亚砜
化学
光化学
光催化
硫化物
共价键
三嗪
X射线光电子能谱
硫
催化作用
组合化学
有机化学
化学工程
盐(化学)
工程类
作者
Zhu Qi-long,Haiyan An,Tao Xu,Yanhong Chen,Yuting Wei,Hongliang Sun
出处
期刊:ACS Sustainable Chemistry & Engineering
[American Chemical Society]
日期:2024-01-17
标识
DOI:10.1021/acssuschemeng.3c07186
摘要
For environmentally friendly and sustainable development demands, visible-light-driven oxidation of sulfides has become one of the most popular strategies to synthesize functionalized sulfoxides and degrade mustard gas simulants. Herein, three novel polyoxometalate-based covalent triazine frameworks, SiW12-CTF (1), PW12-CTF (2) and PMo12-CTF (3) (CTF = covalent triazine framework), were synthesized via hydrothermal reaction and characterized by infrared spectroscopy, powder X-ray diffraction, XPS spectroscopy and UV–vis DRS, etc. These compounds are excellent photocatalysts for visible-light-driven selective synthesis of various sulfoxides as well as degradation of 2-chloroethyl ethyl sulfide (CEES) illuminated by a 10 W 425 nm LED in an O2 atmosphere. Oxygen-rich POMs with strong electronegativity modulate the electronic structure and create a built-in electric field in POM-CTFs, which promotes the separation and migration of photogenerated carriers. Meanwhile, encapsulation of various POM guests into the CTF induces different electron transfer behaviors, resulting in different photocatalytic activities. Specifically, SiW12-CTF and PW12-CTF, in visible-light-induced oxidation of methyl phenyl sulfide, obtain sulfoxide yields of 96% and 88% within 2 h, respectively, which is higher than the CTF (68%) and SiW12 (5%). However, PMo12-CTF exhibits inferior photocatalytic properties, and the sulfoxide yield is 35% under the same conditions. The in-depth mechanism reveals that the electron transfer process dominated by the O2•– and the energy transfer process induced 1O2 exist in the photocatalytic system. In addition, SiW12-CTF can be used to catalyze various sulfur-containing compounds and maintains boosted structural stability and catalytic activity after the reaction.
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