SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2022, Vol. 49 ›› Issue (9): 245-252.DOI: 10.1016/j.cjche.2021.08.004

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

Yao Zhong1, Cuiying Huang1, Lijie Li1, Qiang Deng1, Jun Wang1, Zheling Zeng1, Shuguang Deng2   

  1. 1. Key Laboratory of Poyang Lake Environment and Resource Utilization (Nanchang University) of the Ministry of Education, School of Resource, Environmental and Chemical Engineering, Nanchang University, Nanchang 330031, China;
    2. School for Engineering of Matter, Transport and Energy, Arizona State University, Arizona 85287, United States
  • Received:2021-06-04 Revised:2021-07-30 Online:2022-10-19
  • Contact: Qiang Deng,E-mail:dengqiang@ncu.edu.cn
  • Supported by:
    The authors appreciate support from the National Natural Science Foundation of China (21878138, 21666021, and 21706112), and the Postdoctoral Science Foundation of China (2017M622104, 2018T110660).

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

Yao Zhong1, Cuiying Huang1, Lijie Li1, Qiang Deng1, Jun Wang1, Zheling Zeng1, Shuguang Deng2   

  1. 1. Key Laboratory of Poyang Lake Environment and Resource Utilization (Nanchang University) of the Ministry of Education, School of Resource, Environmental and Chemical Engineering, Nanchang University, Nanchang 330031, China;
    2. School for Engineering of Matter, Transport and Energy, Arizona State University, Arizona 85287, United States
  • 通讯作者: Qiang Deng,E-mail:dengqiang@ncu.edu.cn
  • 基金资助:
    The authors appreciate support from the National Natural Science Foundation of China (21878138, 21666021, and 21706112), and the Postdoctoral Science Foundation of China (2017M622104, 2018T110660).

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