镁铝复合金属氧化物负载钌纳米颗粒催化HMF选择性氧化制FDCA  

Ru nanoparticles supported on Mg-Al mixed metal oxide catalysts for selective oxidation of HMF me thylfurfural in to FDCA

作　　者：王凌晨 谌春林[2] 张敏[1] WANG Lingchen;CHEN Chunlin;ZHANG Min(College of Sciences,Shanghai University,Shanghai 200444,China;Ningbo Institute of Industrial Technology,Chinese Academy of Sciences,Ningbo 315201,Zhejiang,China)

机构地区：[1]上海大学理学院,上海200444 [2]中国科学院宁波材料技术与工程研究所,浙江宁波315201

出　　处：《上海大学学报（自然科学版）》2020年第4期552-561,共10页Journal of Shanghai University:Natural Science Edition

基　　金：国家自然科学基金资助项目(21272153)。

摘　　要：采用水热-氢气还原法合成了镁铝复合金属氧化物负载Ru纳米颗粒催化剂,利用X射线衍射(X-ray diffraction,XRD)、扫描电镜(scanning electron microscope,SEM)、透射电镜(transmission electron microscope,TEM)、N2物理吸附、CO2-程序升温脱附(CO2-temperature programmed desorption,CO2-TPD)、电感耦合等离子体发射光谱(inductively coupled plasma-optical emission spectroscopy,ICP-OES)等表征手段对催化剂进行结构、形貌和组成分析。结果表明,镁铝物质的量之比n(Mg):n(Al)=5:1的催化剂载体具有最强的碱性(142.81 mmol·g-1)和较大的比表面积(97.0 m2·g-1),有利于负载高分散的Ru纳米颗粒。在最佳反应条件(120℃、2 MPa O2、5 h)下,负载量为2.0%的RO-5催化剂能够高效催化5-羟甲基糠醛(5-hydroxymethylfurfural,HMF)氧化制备2,5-呋喃二甲酸(2,5-furandicarboxylic acid,FDCA),HMF转化率和FDCA产率分别达到100.0%和99.0%。条件优化实验进一步证实,HMF催化氧化的反应路径为生成2,5-呋喃二甲醛(2,5-diformylfuran,DFF)和5-甲酰基-2-呋喃甲酸(5-formyl-2-furancarboxylic acid,FFCA)中间产物的过程。Ru nanoparticles supported on Mg-Al mixed metal oxide catalysts have been prepared via the hydrothermal-reduction method.The structure,morphology and composition of the catalysts have been systematically analyzed using X-ray diffraction(XRD),scanning electron microscope(SEM),transmission electron microscope(TEM),N2 physisorption,CO2-temperature programmed desorption(CO2-TPD)and inductively coupled plasma-optical emission spectroscopy(ICP-OES).The characterization results show that the highly dispersed Ru nanoparticles benefit from the strongest alkalinity(142.81 mmol·g^-1)and the competitive specific surface area(97.0 m^2·g^-1)of mixed metal oxides with n(Mg):n(Al)=5:1.The RO-5 catalyst with Ru loading of 2.0%can efficiently catalyze aerobic oxidation of 5-hydroxymethylfurfural(HMF),obtaining 100.0%HMF conversion and 99.0%2,5-furandicarboxylic acid(FDCA)yield under the optimal reaction condition(120℃,2 MPa O2,5 h).According to the optimizing results,the reaction pathway for the conversion of HMF to FDCA is further confirmed for the formation of 2,5-diformylfuran,(DFF)and 5-formyl-2-furancarboxylic acid(FFCA)intermediates.

关 键 词：镁铝复合氧化物 Ru纳米颗粒 氧化 羟甲基糠醛 呋喃二甲酸 

分 类 号：O643.3[理学—物理化学]