Studies of the factors effecting the preparation of heterogeneous platinum-based catalyst on silica supports

Pt nanoparticles with an average size of ∼3 nm were successfully immobilized on the surface of SiO₂ functionalized with -NH₂ and -SH groups through chemical reduction process using polyvinylpyrrolidone as a stabilizer and different reducing agents. The effects of molecular weight of polyvinylpyrrolidone, molar ratio of reducing agent to Pt salt, type of reducing agent on the size and degree of agglomeration of Pt nanoparticles on the SiO₂ surface were investigated. The X-ray diffraction and transmission electron micrograph analyses were performed to identify the product phase, size and morphology of immobilized Pt onto SiO₂. UV-vis analysis was also conducted to identify the degree of reduction of Pt ions. The Pt-SiO₂ nanocomposite prepared from both NH₂- and SH-functionalized SiO₂ exhibited similar behavior. The number of immobilized Pt nanoparticles and their average size was increased with polyvinylpyrrolidone concentration while the number of immobilized Pt was decreased with its molecular weight.     

Preparation and magnetic characterization of core–shell structure stainless steel/silica nanoparticles

SiO₂-coated martensite stainless steel nanoparticles were prepared using wire electrical explosion technique combined with sol–gel technique, and their structural and magnetic properties were studied. The coating silica on stainless steel nanoparticles was based on the use of silane coupling agent 3-mercaptopropyltrimethoxysilane (HS-(CH₂)₃Si(OCH₃)₃, MPTS) as a primer to render the stainless steel surface vitreophilic, thus rendering stainless steel surface compatible with silica. The control over the silica coating layer thickness can be achieved by varying the reaction time. For stainless steel nanoparticles, their saturation and remnant magnetizations decreased upon silica coating, and their saturation magnetizations obviously decreased with increasing the thickness of SiO₂ coating layer. These stainless steel/silica core–shell nanoparticles can be utilized as precursors for making property-tunable magnetic nanoparticles, thin films, and multilayered core–shell structure nanocomposites.     

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.     

Preparation of MnO<Subscript>2</Subscript>/porous carbon material with core–shell structure and its application in supercapacitor

Tubular manganese dioxide (MnO₂) is synthesized by hydrothermal method, and a silicon dioxide (SiO₂) used as template is wrapped on the as-synthesized MnO₂. Then poly(styrene-co-divinylbenzene) (PS) as heteropolymeric carbon precursor was wrapped on as-prepared MnO₂/SiO₂ to form intermediate product MnO₂@SiO₂@PS. The intermediate products were treated by carbon tetrachloride, stripped template and carbonized, thus the final product MnO₂/porous carbon composite (MnO₂@PC) with core–shell structure was obtained. The core–shell structural composite is used as an electrode of supercapacitors, which combines high conductivity and high surface specific area of porous carbon material and high electrochemical activity of MnO₂. The resulting core–shell MnO₂@PC exhibits a maximum specific capacitance of 196.2 F g^?1 at a discharge density of 1 A g^?1 with capacitance retention of 78.52% over 5000 discharge/charge cycles.     

Novel hollow sub-microspheres with movable Au nanoparticles and excessive Pt nanoparticles in core and silica as shell

A simple route has been designed for the syntheses of a kind of electrocatalyst, i.e., hollow spheres with Au and excessive Pt nanoparticles in core and silica as shell. The Au@carbon spheres synthesized by hydrothermal process can act as the transitional templates, and the carbonaceous matrix can in situ reduce H₂PtCl₆·H₂O solution and load with Pt nanoparticles, and then a slightly modified Stöber process was applied to encapsulate the structures with silica shell. Further calcination at high temperatures removed the carbon matrix to form the hollow spheres with Au and excessive Pt nanoparticles in core and silica as shell. This new kind of structures shows excellent electrocatalytic properties compared with that of similar hollow spheres but only with pure Pt nanoparticles inside, and it might provide an efficient way to improve the electrocatalytic property of a bulk Pt/GC electrode.     

Preparation and characterization of polyimide/silica nanocomposite spheres

Silica (SiO₂) nanocomposite spherical particles coated with polyimide had been synthesized by a dispersion polymerization method. The chemical structure of polyimide/silica (PI/SiO₂) nanocomposite spherical particles was investigated by using FT-IR, and the surface morphology characterization was performed with SEM. The TEM showed that SiO₂ core was surface-coated with a multilayer composite and the multilayer thickness was about 20 nm. Moreover, the particles were homogeneously distributed and interconnected very fine. Basing the results, it was found that the PI/SiO₂ nanocomposite particles were core–shell structure.     

A synergistically enhanced photothermal transition effect from mesoporous silica nanoparticles with gold nanorods wrapped in reduced graphene oxide

In this work, near-infrared (NIR)-responsive core–shell gold nanorods/mesoporous silica/reduced graphene oxide (Au/SiO₂/rGO) nanoparticles with synergistically enhanced photothermal stability and transition effect had been prepared via electrostatic interaction. Gold nanorods (AuNRs) and rGO were employed as the NIR-responsive components. UV–Vis–NIR extinction spectra revealed that the surface plasmon resonance peak of AuNRs from Au/SiO₂/rGO nanohybrids remained unchanged after 9 h NIR exposure. UV–Vis–NIR extinction results also showed that thin silica shell was superior to the thick ones in the photothermal stability improvement of Au/SiO₂/rGO nanoparticles. Moreover, the doxorubicin release of Au/SiO₂/rGO was more rapid than that of Au/SiO₂ upon NIR irradiation, indicating that synergistically enhanced photothermal effect between rGO and AuNRs endowed Au/SiO₂/rGO nanoparticles with excellent photothermal transition efficiency. Such novel NIR-responsive core–shell hybrid nanoparticles with enhanced photothermal stability and transition effect are well suited for further biological applications, such as photothermal therapy, bioimaging and drug delivery.     

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.     

Fabrication of silica/platinum core-shell particles by electroless metal plating

An electroless metal plating method was used to form Pt shells on sub-micrometer-sized silica (SiO₂) particles fabricated by a sol-gel method. The electroless metal plating method was comprised of three steps: (1) surface-modification of SiO₂ particles with polyvinylpyrrolidone (PVP) (SiO₂/PVP) or poly-diallyldimethylammonium chloride (PDADMAC) (SiO₂/PDADMAC), (2) pre-deposition of Pt nuclei or Pt fine particles on the SiO₂ particles by reducing Pt ions in the presence of SiO₂/PVP particles (SiO₂/PVP-Pt) or SiO₂/PDADMAC particles (SiO₂/PDADMAC-Pt), and (3) growth of the pre-deposited Pt by immersing the SiO₂/PVP-Pt or SiO₂/PDADMAC-Pt particles in a Pt-plating solution. The pre-deposition of Pt nanoparticles was successfully performed for the surface-modified SiO₂ particles since the surface modification possibly strengthened the affinity between the SiO₂ particle surfaces and Pt ions. The Pt nanoparticles were pre-deposited more uniformly in the case of PVP because the pre-deposition took place more slowly for the PVP, which provided uniform surface-modification followed by the uniform pre-deposition of Pt nanoparticles. The formation of Pt shells was successfully performed on the SiO₂/PVP-Pt particles in the electroless metal plating process because Pt nuclei were generated by the reduction of H₂PtCl₆ and then further deposited on the Pt particle surfaces on the SiO₂/PVP-Pt particles.     

Preparation of ultra-low dielectric constant silica/polyimide nanofiber membranes by electrospinning

Ultra-low dielectric constant silica/polyimide (SiO₂/PI) composite nanofiber membranes are prepared by the combined sol–gel and electrospinning techniques. The emulsion composed of partially hydrolyzed tetraethoxysilane (TEOS) and polyamic acid (PAA) is spun to yield the precursor of the SiO₂/PI fibers with a core–shell structure due to phase separation. The dielectric constant (k) of the composite membranes varies from 1.78 to 1.32 with increasing content of SiO₂. The fibers accumulate and form the film with a large amount of pores leading the lower k. In addition, the interfacial reaction between SiO₂ and the PI matrix reduces the value of k as the SiO₂ concentration is increased. The thermal stability of PI increase after mixing with SiO₂ and the SiO₂/PI composite fibers have large commercial potential in the electronics industry.     

Rattle-type silica colloidal particles prepared by a surface-protected etching process

This paper explores the capability of the “surface-protected etching” process for the creation of rattle-type SiO₂@void@SiO₂ colloidal structures featuring a mesoporous silica shell and a mesoporous movable silica core. The surface-protected etching process involves stabilization of the particle surface using a polymer ligand, and then selective etching of the interior to form hollow structures. In this paper, this strategy has been extended to the formation of rattle-like structures by etching SiO₂@SiO₂ core shell particles which are synthesized by a two-step sol gel process. The key is to introduce a protecting polymer of polyvinylpyrrolidone (PVP) to the surface of both core and shell in order to tailor their relative stability against chemical etching. Upon reacting with NaOH, the outer layer silica becomes a hollow shell as only the surface layer is protected by PVP and the interior is removed, while the core remains its original size thanks to the protection of PVP on its surface. This process can be carried out at room temperature without the need of additional templates or complicated heterogeneous coating procedures. The etching process also results in the rattle-type colloids having mesoscale pores with two distinct average sizes. In our demonstration of a model drug delivery process, such mesoporous structures show an interesting two-step elution profile which is believed to be related to the unique porous rattle structures. This article is published with open access at Springerlink.com     

Hollow polymer microspheres containing a gold nanocolloid core adsorbed on the inner surface as a catalytic microreactor

Hollow polymer microspheres with different polarity and functional group for the shell layer containing gold nanocolloid cores adsorbed on the inner surface were prepared by selective removal of sandwiched silica layer from the corresponding gold/silica/polydivinylbenzene (Au/SiO₂/PDVB), Au/SiO₂/poly(ethyleneglycol dimethacrylate) (Au/SiO₂/PEGDMA), and Au/SiO₂/poly(ethyleneglycol dimethacrylate-co-methacrylic acid) (Au/SiO₂/P(EGDMA-co-MAA) tri-layer microspheres, respectively. The tri-layer microspheres were synthesized by distillation precipitation polymerizations of divinylbenzene (DVB), ethyleneglycol dimethacrylate (EGDMA), EGDMA together with methacrylic acid (MAA) in presence of 3-(methacryloxy)propyltrimethoxysilane (MPS)-modified gold/silica (Au/SiO₂) core–shell particles as seeds, which were prepared by coating of a layer of silica onto the surface of Au nanocolloids with the aid of polyvinylpyrrolidone (PVP) via a modified Stöber method. The catalytic property and stability as a microreactor of the hollow polymer microspheres with Au nanocolloid cores adsorbed on the inner surface were studied by the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AnP) with sodium borohydride (NaBH₄) as reductant. Transmission electron microscopy (TEM) and Fourier transform infrared spectra (FT-IR) were used for characterizing the morphology and structure of the resultant microspheres.     

Preparation of silica/polyacrylamide/polyethylene nanocomposite via in situ polymerization

SiO₂/polyacrylamide (PAM) composite was prepared via the polymerization of acrylamide in the presence of silica sol in water/hexane emulsion, and pure SiO₂ was also prepared without the use of acrylamide in the same way. Field emission scanning electron micrographs (FESEM) showed that PAM covered the silica nanoparticles to form SiO₂/PAM nanospheres, which loosely agglomerated to form SiO₂/PAM secondary particles, while SiO₂ secondary particles were made up of tightly agglomerated silica nanoparticles. Metallocene catalyst was then immobilized over SiO₂ and SiO₂/PAM respectively to prepare supported metallocene catalyst for ethylene polymerization. Transmission electron micrographs (TEM) showed that support particles broke up to smaller particles and even nanoparticles in polyethylene (PE) matrix when the support particles were the fragile SiO₂/PAM secondary particles, which shows a novel way to prepare silica/polyacrylamide/polyethylene nanocomposite.     

A dual template method for synthesizing hollow silica spheres with mesoporous shells

PS/silica core/shell composites were synthesized by the modified Stöber method using polystyrene spheres and cetyltrimethylammonium bromide as dual templates under room temperature. The silicate species and the templates were self-assembled to form mesoporous silica shell on the surface of the PS spheres. Hollow silica spheres with mesoporous shell were obtained by removing the polymer core and the templates through calcination. The hollow silica spheres showed high specific surface area of 1099.5 m²/g and narrow pore size distribution centered at 2.31 nm.     

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.     

Preparation of porous hollow silica spheres via a layer-by-layer process and the chromatographic performance

Hollow silica spheres possessing excellent mechanical properties were successfully prepared through a layer-by-layer process using uniform polystyrene (PS) latex fabricated by dispersion polymerization as template. The formation of hollow SiO₂ micro-spheres, structures and properties were observed in detail by zeta potential, SEM, TEM, FTIR, TGA and nitrogen sorption porosimetry. The results indicated that the hollow spheres were uniform with particle diameter of 1.6 μm and shell thickness of 150 nm. The surface area was 511 m²/g and the pore diameter was 8.36 nm. A new stationary phase for HPLC was obtained by using C₁₈-derivatized hollow SiO₂ micro-spheres as packing materials and the chromatographic properties were evaluated for the separation of some regular small molecules. The packed column showed low column pressure, high values of efficiency (up to about 43 000 plates/m) and appropriate asymmetry factors.     

Synthesis and characterization of SiO2-CaO-P2O5 hollow nanospheres for biomedical applications

A ternary system of SiO₂-CaO-P₂O₅ hollow nanospheres has been successfully prepared by sol-gel method using polystyrene (PS) nanospheres as template. The inorganic shell was produced using tetraorthosilicate (TEOS) as the silica source and tri-calciumphospate as calcium and phosphorus sources, respectively. The positive surface charge of the template and the [template]/[TEOS] ratio were the key parameters for the creation of a stable primary inorganic network and the further growth of the shell. The removal of the polymeric core through a thermal treatment procedure created an inner void space with mean diameter 250 nm while the outer mean diameter was 330 nm.     

Synthesis and characterization of silica core/nano-ferrite shell particles

Core/shell particles were synthesized by assembling oppositely charged ferrite (Fe₃O₄ or NiFe₂O₄) nanoparticles on the surface of monodispersed silica core particles (having size ～0.4 μm) prepared by hydrolysis and condensation of tetraethylortosilicate. Optimal conditions for synthesis of silica core/nano-Fe₃O₄ shell particles were found at pH ～ 5.4. The obtained particles have superparamagnetic behavior above a blocking temperature of ≈25 K, which make them very attractive for a broad range of biomedical and bioengineering applications. Incorporation of nickel into ferrite structure could not be achieved at lower pH value, so functionalization of core particles was required. Incorporation of nickel into ferrite structure was successful at pH above 7, however at higher pH the formation rate of nickel–ferrite particles becomes very fast and the self-aggregation dominates the competing formation of the nickel–ferrite shell. Because of that the self-aggregation was prevented by surface modification of nickel–ferrite nanoparticles with citric acid before their deposition on the functionalized silica core and homogenous and continuous NiFe₂O₄ shell was finally obtained.     

Molecular orientation of nonlinear optical polymer nanosheets on silica nanoparticle monolayer studied by optical waveguide spectroscopy

The paper describes molecular orientation of nonlinear optical (NLO) polymer monolayer transferred onto a sphere-shaped silica nanoparticle monolayer using optical waveguide spectroscopy. Structurally well-defined hybrid polymer nanoassemblies were constructed through bottom-up approaches: Langmuir–Blodgett technique and immersion method. Silica nanoparticles (SiO₂ NPs, 40–50 nm diameter) were immobilized on a quartz waveguide using cationic polymer Langmuir–Blodgett films (nanosheets) as a template. The SiO₂ NPs took a uniformly distributed monolayer formation without any aggregates, which minimizes light scattering. This allows us to gain reproducible absorption spectra of dye molecules embedded in polymer nanosheet monolayer on the nanoscale rough surface using optical waveguide spectroscopy. The NLO polymer nanosheets containing disperse red 1 (DR) were transferred onto the SiO₂ NP monolayer. The polarized absorption spectra were obtained; the s-light absorption was larger than the p-light absorption, indicating that polymer nanosheets are wrapped around SiO₂ NPs so that DR moieties undergo molecular disorientation not to form H-aggregates. This method provides us with useful information on structure–property relationship between nanoshaped inorganic nanoparticle and organic functional molecules in hybrid nanoassemblies.     

Core/shell structured sSiO2/mSiO2 composite particles: The effect of the core size on oxide chemical mechanical polishing

In a typical chemical mechanical polishing (CMP) process, the type, morphology, structure, mechanical, and surface characteristics of abrasive particles play an important role in influencing the material removal process. The novel abrasive particles with special mechanical and/or tribochemical properties have been introduced into CMP processes for the improvement of surface quality and finishing efficiency. In this work, the composite particles containing solid silica (sSiO₂) cores and mesoporous silica (mSiO₂) shells were prepared via a developed Stöber method using cetyltrimethylammonium bromide as a structure-templating surfactant. The as-synthesized core/shell structured sSiO₂/mSiO₂ composite particles were characterized by powder X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and nitrogen sorption–desorption measurements. The effect of the sSiO₂ core size of the composite particles on oxide CMP performance was evaluated in terms of surface roughness and material removal rate (MRR). The root-mean-square surface roughness (0.15–0.31 nm) of the polished substrates slightly increased with increasing of the sSiO₂ core size (168–353 nm) of the composites with a comparable mSiO₂ shell thickness (16–18 nm). The sSiO₂/mSiO₂ composite particles with a relatively smaller or larger core presented a relatively high MRR for silicon oxide films. These oxide CMP results could be rationalized according to the contact area mechanism and indentation-based mechanism, incorporating the total contact area and chemical reactivity between particles and wafers, and the indentation depth of an abrasive particle onto the substrate surface.