具有单向电子转移的共价三嗪框架用于增强光催化氧化反应,ACS Catalysis

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具有单向电子转移的共价三嗪框架用于增强光催化氧化反应
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-08-29 , DOI: 10.1021/acscatal.3c02122
Sizhe Li ₁ , Lingling Hu ₂ , Zhuangfei Qian ₁ , Jie Yin ₁ , Juntao Tang ₂ , Chunyue Pan ₂ , Guipeng Yu ₂ , Kai A. I. Zhang ₁

Affiliation

在生物系统中，氧化还原驱动的催化过程通过具有明确定义的逐步电荷转移途径的可控活性位点有效地发生。对于人工催化系统，特别是纯有机、聚合物和多相光催化剂，主要挑战在于通过催化活性位点获得电子转移途径的精确控制。在这里，我们设计了结晶吩噻嗪锚定的共价三嗪框架（CTF）作为具有精确可控单向电子转移途径的纯有机光催化剂的基准示例。单官能化吩噻嗪单元共聚到 CTF 上，在光诱导电荷分离时，在具有强偶极子和高内置电场的聚合物网络内产生确定的电子转移。通过结合原位光谱方法和瞬态时间依赖性密度泛函理论计算，我们揭示了吩噻嗪单元上的硫原子是光生空穴形成的主要氧化位点。伯胺的氧化偶联、苯并咪唑的形成、苯并咪唑的氧化甲酰化等重要的氧化反应证明了所设计的CTF的高催化活性、可回收性和普遍适用性。N , N-二甲基苯胺和醛肟的脱水。

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Covalent Triazine Frameworks with Unidirectional Electron Transfer for Enhanced Photocatalytic Oxidation Reactions

In biological systems, redox-driven catalytic processes efficiently occur through controllable active sites with a clearly defined stepwise charge transfer pathway. For artificial catalytic systems, especially pure organic, polymeric, and heterogeneous photocatalysts, the main challenge lies in gaining precise control of electron transfer pathways through the catalytic active sites. Here, we design crystalline phenothiazine-anchored covalent triazine frameworks (CTFs) as a benchmark example of pure organic photocatalysts with precisely controllable unidirectional electron transfer pathways. Monofunctionalized phenothiazine units were copolymerized onto CTFs, leading to defined electron transfer within the polymer network with a strong dipole and a high built-in electric field upon light-induced charge separation. By combining in situ spectroscopic methods and transient time-dependent density functional theory calculations, we reveal that sulfur atoms on phenothiazine units were the major oxidative sites by formation of photogenerated holes. High catalytic activity, recyclability, and general applicability of the designed CTFs were demonstrated by important oxidation reactions such as oxidative coupling of primary amines, formation of benzimidazoles, oxidative formylation of N, N-dimethylanilines, and dehydration of aldoximes.

更新日期：2023-08-29

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