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.
高效的光催化劑依賴于構建具有合理結構的異質結。在本研究中，通過Suzuki偶聯反應，将苝二酰亞胺和二苯并噻吩砜進行縮聚，并引入聯苯作為π橋，制備了一種具有D-π-A結構的新型共轭聚合物。通過調整聯苯的添加量，引入不同質量分數的π橋，優化了這些共聚物的光催化産氫性能。優化後的PyBpDBSO-5共聚物含有17 wt.%的苝二酰亞胺和5 wt%的聯苯，在可見光下（未添加Pt助催化劑）實現了48.54 mmol/h g^-1的光催化産氫效率，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%。基于對物理化學性質和電化學測試的分析，證實了D-π-A結構在促進光吸收、光生載流子轉移和分離方面的顯著優勢，這一結果進一步通過密度泛函理論（DFT）計算表明該聚合物具有更大的共平面性得到了合理解釋。本研究為構建高效光催化劑的共轭有機聚合物提供了新的啟發。
