Clarifying the local microenvironment of metal–organic frameworks and their derivatives for electrochemical CO2 reduction: advances and perspectives

Abstract

The conversion of carbon dioxide (CO₂) into fuels, value-added products and electricity is one of the most effective ways to reduce the atmospheric CO₂ concentration, and thus mitigate the greenhouse effect, simultaneously resolving the environmental and energy crises. In this case, metal–organic frameworks (MOFs) show good application prospect in the catalytic CO₂ reduction reaction because of their well-defined porous structure, rich active sites and feasible functionalization. Herein, we summarize the latest research progress of MOFs and their derivatives for catalytic CO₂ electroreduction and discuss their mechanism, kinetics, thermodynamics and catalytic performance. Moreover, the effect of first-, secondary and out-sphere coordination on the metal active centers and the local microenvironment of MOFs, which can be manipulated by adjusting their metal nodes, organic linkers, and solvents, are addressed in-depth to clarify the key to their great electrocatalytic performance. Based on this, the main challenges and future outlook of MOF catalysts are summarized and perspectives presented.