Abstract Two analogous positional polymers P16PySO and P27PySO have been synthesized via the copolymerization from dibenzothiophene-S,S-dioxide and pyrene building blocks. The effect of the linking pattern on the molecular packing, photophysical and photocatalytic properties of the two isomers was investigated. It was interestingly found that a minor change at the substitution position of pyrene unit was demonstrated to largely influence the photocatalytic properties of the two isomers. P16PySO exhibited an encouraging average hydrogen evolution rate (HER) of 619.5 μmol h−1 and the maximum HER of 774 μmol h−1, much higher than that of 2,7-counterpart with a moderate rate of 282 μmol h−1. The increased photocatalytic activity of P16PySO is mainly ascribed to its more ordered molecular packing, broader absorption region, better wettability, and higher photo-generated charge mobilities. Moreover, the optimum HER was increased from 774 to 1013 μmol h−1 when the amount of the photocatalyst P16PySO was increased from 50 to 100 mg, which is among the top solar-to‑hydrogen conversion efficiencies reported so far for the polymeric photocatalysts.

中文翻译：

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用于高效光催化制氢的芘-alt-二苯并噻吩-S,S-二氧化物共聚物：连接模式的作用

摘要 通过二苯并噻吩-S,S-二氧化物和芘结构单元的共聚反应合成了两种类似的位置聚合物P16PySO和P27PySO。研究了连接模式对两种异构体的分子堆积、光物理和光催化性能的影响。有趣的是，芘单元取代位置的微小变化被证明会极大地影响两种异构体的光催化性能。P16PySO 表现出令人鼓舞的平均析氢速率 (HER) 为 619.5 μmol h-1，最大 HER 为 774 μmol h-1，远高于具有中等速率 282 μmol h-1 的 2,7-对应物。P16PySO 光催化活性的提高主要归因于其更有序的分子堆积、更宽的吸收区域、更好的润湿性、和更高的光生电荷迁移率。此外，当光催化剂 P16PySO 的量从 50 mg 增加到 100 mg 时，最佳 HER 从 774 μmol h-1 增加到 1013 μmol h-1，这是迄今为止报道的聚合物光催化剂的最高太阳能-氢气转换效率之一。