1D Covalent Organic Frameworks Triggering Highly Efficient Photosynthesis of H₂ O₂ 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-H₂ O₂ 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 H₂ O₂ photosynthesis, which enriches the topological database in reticular chemistry and promotes the exploration of structure-catalysis correlation.