Fan Yulong , Kong Chencheng , Linfeng Zhang , Wu Huadong , Jianding Li , Guo Jia , Qun Yi
2025 SEPARATION AND PURIFICATION TECHNOLOGY355:129721
Abstract
Efficient photocatalysts rely on constructing heterostructure with reasonable configuration. In this study, a novel conjugated polymer with a D-π-A structure was fabricated from polycondensation of perylene diimide and dibenzothiophene sulfone through the suzuki coupling reaction, during which the biphenyl was incorporated as a π-bridge. The photocatalytic hydrogen evolution performance of these copolymers were optimized by introducing different mass fractions of π-bridges via adjusting the additions of biphenyls The optimized PyBpDBSO-5 copolymer, with 17 wt.% perylene diimide and 5 wt% biphenyl, obtained photocatalytic hydrogen productivity of 48.54mmol/h g−1 under visible light without adding Pt as cocatalyst, which is 146.1 % improvement compared to the poly(dibenzothiophene-S,S-dioxide) (PDBTSO, 19.72mmol/h g−1). Based on the analysis of physical and chemical properties, electrochemical testing, the significant advantages of D-π-A configuration in promoting light absorption, photogenerated carriers transfer and separation was confirmed, which was further rationalized by the larger co-planarity of the polymer based on DFT calculations. This study provides inspiration about construction of conjugated organic polymer catalyst towards efficient photocatalysts.
高效的光催化剂依赖于构建具有合理结构的异质结。在本研究中，通过Suzuki偶联反应，将苝二酰亚胺和二苯并噻吩砜进行缩聚，并引入联苯作为π桥，制备了一种具有D-π-A结构的新型共轭聚合物。通过调整联苯的添加量，引入不同质量分数的π桥，优化了这些共聚物的光催化产氢性能。优化后的PyBpDBSO-5共聚物含有17 wt.%的苝二酰亚胺和5 wt%的联苯，在可见光下（未添加Pt助催化剂）实现了48.54 mmol/h g^-1的光催化产氢效率，相比聚（二苯并噻吩-S,S-二氧化物）（PDBTSO，19.72 mmol/h g^-1）提升了146.1%。基于对物理化学性质和电化学测试的分析，证实了D-π-A结构在促进光吸收、光生载流子转移和分离方面的显著优势，这一结果进一步通过密度泛函理论（DFT）计算表明该聚合物具有更大的共平面性得到了合理解释。本研究为构建高效光催化剂的共轭有机聚合物提供了新的启发。
