了新的启示.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2017YFA0206701) and the National Natural Science Foundation of China (51825201).

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Authors and Affiliations

  1. Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering, Peking University, Beijing, 100871, China

    Kexin Zhang  (张珂新), Zitao Zhang  (张子韬), Haoming Shen  (沈昊明), Yanqun Tang  (唐彦群), Zibin Liang  (梁子彬) & Ruqiang Zou  (邹如强)

  2. Institute of Clean Energy, Peking University, Beijing, 100871, China

    Kexin Zhang  (张珂新), Zitao Zhang  (张子韬), Yanqun Tang  (唐彦群), Zibin Liang  (梁子彬) & Ruqiang Zou  (邹如强)

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  1. Kexin Zhang  (张珂新)
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  2. Zitao Zhang  (张子韬)
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  3. Haoming Shen  (沈昊明)
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  4. Yanqun Tang  (唐彦群)
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Contributions

Author contributions Zhang K designed and engineered the samples, performed the experiments, and wrote the manuscript; Zhang Z performed the experiments; Shen H performed theoretical calculations; Tang Y performed XPS experiments; Liang Z drew the scheme; Zou R administrated the project, supervised the experiments and reviewed the manuscript. All authors contributed to the general discussion.

Corresponding author

Correspondence to Ruqiang Zou  (邹如强).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Supporting data are available in the online version of the paper.

Kexin Zhang obtained her BS degree from the School of Chemistry and Chemical Engineering, Beijing Institute of Technology in 2017. Currently she is a PhD candidate under the supervision of Prof. Ruqiang Zou at the School of Materials Science and Engineering, Peking University. Her research interests focus on the synthesis and design of functional nanomaterials based on metal-organic frameworks for energy conversion applications.

Ruqiang Zou is currently a professor at the School of Materials Science and Engineering, Peking University, China. He received his PhD degree in engineering in 2008 from Kobe University and the National Institute of Advanced Industrial Science and Technology, Japan. He held the Japan Society for the Promotion of Science (JSPS) Younger Scientist during his doctoral course and was a Director’s Postdoc Fellow at Los Alamos National Laboratory from 2008 to 2010. His research interests focus on the controllable preparation and application of hierarchically porous functional materials for energy and environmental applications.

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Zhang, K., Zhang, Z., Shen, H. et al. Electronic modulation of Ni2P through anion and cation substitution toward highly efficient oxygen evolution. Sci. China Mater. 65, 1522–1530 (2022). https://doi.org/10.1007/s40843-021-1947-8

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  • DOI: https://doi.org/10.1007/s40843-021-1947-8

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