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.

Graphical abstract

Keywords

metal−organic frameworks (MOFs) / UIO-66 / hydrolysis of cyclohexyl acetate / hydrophobicity / Brønsted acidity

References

[1] Cirujano F G, Llabres I X F X. Tuning the catalytic properties of UiO-66 metal–organic frameworks: from Lewis to defect-induced Bronsted acidity. Journal of Physical Chemistry Letters, 2020, 11(12): 4879–4890

[2] Longa J R, Yaghi O M. The pervasive chemistry of metal–organic frameworks. Chemical Society Reviews, 2009, 38(5): 1213–1214

[3] Wang C, An B, Lin W. Metal–organic frameworks in solid–gas phase catalysis. ACS Catalysis, 2019, 9(1): 130–146

[4] Liu J, Chen L, Cui H, Zhang J, Zhang L, Su C Y. Applications of metal–organic frameworks in heterogeneous supramolecular catalysis. Chemical Society Reviews, 2014, 43(16): 6011–6061

[5] Dhakshinamoorthy A, Santiago-Portillo A, Asiri A M, Garcia H. Engineering UiO-66 metal organic framework for heterogeneous catalysis. ChemCatChem, 2019, 11(3): 899–923

[6] Jiao L, Wang Y, Jiang H L, Xu Q. Metal–organic frameworks as platforms for catalytic applications. Advanced Materials, 2018, 30(37): e1703663

[7] Wang Y, Li L, Dai P, Yan L, Cao L, Gu X, Zhao X. Missing-node directed synthesis of hierarchical pores on a zirconium metal–organic framework with tunable porosity and enhanced surface acidity via a microdroplet flow reaction. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2017, 5(42): 22372–22379

[8] Jiang J, Yaghi O M. Bronsted acidity in metal–organic frameworks. Chemical Reviews, 2015, 115(14): 6966–6997

[9] Corma A. Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chemical Reviews, 1995, 95(3): 559–614

[10] Furukawa H, Muller U, Yaghi O M. “Heterogeneity within order” in metal–organic frameworks. Angewandte Chemie International Edition, 2015, 54(11): 3417–3430

[11] Shepherd N D, Wang T, Ding B, Beves J E, D’Alessandro D M. Visible light stimulated bistable photo-switching in defect engineered metal–organic frameworks. Inorganic Chemistry, 2021, 60(16): 11706–11710

[12] Tanabe K K, Cohen S M. Postsynthetic modification of metal–organic frameworks—a progress report. Chemical Society Reviews, 2011, 40(2): 498–519

[13] Deng H, Doonan C J, Furukawa H, Ferreira R B, Towne J, Knobler C B, Wang B, Yaghi O M. Multiple functional groups of varying ratios in metal–organic frameworks. Science, 2010, 327(5967): 846–850

[14] Zhang Y B, Furukawa H, Ko N, Nie W, Park H J, Okajima S, Cordova K E, Deng H, Kim J, Yaghi O M. Introduction of functionality, selection of topology, and enhancement of gas adsorption in multivariate metal–organic framework-177. Journal of the American Chemical Society, 2015, 137(7): 2641–2650

[15] Chen J, Li K, Chen L, Liu R, Huang X, Ye D. Conversion of fructose into 5-hydroxymethylfurfural catalyzed by recyclable sulfonic acid-functionalized metal–organic frameworks. Green Chemistry, 2014, 16(5): 2490–2499

[16] Desidery L, Yusubov M S, Zhuiykov S, Verpoort F. Fully-sulfonated hydrated UiO66 as efficient catalyst for ethyl levulinate production by esterification. Catalysis Communications, 2018, 117: 33–37

[17] Morales G, Athens G, Chmelka B, Vangrieken R, Melero J. Aqueous-sensitive reaction sites in sulfonic acid-functionalized mesoporous silicas. Journal of Catalysis, 2008, 254(2): 205–217

[18] da Silva Rocha K A, Hoehne J L, Gusevskaya E V. Phosphotungstic acid as a versatile catalyst for the synthesis of fragrance compounds by alpha-pinene oxide isomerization: solvent-induced chemoselectivity. Chemistry, 2008, 14(20): 6166–6172

[19] Liu L, Tao Z P, Chi H R, Wang B, Wang S M, Han Z B. The applications and prospects of hydrophobic metal–organic frameworks in catalysis. Dalton Transactions, 2021, 50(1): 39–58

[20] Cai M, Li Y, Liu Q, Xue Z, Wang H, Fan Y, Zhu K, Ke Z, Su C Y, Li G. One-step construction of hydrophobic MOFs@COFs core-shell composites for heterogeneous selective catalysis. Advanced Science, 2019, 6(8): 1802365

[21] Isaka Y, Kawase Y, Kuwahara Y, Mori K, Yamashita H. Two-phase system utilizing hydrophobic metal–organic frameworks (MOFs) for photocatalytic synthesis of hydrogen peroxide. Angewandte Chemie International Edition, 2019, 58(16): 5402–5406

[22] Vo K, Le V N, Yoo K S, Song M, Kim D, Kim J. Facile Synthesis of UiO-66(Zr) using a microwave-assisted continuous tubular reactor and its application for toluene adsorption. Crystal Growth & Design, 2019, 19(9): 4949–4956

[23] Taddei M, Steitz D A, Bokhoven J A, Ranocchiari M. Continuous-flow microwave synthesis of metal–organic frameworks: a highly efficient method for large-scale production. Chemistry, 2016, 22(10): 3245–3249

[24] Li H, Deng Q, Chen H, Cao X, Zheng J, Zhong Y, Zhang P, Wang J, Zeng Z, Deng S. Benzenesulfonic acid functionalized hydrophobic mesoporous biochar as an efficient catalyst for the production of biofuel. Applied Catalysis A: General, 2019, 580(25): 178–185

[25] Li B, Zhang Y, Ma D, Li L, Li G, Li G, Shi Z, Feng S. A strategy toward constructing a bifunctionalized MOF catalyst: post-synthetic modification of MOFs on organic ligands and coordinatively unsaturated metal sites. Chemical Communications, 2012, 48(49): 6151–6153

[26] Han Y, Liu M, Li K, Zuo Y, Wei Y, Xu S, Zhang G, Song C, Zhang Z, Guo X. Facile synthesis of morphology and size-controlled zirconium metal–organic framework UiO-66: the role of hydrofluoric acid in crystallization. CrystEngComm, 2015, 17(33): 6434–6440

[27] Ordomsky V V, Sushkevich V L, Schouten J C, van der Schaaf J, Nijhuis T A. Glucose dehydration to 5-hydroxymethylfurfural over phosphate catalysts. Journal of Catalysis, 2013, 300: 37–46

[28] Qiu J, Feng Y, Zhang X, Jia M, Yao J. Acid-promoted synthesis of UiO-66 for highly selective adsorption of anionic dyes: adsorption performance and mechanisms. Journal of Colloid and Interface Science, 2017, 499: 151–158

[29] Morris W, Wang S, Cho D, Auyeung E, Li P, Farha O K, Mirkin C A. Role of modulators in controlling the colloidal stability and polydispersity of the UiO-66 metal–organic framework. ACS Applied Materials & Interfaces, 2017, 9(39): 33413–33418

[30] Lin Foo M, Horike S, Fukushima T, Hijikata Y, Kubota Y, Takata M, Kitagawa S. Ligand-based solid solution approach to stabilisation of sulphonic acid groups in porous coordination polymer Zr₆O₄(OH)₄(BDC)₆ (UiO-66). Dalton Transactions, 2012, 41(45): 13791–13794

[31] Smith J L, Herman R G, Terenna C R, Galler M R, Klier K. Sorption of nitrogen bases and XPS study of mesoporous solid acid SBA-15. Journal of Physical Chemistry A, 2004, 108(1): 39–46

[32] Chellappan S, Aparna K, Chingakham C, Sajith V, Nair V. Microwave assisted biodiesel production using a novel Brønsted acid catalyst based on nanomagnetic biocomposite. Fuel, 2019, 246(15): 268–276

[33] Jeremy L, Smith R G H, Terenna C R, Galler M R, Klier K. Sorption of nitrogen bases and XPS study of mesoporous solid acid SBA-15. The Journal of Chemical Physics A, 2004, 108(1): 39–46

[34] Wißmann G, Schaate A, Lilienthal S, Bremer I, Schneider A M, Behrens P. Modulated synthesis of Zr-fumarate MOF. Microporous and Mesoporous Materials, 2012, 152: 64–70

[35] Liu X, Zhao X, Zhou M, Cao Y, Wu H, Zhu J. Highly stable and active palladium nanoparticles supported on a mesoporous UiO66@reduced graphene oxide complex for practical catalytic applications. European Journal of Inorganic Chemistry, 2016, 2016(20): 3338–3343

[36] Chavan S M, Shearer G C, Svelle S, Olsbye U, Bonino F, Ethiraj J, Lillerud K P, Bordiga S. Synthesis and characterization of amine-functionalized mixed-ligand metal–organic frameworks of UiO-66 topology. Inorganic Chemistry, 2014, 53(18): 9509–9515

[37] Vakili R, Xu S, Al-Janabi N, Gorgojo P, Holmes S M, Fan X. Microwave-assisted synthesis of zirconium-based metal organic frameworks (MOFs): optimization and gas adsorption. Microporous and Mesoporous Materials, 2018, 260: 45–53

[38] Ambrosi M, Fratini E, Canton P, Dankesreiter S, Baglioni P. Bottom-up/top-down synthesis of stable zirconium hydroxide nanophases. Journal of Materials Chemistry, 2012, 22(44): 23497–23505

[39] Russo V, Milicia A, Di Serio M, Tesser R. Falling film reactor modelling for sulfonation reactions. Chemical Engineering Journal, 2019, 377: 120464

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

This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

RIGHTS & PERMISSIONS

2023 The Author(s). This article is published with open access at link.springer.com and journal.hep.com.cn