Li Luoning, Liu Yanan, Wang Jing, Cai Minzhen, Ma Pengtao, Wang Jingping, Niu Jingyang
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Molecular Sciences, Henan University, Kaifeng, Henan 475004, P. R. China.
Puyang Institute of Technology, Henan University, Puyang, Henan 457000, P. R. China.
Inorg Chem. 2025 Apr 7;64(13):6612-6620. doi: 10.1021/acs.inorgchem.5c00125. Epub 2025 Mar 27.
The photocatalytic oxidative coupling of thiols to disulfides by using visible light represents an economically viable and environmentally sustainable strategy. A novel POM@MOF photocatalyst (Ru-CdS-SiW) was synthesized through the encapsulation of Keggin-type [SiWO] within a MOF composed of Ru metalloligands and {CdSO} clusters. In this structure, the incorporation of POMs to the MOFs reduced the charge transport distance, facilitated the separation and transfer of photogenerated charges and holes, and prevented the recombination of electron-hole pairs. The Ru-CdS-SiW catalyst demonstrated exceptional catalytic performance, achieving a 98.1% yield in the S-S bond formation from 4-methylthiophenol coupling with an apparent quantum yield of 4.8% at 440 nm. Through comprehensive exploratory experiments and electron paramagnetic resonance (EPR) measurements, we elucidated the mechanism underlying the photoinduced oxidative coupling of thiols. Notably, this catalytic reaction operates under mild visible-light conditions and exhibits remarkable recyclability, presenting significant potential for applications in sensitive systems, such as protein disulfide bond formation.
利用可见光将硫醇光催化氧化偶联为二硫化物是一种经济可行且环境可持续的策略。通过将Keggin型[SiWO]封装在由Ru金属配体和{CdSO}簇组成的金属有机框架（MOF）中，合成了一种新型的POM@MOF光催化剂（Ru-CdS-SiW）。在这种结构中，将多金属氧酸盐（POMs）引入MOFs缩短了电荷传输距离，促进了光生电荷和空穴的分离与转移，并防止了电子-空穴对的复合。Ru-CdS-SiW催化剂表现出优异的催化性能，4-甲基苯硫酚偶联形成S-S键的产率达到98.1%，在440 nm处的表观量子产率为4.8%。通过全面的探索性实验和电子顺磁共振（EPR）测量，我们阐明了硫醇光诱导氧化偶联的机理。值得注意的是，这种催化反应在温和的可见光条件下进行，具有显著的可回收性，在敏感系统（如蛋白质二硫键形成）的应用中具有巨大潜力。
