三嗪基共轭微孔聚合物的合成及其光催化产氢性能研究  

Synthesis and Photocatalytic Hydrogen Evolution Study of Triazine-Based Conjugated Microporous Polymers

作　　者：杨光 王千 李青音 任世杰[1] YANG Guang;WANG Qian;LI Qingyin;REN Shijie(State Key Laboratory of Polymer Materials Engineering,College of Polymer Science and Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]四川大学高分子科学与工程学院,高分子材料工程国家重点实验室,成都610065

出　　处：《功能高分子学报》2021年第1期66-73,共8页Journal of Functional Polymers

基　　金：国家自然科学基金(51973128,21574087);四川省科技计划项目(2019YFG0277,2019YJ0128)。

摘　　要：共轭微孔聚合物(CMPs)具有合成方法多样、能带结构和电子结构可调等特点,近年成为了一类备受关注的新型光催化剂,在光催化制氢领域具有良好的应用潜力。为了探究分子结构对CMPs光催化性能的影响,通过分子设计,经Pd催化的Suzuki偶联反应合成了4种三嗪基共轭微孔聚合物(TCMPs),其中TTCMP1和TTCMP2具有噻吩单元,TFCMP1和TFCMP2具有芴单元。这些TCMPs具有较大的比表面积和与光催化分解水相匹配的光学带隙。通过对TCMPs光学性能的分析表明,功能单元结构和连接体长度的变化可以影响其能带带隙,从而调节聚合物的产氢性能。其中,含芴单元的TCMPs具有更好的光催化产氢性能,具有较长连接单元的TFCMP2在可见光下显示出更高的氢释放速率(244μmol/(h·g))。Photocatalytic water splitting to produce hydrogen is one of the effective ways to achieve solar energy utilization,in which the key point is to develop efficient and cheap photocatalysts.Conjugated microporous polymers(CMPs),allowing the fine synthetic control over their chemical structures and electronic properties,have become a new type of photocatalysts due to their diverse synthetic modularity.In order to investigate the effects of molecular structures on the photocatalytic performance of CMPs,four triazine-based conjugated microporous polymers(TCMPs)were designed and synthesized by Suzuki coupling reaction in this work,among which,TTCMP1 and TTCMP2 contain thiophene units,and TFCMP1 and TFCMP2 possess fluorene units.These TCMPs have high specific surface areas and appropriate optical band gaps.Through optical analysis of these TCMPs,it is found that the structural change of functional units and the length of linkers can tune the energy band gap,thereby influencing the hydrogen production performance of the polymers.Results show that TFCMPs containing fluorene units show better photocatalytic hydrogen production performance.And TFCMP2 with longer linking units shows the highest hydrogen release rate of 244μmol/(h·g)under visible light(λ≥420 nm).This work provides a promising strategy for exploring the relationship between the structure and performance of CMPs for photocatalytic hydrogen evolution.

关 键 词：共轭微孔聚合物 光催化 水分解制氢 

分 类 号：O63[理学—高分子化学]