Decoupling Interlayer Interactions Boosts Charge Separation in Covalent Organic Frameworks for High‐Efficiency Photocatalytic CO2 Reduction

Abstract Covalent organic frameworks (COFs) have emerged as promising photocatalysts owing to their structural diversity, tunable bandgaps, and exceptional light‐harvesting capabilities. While previous studies primarily focus on developing narrow‐bandgap COFs for broad‐spectrum solar energy utilization, the critical role of interlayer coupling in regulating charge transfer dynamics remains unclear. Conventional monolayer‐based theoretical models inadequately address interlayer effects that potentially hindering intralayer electron transport to catalytic active sites. This work employs density functional theory (DFT) calculations to investigate the influence of interlayer interactions on intralayer charge transfer in imine‐based COFs. Theoretical analyses reveal that bilayer architectures exhibit pronounced interlayer interference in intramolecular charge transfer processes which has not been observed in monolayer models. Based on these mechanistic insights, this work designs two isomeric pyrene‐based COFs incorporating identical electron donor (pyrene) and acceptor (nickel bipyridine) units but with distinct interlayer coupling strengths. Strikingly, the optimized COF with weakened interlayer interactions demonstrates exceptional photocatalytic CO 2 reduction performance, achieving a CO evolution rate of 553.3 µmol g −1 h −1 with 94% selectivity under visible light irradiation without additional photosensitizers or co‐catalysts. These findings establish interlayer engineering as a crucial design principle for developing high‐performance COF‐based photocatalysts for solar energy conversion applications.