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Research Article

High selective epoxidation of 2-methylpropene over a Mo-based oxametallacycle reinforced nano composite

Chao Xiong1Hao Liu1Jie Zhou1Dejing Xu2Yichao Liang2Xiantai Zhou2Can Xue2( )Hongbing Ji1( )
Fine Chemical Industry Research Institute, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
School of Chemical Engineering and Technology, Sun Yat-Sen University, Zhuhai 519082, China
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Graphical Abstract

We propose an oxidative pretreatment method to synthesize an oxametallacycle reinforced nanocomposite (Mo(O2)2@RT). This catalyst exhibits excellent catalytic activity in 2-methylpropene epoxidation to produce 2-methylpropylene oxide (select.: 99.7%; yield: 92%; tert-butyl hydroperoxide (TBHP) utilization: 81%), along with good reusability and scalability. In this contribution, the composite achieves the dual activation of the oxidant and light olefins in one reaction system.

Abstract

Compared with the gas-solid phase reactions, the epoxidation of light olefins in the liquid phase could realize the highly selective preparation of epoxides at a lower temperature. Nevertheless, the C=C bond of light olefins is more difficult to activate, and it is still a challenge to realize the dual activation of the oxidant and light olefins in one reaction system. In this contribution, an oxametallacycle reinforced nanocomposite (Mo(O2)2@RT) is prepared via an oxidative pretreatment strategy, and its epoxidation performance to 2-methylpropene in liquid-phase with tert-butyl hydroperoxide (TBHP) as an oxidant is evaluated. A set of advanced characterizations including field emission scanning electron microscopy, X-ray photoelectron spectroscopy, in-situ Fourier transform infrared spectroscopy (FT-IR), electron spin-resonance spectroscopy, and high-resolution mass spectrometer are implemented to confirm the physicochemical properties and the catalytic behaviors of Mo(O2)2@RT. This catalyst has a fast kinetic response and exhibits excellent catalytic activity in 2-methylpropene epoxidation to produce 2-methylpropylene oxide (MPO; select.: 99.7%; yield: 92%), along with good reusability and scalability. Moreover, the main epoxidation mechanism is deduced that TBHP is activated by Mo(O2)2@RT to generate the highly active tert-butyl peroxide radical, which realizes the epoxidation of 2-methylpropene to yield MPO.

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Nano Research
Pages 209-218
Cite this article:
Xiong C, Liu H, Zhou J, et al. High selective epoxidation of 2-methylpropene over a Mo-based oxametallacycle reinforced nano composite. Nano Research, 2023, 16(1): 209-218. https://doi.org/10.1007/s12274-022-4686-7
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Received: 25 March 2022
Revised: 25 May 2022
Accepted: 21 June 2022
Published: 14 July 2022
© Tsinghua University Press 2022
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