Spectroscopy of an optical excited Ga doped SiO2 surface

We present the first spectroscopical analysis of the Ga/SiO₂ surface interaction in hot environment. This interaction gives rise to inclusions of Ga atoms inside the silica matrix that produce structural changes and modify the SiO₂ optical characteristics. This paper discusses both the time- and the frequency-resolved spectra of the fluorescence emission following UV pulsed laser excitation of the so “doped” silica in the range 15,000–28,000 cm⁻¹. The investigation is completed by the electron paramagnetic resonance (EPR) spectra of two high-purity synthetic silica samples of commercial origin after thermal treatment in presence and in absence of a Ga atmosphere.     

The location and ordering of fluoride ions in pure silica zeolites with framework types IFR and STF; implications for the mechanism of zeolite synthesis in fluoride media

Single-crystal X-ray diffraction studies carried out at a synchrotron radiation source have allowed the structure solution and location of fluoride ions inside as-made pure silica zeolites with the IFR and STF framework structures. The local environment of the fluoride has been identified, and unusual ordering of the fluoride ions has been discovered in both cases. The details of the crystal structures are used to suggest structural features that are important in determining the ordering of fluoride ions in zeolites. A mechanism for how the fluoride ordering occurs is suggested for IFR and STF based on the local structure of small cages that make up these zeolites, and the implications for the mechanism of crystal growth are discussed.     

Imaging the Atomic Position of Light Cations in a Porous Network and the Europium(III) Ion Exchange Capability by Aberration‐Corrected Electron Microscopy

In the present work, ETS‐10 microporous titanosilicate has been synthesized and its structure characterized by means of powder XRD and aberration corrected scanning transmission electron microscopy (C_s‐corrected STEM). For the first time, sodium ions have been imaged sitting inside the 7‐membered rings. The ion‐exchange capability has been tested by the inclusion of rare earth metals (Eu, Tb and Gd) to produce a luminescent material which has been studied by atomic‐resolution C_s‐corrected STEM. The data produced has allowed unambiguous imaging of light atoms in a microporous framework as well as determining the cationic metal positions for the first time, providing evidence of the importance of advanced electron microscopy methods for the study of the local environment of metals within zeolitic supports providing unique information of both systems (guest and support) at the same time.     

Slightly surface-functionalized polystyrene microspheres prepared via Pickering emulsion polymerization using for electrophoretic displays

Europium (III) (Eu(3+))-doped nanoporous silica spheres were synthesized, and the states of Eu(3+) ions in the silica framework structure were investigated. The ordered nanopores were preserved with the doping at the Eu(3+) molar concentration to Si up to 10 mol%, and the O-Si-O and Si-OH groups in the structures were clearly rearranged with the doping, indicating the interaction of Eu(3+) with the O atoms. The significant morphological changes in the spheres were observed with the doping. The photoluminescence spectral shapes due to the transitions of (5)D(0)-(7)F(1) and (5)D(0)-(7)F(2) were indicative of the presence of the Eu(3+) in an environment of a low symmetry. It was found that the Eu(3+) was located inside the silica framework to electrostatically interact with the environmental O atoms, which would prevent the aggregation among Eu(3+) ions to show the efficient luminescence. Therefore, the interactions between the Eu(3+) ions and silica framework structures in the spheres were successfully clarified.     

Investigation of the electronic structure and properties of cluster models of silica by the MNDQ method

Using the LCAO MO SCF method in the MNDO valence approximation, we have carried out a systematic study of the electronic and spatial structure of cluster models of the bulk phase and the hydroxylated and chemically modified surface of silica surface. We propose a technique for taking into account the crystallochemical environment of the clusters modeling the bulk phase of SiO₂, based on passivation of the abnormal valencies at the boundary of the clusters by hydrogen atoms, the geometrical location of which ensures homogeneity in the electron density distribution on the silicon atoms of the model fragment. We give a comparative analysis of the electronic characteristics of the studied cluster models. We consider the nature of the adsorption centers and the properties of the hydroxylated and modified silica surface.Translated from Teoreticheskaya i Éxperimental'naya.Khimiya, Vol. 22, No. 5, pp. 533–545, September–October, 1986.     

The SiH band as surface “probe”

The Sihalogen bands of structures on silica surfaces cannot be observed with infrared spectroscopy because the absorptions fall in a spectral region where the adsorbent is usually opaque. However, as the SiH band is affected by the electronegativity of other atoms bonded to the Si, reactions occuring at the SiCl group of a surface structure such as Si (H)Cl make themselves felt as changes in the SiH band. The utility of the SiH band as a probe of local environment is illustrated by examples involving the adsorption of NH₃ or CH₃OH on HSiCl₃ - treated silica.     

Review of development of a silica-based thermoluminescence dosimeter

Development of a silica-based material suitable for thermoluminescence dosimetry (TLD) is described. Doped silica samples were prepared in-house using the sol–gel technique. Results from a micro-X-ray fluorescence (μ-XRF) study of Zn-doped silica have confirmed the capability of the sol–gel processing steps in producing homogeneously doped samples. The ability of sol–gel processing in producing doped samples with different dopant charge states has been illustrated in the case of copper (I)- and copper (II)-doped silica samples. The charge states of the dopants have been verified using the technique of X-ray absorption near-edge structure (XANES). X-ray diffraction (XRD) investigations have shown the structure of samples doped with erbium, copper (I) and copper (II) (listed in order of decreasing effect) to be altered by the dopants, albeit with the samples remaining in an amorphous state. Local structure studies, carried out using the method of extended X-ray absorption fine structure (EXAFS), reveal that in most cases the local environment of the dopant is similar to the respective native structure of the respective metal oxides. Conversely, in a number of cases, the dopant atoms occupy the silicon sites in the silica tetragonal geometry. Thermoluminescence (TL) studies were carried out on aluminium, copper (I), germanium, manganese, tin, and zinc-doped silica samples. Weight for weight, the most sensitive thermoluminescent material was found to be 4.0 mol% aluminium-doped silica, providing 3.5 times the TL yield of TLD100 and 5.4 times that of germanium-doped silica. The photon dose response of aluminium-doped silica was observed to be linear over the range of investigated dose, 0.5–10.0 Gy.     

Dynamic and molecular association in premicellar aqueous solutions of dicarboxylate amino acid-based surfactant as studied by 1H NMR

We examined a series of amino acid-based surfactants with two carboxylic groups separated by a spacer of one, two, or three carbon atoms with sodium and calcium counterions in the premicellar concentration region near the CMC. ¹H nuclear magnetic resonance (NMR) spectroscopy and NMR diffusometry techniques were used to study the local environment, association, and translational dynamics of the surfactant's molecules. We measured the self-diffusion coefficients of the micelles, calculated the effective hydrodynamic radii, and determined the temperature region in which the premicelles exist. With an increase in temperature from 295 to 335 K, the premicellar state of the surfactant is replaced by the monomeric state.     

用实验和模拟计算确定SiO2空心微球的孔径分布

用巨正则系综蒙特卡罗（GCMC）模拟方法结合统计积分方程（SIE）计算了SiO2空心微球球壳上的孔径分布（PSD）.HRTEM、XRD及氮气吸附等实验测试表明,SiO2空心微球的球壳上有无序的介孔孔道.在模拟中,基于实验数据,将SiO2空心微球模型化为具有一定孔径分布的园柱孔,流体模型化为Lennard-Jones(LJ)球,流体分子和孔壁间的相互作用采用Wang等人[10]最近提出的完全解析的势函数描述.模拟结果显示,用孔径分布拟合的吸附数据和实验吸附等温线吻合良好,说明PSD能够十分有效地表示SiO2空心微球的微孔结构.     

Fumed silica synthesis: influence of small molecules on the particle formation process

Burning silicon tetrachloride in an oxygen‐hydrogen flame produces fumed silica. This process is known for at least 50 years [1‐5], but some important details are still uncertain. We would like to study several starting steps of fumed silica synthesis on the way from molecules to products. To do this we have performed quantum‐level simulations of protoparticle and primary particle formation, from silicon dioxide molecules. Additionally, we have simulated the behavior of silica clusters in the presence of small molecules like water and hydrochloric acid. The reaction of silicon dioxide molecules leads to a silica cluster, which is covered with chemicaly highly active sites of one‐coordinated oxygen atoms and three‐coordinated silicon atoms. These clusters interact together and produce silica bulk like quartz glass. Reaction with water terminates the silica particle surface and leads to a complicated structure of the particle surfaces. The hydroxyl shell protects the particle body against the increase in particle size, but leads to aggregate and agglomerate formation.     

Computational Study of the Surface‐Enhanced Raman Scattering from Silica‐Coated Silver Nanowires

Surface‐enhanced Raman scattering (SERS) is a popular vibrational spectroscopic technique that can have several applications in chemical and biological sensing. Within the last decade or so, our ability to chemically synthesize nanostructures has improved to the point that the rational design of a variety of SERS substrates is now viable. In this report, we describe a computational study using the finite element method (FEM) to investigate the effects of patchy silica coatings on silver nanowires. We found that varying the degree of silica coating on silver nanowires impacts the enhancement and may be explained through two processes. The first process is a consequence of changes in the dielectric environment surrounding the nanowire due to the silica. As additional layers of silica coat the nanowire, the localized surface plasmon resonance of the nanowire redshifts. The second process is a result of silica distorting the local electric field around the nanowire surface. Anisotropic silica coating can influence anticipated enhancement depending on its spatial localization with respect to excited plasmon modes in the nanowire. We propose that the design of nanostructures with patchy silica coatings can be a viable tool for increasing surface enhancement.     

Rapid and efficient enzyme encapsulation in a dendrimer silica nanocomposite

We report the entrapment of horseradish peroxidase and quantitative encapsulation of glucose oxidase within silica nanoparticles by utilizing an amine-terminated dendritic template. Our improved strategy employs a water-soluble biomimetic template which is able to catalyze the condensation of Si(OH)(4) to silica nanoparticles while trapping an enzyme inside the mesoporous material. Kinetic analysis shows enzyme functionality to be mostly unchanged. Also, the role of pI and ionic strength within the encapsulation environment was found to strongly influence encapsulation. These results suggest that the electrostatic manipulation of a strong supramolecular silica-precipitating complex of enzyme and dendrimer has the potential of adding a vast array of chemical and biological activity to hybrid materials. [image: see text] Enzyme immobilization within a silica nanocomposite.     

Spanning set of silica cluster isomer topologies from QTAIM

Structural and chemical properties of the building block of silica nanowires, (SiO(2))(6), are investigated with the theory of atoms and molecules (QTAIM). Twenty-five conformers have been analyzed, ten of which have not been reported before. We extend the silica (SiO(2))(6) topology phase space using QTAIM; the Poincaré-Hopf topological sum rules are applied and used to identify the spanning set of topologies, and this includes finding eight new distinct topologies that satisfy the Poincaré-Hopf relation. A simple phase diagram of the solutions of the Poincaré-Hopf relation is created with the aid of a new classification scheme to determine the boundary between topological stability and instability. Sum rules are then found to be applicable to any set of isomers. We determine that O-O bonding interactions exist for the silica (SiO(2))(6) conformers in regions where the energy surface is flattest. In addition, we identify unstable local minima in the topology of the charge density in order to further compare conformer instabilities. We quantify the dimensionality of a molecule using the Poincaré-Hopf relation instead of Euclidean geometry. This quantum topological definition of geometry shows that the four most energetically stable (SiO(2))(6) conformers are quantified as two-dimensional within the new quantum topology.     

A Grand Canonical Monte-Carlo Simulation Study of Xenon Adsorption in a Vycor-like Porous Matrix

We have performed atomistic Grand Canonical Monte-Carlo (GCMC) simulations of adsorption of xenon in a Vycor-like matrix at 195 K. The disordered mesoporous network is obtained by applying a numerical 3D off-lattice reconstruction procedure to a simulation box originally containing silicon and oxygen atoms of a non-porous silica solid. In order to reduce the computational cost, we have applied a homothetic decrease of the simulation box dimensions which preserves the morphology and the topology of the pore network (the average pore dimension is then around 30 Å). The surface chemistry is obtained in a realistic fashion by saturating all dangling bonds with hydrogen atoms. Small angle scattering spectra calculated on different numerical samples have evidenced a departure from Porod's law due to surface roughness. The simulated isotherms calculated on such disordered connected porous networks, show the capillary condensation phenomenon. The shape of the adsorption curves differs from that obtained for simple pore geometries. The analysis of the adsorbed quantity distribution indicates partial molecular-film formation depending on the local surface curvature and roughness.     

水中受拉伸负载下单壁纳米碳管机械性质的分子动力学研究

利用分子动力学方法研究了(5,5)扶手椅型和(10,10)锯齿型纳米碳管在水中受拉伸负载下的机械性质.通过计算纳米碳管中氧和氢原子的局部密度分布研究了限制效应.结果表明,碳管在水中的杨式系数与在真空下相同,而碳管在水中的拉伸应力小于在真空中的.     

Nanovalve-controlled cargo release activated by plasmonic heating

The synthesis and operation of a light-operated nanovalve that controls the pore openings of mesoporous silica nanoparticles containing gold nanoparticle cores is described. The nanoparticles, consisting of 20 nm gold cores inside ~150 nm mesoporous silica spheres, were synthesized using a unique one-pot method. The nanovalves consist of cucurbit[6]uril rings encircling stalks that are attached to the ~2 nm pore openings. Plasmonic heating of the gold core raises the local temperature and decreases the ring-stalk binding constant, thereby unblocking the pore and releasing the cargo molecules that were preloaded inside. Bulk heating of the suspended particles to 60 °C is required to release the cargo, but no bulk temperature change was observed in the plasmonic heating release experiment. High-intensity irradiation caused thermal damage to the silica particles, but low-intensity illumination caused a local temperature increase sufficient to operate the valves without damaging the nanoparticle containers. These light-stimulated, thermally activated, mechanized nanoparticles represent a new system with potential utility for on-command drug release.     

Structure of the products of TiCl4 chemisorption on the surface of porous silica in the process of vapor-phase hydrolysis

Changes in coordination environment of titanium atoms in the composition of the titanium oxychloride groups chemisorbed on the surface of porous silica after the vapor-phase hydrolysis are considered. It is shown that after the substitution of chlorine atoms by the OH groups, additional coordination bonds between the titanium-containing group and neighboring hydroxo groups are formed, that leads to an increase to 6 in the coordination number of titanium in the composition of the surface polyhedra.     

Unique adsorption behavior of H2 and CO over group 8-10 metals encapsulated inside silica nanotubes and nanocapsules

Various silica nanotubes and nanocapsules have been prepared successfully, possessing unique silica walls of selective H2 permeation and encapsulate group 8-10 metal particles inside and exhibit a marked stabilization effect of H2 and CO over the metals in the network of silica wall and inside nanoscale cavities.     

Evidence for rigid binding of rhodamine 6G to silica surfaces in aqueous solution based on fluorescence anisotropy decay analysis

Strong ionic binding of the cationic probe rhodamine 6G (R6G) to the anionic surface of silica particles in water provides a convenient labeling procedure to study both particle growth kinetics and surface modification by time-resolved fluorescence anisotropy (TRFA). The decays for R6G dispersed in diluted Ludox silica sols usually fit to a sum of picosecond and nanosecond decay components, along with a significant residual anisotropy component. The origin of the nanosecond decay component (phi2) is not fully understood, and has been ascribed to wobbling of the probe on the silica surface, the presence of a subpopulation of small nanoparticles in the Ludox sol, or rapid exchange between free and bound R6G. To elucidate the physical meaning of phi2, measurements were performed in various silica-based colloidal systems using different concentrations of silica. We found that the fraction of phi2 was generally higher in Ludox than in aqueous sodium silicate and decreased with increasing silica concentration; phi2 vanished upon gelation of sodium silicate at pH 7 leading to a total loss of R6G depolarization (r(t) = const). These results rule out the presence of local R6G wobbling when bound ionically to colloidal silica and support the rigid sphere model to describe the TRFA decays for R6G-Ludox. This conclusion is entirely supported by steady-state anisotropy data and structural considerations for the R6G molecule and the silica surface.