Ice tessellation on a hydroxylated silica surface

The adsorption of water on a fully hydroxylated silica surface is studied by using density-functional total-energy and molecular dynamics calculations. The (100) surface of beta(alpha)-cristobalite covered by geminal hydroxyls has been taken as the substrate. A well-ordered and stable two-dimensional ice with quadrangular and octagonal patterns of hydrogen bond (H-bond) networks-an ice tessellation-is found on the surface for the first time. With the vibrational recognition, the four water molecules in the quadrangle are found to be bonded by strong H bonds while the quadrangles are connected to each other by weak H bonds. This configuration is the most stable, because all the water molecules are fully saturated with H bonds either to each other or to the surface hydroxyl groups.     

Electron trapping at point defects on hydroxylated silica surfaces

The origin of electron trapping and negative charging of hydroxylated silica surfaces is predicted based on accurate quantum-mechanical calculations. The calculated electron affinities of the two dominant neutral paramagnetic defects, the nonbridging oxygen center, identical with Si-O*, and the silicon dangling bond, identical with Si*, demonstrate that both defects are deep electron traps and can form the corresponding negatively charged defects. We predict the structure and optical absorption energies of these diamagnetic defects.     

Polyurethane nano-composite with functionalized silica particle

Nano-size silica particles were functionalized with vinyl isocyanate and subsequently UV cured to synthesize polyurethane–silica nano-composites which were tested for mechanical, dynamic mechanical, cross-link density, contact angle and XPS. The modified silica provides composites with cross-links that are pinned at the surfaces and which effectively reinforce the materials mechanically as well as thermally.     

Evolution of pores in mesoporous silica films: Porogen loading effect

Mesoporous silica films were synthesized via a sol-gel process under an acidic condition. Various amounts of triblock copolymer F38 were loaded to precursor sols as the pore generator. The evolution of the pores generated by porogen decomposition was investigated as a function of F38 loading by positron annihilation gamma-ray energy spectroscopy and positron annihilation lifetime spectroscopy based on slow positron beams. The threshold of pore percolation is found to be around 10 wt% of F38 loading by positron annihilation gamma-ray energy spectroscopy. Positron annihilation lifetime spectroscopy in the films show that the pore size increases from 1 nm to 3 nm with increasing F38 loading from 5 wt% to 30 wt%.     

Morphological and textural characterization of functionalized particulate silica xerogels

The functionalization of xerogels for use in chromatography and catalysis was carried out by solubilization of amorphous silica using a soxhlet extractor. Xerogels were prepared by sol-gel method using tetraethoxysilane, TEOS, ethanol, and water in a 1/3/10 molar ratio with HCl and HF as catalysts. The samples were prepared in monolithic form and dried at 70 °C and 550 °C for 1 h each. After functionalization, changes in textural and morphological characteristics of xerogels were investigated by means of nitrogen gas adsorption, positron annihilation lifetime spectroscopy (PALS), and scanning electron microscopy (SEM). As the analysis methods are based on different physical principles, the results are complementary, leading to a good knowledge of the texture of the samples studied.     

Density profile of water confined in cylindrical pores in MCM-41 silica

Recently, water absorbed in the porous silica material MCM-41-S15 has been used to demonstrate an apparent fragile to strong dynamical crossover on cooling below ～220 K, and also to claim that the density of confined water reaches a minimum at a temperature around 200 K. Both of these behaviours are purported to arise from the crossing of a Widom line above a conjectured liquid-liquid critical point in bulk water. Here it is shown that traditional estimates of the pore diameter in this porous silica material (of order 15 ?) are too small to allow the amount of water that is observed to be absorbed by these materials (around 0.5 g H(2)O/g substrate) to be absorbed only inside the pore. Either the additional water is absorbed on the surface of the silica particles and outside the pores, or else the pores are larger than the traditional estimates. In addition the low Q Bragg intensities from a sample of MCM-41-S15 porous silica under different dry and wet conditions and with different hydrogen isotopes are simulated using a simple model of the water and silica density profile across the pore. It is found the best agreement of these intensities with experimental data is shown by assuming the much larger pore diameter of 25 ? (radius 12.5 ?). Qualitative agreement is found between these simulated density profiles and those found in recent empirical potential structure refinement simulations of the same data, even though the latter data did not specifically include the Bragg peaks in the structure refinement. It is shown that the change in the (100) peak intensity on cooling from 300 to 210 K, which previously has been ascribed to a change in density of the confined water on cooling, can equally be ascribed to a change in density profile at constant average density. It is further pointed out that, independent of whether the pore diameter really is as large as 25 ? or whether a significant amount of water is absorbed outside the pore, the earlier reports of a dynamic crossover in supercooled confined water could in fact be a crystallization transition in the larger pore or surface water.     

Synthesis and characterization of silica microspheres functionalized with porphyrin monolayer

A new type of inorganic and organic composite (SiO₂-MPS-TAPPI), oppositely charged meso-tetra-(4-trimethylaminophenyl)porphyrin iodide (TAPPI) bonded on the surface of silica microspheres coated with mercaptopropyltrimethoxysilane (MPS), was prepared by self-assembly method. The composite was tested by TEM, XRD and TG. The TEM images show that SiO₂-MPS microspheres in the composite are uniform. There are linkages among some different SiO₂-MPS microspheres. The XRD measurement bears out that the composite structure is the same with SiO₂-MPS. TG curves show that thermal stability of TAPPI assembled onto SiO₂-MPS microspheres is higher than that of TAPPI. Solid UV diffusion reflection spectra and fluorescence spectra are used to investigate the photophysical properties of the SiO₂-MPS-TAPPI composite. It is showed that the spectra of the composite exhibit significant enhancement of the spectra range. The strong interaction between TAPPI and SiO₂-MPS in the composite is responsible for the different spectra.     

An aqueous route to organically functionalized silica diatom skeletons

Diatomaceous earth was functionalized by grafting organotrialkoxysilane precursors onto the surface of the porous silica cell walls of this biomineral. Vinyl- and mercapto-containing structures were prepared in aqueous media without disruption of the diatomic architecture. Successful grafting of the organic moieties was confirmed using solid state ²⁹Si MAS NMR spectroscopy, and the presence of the intact diatom framework by scanning electron microscopy. The sorption properties of mercaptopropyl-functionalized diatoms towards heavy metals was studied by measuring the accessibility and diffusion rates of mercury(II) species to the binding sites (-SH) by the means of electrochemical methods.     

Structural change of mesoporous silica with sonochemically prepared gold nanoparticles in its pores

Ultrasonic irradiation of mesoporous silica soaked in a mixture of chloroauric acid and isopropanol for 120 min in Ar atmosphere at room temperature yielded Au/SiO₂ mesoporous composite, which was characterized by high resolution transmission electron microscopy and optical absorption measurement. The structure of mesoporous silica after sonochemical preparation of gold (Au) nanoparticles within its pores was studied by nitrogen adsorption technique. It has been shown that the structural parameters, such as specific surface area (SSA), porosity (P), the mean pore diameter (l_p) were increased significantly after ultrasonic irradiation. It is suggested that the collision of Au nanoparticles with pore walls and localized erosion induced by the asymmetric implosive collapse of cavities on the extensive liquid–solid interface that are responsible for the structural change in the mesoporous solid.     

Preparation and size control of highly monodisperse vinyl functionalized silica spheres

Vinyl functionalized silica spheres (VFSSs) are prepared by one-step reaction using the aqueous solution of organosilane. The synthetic method is effective and reproducible with one process used. The VFSSs could self-assemble into three-dimensional (3D) fcc photonic crystals. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed that the VFSSs were highly monodisperse and their surfaces were sufficiently smooth. The size of the VFSSs could be controlled by adjusting the reaction temperature. The sphere size reached its minimum, 394 nm, around 45 °C and became larger when the temperature was either elevated or lowered. The maximum sphere size, 515 nm, was obtained around 15 °C. This work is expected to extend to the preparation and size control of other kinds of hybrid silica spheres.     

Dielectric and calorimetric investigations of KNO3 in pores of nanoporous silica matrices MCM-41

The temperature dependences of the linear dielectric permittivity, the third harmonic amplitude, and the heat capacity of nanoporous silica matrices MCM-41 with cellular channels (3.7 and 2.6 nm in diameter) filled with KNO₃ have been investigated in comparison with those obtained for bulk potassium nitrate. Measurements have been performed during heating and cooling in the range from room temperature to 463 K. Anomalies corresponding to structural phase transitions have been observed. A significant broadening of the temperature region of the existence of the ferroelectric phase III of potassium nitrate upon cooling has been revealed. This broadening increases with a decrease in the size of pores. It has been shown that, in the nanocomposites with potassium nitrate, the ferroelectric phase can also be formed during heating. The efficiency of observation of the third harmonic generation for studying nanocomposites with the ferroelectric phase has been demonstrated.     

Er3+在二氧化硅介孔分子筛中的高效率发光及其分析

研究了一种新型的负载Er3 的二氧化硅介孔分子筛纳米材料,分析了其在有无功能化试剂全氟甲基磺酰(bis(perfluoromethylsulfonyl)amine)修饰作用下的吸收和荧光光谱特性,获得了高强度的荧光发射.应用Judd-OfelI理论计算了强度参数(Ω2=1.88×10-20,Ω4=5.45×10-20 cm2,Ω6=3.11×1O-20cm2)、跃迁振子强度、自发跃迁概率、能级辐射寿命等重要的光谱参数,讨论了吸收和发射跃迁截面(Ωem=10.9×10-21 cm2),研究了在介孔分子筛纳米材料中的Er3 在不同的抽运功率条件下的荧光强度变化情况.比较了Er3 在不同基质材料中的带宽特性.研究表明二氧化硅介孔分子筛有利于实现高效率的激光输出或具有较宽带宽的高增益光放大,能够成为掺铒激光器或光放大器的新型基质材料.     

Photoacoustic infrared spectroscopic studies of silica gels with organically functionalized surface

The article shows the application of photoacoustic Fourier transform infrared spectroscopy as a tool for identification of signal characteristics of organic ligands immobilized at the silica gel. Each of the compounds studied had an alkyl chain. Therefore, the differences could be observed on the basis of the position (wavenumbers) and appearance of bands typical of the carbon–hydrogen stretching vibrations. However, an important observation was that depending on the organic unit at the silica surface, it was possible to easily distinguish between signals specific to the ligand. The only exception was the system with functional groups whose signals coincided with the bands typical of inorganic silica.     

Adsorption of surface functionalized silica nanoparticles onto mineral surfaces and decane/water interface

The adsorption of silica nanoparticles onto representative mineral surfaces and at the decane/water interface was studied. The effects of particle size (the mean diameters from 5 to 75?nm), concentration and surface type on the adsorption were studied in detail. Silica nanoparticles with four different surfaces [unmodified, surface modified with anionic (sulfonate), cationic (quaternary ammonium (quat)) or nonionic (polyethylene glycol (PEG)) surfactant] were used. The zeta potential of these silica nanoparticles ranges from ?79.8 to 15.3?mV. The shape of silica particles examined by a Hitachi-S5500 scanning transmission electron microscope (STEM) is quite spherical. The adsorption of all the nanoparticles (unmodified or surface modified) on quartz and calcite surfaces was found to be insignificant. We used interfacial tension (IFT) measurements to investigate the adsorption of silica nanoparticles at the decane/water interface. Unmodified nanoparticles or surface modified ones with sulfonate or quat do not significantly affect the IFT of the decane/water interface. It also does not appear that the particle size or concentration influences the IFT. However, the presence of PEG as a surface modifying material significantly reduces the IFT. The PEG surface modifier alone in an aqueous solution, without the nanoparticles, yields the same IFT reduction for an equivalent PEG concentration as that used for modifying the surface of nanoparticles. Contact angle measurements of a decane droplet on quartz or calcite plate immersed in water (or aqueous nanoparticle dispersion) showed a slight change in the contact angle in the presence of the studied nanoparticles. The results of contact angle measurements are in good agreement with experiments of adsorption of nanoparticles on mineral surfaces or decane/water interface. This study brings new insights into the understanding and modeling of the adsorption of surface-modified silica nanoparticles onto mineral surfaces and water/decane interface.     

Preparation and characterization of hexadecyl functionalized magnetic silica nanoparticles and its application in Rhodamine 6G removal

In this paper, a new adsorbent, hexadecyl functionalized magnetic silica nanoparticles (C₁₆/SiO₂-Fe₃O₄ NPs), was prepared by a facile method. The final product was characterized by X-ray diffractometer, transmission electron microscope, Fourier transform infrared spectrometer and vibration sample magnetometer. The preparation and adsorption conditions of the adsorbent were optimized. The adsorbent prepared maintaining volume ratio of tetraethylorthosilicate to hexadecyltrimethoxysilane at 1:0.5 and their total volume at 1100 μL exhibited high adsorption capacity. The optimum pH value for the adsorption experiments was 11.00. The adsorption behavior of Rhodamine 6G onto C₁₆/SiO₂-Fe₃O₄ NPs obeyed pseudo-second-order kinetic model and Langmuir isotherm. Thermodynamic data indicated that the adsorption process was spontaneous and exothermic. The adsorption capacity of the adsorbent could reach to 35.6 mg g⁻¹, owing to the hydrophobic attraction and the enhanced electrostatic attraction. The saturation magnetization of the magnetic adsorbent was 35 emu g⁻¹, which ensured the magnetic separation after adsorption.     

NMR study of the vapor phase contribution to diffusion in partially filled silica glasses with nanometer and micrometer pores

The contribution of the vapor phase to molecular diffusion in porous silica glasses with nanometer (Vycor) and micrometer (VitraPor#5) pores partially filled with water (polar) or cyclohexane (nonpolar) was investigated with the aid of field-gradient NMR diffusometry. Due to the vapor phase, the effective diffusion coefficient of cyclohexane filling micrometer pores (VitraPor#5) increased up to 10 times relative to the value in bulk liquid upon reduction of the pore space filling factor. On the other hand, the effective diffusion coefficient of water first decreases and then increases when the liquid content is reduced. The dependence of the effective diffusion coefficient on the pore filling factor is strongly related to the pore dimension. A general two-phase exchange model is presented that is well accounting for all experimental diffusion features.     

Er3+在二氧化硅介孔分子筛中的高效率发光及其分析

研究了一种新型的负载Er³⁺的二氧化硅介孔分子筛纳米材料,分析了其在有无功能化试剂全氟甲基磺酰(bis(perfluoromethylsulfonyl)amine)修饰作用下的吸收和荧光光谱特性,获得了高强度的荧光发射. 应用Judd-Ofelt理论计算了强度参数(Ω₂＝1.88×10^-20cm²,Ω₄＝5.45×10^-20cm^{2关键词： 发光 二氧化硅介孔分子筛 稀土离子 Judd-Ofelt理论}     

Modification of functionalized mesoporous silica on the formation and the catalytic performance of platinum nanocatalysts

Several functionalized mesoporous silicas (MCM-41 and SBA-15 terminated with amino groups by multistep graft) are prepared and used as carriers for platinum nanoparticles. Modification of the grafted molecules is investigated on the component of the silicas and the formation of nanoparticles. Catalytic performance of the loaded platinum nanocatalysts is tested on selective hydrogenation of ortho-chloronitrobenzene (o-CNB). Results indicate that SBA-15 can be grafted with more amino groups than MCM-41. In most cases, small quantity of platinum precursor benefits the formation of small platinum nanoparticles on the functionalized silicas. The platinum nanocatalysts loaded on the one-step grafted silicas hold better catalytic activity and slightly lower selectivity to ortho-chloroaniline (o-CAN) than those loaded on the two-step grafted silicas. Besides the advantage of reuse, the loaded platinum catalysts on the functionalized silicas have similar catalytic property as the colloidal platinum nanocatalysts.     

A novel method for preparation of 8-hydroxyquinoline functionalized mesoporous silica: Aluminum complexes and photoluminescence studies

8-Hydroxyquinoline (8-HQ) was attached to mesoporous silica by sulfonamide bond formation between 8-hydroxyquinoline-5-sulfonyl chloride (8-HQ-SO₂Cl) and aminopropyl functionalized SBA-15 (designated as SBA-SPS-Q) and then aluminum complexes of 8-HQ was covalently bonded to SBA-SPS-Q using coordinating ability of grafted 8-HQ.The prepared materials were characterized by powder X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FT-IR), thermal analysis (TGA-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), elemental analysis and fluorescence spectra. The environmental effects on the emission spectra of grafted 8-HQ and its complexes were studied and discussed in details.     

Heterogeneous nucleation in and out of pores

We study the nucleation of a new thermodynamic phase in pores and find that the nucleation often proceeds via two steps: nucleation of pore filling, and nucleation out of the pore. These two rates have opposing dependencies on pore size, resulting in a pore size at which the nucleation rate of the new phase is maximal. This finding is relevant to attempts to design and use porous media to crystallize proteins.