Abstract
The heterogenized metallomacrocycles with atomically dispersed active sites are identified as the promising candidates for electrocatalytic CO2 reduction reaction (CO2RR), where their unique heterointerface with interaction between sp~2 carbon and macrocyclic molecules is important but remains vague. Herein, based on well-structured nickel phthalocyanine and porphyrin with the same functional groups (MeNiPc and MeNiPp), the influences of heterointerfacial effect on catalytic performances are systematically disclosed. Through the molecular structure-induced self-adaptive adsorption with optimized heterointerfacial distance, MeNiPc/graphene reveals a high CO Faradaic efficiency of -99% in a wide potential window, greatly outperforming the MeNiPp/ graphene counterpart (≤29.6%). Detailed measurements and theoretical calculations decipher that the higher CO2RR activity of MeNiPc/graphene is attributed to the unique electronic structures of the Ni-N4 configurations suitable for well-suited heterointerfacial charge transfer and rapid CO desorption. Additionally, the extended research confirms the universality of heterointerface engineering on boosting the catalytic performances.
NSTL