Sol–gel synthesis and structure of silica hybrid materials

In this work the research results on the sol–gel synthesis and structure of silica nanocomposites, containing carrageenan and their application as carriers for cell immobilization were described. The samples were prepared at room temperature by replacing different quantity of the inorganic precursor with κ-carrageenan. For studying the structure of the synthesized hybrids the following methods were used: FT-IR, XRD, BET-Analysis, SEM, AFM and Roughness Analysis. The influence of the type of silicon precursors, nature and quantity of organic component on the structure, surface area, design and size of nanostructures was established. The possibility of application of the synthesized biocatalysts in an enzyme degradation process of the toxic, carcinogenic and mutagenic substances benzonitrile, fumaronitrile, o-, m-, and p-tolunitriles was investigated at batch experiments. A two-step biodegradation process in a column bioreactor of fumaronitrile was followed. After operation of the system for 8 h at a flow rate 45 mL h^?1 and at 60 °C, the overall conversion was 89%, showing a good stability of the developed process.     

Sol–gel derived organic–inorganic composites recognizing molecular asymmetry

A new type of optically active organic-inorganic composite was prepared by a sol–gel method in which tetraethoxysilane (TEOS) is hydrolyzed in the presence of an optically active organic compound (d-lactose, d-glucose, d-sorbitol, d-fructose, l-tartaric acid, l-malic acid, or l-mandelic acid). Optical resolution of tris(pentane-2,4-dionato)metal complexes was performed by using the new sol–gel derived composites, composites prepared by conventional techniques (kneading with l-lactose, l-fructose or l-tartaric acid, and impregnation with an l-lactose, l-fructose or l-tartaric acid solution) and the optically active organic compounds themselves. The sol–gel derived composites showed much higher optical resolution abilities than the composites prepared by conventional techniques. In addition, the optically active organic compounds could not resolve the racemate into the enantiomers under similar conditions. X-ray diffraction and NMR results disclosed that an optically active organic compound in the sol–gel derived composite is highly dispersed, most likely, because it bonds to silicon atoms. Thus, it was deduced that optically active molecules dispersed at a molecular level recognize the chirality of the metal chelate compound. The high-resolution ability of the sol–gel derived composites arises from the combined effect of the silica support (adsorbing power) and the highly dispersed molecules (chiral recognition power).     

Sol–gel derived dye-bridged hybrid materials for white luminescence

Novel yellow and blue emissive dyes have been synthesized using 2,5-diamino-3,6-dicyanopyrazine and various alkoxysilanes and they are covalently bridged to cycloaliphatic epoxy functional oligosiloxane via non-hydrolytic sol–gel reaction. Dye-bridged hybrid materials (DBH) are fabricated by thermal curing the dye-bridged oligosiloxane. Structure and formation of dyes and siloxane network is studied using analysis method. Four components of red, yellow, green and blue emitting DBH cover entire visible range and white luminescence with high color rendering index is realized by controlling their combinations. We have ensured superior thermal stability DBH at 120 °C for 200 h caused by covalently bridged structure and robust siloxane matrix.     

Design and fabrication of single mode rib waveguides using sol–gel derived organic–inorganic hybrid materials

Multi-layer buried rib waveguides were fabricated using sol–gel derived photopatternable organic–inorganic hybrid materials through multi-step spin coating and photolithography. A single mode circular waveguide at 1,550 nm was designed and fabricated using the equivalent refractive index method. Propagation loss in the order of 1.0 dB/cm was measured by cutback method. Waveguide thermal stability and thermo-optic coefficient were investigated using thermogravimetric analysis (TGA) and spectroscopic ellipsometry, respectively. Results suggest that the single mode waveguide can be used to develop thermal optical devices such as thermo-optic switches.     

Sol–gel derived silica-based organic–inorganic hybrid materials as “composite precursors” for the synthesis of highly homogeneous nanostructured mixed oxides: an overview

The present contribution reports on our results concerning the synthesis of different binary and ternary oxide systems by using hybrid materials as “composite” precursors. In the last years, we have developed and explored a valuable strategy to yield a very homogeneous dispersion of nanoparticles of early metal transition oxide, MO₂ (M = Zr, Hf) inside a silica matrix. This route is based on the use of the sol–gel process to obtain organic–inorganic hybrid silica-based materials embedding the oxide precursors (Zr and/or Hf oxoclusters), which are then calcined at high (T > 500 °C) temperatures to give the desired oxides. The “precursor” hybrid materials are prepared by a modified sol–gel process, involving the copolymerisation of the organically modified oxozirconium or oxohafnium clusters (M₄O₂(OMc)₁₂ (M = Zr, Hf and OMc = methacrylate) with (methacryloxymethyl)triethoxysilane (MAMTES) or (methacryloxypropyl)trimethoxysilane (MAPTMS). Free radical copolymerisation of the 12 methacrylate groups of the oxoclusters with the methacrylate-functionalised siloxanes allows a stable anchoring of the oxoclusters to the silica network formed by the hydrolysis and condensation of the alkoxy groups. The sol–gel reactions of the two methacrylate-modified silanes methacryloxymethyltriethoxysilane and methacryloxypropyltrimethoxysilane were followed by using two independent time-resolved spectroscopic methods, viz., IR ATR and NMR with the aim to optimise their pre-hydrolysis times and consequently their use as precursors for hybrid materials. As mentioned, thermal treatment at high temperature of the hybrid yields a very homogeneous dispersion of ZrO₂ and/or HfO₂ nanoparticles in the silica matrix, since the molecular homogeneity of the starting hybrid is retained in the final mixed oxide. This route was successfully applied both to the synthesis of bulk materials and thin films characterised by different compositions (in term of M/Si molar ratios and M nature), heating route (conventional or microwave-assisted) and final temperature of annealing (from RT to 1,100 °C). The first example of the ZrO₂–HfO₂–SiO₂ ternary oxide system was also prepared by this approach. The prepared systems, both in the form of hybrid materials as well as in the final form of binary or ternary oxides, were thoroughly characterised by a wide variety of analytical tools from a compositional, structural, morphological point of view. Moreover, in the case of the binary ZrO₂–SiO₂ bulk materials, also the evolution under heating was followed by different methods. In particular, the composition of the hybrid as well as of the final oxidic materials was determined by X-Ray Photoelectron Spectroscopy and elemental analysis, whereas FT-IR and multinuclear solid-state NMR spectroscopies shed light on the changes occurring in the composition upon thermal heating and the degree of condensation of the silica network. The morphology and the microstructure of the hybrids and of the oxides were studied by nitrogen sorption and Scanning Electron Microscopy. X-Ray Diffraction, Transmission Electron Microscopy and X-ray Absorption Fine Structure Spectroscopy X-ray Absorption Fine Structure Spectroscopy were used to follow the conversion of the amorphous oxides to the final materials consisting of crystalline zirconia or hafnia dispersed in amorphous silica. On selected systems, functional properties (surface reactivity, dielectric properties) were furthermore investigated. The obtained binary oxides were also used as substrates for functionalisation experiments with (1) dialkycarbamates and (2) long alkyl chains to produce functional materials for catalysis and HPLC applications, respectively.     

Synthesis and characterizations of new negatively charged organic–inorganic hybrid materials: effect of molecular weight of sol–gel precursor

A series of negatively charged hybrid (organic–inorganic) materials were prepared through sol–gel process. The alkoxysilane-containing sol–gel precursors PEO-[Si(OEt)₃]₂SO₃H were obtained by endcapping polyethylene oxide (PEO) of different molecular weights with 2,4-diisocyanate toluene (TDI), followed by a coupling reaction with phenylaminomethyl triethoxysilane (ND-42) and sulfonation afterwards. The negatively charged precursors were then hydrolyzed and condensed to generate hybrid sol–gel materials, which were characterized by IR, TGA, XRD as well as the conventional ion exchange measurements. The results showed that in the hybrid sol–gel precursors PEO-[Si(OEt)₃]₂SO₃H organic PEO component was incorporated with alkoxysilane-containing ND-42 covalently. As the molecular weight of the precursors increased, thermal stability and cation-exchange capacity of the hybrid material decreased. All the hybrid materials were amorphous and those prepared from higher molecular weight precursors were flexible.     

Sol–gel synthesis and enhanced properties of a novel transparent PMMA based organic–inorganic hybrid containing phosphorus,nitrogen and silicon

A novel flame-retardant silane containing phosphorus and nitrogen, tetramethyl(3-(triethoxysilyl)propylazanediyl) bis(methylene) diphosphonate (TMSAP), is firstly synthesized and then incorporated into poly(methyl methacrylate) (PMMA) matrix through sol–gel method to produce organic–inorganic hybrids. The chemical structure of TMSAP was confirmed by Fourier transform infrared spectra, ¹H nuclear magnetic resonance (NMR) and ³¹P NMR spectra. The hybrids obtained maintain relatively high transparency, and exhibit a significant improvement in thermal properties, mechanical performance and flame retardancy when compared to pure PMMA, including increased glass transition temperature (T _g ) by 11.4 °C, increased onset thermal degradation temperature (T_0.1) by 82.6 °C, increased half thermal degradation temperature (T_0.5) by 42.0 °C, increased hardness, increased limited oxygen index and decreased heat release rate. Morphological studies of hybrids by scanning electron microscopy (SEM) and ²⁹Si MAS NMR suggest that cross-linked silica network is formed in the hybrids and the inorganic silica particles are distributed well in the polymer matrix. Thermal degradation behaviors investigated by thermogravimetric analysis and char structure analysis studied by SEM and X-ray photoelectron spectroscopy demonstrate the catalytic charring function of TMSAP, and synergistic effect between phosphorus, nitrogen and silicon element. The formation of network structure, homogeneous distribution of silica and the char formation during degradation play key roles in these property enhancements. Detailed mechanisms for these enhancements are proposed.     

Sol–gel synthesis and thermal behavior of bioactive ferrous citrate–silica hybrid materials

Journal of Thermal Analysis and Calorimetry - Imbalance of the iron level in the body causes several diseases. In particular, the low level of iron, during pregnancy, is responsible for the iron...     

Sol–gel preparation of aminopropyl-silica-magnesia hybrid materials

A series of aminopropyl-silica-magnesia hybrid materials has been prepared by the sol–gel method from tetraethoxysilane (TEOS), magnesium chloride (MgCl₂) and aminopropyltriethoxysilane (APTES) under acid conditions. The APTES:TEOS ratio was varied between 0:1 and 1:0. The aminopropyl coverage concentrations for APTES-silica-Mg samples were in the range of 0.3–2.3 mmol g⁻¹. The hybrid materials were characterized by numerous techniques, including X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Fourier transform Raman spectroscopy (FT-Raman), solid-state ¹³C and ²⁹Si nuclear magnetic resonance (¹³C- and ²⁹Si-NMR), thermogravimetry (TGA), N₂ adsorption–desorption, small-angle X-ray scattering (SAXS), and scanning electron microscopy (SEM). The increase of APTES content in the silica network resulted in the increase of six-membered siloxane rings. The hybrid systems were shown to be formed from fully-condensed, trifunctional APTES species. The porosity and morphology of the hybrid materials were influenced by the initial TEOS/APTES ratio. The radius of gyration of the primary particles, determined by SAXS, was between 1.1 and 2.9 nm.     

Sol–gel synthesis of sodium and lithium based materials

Sodium and lithium cobaltates are important materials for thermoelectric and battery applications due to their large thermoelectric power and ability to (de-) intercalate the alkali metal. For these applications, phase pure materials with controlled microstructure are required. We report on the sol?Cgel synthesis of sodium- and lithium-based materials by using acetate precursors. The produced Na_2/3CoO₂, Li(Ni_1/3Mn_1/3Co_1/3)O₂, and Li(Ni_1/2Co_1/2)O₂ powders are phase pure with grain sizes below 1???m. X-ray diffraction and energy-dispersive spectral analyses show that the cation stoichiometry is preserved in the lithium-based compounds. Despite the low temperatures, the sodium content is reduced by 1/3 as compared to the initial value. Chemical phases of the investigated powders are formed in the sol?Cgel route at temperatures typically 100?C200?K lower than those used in the conventional solid-state synthesis of these materials. The suggested sol?Cgel synthesis is a low temperature process suited for production of phase pure and homogeneous materials with volatile cations.     

Hybrid organic–inorganic sol–gel materials for micro and nanofabrication

In this review hybrid organic–inorganic (HOI) resists as emerging materials alternative to organic polymers for micro and nanolithography are presented and discussed. In particular, results on sol–gel materials belonging to 3-glycidoxypropyltrimethoxysilane based HOI are presented and reviewed, highlighting as various lithographic techniques can be used to pattern their surface and showing examples of micro- and nano-patterned structures achieved with radiation assisted lithography (UV, X-rays and electron beam) or imprint techniques. It will be demonstrated the particular versatility shown by some of these materials, that in some case can be processed with all the lithographic methods herein considered, without any significant modification of their main composition and synthesis procedure. Moreover, results about the investigation of interaction between radiation and HOI materials and thermal treatment will be discussed, as well as possible synthesis strategies and composition modification developed in order to improve efficiency of curing, tailor HOI properties to specific needs (optical properties, resist composition, mechanical stability, etc.) and explore innovative and non conventional patterning techniques. The reported results highlight as these novel materials, thanks to their solution processability and higher performances respect to commercial polymeric resists, allow to use the above mentioned lithographic techniques in a direct patterning process, strongly simplifying conventional technique and reducing their processing time and costs.     

Sol–gel synthesis of nanosilver embedded hybrid materials using combined organosilica precursors

A facile sol–gel route to the fabrication of size-controllable nanosilver embedded hybrid materials at room-temperature is presented. The preparation process involves using three kind of organosilica precursors, i.e. tetraethoxysilane, 3-mercaptopropyltrimethoxysilane and polymethylhydrosiloxane, which behaved as framework constructor, complexing agent toward metal ions and in situ reducing agent for Ag⁺ ions, respectively, under alcohol-rich synthesis conditions. The prepared hybrid materials were characterized by Ultraviolet–visible diffuse reflectance spectra, Fourier transform infrared, transmission electron microscopy, X-ray diffraction, nitrogen adsorption–desorption measurements. It was shown that well-dispersed silver nanoparticles (AgNPs) with small particle size were successfully embedded in the hybrid skeleton, and the mean particle size of AgNPs could be controlled at ca. 2–5 nm.     

Liquid-phase synthesis and application of monolithic porous materials based on organic–inorganic hybrid methylsiloxanes, crosslinked polymers and carbons

Our recent progress in porous materials based on organic–inorganic hybrids, organic crosslinked polymers, and carbons is summarized. Flexible aerogels and aerogel-like xerogels with the polymethylsilsesquioxane (PMSQ) composition are obtained using methyltrimethoxysilane (MTMS) as the sole precursor. Preparation process and the flexible mechanical properties of these aerogels/xerogels are overviewed. As the derivative materials, hierarchically macro- and mesoporous PMSQ monoliths and marshmallow-like soft and bendable porous monoliths prepared from dimethyldimethoxysilane /MTMS co-precursors have been obtained. Organic crosslinked polymer monoliths with well-defined macropores are also tailored using gelling systems of vinyl monomers under controlled/living radical polymerization. The obtained polymer monoliths are carbonized and activated into activated carbon monoliths with well-defined pore properties. The activated carbon monoliths exhibit good electrochemical properties as the monolithic electrode. Some possibilities of applications for these porous materials are also discussed.     

Sol–gel derived ion-imprinted silica-supported organic–inorganic hybrid sorbent for selective removal of lead(II) from aqueous solution

The current paper presents a novel Pb(II) ion-imprinted silica-supported organic–inorganic hybrid sorbent functionalized with Schiff base by coupling a surface imprinting technique with a sol–gel process for the selective removal of Pb(II) ions from aqueous solution. Fourier transmission infrared spectroscopy, scanning electron microscopy, N₂ adsorption–desorption isotherms and thermogravimetric analysis were used to characterize the Pb(II)-imprinted hybrid sorbent. The adsorption equilibrium was finished with 30 min. The experiment value of maximum adsorption capacity was found to be 54.9 mg g^?1. There were not significantly influence on the adsorption capacity of Pb(II) in the range of pH 3.5–6.5. The equilibrium data were fitted very well to the Langmuir isotherm model and pseudo-first-order kinetics model. Under competitive adsorption conditions, the Pb(II)-imprinted hybrid sorbent was 3.09, 4.73, 3.34 and 4.96 times more selective than the corresponding non-imprinted sorbent for the systems of Pb(II)/Cu(II), Pb(II)/Cd(II), Pb(II)/Ni(II) and Pb(II)/Zn(II), respectively. The thermodynamic results demonstrated that the adsorption of Pb(II) onto the Pb(II)-imprinted hybrid sorbent took place by a spontaneous and endothermic process with further increase in the degree of freedom at the solid–solution interface.     

Investigation of inorganic–organic hybrid materials containing polyoxometalate cluster anions and organic dye cations

Two new ionic-pair salts containing an organic dye cation, i.e. New Fuchsin or Pararosaniline cation, with Keggin-type POMs, [SiW₁₂O₄₀]^4? and [BW₁₂O₄₀]^6?, have been isolated under hydrothermal conditions. [(C₂₂H₂₄N₃)₄][SiW₁₂O₄₀] (1) and [(C₁₉H₁₈N₃)₆][BW₁₂O₄₀] (2) have been characterized by elemental analyses, FT-IR and single crystal X-ray crystallography. Both of these complexes have strong absorption in the visible-light range due to the involvement of the organic dye and both show weak fluorescence emission.     

Functionalization of mesostructured inorganic–organic and porous inorganic materials

The capability to functionalize the interior channels and/or high internal surface areas of mesostructured inorganic–organic or porous inorganic solids with specific organic or inorganic moieties has dramatically expanded the potential applications for these versatile materials in catalysis, separations, optical and opto-electronic devices, drug delivery, sensors, and energy conversion. Key to the widespread application of these materials are the various synthetic schemes that have been developed to provide control over the types of species incorporated and, more importantly, their distributions within the mesostructured hosts. Furthermore, multiple active species can often be independently incorporated and collectively optimized to yield multifunctional properties that widen application prospects. Several recent developments and examples in this rapidly growing field of materials chemistry and engineering are highlighted and discussed.     

Biodegradable and biocompatible inorganic–organic hybrid materials. I. Synthesis and characterization

The hydroxyl or vinyl end-groups of linear or three-arm star-shaped poly(ε-caprolactone) (PCL) chains have been derivatized into triethoxysilane groups reactive in the sol-gel process. New transparent hybrid materials that combine tetraethylorthosilicate (TEOS) and PCL known for biodegradability and biocompatibility have accordingly been prepared. The sol-gel process is, however, limited by the early vitrification of the reactive system. However, thermal posttreatment can overcome these diffusional and/or kinetic limitations as assessed by a set of analytical methods. The thermal stability of PCL is improved by incorporation into the silica network. Conversely, the thermal stability of the ceramer depends on the effective PCL content. The extent of PCL incorporation into the silica network depends on PCL molecular weight, number, and reactivity of the PCL functional groups. IR spectroscopy has shown that hydrogen bonding occurs between the ester groups of PCL and residual OH groups of the silicate component. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2295–2309, 1997     

Elastic organic–inorganic hybrid aerogels and xerogels

Novel aerogels and xerogels with methylsilsesquioxane (MSQ, CH₃SiO_1.5) networks have been prepared by a modified sol–gel process using surfactant and urea as a phase-separation inhibitor and as an accelerator for the condensation reaction, respectively. Optimized aerogels dried under a supercritical condition not only showed the similar properties as conventional pure silica aerogels such as high transparency and porosity etc, but also demonstrated outstanding mechanical strength against compression; the aerogel drastically shrank upon loading and then recovered when unloaded, which is called a “spring-back” behavior. On ambient pressure drying, the wet gel also exhibited the similar response against compression stress originated from the capillary pressure, and thus xerogels with the comparative structure and properties to those of corresponding aerogels have also been obtained. This unusual mechanical behavior is attributed to the trifunctional flexible networks of MSQ, low silanol concentration which prevents the irreversible shrinkage, and high concentration of a hydrophobic methyl group directly attached to every silicon atom which helps re-expansion after the temporal shrinkage.