EDOT-based conjugated polymers accessed via C–H direct arylation for efficient photocatalytic hydrogen production |
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Authors: | Zhi-Rong Tan Yu-Qin Xing Jing-Zhao Cheng Guang Zhang Zhao-Qi Shen Yu-Jie Zhang Guangfu Liao Long Chen Shi-Yong Liu |
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Institution: | 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 ; Engineering Research Center of Nano-Geomaterials of Ministry of Education, China University of Geosciences, Wuhan 430074 China |
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Abstract: | 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, i.e., BSO2–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 BSO2–EDOT renders the highest hydrogen evolution rate (HER) among the linear conjugated polymers (CPs) ever reported. A HER up to 0.95 mmol h−1/6 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 BSO2 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 H2O/NMP mixed solvent rendered BSO2–EDOT as one of the best CP photocatalysts toward PHP.The excellent reactivity toward C–H direct arylation, water wettability and O–C p–π conjugation endow EDOT to be an attractive electron donor unit for CP photocatalysts, yielding an unprecedented hydrogen evolution rate up to 0.95 mmol h−1/6 mg catalyst. |
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