Phthalocyanine-Derived Catalysts Decorated by Metallic Nanoclusters for Enhanced CO2 Electroreduction

ABSTRACT Electrochemical CO2 reduction (CO2RR) over molecular catalysts is a paramount approach for CO2 conversion to CO. Herein, we report a novel phthalocyanine-derived catalyst synthesized by a two-step method with a much improved electroconductivity. Furthermore, the catalyst contains both Ni-N4 sites and highly dispersed metallic Ni nanoclusters, leading to an increased CO2RR currents by two folds. Isotope labelling study and in situ spectroscopic analysis demonstrate that the existence of metallic Ni nanoclusters is the key factor for the activity enhancement and can shift the CO2RR mechanism from being electron transfer (ET)-limited (forming *COO-) to concerted proton-electron transfer (CPET)-limited (forming CO).