具有全光谱响应的仿生供体-受体共轭微孔聚合物的分子工程和用于增强铀（VI）光还原的不寻常的电子穿梭机,Chemical Engineering Journal

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具有全光谱响应的仿生供体-受体共轭微孔聚合物的分子工程和用于增强铀（VI）光还原的不寻常的电子穿梭机
Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2023-05-02 , DOI: 10.1016/j.cej.2023.143285
Fengtao Yu , Shanshan Yu , Chuangye Li , Zifan Li , Fangru Song , Zhenzhen Xu , Yean Zhu , Chunhui Dai , Xiaohong Cao , Zhibin Zhang , Yunhai Liu , Jianding Qiu

使用无金属共轭聚合物实现高效的光化学铀还原过程是非常理想的，但也极具挑战性，因为它需要广泛的光响应范围和高效的电子传输通道。在此，成功构建了三种新型全光谱（200 ≤ λ ≤ 800 nm）响应仿生供体-受体共轭微孔聚合物（CMP），通过分子工程策略光还原铀。通过各种含醌受体可以方便地优化 CMP 的光学带隙和内置电场。此外，含醌的嵌段表现出出色的氧化还原活性，可以作为独特的电子穿梭来快速转移电子。因此，具有 2,6-二溴苯并[1,2-b:4,5-b']二噻吩-4,8-二酮嵌段的 ECUT-TQ 表现出低至 1.70 eV 的窄带隙，具有更强的内建电性能。场和更有效的电荷分离，实现了 97.4% 的光催化 U(VI) 还原效率，光反应速率常数为 0.057 分钟。详尽的机理分析表明，U(VI) 被还原为UO 的光催化过程中的主要活性物质是光电子和•O 自由基。这项工作为设计用于消除放射性污染的高性能绿色仿生光催化剂提供了一种新方法。

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Molecular engineering of biomimetic donor-acceptor conjugated microporous polymers with full-spectrum response and an unusual electronic shuttle for enhanced uranium(VI) photoreduction

Realizing an efficient photochemical uranium reduction process using metal-free conjugated polymers is highly desirable, but is extremely challenging, as it requires a broad photo-response range and efficient electron transmission channels. Herein, three novel full-spectrum (200 ≤ λ ≤ 800 nm) responsive biomimetic donor–acceptor conjugated microporous polymers (CMPs) were successfully constructed to photoreduce uranium through a molecular engineering strategy. The optical band gap and built-in electric field of the CMPs were conveniently optimized via various quinone-containing acceptors. Furthermore, the quinone-containing block exhibited outstanding redox activity, which could serve as an unique electron shuttle to rapidly transfer electrons. Consequently, ECUT-TQ with 2,6-dibromobenzo[1,2-b:4,5-b']dithiophene-4,8-dione block exhibits a narrow band gap as low as 1.70 eV, a stronger built-in electric field and more efficient charge separation, achieving 97.4% photocatalytic U(VI) reduction efficiency with a photoreaction rate constant of 0.057 min. The exhaustive mechanism analysis illustrates that the dominant active species in the photocatalytic process where U(VI) is reduced to UO are photoelectrons and •O radicals. This work provides a novel approach for designing high-performance green biomimetic photocatalysts for removing radioactive pollution.

更新日期：2023-05-02

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