Functional group engineering for boosting catalytic activity: high turnover frequency in electrocatalytic CO2 reduction and Zn-CO2 batteries

Functionalized cobalt phthalocyanine (CoPc) supported on carbon supports are promising electrocatalyst for the electrochemical reduction of carbon dioxide (eCO 2 RR), yet the role of functional groups on catalytic activity is pending for clarification and optimization to maximize the reaction kinetics. Herein, a series of eCO 2 RR catalysts are fabricated by affixing functionalized molecular catalysts onto the nitrogen-doped porous carbon (NPC), denoted as CoPc-4x@NPC (x = H, NH 2 and NO 2 ). Among them, CoTNPc@NPC exhibits exceptional eCO 2 RR performance: in an H-type cell, it achieves a current density of 45 mA cm −2 at −0.91 V vs. RHE with CO Faradaic efficiency (FE CO ) exceeding 93.5% over a wide potential range, long-term stability over 40 h, and a remarkable turnover frequency (TOF) of 23.49 s −1 . In a flow cell configuration, the CO partial current density ( J CO ) further increases to 224.1 mA cm −2 at −0.91 V. Density functional theory (DFT) calculations reveal that the nitro group upshifts the d -band center, enhances Co center electrophilicity, pre-donates electrons for *COOH formation, and underlies the higher turnover frequency. Integrating CoTNPc@NPC into a Zn-CO 2 battery delivers a maximum discharge power density of 3.86 mW cm −2 and stable operation for over 15 h. This work highlights the potential of molecularly engineered CoPc catalysts for eCO 2 RR and Zn-CO 2 battery applications, providing new insights for the rational design of high-performance electrocatalysts.