SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2021, Vol. 33 ›› Issue (5): 167-174.DOI: 10.1016/j.cjche.2020.09.018

• Catalysis, Kinetics and Reaction Engineering • 上一篇    下一篇

Functionalized metal-organic frameworks with strong acidity and hydrophobicity as an efficient catalyst for the production of 5-hydroxymethylfurfural

Huan Li1, Yao Zhong1, Luxi Wang1, Qiang Deng1, Jun Wang1, Zheling Zeng1, Xinxiang Cao2, Shuguang Deng3   

  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 Laboratory for Development & Application of Cold Plasma Technology, College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, China;
    3 School for Engineering of Matter, Transport and Energy, Arizona State University, 551 E. Tyler Mall, Tempe, AZ 85287, United States
  • 收稿日期:2020-03-19 修回日期:2020-08-03 出版日期:2021-05-28 发布日期:2021-08-19
  • 通讯作者: Qiang Deng
  • 基金资助:
    The authors appreciate support from the National Natural Science Foundation of China (21878138, 21706112), the Postdoctoral Science Foundation of China (2017M622104, 2018T110660), the Key Scientific and Technological Project of Henan Province (182102410072) and the start-up funds from Nanchang University and Arizona State University.

Functionalized metal-organic frameworks with strong acidity and hydrophobicity as an efficient catalyst for the production of 5-hydroxymethylfurfural

Huan Li1, Yao Zhong1, Luxi Wang1, Qiang Deng1, Jun Wang1, Zheling Zeng1, Xinxiang Cao2, Shuguang Deng3   

  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 Laboratory for Development & Application of Cold Plasma Technology, College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, China;
    3 School for Engineering of Matter, Transport and Energy, Arizona State University, 551 E. Tyler Mall, Tempe, AZ 85287, United States
  • Received:2020-03-19 Revised:2020-08-03 Online:2021-05-28 Published:2021-08-19
  • Contact: Qiang Deng
  • Supported by:
    The authors appreciate support from the National Natural Science Foundation of China (21878138, 21706112), the Postdoctoral Science Foundation of China (2017M622104, 2018T110660), the Key Scientific and Technological Project of Henan Province (182102410072) and the start-up funds from Nanchang University and Arizona State University.

摘要: In the dehydration of fructose to 5-hydroxymethyl furfural (HMF), in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF, causing unsatisfactory catalytic activity and selectivity. In this work, a class of benzenesulfonic acid-grafted metal-organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent. The resultant MOFs have a specific surface area of greater than 250 m2·g-1, acid density above 1.0 mmol·g-1, and water contact angle up to 129 . The hydrophobic MOF-PhSO3H exhibits both higher catalytic activity and selectivity than MOF-SO3H in the HMF synthesis due to its better hydrophobicity and olephilicity. Moreover, the catalyst has a high recycled stability. At last, fructose is completely converted, and 98.0% yield of HMF is obtained under 120 C in a DMSO solvent system. The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.

关键词: Catalysis, Catalyst, Biomass, Metal-organic framework, Fructose, 5-Hydroxymethylfurfural

Abstract: In the dehydration of fructose to 5-hydroxymethyl furfural (HMF), in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF, causing unsatisfactory catalytic activity and selectivity. In this work, a class of benzenesulfonic acid-grafted metal-organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent. The resultant MOFs have a specific surface area of greater than 250 m2·g-1, acid density above 1.0 mmol·g-1, and water contact angle up to 129 . The hydrophobic MOF-PhSO3H exhibits both higher catalytic activity and selectivity than MOF-SO3H in the HMF synthesis due to its better hydrophobicity and olephilicity. Moreover, the catalyst has a high recycled stability. At last, fructose is completely converted, and 98.0% yield of HMF is obtained under 120 C in a DMSO solvent system. The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.

Key words: Catalysis, Catalyst, Biomass, Metal-organic framework, Fructose, 5-Hydroxymethylfurfural