基于苯并三噻吩的共轭微孔聚合物中的带隙工程：筛选无金属的非均相光催化剂的策略,Journal of Materials Chemistry A

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基于苯并三噻吩的共轭微孔聚合物中的带隙工程：筛选无金属的非均相光催化剂的策略
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2020-12-8 , DOI: 10.1039/d0ta10232f
Songjie Han _{1,

2,

3,

4} , Ziping Li _{1,

2,

3,

4} , Si Ma _{1,

2,

3,

4} , Yongfeng Zhi _{1,

2,

3,

4} , Hong Xia _{2,

3,

4,

5,

6} , Xiong Chen _{1,

4,

7,

8,

9} , Xiaoming Liu _{1,

2,

3,

4}

Affiliation

无金属的共轭微孔聚合物（CMP）作为可见光活性和可回收的光催化剂，为传统的基于金属的光敏剂提供了绿色且可持续的替代品。但是，迄今为止尚未解释筛选基于CMP的多相光催化剂的策略。本文中，我们提出了一种获得优异的固体光催化剂的一般策略，即在相同系列的材料中实施带隙工程。作为概念证明，三种包含苯并[1,2-b：3,4- b '：5,6- b的共轭多孔材料'']]三噻吩结构单元（BTT-CMP1，BTT-CMP2和BTT-CMP3）已成功构建。它们具有永久的孔隙率，具有大的比表面积和出色的稳定性。通过改变苯并三噻吩单元之间的连接基，可以方便地调节BTT-CMP的带隙，能级和光电性能，包括吸收，瞬态光电流响应和光催化性能。实际上，在三种CMP材料中，BTT-CMP2对可见光诱导的苯并咪唑合成表现出最佳的催化活性，甚至高于小分子光催化剂。有趣的是，作为一种无金属的光催化剂，经筛选的BTT-CMP2还显示出广泛的底材适用性和出色的可回收性。另外，

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Bandgap engineering in benzotrithiophene-based conjugated microporous polymers: a strategy for screening metal-free heterogeneous photocatalysts

Metal-free conjugated microporous polymers (CMPs) as visible-light active and recyclable photocatalysts offer a green and sustainable alternative to classical metal-based photosensitizers. However, the strategy for screening CMP-based heterogeneous photocatalysts has not been interpreted up to now. Herein, we present a general strategy for obtaining excellent solid photocatalysts, which is to implement bandgap engineering in the same series of materials. As a proof of concept, three conjugated porous materials containing benzo[1,2-b:3,4-b′:5,6-b′′]trithiophene building blocks (BTT-CMP1, BTT-CMP2 and BTT-CMP3) were successfully constructed. They possess permanent porosity with a large specific surface area and excellent stability. By changing the linker between benzotrithiophene units, the bandgaps, energy levels and photoelectric performances including the absorption, transient photocurrent responses and photocatalytic performances of BTT-CMPs could be handily modulated. Indeed, BTT-CMP2 displayed the best catalytic activity for visible-light-induced synthesis of benzimidazoles among the three CMP materials, even higher than that of small molecule photocatalysts. As a metal-free photocatalyst, interestingly, the screened BTT-CMP2 also showed extensive substrate applicability and outstanding recyclability. Additionally, we have the opinion that this strategy will prove to be a guiding principle for screening superior CMP-based photocatalysts and broaden their application fields.

更新日期：2020-12-24

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