Chi Wenwen, Wu Jiale, Dong Yuming, Wu Jie, Zhu Yongfa
International Joint Research Center for Photoresponsive Molecules and Materials, Key Laboratory of Synthetic and Biological Colloids, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, P.R. China.
Department of Chemistry, National University of Singapore, Singapore, 117543, Singapore.
Angew Chem Int Ed Engl. 2025 Aug 4;64(32):e202508690. doi: 10.1002/anie.202508690. Epub 2025 Jun 12.
Achieving effective exciton dissociation and charge transport in linear polymer photocatalysts for HO 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 HO production. By strategically modulating the third component, we precisely tuned the electronic structure, significantly lowering exciton binding energy and enlarging the 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 HO production rate of 3351 µmol g h. Notably, we constructed a circulation-flow reactor for the photocatalytic synthesis of HO. Benefiting from improved gas-liquid mass transfer and efficient light irradiation, this high-speed flow system achieved a 5.2-fold increase in HO production compared to a conventional batch reactor under the light intensity of 27 mW cm, 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 HO photosynthesis.
在用于光催化产过氧化氢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组分合理引入双组分线性聚合物中来制备三组分交联聚合物，将其用于循环流光催化产过氧化氢。通过策略性地调节第三种组分，我们精确调整了电子结构，显著降低了激子结合能并增大了分子偶极矩。与原始的线性结构相比，所得的交联结构形成了多方向的电子传输通道。结合实验和计算研究表明，这些协同效应共同促进了激子解离和分子内电子转移。具有优化第三组分的PAQ-TABPB光催化剂通过降低*OOH结合能加速了氧到超氧自由基的转化，从而促进了两步单电子氧还原途径，实现了3351 μmol g⁻¹ h⁻¹的优异产过氧化氢速率。值得注意的是，我们构建了一个用于光催化合成过氧化氢的循环流反应器。受益于改善的气液传质和高效的光照射，在27 mW cm⁻²的光强下，该高速流动系统的过氧化氢产量比传统间歇反应器提高了5.2倍，达到了3125 μmol g⁻¹的累积产量且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光催化产过氧化氢方面的潜力。
