Progress of photocatalytic CO₂ reduction toward multi-carbon products

The photocatalytic CO₂ reduction reaction (CO₂RR) represents a promising solution to alleviate environmental and energy issues stemming from CO₂ emissions while simultaneously enabling the production of high-value multi-carbon fuels. However, the efficient generation of multi-carbon products remains challenging due to high kinetic barriers, sluggish C–C coupling processes, and intricate reaction pathways. This review provides a comprehensive overview of the latest advancements in synthesizing C₂₊ products through CO₂ photoreduction, highlighting the crucial role of active site design and the C–C coupling mechanism. Specifically, we emphasize the correlation between the structure of active sites and the key intermediates of C–C coupling, which is fundamental for achieving deep photoconversion of CO₂. Finally, we offer a glimpse into future challenges and prospects, outlining potential directions for the development of CO₂-to-multicarbon photoconversion, aiming to contribute novel insights to this exciting field.