Photo- and Electrochemical Valorization of Carbon Dioxide Using Earth-Abundant Molecular Catalysts

The dramatic increase in anthropogenic carbon dioxide emissions in recent decades has forced us to look for alternative carbon-neutral processes for the production of energy vectors and commodity chemicals. Photo- and electrochemical reduction of CO₂ are appealing strategies for the storage of sustainable and intermittent energies in the form of chemical bonds of synthetic fuels and value-added molecules. In these approaches, carbon dioxide is converted to products such as CO, HCOOH and MeOH through proton-coupled electron transfer reactions. The use of earth-abundant elements as components of the catalytic materials is crucial for the large-scale applicability of this technology. This review summarizes the most recent advances related to this issue, with particular focus on studies where molecular metal complexes are used as catalysts. In addition, with the aim of aiding in the design of more robust and efficient non-noble metal-based catalysts, we discuss the lessons learned from the corresponding mechanistic studies.