Molecular Engineering of Metalloporphyrins and Phthalocycanines for Homogeneous and Heterogeneous CO 2 Electroreduction

Abstract

This review provides an overview of recent advances in CO2 electrocatalysis, starting with the development of homogeneous electrocatalytic systems. We focused on porphyrin and phthalocyanine based molecular catalysts where different chemical strategies have been implemented drawing inspiration from natural enzyme systems that process CO2, such as hydrogen bonding, proton relay, bimetallic cooperative action, electrostatic interactions and structural dynamics to help enhancing the selectivity and efficiency of electrochemical CO2 reduction. The discussion then expands to heterogeneous processes in traditional H-cells, and more relevant flow-cell setups integrated with gas diffusion electrodes. A special focus is given to the growing trend of hybrid molecular-metallic co-catalyst systems, which are driving significant progress in heterogeneous CO2 electrocatalysis.