Designing of luminescent GdPO4:Eu@LaPO4@SiO2 core/shell nanorods: Synthesis,structural and luminescence properties

GdPO₄:Eu³⁺ (core) and GdPO₄:Eu@LaPO₄ (core/shell) nanorods (NRs) were successfully prepared by urea based co-precipitation process at ambient conditions which was followed by coating with amorphous silica shell via the sol-gel chemical route. The role of surface coating on the crystal structure, crystallinity, morphology, solubility, surface chemistry and luminescence properties were well investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Fourier Transform Infrared (FTIR), UV-Vis, and photoluminescence spectroscopy. XRD pattern revealed highly purified, well-crystalline, single phase-hexagonal-rhabdophane structure of GdPO₄ crystal. The TEM micrographs exhibited highly crystalline and narrow size distributed rod-shaped GdPO₄:Eu³⁺ nanostructures with average width 14–16 nm and typical length 190–220 nm. FTIR spectra revealed characteristic infrared absorption bands of amorphous silica. High absorbance in a visible region of silica modified core/shell/Si NRs in aqueous environment suggests the high solubility along with colloidal stability. The photoluminescence properties were remarkably enhanced after growth of undoped LaPO₄ layers due to the reduction of nonradiative transition rate. The advantages of presented high emission intensity and high solubility of core/shell and core/shell/Si NRs indicated the potential applications in monitoring biological events.     

The role of the sol–gel route on the interaction between rhodamine B and a silica matrix

A series of silica xerogels having rhodamine B (RhB) as a template and Ti centers were synthesized by distinct sol–gel routes, namely, acid-catalyzed, base-catalyzed, acid-catalyzed with base-catalyzed (two steps) hydrolytic routes and a FeCl₃-catalyzed non-hydrolytic route. The interaction of RhB with the prepared silica matrix was investigated by Fourier transform infrared spectroscopy, attenuated total reflectance, diffuse reflectance spectroscopy in the ultraviolet–visible region, Raman spectroscopy, mass spectrometry, X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and confocal microscopy. Raman spectroscopy suggested the presence of Ti–O and Si–O–Ti moieties within the silica matrix. Infrared band shifts provided insight into potential interaction sites. Taking into account the results from ART, XPS, PL and confocal microscopy, encapsulation of RhB preferentially occurs inside the silica network for acid 1, basic and two-steps routes, and the presence of Ti occurs on the surface of the silica occurs for acid 2, basic and two-steps routes. Also, we have shown that although the structural characteristics of the encapsulated and extracted systems are affected by the route, the molecular structure is conserved during and after the encapsulation process.     

Surface Characterisation of Cerium-Doped Silica Coatings Obtained by Sol-Gel

The chemical composition of cerium-doped silica coatings prepared via sol-gel were studied using X-ray photoelectron spectroscopy (XPS) in conjunction with Ar⁺-ion sputtering, Rutherford back-scattering spectroscopy (RBS) and photoluminescence (PL) spectroscopy. XPS results showed that cerium was incorporated in the silica network as Ce(III). The absence of PL emissions from Ce(III) was explained by a clustering of the ions producing a quenching of the luminescence. XPS combined with Ar⁺ and RBS showed that the distribution of Ce is not uniform across the coating, showing a maximum concentration in an inner layer of the coating.     

A review on polysiloxane-immobilized ligand systems: Synthesis, characterization and applications

The immobilized silica gel ligand systems made by modification of silica surfaces have been briefly summarized. Short background was described based on the synthesis methods and their applications. In this review more attention towards the functionalized polysiloxane xerogels and their postmodification has been given. Polysiloxane-immobilized ligand systems bearing organofunctionalized ligand groups of general formula P-(CH₂)₃-X (where P represents a three-dimensional silica like network-matrix and X is an organofunctional group) were prepared through the sol-gel process by hydrolytic polycondensation of Si(OR)₄ and the appropriate silane coupling agent (RO)₃Si(CH₂)₃X (where R is an alkyl group, e.g CH₃ or C₂H₅). There are many other immobilized ligand systems, which were prepared by treatment of post-polysiloxane precursors with an appropriate organofunctional ligand. Variety of functionalized materials ranging from simple up to macrocyclic immobilized ligand systems were prepared and well characterized. These materials have the advantage over the functionalized silica, as they can be prepared using different molar ratios of Si(OR)₄ and (RO)₃Si(CH₂)₃X silane agents, and therefore their metal uptake capacities can be altered. A mixture of two different ligand groups can also be achieved on the same matrix. Analytical and environmental applications of these materials have been reported including extraction, separation and preconcentration of metal ions. A variety of physical chemistry techniques that were employed to characterize the surface and the bulk of the immobilized systems were reported. These included high-resolution solid-state nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR).     

Preparation of C60–Silica Hybrid Monolith by Sol-Gel Process

A C₆₀–silica hybrid monolith was prepared by the hydrosilylation of C₆₀ in the presence of platinum catalyst followed by sol-gel process with tetraethoxysilane. The hydrosilylation with trichlorosilane, triethoxysilane, chlorodiphenylsilane, and dichlorophenylsilane gave silylated C₆₀s as a brown pasty liquid. The formula was estimated to be C₆₀{Si(OEt)₃}_2.6H_2.6 or C₆₀(SiPh₂Cl)_3.2H_3.2 based on the proton nuclear magnetic resonance spectrum. A C₆₀–silica hybrid gel monolith was obtained by sol-gel process of the silylates and tetraethoxysilane in ethanol followed by aging for 3 weeks at room temperature. The monolith was brown and transparent with a diameter of 25 mm. On the other hand, the sol-gel reaction of tetraethoxysilane, trimethoxyphenylsilane, and C₆₀ provided a heterogeneous gel with a phase separation of C₆₀.     

Preparation and properties of amino-terminated anionic waterborne-polyurethane-silica hybrid materials through a sol-gel process in the absence of an external catalyst

A series of polymer-silica hybrid materials consisting of amino-terminated anionic waterborne-polyurethane (WPU) and inorganic silica particles have been prepared through a sol-gel process in the absence of an external catalyst. Typically, amino-terminated anionic WPU was first synthesized from polycaprolactone, dimethylol propionic acid, and 4,4′-methylenebis(cyclohexyl isocyanate) with specific molar ratios, followed by further reaction with triethylamine and triethylene tetramine to give as-prepared WPU. The WPU obtained was characterized by FTIR spectroscopy and gel permeation chromatography. Subsequently, a series of hybrid materials with different silica contents were prepared by performing sol-gel reactions with tetraethyl orthosilicate (TEOS) in an amino-terminated WPU matrix without the addition of an external catalyst. This was followed by examination by transmission electron microscopy and ²⁹Si solid-state NMR. The terminated primary amine groups attached to the as-prepared WPU chains functioned as an internal base catalyst for the sol-gel process of TEOS. The effect of composition on the thermal stability, mechanical strength, surface wettability, and optical clarity of the hybrid materials was evaluated by the thermogravimetric analysis, dynamic mechanical analysis, contact angle measurement, and UV-visible transmission spectroscopy, respectively.     

Synthesis and characterization of poly(EMA-co-HEA)/SiO2 nanohybrids

A series of silica-based organic-inorganic nanocomposites, which attempt to mimic the properties of mineralized matrix tissues from natural bone or dentin, have been prepared and characterized as potential candidates for the synthetic matrix of scaffolds for bone or dentin regeneration. The synthesis procedure consisted in the copolymerization of ethyl methacrylate (EMA) and hydroxyethyl acrylate (HEA) during the simultaneous acid-catalyzed sol-gel polymerization of tetraethoxysilane (TEOS) as a silica precursor, giving rise to poly(EMA-co-HEA)/SiO₂ nanohybrids with silica contents in the range of 0-30 wt%. Different structures of silica within the organic polymeric matrix were inferred from infrared spectroscopy, energy dispersive X-ray spectroscopy, thermogravimetry, pyrolysis, density assessments, solvent uptake and transmission electron microscopy. TEOS was efficiently hydrolyzed and condensed to silica during the sol-gel process in all cases, and presented a homogeneous distribution in the polymeric matrix, in the form of nanodomains either interdispersed or continuously interpenetrated with the organic network, depending on the silica content. Silica contents above 10% produced co-continuous interpenetrated structures where the silica network reinforces mechanically the organic matrix and at the same time confers bioactivity to the surfaces.     

有机改性先驱体对含铕配合物的凝胶玻璃结构及性能的影响

分别采用γ-缩水甘油氧基三甲氧基硅烷(CH₂OCHCH₂O(CH₂)₃Si(OCH₃)₃) (GPTMS), 甲基三甲氧基硅烷(MTMS)和乙烯基三乙氧基硅烷(VTES)作为有机改性先驱体, 采用原位合成技术, 用溶胶-凝胶法制备了Eu^3＋, β-二酮噻吩甲酰三氟丙酮(TTA)及协同体1,10-菲啰啉(phen)共掺的三种有机改性二氧化硅(ormosil)玻璃. 测量了它们的发射光谱和红外光谱, 并进行了XRD, SEM和TG-DSC测试. 探讨了不同有机改性先驱体及热处理温度对原位合成的稀土有机配合物掺杂二氧化硅凝胶玻璃的发光性能、热稳定性及机械性能的影响. 结果表明, 有机改性先驱体能使凝胶玻璃结构致密, 但同时热稳定性降低; 对于荧光性能, MTMS和VTES可使其有一定的提高, 但它们的最大含量不能超过50%, 否则凝胶易失透, 而GPTMS能大幅提高凝胶的荧光性能. 通过综合比较, 选取出各种性能都较好的配方, 为今后制备较实用的具有较强荧光的含铕的凝胶玻璃提供了一定的依据.     

Luminescence of Silica-Pillared Clays and Gels Derived from Aminofunctional Silanes

Silica-pillared clays were prepared by reacting Na-montmorillonite aqueous suspensions with (3-aminopropyl)triethoxysilane (APTEOS). It was indicated that cubic octamers [NH ₃ ⁺ (CH₂)₃SiO_3/2]₈ derived from APTEOS are intercalated with two different conformations of the alkyl chains. Namely, the cubic octamers are intercalated with the alkyl chains parallel to the silicate layers at low concentration of APTEOS, and then intercalated with the alkyl chains normal to the silicate layers with increase in APTEOS. Gels were prepared from the reaction of APTEOS with acetic acid and by the conventional sol-gel process using (3-aminopropyl)trimethoxysilane (APTMOS). The luminescence spectra of the gel prepared by the sol-gel process and the intercalated clays were similar to that of silica gels. The gel from APTEOS with acetic acid showed broad visible luminescence. The luminescence spectra and the structures of these materials were described.     

Encapsulation of Proteins in Bulk and Thin Film Sol-Gel Matrices

This paper considers the nature of the interactions between the sol-gel derived inorganic matrix and a specific biomolecule, cytochrome c. Optical absorption and impedance spectroscopies are used to characterize the influence of synthesis conditions on the protein’s stability and conformation within the silica matrix. In some instances, encapsulation within the sol-gel matrix provides stabilization. For example, protein denaturation is reversible and aggregation is prevented. Moreover, the drying process does not negatively affect the protein; it is possible to regenerate the aged gel state by rehydration. The flexibility of the sol-gel process enables high quality cytochrome c-doped SiO₂ thin films to be prepared. These films possess the characteristic reactivity and chemical function of cytochrome c in solution.     

The synthesis and characteristic study of 6FDA-6FHP-NLO polyimide/SiO2 nanohybrid materials

Hybrid nanocomposite films of silica (SiO₂) in polyimide (PI) from 4,4^′-(hexafluoroisopropylidene) diphthalic arhydride (6FDA), 2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FHP) and nonlinear optical (NLO) molecule have been successfully fabricated by an in situ sol-gel process. The silica content in the hybrid films was varied from 0 to 22.5 wt%. These nanocomposite films exhibit fair good optical transparency. Fourier transform infrared (FTIR) spectroscopy results confirm the formation of SiO₂ particles in PI matrix. Scanning electron microscope (SEM) images show that the SiO₂ phase is well dispersed in the polymer matrix. Their glass transition behavior and thermal stability were investigated by differential scanning calorimeter (DSC) and thermal gravimetric analysis (TG).     

The interaction between TEOS and some polyols

Hybrid organic-inorganic materials, silica – polyols (ethylene-glycol – EG; 1,2 propane diol – 1,2PG; 1,3 propane diol – 1,3PG and glycerol – GL), were prepared by a sol-gel process starting from tetraethylorthosilicate (TEOS) and polyols, in acid catalysis. The resulting materials were studied by thermal analysis (in air and nitrogen), FTIR and solid state ²⁹Si-NMR spectroscopy. These techniques evidenced the presence of polyols in the silica matrix both hydrogen bounded and chemically bounded in the silica network. The thermal analysis proves to be the most appropriate technique to evidence the organic chains linked in the matrix network and to follow the thermal evolution of the gels to the SiO₂ matrix.     

Incorporation of niobium into bridged silsesquioxane based silica networks

In this work different synthesis routes were evaluated with the aim of optimizing the incorporation of niobium within a hybrid silica matrix on an atomic scale. The fast kinetics of the hydrolysis/polycondensation of the organic Nb precursor Nb(OEt)₅ entails a segregation of the resulting material into Nb₂O₅ and a silica based network. To overcome this effect we (a) performed a prehydrolysis of 1,2-bis-triethoxy-ethane (BTESE) prior to adding niobium penta-ethoxide, or (b) attempted to reduce the availability of Nb via a complexation of Nb by either acetylacetone or 2-methoxyethanol. The network organization was evaluated from results of Fourier transform infrared as well as ¹³C, ²⁹Si and ¹⁷O MAS NMR spectroscopy. Whereas the prehydrolysis of BTESE and the addition of 2-methoxyethanol induced only moderate mixing of Nb and Si, leading to a network in which islands of Nb₂O₅ are linked to the hosting silica based matrix via Nb–O–Si bonds, the use of acetylacetonate lead to a mixing of Nb and Si on the atomic scale, forming a mixed Nb–O–Si network without any extended clusters of segregated Nb₂O₅. The Si–C–C–Si bridge from the silsesquioxane is found to survive the condensation process and is even present in the resulting materials after annealing at 200 °C.     

Preparation and microstructure of sol-gel derived silver-doped silica

Silver-doped silica was prepared by hydrolysis and condensation of tetraethyl orthosilicate (TEOS, Si(OC₂H₅)₄) in the presence of a silver nitrate (AgNO₃) solution by two different synthesis methods. In the first synthesis route, sol-gel mixtures were prepared using an acid catalyst. In the second synthesis route, silver-doped silica gels were formed by two-step acid/base catalysis. For the same concentration of silver dopant [AgNO₃]/[TEOS] = 0.015 acid-catalyzed sol-gel formed a microporous silica with an average pore size of <25 Å whereas the two-step catalyzed silica had an average pore size of 250 Å and exhibited a mesoporous structure when fully dried. The differences in the pore size affected the silver particle formation mechanism and post-calcination silver particle size. After calcination at 800 °C for 2 h the acid-catalyzed silica contained metallic silver particles size with an average particle size of 24 ± 2 nm whereas two-step catalyzed silica with the same concentration of [AgNO₃]/[TEOS] = 0.015 contained silver nanoparticles with an average size of approximately 32 ± 2 nm. Mechanisms for silver particle formation and for silica matrix crystallization with respect to the processing route and calcination temperature are discussed.     

Synthesis and Structural Analysis of Au-Doped TiO2/SiO2 Mixed Oxide Films Prepared by Sol-Gel Process

The systematic modifications of silica matrix as a function of modified Ti-alkoxide contents (Au nanocrystals doped TiO₂/SiO₂ mixed oxide thin films) have been investigated by the sol-gel process. A structural analysis on the various steps of the hydrolysis-condensation process as well as solid powder is determined by IR, UV-Visible, and ²⁹Si NMR spectroscopy. ²⁹Si MAS spectra are characterized by broad lines for the three types of sites. Different distributions (Q ², Q ³, and Q ⁴ units) observed in the TiO₂/SiO₂ (1 : 3) sample. Proper control of the process condition, modifying the Ti alkoxide as a less reactive precursor, improves the increase the amount of Ti–O–Si bonding in the silica network of TiO₂/SiO₂ mixed oxide matrices and the distribution of metal oxides. This method can be used for the preparation of homogeneous metal and metal-metal alloy nanocrystals deposition from mixed oxide thin films.     

Preparation and Characterization of the Nanocomposites SiO2/H-Bond Hydrogensulphate (Hydrogenselenate)

The nanocomposites representing interesting H-bond compounds (Na₃H(SO₄)₂, RbHSO₄, RbHSeO₄, and Rb₃H(SeO₄)₂) in the silica matrix were prepared by the sol-gel method. Resulting samples were characterised by X-ray diffraction, IR spectroscopy and electron microscopy. Transition temperatures of the nanocomposites were determined using DSC and compared with the T _C of the pure bulk active compounds. The shifts of the T _C towards lower temperatures or the disappearing of the certain effects in the case nanocomposites were observed. A possible explanation of these phenomena was proposed using the analogy with the superparamagnetic compounds.     

Synthesis,Characterization and Properties of (Vinyl Triethoxy Silane-grafted PP)/Silica Nanocomposites

A new route has been developed to produce PP/silica nanocomposites starting from porous PP reactor powder and making use of sol-gel chemistry. Silica-like, nano-sized particles were prepared in the pores of the PP reactor powder with a controlled degree of adhesion between PP and silica. Magic-angle spinning (MAS) ²⁹Si NMR spectra showed that the chemical building blocks of the silica-like clusters are of Q³ and Q⁴-type. For (vinyl triethoxy silane (VTES)-grafted PP)/silica nanocomposites, VTES was grafted via solid-state modification (SSM) in porous PP particles. Subsequently, silica particles were prepared by sol-gel technology in the VTES-grafted PP. MAS ²⁹Si NMR and FT-IR spectroscopy showed that the grafted VTES becomes part of the in-situ formed silica particles. The study on the mechanical properties of (VTES-grafted PP)/silica nanocomposites showed that the silica particles improved the impact toughness of PP by a factor of 2, when there is no chemical interaction between the particles and the matrix, while for (VTES-grafted PP)/silica nanocomposites the impact toughness decreased. This indicates that chemical bonding between the filler particles and the PP-matrix results in brittle failure and supports the hypothesis that debonding is necessary for improving the impact toughness of PP with inorganic fillers.     

Fluorescence of Pyranine in Sol-Gel Based Silica and Hybrid Thin Films

The sensitivity of the pyranine fluorescence to protonation/deprotonation is used to follow modifications in cured sol-gel thin films. The acid concentration in the sol-gel solution is varied for TEOS-based coatings and a series of organically modified silanes Si(OR)₃R’ are added to the TEOS solution. The concentration of the organically modified silane is varied as well as the chain length of the alkylgroup (R’). The stationary fluorescence measurements show that the equilibrium between the protonated and the deprotonated form of pyranine changes depending on the type of silica matrix. The deprotonated form is dominant in the cured SiO₂ films and the protonation/deprotonation ratio of pyranine is constant for the different acid concentrations used. The protonated form becomes dominant as the concentration of Si(OR)₃R’ is increased and as the alkyl chain length (R’) of the organically modified silanes is augmented. Emission anisotropy measurements of pyranine in the same coatings show that the rotational freedom of the molecule changes due to modifications in the cages for the TEOS-based coatings. These modifications are produced by the acid concentration used to prepare the coatings. An increase in the rotational freedom of pyranine is observed in the TEOS-Si(OR)₃R’ systems.     

Aerosol-Gel Deposition of Optically Active Thin Films in the System Y2Ti2O7-Er2Ti2O7

Optically active thin films in the system Y₂Ti₂O₇-Er₂Ti₂O₇ (YETO) have been deposited using the Aerosol-gel process. Depending on the heat-treatment temperature, amorphous or crystalline films could be prepared in the range 600–950°C. The study shows that dilution of erbium ions within a Y₂Ti₂O₇ (YTO) matrix allows to prevent short range distance interactions between those ions and to promote good photoluminescence properties of YETO films. These properties are discussed and compared with those of sol-gel derived silica films doped with erbium.     

Reduction of Cr(VI) Assisted by Sol-Gel Generated Electron-Hole Centers

We report an in-situ harvesting technique of electron-hole (e⁻-h⁺) carriers (e.g., the defect electrons in the O^{2 −} matrix and the self-trapped holes, Si–O⁻–Si) generated during sol-gel processing. In the absence of redox species, the e⁻-h⁺ centers created during room temperature sol-gel polycondensation steps are quickly annihilated and deactivated. However, when Cr(VI) ions are pre-dispersed in sol-gel solutions, the ejected electrons can be effectively harvested for the reduction of Cr(VI) to Cr(III) ions which are encapsulated in the silica gel matrix. The Cr(VI) ions, the possible intermediate oxidation states of chromium ions such as Cr(V) and/or Cr(IV), and the stable Cr(III)-hole complexes in the sol-gel matrix are investigated using uv-visible spectroscopy, electron paramagnetic resonance spectroscopy, and cyclic voltammetry. The chemical stability of Cr(VI) and Cr(III) in sol-gel networks is compared to that in aqueous solutions. The results indicate that the utilization of e⁻-h⁺ carriers generated in the sol-gel can be an effective and selective means for investigating the redox process of Cr(VI) and encapsulating the stable Cr(III) ions in the confined sol-gel environments.