Tailored Local Electronic Environment of Co‐N4 Sites in Cobalt Phthalocyanines for Enhanced CO2 Reduction Reaction

Abstract Atomically dispersed Co‐N 4 ‐based catalysts have been recently emerging as one of the most promising candidates for facilitating CO 2 reduction reaction (CO 2 RR). The local electronic environment of Co‐N 4 sites in these catalysts is considered to play a critical role in adjusting the catalytic performance, the effort of which however is not yet clearly verified. Herein, a series of cobalt phthalocyanines with different peripheral substituents including unsubstituted phthalocyanine Co(II) (CoPc), 2,9,16,23‐tetramethoxyphthalocyaninato Co(II) (CoPc‐4OCH 3 ), and 2,9,16,23‐tetranitrophthalocyaninato Co(II) (CoPc‐4NO 2 ) are supported onto the surface of the multi‐walled carbon nanotubes (CNTs), affording CoPc@CNTs, CoPc‐4OCH 3 @CNTs, and CoPc‐4NO 2 @CNTs. X‐ray photoelectron spectroscopy and X‐ray absorption near‐edge structure measurements disclose the influence of the peripheral substituents on the local electronic structure of Co atoms in these three catalysts. Electrochemical tests indicate the higher CO 2 RR performance of CoPc‐4OCH 3 @CNTs compared to CoPc@CNTs and CoPc‐4NO 2 @CNTs as exemplified by the higher Faraday efficiency of CO, larger part current densities, and better stability displayed by CoPc‐4OCH 3 @CNTs at the applied voltage range from −0.6 to −1.0 V versus RHE in both H‐cell and flow cell. These results highlight the effect of the electron‐donating ‐OCH 3 substituent on the enhanced catalytic activity of CoPc‐4OCH 3 @CNTs, which will help develop Co‐N 4 ‐based catalysts with promising catalytic performance toward CO 2 RR.