Production of Enzymes by Plant Cells Immobilized by Sol-Gel Silica

Ajuga reptans cells are cultivated and used for production of invertase. These plant cells are immobilized by a sol-gel SiO₂ membrane, which is built up directly on the cell surface by exposure to a gaseous flow of silicon alcoxide precursors. The immobilization modifies the metabolic activity of cells, resulting in a 40-fold increase in invertase production with respect of free cells. Results concerning total release of proteins, cell growth and produced invertase activity are discussed, considering the absence of breeding, induced by SiO₂ immobilization, the prominent factor promoting the observed exceptional increase in invertase productivity.     

Preparation of Cu/SiO2 Catalyst by Solution Exchange of Wet Silica Gel

Structural formation process of Ni/SiO₂ and Cu/SiO₂ catalysts prepared by solution exchange of wet silica gel was investigated. Microstructures of Cu/SiO₂ and Ni/SiO₂ were quite different from each other. In the case of Cu/SiO₂, Cu particles with diameter of ca. 3–5 nm dispersed homogeneously at less Cu content, and the particle size of Cu as well as pore size of silica gel support increased with increasing Cu content. In the Ni/SiO₂, the Ni particles with diameter of ca. 6–10 nm gathered densely to form aggregates in silica matrix resulting in sea-island structure, whereas the size of Ni particle slightly increased with increasing Ni content. The difference in the structure of the metal-silica composites is probably caused by the difference in interaction between silica gel network and metal ions during drying and heating processes.     

Preparation and characterization of CuO/SiO2 and NiO/SiO2 with bimodal pore structure by sol-gel method

CuO/SiO₂ and NiO/SiO₂ with bimodal pore structure were prepared by sol-gel reactions of Tetra-methoxysilane (TMOS) and the respective metal nitrate in the presence of poly (ethylene oxide) (PEO) with an average molecular weight of 10 000 and the catalyst of acetic acid. In this process, the interconnected macroporous morphology was formed when transitional structures of spinodal decomposition were frozen by the sol-gel transition of silica. The addition of copper and nickel into the silica-PEO system had a negligible effect on the morphology formation. In gel formation, it was found that NiO crystalline sizes in the samples increased with decreasing Si/Ni molar ratio. It was considered that PEO interacted with both silica and nickel cations. In the CuO/SiO₂ with the presence of PEO_, CuO crystalline sizes were larger than those of NiO/SiO_2. It was considered that there was no obvious interaction between the Cu cation and PEO, most of the copper ions in wet silica gel were present in the outer solution. They easily aggregated as copper salts in the drying process of wet gel and decomposed into CuO particles in heating. While in the CuO/SiO₂ with the absence of PEO, the Cu was selectively entrapped as small particles in the gel skeleton due to the interaction between Cu aqua complex and silica gel network.     

Supported oxorhenate catalysts prepared by thermal spreading of metal Re for methanol conversion to methylal

TiO₂-anatase and SiO₂ supported oxorhenate catalysts were prepared by an original and simple technique based on the oxidative dispersion of metallic rhenium under dry conditions. The dispersion process of the supported oxorhenate phase as a function of the rhenium coverage and the support properties are discussed on the base of in situ characterization. The structures of the as prepared catalysts were found to be comparable to those of materials prepared using the incipient wetness impregnation technique. The absence of water in the preparation technique has made it possible to highlight the role of the hydration level on the rhenium oxide volatilization. The as-prepared Re/TiO₂ catalysts were found to be effective for the direct conversion of methanol to methylal.     

Densification of Sol-Gel Thin Films by Ultraviolet and Vacuum Ultraviolet Irradiations

Structural changes in SiO₂ and TiO₂ gel films were investigated using ultraviolet (UV) and vacuum ultraviolet (VUV) irradiations. A significant compaction with dehydration of SiO₂ gel films was induced by irradiation of photons in the range of 9–18 eV. The refractive index and the shrinkage of the irradiated SiO₂ gel films were comparable to those obtained by sintering at 1000°C. Densification of TiO₂ gel films was also observed with irradiation of 5–14 eV photons. However, effects of the irradiation on TiO₂ gel were smaller that those on SiO₂ gel. The structural changes in the gel films are attributed to electronic excitations which are induced by irradiation with photons having higher energies than the bandgap of the oxides. The photo-induced effects are presumed to depend on the optical properties and structure of the gels.     

吸附法制备CuO-Ag/SiO2纳米复合物

利用吸附法原位制备CuO/SiO2、CuO-Ag/SiO2纳米复合物,研究了不同吸附质体系中预负载的纳米Ag粒子对CuO的影响。结果表明:Ag粒子对CuO的影响因吸附质的不同而不同。以Cu(Ac)2为吸附质,纳米Ag几乎没有影响;以NaOH为吸附质,纳米Ag使得CuO的晶粒粒径增大。这一结果与铜物种对Ag晶粒粒径的影响规律完全不同。通过比较不同吸附质的吸附行为,Cu(OH)2与硅胶表面的相互作用被认为是导致这一现象的原因。     

Syntheses of MO2 (M=Si, Ce, Sn) nanoparticles by solid-state reactions at ambient temperature

Nano oxides (SiO₂, CeO₂, SnO₂) were successfully synthesized by solid-state reactions at ambient temperature. The nanoparticles were characterized by X-ray powder diffraction, TEM, BET, and TGA-DTA. The SiO₂ particles were also investigated using IR spectra. Effects of calcination on the nanoparticles were studied in this paper. The solid-state reaction technique is a convenient, inexpensive and an effective preparation method of monodisperse oxide nanoparticles in high yield. The mechanisms of the formation of nano materials by solid-state reactions at ambient temperature were primarily investigated.     

Sol-gel coatings for chemical protection of stainless steel

Sol-gel thin coatings of ZrO₂, SiO₂, 70SiO₂-30TiO₂ and 88SiO₂-12Al₂O₃ compositions (mole %) have been prepared from sonocatalyzed sols and deposited by dip-coating technique on 316L stainless steel foils. The influence of the coatings on the chemical corrosion of the substrate has been measured through potentiodynamic polarization curves in aqueous 15% H₂SO₄ solution between 25 and 50°C. The values of the corrosion potential, polarization resistance and corrosion rate have been determined. Analysis of the data combined with scanning electron microscopy studies indicate that the films act as a geometric blocking against exposure to the corrosive media and increase the lifetime of the substrate up to a factor 8.5.     

静电自组装制备纳米TiO2/SiO2光催化材料

采用静电自组装方法制备了纳米TiO2/SiO2光催化材料。采用巯丙基三甲氧基硅烷偶联剂对SiO2进行干法改性,采用双氧水/冰醋酸将偶联剂巯基基团氧化为磺酸基基团。在正负电荷的吸引下,带负电荷的SiO2与带正电荷的钛聚合阳离子自发地组装在一起,经一定温度热处理得到纳米TiO2/SiO2光催化材料。采用XRD、FTIR、PL、UV-Vis DRS、SEM和ICP等对材料进行了分析和表征。采用甲基橙溶液评价材料的光催化性能。结果表明:SiO2促使锐钛矿的形成,抑制锐钛矿向金红石的转变,减小TiO2的晶粒尺寸,使得TiO2光吸收波长发生蓝移。TiO2与SiO2通过Si-O-Ti键发生结合。采用静电自组装方法制备的材料中TiO2的含量高于传统方法,导致材料的光催化性能有所提高。     

共沉淀法和模板法制备均匀负载CeO2/ SiO2的研究

CeO2是三效催化剂(简称TWC)中被广泛应用的涂层材料[1],其优良的储放氧能力(OSC)可以扩大TWC的工作窗口,并可以在与γ-Al2O3的相互作用中提高Al2O3的高温稳定性[2]。在高温下,CeO2会因晶粒迅速长大而失去储放氧能力。为了提高CeO2的高温抗烧结能力,以及进一步提高其氧化还原能力,大部分研究者选择了在CeO2晶格中掺入其他离子的方法,如:Zr4 、Pr3 、La3 等[3￣5],这些离子在CeO2晶格中引入了晶格缺陷,不但稳定了结构,而且提高了氧传输能力。SiO2具有很高的化学稳定性、高比表面及高热稳定性,是载体的理想选择。研究表明,CeO2负载…     

Immobilization of glucose oxidase on rod-like and vesicle-like mesoporous silica for enhancing current responses of glucose biosensors

The use of rod-like and vesicle-like mesoporous SiO₂ particles for fabricating high performance glucose biosensors is reported. The distinctively high surface areas of mesoporous structures of SiO₂ rendered the adsorption of glucose oxidase (GOx) feasible. Both morphologies of SiO₂ enhanced the sensitivities of glucose biosensors, but by a factor of 36 for vesicle-like SiO₂ and 18 for rod-like SiO₂, respectively. The greater enhancement of vesicle-like SiO₂ can be accounted for by its higher specific surface area (509 m² g⁻¹) and larger total pore volume (1.49 cm³ g⁻¹). Interestingly, the current responses of GOx immobilized in interior channels of the mesoporous SiO₂ were enhanced much more than those of simple mixtures of GOx and the mesoporous SiO₂. This suggests that the enhancement of current responses arise not only from the high surface area of SiO₂ for high enzyme loading, but also from the improved enzyme activity upon its adsorption on mesoporous SiO₂. Also compared were the performances of glucose biosensors with GOx immobilized on mesoporous SiO₂ by physical adsorption and by covalent binding to 3-aminopropyltrimethoxysilane (APTMS) modified SiO₂ using glutaraldehyde as the cross-linker. The covalent binding approach resulted in higher enzyme loading but lower current sensitivity than with the physical adsorption.     

SiO2-TiO2 membranes by the sol-gel process

The use of membranes for gas separation represents an important alternative from the viewpoint of energy conservation in industrial separation processes. Polymeric Si-Ti sols prepared from titanium isopropoxide (Ti(OPrⁱ)₄) and tetraethoxysilane (TEOS) were used to deposit membranes on α-Al₂O₃ supports. Acetylacetone (2,4 pentanedione, acacH) and isoeugenol (2-methoxy-4-propenylphenol, isoH) were employed separately to chelate the Ti precursor in order to slow down the chemical reactivity, avoiding precipitation. The radial distribution functions (RDF) of the gels aging at room temperature were obtained. The xerogels were studied by Thermal Gravimetric (TGA) and Differential Thermal (DTA) Analysis in air. The Microporosity of the solids calcined at 773 K was determined by N₂-adsorption at 77 K. The membrane thickness was determined from SEM photographs. Preliminary permeance results of the supported membranes on commercial alumina support were obtained for He, N₂ and CO₂ in a single gas equipment. At 773 K the separation factors α(He/CO₂) and α(N₂/CO₂) for both membranes exceeds the theoretical Knudsen limit.     

Ammonia synthesis by means of plasma over MgO catalyst

Ammonia synthesis from H₂-N₂ mixed gas was studied at room temperature in a glow-discharge plasma in the presence of metals or metal oxides. Magnesia (MgO) and calcia (CaO), which are oxides with solid basicity, revealed catalytic activity in the plasma synthesis of ammonia, although they are catalytically inactive in industrial ammonia synthesis. The acidic oxides (Al₂O₃, WO₃, and SiO₂-Al₂O₃) lead to the consumption of the reactant, i.e., the H₂-N₂ mixed gas. No ammonia was isolated. Metal catalysts showed higher activity than the above basic oxides. They have, however, different activities. The reaction was faster over the active materials than over sodium chloride (NaCl) or glass wool or in a blank reactor without any catalyst.     

Growth Modes of SiO x Films Deposited by Evaporation and Plasma-Enhanced Chemical Vapor Deposition on Polymeric Substrates

In order to study the very first stages of plasma-enhanced chemical vapor deposition (PECVD) of SiO₂ on polymer substrates, we used a distributed electron cyclotron resonance (DECR) reactor, with the substrate placed (I) in the active glow zone, (II) downstream therefrom, and (III) downstream, but shielded from photon emission (e.g., VUV) from the plasma. For comparison, we also study films deposited by physical vapor ddposition (PVD, thermal evaporation). To characterize the ultra-thin deposits, we used oxygen plasma etching combined with scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Rutherford backscattering spectroscopy (RBS). We elucidate the roles of various energetic species (VUV photons, ions, atomic oxygen, and other radicals) in the plasma during the earliest growth phase, and the origin of the interphase which is present between the deposited SiO₂ and the polymer substrate.     

Fabrication of Erbium-Doped Channel Waveguides by a Combination of Ion Exchange and Sol-Gel Techniques

Erbium-doped germano-silicate thin films of good optical quality were produced by the sol-gel technique. High refractive index changes of up to 0.018 were obtained by sodium-silver ion exchange. Monomode optical waveguides with Gaussian mode profile were fabricated by this technique. It is shown that, if the ion exchange process parameters are well chosen, the influence of the waveguide fabrication on the active properties of the material is negligible.     

Preparation and Characterization of Porous Silica Films by a Modified Base-Catalyzed Sol-Gel Process Containing PVA: I. The Precursor Solution Synthesis

A novel modified base-catalyzed Sol-Gel process containing polyvinyl alcohol (PVA) has been proposed to prepare the porous SiO₂ film. In this process, the growth of the sol particles was artificially broken off and controlled by acid-stabilising agent and PVA. As a result, a uniform and stable precursor solution was obtained in which the size of sol particles was stable. This new process efficiently overcomes the shortcomings of the traditional base-catalysed Sol-Gel process and can be employed to prepare porous SiO₂ films with desired porosity and thickness. The influence of the catalyst, the reaction temperature, the pH value, the stabilizing agent and the PVA additive on the size of the SiO₂ sol particles is systematically studied in part I.     

吸附相反应技术制备MnOx/CeO2/SiO2催化剂及其低温选择性催化还原Nox

采用吸附相反应技术制备得到了MnO_x/CeO₂/SiO₂催化剂,通过X 射线衍射（XRD）、透射电子显微镜（TEM）、高分辨透射电子显微镜（HRTEM）、紫外激光拉曼（Raman）等手段对催化剂进行了表征. HRTEM分析表明活性组分MnO_x与CeO₂都均匀分布在载体SiO₂表面;XRD分析表明Mn₃O₄特征峰随着CeO₂含量的增加逐渐减小至完全消失,CeO₂的加入降低了MnO_x的结晶程度,增加了MnO_x的分散性;Raman光谱表明催化剂表面的Mn离子能够进入CeO₂晶格,激发出空穴氧,随着CeO₂负载量的增加,催化剂氧空穴浓度先升高后降低.以NH₃为还原剂,考评催化剂的NO_x低温选择性催化还原（SCR）性能,催化剂催化活性随CeO₂负载量增加先升高后降低,与催化剂氧空穴浓度变化规律一致,说明催化剂活性受氧空穴浓度影响,氧空穴浓度升高,催化剂催化活性升高.     

Sol–Gel SiO2-ZrO2 Coatings for Optical Applications

SiO₂-ZrO₂ based nanostructured multilayers films have been prepared by sol–gel processing from metallorganic precursors by low temperature inorganic polymerization reactions. Simultaneous gelation of both precursors was realized. Homogeneous and transparent films were obtained at room temperature by dip- and spin-coating on glass and silicon wafer substrates. Samples with successively deposited layers (1–3 layers) and successive thermal treatments have been also studied. Each deposited layer was thermally treated for 1 h at 300°C. The coatings were characterized by XRD, spectroellipsometry (SE), UV-VIS spectroscopy and AFM methods. The influence of substrates, number of coatings and number of thermal treatments on the optical and structural properties of the films was established. The thickness of three deposited SiO₂-ZrO₂ layers is about 496 nm on glass substrates and 413 nm on the silicon wafer substrate. The films deposited on glass are more porous than those deposited on silicon. The properties of optical waveguide prepared from SiO₂-ZrO₂ layers on silicon substrates will be discussed.     

大尺寸TiO2/SiO2大孔材料的制备及光降解性能

先以三维骨架聚合物为整体型模板,利用硅酸酯原位溶胶-凝胶过程并结合高温烧结的方法制备出大尺寸大孔径的SiO2载体,然后通过钛酸丁酯溶液浸渍、原位水解、煅烧制备出大尺寸的TiO2/SiO2大孔材料并用SEM、TEM、FTIR、XRD和XPS对其表征,结果表明SiO2载体具有三维连续的超薄层,TiO2以纳米薄层方式均匀地沉积在SiO2的三维超薄层上,形成TiO2/SiO2/TiO2三层夹心结构,层与层界面存在Si-O-Ti键,同时复合结构提高了TiO2由锐钛矿相向金红石相的转变温度.以甲基橙为目标降解物考察不同条件下制备的复合材料的光催化活性,采用复合材料吸入甲基橙溶液的方式,并借助甲醇萃取手段研究光降解动力学过程.结果表明,该复合材料具有较好的光降解催化活性,当焙烧温度为600℃和TiO2的负载量为54.5wt%时,其活性最大且降解速率常数达到1.78 h-1.     

Hydrolysis-Polycondensation in Binary Phosphorus Alkoxides—TEOS System Studied by GC-MS

It is well known that various phosphorus precursors exhibit different reactivities towards hydrolysis-polycondensation in acidic media. The hydrolysis-condensation in binary P-alkoxides—TEOS system was studied by GC-MS, in relation to the mentioned reactivity. As P-precursors, the following reagents were used: PO(OMe)₃, PO(OEt)₃, PO(OBu)₃, P(OEt)₃ and HOP(OMe)₂. PO(OMe)₃, PO(OEt)₃ and PO(OBu)₃ do not hydrolyze, but change the TEOS hydrolysis-polycondensation ratio. P(OEt)₃ partially hydrolyzes and transforms into a very stable HOP(OEt)₂ form, while HOP(OMe)₂ reacts very fast with nonparental solvent and undergoes transesterification. Si–O–P bonds have not been observed in early stages of hydrolysis-polycondensation. However, the gelling tendency is strongly influenced by the P-precursor.