Fully Conjugated 2D sp2 Carbon‐Linked Covalent Organic Frameworks for Photocatalytic Overall Water Splitting

Abstract Covalent organic frameworks (COFs) hold great promise for solar‐driven hydrogen production. However, metal‐free COFs for photocatalytic overall water splitting remain elusive, primarily due to challenges in simultaneously regulating their band structures and catalytic sites to enable concurrent half‐reactions. Herein, two types of π‐conjugated COFs containing the same donor–acceptor structure are constructed via Knoevenagel condensation and Schiff base reaction to afford cyanovinylene‐ and imine‐bridged COFs, respectively. The difference in the linkage leads to a remarkable difference in their photocatalytic activity toward water splitting. The 2D sp 2 carbon‐linked COF exhibits notable activity for photocatalytic overall water splitting, which can reach an apparent quantum efficiency of 2.53% at 420 nm. In contrast, the 2D imine‐linked COF cannot catalyze the overall water‐splitting reaction. Mechanistic investigations reveal that the cyanovinylene linkage is essential in modulating the band structure and promoting charge separation in COFs, thereby enabling overall water splitting. Moreover, it is further shown that crystallinity substantially impacts the photocatalytic performance of COFs. This study represents the first successful example of developing metal‐free COFs with high crystallinity for photocatalytic overall water splitting.