水溶性Fe_3O_4磁性纳米催化剂的合成及应用
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摘要
利用对氨基苯磺酸氟硼酸重氮盐与Fe_3O_4磁性纳米粒子(MNPs)的偶联反应,非常方便地制备出表面含有磺酸基的Fe_3O_4磁性纳米粒子。透射电子显微镜(TEM)测试结果表明,粒子的平均粒径在20 nm左右。溶解性实验表明,该纳米粒子具有较好的水溶性,但不溶于常用的有机溶剂,因此可利用其磁性回收并循环使用。将该纳米粒子用于催化羧酸与醇的酯化反应,产物酯的收率为71%～86%。催化剂在酯化反应中的最优使用量为1. 5%(质量分数)。同时,该催化剂可催化果糖合成5-羟甲基糠醛(HMF),收率为32%。
Fe_3O_4 magnetic nano particles( MNPs) with sulfonic acid groups on the surface were readily prepared via coupling reaction between 4-amino phenylsulfonic acid diazonium tetrafluoroborate and Fe_3O_4 nano particles. Transmission electron microscopy( TEM) images reveal that the average size of these acidic particles is about 20 nm. These acidic particles show good solubility in water,but they are insoluble in most of common organic solvents,allowing easy isolation and recycling of the particles by their magnetic property in catalytic reactions. In terms of application, when the acidic magnetic particles were used to catalyze esterification reactions between carboxylic acids and alcohols,moderate to high isolated yields( 71% ～ 86%)of ester products were obtained. The optimized catalyst loading is 1. 5%( mass fraction). Furthermore,5-hydroxymethyl furfural( HMF) was also synthesized in a 32% yield from fructose utilizing the acidic magnetic particles as a catalyst.
Fe_3O_4 magnetic nano particles( MNPs) with sulfonic acid groups on the surface were readily prepared via coupling reaction between 4-amino phenylsulfonic acid diazonium tetrafluoroborate and Fe_3O_4 nano particles. Transmission electron microscopy( TEM) images reveal that the average size of these acidic particles is about 20 nm. These acidic particles show good solubility in water,but they are insoluble in most of common organic solvents,allowing easy isolation and recycling of the particles by their magnetic property in catalytic reactions. In terms of application, when the acidic magnetic particles were used to catalyze esterification reactions between carboxylic acids and alcohols,moderate to high isolated yields( 71% ～ 86%)of ester products were obtained. The optimized catalyst loading is 1. 5%( mass fraction). Furthermore,5-hydroxymethyl furfural( HMF) was also synthesized in a 32% yield from fructose utilizing the acidic magnetic particles as a catalyst.
引文
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[2]Wang J,Li Y,Zhang Y.Nanocatalysts:Precious-Metal-Free Nanocatalysts for Highly Efficient Hydrogen Production from Hydrous Hydrazine[J].Adv Funct Mater,2014,24(45):7073-7077.
[3]Hu H W,Xin J H,Hu H,et al.Synthesis and Stabilization of Metal Nanocatalysts for Reduction Reactions-A Review[J].J Mater Chem A,2015,3(21):11157-11182.
[4]CHEN Ziting,LIANG Ying.Preparation and Application of Pd Nanomaterials Grown in situ on Non-Through-Hole Porous Alumina[J].Chinese J Appl Chem,2017,34(6):705-711(in Chinese).陈梓庭,梁营.非通孔多孔氧化铝基底上原位生成Pd纳米材料的制备及应用[J].应用化学,2017,34(6):705-711.
[5]Wang D,Astruc D.Fast-Growing Field of Magnetically Recyclable Nanocatalysts[J].Chem Rev,2014,114(14):6949-6985.
[6]Gawande M B,Brancoa P S,Varma R S.Three Dimensional Macroporous Architectures and Aerogels Built of Carbon Nanotubes and/or Graphene:Synthesis and Applications[J].Chem Soc Rev,2013,42(2):3371-3393.
[7]FU Pengyuan,YANG Chun.Preparation and Catalytic Performance of Zr(SO4)2·4H2O/SBA-15 Solid Acid Catalysts[J].Chinese J Appl Chem,2010,27(8):924-930(in Chinese).傅鹏远,杨春.Zr(SO4)2·4H2O/SBA-15固体酸催化剂的制备及其催化性能[J].应用化学,2010,27(8):924-930.
[8]ZHAO Bo,HU Shanglian,GONG Daoyong,et al.New Advances on Hydrolysis of Cellulose to Glucose by Solid Acid[J].Chem Ind Eng Prog,2017,36(2):555-567(in Chinese).赵博,胡尚连,龚道勇,等.固体酸催化纤维素水解转化葡萄糖的研究进展[J].化工进展,2017,36(2):555-567.
[9]HUANG Qinghua,CHEN Ming,BAI Xiongxiong,et al.Facile Synthesis of Ethyl Carboxylates via H2NSO3H/H2SO4Synergistic Catalysis[J].Chem Res Appl,2014,26(2):277-280(in Chinese).黄庆华,陈明,白雄雄,等.氨基磺酸/浓硫酸协同催化合成羧酸乙酯[J].化学研究与应用,2014,26(2):277-280.
[10]Veisi H,Taheri S,Hemmati S.Preparation of Polydopamine Sulfamic Acid-Functionalized Magnetic Fe3O4Nanoparticles with a Core/Shell Nanostructure as Heterogeneous and Recyclable Nanocatalysts for the Acetylation of Alcohols,Phenols,Amines and Thiols under Solvent-Free Conditions[J].Green Chem,2016,18(23):6337-6348.
[11]Kolvari E,Koukabi N,Armandpour O.A Simple and Efficient Synthesis of 3,4-Dihydropyrimidin-2-(1H)-Ones via Biginelli Reaction Catalyzed by Nanomagnetic-Supported Sulfonic Acid[J].Tetrahedron,2014,70(6):1383-1386.
[12]Koukabi N,Kolvari E,Zolfigol M A,et al.A Magnetic Particle-Supported Sulfonic Acid Catalyst:Tuning Catalytic Activity Between Homogeneous and Heterogeneous Catalysis[J].Adv Synth Catal,2012,354(10):2001-2008.
[13]Griffete N,Herbst F,Pinson J,et al.Preparation of Water-Soluble Magnetic Nanocrystals Using Aryl Diazonium Salt Chemistry[J].J Am Chem Soc,2011,133(6):1646-1649.
[14]WANG Jun,ZHANG Chunpeng,OUYANG Pingkai.Advances in Production and Application of 5-Hydroxymethyl Furfural[J].Chem Ind Eng Prog,2008,27(5):702-707(in Chinese).王军,张春鹏,欧阳平凯.5-羟甲基糠醛制备及应用的研究进展[J].化工进展,2008,27(5):702-707.
[15]Rosatella A A,Simeonov S P,Frade R F M.5-Hydroxymethylfurfural(HMF)as a Building Block Platform:Biological Properties,Synthesis and Synthetic Applications[J].Green Chem,2011,13(4):754-793.
[16]Wang S G,Zhang Z H,Liu B.Catalytic Conversion of Fructose and 5-Hydroxymethylfurfural into 2,5-Furandicarboxylic Acid over a Recyclable Fe3O4-Co OxMagnetite Nanocatalyst[J].ACS Sustainable Chem Eng,2015,3(3):406-412.
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