纳米二氧化硅的表面改性研究

以γ-缩水甘油醚丙基三甲氧基硅烷(GPTMS)对酸催化水解正硅酸乙酯(TEOS)聚合得到的纳米二氧化硅胶粒表面进行接枝改性,用激光粒径仪测定二氧化硅颗粒的粒径,并用透射电子显微镜(TEM)观察了改性前后二氧化硅胶粒的分散状况,采用傅立叶红外(FTIR)光谱法对改性前后的二氧化硅粉体进行了分析,通过热失重分析(TGA)法对GPTMS接枝改性二氧化硅胶粒表面的接枝度进行分析计算,同时对颗粒溶胶的ζ电位进行了测试,结果表明:改性后二氧化硅胶粒分散性大大提高,硅烷偶联剂浓度对接枝度有显著影响,当GPTMS的浓度为1mL/S iO2(g)时,接枝度达到最大,且颗粒表面的物理化学性能发生显著变化。     

Preparation and pervaporation performance of high-quality silicalite-1 membranes

High-performance silicalite-1 membranes were successfully synthesized on novel porous silica tubes by two-step in-situ hydrothermal synthesis.The flux and separation factor towards ethanol/water mix- ture at 60℃were 0.56 kg/(m2·h)and 84,respectively.The as-synthesized silicalite-1 membranes were characterized by scanning electron microscopy(SEM).The influence of different synthesis conditions on the separation performance of the silicalite-1 membranes was investigated.It was found that the average flux of silicalite-1 membranes was improved by about 26?ter filling the silica tubes with mixed solution containing glycerol and water.After calcinating at 400℃for 5 h repeatedly,membrane synthesized on silica tube still showed high pervaporation performance towards ethanol/water mixture even at a calcination rate of 4℃/min,which suggested that silica support was more suitable for pre- paring high-performance silicalite-1 membranes.     

高温合成NaY沸石

提出了应用NaY沸石导向剂提供全部硅源合成NaY沸石的新方法, 研究了高温条件下合成NaY沸石的规律和特点, 发现在高温条件下合成NaY沸石不仅晶化速度快, 而且可以在不加有机物的条件下合成较高硅铝比[n(SiO2)/n(Al2O3)=6]的NaY沸石.     

Electrochromatography in packed tubes using 1.5 to 50 μm silica gels and ODS bonded silica gels

Summary Electrochromatography (that is HPLC where the eluent is driven along the column by electro-osmosis using fields of up to 100 kV m⁻¹) promises plate efficiencies for HPLC which are comparable to those attained in capillary gas chromatography, but this requires that narrow-bore columns can be successfully packed with submicron particles. This paper demonstrates that we have now moved a considerable distance towards this goal. We show (1) that, following theory, there is no evidence of any reduction in electroosmotic velocity in columns packed with particles down to 1.5 μm diameter, (2) that reduced plate heights as low as unity are attainable for unretained solutes using both slurrypacked and drawn-packed columns 30 to 200 μm bore and up to 1 m long when packed with conventional 3 and 5 μm silica gels or with 1.5 μm impermeable silica spheres, (3) that columns driven electrically show higher plate efficiencies than identical columns driven by pressure, and (4) that 100,000 plate HPLC separations can be achieved in relatively short times of 30 minutes using in situ derivatised drawn packed capillaries containing 3 and 5 μm ODS-silica gels.     

MoPO／SiO2催化剂上丙烷选择氧化制丙烯醛

 研究了MoPO／SiO2催化剂对丙烷选择氧化制丙烯醛的催化性能．MoO／SiO2催化剂主要表现出对丙烷氧化脱氢的催化性能，在该催化剂中添加磷后，丙烷转化率和选择氧化产物丙烯醛的选择性明显提高．催化剂的X射线衍射、拉曼光谱、程序升温还原、吡啶吸附红外光谱和程序升温脱附等表征结果表明，MoO／SiO2催化剂主要含有MoO3晶相，添加磷后，形成了表面多钼酸物种，磷以PO4四面体结构存在于表面，可能形成部分Mo—O—P键，从而抑制了MoO3在MoPO／SiO2上的形成，起到分隔活性中心的作用．在MoO／SiO2催化剂中添加磷后，催化剂的B酸和L酸酸性均增强，有利于丙烷在MoPO／SiO2催化剂表面活性的提高．由此可见，催化剂表面结构和酸性的变化可能是导致MoPO／SiO2催化性能提高的原因．     

Action of a Fluorescent Chemosensor for Cu2+ Encapsulated in Silica Xerogel

The fluorescent chemosensor of the type Ant-NH-O-O-NH-Ant for Cu²⁺ ions has been designed by means of a supramolecular approach, as follows: two anthracene (Ant) fragments as fluorophore subunits have been linked by a noncyclic NH-O-O-NH quadridentate ligand as a receptor. The interaction of Cu²⁺ - receptor is signalled through the enhancement of the anthracene fluorescence when the receptor, i.e., the dioxodiamine chain subunit of the sensor is able to stop a photoinduced electron-transfer mechanism. The experiments with the chemosensor encapsulated in silica xerogel by the sol-gel processing are described.     

Peculiarities of the silica surface center structure in rigid dehydroxidation conditions

A model of molecular claster and nonempirical calculation schemes MP2/6‐31G*, MP4/6‐31G*, and MP2/DZVP2 were applied to study electronic and energy characteristics of the surface centers of different SiO₂ modifications in rigid dehydroxidation conditions. It was established that depending on an angle α = Si′O′Si″ (where O′ is an oxygen atom of the nearest to the surface layer), O* atom corresponding with two surface Si atoms, could (i) form a chemical bond with one of the Si′ or Si″‐centers (an asymmetric configuration, α > 118° ÷ 120°); or (ii) be common for these centers (a symmetric configuration, α < 118° ÷ 120°). It was also established that when α > 132° ÷ 133°, the basic state was triple and at α < 132° ÷ 133°, it was single. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Polyacrylate/silica hybrid materials: A step towards multifunctional properties

Organic/Inorganic hybrid systems present a promising alternative for the creation of high-performance materials due to their biphasic structure that imparts multifunctional properties. The sol-gel process which initiated with the synthesis of inorganic glasses has now become a synthetic route for organic-inorganic assemblies due to several advantages such as mild processing conditions and the freedom to play with the structures of precursors. This versatility of the low-temperature sol-gel process provides an opportunity to engineer both the phases resulting in a synergistic combination or entirely new set of properties fruitful for different applications. This review highlights the several pathways for synthesis of silica particles, the interfacial modification and the classification of hybrid materials based on the method of incorporation of an inorganic moiety in the organic matrix along with the structure-property relationship, and the characterization to develop a fundamental understanding of the process. The nature of bonding between the two different species greatly affects the hybrid nanostructure and thus, the bulk properties of the system. In particular, acrylate/silica system has been focused due to its distinctive properties such as transparency, gloss, and strength that find large-scale application in the field of coatings, plastics and rubbers.Abbreviations: °: Degree; °C: Degree Celsius; ¹H NMR: Proton nuclear magnetic resonance; A°: Angstrom; AHAS: N-(3-acryloxy-2-hydroxyl propyl)-3-amino-propyltriethoxysilane; AIBA: 2,2′-Azobis(2-methylpropionamidine) dihydrochloride; AIBN: 2,2′-Azobis(2-methylpropionitrile); Al: Aluminium; APDMES: Aminopropyldimethylethoxysilane; APTES: 3-Aminopropyltriethoxysilane; ATRP: Atom transfer radical polymerization; CERAMERS: Ceramically Modified Monomers; CTAB: Cetyltrimethylammonium bromide; DFMA: Dodecafluoroheptyl methacrylate; DMF: Dimethylformamide; DPSD: Diphenylsilanediol; FESEM: Field Emission Scanning Electron Microscope; FTIR: Fourier-transform infrared spectroscopy; GPTMS: 3-Glycidoxypropyltrimethoxysilane; HDTMS: Hexadecyltrimethoxysilane; HEMA: 2-Hydroxyethyl methacrylate; HLB: Hydrophilic-Lyophilic Balance; HMDS: Hexamethyldisilazane; HPC: Hydroxypropyl Cellulose; IPN: Interpenetrating Network; KPS: Potassium persulfate; LCST: Lower critical solution temperature; McPTMS: 3-Mercaptopropyltrimethoxysilane; MOI: 2-(methacryloyloxy)ethyl isocyanate; MPEGMA: Monomethoxy-capped poly(ethylene glycol) methacrylate; MPTMS: 3-methacryloxypropyltrimethoxysilane; MTC: 2-(methacryloyl) ethyltrimethylammonium chloride; MTES: Methyltriethoxysilane; MTMS: Methyltrimethoxysilane; NMP: Nitroxide-Mediated Polymerization; ORMOCERs: Organically Modified Ceramics; ORMOSILs: Organically Modified Silica; OTES: Octyltriethoxysilane; OTMS: Octadecyltrimethoxysilane; PAA: Poly(acrylic acid); PDMS: Polydimethylsiloxane; PEO-PPO-PEO: Poly (ethylene oxides)-b-poly (propylene oxides)-b-poly (ethylene oxides); PHPS: Perhydropolysilazane; PMMA: Poly(methyl methacrylate); POSS: Polyhedral Oligomeric Silsesquioxane; PTMO: Poly(tetramethylene oxide); PTMS: Phenyltrimethoxysilane; PTMS: Phenyltrimethoxysilane; PVP: Poly (vinylpyrrolidone); RAFT: Reversible addition- fragmentation chain transfer; Si: Silicon; Sn: Tin; Ta: Tantalum; TBN: 4-(triethoxysilyl)butyronitrile; TEM: Transmission Electron Microscopy; TEMED: N,N,N′,N′-tetramethylethylenediamine; TEOS: Tetraethoxysilane; Tg: Glass-Transition Temperature; THF: Tetrahydrofuran; Ti: Titanium; TMOS: Tetramethoxysilane; UV: Ultraviolet; VTES: Vinyltriethoxysilane; VTMS: Vinyltrimethoxysilane; Zr: Zirconium

• Highlights

• Advantages of hybrid systems over the conventional materials

• Discusses the fundamental aspects of sol-gel chemistry

• Focusses on a detailed classification of hybrid polymers

• Covers different synthetic strategies, properties, and applications in diverse fields

     

Structural analysis of water adsorbed in silica gel

The melting point, T _f of water in a pore decreases as the surface area to pore volume ratio of the pore decreases. Analysis of water absorbed in the pores of silica gels using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS) shows that the thickness of the bound, non-freezing water layer adjacent to the pore surface increases as its temperature increases, but that it is independent of the surface silanol concentration, [Si_sOH]. In contrast, the thickness decreases as the cylindrical pore radius r _H decreases. Thus, the increase in the bound water thickness from 0.45 nm for gels with r _H =1.2 nm to 1.2 nm for gels with r _H =7.5 nm is due to the increase from –53°C to –7°C of the temperature (e.g., the melting point T _f ) at which the bound water thickness was measured, and not due to the increase in t _H or the decrease in [Si_sOH]. The T _f of bulk water measured in a DSC was –0.3°C. The boiling point T _v of bulk water measured in a DSC was 81.3°C. T _v increased to 94°C in 7.5 nm pores and to 109°C K in 1.2 nm pores.     

Stepwise gradient of buffer concentration for capillary electrochromatography of peptides on sulfonated naphthalimido-modified silyl silica gel

The advantage of using a stepwise gradient of buffer concentration in CEC was demonstrated with the mixed-mode stationary phase, 3-(4-sulfo-1,8-naphthalimido)propyl-modified silyl silica gel (SNAIP). Before the application of a stepwise gradient, the effect of buffer concentration on the separations of six peptides and tryptic digests was investigated. Bubble formation caused by Joule heating at currents up to 95 microA was successfully suppressed by using SNAIP column even without pressurization, which contributed to a stepwise gradient of buffer concentration. Utilizing the stepwise gradient improved and shortened the separation of six peptides as compared to the separation under an isocratic elution.