光增强CuOx/TiO2催化丙烯氧气直接环氧化反应

doi:10.3866/PKU.WHXB202408015

Abstract

Abstract:

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.

Key words: Photo-thermo-catalysis, Cu/TiO₂, Selective oxidation, Direct propylene epoxidation, Oxygen activation

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 Phys. -Chim. Sin. 2025, 41(4), 100038. doi: 10.3866/PKU.WHXB202408015

Figures/Tables 8

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Scheme 1

References 53

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Sample	Shell	CN ^a	R (Å)	σ²	ΔE₀ (eV)	R factor (%)
CuO_x/TiO₂-Dark	Cu-O	3.5	1.95 ± 0.004	0.005	−0.8	0.2
	Cu-Cu₁	2.0	2.92 ± 0.01	0.006
	Cu-Cu₂	2.0	3.07 ± 0.01	0.005
CuO_x/TiO₂-Light	Cu-O	3.5	1.95 ± 0.01	0.006	−0.5	0.4
	Cu-Cu₁	1.1	2.85 ± 0.02	0.006
	Cu-Cu₂	3.0	3.01 ± 0.02	0.013

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