Recent Trends in Bioinspired Photocatalysis and Photoenzymatic Catalysis for CO2 Reduction to Formic Acid

The conversion of CO2 into fuels and chemical feedstocks represents a sustainable pathway to develop carbon‐neutral economy. Typically, among the accessible C1 commodities, formic acid has been a critical liquid product of CO2 reduction as an essential chemical intermediate or hydrogen storage medium. However, the activity and typical selectivity regulation of CO2‐to‐HCOOH are still far from the scale implementation requirement due to both thermodynamic and kinetic challenges. Billions of years of evolution have allowed natural CO2 reductases to achieve CO2 selective utilization by their unique active sites surrounded by elaborate protein scaffolds, confined pockets for reaction intermediates, long‐range electron and proton delivery chains, and hydrophobic CO2 transfer channels. Consequently, learning from formate dehydrogenase (FDH) may inspire bioinspired design in artificial photosynthesis, including the reactive center, multilevel coordination microenvironments, substrate channel, and synergistic effect. Herein, recent works about biomimetic photocatalysis and photoenzymatic catalysis of selective CO2 valorization to HCOOH are summarized, which is hoped to lift the application of bioinspiration in highly selective CO2 reduction systems designation or technique development.