ABSTRACT Photocatalytic H 2 O 2 production represents a sustainable and environmentally benign alternative to the energy‐intensive industrial anthraquinone process. Nevertheless, its practical viability remains fundamentally bottlenecked by the sluggish kinetics of the water oxidation reaction (WOR). Herein, we report a pore microenvironment engineering within covalent organic frameworks (COFs) to precisely steer the WOR paths. Inspired by the spatial arrangement of functional groups in natural enzymes, we construct a biomimetic microenvironment by integrating synergistic bipyridine and hydroxyl moieties into the COF backbone. This design successfully diverts the mechanism from the kinetically formidable four‐electron pathway toward a kinetically privileged two‐electron route. The resulting BPD‐COF achieves a remarkable hydrogen peroxide (H 2 O 2 ) production rate of 5145 µmol g −1 h −1 in air and pure water, outperforming its monofunctional counterparts by factors of 2.0 and 4.3, respectively. Theoretical simulations reveal that the targeted introduction of hydroxyl groups substantially amplifies the localized dipole moment and optimizes the electron–hole separation descriptors, thereby inducing favorable electronic states that reconfigures the thermodynamic energy barriers for critical *OH, *HOOH, and *O intermediates. This work highlights the pivotal role of pore microenvironment engineering in dictating reaction pathways and offers a conceptual blueprint for the rational design of high‐performance artificial photosynthesis platforms.
Xu et al. (Sun,) studied this question.