1D Covalent Organic Frameworks Triggering Highly Efficient Photosynthesis of H2O2 via Controllable Modular Design

The topological diversity of covalent organic frameworks (COFs) enables considerable space for exploring their structure‐performance relationships. In this study, we report a sequence of novel 1D COFs (EO, ES, and ESe‐COF) with typical 4‐c sql topology that can be interconnected with VIA group elements (O, S, and Se) via a modular design strategy. It is found that the electronic structures, charge delivery property, light harvesting ability, and hydrophilicity of these 1D COFs can be profoundly influenced by the bridge‐linked atom ordinal. Finally, EO‐COF, possessing the highest quantity of active sites, the longest lifetime of the active electron, the strongest interaction with O2, and the lowest energy barrier of O2 reduction, exhibits exceptional photocatalytic O2‐to‐H2O2 activity under visible light, with a production rate of 2675 μmol g−1 h−1 and a high apparent quantum yield of 6.57 % at 450 nm. This is the first systematic report on 1D COFs for H2O2 photosynthesis, which enriches the topological database in reticular chemistry and promotes the exploration of structure‐catalysis correlation. A sequence of novel VIA group elements (O, S, Se)‐bridged 1D COFs with typical 4‐c sql topology were synthesized and applied as catalysts in the photosynthesis of H2O2. Thanks to their 1D configurations, more active sites are accessible, the proton interlaminar shuttle are accelerated, and the directional transfer of electrons is also improved. The bridge‐atoms (O, S, Se) in the 1D COFs play a crucial role for the catalytic activity and selectivity.