Multistage orbital hybridization induced by multisite exchange interactions in high-entropy perovskites for high oxygen evolution reaction

Zuozheng Xu; Lijing Wang; Yichen Liu; Yaqi Liu; Yun Shan; Tianle Chen; Guangqing Liu; Yang Shao; Lizhe Liu; Xinglong Wu

doi:10.1016/j.jcis.2023.07.182

Multistage orbital hybridization induced by multisite exchange interactions in high-entropy perovskites for high oxygen evolution reaction

J Colloid Interface Sci. 2023 Dec:651:376-383. doi: 10.1016/j.jcis.2023.07.182. Epub 2023 Jul 29.

Authors

Zuozheng Xu¹, Lijing Wang², Yichen Liu³, Yaqi Liu³, Yun Shan⁴, Tianle Chen⁵, Guangqing Liu⁵, Yang Shao⁵, Lizhe Liu⁶, Xinglong Wu⁷

Affiliations

¹ Jiangsu Key Laboratory for Nanotechnology and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, People's Republic of China; Nanjing Key Laboratory of Advanced Functional Materials, Nanjing Xiaozhuang University, Nanjing 211171, People's Republic of China.
² Henan Engineering Center of New Energy Battery Materials, Henan D&A Engineering Center of Advanced Battery Materials, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000, People's Republic of China.
³ Jiangsu Key Laboratory for Nanotechnology and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, People's Republic of China.
⁴ Nanjing Key Laboratory of Advanced Functional Materials, Nanjing Xiaozhuang University, Nanjing 211171, People's Republic of China. Electronic address: yshan@njxzc.edu.cn.
⁵ Nanjing Key Laboratory of Advanced Functional Materials, Nanjing Xiaozhuang University, Nanjing 211171, People's Republic of China.
⁶ Jiangsu Key Laboratory for Nanotechnology and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, People's Republic of China. Electronic address: lzliu@nju.edu.cn.
⁷ Jiangsu Key Laboratory for Nanotechnology and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, People's Republic of China. Electronic address: hkxlwu@nju.edu.cn.

PMID: 37544226
DOI: 10.1016/j.jcis.2023.07.182

Abstract

The oxygen evolution reaction (OER) has garnered considerable attention because of its promising prospects in electrochemical energy conversion applications, but a significant challenge is faced by the insufficient understanding of sluggish OER kinetics. In fact, the intrinsic "acceptance-donation" process of electrons between active sites and reactants is responsible for improving OER activity. Herein, we suggest a multielement hybridization strategy to rematch spin electron occupation and energy splitting in high-entropy perovskites with multiple orbital coordination. In this concept, electronic hopping between t_2g and e_g orbitals among particular catalytic sites can be obviously enforced due to introducing more favorable energy levels from neighboring metal sites, which can demonstrate multistage orbital hybridization reaction activity. As a result, our proposed multistage-hybridized high-entropy perovskites display an impressive activity of 199.8 mA cm^-2 as an overpotential of ∼0.46 V, which is ∼5.3 times that of pristine perovskite. Different from traditional catalyst designs, this study focuses on multistage orbital hybridization and electron exchange interactions through a multisite coordination mechanism to construct a fast reaction pathway. Our findings provide a new strategy for accelerating OER catalytic kinetics.

Keywords: Exchange interaction; High-entropy perovskite; Multi-site coordination mechanism; Multistage orbital hybridization; Oxygen evolution reaction.