Visible-light-mediated oxidation of saturated C(sp3)-H bonds over [W10O32]4−-POMOFs

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL Journal of Catalysis Pub Date : 2025-03-17 DOI:10.1016/j.jcat.2025.116088

Yanjie Lv, Dianxiang Peng, Wenxi Zhang, Jing Sun, Huiying Sun, Xin Wang, Xiao Li, Mingwei Ma, Zhongmin Su

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Abstract

How to efficiently oxidize cyclohexane through C(sp³)-H bond activation has been a major challenge in industry. In this paper, a new polyoxometalate based metal–organic frameworks, named as CUST-906 is designed and synthesized with the formula of Cu(bix)₂(W₁₀O₃₂)_0.5, (bix = 1,4-Bis(imidazol-1-ylmethyl)benzene). Decatungstate as photosensitizer, CUST-906 can catalyze the oxidation reaction of cyclohexane under visible light with mild reaction conditions, the conversion rate can reach high as 33.4 %, which is far higher than that of the industrial level (less than 4 %), and the selectivity of cyclohexanol and cyclohexanone (KA oil) is greater than 99 %. CUST-906 exhibits excellent light absorption ability and photogenerated carrier separation ability under visible light, which endows CUST-906 strong catalytic oxidation capacity and good recyclability for the oxidation reaction of cyclohexane. We delve into the discussion the activation of C(sp³)-H bonds by the hydrogen atom transfer (HAT) process of decatungstate, which synergies with the central metal to achieve the photocatalytic oxidation process via ·O₂⁻ and h⁺. This work provides a new idea for heterogeneous catalysis of cyclohexane oxidation.

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.