CO2 Electroreduction on Carbon-Based Electrodes Functionalized with Molecular Organometallic Complexes—A Mini Review

Heterogeneous electrochemical CO2 reduction has potential advantages with respect to the homogeneous counterpart due to the easier recovery of products and catalysts, the relatively small amounts of catalyst necessary for efficient electrolysis, the longer lifetime of the catalysts, and the elimination of solubility problems. Unfortunately, several disadvantages are also present, including the difficulty of designing the optimized and best-performing catalysts by the appropriate choice of the ligands as well as a larger heterogeneity in the nature of the catalytic site that introduces differences in the mechanistic pathway and in electrogenerated products. The advantages of homogeneous and heterogeneous systems can be preserved by anchoring intact organometallic molecules on the electrode surface with the aim of increasing the dispersion of active components at a molecular level and facilitating the electron transfer to the electrocatalyst. Electrode functionalization can be obtained by non-covalent or covalent interactions and by direct electropolymerization on the electrode surface. A critical overview covering the very recent literature on CO2 electroreduction by intact organometallic complexes attached to the electrode is summarized herein, and particular attention is given to their catalytic performances. We hope this mini review can provide new insights into the development of more efficient CO2 electrocatalysts for real-life applications.