Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF

SU Ye; BAO Zongbi; ZHANG Zhiguo; XING Huabin; YANG Qiwei; SU Baogen; YANG Yiwen; REN Qilong

doi:10.11949/j.issn.0438-1157.20160115

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Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF

更新时间：2025-11-26

- Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF
- CIESC Journal Issue 7, Pages: 2799-2807(2016)
- 作者机构：
  
  浙江大学化学工程与生物工程学院, 生物质化工教育部重点实验室,浙江,杭州,310029
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20160115
  CLC： 643.36
- Online First：05 July 2016，
  
  Published：05 July 2016
- 稿件说明：
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SU Ye, BAO Zongbi, ZHANG Zhiguo, et al. Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF[J]. CIESC Journal, 2016, (7): 2799-2807.
DOI：

SU Ye, BAO Zongbi, ZHANG Zhiguo, et al. Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF[J]. CIESC Journal, 2016, (7): 2799-2807. DOI： 10.11949/j.issn.0438-1157.20160115.

摘要

以九水合硝酸铬和单磺酸钠对苯二甲酸为原料，水为溶剂，采用水热法合成系列磺酸功能化MIL-101（Cr），通过调节反应温度和时间，合成不同Lewis/Brönsted催化位点比例的磺酸功能化MIL-101（Cr），采用PXRD、EDX、SEM、ICP-AAS及BET比表面积分析等技术对材料进行综合表征，并研究磺酸功能化MIL-101（Cr）催化葡萄糖脱水制备5-羟甲基糠醛的催化活性。催化反应动力学研究结果表明，MIL-101（Cr）-SO3H中的Cr（Ⅲ）作为葡萄糖异构化反应的Lewis酸位点，－SO3H作为果糖脱水反应的Brönsted酸催化位点，当催化剂的Brönsted酸和Lewis酸的摩尔比为1.1时，150℃下反应，5-羟甲基糠醛的选择性最高可以达到47.15%，5-羟甲基糠醛的产率最高达到46.0%。

Abstract

A series of Cr-terephthalates metal-organic frameworks functionalized by sulfonic acid group (-SO3H) [MIL-101(Cr)-SO3H]

featuring varied ratios of Lewis acid site to Brönsted acid site

were synthesized by hydrothermal reaction method starting from Cr(NO3)3·9H2O and sodium 2-sulfoterephthalate under various conditions of temperature and reaction time. The catalysts were characterized by techniques of PXRD

EDX

SEM

ICP-AAS and BET surface area

and the catalytic performances for glucose conversion to 5-HMF were evaluated. It showed that

in terms of the catalysis kinetics

Cr3+ serves as the Lewis acid sites of MIL-101(Cr)-SO3H for glucose isomerization

and sulfonic acid group

the Brönsted acid site for the fructose dehydration. The highest HMF selectivity of 47.15% and the highest HMF yield of 46.0% was achieved under conditions of molar ratio of Brönsted acid site to Lewis acid site of 1.1

150℃ for 2 h.

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