Synergistic Fluorine and Cyanide Co‐Modification to Reinforce Photoinduced Excitons Formation and Transfer for Efficient CO ₂ Photoreduction

Abstract Polymeric carbon nitride (PCN) is a promising CO 2 photoreduction catalyst, yet its ordered structure limits interfacial reactivity. To address this, we synergistically introduced F‐doping and cyanide (─CN) groups into PCN, constructing a co‐modified material denoted as FCCN. Structural characterization confirms the coexistence of co‐modifications within the same s‐triazine heterocycle, while such architecturally tailored PCN materials remain a seldom‐achieved configuration for CO 2 photoreduction. FCCN achieves efficient photocatalytic CO 2 reduction in gas‐solid reactions, with CO as the primary reduction product and O 2 as the oxidation product. The CO evolution rate reaches 106.5 µmol·g −1 ·h −1 (96.8% selectivity), representing the highest performance level among all PCN‐based photocatalytic systems reported to date. Mechanistic investigations confirm that co‐modification‐induced built‐in fields not only enhance exciton generation kinetics but also regulate charge transfer dynamics. Concurrently, reactivation of dormant structural zones elevates the density of catalytically active sites for CO 2 adsorption/activation. Furthermore, its regulation of the formation energy of key intermediates COOH * and CHO * in the CO 2 reduction process enables the planning of reaction pathways, providing support for the efficient conversion of CO 2 to CO. This work provides a new approach for developing highly active PCN‐based photocatalysts and brings new opportunities for efficient directional conversion of CO 2 .