空心Cu(Fe)@SiO_2核壳纳米颗粒的合成
摘要
复合纳米材料可以联合两种或者两种以上的组分,从而使它能够展现一些单组份材料所没有的性能,并且还可以通过组分互补性,赋予复合材料许多新的性能。而核壳材料作为复合材料的一个独特分支,根据结构、大小、组成排列的不同,可具有特殊的光、电、化学特性,因此越来越多的受到人们的青睐。
在核壳材料中,空心核壳材料由于其独特的空腔结构以及热和机械性能好等特点而成为核壳材料中研究的热点。在空心核壳材料众多的合成方法中,软模板法由于操作简单、反应时间短、效率高、形成的壳体结构疏松等优点而被广泛采用。
本论文采用非离子表面活性剂Brij(?)58作为软模板,在环己烷形成的反胶束微乳体系中,加入双功能配体,使配体的一端稳定住金属离子,另一端与表面活性剂的氧形成氢键,通过原位还原、包覆二氧化硅,分别合成了具有新型结构、颗粒尺寸40 nm左右的Cu@SiO2和Fe@SiO2空心核壳纳米颗粒,并对合成样品进行了透射电镜、XPS、XRD等表征,确定了样品的结构和组成,并探讨了空心核壳纳米颗粒的形成机理。另外,通过改变反应条件,考察了配体结构、配体浓度、还原剂种类、还原时间、氨水加入量等因素对Cu@SiO2及Fe@SiO2空腔形貌的影响,为以后合成形貌规整的样品奠定实验基础。
此外,本论文还考察了R值(水与表面活性剂的摩尔比)、剪切速率、电解质加入量等因素对Brij(?)58反胶束体系黏度的影响,其可能为反胶束体系中纳米粒子的可控合成提供实验指导。
Hybrid nano-material is composed of two or more kinds of components. It shows properties that one-component material does not and also behaves some new properties. Core-shell material has special optical, electrical and chemical properties according to their different structure, size and composition arrangement. This character of core-shell wins it more and more attention nowadays.
Due to its unique cavity structure, good thermal and mechanical performance, hollow core-shell material has become a hot topic recently. Though there are various synthetic approaches for hollow core-shell material, the soft template method has been more widely used for its advantages, such as short reaction time, high product yields and structural robustness of the shells.
This paper is about use the Brij(?)58 as a soft template to get reverse micelles microemulsion in cyclohexane and added the bifunctional ligand (one group to stablizie the metal ion, the other group to form hydrogen bonds with oxygen atoms of Brij(?)58) into the system, reducted, then encapsulated in silica to synthesize a new structure and particles size about 40 nm hollow Cu@SiO2 and Fe@SiO2 core-shell nanoparticles. The materials were characterized by TEM, XPS, XRD technologies. We further investigated the effects of ligand structure, ligand concentration, reducing agent type, reduction time, the quantity of ammonia and other factors on the sample morphology in different reaction conditions.
In addition, the effects of R (mole ratio of water to surfactant), amount of electrolyte and shear rate on the viscosity of Brij(?)58/cyclohexane/water reverse microemulsion were also investigated. It might provide experimental guidance for controlled synthesis of nanoparticles.
在核壳材料中,空心核壳材料由于其独特的空腔结构以及热和机械性能好等特点而成为核壳材料中研究的热点。在空心核壳材料众多的合成方法中,软模板法由于操作简单、反应时间短、效率高、形成的壳体结构疏松等优点而被广泛采用。
本论文采用非离子表面活性剂Brij(?)58作为软模板,在环己烷形成的反胶束微乳体系中,加入双功能配体,使配体的一端稳定住金属离子,另一端与表面活性剂的氧形成氢键,通过原位还原、包覆二氧化硅,分别合成了具有新型结构、颗粒尺寸40 nm左右的Cu@SiO2和Fe@SiO2空心核壳纳米颗粒,并对合成样品进行了透射电镜、XPS、XRD等表征,确定了样品的结构和组成,并探讨了空心核壳纳米颗粒的形成机理。另外,通过改变反应条件,考察了配体结构、配体浓度、还原剂种类、还原时间、氨水加入量等因素对Cu@SiO2及Fe@SiO2空腔形貌的影响,为以后合成形貌规整的样品奠定实验基础。
此外,本论文还考察了R值(水与表面活性剂的摩尔比)、剪切速率、电解质加入量等因素对Brij(?)58反胶束体系黏度的影响,其可能为反胶束体系中纳米粒子的可控合成提供实验指导。
Hybrid nano-material is composed of two or more kinds of components. It shows properties that one-component material does not and also behaves some new properties. Core-shell material has special optical, electrical and chemical properties according to their different structure, size and composition arrangement. This character of core-shell wins it more and more attention nowadays.
Due to its unique cavity structure, good thermal and mechanical performance, hollow core-shell material has become a hot topic recently. Though there are various synthetic approaches for hollow core-shell material, the soft template method has been more widely used for its advantages, such as short reaction time, high product yields and structural robustness of the shells.
This paper is about use the Brij(?)58 as a soft template to get reverse micelles microemulsion in cyclohexane and added the bifunctional ligand (one group to stablizie the metal ion, the other group to form hydrogen bonds with oxygen atoms of Brij(?)58) into the system, reducted, then encapsulated in silica to synthesize a new structure and particles size about 40 nm hollow Cu@SiO2 and Fe@SiO2 core-shell nanoparticles. The materials were characterized by TEM, XPS, XRD technologies. We further investigated the effects of ligand structure, ligand concentration, reducing agent type, reduction time, the quantity of ammonia and other factors on the sample morphology in different reaction conditions.
In addition, the effects of R (mole ratio of water to surfactant), amount of electrolyte and shear rate on the viscosity of Brij(?)58/cyclohexane/water reverse microemulsion were also investigated. It might provide experimental guidance for controlled synthesis of nanoparticles.
引文
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[3]TEMPLTON A C, WUELFING W P, Murray R W. Monolayer protected clustermolecules [J]. ACC. Chem. Res.,2000,33:27-32.
[4]ZHONG C J, MAYE M M. Core/Shell assemblyed nanoparticles as catalysts [J]. Adv. Mater., 2001,13:1507-1511.
[5]DOKOUTCHAEV A, JAMES J T, KOENE S C, et al. Colloid almetal deposition onto functionalized polystyrene microspheres [J]. Chem.Mater.,1999,11:2389-2399.
[6]段涛,杨玉山,彭同江,等.核壳型纳米复合材料的研究进展[J].材料导报：综述篇,2009,23，2：19-24.
[7]孟永德.钴基核壳纳米结构材料及空心纳米结构的制备与性能研究[D].山东：山东大学材料学院,2007.
[8]RADTCHENKO I L, SUKHORUKOV G B, GAONIK N, et al. Core-Shell Structures Formed by the Solvent-Controlled Precipitation of Luminescent CdTe Nanocrystals on Latex Spheres [J]. Adv. Mater.,2001,13(22):1684-1692.
[9]张小塔,宋武林.核壳结构纳米复合材料的研究进展[J].材料导报,2006,11：20-26.
[10]赵雯,卢婷利,张宏,等.核壳结构有机／无机复合微球的制备与应用进展[J].材料导报：综述篇,2009,23,4：106-108.
[11]ZHANG J, COOMBS N, KUMACHEVA E. A new approach to hybrid polymer-metal and polymer-semiconductor particles [J]. Adv. Mater.,2002,14:1856-1864.
[12]OU J L, CHANF C P, SUNG Y, et al. Uniform polystyrene microspheres decorated with noble metal nanoparticles formed without using extra reducing agent [J]. Colloids Surfa:Physicochem. Eng. Aspects,2007,305(1-3):36-42.
[13]HYUNG B L, YOUNG M Y, HAN Y H. Characteristic optical properties and synthesis of gold-silica core-shell colloids [J]. Scripta Materialia, 2006,55 (12):1127-1129.
[14]王毅,姜炜,程志鹏,等.Ni(Cu,Co)／Al微纳米复合粒子的制备及其与Fe2O2的热反应性能表征[J].稀有金属材料与工程,2008,7：36-38.
[15]ZHANG M, BRIAN L, CHARLES J. Synthesis and characterization of monodisperse ultra-thin silica-coated magnetic nanoparticles [J]. Nanotechnology,2008,19(8):1-5.
[16]CARUSO E, SPASOVA M, SUSHA A, et al. A Magnetic Nanocomposite Particles and Hollow Spheres Constructed by a SequentialLayedngApproach [J]. Chem. Mater. 2001,13,109-116.
[17]JI T, LIRTSMAN V G, YAUN Y, et al. Nano-and Microengineering:3-D Colloidal Photonic Crystals Prepared from Sub-m-sized Polystyrene Latex Spheres Pre-Coated with Luminescent Polyelectrolyte/Nanocrystal [J]. Adv. Mater.,2000,12(5):333-337.
[18]CARUSO E, SHI X, CARNSOLP R A, et al. Hollow Titania Spheres from Layered Precursor Deposition on Sacrificial Colloidal Core Particles [J]. Adv. Mater.,2001,3(10): 740-744.
[19]ZHAO W, ZHANG Q Y, ZHANG J P, et al. Preparation and thermal decomposition of PS/Ag microspheres [J]. Polymer Composites,2009,30(7):891-896.
[20]王为,郭鹤铜,高建平,等.PS微球表面化学沉积金属铜[J].化工进展,1998,4,38-40.
[21]LOU D, LYNDEN A A, YANG Z H. Hollow Micro-/Nanostructures: Synthesis and Applications [J]. Adv.Mater.,2008,20:3987-4019.
[22]CARUSO F, CARUSO R A, MOHWALD H. Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating [J]. Science,1998,282(5391):1111-1114.
[23]IKEDA S, TACHI K, NG Y H, et al. Selective adsorption of glucos-Derived carbon precursor on amino-functionalized porous silica for fabrication of hollow carbon spheres with porous walls [J]. Chem. Mater.,2007,19(17):4335-4340.
[24]ZHONG Z Y, YIN Y D, XIA Y N, et al. Preparation of Mesoscale Hollow Spheres of Ti02 and SnO2 by Templating Against Crystalline Arrays of Polystyrene Beads [J]. Adv. Mater. 2000,12(3):206-209.
[25]BREEN M L, DINSMORE A D, PINK R H, et al. Sonochemically produced ZnS-coated polystyrene core-shell particles for use in photonic crystals [J]. Langmuir,2001,17(3):903-907.
[26]WANG J, LOH K P, ZHONG Y H, et al. Bifunctional FePt core-shell and hollow spheres: Sonochemical preparation and self-assembly [J]. Chem.Mater.,2007,19(10): 2566-2572.
[27]NAKASHIMA N, KIMIZUKA. Interfacial synthesis of hollow TiO2 microspheres in ionic liquids [J]. J. Am. Chem. Soc.,2003,125(21):6386-6387.
[28]OH C, LEE Y G, JON C U, et al. Synthesis and characterization of hollow silica microspheres functionalized with magnetic particles using W/O emulsion method [J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2009,337:208-212.
[29]WUB W, CHENG C L, SHENA S L, et al. Colloids and Surfaces A:Physicochemical and Engineering Aspects Colloids and Surfaces A:Physicochem. Eng. Aspects,2009,334: 131-136.
[30]XU H L, WANG W Z. Template Synthesis of Multishelled Cu20 Hollow Spheres with a Single-Crystalline Shell Wall [J]. Angew. Chem. Int. Ed.,2007,46(9):1489-1492.
[31]HAN Y S, HADIKO G, FUJI M, et al. A novel approach to synthesize hollow calcium carbonate particles [J]. Chem. Lett.,2005,34(2):152-153.
[32]WU C L, XIE Y, LEI Y L, et al. Synthesis of New-Phased VOOH Hollow Dandelions and Their Application in Lithium-Ion Batteries [J]. Adv.Mater.,2006,18(13):1727-1732.
[33]LI X X, XIONG Y J, LI Z Q, et al. Large-scale fabrication of TiO2 hierarchical hollow spheres [J]. Inorg. Chem.,2006,45(9):3493-3495.
[34]HOU H W, PENG Q, ZHANG S Y, et al. A "user-friendly" chemical approach towards paramagnetic cobalt phosphide hollow structures:Preparation, characterization, and formation mechanism of Co2P hollow spheres and tubes [J]. Eur. J.Inorg. Chem., 2005,13:2625-2630.
[35]YIN Y D, RIOUX R M, ERDONMEZ C K, et al. Formation of hollow nanocrystals through the nanoscale Kirkendall Effect [J]. Science,2004,304(5671):711-714.
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