Merging bioinspired incubation with supramolecular photocatalysis for Michaelis CO2 reduction beyond enzymes

The conversion of carbon dioxide into chemicals and fuels via photoreduction represents a groundbreaking opportunity to forge a sustainable and carbon-neutral future, but the low concentration of photosensitized transition species and the related sluggish reaction kinetics significantly hindered the current energy efficiency toward industrial application. Herein, a bioinspired incubation to pretreat artificial cofactor BIH with photocatalyst is reported to enrich photogenerated reactive species for saturating the pocket of Fe ^III -porphyrin-modified capsule, and facilitating an ultra-fast photocatalytic CO ₂ -to-CO conversion via a promisingly saturated enzymatic kinetics. The strategy included preincubating of photosensitizer, Ir(ppy) ₃ with cofactor mimicking BIH for sufficiently producing reactive anionic Ir ^II (ppy) ₃ species initially, followed by the thermodynamically favored abstraction of the species inside the cationic lantern-shaped capsule to facilitate the enzymatic conversion under saturated conditions and compatible substrate-product exchange kinetics. The improved and synergistic dynamics of both the iron-based CO ₂ reduction and photosensitization bestow the bioinspired system with a turnover number (TON) about 180,000 and an ultrafast turnover frequency (TOF) about 165 s ⁻¹ in targeted CO ₂ to CO conversion, surpassed most of reported photocatalytic CO ₂ -to-CO systems and typical CO ₂ reductases. This pseudo-enzymatic transformation allows concurrent intramolecular cyclic dehydrogenation of imines and CO ₂ reduction, unlocking new opportunities for facilitating the conversion of high-energy-barrier photocatalysis under mild condition.