Postsynthetic acid modification of amino-tagged metal-organic frameworks: Structure-functionrelationship for catalytic 5-hydroxymethylfurfural synthesis

doi:10.1016/j.cjche.2021.08.004

Abstract

Abstract: Developing an efficient and selective catalyst for the dehydration of fructose to 5-hydroxymethylfurfural (HMF) is significant for biomass conversion. Herein, a metal-organic framework (MOF) with acidity and strong hydrophobicity is first reported by the condensation of amino-tagged MOFs with mercapto carboxylic acids and subsequent oxidation. The hydrophobic acidic MOFs possess acid densities ranging from 0.2-1.0 mmol·g^-1, H₂O contact angles of 114°-125°, and specific surface areas above 260 m²·g^-1. Compared to the methyl sulfo-functionalized MOF, the benzene sulfo-functionalized MOF with a strong hydrophobicity shows much higher activity and selectivity for the conversion of fructose to 5-hydroxymethylfurfural. In particular, 2.99% (mass) UiO-PhSO₃H shows the best catalytic performance with a 90.4% HMF yield due to its suitable hydrophobicity and abundant acidic sites. Moreover, the catalyst shows great stability after recycling for 5 runs. This work provides an interesting design strategy for the preparation of hydrophobic acidic MOFs and shows the powerful synergistic effect of acidity and hydrophobicity.

Key words: Metal-organic framework, 5-Hydroxymethylfurfural, Fructose, Acidity, Hydrophobicity

摘要： Developing an efficient and selective catalyst for the dehydration of fructose to 5-hydroxymethylfurfural (HMF) is significant for biomass conversion. Herein, a metal-organic framework (MOF) with acidity and strong hydrophobicity is first reported by the condensation of amino-tagged MOFs with mercapto carboxylic acids and subsequent oxidation. The hydrophobic acidic MOFs possess acid densities ranging from 0.2-1.0 mmol·g^-1, H₂O contact angles of 114°-125°, and specific surface areas above 260 m²·g^-1. Compared to the methyl sulfo-functionalized MOF, the benzene sulfo-functionalized MOF with a strong hydrophobicity shows much higher activity and selectivity for the conversion of fructose to 5-hydroxymethylfurfural. In particular, 2.99% (mass) UiO-PhSO₃H shows the best catalytic performance with a 90.4% HMF yield due to its suitable hydrophobicity and abundant acidic sites. Moreover, the catalyst shows great stability after recycling for 5 runs. This work provides an interesting design strategy for the preparation of hydrophobic acidic MOFs and shows the powerful synergistic effect of acidity and hydrophobicity.

关键词: Metal-organic framework, 5-Hydroxymethylfurfural, Fructose, Acidity, Hydrophobicity

Yao Zhong, Cuiying Huang, Lijie Li, Qiang Deng, Jun Wang, Zheling Zeng, Shuguang Deng. Postsynthetic acid modification of amino-tagged metal-organic frameworks: Structure-functionrelationship for catalytic 5-hydroxymethylfurfural synthesis[J]. Chinese Journal of Chemical Engineering, 2022, 49(9): 245-252.

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