Constructing Bipolar Dual-Active Sites through High-Entropy-Induced Electric Dipole Transition for Decoupling Oxygen Redox.

It remains a significant challenge to construct active sites to break the trade-off between oxidation and reduction processes occurring in battery cathodes with conversion mechanism, especially for the oxygen reduction and evolution reactions (ORR/OER) involved in the Zinc-air batteries (ZABs). Here, we propose using a high-entropy-driven electric dipole transition strategy to activate and stabilize the tetrahedral sites, while enhancing the activity of octahedral sites through orbital hybridization in a FeCoNiMnCrO spinel oxide, thus constructing bipolar dual-active sites with high-low valence states, which can effectively decouple ORR/OER. The FeCoNiMnCrO high-entropy spinel oxide (HESO) with severe lattice distortion, exhibits a strong 1s→4s electric dipole transition and intense t 2g (Co)/e g (Ni)-2p(O L ) orbital hybridization that regulates the electronic descriptors, e g and t 2g , which leads to the formation of low-valence Co tetrahedral sites (Co th ) and high-valence Ni octahedral sites (Ni oh ), resulting in a higher half-wave potential of 0.87 V on Co th sites and a lower overpotential of 0.26 V at 10 mA cm -2 on Ni oh sites as well as a superior performance of ZABs compared to low/mild entropy spinel oxides (L/MESO). Therefore, entropy engineering presents a distinctive approach for designing catalytic sites by inducing novel electromagnetic properties in materials across various electrocatalytic reactions, particularly for decoupling systems. This article is protected by copyright. All rights reserved.