Unprecedented Photocatalytic Hydrogen Peroxide Production via Covalent Triazine Frameworks Constructed from Fused Building Blocks

Abstract Covalent organic frameworks (COFs) have garnered attention for their potential in photocatalytic hydrogen peroxide (H 2 O 2 ) production. However, their photocatalytic efficiency is impeded by insufficient exciton dissociation and charge carrier transport. Constructing COFs with superior planarity is an effective way to enhance the π‐conjugation degree and facilitate electron‐hole separation. Nonetheless, the conventional linear linkers of COFs inevitably introduce torsional strain that disrupts coplanarity. Herein, we address this issue by introducing inherently coplanar triazine rings as linkers and fused building blocks as monomers to create covalent triazine frameworks (CTFs) with superior coplanarity. Both experimental and theoretical calculations confirm that CTFs constructed from fused building blocks significantly enhance the electron‐hole separation efficiency and improve the photocatalytic performance, compared to the CTFs constructed with non‐fused building blocks. The frontier molecular orbitals and electrostatic potentials (ESP) revealed that the oxygen reduction reaction (ORR) is preferentially facilitated by the triazine rings, with the water oxidation reaction (WOR) likely occurring at the thiophene‐containing moiety. Remarkably, CTF‐BTT achieved an exceptional H 2 O 2 production rate of 74956 μmol g −1 h −1 when employing 10 % benzyl alcohol (V/V) as a sacrificial agent in an O 2 ‐saturated atmosphere, surpassing existing photocatalysts by nearly an order of magnitude. Our findings provide valuable insights for designing highly coplanar polymer‐based photocatalysts that enhance the solar‐to‐chemical energy conversion process.