Using silole as a basic structure unit,we synthesized four novel conj ugated polymers which pos-sessed low optical band gaps and a lowest unoccupied molecular orbital(LUMO)energy levels by Sonogashira-Hagihara coupling reaction,and investigated the effects of comonomer and functional group on performance of photocatalytic hydrogen evolution from water.The results indicate that four conj ugated polymers exhibite excel-lent physicochemical and thermal stability,and the thermodynamic decomposition temperature are up to 400 ℃. The performance of pyrene-containing polymers for photocatalytic hydrogen evolution from water are better than those of tetraphenyl ethylene-containing polymers,among which polymer PMS-PY copolymerized from pyrenyl(PY)and 1-methyl-1,3,4-triphenylsilole(PMS)has the best performance of photocatalytic hydrogen e-volution from water with the hydrogen evolution rate is 2.9 μmol·h-1.The results indicate that the introduc-tion of rigid aromatic ring will increase the overlap of polymer electron orbit,make the formation ofπ-π conj u-gate structure in the polymer molecule,and decrease molecular band gap,which make of the visible light absorp-tion stronger,performance of photocatalytic hydrogen evolution from water better.%以噻咯为基本构筑单元,通过 Sonogashira-Hagihara 偶联反应合成了 4 种窄带隙、低 LUMO 能级的新型共轭聚合物,研究了共聚单体和官能团对其光催化水制氢性能的影响.结果表明,4 种噻咯类共轭聚合物均具有优良的物理化学及热稳定性,热力学分解温度均超过400 ℃,同噻咯类型的含芘基聚合物的光催化水制氢性能优于含四苯乙烯聚合物,其中由芘基(PY)和 1-甲基-1 ,3 ,4-三苯基噻咯(PMS)共聚的聚合物 PMS-PY 的光催化水制氢性能最好,制氢速率为 2 .9 μmol·h-1.表明,刚性芳环的引入会导致聚合物电子轨道重叠增大,使聚合物分子内形成 共轭结构,有利于缩小分子带隙,使得可见光吸收更强,光催化水制氢效果更好.
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