Metal-Organic Frameworks and Their derivatives for Electrochemical CO2 Reduction Reaction: Insights from Molecular Engineering

Abstract

Excessive fossil fuel consumption has led to a rapid increase in CO2 concentration, posing a threat to the global environment. The electrochemical conversion of CO2 back into valuable carbon-containing products offers a promising solution, however the lack of efficient electrocatalysts remains a challenge for high-efficiency CO2 reduction reaction (CO2RR). Metal-organic frameworks (MOFs) have emerged as promising electrocatalysts owing to their superior activity and well-defined active sites, which are recognized as model electrocatalysts for fundamental study of the electrocatalytic reaction mechanisms. In this review, focusing on the roles of metal and coordination environment, we have discussed the molecular engineering of MOF electrocatalysts for CO2RR, including regulation of metal nodes, modulation of surrounding organic ligands, and post-modification of MOFs. In addition, stability of MOFs and transformation strategies through wet chemistry method and pyrolysis treatment to obtain MOF derivatives are summarized. The metal centers, coordination environment of N atoms and other heteroatoms of the MOF derivatives are discussed for their performance in CO2RR. Furthermore, computational simulations and advanced characterizations are also summarized to understand the correlation of structure and performance for MOFs and their derivatives. By overviewing the progress and current challenges of the MOF electrocatalysts and their derivatives for CO2RR, we are aiming to provide insights into design principles and propose future directions for high-efficiency electrocatalysts, paving the way toward carbon neutrality.