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Hydrogen bond-mediated polyoxometalate-based metal-organic networks for efficient and selective oxidation of aryl alkenes to aldehydes

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Abstract

Selective oxidation of aryl alkenes to aldehydes is an important approach to produce industrial raw materials, in which the exploration of an efficient heterogeneous catalyst is significant but challenging. In this work, three hydrogen bond-mediated polyoxometalate(POM)-contained metal–organic networks with the formulas of [Ni(BTD)2(H2O)2]2[SiW12O40]·12H2O (1), [Ni(BTD)2(H2O)]2[SiW12O40]·6H2O (2) and [Zn(BTD)2(H2O)]2[SiW12O40]·6H2O (3) (BTD = 4H,4ʹH-[3,3ʹ-bi(1,2,4-triazole)]-5,5ʹ-diamine) were hydrothermally synthesized, in which the metal–organic fragments interact with POM clusters via abundant hydrogen bonding to extend the structure into three-dimensional supramolecular networks. To be explored as heterogenous catalysts, compounds 1–3 showed high catalytic activity and selectivity for the selective oxidation of styrene to benzaldehyde. Among them, compound 1 exhibits the highest performance with ca. 99% styrene conversion and ca. 99% selectivity of benzaldehyde in 5 h. Moreover, compound 1 displays rich substrate compatibility, recyclability and good structural stability. A series of experiments demonstrated that the high performance of compound 1 should be attributed to the synergistic effect among polyoxoanion and coordination-unsaturated metal centers in metal–organic fragments, which facilitates the activation of H2O2 and styrene substrates, thus enhancing the catalytic performance.

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Data availability

CCDC 2104718 and 2104720–2104721 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033.

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Acknowledgements

This work was financially supported by National Natural Science Foundation of China (Grants 21901060, 21871076), Natural Science Foundation of Hebei Province (Grants B2019205074, B2020205008 and B2016205051), Science and Technology Project of Hebei Education Department (Grant BJ2020037), Project funded by China Postdoctoral Science Foundation (No. 2021TQ0095), Science Foundation of Hebei Normal University (L2019B15). Graduate Student Innovation Funding Project of Hebei Normal University (CXZZSS2021056).

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  1. Hebei Key Laboratory of Organic Functional Molecules, National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang, 050024, China

    Wen-Jing Cui, Si-Meng Zhang, Ze-Yu Tian, Chen Li, Yi-Meng Wang, Bo-Rong Yu, Yuan-Yuan Ma & Zhan-Gang Han

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  1. Wen-Jing Cui
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W-J Cui, S-M Zhang, Z-Y Tian, C Li and Y-M Wang wrote the draft and collected the data; Y-Y Ma and Z-G Han contributed to conceive the idea of the study. All authors contributed to the writing and revisions.

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Correspondence to Yuan-Yuan Ma or Zhan-Gang Han.

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Cui, WJ., Zhang, SM., Tian, ZY. et al. Hydrogen bond-mediated polyoxometalate-based metal-organic networks for efficient and selective oxidation of aryl alkenes to aldehydes. Tungsten 4, 109–120 (2022). https://doi.org/10.1007/s42864-021-00130-5

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