Synergistic strategies of selectivity regulation and microenvironment modulation in metal-organic frameworks for CO2 electroreduction
摘要
Electrochemical CO2 reduction reaction (CO2RR) is crucial for sustainable carbon cycling, while its efficiency is hindered by sluggish kinetics, competitive hydrogen evolution reaction (HER), and CO2 mass transport limitation. Metal-organic frameworks (MOFs) feature tunable structures, high porosity, and diverse functionalities, making them highly valuable for the CO2RR. They can not only serve as direct CO2RR catalysts, producing C1 or C2+ products via their metal nodes, organic linkers, or guest species, but also function as effective modulators of the reaction microenvironment. Notably, MOFs can improve the local CO2 concentration through adsorption and molecular sieving, modulate surface hydrophobicity to stabilize the triple-phase boundary (TPB) and suppress HER, as well as precisely tune ion conduction to reduce the resistance and stabilize key reaction intermediates. This review summarizes recent advancements in MOF-based catalysts for CO2RR, exploring their diverse active sites for C1 and C2+ products formation, highlighting strategies for performance enhancement through microenvironment modulation, and proposing future research directions for employing MOFs to advance CO2RR.