Tan Zhi-Rong, Xing Yu-Qin, Cheng Jing-Zhao, Zhang Guang, Shen Zhao-Qi, Zhang Yu-Jie, Liao Guangfu, Chen Long, Liu Shi-Yong
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, Department of Chemistry, Jiangxi University of Science and Technology Ganzhou 341000 China
Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University Tianjin 300072 China.
Chem Sci. 2022 Jan 14;13(6):1725-1733. doi: 10.1039/d1sc05784g. eCollection 2022 Feb 9.
3,4-Ethylene dioxythiophene (EDOT), as a monomer of commercial conductive poly(3,4-ethylene dioxythiophene) (PEDOT), has been facilely incorporated into a series of new π-conjugated polymer-based photocatalysts, , BSO-EDOT, DBT-EDOT, Py-EDOT and DFB-EDOT, through atom-economic C-H direct arylation polymerization (DArP). The photocatalytic hydrogen production (PHP) test shows that donor-acceptor (D-A)-type BSO-EDOT renders the highest hydrogen evolution rate (HER) among the linear conjugated polymers (CPs) ever reported. A HER up to 0.95 mmol h/6 mg under visible light irradiation and an unprecedented apparent quantum yield of 13.6% at 550 nm are successfully achieved. Note that the photocatalytic activities of the C-H/C-Br coupling-derived EDOT-based CPs are superior to those of their counterparts derived from the classical C-Sn/C-Br Stille coupling, demonstrating that EDOT is a promising electron-rich building block which can be facilely integrated into CP-based photocatalysts. Systematic studies reveal that the enhanced water wettability by the integration of polar BSO with hydrophilic EDOT, the increased electron-donating ability by O-C p-π conjugation, the improved electron transfer by D-A architecture, broad light harvesting, and the nano-sized colloidal character in a HO/NMP mixed solvent rendered BSO-EDOT as one of the best CP photocatalysts toward PHP.
3,4-亚乙基二氧噻吩（EDOT）作为商业化的聚（3,4-亚乙基二氧噻吩）（PEDOT）的单体，已通过原子经济性的C-H直接芳基化聚合反应（DArP）被简便地引入到一系列新型的基于π共轭聚合物的光催化剂中，即BSO-EDOT、DBT-EDOT、Py-EDOT和DFB-EDOT。光催化产氢（PHP）测试表明，供体-受体（D-A）型的BSO-EDOT在已报道的线性共轭聚合物（CPs）中具有最高的析氢速率（HER）。在可见光照射下，HER高达0.95 mmol h/6 mg，在550 nm处成功实现了前所未有的13.6%的表观量子产率。值得注意的是，由C-H/C-Br偶联衍生的基于EDOT的CPs的光催化活性优于其由经典的C-Sn/C-Br Stille偶联衍生的对应物，这表明EDOT是一种有前景的富电子结构单元，可被简便地整合到基于CP的光催化剂中。系统研究表明，通过将极性的BSO与亲水性的EDOT整合提高了水润湿性，通过O-C p-π共轭增强了供电子能力，通过D-A结构改善了电子转移，拓宽了光捕获范围，以及在HO/NMP混合溶剂中的纳米级胶体特性，使得BSO-EDOT成为用于PHP的最佳CP光催化剂之一。
