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Interfacial Covalent Bonds Regulated Electron‐Deficient 2D Black Phosphorus for Electrocatalytic Oxygen Reactions
Author(s) -
Wang Xia,
Raghupathy Ramya Kormath Madam,
Querebillo Christine Joy,
Liao Zhongquan,
Li Dongqi,
Lin Kui,
Hantusch Martin,
Sofer Zdeněk,
Li Baohua,
Zschech Ehrenfried,
Weidinger Inez M.,
Kühne Thomas D.,
Mirhosseini Hossein,
Yu Minghao,
Feng Xinliang
Publication year - 2021
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.202008752
Subject(s) - overpotential , bifunctional , covalent bond , oxygen evolution , electrocatalyst , materials science , catalysis , lone pair , electrochemistry , metal , density functional theory , phosphide , inorganic chemistry , photochemistry , chemistry , molecule , computational chemistry , organic chemistry , electrode , metallurgy
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 PN 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+RuO 2 ‐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.