Permanent Oxidative Dipole Engineering in Quinoline COFs for Boosting Exciton Dissociation and Oxygen Activation in H 2 O 2 Photosynthesis

Despite their robust stability, fully conjugated quinoline‐linked covalent organic frameworks suffer from highly delocalized electron distributions and a homogeneous electrostatic potential, which physically cause high exciton binding energies and poor oxygen activation that severely limit photocatalytic H 2 O 2 production. To fundamentally disrupt this electronic uniformity, we propose a permanent oxidative dipole (POD) strategy, where site‐selective oxidation of quinoline nitrogen atoms, synthesized via one‐pot [4+2] annulation, precisely embeds N +– O − dipole pairs into the NQ‐COF BD framework. These POD sites trigger localized charge polarization, producing a triple synergistic effect: a strengthened built‐in electric field (dipole moment increases from 1.08 to 2.08 D), a lowered exciton dissociation barrier (binding energy drops from 44.7 to 20.3 meV), and accelerated charge carrier transport (surface potential rising by a factor of 1.26). Crucially, the POD sites construct spatially decoupled redox dual‐centers that drastically reduce the kinetic barrier of the ORR rate‐determining step, with the *OOH formation energy lowered by 0.77 eV. Consequently, NQ‐COF BD ‐O achieves a remarkable H 2 O 2 production rate of 4,569 µmol g −1 h −1 under visible light without sacrificial agents (a 1.89‐fold enhancement), with an apparent quantum yield of 6.1% at 460 nm, and this strategy is also validated in another quinoline system with a 1.86‐fold improvement.