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Highly stable chromium(III) terephthalate metal organic framework (MIL-101) encapsulated 12-tungstophosphoric heteropolyacid as a water-tolerant solid catalyst for hydrolysis and esterification

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Abstract

A heterogeneous catalyst, chromium(III) terephthalate metal organic framework (MIL-101) encapsulated 12-tungstophosphoric heteropolyacid (HPW), HPW@MIL-101, was prepared by a simple one-step hydrothermal reaction of aqueous mixtures of Cr(NO3)3, terephthalic acid, and HPW. The obtained catalyst was systemically characterized by XRD, N2 adsorption, FT-IR, acid–base titration, and 31P MAS NMR techniques as well as by elemental analysis. The catalytic activity and reusability of HPW@MIL-101 were evaluated in the liquid-phase hydrolysis of ethyl acetate and in esterification of acetic acid with n-hexanol. In both reactions, water exists as a reactant/solvent and as a product. HPW@MIL-101 shows a high activity and excellent reusability in both of the reactions, behaving as a water-tolerant heterogeneous acid catalyst without agglomeration, leaching and deactivation of HPW during its repeated use. The unique characteristics of MIL-101 and the well-dispersed level of HPW confined as noncoordinating guests in the mesoporous cages of the MIL-101 matrix with the integrated protonic acidity of HPW may account for the high catalytic properties of HPW@MIL-101.

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Acknowledgments

Prof. Dr. Weidong Zhu is gratefully acknowledged for fruitful discussions. The financial supports by the National Natural Science Foundation of China (20806075), the Program for Changjiang Scholars and Innovative Research Team in Chinese Universities (IRT0980) and Analysis and Testing Project of Zhejiang Province (2011C37051) are gratefully acknowledged.

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Authors and Affiliations

  1. Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry and Life Sciences, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, People’s Republic of China

    Yindi Zang, Jing Shi, Xiaomin Zhao, Lichun Kong, Fumin Zhang & Yijun Zhong

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  1. Yindi Zang
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  2. Jing Shi
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  3. Xiaomin Zhao
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  4. Lichun Kong
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  5. Fumin Zhang
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  6. Yijun Zhong
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Correspondence to Fumin Zhang.

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Zang, Y., Shi, J., Zhao, X. et al. Highly stable chromium(III) terephthalate metal organic framework (MIL-101) encapsulated 12-tungstophosphoric heteropolyacid as a water-tolerant solid catalyst for hydrolysis and esterification. Reac Kinet Mech Cat 109, 77–89 (2013). https://doi.org/10.1007/s11144-013-0547-4

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  • DOI: https://doi.org/10.1007/s11144-013-0547-4

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