Construction of COF/COF Organic S‐Scheme Heterostructure for Enhanced Overall Water Splitting

Covalent organic frameworks (COFs) as a new type of photocatalysts have shown unique advantages in visible-light-driven hydrogen evolution, while the reported overall water-splitting systems are still very rare among various COF-based photocatalysts. Herein, two COFs are integrated to construct a type of organic S-scheme heterojunction for improved overall water splitting. In this system, TpBpy-COF and COF-316 serve as H₂- and O₂-evolving components, respectively, which are combined through π-π interaction between conjugated aromatic rings. By introducing ultra-small Pt nanoparticles (NPs) into the pores of the TpBpy-COF nanosheets (NS), the resultant COF-316/Pt@TpBpy-COF NS heterostructure achieves extremely high H₂ and O₂ evolution rates of 220.4 and 110.2 µmol g^-1 h^-1, respectively, under visible light irradiation (λ ≥ 420 nm). The results of transient absorption spectra (TAS) and photoelectronic measurements indicate that the organic heterojunction interface notably facilitates the separation and transfer of photogenerated electron-hole pairs. Further, theoretical calculations and in situ experiments confirm the spontaneous formation of the COF/COF heterojunction interface and the active sites for overall water splitting.