Insight on Reaction Pathways of Photocatalytic CO₂ Conversion

Photocatalytic CO₂ conversion to value-added chemicals is a promising solution to mitigate the current energy and environmental issues but is a challenging process. The main obstacles include the inertness of CO₂ molecule, the sluggish multi-electron process, the unfavorable thermodynamics, and the selectivity control to preferable products. Furthermore, the lack of fundamental understanding of the reaction pathways accounts for the very moderate performance in the field. Therefore, in this Perspective, we attempt to discuss the possible reaction mechanisms toward all C₁ and C₂ value-added products, taking into account the experimental evidence and theoretical calculation on the surface adsorption, proton and electron transfer, and products desorption. Finally, the remaining challenges in the field, including mechanistic understanding, reactor design, economic consideration, and potential solutions, are critically discussed by us.