Synthesis and properties of hollow silica nanoparticles

Hollow nanoparticles of silicon dioxide (SiO₂) have been obtained using Cu/SiO₂ core-shell nanoparticles as precursors. An original technique based on heating the precursor nanoparticles to T = 400°C followed by a nanochemical reaction of copper oxide separation from hollow silica particles has been proposed and implemented for the first time. The obtained hollow SiO₂ nanoparticles have been studied by transmission electron microscopy. Mechanisms involved in the formation of hollow silica nanoparticles are discussed.     

Fabrication of nanocomposite particles with superparamagnetic and luminescent functionalities

A new kind of superparamagnetic luminescent nanocomposite particles has been synthesized using a modified Stöber method combined with an electrostatic assembly process. Fe₃O₄ superparamagnetic nanoparticles were coated with uniform silica shell, and then 3-aminopropyltrimethoxysilane was used to terminate the silica surface with amino groups. Finally, negatively charged CdSe quantum dots (QDs) were assembled onto the surface of the amino-terminated SiO₂/Fe₃O₄ nanoparticles through electrostatic interactions. X-ray diffraction (XRD), transmission electron microscopy (TEM), microelectrophoresis, UV-vis absorption and emission spectroscopy and magnetometry were applied to characterize the nanocomposite particles. Dense CdSe QDs were immobilized on the silica surface. The thickness of silica shell was about 35 nm and the particle size of the final products was about 100 nm. The particles exhibited favorable superparamagnetic and photoluminescent properties.     

Structural verification and optical characterization of SiO2–Au–Cu2O nanoparticles

In this paper, SiO₂–Au–Cu₂O core/shell/shell nanoparticles were synthesized by reducing gold chloride on 3-amino-propyl-triethoxysilane molecules attached silica nanoparticle cores for several stages. Cu₂O nanoparticles were synthesized readily with the size of 4–5 nm using a simple route of sol–gel method Then, they were clung to the surface of Au seeds. The morphology of the resultant particles was studied using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Transmission electron microscopy images demonstrate growth of monodispersed gold seeds and Cu₂O nanoparticles in narrow size up to 10 nm and 5 nm, respectively. The presence of gold and Cu₂O coating was confirmed by X-ray diffraction, Fourier transform infrared spectroscopy and UV–Vis spectroscopy. Absorption spectroscopy shows considerably 40 nm blue shift in absorption edge for SiO₂–Au–Cu₂O nanostructure rather than SiO₂–Au core/shell nanoparticles.     

Highly photostable dye entrapped core-shell particles

Organic dye namely Coumarin 7 has been entrapped in silica particles using a single silica precursor viz. tetraethylorthosilicate. Both bare Coumarin 7 dye and dye incorporated core-shell particles were studied. Investigations of these core-shell composites were carried out using different characterization techniques such as energy dispersive X-ray analysis, X-ray photoelectron spectroscopy and transmission electron microscopy. It has been shown that the photostability of dye molecules is improved along with an increase in photoluminescence.     

Synthesis of core-shell nanostructures of Co3O4@SiO2 with controlled shell thickness (5-20 nm) and hollow shells of silica

Synthesis of uniform silica shell over Co3O4 nanoparticles was carried out using the colloidal solutions of Tergitol and cyclohexane. The shell could be controlled to a thickness of up to 20 nm by varying different parameters such as the amount of tetraethylorthosilicate, concentration of Co3O4 nanoparticles, reaction time and the presence of water and 1-octanol. Control of the amount of water (required for hydrolysis) appears to be the key factor for controlling the shell thickness. The methodology used is suitable to form shell over nanoparticles (present in powder form; synthesized at high temperature) which have high degree of agglomeration. Hollow shells of silica were obtained by the dissolution of the oxide core of Co3O4@SiO2 core-shell nanostructures. The composition of these core-shell nanostructures was confirmed by high-resolution transmission electron microscopy and elemental mapping by energy dispersive X-ray analysis. The hollow shells were characterized by using TEM, EDX and IR. Electron paramagnetic resonance studies of the core-shell nanostructures indicate the presence of free radicals on silica shell due to the presence of dangling bonds in the silica. Increase in the magnetic susceptibility was observed for these core-shell nanostructures.     

Self-assembly of monodisperse SiO2-zinc borate core-shell nanospheres for lubrication

Spherical SiO₂ particles have been successfully coated with zinc borate layers through a self-assembly process. The resulted SiO₂-Zn₅B₄O₁₁ core-shell nanospheres were characterized by X-ray diffraction (XRD), infrared spectra (IR), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) equipped with an energy-dispersive X-ray spectrometer (EDS). The obtained SiO₂-Zn₅B₄O₁₁ core-shell nanospheres have perfect spherical shape with narrow size distribution (average diameters 50 nm), i.e., the cores with mean diameters of 40 nm and the shells with an average thickness of 5 nm, monodisperse and smooth surface. Moreover, the friction coefficient of the base oil was decreased by the addition of SiO₂-Zn₅B₄O₁₁ core-shell nanospheres.     

NiO/SiO2 nanostructure and the magnetic moment of NiO nanoparticles

We report on the synthesis, morphology and magnetic properties of a novel NiO/SiO₂ nanostructure. The NiO/SiO₂ nanostructure was synthesized by a method based on the contribution of sol-gel and combustion processes. X-ray powder diffraction (XRPD) showed the formation of the nanocrystalline NiO phase. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) revealed perfectly spherical NiO nanoparticles with diameter of about 5 nm. Amorphous silica shell around the NiO nanoparticles was also observed by HRTEM showing NiO/SiO₂ core-shell nanostructure. Magnetic measurements show hysteretic behavior at 2 K with coercivity H_C = 700 Oe, remanent magnetization M_r = 3.9 emu/g, saturation magnetization M_S = 28.2 emu/g and huge magnetic moment m_p ≈ 1300 μ_B of the nanoparticles.     

Characterization of SiO2/Ag composite particles synthesized by in situ reduction and its application in electrically conductive adhesives

In the study, SiO₂/Ag composite particles with silver coating onto the surface of silica have been successfully prepared via a novel and facile approach (Oxidation–Reduction Method). In this approach, the SiO₂ particles were first modified with 3-ammoniatriethoxysilane (APTES) and glyoxalic acid (GA) through two-step reaction, the aldehyde group (CHO) were anchored onto the surfaces of silica spheres via electrostatic attraction, these [Ag(TEA)₂]⁺ ions in the solution were then reduced by the CHO and coated onto the surface of silica to obtain SiO₂/Ag composite particles. The effects of the reaction conditions on silver content and synthetic mechanism had also been discussed. The structure, morphology and optical properties of the SiO₂/Ag composite particles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV–vis spectroscopy. The results showed the surface of SiO₂ was surrounded by pure silver nanoparticles, and the silver nanoparticles had face-centered-cubic structure, the SiO₂/Ag composite particles with core–shell morphology and special optical properties. And the small content SiO₂/Ag composite particles applied in electrically conductive adhesives (ECAs) improved the electrical bulk resistivity and tensile shear strength.     

Fabrication of superparamagnetic hydroxyapatite with highly ordered three-dimensional pores

Hydroxyapatite (HA) with highly ordered three-dimensional pores, whose size is about 300 nm, was prepared by colloidal template method. The effect of the surface modification of silica spheres on the order degree of porous structure was investigated by field emission scanning electron microscopy (FESEM). Then, superparamagnetic Fe₃O₄ nanoparticles were fabricated via redox reaction, followed by coating with silica via a sol–gel process, in which a certain amount of TEOS was used in order to control the thickness of the silica shell. X-ray diffraction (XRD), transmission electron microscopy (TEM), and magnetometry were applied to characterize the properties. Finally, Fe₃O₄ magnetic nanoparticles coated with silica were adsorbed in the mesopores of HA with highly ordered three-dimensional pores by capillarity. The influence of dispersing agent on the adsorption results has been studied. Magnetometry was applied to characterize the magnetic properties of superparamagnetic HA. The quantities of adsorbed SiO₂/Fe₃O₄ nanoparticles with core–shell have been compared by variation of saturation magnetization before and after adsorption.     

Synthesis of Pt-immobilized on silica and polystyrene-encapsulated silica and their applications as electrocatalysts in the proton exchange membrane fuel cell

Nano sized Pt particles were successfully immobilized onto SiO₂ and polystyrene-encapsulated silica core shell (SiO₂@PS). To make the immobilization of Pt onto both silica and polystyrene-encapsulated silica core shell, SiO₂ was first functionalized with -NH₂ using 3-amino propyl trimethoxysilane (APTMS) while for core shell, the negatively charged surface of polystyrene (PS) was changed with positive charge by cationic surfactant such as cetyltrimethylammonium chloride (CTACl) to make the formation of SiO₂ shell on preformed PS sphere. Transmission electron micrograph (TEM) images shows that Pt nanoparticles immobilized onto SiO₂ and SiO₂@PS were to be 3-4 nm without agglomeraiton. The energy dispersive spectroscope (EDS) shows that Pt contents on both SiO₂ and SiO₂@PS were to be 21.45% and 20.28%, respectively. In case of Pt-SiO₂@PS, it is believed that Pt should have been immobilized onto PS surface and pore within SiO₂ shell as well as SiO₂ surface. The MEA fabricated with Pt-SiO₂@PS shows better cell performance than of Pt-SiO₂.     

Synthesis of cubic type hollow silica particles

Cubic-type hollow silica particles were prepared from Fe₂O₃-SiO₂ core-shell composite particles by selectively leaching the iron oxide core materials using acidic solution. The cubic Fe₂O₃ core particles were obtained by the hydrolysis reaction of iron salts. The Fe₂O₃-SiO₂ core-shell type particles were prepared by the deposition of a SiO₂ layer onto the surface of Fe₂O₃ particles using a two-step coating process. The first step involved primary coating with sodium silicate solution followed by subsequent coating by controlled hydrolysis of tetraethoxysilicate (TEOS). The core Fe₂O₃ was removed by dissolution in an acidic solution which gave rise to the hollow type silica particles. Scanning electron microscopic observation clearly revealed that the morphology is closely related to those of core the Fe₂O₃ particles. The cross sectional view determined by transmission electron microscopy revealed a silica shell with a thickness of about 50 nm. The porous texture of the hollow type silica particles is further characterized by nitrogen adsorption-desorption isotherm measurements.     

Synthesis of magnetically separable Sn doped magnetite/silica core-shell structure and photocatalytic property

Sn doped Fe₃O₄/SiO₂ core-shell structures with the magnetic and photocatalytic properties have been successfully synthesized using Fe₃O₄ microspheres as the precursor. The morphology, phase and structure of the bifunctional products were investigated by X-ray powder diffraction, transmission electron microscopy, selected-area electron diffraction, high-resolution transmission electron microscopy, energy dispersive spectroscopy, and scanning electron microscopy. The effects of the amount and hydrolysis rate of tetraethyl orthosilicate on the preparation of the Fe₃O₄/SiO₂ core-shell structures were investigated. Low concentration and slow hydrolysis rate of tetraethyl orthosilicate were useful to obtain the uniform silica coated Fe₃O₄. The magnetic measurements indicated that the Sn doped Fe₃O₄/SiO₂ core-shell structures showed ferromagnetic property and the magnetic saturation value slightly decreased after coated the silica layer. The magnetic Sn doped Fe₃O₄/SiO₂ core-shell structures exhibited good photocatalytic activity in the degradation of methyl orange and could be separated by applying an appropriate magnetic field.     

Novel approach to the synthesis of core-shell particles by sacrificial polymer shell method

In this work a new approach has been developed for the synthesis of SiO₂@Y₂O₃ particles with core-shell structure. The method is based on the synthesis of a covalently bonded sacrificial polymer shell grown onto silica particles. It is suitable to promote and stabilize the adsorption of different ions, namely Yttrium from its nitrate solution. After calcination and consequent elimination of the sacrificial polymer shell, the SiO₂@Y₂O₃ core-shell particles are obtained. Results reveal that the shell thickness of these core-shell particles is higher and more uniform than that of particles prepared without sacrificial polymer shell.     

Synthesis and optical properties of luminescent core-shell structured silicate and phosphate nanoparticles

Monodisperse, luminescent core-shell structured inorganic nanoparticles were synthesized by sol-gel technology. They exhibit an amorphous SiO₂ core and a crystalline luminescent shell. Zn₂SiO₄:Mn²⁺ and Ca₁₀(PO₄)₆OH:Eu³⁺ shell materials are investigated. The influence of the doping concentration on optical and structural properties was studied. The resulting nanoparticles were characterized by X-ray diffraction analysis, transmission electron microscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy.     

Simple and convenient preparation of Au-Pt core-shell nanoparticles on surface via a seed growth method

Au-Pt core-shell nanoparticles were prepared on glass surface by a seed growth method. Gold nanoparticles were used as seeds and ascorbic acid-H₂PtCl₆ solutions as growth solutions to deposit Pt shell on the surface of gold nanoparticles. These core-shell nanoparticles and their growth process were examined by UV-Vis spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and field-emission environmental scanning electron microscopy and the results indicated that the deposition speed was fast and nanoparticles with obvious core-shell structure could be obtained after 2 min. Moreover, this seed growth method for preparation of the core-shell nanoparticles is simple and convenient compared with other seed growth methods with NH₄OH as a mild reductant. In addition, electrochemical experiments indicated that these Au-Pt core-shell nanoparticles had similar electrochemical properties to those of the bulk Pt electrode.     

Synthesis and luminescence properties of monodisperse SiO2@SiO2:Eu3+ microspheres

Monodisperse core–shell structured SiO₂@SiO₂:Eu³⁺ microspheres were synthesized in a seeded growth way. In that way, a thin shell of Eu³⁺-doped silica was grown on the prepared monodisperse silica colloids. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDX), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR), thermal analysis (TGA-DSC) and photoluminescence (PL) spectroscopy. The results reveal that the SiO₂ spheres have been successfully coated by SiO₂:Eu³⁺ phosphors and the obtained SiO₂@SiO₂:Eu³⁺ particles have perfect spherical shape with narrow size distribution. Additionally, the monodisperse SiO₂@SiO₂:Eu³⁺ microspheres exhibit considerably strong photoluminescence (PL) of Eu³⁺ under the excitation of 393 nm compared with the SiO₂:Eu³⁺ samples with polydispersed or irregular shapes and sizes obtained by base-catalyzed Stöber method. Furthermore, the PL intensity increases with the increasing of Eu³⁺ concentration in SiO₂ microspheres shell, and concentration quenching occurs when Eu³⁺ concentration exceeds 5.0 mol%.     

A method for synthesizing the core (Ag)/shell (PSt) composite nanoparticles

Core-shell composite materials have been widely used in many fields. In this paper, the core (Ag)-shell (PSt) composite nanoparticles have been successfully fabricated in microemulsions at ambient pressure. Firstly, Ag nanoparticles with about 60-100 nm in diameters were synthesized by reducing silver nitrate by ascorbic acid, and then, styrene polymerized at the surface of Ag nanoparticles by K₂S₂O₄ initiator in microemulsion solutions. The Ag/PSt core-shell composite nanoparticles were identified by transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and infrared spectra (IR). Results show that Ag-core nanoparticles were coated with ultra thin PSt shell with thickness of about 3-6 nm.     

Preparation and characteristics of core–shell structure cobalt/silica nanoparticles

The silica nanolayer with different thickness was coated on the spherical cobalt nanoparticles (an average diameter of 67 nm) to form core–shell structure by the controlled hydrolysis and condensation of tetraethyl orthosilicate (TEOS). This coating process was based on the use of silane coupling agent 3-mercaptopropyltrimethoxysilane (HS-(CH₂)₃Si(OCH₃)₃, MPTS) as a primer to render the cobalt surface vitreophilic, thus rendering cobalt surface compatible with silica. The control over the silica coating layer thickness can be achieved by varying the reaction time. The cobalt nanoparticles and the cobalt coated with silica shell were confirmed by transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) was used to gain insight into the way in which the MPTS is bound to the surface of the cobalt nanoparticles. Result of the thermogravimetric analysis (TGA) and differential thermal analysis (DTA) indicate that the thermal stability of cobalt/silica is better than that of pure cobalt nanoparticles. Magnetic properties of these powders have been evaluated. These cobalt/silica core–shell nanoparticles can be utilized as precursors for making property-tunable magnetic nanoparticles, thin films, and multilayered core–shell structure nanocomposites.     

One-pot morphology-controlled synthesis of various shaped mesoporous silica nanoparticles

A simple synthetic method has been developed for synthesis of mesoporous silica nanoparticles with versatile morphologies by adopting CTAB and C₁₂–OH as dual soft templates. In such a simple method, only by regulating the dose of C₁₂–OH and temperature, we can well-realize the silica nanoparticle morphological transformation from sphere to shell-like, rugby-like, peanut-like, hollow, and complex yolk–shell structures. These as-fabricated silica nanoparticles were characterized by scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller (BET), and small-angle powder X-ray diffraction. The as-prepared mesoporous silica nanoparticles with versatile morphologies possessing varying BET surface areas, pore diameter, and pore distributions have some potential applications in separation, sensing, and heterogeneous catalysis.     

Synthesis and characterization of ZnO/SiO2 core/shell nanocomposites and hollow SiO2 nanostructures

In this paper, we prepared the ZnO nanoparticles by a simple hydrothermal method and fabricated the ZnO/SiO₂ core/shell nanostructures through a sol-gel chemistry process successfully. The hollow SiO₂ nanostructures were obtained by selective removal of the ZnO cores. The structure, morphology and composition of the products were determined by the techniques of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The results indicated that the ZnO nanoparticles were sphere-like shape with the average size of 60 nm and belonged to hexagonal wurtzite crystal structure. With the coating of SiO₂, the vibration modes of Si-O-Si and Si-OH were found. Furthermore, the measurement results of optical properties showed that spectra of bare ZnO nanoparticles and ZnO/SiO₂ core/shell nanocomposites exhibited similar emission features, including a blue emission peak and an orange emission band.