Zhang Fulin, Dong Xiaoyun, Wang Yuexin, Lang Xianjun
Sauvage Center for Molecular Sciences, Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China.
Small. 2023 Sep;19(38):e2302456. doi: 10.1002/smll.202302456. Epub 2023 May 17.
Fully conjugated covalent organic frameworks (COFs) can exhibit great potential in semiconductor photocatalysis. But their syntheses remain elusive due to the low reversibility of vinylene linkage. Herein, by tuning the amount of base and temperature, a novel triazine-based sp carbon-conjugated COF (TA-sp c-COF) is successfully constructed over Cs CO . Besides, the influence of modulating factors on the chemical and optoelectronic properties of TA-sp c-COF is thoroughly investigated. TA-sp c-COF adopts an eclipsed AA stacking structure with uniform micropores (1.4 nm). The blue light photocatalysis of the highly crystalline TA-sp c-COF is established for the selective oxidative coupling of amines with oxygen, and the predominant role of superoxide is identified in forming imines. This work foretells that meticulous modulation of reaction conditions is the key to constructing sp carbon-conjugated COFs toward solar photocatalysis.
完全共轭的共价有机框架（COF）在半导体光催化方面具有巨大潜力。但由于亚乙烯基键的可逆性低，其合成仍然难以实现。在此，通过调节碱的用量和温度，在碳酸铯上成功构建了一种新型的基于三嗪的sp碳共轭COF（TA-sp c-COF）。此外，还深入研究了调节因素对TA-sp c-COF化学和光电性质的影响。TA-sp c-COF采用具有均匀微孔（1.4纳米）的重叠AA堆积结构。高结晶度的TA-sp c-COF的蓝光光催化作用被用于胺与氧气的选择性氧化偶联反应，并且超氧化物在形成亚胺过程中的主要作用得以确定。这项工作预示着精细调节反应条件是构建用于太阳能光催化的sp碳共轭COF的关键。
