Zhen Lin,Namei Wu,Wensong Yao,Jinyuan Chen,Shaoguang Li,Ailin Liu,Xinhua Lin
Chemiluminescence (CL) happened in chemical reactions, in which electronically excited intermediates or products were obtained and subsequently released energy with emission of light. CL is a useful approach to investigate active radicals involved in one system. In the present work, we first found SiC·SiOx, a new kind of zero-dimensional silicon-based nanomaterial, owned CL properties in the presence of Ce(IV)–Na2SO3. The CL mechanism was further investigated by the CL, ultraviolet-visible light (UV-vis), and electron spin resonance (ESR) spectra. Mechanistic investigation indicated SiC·SiOx increased the generation of singlet oxygen in the Ce(IV)–Na2SO3 system and excited SiC·SiOx could be produced from the combination of hole and electron injected SiC·SiOx. This opens up an avenue for investigating the CL properties of SiC·SiOx and promotes their application in various fields.
Epoxides are important bulk chemicals, playing irreplaceable role in the chemical industry, but facing serious pollution and low productivity in the production process. Therefore, the development of green and efficient epoxidation of olefins by stable catalysts with low prices is of great significance. In this study, a Mo-MATP catalyst was prepared by modifying Mo(CO)₆ on attapulgite through Si-O bonding. Mo-MATP exhibits excellent performance (99% yield of cyclooctane oxide, CYCO) and stability (80% selectivity of CYCO after 17 cycles), highly tert -butyl hydroperoxide (TBHP) utilization, and extensive substrate scalability. Furthermore, the in-situ Fourier Transform Infrared Spectroscopy (FT-IR), Electron Spin-resonance Spectroscopy (ESR) and High Resolution Mass Spectrometry (HRMS) spectra suggest that TBHP would be activated by Mo-MATP to generate peroxyl radicals, which then oxidize alkenes to their corresponding epoxides. In this study, the stable loading of Mo would largely solve the problem of Mo loss during the catalytic process, thus providing a stable and dispersed Mo active center, enabling the catalyst to possess high catalytic performance and recycling stability.
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