Integrating Multipolar Structures and Carboxyl Groups in sp2‐Carbon Conjugated Covalent Organic Frameworks for Overall Photocatalytic Hydrogen Peroxide Production

The direct production of hydrogen peroxide (H2O2) through photocatalytic reaction via H2O and O2 is considered as an ideal approach. However, the efficiency of H2O2 generation is generally limited by insufficient charge and mass transfer. Covalent organic framework (COFs) offer a promising platform as metal‐free photocatalyst for H2O2 production due to their potential for rational design at the molecular level. Herein, we integrated the multipolar structures and carboxyl groups into COFs to enhance the efficiency of photocatalytic H2O2 production in pure water without any sacrificial agents. The introduction of octupolar and quadrupolar structures, along with an increase of molecular planarity, created efficient oxygen reduction reaction (ORR) sites. Meanwhile, carboxyl groups could not only boost O2 and H2O2 movement via enhancement of pore hydrophilicity, but also promote proton conduction, enabling the conversion to H2O2 from ⋅O2−, which is the crucial intermediate product in H2O2 photocatalysis. Overall, we demonstrate that TACOF‐1‐COOH, consisting of optimal octupolar and quadrupolar structures, along with enrichment sites (carboxyl groups), exhibited a H2O2 yield rate of 3542 μmol h− 1 g−1 and a solar‐to‐chemical (SCC) efficiency of 0.55 %. This work provides valuable insights for designing metal‐free photocatalysts for efficient H2O2 production. A series of fully conjugated sp2‐c covalent organic framework integrated with multipolar structures and enrichment sites have been prepared for overall photosynthesis of H2O2. Benefiting from optimal multipolar structures and functional sites, TACOF‐1‐COOH facilitated charge transfer and mass movement during the photocatalysis process, leading to highly efficient ORR performance with a H2O2 production rate of 3542 μmol g−1 h−1.