Achieving effective exciton dissociation and charge transport in linear polymer photocatalysts for H2O2 photosynthesis remains a formidable challenge. Herein, we fabricated three-motif cross-linked polymers by rationally introducing a third functional component into a two-motif linear polymer, which were employed for circulation-flow photocatalytic H2O2 production. By strategically modulating the third component, we precisely tuned the electronic structure, significantly lowering exciton binding energy and enlarging molecular dipole moment. Compared to the original linear configuration, the resulting cross-linked structure creates multidirectional electron transport channels. Combined experimental and calculation investigations demonstrate that these synergistic effects collectively promote exciton dissociation and intramolecular electron transfer. PAQ-TABPB photocatalyst with optimized third-motif accelerates oxygen-to-superoxide radical transformation by lowering the *OOH binding energy, thereby facilitating the two-step single-electron oxygen reduction pathway, attaining an exceptional H2O2 production rate of 3351 μmol/g/h. Notably, we constructed a circulation-flow reactor for photocatalytic synthesis of H2O2. Benefiting from improved gas-liquid mass transfer and efficient light irradiation, this flow-system achieved a 5.2-fold increase in H2O2 production compared to conventional batch reactor under the light intensity of 27 mW cm-2, reaching an accumulated yield of 3125 μmol/g with stable recyclability. This work highlights the potential of multi-component polymeric photocatalysts and circulation-flow reactors for H2O2 photosynthesis.

中文翻译：

---

通过第三基序工程共轭聚合物加速激子解离和电荷转移，用于 H2O2 的光催化循环流合成

在用于 H2O2 光合作用的线性聚合物光催化剂中实现有效的激子解离和电荷传输仍然是一项艰巨的挑战。在此，我们通过将第三种功能成分合理地引入双基序线性聚合物中，制备了三基序交联聚合物，用于循环流光催化 H2O2 生产。通过战略性地调制第三个分量，我们精确调整了电子结构，显着降低了激子结合能并扩大了分子偶极矩。与原始的线性配置相比，所得的交联结构产生了多向电子传输通道。结合实验和计算研究表明，这些协同效应共同促进激子解离和分子内电子转移。具有优化的第三基序的 PAQ-TABPB 光催化剂通过降低 *OOH 结合能加速氧到超氧自由基的转化，从而促进两步单电子氧还原途径，获得 3351 μmol/g/h 的 H2O2 生成速率。值得注意的是，我们构建了一个用于光催化合成 H 2 O 2 的循环流反应器。得益于改进的气液传质和高效的光照射，在 27 mW cm-2 的光强度下，该流动系统的 H2O2 产量比传统间歇式反应器增加了 5.2 倍，累积产率达到 3125 μmol/g，具有稳定的可回收性。这项工作突出了多组分聚合物光催化剂和循环流反应器在 H2O2 光合作用中的潜力。