摘要
Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.
传统聚合物光催化剂通常采用芳香环构建基元以增强π共轭,然而其固有的疏水性和刚性结构导致其在水溶液中分散性较差,进而引发显著光学损失和激子复合。本研究创新性地将亲水性非共轭聚乙二醇(PEG)链段引入聚合物主链和侧链,设计并合成了2个系列共6种新型聚合物光催化剂(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSOPEG30)。通过精确调控PEG链段的摩尔分数,在保持聚合物吸收能力的同时显著改善水分散性。实验结果显示优化后的FLUSO-PEG10表现出优异的光催化析氢速率,达到33.9 mmol/(g·h),较全共轭对应物提升近3倍。水接触角和粒径分析进一步证实,在主链中引入非共轭链段可增强聚合物/水界面相容性,抑制颗粒聚集,从而提升光催化剂的分散性,并促进电荷生成。
出处
《功能高分子学报》
北大核心
2025年第3期216-227,共12页
Journal of Functional Polymers
基金
国家自然科学基金(T2488302,22422805,22338006,92356301,9235630033,22375062)
上海市科学技术委员会(24DX1400200,24160711900)
上海市基础研究试点项目(22TQ1400100-10)
中央高校基本科研业务费专项资金
上海市教育发展基金会、市教委“晨光计划”项目(22CGA32)
CAST青年精英科学家资助项目(2023QNRC001)。
作者简介
田昌昊(2000—),男,安徽蚌埠人,硕士,主要研究方向为有机半导体光催化剂合成及其析氢性能研究。E-mail:18855253574@163.com;通信联系人:车瑜,E-mail:yuche@sxu.edu.cn;通信联系人:张维伟,E-mail:zhangweiwei@ecust.edu.cn;通信联系人:朱为宏,E-mail:whzhu@ecust.edu.cn。
