纳米TiO<sub>2</sub>溶胶催化葡萄糖合成5-羟甲基糠醛

陈烨婷; 左雄军; 顾凤龙

doi:10.6054/j.jscnun.2021040

纳米TiO₂溶胶催化葡萄糖合成5-羟甲基糠醛

1.
教育部环境理论化学重点实验室//华南师范大学化学学院，广州 510006
2.
华南师范大学分析测试中心，广州 510006

基金项目:

国家自然科学基金项目 21673085

粤港科技合作资助计划项目 2017A050506048

详细信息

通讯作者:
顾凤龙，Email: gu@scnu.edu.cn

中图分类号: O643
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- 文章访问数: 444
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出版历程
- 收稿日期: 2020-11-09
- 网络出版日期: 2021-07-05
- 刊出日期: 2021-06-24

The Catalytic Formation of 5-Hydroxymethyl Furfuraldehyde from Glucose with Nano-TiO₂ Gel

1.
MOE Key Laboratory of Theoretical Chemistry of Environment//School of Chemistry, South China Normal University, Guangzhou 510006, China
2.
Analysis and Testing Centre, South China Normal University, Guangzhou 510006, China

摘要

摘要: 采用溶胶凝胶法合成了纳米TiO₂溶胶和PEG-TiO₂溶胶，将其作为葡萄糖转化为5-羟甲基糠醛(HMF)的催化剂，对比研究了纳米TiO₂粉体和TiO₂溶胶的催化性能. 结果表明: 以纳米TiO₂溶胶为催化剂，葡萄糖转化为HMF的转化率为93.7%，HMF的收率为21.7%；以纳米TiO₂为催化剂，葡萄糖的转化率接近100%，而HMF的收率仅为1.4%. 采用聚乙二醇(PEG 200)和钛酸乙酯为原料，制备了具有更高TiO₂固含量的PEG-TiO₂溶胶，方便运输、储存和使用. 在最佳条件下，以PEG-TiO₂溶胶和甲酸为催化剂，以水为反应溶剂，葡萄糖的转化率达到92.0%，HMF的收率达到56.2%，反应温度为100 ℃，反应时间为12 h. 研究结果为工业上大规模绿色高效催化葡萄糖转化为HMF提供了一种新的方法.
- 纳米TiO₂ /
- 葡萄糖转化 /
- 5-羟甲基糠醛(HMF) /
- PEG-TiO₂溶胶
Abstract: Nano TiO₂ gel and PEG-TiO₂ gel were synthesized with the sol-gel method and were used as catalysts for glucose conversion into 5-hydroxymethyl furfuraldehyde (HMF). The catalytic properties of nano TiO₂ gel and TiO₂ powder were compared. The results show that with nano TiO₂ gel as catalyst, the conversion rate of glucose into HMF was 93.7%, and the yield of HMF was 21.7% and with nano TiO₂ as catalyst, the glucose conversion rate was close to 100%, while the yield of HMF was only 1.4%. PEG-TiO₂ with higher gelid content of TiO₂ was prepared using polyethylene glycol (PEG 200) and ethyl titanate as raw materials, which was convenient for transportation, storage and use. Under the optimal conditions, with PEG-TiO₂ gel and formic acid as catalyst and water as reaction liquid, the glucose conversion rate reached 92.0%, the yield of HMF reached 56.2%, the reaction temperature was 100 ℃, and the reaction time was 12 h. The results provide a new method for large-scale green and efficient catalytic conversion of glucose into HMF in industry.
- nano TiO₂ /
- glucose conversion /
- 5-Hydroxymethylfurfural (HMF) /
- PEG-TiO₂ gel

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图 1 不同催化剂的TEM、SEM图

Figure 1. The TEM and SEM images of different catalysts

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图 2 不同催化剂的XRD图谱

注：a为干燥的PEG-TiO₂溶胶，b为600 ℃下烧结得到的PEG-TiO₂溶胶，c为700 ℃下烧结得到的PEG-TiO₂溶胶，d为800 ℃下烧结得到的PEG-TiO₂溶胶.

Figure 2. The XRD pattern of different catalysts

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图 3 纳米TiO₂溶胶和粉体的催化效果

注：A采用100 mL纳米TiO₂溶胶和0.5 g葡萄糖，在79 ℃下反应; B采用100 mL水和2 g葡萄糖，在100 ℃下反应.

Figure 3. The catalytic effects of nano TiO₂ gel and powders

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图 4 催化剂体积对收率和转化率的影响

注：以PEG-TiO₂溶胶为催化剂，加水至反应液总体积为100 mL，葡萄糖为0.5 g，温度为100 ℃，反应时间为6 h.

Figure 4. The effect of catalyst volume on the yield and the conversion rate

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图 5 甲酸体积和反应时间对收率和转化率的影响

注：反应液总体积为100 mL，葡萄糖为2 g，温度为100 ℃.

Figure 5. The effects of the volume of formic acid and reaction time on the the yield and the conversion rate

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图 6 催化剂的循环使用次数对收率和转化率的影响

注：采用30 mL水、30 mL PEG-TiO₂溶胶、40 mL甲酸、2 g葡萄糖，在100 ℃下反应6 h.

Figure 6. The influence of catalyst cycle times on the yield and the conversion rate

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表 1 催化剂的平均粒径

Table 1 The average particle size of catalysts

样品	平均粒径/nm	PdI
纳米TiO₂溶胶^a	52	0.184
纳米TiO₂溶胶^b	352	0.303
PEG-TiO₂溶胶^c	1 510	1.000
PEG-TiO₂溶胶^d	1 580	1.000
注：a为新制的纳米TiO₂溶胶; b为放置2 d后的纳米TiO₂溶胶；c为新制的PEG-TiO₂溶胶; d为放置2 d后的PEG-TiO₂溶胶.

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