Abstract

Abstract Designing multifunctional catalysts with high activity, stability, and low‐cost for energy storage and conversion is a significant challenge. Herein, a trifunctional electrocatalyst is synthesized by anchoring individually dispersed Co atoms on N and S codoped hollow carbon spheres (CoSA/N,S‐HCS), which exhibits outstanding catalytic activity and stability for the oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction. When equipped in liquid or flexible solid‐state rechargeable Zn–air batteries, CoSA/N,S‐HCS endows them with high power and energy density as well as excellent long‐term cycling stability, outperforming benchmark batteries based on a commercial Pt/C + RuO 2 dual catalyst system. Furthermore, a self‐driven water splitting system powered by flexible Zn–air batteries is demonstrated using CoSA/N,S‐HCS as the sole catalyst, giving a high H 2 evolution rate of 184 mmol h −1 . The state‐of‐art experimental characterizations and theoretical calculations reveal synergistic cooperation between atomically dispersed CoN 4 active sites, nearby electron‐donating S dopants, and the unique carbon support to single‐atom catalysts (SACs). This work demonstrates a general strategy to design various multifunctional SAC systems with a tailored coordination environment.