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

doi:10.1007/s11705-022-2285-5

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (10) : 1389-1398 https://doi.org/10.1007/s11705-022-2285-5

RESEARCH ARTICLE

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

Zongliang Kou¹, Guanlun Sun¹, Qiuyan Ding¹, Hong Li¹(

), Xin Gao^1,², Xiaolei Fan^3,⁴(

), Xiaoxia Ou⁴, Qinhe Pan⁵(

)

¹. School of Chemical Engineering and Technology, National Engineering Research Center of Distillation Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China
². Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China
³. Department of Chemical Engineering, School of Engineering, The University of Manchester, Manchester M13 9PL, UK
⁴. Nottingham Ningbo China Beacons of Excellence Research and Innovation Institute, University of Nottingham Ningbo China, Ningbo 315100, China
⁵. Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, School of Chemical Engineering and Technology, Hainan University, Haikou 570228, China

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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.

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

Corresponding Author(s): Hong Li,Xiaolei Fan,Qinhe Pan

Online First Date: 12 April 2023 Issue Date: 07 October 2023

Cite this article:

Zongliang Kou,Guanlun Sun,Qiuyan Ding, et al. Benzenesulfonic acid-grafted UIO-66 with improved hydrophobicity as a stable Brønsted acid catalyst[J]. Front. Chem. Sci. Eng., 2023, 17(10): 1389-1398.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2285-5
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I10/1389

Fig.1 Schematic diagram of (a) preparation for UIO-66, (b) preparation for UIO-66−PhSO₃H, (c) a hydrophobic surface, and (d) the hydrolysis reaction.

Fig.2 Structure analysis of UIO-66, UIO-66−SO₃H (3 wt %), and UIO-66−PhSO₃H (3 wt %) by (a) FTIR, (b) XRD, and XPS spectra of (c) C 1s, (d) O 1s, and (e) S 2p.

Tab.1 Textural properties of the materials under investigation

Fig.3 TGA profiles of (a) UIO-66, (b) UIO-66−SO₃H (3 wt %), and (c) UIO-66−PhSO₃H (3 wt %).

Fig.4 Topography (I: SEM; II: TEM) of (a) UIO-66, (b) UIO-66−PhSO₃H (3 wt %), and (c) UIO-66−SO₃H (3 wt %) (insets: relevant lattice fringes and EDS mapping analysis for S content in UIO-66−SO₃H and UIO-66−PhSO₃H).

Fig.5 (a) Conversion and selectivity of the hydrolysis of cyclohexyl acetate to cyclohexanol over the UIO-66−PhSO₃H catalysts with different PhSO₃H loading, and (b) the catalytic mechanism.

Fig.6 Reusability of the UIO-66, UIO-66−SO₃H (3 wt %), UIO-66−PhSO₃H (3 wt %) catalysts.

Fig.7 Schematic diagram for the stability mechanism of the catalysts: (a) the contact angle of catalysts and the mechanism of action between water molecules and catalysts, and (b) catalyst regeneration mechanism.

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