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.

Center for Advancing Electronics Dresden and Faculty of Chemistry and Food Chemistry Technische Universität Dresden Mommsenstrasse 4 Dresden 01062 Germany

Department of Inorganic Chemistry University of Chemistry and Technology Prague Technická 5 Prague 6 16628 Czech Republic

Dynamics of Condensed Matter and Center for Sustainable Systems Design Chair of Theoretical Chemistry University of Paderborn Warburger Str 100 Paderborn 33098 Germany

Fraunhofer Institute for Ceramic Technologies and Systems Maria Reiche Strasse 2 Dresden 01109 Germany

Institute for Complex MateSrials Leibniz Institute for Solid State and Materials Research Dresden 01069 Germany

Shenzhen Key Laboratory of Power Battery Safety and Shenzhen Geim Graphene Center Tsinghua Shenzhen International Graduate School Tsinghua University Shenzhen 518055 China

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