Utilizing Hairy Hollow Conjugated Microporous Polymers and Native Enzymes for Precise Aerobic Photocatalysis Under Near‐Infrared Wavelengths

Abstract Utilizing photoregenerated cofactors in conjunction with enzymes in a sequential manner presents an effective approach for the synthesis of targeted compounds in gentle reaction conditions. Nevertheless, the integration of enzymes and photocatalysts has faced challenges due to the swift breakdown of biomaterials caused by high‐energy or blue lights and photoinduced reactive oxygen species, leading to the denaturation and deactivation of enzymatic materials. This study details the deliberate development and production of hairy hollow conjugated microporous polymers (S‐ h PrTZ‐P HCMPs), achieved via Sonogashira–Hagihara coupling on SiO 2 templates, followed by sulfonation, polymer grafting and ultimately eliminating the SiO 2 cores. This technique leverages the distinctive characteristics of low‐energy near‐infrared light, such as its superior penetration ability, to effectively regenerate the enzymatic cofactor NAD + from NADH. It can accomplish this feat even when faced with synthetic or biological barriers that are impermeable to visible light. Simultaneously, photogenerated reactive oxygen species are captured and neutralized by the hydrophilic polymer brushes, safeguarding the integrity of the enzymatic material. The adaptability of S‐ h PrTZ‐P with photocatalytic properties is showcased alongside glucose 1‐dehydrogenase and glycerol dehydrogenase. This structure and morphology‐controlled strategy offers a promising pathway for various enzymatic photobiocatalysis employing stable, efficient, and reusable hairy HCMPs.