Preparation of Silica Microspheres Containing Ag Nanoparticles

Two sol-gel fabrication processes were investigated to make silica spheres containing Ag nanoparticles: (1) a modified Stöber method for silica spheres below 1 m size, and (2) a SiO₂-film formation method on spheres of 3–;7 m size. The spheres were designed to incorporate silver nanoparticles of high ⁽³⁾ in a spherical optical cavity structure for the resonance effect. For the incorporation, interaction between [Ag(NH₃)₂]⁺ ion and Si-OH was important. In the Stöber method, the size of the silica spheres was determined by a charge balance of plus and minus ions on the silica surface. In the film formation method, the capture of Ag complex ion on the silica surface depended on whether the surface was covered with OH groups or not. After doping [Ag(NH₃)₂]⁺ into silica particles or SiO₂ films on the spheres, these ions w ere reduced by NaBH₄ to form silver nanoparticles. From plasma absorption at around 420 nm wavelength and TEM photographs of nanometer-sized silver particles, their formation inside the spherical cavity structures was confirmed.     

Photogeneration of nanosized gold on the surface of mesoporous silica modified by benzophenone

We have studied the photocatalytic activity of porous silicas (silica gel, mesoporous sol-gel films) modified by benzophenone molecules, in the reaction of reduction of gold from tetrachloroaurate ions. Stable colloids of nanosized gold were obtained as a result of irradiating aqueous alcoholic solutions of HAuCl₄·3H₂O in the presence of the photocatalyst SiO₂-BP using as the stabilizers: a colloidal solution of silica (Ludox) or the surfactant sodium dodecyl sulfate (SDS). We have studied the effect of the stabilizer on the kinetics of the photoreduction reaction, and also on the shape and size of the nanoparticles formed. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 41, No. 6, pp. 348–353, November–December, 2005.     

Facile,single-pot preparation of nanoporous SiO2 particles (carrier) with AgNPs at core and crust for controlled disinfectant release

This study demonstrates a novel, facile and one-pot approach to synthesize silica nanoparticles with silver at core and crust (SiNP-AgCC). A modified Stöber method was used to make SiNP-AgCC. A significant reduction in the size of SiO₂ nanoparticles was seen, with 2–5 nm AgNPs being uniformly distributed on the surface and 10–20 nm AgNPs in the center. A typical mesoporous SiO₂ particle (SiNP) produced using the Stöber method was transformed to nanoporous SiO₂ by this modified Stöber method. Nanoporous SiO₂ particles with silver in the center are advantageous for slow and consistent Ag⁺ release, which was confirmed by Ag⁺ ion release test. Antibacterial activities of the samples were tested to evaluate the disinfection performance of the samples on gram-negative bacteria (Escherichia coli) using disk diffusion and the LB-agar method. SiNP-AgCC showed prolonged silver release for more than 20 days and improved antibacterial properties even after five days of incubation.     

Silver and gold nanoparticles in silica matrices: synthesis,properties, and application

Methods of synthesis, optical characteristics, morphology, and catalytic and bactericidal characteristics of composite materials based on silica (films and powders) containing nanoparticles of silver, gold, and their binary compounds with alloy or core–shell structure are examined. The photochemical reduction of Au³⁺ and Ag⁺ with a photocatalyst (a film of SiO₂ with adsorbed benzophenone) makes it possible to generate stable nanoparticles of gold and silver in solutions for subsequent introduction into adsorbents and catalysts. Examples of the use of nanosized composites in catalysis and in microbiological experiments are presented.     

Synthesis of silica–silver wires by a sol–gel technique

SiO₂–Ag wires were synthesized by a sol–gel technique. A two step approach was followed, focusing mainly on the effect of acid concentration on the first stage and processing temperature on the second. This acid-catalyzed reaction on the first stage yielded SiO₂–AgCl wires with diameters as low as 800 nm average, and lengths ranging up to 100 μm, as determined by LV-SEM and TEM. A thermal treatment at different temperatures on the second step, under H₂ atmosphere, yields silica–silver unidirectional structures. The chemical composition of these structures was determined by EDS, indicating the presence of Si, O and Ag. The transformation of the wires as a function of temperature under reducing atmosphere was followed by electron microscopy analysis. At 400 °C and above the silica starts to cover the reduced silver while maintaining the unidirectional conformation, suggesting a tendency to form silver wires covered by a silica layer.     

Composition,Enthalpy, and Vaporization Temperature Calculation of Ag‐SiO<Subscript>2</Subscript> Plasmas with Air in the Temperature Range from 1000 to 6000 K and for Pressure Included between 1 and 50 bars

With the Gibbs free energy minimization method, the molar fraction of chemical species are determined in temperature range included between 1000 and 6000 K for several proportions of air, silver and silica and for pressures included between 1 and 50 bars. The enthalpy and the vaporization temperature of liquid silver and liquid silica are studied. The key role of pressure on composition, enthalpy and the vaporization temperature is shown. The electrical neutrality is study, and the importance of ionized gaseous silver at low temperature is shown even for low amount of silver. The increase of electronegative ions (Ag^– and O^–) with pressure is shown. The vapor pressures fitting coefficients of Ag and SiO₂ are given.     

Synthesis of silver nanoparticles in mesoporous high-aluminum aluminosilicate matrices

A new method for the synthesis of Ag/Al_xSi_1–x O_2–0.5x nanocomposite materials was proposed. The method is based on the use of charged mesoporous aluminosilicate matrices as nanoreactors. The porous structure of the matrices was characterized by ²⁷Al NMR spectroscopy and nitrogen capillary sorption at 77 K. An increase in the aluminum loading destroys the matrix structure and decreases the specific surface area. The resulting aluminosilicates were used as matrices for the synthesis of silver nanoparticles. The nanocomposites were examined by transmission electron microscopy and chemical analysis to estimate the silver percentage in specimens. Silver nanowires (20% Ag) are formed in the low-aluminum (<10 mol.%) matrices, whereas an increase in the aluminum percentage affords both nanowires and spherical particles 3–10 nm in size and decreases the total amount of silver in the nanocomposite.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2391–2393, November, 2004.     

Sorption-desorption of radiocesium on various sorbents in presence of humic acid

In general, the amount of radiocesium sorbed by the five sorbents with 0.01 mol·dm^–3 NaCl was in order zeolite > NiFeCN–SiO₂ > montmorillonite > aerogel > silica gel. Addition of humic acid solution to the sorbents depressed the sorption of cesium by all sorbents, except for NiFeCN–SiO₂ was not seen, with the greatest effect showing to the aerogel. The presence of humic acid resulted in an enhanced desorption of cesium from zeolite, NiFeCN–SiO₂ and to a lesser extent from montmorillonite and silica gel. The order of cesium retention following desorption for both sorbent and sorbent/humic-acid mixtures was zeolit > NiFeCN–SiO₂ > montmorillonite > silica gel. The presence of humic acid resulted in decreasing of distribution coefficient values for both sorption and desorption processes.     

Highly efficient and green oxidation of alkanes and alkylaromatics with hydrogen peroxide catalysed by silver and vanadyl on mesoporous silica‐coated magnetite

A heterogeneous catalyst (FeSi/Ag/VO) based on silver and vanadyl as active sites and mesoporous silica‐coated nanospheres of magnetite (Fe₃O₄@m‐SiO₂) as support was successfully prepared by deposition of Ag nanoparticles and the covalent grafting of vanadyl(IV) acetylacetonate on Fe₃O₄@m‐SiO₂. The catalyst exhibited excellent activity for the oxidation of alkanes, benzene and alkylaromatics using green oxidant H₂O₂ and oxalic acid in acetonitrile at 60 °C.     

Preparation and characterization of stable monodisperse silver nanoparticles via photoreduction

Silver nanoparticles were synthesized by UV irradiation of [Ag(NH₃)₂]⁺ aqueous solution using poly(N-vinyl-2-pyrrolidone) (PVP) as both reducing and stabilizing agents. The formation of silver nanoparticles was confirmed from the appearance of surface plasmon absorption maxima around 420 nm. It was found that the formation rate of silver nanoparticles from Ag₂O was much quicker than that from AgNO₃, and the absorption intensity increased with PVP concentration as well as irradiation time. The maximum absorption wavelength (λ_max) was blue shift with increasing PVP content until 8 times concentration of [Ag(NH₃)₂]⁺ (wt%). The transmission electron microscopy (TEM) showed the resultant particles were 4–6 nm in size, monodisperse and uniform particle size distribution. X-ray diffraction (XRD) demonstrated that the colloidal nanoparticles were the pure silver. In addition, the silver nanoparticles prepared by the method were stable in aqueous solution over a period of 6 months at room temperature (25 °C).     

The state of nickel in the silver modified NiMg/SiO<Subscript>2</Subscript> vegetable oil hydrogenation catalysts

Two series of silver modified Ni-Mg materials were synthesized by precipitation-deposition on SiO₂ support derived from two silica sources: diatomite activated at 800°C (Series a; Mg/Ni = 0.1 and SiO₂/Ni = 1.07) and synthetic water glass (Series b; Mg/Ni = 0.1 and SiO₂/Ni = 1.15). The modification with silver was made at three molar Ag/Ni ratios, namely 0.0025, 0.025, and 0.1. The effects of the source of the silica support and the silver presence and content on the nickel state in the silver modified reduced-passivated NiMg/SiO₂ precursors of the vegetable oil hydrogenation catalyst were established by X-ray diffraction and X-ray photoelectron spectroscopy techniques. The passivation procedure was applied in order to protect the metallic nickel particles from further oxidation. The crystallization of the formed nickel hydrosilicate phases depends on the source of the silica support, more expressed in the diatomite supported samples. It was shown that the silver modification of the NiMg/SiO₂ precursors enhances the reduction of the nickel hydrosilicates accompanied by formation of relatively smaller metallic nickel particles, more pronounced in the water glass supported precursors. The increase of the silver content in the water glass deposited samples is responsible for the metallic nickel dispersion increase. The higher content of the Ni⁰ particles on the surface of the diatomite deposited samples is in accordance with the higher stability of the larger metallic nickel crystallites to oxidation during the passivation step. On contrary, higher dispersed Ni⁰ particles on the surface of the water glass supported samples are more susceptible to the oxida The article is published in the original.     

Evaluation of Chitosan Derivatives Modified Mesoporous Silica Nanoparticles as Delivery Carrier

Chitosan is a non-toxic biological material, but chitosan is insoluble in water, which hinders the development and utilization of chitosan. Chitosan derivatives N-2-Hydroxypropyl trimethyl ammonium chloride (N-2-HACC) and carboxymethyl chitosan (CMCS) with good water solubility were synthesized by our laboratory. In this study, we synthesized mesoporous SiO₂ nanoparticles by the emulsion, and then the mesoporous SiO₂ nanoparticles were modified with γ-aminopropyltriethoxysilane to synthesize aminated mesoporous SiO₂ nanoparticles; CMCS and N-2-HACC was used to cross-link the aminated mesoporous SiO₂ nanoparticles to construct SiO₂@CMCS-N-2-HACC nanoparticles. Because the aminated mesoporous SiO₂ nanoparticles with positively charged can react with the mucous membranes, the virus enters the body mainly through mucous membranes, so Newcastle disease virus (NDV) was selected as the model drug to evaluate the performance of the SiO₂@CMCS-N-2-HACC nanoparticles. We prepared the SiO₂@CMCS-N-2-HACC nanoparticles loaded with inactivated NDV (NDV/SiO₂@CMCS-N-2-HACC). The SiO₂@CMCS-N-2-HACC nanoparticles as delivery carrier had high loading capacity, low cytotoxicity, good acid resistance and bile resistance and enteric solubility, and the structure of NDV protein encapsulated in the nano vaccine was not destroyed. In addition, the SiO₂@CMCS-N-2-HACC nanoparticles could sustain slowly released NDV. Therefore, the SiO₂@CMCS-N-2-HACC nanoparticles have the potential to be served as delivery vehicle for vaccine and/or drug.     

Effect of transition metal oxide additives on the activity of an Ag/SiO2 catalyst in carbon monoxide oxidation

The catalysts of silver supported on mesoporous silica modified with Co₃O₄, CeO₂, and ZrO₂ were prepared by an impregnation method; characterized by X-ray diffraction analysis, temperature-programmed reduction, and low-temperature nitrogen adsorption; and studied in a model reaction of CO oxidation. It was found that the Ag/SiO₂ system exhibited high activity in the reaction of CO oxidation, and the addition of transition metal oxides led to reduction of the temperature of 50% CO conversion by 40°C. The modification of Ag/SiO₂ with cerium dioxide was found most effective because of the interaction of silver particles and CeO₂ on the surface of silica gel.     

Sensitive determination of the endocrine disruptor bisphenol A at ultrathin film based on nanostructured hybrid material SiO<Subscript>2</Subscript>/GO/AgNP

In this work, we described an electrochemical sensor using a nanocomposite based on graphene oxide (GO), silver nanoparticles (AgNP), and disordered mesoporous silica (SiO₂), which was used for the determination of bisphenol A in water samples. Initially, the hybrid material SiO₂/GO was synthesized via sol-gel process, subsequently decorated with AgNP with an approximate 20 nm particle size prepared directly on the surface of the SiO₂/GO using N, N-dimethylformamide (DMF) as an agent reducer. A glassy carbon electrode was modified with SiO₂/GO/AgNP and used in developing a sensitive electrochemical sensor for the determination of bisphenol A in phosphate buffer 0.1 mol L^?1 (pH 7.0). The detection limit was 45.2 nmol L^?1 with a linear response range between 1.0 × 10^?7 and 2.6 × 10^?6 mol L^?1 and a sensitivity of 1.27 × 10^?7 A mol^?1 L. Finally, the optimized electrochemical sensor was used for the quantitation of endocrine interfering in natural waters.     

银纳米修饰电极的制备及电化学行为

金属纳米粒子由于其小的体积和大的比表面积而具有独特的电子、光学和异相催化特性,是目前表面纳米工程及功能化纳米结构制备的一种理想研究对象[1]。银纳米粒子可广泛应用于催化剂材料、电池的电极材料、低温导热材料和导电材料等,成为近年来人们研究的热点[2,3]。在电化学方面,银纳米粒子具有比其他纳米粒子更为优异的导电性能和电催化性能。因此,研究银纳米粒子修饰电极有重要的应用价值和前景[4]。1实验部分1.1仪器CHI660电化学工作站(USA);TU-1901型双光束紫外可见分光光度计(北京普析通用仪器公司);KQ-100型超声清洗器(昆山市超声…     

Green preparation of hollow mesoporous silica nanosphere inside-loaded gold nanoparticles and the catalytic activity

In this work, an active nano-catalyst with gold nanoparticles loaded in hollow mesoporous silica nanospheres (HMSNs/Au) was prepared by a one-pot sol-gel method, in which gold ions were loaded in hollow mesoporous silica spheres followed by sodium alginate reduction. The characterization of the HMSNs/Au were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms (BET). The high catalytic activity of HMSNs/Au, denoted as apparent turn-over frequency (TOF), was detected by UV-Vis spectrophotometer for the catalytic reduction of 4-nitrophenol (74.5 h^?1) and 2-nitrophenol (108.7 h^?1) in the presence of sodium borohydride solution due to the small gold nanoparticles size and overall exposure of active sites. It is expected that this ecofriendly approach to prepare inorganic composited nanoparticles as high active catalysts based on hollow mesoporous materials was a promising platform for loading noble metal nanoparticles.     

An improved preparation of mesoporous silica‐supported Pd as sustainable catalysts for phosphine‐free Suzuki–Miyaura and Heck coupling reactions

An improved and eco‐friendly procedure has been developed to generate mesoporous silica‐supported palladium nanoparticles (SiO₂@PdNP) that could be used as a sustainable heterogeneous Pd catalyst for phosphine‐free Suzuki–Miyaura and Heck coupling reactions with excellent turnover number and turnover frequency. The presence of Pd on the silica surface was detected by X‐ray diffraction and the structural morphology of SiO₂@PdNP was obtained by transmission electron microscopy. The heterogeneous catalytic system is recyclable and leaching of the metal after the reaction is not apparently observed. Copyright © 2013 John Wiley & Sons, Ltd.     

纳米银掺杂二氧化硅复合颗粒的制备及表征

0引言金属纳米颗粒因其粒子尺寸小(1￣100nm),比表面积大,表面原子数多,表面能和表面张力随粒径的下降急剧增大而具有量子尺寸效应[1]、小尺寸效应[2]、表面效应[3]及宏观量子隧道效应[4]等,从而出现了不同于常规固体的新奇特性,如:光学性质、磁性质以及电磁学性质[5],使其在催化、信息存储及非线性光学等领域展示了广阔的应用前景[6]。虽然制备金属纳米颗粒的方法有很多[6],但是由于纳米尺寸的金属颗粒具有较高的表面能,容易发生聚集,所以如何保持其稳定性依旧是比较困难的问题。随着纳米科技的发展,人们正尝试用各种方法来解决这个问题:如…     

Sol–gel synthesis of mesoporous silicas containing albumin and guanidine polymers and its application to the bilirubin adsorption

The organic–inorganic composite materials based on mesoporous silica were synthesized using sol–gel method. The surface area of silicas was modified by bovine serum albumin (BSA) and guanidine polymers: polyacrylate guanidine (PAG) and polymethacrylate guanidine. The mesoporous silicas were characterized by nitrogen adsorption–desorption analysis, Fourier transform infrared spectroscopy, transmission electron microscopy. The obtained materials were used as adsorbents for selective bilirubin removal. It was shown that the structural properties and surface area of modified materials depend on the nature of polymers. Incorporation of polymers in silica gel matrix during sol–gel process leads to the formation of mesoporous structure with high pore diameter and a BET surface area equals to 346 m²/g for SiO₂/BSA and 160 m²/g for SiO₂/PAG. Analysis of adsorption isotherms showed that modification of silica by BSA and guanidine polymers increases its adsorption ability to bilirubin molecules. According to Langmuir model, the maximum bilirubin adsorption capacity was 1.18 mg/g.     

Acetalization of glycerol using mesoporous MoO3/SiO2 solid acid catalyst

Acetalization of glycerol with various aldehydes has been carried out using mesoporous MoO₃/SiO₂ as a solid acid catalyst. A series of MoO₃/SiO₂ catalysts with varying MoO₃ loadings (1–20 mol%) were prepared by sol–gel technique using ethyl silicate-40 and ammonium heptamolybdate as silica and molybdenum source respectively. The sol–gel derived samples were calcined at 500 °C and characterized using various physicochemical characterization techniques. The XRD of the calcined samples showed the formation of amorphous phase up to 10 mol% MoO₃ loading and at higher loading of crystalline α-MoO₃ on amorphous silica support. TEM analyses of the materials showed the uniform distribution of MoO₃ nanoparticles on amorphous silica support. Raman spectroscopy showed the formation of silicomolybdic acid at low Mo loading and a mixture of α-MoO₃ and polymolybdate species at high Mo loadings. Moreover the Raman spectra of intermediate loading samples also suggest the presence of β-MoO₃. Acetalization of glycerol with benzaldehyde was carried out using series of MoO₃/SiO₂ catalysts with varying MoO₃ loadings (1–20 mol%). Among the series, MoO₃/SiO₂ with 20 mol% MoO₃ loadings was found to be the most active catalyst in acetalization under mild conditions. Maximum conversion of benzaldehyde (72%) was obtained in 8 h at 100 °C with 60% selectivity for the six-membered acetal using 20% MoO₃/SiO₂. Interestingly with substituted benzaldehydes under same reaction conditions the conversion of aldehydes decreased with increase in selectivity for six-membered acetals. These results indicate the potential of this catalyst for the acetalization of glycerol for an environmentally benign process.