Benzenesulfonic acid-grafted UIO-66 with improved hydrophobicity as a stable Brønsted acid catalyst

Abstract

Hydrothermal and catalytic stability of UIO-66 MOFs with defective structures are critical aspects to be considered in their catalytic applications, especially under the conditions involving water, moisture and/or heat. Here, we report a facile strategy to introduce the macromolecular acid group to UIO-66 to improve the stability of the resulting UIO-66−PhSO₃H MOF in aqueous phase catalysis. In detail, UIO-66−PhSO₃H was obtained by grafting benzenesulfonic acid on the surface of the pristine UIO-66 to introduce the hydrophobicity, as well as the Brønsted acidity, then assessed using catalytic hydrolysis of cyclohexyl acetate (to cyclohexanol) in water. The introduction of hydrophobic molecules to UIO-66 could prevent the material from being attacked by hydroxyl polar molecules effectively, explaining its good structural stability during catalysis. UIO-66−PhSO₃H promoted the conversion of cyclohexyl acetate at ca. 87%, and its activity and textural properties were basically intact after the cyclic stability tests. The facile modification strategy can improve the hydrothermal stability of UIO-66 significantly, which can expand its catalytic applications in aqueous systems.

Key words： metal−organic frameworks (MOFs); UIO-66; hydrolysis of cyclohexyl acetate; hydrophobicity; Brønsted acidity

Acknowledgements

This project has received funding from the European Union’s Horizon 2020 Research and Innovation Program (Grant No. 872102). The Chinese colleagues thank the National Key R&D Program of China (Grant No. 2019YFE0123200). Fan X and Pan Q thank the International Science & Technology Cooperation Program of Hainan Province (Grant No. GHYF2022006) for the collaborative research.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2285-5 and is accessible for authorized users.

Open Access

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