Wang Yuexin, Li Xia, Dong Xiaoyun, Zhang Fulin, Lang Xianjun
Sauvage Center for Molecular Sciences and Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Sauvage Center for Molecular Sciences and Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
J Colloid Interface Sci. 2022 Jun 15;616:846-857. doi: 10.1016/j.jcis.2022.02.114. Epub 2022 Feb 24.
Recently, triazine-based two dimensional (2D) porous materials have received increasing attention in photocatalysis. Herein, CTF-1, a covalent triazine framework, was adopted as the blueprint for designing a 2D bespoke photocatalyst. The thiazolo[5,4-d]thiazole (TzTz) linkage was inserted into the framework of CTF-1, affording TzTz-TA, which belongs to conjugated microporous polymers (CMPs). Rather than the direct insertion via the challenging CH activation, TzTz-TA was assembled from 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and dithiooxamide, in which TzTz was formed in situ by a process of catalyst-free solvothermal condensation. Both CTF-1 and TzTz-TA had similar energy gaps (E), photocurrents, and charge carrier lifetimes, in line with the similar molecular underpinnings. However, the reduction potential of TzTz-TA is less negative than that of CTF-1 due to the insertion of TzTz linkage, in a more appropriate position for activating O to superoxide (O). In return, blue light-mediated oxidation of sulfides to sulfoxides with O over TzTz-TA was accomplished with significantly superior conversions to those over CTF-1. Intriguingly, extensive sulfides could be oxidized to corresponding sulfoxides with outstanding recycling stability of TzTz-TA. Notably, attendance of an induction period was observed during TzTz-TA photocatalysis. This work highlights the vast potential of designing triazine-based porous materials to meet the tailor-made demands, such as the oxidative transformation of organic molecules with O.
最近，基于三嗪的二维（2D）多孔材料在光催化领域受到了越来越多的关注。在此，共价三嗪框架CTF-1被用作设计定制2D光催化剂的蓝本。噻唑并[5,4-d]噻唑（TzTz）键被插入到CTF-1的框架中，得到了属于共轭微孔聚合物（CMPs）的TzTz-TA。与通过具有挑战性的C-H活化直接插入不同，TzTz-TA是由2,4,6-三（4-甲酰基苯基）-1,3,5-三嗪和二硫代草酰胺组装而成，其中TzTz通过无催化剂的溶剂热缩合过程原位形成。CTF-1和TzTz-TA具有相似的能隙（E）、光电流和电荷载流子寿命，这与相似的分子基础一致。然而，由于TzTz键的插入，TzTz-TA的还原电位比CTF-1的还原电位更正，处于激活O生成超氧阴离子（O）的更合适位置。作为回报，在TzTz-TA上用O将硫化物蓝光介导氧化为亚砜，其转化率明显优于在CTF-1上的转化率。有趣的是，大量的硫化物可以被氧化为相应的亚砜，并且TzTz-TA具有出色的循环稳定性。值得注意的是，在TzTz-TA光催化过程中观察到了诱导期的存在。这项工作突出了设计基于三嗪的多孔材料以满足定制需求的巨大潜力，例如用O对有机分子进行氧化转化。
