Citation: Zhuoyan Lv, Yangming Ding, Leilei Kang, Lin Li, Xiao Yan Liu, Aiqin Wang, Tao Zhang. Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst[J]. Acta Physico-Chimica Sinica, ;2025, 41(4): 100038. doi: 10.3866/PKU.WHXB202408015 shu

Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst

Zhuoyan Lv ^1,2 ,
Yangming Ding ¹ ,
Leilei Kang ^1,, ,
Lin Li ¹ ,
Xiao Yan Liu ^1,, ,
Aiqin Wang ¹ ,
Tao Zhang ¹

1.
CAS Key Laboratory of Science and Technology on Applied Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Leilei Kang, Xiao Yan Liu,
Received Date: 27 August 2024
Revised Date: 25 September 2024
Accepted Date: 2 October 2024

Fund Project: This work was financially supported by the NSFC Center for Single-Atom Catalysis (22388102), the Fundamental Research Funds for the Central Universities (20720220009), the DNL Cooperation Fund, CAS (DNL202002), LiaoNing Revitalization Talents Program (XLYC2007070), and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0540000).

Direct epoxidation of propylene (DEP) by molecular oxygen is an ideal way to synthesize propylene oxide (PO), yet it remains quite challenging. We demonstrated here that the PO formation rate and selectivity could be enhanced simultaneously through photo-thermo-catalysis over the Cu/TiO₂ catalyst. At 180 ℃, by introducing light, the PO formation rate increased more than 20-fold (from 8.2 to 180.6 μmol∙g⁻¹∙h⁻¹) and the corresponding selectivity improved more than 3-fold (from 8% to 27%), breaking the traditional perception that the semiconductors exhibit very low reactivity for this reaction. Kinetic study results showed that the apparent activation energy for PO formation could sharply decrease under light irradiation (from 95 to 40 kJ∙mol⁻¹). In situ electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were applied to characterize the dynamics of the valence state of the copper oxide species and the activation intermediates of molecular oxygen. Evidence for the activation of oxygen, which could direct to the PO formation pathway, was captured. The light-driven electrons could promote the formation of active Cu⁺, which could form the side-on μ-peroxo Cu(II)₂ structure, weaken the O―O bond, and improve the PO formation rate and selectivity. This work paves a new way for designing semiconductor-supported photocatalysts for DEP reactions with molecular oxygen.
- Photo-thermo-catalysis,
- Cu/TiO₂,
- Selective oxidation,
- Direct propylene epoxidation,
- Oxygen activation
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Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuOx/TiO2 Catalyst

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Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst