多金属氧酸盐纳米纤维催化O2氧化5-HMF  

POMs nanofibers for the oxidation of 5-HMF with O2

作　　者：李月[1] 李一鸣[1] 张雪艳 王晓红[1] Yue Li;Yiming Li;Xueyan Zhang;Xiaohong Wang(Key Labaratory of Polyoxometalate Science of Ministry of Education,Northeast Normal University,Changchun 130024,China)

机构地区：[1]东北师范大学,多酸科学教育部重点实验室,长春130024

出　　处：《科学通报》2020年第10期940-947,共8页Chinese Science Bulletin

基　　金：国家自然科学基金(201115180)资助。

摘　　要：2,5-二甲基呋喃(DFF)是一种用途广泛的化合物,可作为前体用于合成各种高附加值产品,可通过氧化5-羟甲基糠醛(HMF)得到.然而,5-羟甲基糠醛的有氧氧化有不同的途径,从而会产生DFF,2,5-呋喃甲酸(FDCA)或马来酸酐(MA)等产物.迄今为止,均相和非均相金属催化剂均被作为氧化剂用于对HMF氧化为DFF的研究.特别是含钒的多金属氧酸盐(POMs)被发现可以氧化HMF生产DFF,MA等一系列产品.本文通过采用静电纺丝和表面活性剂成孔技术合成了介孔纳米纤维H5PMo10V2O40/meso-Zr O2(f)并通过IR,31P MAS NMR,XRD,SEM,TEM,N2吸附-脱附测试对其进行了表征.H5PMo10V2O40/meso-Zr O2(f)纳米纤维,其在氧气作为氧化剂氧化5-羟甲基糠醛(5-HMF)到2,5-二甲酰基呋喃(DFF)反应中表现出高的催化活性和产物的选择性,源于复合催化剂良好的氧化还原性、Lewis酸中心、Br?nsted酸中心及纳米纤维高的比表面积.2,5-Diformylfuran(DFF)is a versatile compound that can be used as a precursor in the synthesis of various value-added products,which can be obtained from aerobic oxidation of 5-hydroxymethylfurfural(HMF).However,aerobic oxidation of5-HMF gives rise to several pathways and products containing DFF,2,5-furandicarboxylic acid(FDCA),or maleic anhydride(MA).To date,both homogeneous and heterogeneous metal catalysts have been explored for the oxidation of HMF to DFF with various oxidants.It was found that materials containing vanadium showed higher efficiency with conversions ranging from 84%to 100%and DFF yields of 82%-99.9%at 120-140℃for 3-11 h in dimethyl sulfoxide(DMSO).Selective oxidation of 5-HMF depended on the nature of the catalysts and supports.Polyoxometalates(POMs)are widely applied in catalysis especially in catalytic transformation of biomass.Especially,POMs containing vanadium had been found to be potential for oxidation of HMF to produce a series of products including DFF and MA.The diversity in structure and components allows POMs to be most active in acidic and redox catalysis.Compared to their homogeneous catalysis,heterogeneous systems showed more favorable in easy separation and reuse,introduction of special active sites belonging to supports,enhancement in surface area.Under such circumstances,heterogeneous POM catalysts are developed using microporous,mesoporous and macroporous SiO2,TiO2 and ZrO2 as supports.Compared to powdered mesoporous materials,electrospun nanofibers are good candidates because of their high surface-to-volume ratios.Herein,trifunctional H5 PMo10V2 O40/meso-ZrO2(f)had been synthesized using combined electrospinning and surfactant poreforming technology,which were characterized by IR,31P MAS NMR,XRD,SEM,TEM,and N2 adsorption-desorption measurement.Combination of IR,31P MAS NMR,XRD,BET surface areas,SEM and TEM could confirm that POM molecules were loaded on ZrO2 nanofibers(200-400 nm)with mesoporous structure.It was found that decorating ZrO2 nanofibers by H5 PMo10V2 O40 gene

关 键 词：多金属氧酸盐 纳米纤维 氧气氧化 5-羟甲基糠醛(5-HMF) 

分 类 号：O621.251[理学—有机化学] TB383.1[理学—化学]