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以 TiO2- 和 ZrO2- 为载体的负载型 Pt 催化剂对 5-HMF 选择性有氧氧化为 2,5- 呋喃二甲酸。

Selective aerobic oxidation of 5-HMF into 2,5-furandicarboxylic acid with Pt catalysts supported on TiO2 - and ZrO2 -based supports.

机构信息

IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, UMR5256 CNRS-Université Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France), Fax: (+33) 0472445399.

出版信息

ChemSusChem. 2015 Apr 13;8(7):1206-17. doi: 10.1002/cssc.201403390. Epub 2015 Mar 3.

Abstract

Pt catalysts prepared over different metallic oxide supports were investigated in the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in alkaline aqueous solutions with air, to examine the combined effect of the support and base addition. The base (nature and amount) played a significant role in the degradation or oxidation of HMF. Increasing amounts of the weak NaHCO3 base improved significantly the overall catalytic activity of Pt/TiO2 and Pt/ZrO2 by accelerating the oxidation steps, especially for the aldehyde group. This was highlighted by a proposed kinetic model that gave very good concentration-time fittings. Moreover, the promotion of the catalyst with bismuth yielded a PtBi/TiO2 catalytic system with improved activity and stability. Y2 O3  and La2 O3 ZrO2 -supported catalysts exhibited lower activity than Pt/ZrO2 , which suggests no cooperative effect of the weakly basic properties introduced and the homogeneous base. Quantitative oxidation of HMF (0.1 M) and high yields of FDCA (>99 %) were obtained in less than 5 h by using an HMF/Pt molar ratio of 100 and Na2 CO3 as a weak base over PtBi/TiO2 (Bi/Pt=0.22).

摘要

研究了在碱性水溶液中用空气氧化 5-羟甲基糠醛(HMF)制备 2,5-呋喃二甲酸(FDCA)过程中,不同金属氧化物负载的 Pt 催化剂,考察了载体和碱添加的协同作用。碱(种类和用量)在 HMF 的降解或氧化中起着重要作用。随着弱 NaHCO3 碱用量的增加,Pt/TiO2 和 Pt/ZrO2 的整体催化活性显著提高,这加速了氧化步骤,特别是醛基的氧化。这一现象通过一个提出的动力学模型得到了很好的浓度-时间拟合。此外,用铋对催化剂进行促进,得到了具有改善的活性和稳定性的 PtBi/TiO2 催化体系。与 Pt/ZrO2 相比,Y2 O3 和 La2 O3 ZrO2 -负载的催化剂的活性较低,这表明引入的弱碱性和均相碱之间没有协同作用。在 HMF/Pt 摩尔比为 100、使用弱碱 Na2 CO3 的条件下,PtBi/TiO2(Bi/Pt=0.22)可在不到 5 h 内将 HMF(0.1 M)定量氧化,并获得>99%的 FDCA 高收率。

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