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 : 2025-06-01 Epub 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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[W10O32]4−-POMOFs上饱和C(sp3)-H键的可见光氧化

如何通过C(sp3)-氢键活化高效氧化环己烷一直是工业上面临的主要挑战。本文以Cu(bix)2(W10O32)0.5, （bix = 1,4-双（咪唑-1-甲基）苯）为原料，设计合成了一种新型多金属氧酸盐基金属有机骨架，命名为CUST-906。以十钨酸酯为光敏剂，CUST-906在可见光下反应条件温和，催化环己烷氧化反应，转化率可高达33.4 %，远高于工业水平（小于4 %），环己醇和环己酮（KA油）的选择性大于99 %。CUST-906在可见光下表现出优异的光吸收能力和光生载流子分离能力，这使得CUST-906具有较强的催化氧化能力和良好的环己烷氧化反应可回收性。我们深入讨论了十钨酸盐的氢原子转移（HAT）过程对C(sp3)-H键的激活，该过程通过·O2−和h+与中心金属协同作用实现光催化氧化过程。本研究为环己烷氧化的多相催化提供了新的思路。

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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.