共价三嗪聚合物中可控引入羟基比例对光催化性能的影响

Effect of Controllable Introduction of Hydroxyl Proportion in Covalent Triazine Polymers on Photocatalytic Performance

摘要

针对共价三嗪聚合物(CTP)中官能团引入量对光催化性能影响研究不足的问题，以 2,5-二 (4-氰基苯基) 噻唑并 [5,4-d] 噻唑(TT-BN)为光活性单体合成了羟基化共价三嗪聚合物(CTP-OH)。通过调节光活性单体与含羟基单体的氰基物质的量之比(即投料比)分别为 3∶1、8∶1、18∶1，合成了 3 种不同羟基含量的羟基化共价三嗪聚合物，分别标记为 CTP-OH-3∶1、CTP-OH-8∶1、CTP-OH-18∶1。结果表明，羟基含量最高的 CTP-OH-3∶1 具有最强的光电流响应和最低的界面电荷转移电阻，在蓝光驱动下催化有机脱溴的分离产率为 67%，优于对比样品 CTP-OH-8∶1(分离产率为 53%)和 CTP-OH-18∶1(分离产率为 50%)。随着羟基含量的增加，CTP-OH 在光吸收、激子解离与电荷传输方面的能力也随之增强，从而有效促进了光催化效率的提高。本工作实现了羟基定量调控，揭示了构效关系，为共轭聚合物光催化剂设计提供了新思路。

Abstract

To address the limited understanding of how functional group loading affects the photocatalytic performance of covalent triazine polymers (CTPs), hydroxylated covalent triazine polymers (CTP-OH) were synthesized using 2,5-bis(4-cyanophenyl)thiazolo[5,4-d]thiazole (TT-BN) as the photoactive monomer. Three CTP-OH samples with different hydroxyl contents were prepared by adjusting the cyano molar ratio of the photoactive monomer to the hydroxyl-bearing monomer 4-(hydroxymethyl)benzonitrile (3∶1, 8∶1, and 18∶1), which were labeled as CTP-OH-3∶1, CTP-OH-8∶1, and CTP-OH-18∶1, respectively. The results demonstrated that CTP-OH-3∶1 with the highest hydroxyl content exhibited the strongest photocurrent response and the lowest interfacial charge-transfer resistance. Under blue-light irradiation, photocatalytic organic debromination over CTP-OH-3∶1 achieved a 67% isolated yield, outperforming the control samples CTP-OH-8∶1 (isolated yield of 53%) and CTP-OH-18∶1 (isolated yield of 50%). As the hydroxyl content increased, the capabilities of light absorption, exciton dissociation, and charge transport of CTP-OH were simultaneously enhanced, thereby effectively promoting the photocatalytic performance. This work achieves quantitative regulation of hydroxyl groups, elucidates the structure-activity relationship, and provides new insights for the design of conjugated polymer photocatalysts.

关键词

共价三嗪聚合物 / 官能团引入 / 分子设计 / 光催化 / 脱卤反应

Key words

covalent triazine polymer / functional group incorporation / molecular design / photocatalysis / dehalogenation reaction

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基金资助

国家自然科学基金(22575162)

国家自然科学基金(22505168)

四川省自然科学基金(2026NSFSC0060)