Shu Chang, Han Changzhi, Yang Xiye, Zhang Chong, Chen Yu, Ren Shijie, Wang Feng, Huang Fei, Jiang Jia-Xing
Key Laboratory for Macromolecular Science of Shaanxi Province, Shaanxi Engineering Laboratory for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi'an, Shaanxi, 710062, P. R. China.
Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, P. R. China.
Adv Mater. 2021 Jul;33(26):e2008498. doi: 10.1002/adma.202008498. Epub 2021 May 24.
Recently, great progress has been achieved in the design and preparation of conjugated organic polymer photocatalysts for hydrogen generation. However, it is still challenging to develop an organic polymer photocatalyst with high photoconversion efficiency. Rational structure design of organic polymer photocatalysts holds the key point to realize high photocatalytic performance. Herein, a series of donor-π-acceptor (D-π-A) conjugated organic copolymer photocatalysts is developed using statistical copolymerization by tuning the feed molar ratio of pyrene (donor) to dibenzothiophene-S,S-dioxide (acceptor) units. It reveals that the photocatalytic activity of the resulting copolymers is significantly dependent on the molar ratio of donor to acceptor, which efficiently changes the polymer structure and component. When the monomer feed ratio is 25:75, the random copolymer PyBS-3 of 10 mg with Pt cocatalyst shows a high hydrogen evolution rate of 1.05 mmol h under UV/Vis light irradiation using ascorbic acid as the hole-scavenger, and an external quantum efficiency of 29.3% at 420 nm, which represents the state-of-the-art of organic polymer photocatalysts. This work demonstrates that statistical copolymerization is an efficient strategy to optimize the polymer structure for improving the photocatalytic activity of conjugated organic polymer catalysts.
近年来，共轭有机聚合物光催化剂用于制氢的设计与制备取得了重大进展。然而，开发具有高光转化效率的有机聚合物光催化剂仍然具有挑战性。有机聚合物光催化剂的合理结构设计是实现高光催化性能的关键。在此，通过调节芘（供体）与二苯并噻吩 - S,S - 二氧化物（受体）单元的进料摩尔比，利用统计共聚法制备了一系列供体 - π - 受体（D - π - A）共轭有机共聚物光催化剂。结果表明，所得共聚物的光催化活性显著依赖于供体与受体的摩尔比，这有效地改变了聚合物的结构和组成。当单体进料比为25:75时，10 mg含铂助催化剂的无规共聚物PyBS - 3在以抗坏血酸作为空穴清除剂的紫外/可见光照射下，析氢速率高达1.05 mmol/h，在420 nm处的外量子效率为29.3%，代表了有机聚合物光催化剂的先进水平。这项工作表明，统计共聚是优化聚合物结构以提高共轭有机聚合物催化剂光催化活性的有效策略。
