Heterogenized Pyridine-Substituted Cobalt(II) Phthalocyanine Yields Reduction of CO₂ by Tuning the Electron Affinity of the Co Center

Conversion of CO2 to reduced products is a promising route to alleviate irreversible climate change. Here we report the synthesis of a Co-based phthalocyanine with pyridine moieties (CoPc-Pyr), which is supported on a carbon electrode and shows Faradaic efficiency ∼90% for CO at 490 mV of overpotential (−0.6 V vs reversible hydrogen electrode (RHE)). In addition, its catalytic activity at −0.7 V versus RHE surpasses other Co-based molecular and metal–organic framework catalysts for CO2 reduction at this bias. Density functional theory calculations show that pyridine moieties enhance CO2 adsorption and electron affinity of the Co center by an inductive effect, thus lowering the overpotential necessary for CO2 conversion. Our study shows that CoPc-Pyr reduces CO2 at lower overpotential and with higher activity than noble metal electrodes, such as silver.