Metal–Salen‐Incorporated conjugated microporous polymers as robust artificial leaves for solar‐driven reduction of atmospheric CO₂ with H₂O

Abstract Exploration of efficient and stable photocatalysts to mimic natural leaves for the conversion of atmospheric CO₂ into hydrocarbons utilizing solar light is very important but remains a major challenge. Herein, we report the design of four novel metal–salen‐incorporated conjugated microporous polymers as robust artificial leaves for photoreduction of atmospheric CO₂ with gaseous water. Owing to the rich nitrogen and oxygen moieties in the polymeric frameworks, they show a maximum CO₂ adsorption capacity of 46.1 cm³ g⁻¹ and adsorption selectivity for CO₂/N₂ of up to 82 at 273 K. Under air atmosphere and simulated solar light (100 mW cm⁻²), TEPT‐Zn shows an excellent CO yield of 304.96 μmol h⁻¹ g⁻¹ with a selectivity of approximately 100%, which represents one of the best results in terms of organic photocatalysts for gas‐phase CO₂ photoreduction so far. Furthermore, only small degradation in the CO yield is observed even after 120‐h continuous illumination. More importantly, a good CO yield of 152.52 μmol g⁻¹ was achieved by directly exposing the photocatalytic reaction of TEPT‐Zn in an outdoor environment for 3 h (25–28°C, 52.3 ± 7.9 mW cm⁻²). This work provides an avenue for the continued development of advanced polymers toward gas‐phase photoconversion of CO₂ from air.