Mesoporous silica templated zirconia nanoparticles

Nanoparticles of zirconium oxide (ZrO₂) were synthesized by infiltration of a zirconia precursor (ZrOCl₂·8H₂O) into a SBA-15 mesoporous silica mold using a wet-impregnation technique. X-ray diffractometry and high-resolution transmission electron microscopy show formation of stable ZrO₂ nanoparticles inside the silica pores after a thermal treatment at 550 °C. Subsequent leaching out of the silica template by NaOH resulted in well-dispersed ZrO₂ nanoparticles with an average diameter of ~4 nm. The formed single crystal nanoparticles are faceted with 110 surfaces termination suggesting it to be the preferred growth orientation. A growth model of these nanoparticles is also suggested.     

Magnetic nanocomposite spinel and FeCo core-shell and mesoporous systems

The fabrication of condensed silica and mesoporous silica coated spinel CoFe₂O₄ and FeCo alloy magnetic nanocomposites are reported. The encapsulation of well-defined 5 nm thick uniform silica layer on CoFe₂O₄ magnetic nanoparticles was performed. The formation of mesopores in the shell was a consequence of removal of organic group of the precursor through annealing. The NiO nanoparticles were loaded into the mesoporous silica. The mesoporous silica shells leads to a larger coercivity than that of pure CoFe₂O₄ magnetic nanoparticles due to the decrease of interparticle interactions and magneto-elastic anisotropy. In addition, the FeCo nanoparticles were coated by condensed and mesoporous silica. The condensed silica can protect the reactive FeCo alloy from oxidation up to 300 °C. However, saturation magnetization of FeCo nanoparticles coated by silica after 400 °C annealing is dramatically decreased due to the oxidation of the FeCo core. The mesoporous silica coated magnetic nanostructure loaded with NiO as a final product could be used in the field of biomedical applications.     

Equations for filling factor estimation in opal matrix. Addendum to “Deep level emission of ZnO nanoparticles deposited inside UV opal”, [Opt. Commun. 259 (1) (2006) 378-384]

We consider two equations for the filling factor estimation of infiltrated zinc oxide (ZnO) in silica (SiO₂) opal and gallium nitride (GaN) in ZnO opal. The first equation is based on the effective medium approximation, while the second one—on Maxwell-Garnett approximation. The comparison between two filling factors shows that both equations can be equally used for the estimation of the quantity of infiltrated nanoparticles inside opal photonic crystal.     

Facile Fabrication of Dendritic Mesoporous SiO2@CdTe@SiO2 Fluorescent Nanoparticles for Bioimaging

A seeded watermelon‐like mesoporous nanostructure (mSiO₂@CdTe@SiO₂, mSQS) composed of a novel dendritic mesoporous silica core, fluorescent CdTe quantum dots (QDs), and a protective solid silica shell is successfully fabricated by loading QDs into dendritic mesoporous silica nanoparticles through electrostatic interaction, and then coating with a solid silica shell by the modified Stöber method. The shell thickness of mSQS can be tuned from 0 to 32 nm as desired by controlling the reaction parameters, including the amount of silica precursor, tetraethyl orthosilicate, that is introduced, the solvent ratio (H₂O:ethanol), and the amount of catalyst (NH₃?H₂O). These fluorescent mSiO₂@QDs@SiO₂ nanoparticles possess excellent stability and thickness‐dependent cytotoxicity, and are successfully applied to bioimaging.     

Core-shell structured mesoporous silica nanoparticles equipped with pyrene-based chemosensor: Synthesis, characterization, and sensing activity towards Hg(II)

In this paper, we construct core-shell structured mesoporous silica nanoparticles with spherical SiO₂ as the core and mesoporous silica as the shell, offering both large surface-area-to-volume-ratio and short channels. With this core-shell structured mesoporous silica nanoparticles as supporting medium, a chemosensor of pyrene, owing advantages of large Stokes shift, high quantum yield and excellent photostability, is grafted into the channels of the nanoparticles, aiming at a Hg(II) detector with quick response and high selectivity. The sensing performance of the resulting composite material is investigated in detail. Data suggest that the composite material is thermally stable enough for actual applications and highly selective towards Hg(II), and a linear response with detection limit of 10⁻⁸ mol/L is finally realized, which means that it is a promising biochemo-sensing material for Hg(II) detection.     

Preparation of nano-sized platinum metal catalyst using photo-assisted deposition method on mesoporous silica including single-site photocatalyst

Pt particles in a uniform dispersion were successfully synthesized on single-site photocatalyst (Ti-containing mesoporous silica (Ti-HMS)) under UV-light irradiation by a photo-assisted deposition (PAD) method. Using an aqueous solution of H₂PtCl₆ as a precursor, the nano-sized Pt metal particles were deposited directly on the photo-excited tetrahedrally coordinated titanium oxide moieties within the framework of mesoporous silica (PAD-Pt/Ti-HMS). The Pt catalysts were characterized by means of XRD, Pt L_III-edge XAFS, CO adsorption, and TEM analysis. It was demonstrated that Pt particles had mean diameter of 4 nm in a narrow size distribution. Meanwhile, Pt particles loaded by a conventional impregnation method (imp-Pt/Ti-HMS) showed a wide size distribution ranging from 2 to 30 nm. The PAD-Pt/Ti-HMS catalyst was more active in the CO oxidation than the conventional impregnated imp-Pt/Ti-HMS catalyst. It is suggested that the PAD method using single-site photocatalyst is a useful and unique technique to prepare fine and uniform Pt nanoparticles.     

Fiber-optic chemical sensor of amine-type compounds

A scheme of a fiber chemical sensor of amine-type compounds has been implemented. The sensor includes a film nanostructure deposited on the end face of an optical fiber 600 μm in diameter. The film consists of luminescent silica nanoparticles modified by functional pyrylocyanine dye, silver nanoparticles, and a photonic crystal opal film. An additional coating of the sensor film from above by a porous selective mirror, such as a photonic crystal, and introduction of silver nanoparticles 5–7 nm in diameter into it make it possible to increase the sensor sensitivity by an order of magnitude.     

Novel nanofluids based on mesoporous silica for enhanced heat transfer

Nanofluids, which are liquids with engineered nanometer-sized particles suspensions, have drawn remarkable attraction from the researchers because of their enormous potential to enhance the efficiency in heat-transfer fluids. In the present study, water-based calcined mesoporous silica nanofluids were prepared and characterized. The commercial mesoporous silica (MPSiO₂) nanoparticles were dispersed in deionized water by means of pH adjustment and ultrasonic agitation. MPSiO₂ nanoparticles were observed to have an average particle size of 350 ± 100 nm by SEM analysis. The concentration of MPSiO₂ was varied between 1 and 6 wt%. The physicochemical properties of nanofluids were characterized using various techniques, such as particle size analyzer, zeta-potential meter, TEM, and FT-IR. The thermal conductivity was measured by Transient Plane Source (TPS) method, and nanofluids showed a higher thermal conductivity than the base liquid for all the tested concentrations.     

Comparison of silver nanoparticles confined in nanoporous silica prepared by chemical synthesis and by ultra-short pulsed laser ablation in liquid

Hexagonally ordered mesoporous silica materials, MCM-41 and SBA-15, have been synthesized and loaded with Ag nanoparticles, utilizing both chemical synthesis and ultra-short pulsed laser ablation in liquid. In laser ablation, a silver target, immersed in aqueous suspension of ordered mesoporous silica SBA-15, was irradiated by ultra-short laser pulses to generate silver nanoparticles. For comparison, samples of similar silver contents were prepared either by incorporating silver into the SBA-15 during a hydrothermal synthesis or by introducing silver in MCM-41 by template ion-exchange. Samples were characterized by XRD, N₂ physisorption, TEM and UV–vis spectroscopy. All preparations contained significant amount of 5–50 nm size silver agglomerates on the outer surface of the silica particles. The laser ablation process did not cause significant destruction of the SBA-15 structure and metallic silver (Ag⁰) nanoparticles were mainly generated. It is demonstrated that by laser ablation in aqueous silica suspension smaller and more uniform metallic silver particles can be produced and loaded on the surface of the silica support than by synthesis procedures. Catalytic properties of the samples have been tested in the total oxidation of toluene. Because of its favorable Ag dispersity, the Ag/SBA-15 catalyst, generated by the laser ablation method, had better catalytic stability and, relative to its Ag load, higher activity than the conventional Ag/SBA-15 preparations.     

ZnO nanoparticles embedded in UVM-7-like mesoporous silica materials: Synthesis and characterization

ZnO nanodomains embedded in bimodal mesoporous silica (UVM-7) materials with high Zn content (4≤Si/Zn≤30) have been synthesized by an one-pot surfactant-assisted procedure from a hydro alcoholic medium using a cationic surfactant (CTMABr=cetyltrimethylammonium bromide) as structural directing agent, and starting from molecular atrane complexes of Zn and Si as hydrolytic inorganic precursors. This chemical procedure allows optimizing the dispersion of the ZnO particles in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N₂ adsorption–desorption isotherms. The small intra-particle mesopore system is due to the supramolecular templating effect of the surfactant, while the large pores have their origin in the packing voids generated by aggregation of the primary nanometric mesoporous particles. A limited pore blocking and a high accessibility to the ZnO active nanoparticles have been achieved. The effects induced by the progressive incorporation of ZnO nanoparticles into the mesostructure have been examined, including a careful optical spectroscopic study (PL and UV–visible).     

Dielectric matrices with air cavities as a waveguide photonic crystal

Frequency dependences of the transmission coefficient of a microwave photonic crystal that represents a structure containing alternating layers of ceramic material (Al₂O₃) with a relatively large number of cavities and foam plastic are studied in the presence and absence of distortions of the periodicity of a photonic structure. The frequency dependences of the transmission coefficient can be analyzed using a model of effective medium that makes it possible to consider the interaction of electromagnetic wave and photonic crystal using a transfer matrix of a 1D photonic crystal. The band character of the frequency dependence of the transmission coefficient of the photonic crystal related to the periodicity of the photonic crystal in the transverse plane for the waveguide with a standard cross section is not manifested in a certain range of material permittivities.     

H2O2水热合成双峰介孔硅MCM-48球

在温和的条件下,通过H₂O₂水热处理预合成的MCM-48,得到了有序的双峰介孔硅MCM-48球． 结果表明H₂O₂对于同时去除有机模板剂及形成双峰介孔硅MCM-48球具有重要的作用．采用XRD、TEM、FT-IR和N₂吸附-解吸等方法对双峰介孔MCM-48材料进行了表征,对双峰介孔MCM-48的形成机理也进行了探讨．     

Enhanced omni-directional reflection frequency range in Si-based one dimensional photonic crystal with defect

In the present communication, we study omni-directional reflection in one-dimensional photonic crystal (PC) based on Si/SiO₂ multilayered structure. It has been shown numerically that it is possible to enhance the range of omni-directional reflection in one-dimensional photonic crystal appreciably by introducing a defect in the multilayered structure.     

Optical properties of metamaterial-based devices modulated by a liquid crystal

Due to the fact that it is possible to manipulate light with photonic crystals (PCs), PCs hold a great potential for designing new optical devices. There has been an increase in research on tuning the optical properties of PCs to design devices. We presented a numerical study of optical properties of metamaterial-based devices by liquid crystal infiltration. The plane wave expansion method and finite-difference time-domain method for both TE and TM modes revealed optical properties in photonic crystal structures in an air background for a square lattice. E7 type has been used as a nematic liquid crystal and SrTiO₃ as a ferroelectric material. We showed the possibility of the metamaterials for a two-dimensional photonic crystal cavity on a ferroelectric base infiltrated with a nematic liquid crystal.     

中红外完全带隙Si反蛋白石光子晶体的制备与光学性能研究

通过溶剂蒸发对流自组装法制备SiO2胶体晶体,采用低压化学气相沉积法填充Si,制备得到Si反蛋白石(opal)三维光子晶体.采用扫描电子显微镜对Si反opal的显微形貌进行表征,采用平面波展开法理论模拟Si反opal的光子带隙,采用傅里叶变换红外光谱仪测试其光学性能.研究结果表明:Si在SiO2微球空隙内填充致密均匀,显微红外光谱测试的光子带隙反射峰位置及带宽与理论计算基本符合.变角度反射光谱测试表明,Si反opal沿不同角度入射时在中心波长3319nm处均存在明显的反射峰,证明其具有完全光子带隙,带隙位于中红外大气窗口区域.     

Iron oxide nanoparticles stabilized inside highly ordered mesoporous silica

Nanosized iron oxide, a moderately large band-gap semiconductor and an essential component of optoelectrical and magnetic devices, has been prepared successfully inside the restricted internal pores of mesoporous silica material throughin-situ reduction during impregnation. The samples were characterized by powder XRD, TEM, SEM/EDS, N₂ adsorption, FT-IR and UV-visible spectroscopies. Characterization data indicated well-dispersed isolated nanoclusters of (Fe₂O₃) _n , within the internal surface of 2D-hexagonal mesoporous silica structure. No occluded Fe/Fe₂O₃ crystallites were observed at the external surface of the mesoporous silica nanocomposites. Inorganic mesoporous host, such as hydrophilic silica in the pore walls, directs a physical constraint necessary to prevent the creation of large Fe₂O₃ agglomerates and enables the formation of nanosized Fe₂O₃ particles inside the mesopore     

Engineering the Internal Structure of Magnetic Silica Nanoparticles by Thermal Control

Calcination of hydrated iron salts in the pores of both spherical and rod‐shaped mesoporous silica nanoparticles (NPs) changes the internal structure from an ordered 2D hexagonal structure into a smaller number of large voids in the particles with sizes ranging from large hollow cores down to ten nanometer voids. The voids only form when the heating rate is rapid at a rate of 30 °C min^?1. The sizes of the voids are controlled reproducibly by the final calcination temperature; as the temperature is decreased the number of voids decreases as their size increases. The phase of the iron oxide NPs is α‐Fe₂O₃ when annealed at 500 °C, and Fe₃O₄ when annealed at lower temperatures. The water molecules in the hydrated iron (III) chloride precursor salts appear to play important roles by hydrolyzing Si? O? Si bonding, and the resulting silanol is mobile enough to affect the reconstruction into the framed hollow structures at high temperature. Along with hexahydrates, trivalent Fe³⁺ ions are assumed to contribute to the structure disruption of mesoporous silica by replacing tetrahedral Si⁴⁺ ions and making Fe? O? Si bonding. Volume fraction tomography images generated from transmission electron microscopy (TEM) images enable precise visualization of the structures. These results provide a controllable method of engineering the internal shapes in silica matrices containing superparamagnetic NPs.     

Preparation of colloidal films with different degrees of disorder from monodisperse spherical silica particles

The process of coagulation of suspensions of monodisperse spherical silica particles driven by appropriate coagulants (NH₄Cl, HCl, C₁₆H₃₃N(CH₃)₃Br) has been studied. Films of photonic crystals and photonic glasses have been grown by the sedimentation method. The possibility of controlling the degree of structural disorder in colloidal films by properly varying the resistance of the water suspension of particles to aggregation has been demonstrated.     

Chemisorption of hydrogen sulphide on zinc oxide modified aluminum-substituted SBA-15

Aluminum silicate mesoporous material, ZnO/Al-SBA-15, was synthesized by post-synthesis and immobilization method via microwave-assisted route. Desulphurization tests from a gas mixture with low content H₂S were carried out as the probing reaction on these materials. Chemical effects and the nature of the ZnO additive and textural properties on desulphurization capacity were studied over this material. Material was characterized using N₂ adsorption, XRD, TEM, FTIR, XPS, ICP and other techniques. The analysis suggests that the as-synthesized material had well-ordered hexagonal mesopores and was abundant in micropores. ZnO nanoparticles dispersed well and anchored both in the channel and the wall of mesoporous silica. The material with 2.1 wt.% zinc loading presented the highest H₂S uptake capacity. Both micropores and mesopores are active sites for H₂S capture, especially micropores. The enhancement of H₂S removal capacity was attributed to the integration of the pore structure of mesoporous material and the promising desulphurization properties of ZnO nanoparticles. ZnO/Al-SBA-15 could be an effective alternative to remove H₂S from gaseous streams and it also extends the research of mesoporous material.     

Magnetic properties of Mn-oxide nanoparticles dispersed in an amorphous SiO2 matrix

Samples of Mn-oxide nanoparticles dispersed in an amorphous SiO₂ matrix with manganese concentration 0.7 and 3 at% have been synthesized by a sol-gel method. Transmission electron microscopy analysis has shown that the samples contain agglomerates of amorphous silica particles 10-20 nm in size. In silica matrix two types of Mn-rich particles are dispersed, smaller nanoparticles with dimensions between 3 and 10 nm, and larger crystalline areas consisting of aggregates of the smaller nanoparticles. High-temperature magnetic susceptibility study reveals that dominant magnetic phase at higher temperatures is λ-MnO₂. At temperatures below T_C=43 K strong ferrimagnetism originating from the minor Mn₃O₄ phase masks the relatively weak magnetism of λ-MnO₂ with antiferromagnetic interactions. Magnetic field dependence of the maximum in the zero-field-cooled magnetization for both the samples in the vicinity of 40 K, and a frequency shift of the real component of the ac magnetic susceptibility in the sample with 3 at% Mn suggest that the magnetic moments of the smaller Mn₃O₄ nanoparticles with dimensions below 10 nm are exposed to thermally activated blocking process just below the Curie temperature T_C. Appearance of a maximum in the zero-field-cooled magnetization for both the samples below 10 K indicates possible spin glass freezing of the magnetic moments at low temperatures which might occur in the geometrically frustrated Mn sublattice of the λ-MnO₂ crystal structure.