Rong Xin, Hongqing Zhao, Yijiang Liu, Ying Yuan, Shuzhi Liu, Dan Li, Mei Yang, Bei Liu, Shujiang Ding, Zhiqun Lin
Abstract Developing efficient trifunctional electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is pivotal for advancing sustainable energy technologies. Herein, the crafting of Mott‐Schottky (MS) electrocatalysts is presented, enabling high‐performance Zn‐air batteries (ZABs) and water electrolysis with record‐breaking cycling stability. These catalysts are created through a unique Exfoliation‐Intercalation‐Assembly (EIA) strategy, involving in‐situ constructing homologous metal alloy/metal oxide MS junction anchored on nitrogen‐doped carbon nanosheets. Notably, the resulting MS electrocatalysts manifest exceptional ORR/OER/HER activity and durability, achieved through precise modulation of electronic structure (i.e., conductivity, interface charge polarization/redistribution, and d‐band centre alignment) by integrating homologous heterojunction. Density functional theory (DFT) calculations further reveal that the MS effect optimizes the intermediate formation (i.e., OOH * ) and adsorption/desorption (i.e., H * ), affords a dual‐electron transfer channel, reduces energy barriers, thereby markedly improving ORR/OER/HER performance. The ZABs assembled with MS electrocatalysts deliver high power density, large specific capacity, and ultra‐long cycle life in both aqueous and solid‐sate electrolytes. Additionally, the catalysts exemplify outstanding water splitting performance at a low cell voltage and notable durability, surpassing the benchmark IrO 2 ‐Pt. The superior durability of MS electrocatalysts‐based ZABs and water electrolysis outperforms existing alternatives, underscoring their immense potential for next‐generation renewable energy systems.