Dual Breaking the Geometric and Electronic Symmetry of Covalent Organic Framework for Enhanced H₂O₂ Photosynthesis

The efficient conversion of solar energy into chemicals is fundamentally limited by the rapid, random recombination of photogenerated charges and strong exciton binding in semiconductors. We transcend incremental catalyst optimization by introducing a universal molecular design strategy "simultaneous geometric and electronic symmetry breaking" in covalent organic frameworks that intrinsically programs directional charge flow. Our strategy of replacing symmetric benzene units with asymmetric thiophene rings induces cooperative point-group distortion and asymmetric electron density redistribution, thereby creating a built-in polarization field that slashes exciton binding energy, extends carrier lifetime by over 300%, and steers reaction selectivity. This leads to a record photocatalytic H₂O₂ production rate from just water and air. Crucially, life-cycle assessment confirms this pathway reduces environmental impact by an order of magnitude. The generality of this design strategy is further validated across multiple framework systems and enables stable operation in a continuous-flow photoreactor, demonstrating a robust platform for efficient solar-to-chemical energy conversion.