In situ growth of functionalized cobalt phthalocyanine at Co sites for promoting efficient CO2 electroreduction

The electrochemical CO 2 reduction reaction (CO 2 RR) to CO faces challenges from slow kinetics and complex pathways, necessitating active, selective, and stable catalysts. This study presents a direct coordination strategy that enables the in situ growth of cobalt tetranitrophthalocyanine (CoTNPc) on Co-embedded N-rich carbon matrix (Co/NC), forming a CoTNPc/NC composite. The directly axial coordination regulates the electronic configuration of Co-N sites, accelerating the *CO formation and desorption. The CoTNPc/NC electrocatalyst achieves a peak CO Faradaic efficiency for (FE CO ) of 96.7% at −0.9 V vs. RHE in H-cell. Furthermore, in the Flow-cell, it maintains FE CO  > 90% over a wide potential range (−0.4 V to −0.9 V vs. RHE) and demonstrates durability exceeding 15 h in stability testing. In situ attenuated total reflection infrared (ATR-IR) spectroscopy and Density functional theory (DFT) calculations elucidate that the remarkable performance is driven by the improved electrical conductivity and weakened interaction between the *COOH intermediate and Co sites. This work offers a novel approach to optimizing catalyst-support interactions for electrocatalyst design.