TY - JOUR AB - Abstract Developing resource-abundant and sustainable metal-free bifunctional oxygen electrocatalysts is essential for the practical application of zinc–air batteries (ZABs). 2D black phosphorus (BP) with fully exposed atoms and active lone pair electrons can be promising for oxygen electrocatalysts, which, however, suffers from low catalytic activity and poor electrochemical stability. Herein, guided by density functional theory (DFT) calculations, an efficient metal-free electrocatalyst is demonstrated via covalently bonding BP nanosheets with graphitic carbon nitride (denoted BP-CN-c). The polarized PN covalent bonds in BP-CN-c can efficiently regulate the electron transfer from BP to graphitic carbon nitride and significantly promote the OOH* adsorption on phosphorus atoms. Impressively, the oxygen evolution reaction performance of BP-CN-c (overpotential of 350 mV at 10 mA cm−2, 90\% retention after 10 h operation) represents the state-of-the-art among the reported BP-based metal-free catalysts. Additionally, BP-CN-c exhibits a small half-wave overpotential of 390 mV for oxygen reduction reaction, representing the first bifunctional BP-based metal-free oxygen catalyst. Moreover, ZABs are assembled incorporating BP-CN-c cathodes, delivering a substantially higher peak power density (168.3 mW cm−2) than the Pt/C+RuO2-based ZABs (101.3 mW cm−2). The acquired insights into interfacial covalent bonds pave the way for the rational design of new and affordable metal-free catalysts. AU - Wang, Xia AU - Kormath Madam Raghupathy, Ramya AU - Querebillo, Christine Joy AU - Liao, Zhongquan AU - Li, Dongqi AU - Lin, Kui AU - Hantusch, Martin AU - Sofer, Zdeněk AU - Li, Baohua AU - Zschech, Ehrenfried AU - Weidinger, Inez M. AU - Kühne, Thomas AU - Mirhosseini, Hossein AU - Yu, Minghao AU - Feng, Xinliang ID - 22220 IS - 20 JF - Advanced Materials KW - 2D materials KW - bifunctional oxygen electrocatalysts KW - black phosphorus KW - oxygen evolution reaction KW - zinc–air batteries TI - Interfacial Covalent Bonds Regulated Electron-Deficient 2D Black Phosphorus for Electrocatalytic Oxygen Reactions VL - 33 ER -