Synthesis and characterization of a new hybrid TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> filler for lithium conducting gel electrolytes

This paper describes the synthesis and properties of a new type of ceramic fillers for composite polymer gel electrolytes. Hybrid TiO₂-SiO₂ ceramic powders have been obtained by co-precipitation from titanium(IV) sulfate solution using sodium silicate as the precipitating agent. The resulting submicron-size powders have been applied as fillers for composite polymer gel electrolytes for Li-ion batteries based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF/HFP) copolymeric membranes. The powders, dry membranes and gel electrolytes have been examined structurally and electrochemically, showing favorable properties in terms of electrolyte uptake and electrochemical characteristics in Li-ion cells.     

TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> hybrid nanomaterials: synthesis and variable UV-blocking properties

Silica and core–shell structured titania/silica (TiO₂/SiO₂) nanoparticles with particles size ranging from tens to hundreds of nanometers were prepared and deposited onto cotton fabric substrates by sol–gel process. The morphologies of the nanoparticles were characterized by field-emission scanning electron microscope (FE-SEM). The photocatalytic decomposition properties as well as UV-blocking properties of the fabrics treated with SiO₂ and TiO₂/SiO₂ nanoparticles were investigated.     

Electrodeposition of PbO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> composite materials

The regularities of electrodeposition of composite materials based on PbO₂ containing zirconium dioxide particles are studied. The contents of various phases in the composite depend on the electrolyte composition and conditions of deposition. When a dispersed phase is incorporated into the composite coating, the dimensions of lead dioxide crystals decrease to submicrons.     

Fabrication and characterization of TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> composite nanoparticles and polyurethane/(TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>) nanocomposite films

TiO₂–SiO₂ composite nanoparticles were prepared by a sol–gel process. To obtain the assembly of TiO₂–SiO₂ composite nanoparticles, different molar ratios of Ti/Si were investigated. Polyurethane (PU)/(TiO₂–SiO₂) hybrid films were synthesized using the “grafting from” technique by incorporation of modified TiO₂–SiO₂ composite nanoparticles building blocks into PU matrix. Firstly, 3-aminopropyltriethysilane was employed to encapsulate TiO₂–SiO₂ composite nanoparticles’ surface. Secondly, the PU shell was tethered to the TiO₂–SiO₂ core surface via surface functionalized reaction. The particle size of TiO₂–SiO₂ composite sol was performed on dynamic light scattering, and the microstructure was characterized by X-ray diffraction and Fourier transform infrared. Thermogravimetric analysis and transmission electron microscopy (TEM) employed to study the hybrid films. The average particle size of the TiO₂–SiO₂ composite particles is about 38 nm when the molar ratio of Ti/Si reaches to1:1. The TEM image indicates that TiO₂–SiO₂ composite nanoparticles are well dispersed in the PU matrix.     

Microstructure of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> hybrid electrospun nanofibers and their application in dye degradation

SiO₂/TiO₂ hybrid nanofibers were prepared by electrospinning and applied for photocatalytic degradation of methylene blue (MB). The phase structure, specific surface area, and surface morphologies of the SiO₂/TiO₂ hybrid nanofibers were characterized through thermogravimetry (TG), X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM), etc. XRD measurements indicated that doping of silica into TiO₂ nanofibers can delay the phase transition from anatase to rutile and decrease the grain size. SEM and BET characterization proved that silica doping can remarkably enhance the porosity of the SiO₂/TiO₂ hybrid nanofibers. The MB adsorption capacity and photocatalytic activity of the SiO₂/TiO₂ hybrid nanofibers were distinguished experimentally. It was found that, although increased silica doping content could enhance the MB adsorption capacity, the intrinsic photocatalytic activity gradually dropped. The SiO₂ (10 %)/TiO₂ composite nanofibers exhibited the highest MB degradation rate, being superior to SiO₂ (20 %)/TiO₂ or pure TiO₂.     

Synthesis characterization and catalytic evaluation of Ni/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> aerogels catalysts

The Ni/ZrO₂/SiO₂ aerogels catalysts were synthesized via three different routes: (i) impregnation ZrO₂–SiO₂ composite aerogels with a aqueous solution of Ni(NO₃)₂, (ii) impregnation SiO₂ aerogels with a mixed aqueous solution of Ni(NO₃)₂ and ZrO(NO₃)₂ · 2H₂O, (iii) one-pot sol–gel procedure from precursors Ni(NO₃)₂/ZrO(NO₃)₂ · 2H₂O/Si(OC₂H₅)₄. These catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), ammonia temperature-programmed desorption (NH₃-TPD), N₂ adsorption–desorption isotherms and Fourier transform infrared (FT-IR). The Liquid-phase hydrogenation of maleic anhydride (MA) was performed over these catalysts. The results revealed that the different preparation routes result in a difference between the obtained samples, concerning the crystal structure and composition, surface acidity, mixed level of each component, texture, and catalytic selectivity.     

Nanosized TiO<Subscript>2</Subscript> particles decorated on SiO<Subscript>2</Subscript> spheres (TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>): synthesis and photocatalytic activities

Nanosized TiO₂ and nano-anatase TiO₂ decorated on SiO₂ spherical core shells were synthesized by using a sol–gel method. The synthesized pure TiO₂ nano particle and TiO₂ grafted on SiO₂ sphere with various ratios have been characterized for their structure and morphologies by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrophotometry (FTIR) and transmission electron microscopy (TEM). Their surface areas were measured using the BET method. The photocatalytic activity of all nanocomposites was investigated using methylene blue as a model pollutant. The synthesized TiO₂/SiO₂ particles appeared to be more efficient in the degradation of methylene blue pollutant, as compared to pure TiO₂ particles.     

Moisture and solvent responsive cellulose/SiO<Subscript>2</Subscript> nanocomposite materials

Water responsive SiO₂/cellulose nanocomposite hydrogels and films were constructed, for the first time, by dispersing SiO₂ nanoparticles into cellulose solution in LiOH/urea solvent, and then by crosslinking with epichlorohydrin or regeneration in coagulation bath, respectively. The cellulose nanocomposite materials were characterized by Field emission scanning electron microscopy, FTIR, dynamic rheology, wide angle X-ray diffraction and mechanical test. The SiO₂/cellulose nanocomposites at wet state or in water displayed unique behaviors, showing higher light transmittance than those before contacting with water. The results revealed that strong hydrogen-bonding interaction among water, cellulose and SiO₂ led the good dispersion of SiO₂ nanoparticles in the cellulose matrix. The incorporation of SiO₂ nanoparticles improved the transmittance and mechanical strength of the cellulose hydrogels, and also enhanced the mechanical strength of the films. Especially, the cellulose/SiO₂ nanocomposite films were milky at dry state, and changed to transparent after being soaked in water, different from the cellulose film without the SiO₂ nanoparticles. In our findings, SiO₂ and cellulose with water could form strong hydrogen bonding to create a homogenous network structure. The cellulose/SiO₂ composite as a smart material exhibited moisture and solvent responsiveness, showing potential applications in moisture detection.     

Fabrication,characterization, and photocatalytic performance of TiO<Subscript>2</Subscript> hybridized with SiO<Subscript>2</Subscript>

Nanostructures TiO₂–SiO₂ photocatalysts were successfully synthesized using the sol-gel method, hydro-calcination, co-precipitation and room-temperature solid-phase synthesis technology. X-ray powder diffraction pattern (XRD), Fourier transform infrared spectrum (FTIR), photoluminescence (PL) spectra, thermal analyses (TG–DTA), scanning electron micrographs (SEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) were used to characterize the as-synthesized catalysts. Photocatalytic performances of the catalysts were evaluated by the degradation of methyl orange (MO) under s imulated natural light and the degradation rate of MO is 97.2%. The composites showed a good stability: after five recycling runs there are no significant decreases in the photocatalytic activity. The photodegradation of methylene blue, rhodamine B, methyl violet, naphthol green B, basic fuchsin, malachite green, and methyl red were also tested, and the degradation rate of dyes could reach over 94.2 %. A possible mechanism for the photocatalysis with the TiO₂–SiO₂ was proposed.     

Characterisation of a new sol-gel precursor for a SiO<Subscript>2</Subscript>-rhodamine 6G hybrid class II material

The entrapment of organic dyes in inorganic solids offers several advantage for solid-state laser applications with respect to the use of liquid or polymer hosts. Among the various inorganic hosts, silica is preferred for its superior mechanical, thermal and optical properties. Organic dyes, such as Rhodamine 6G (Rh6G), can be immobilised in SiO₂ both physically (materials of class I), and by covalent bonds (class II materials). In the past years Rh6G-SiO₂ class I hybrids were prepared. In this work we propose, for the first time, a Rh6G-SiO₂ class II hybrids. We describe the preparation of a suitable sol-gel Rh6G precursor verified by FT-IR analysis and report the characterization of the hybrid materials by means of thermal and porosimetric analysis and optical spectroscopy measurements. The precursor is thermally stable up to ∼250°C, and its optical characteristics (UV-VIS absorbance and photoluminescence, PL) do not change with respect to those of the pristine dye molecule. The PL spectra of the final hybrids show that they are promising candidates for applications in solid state dye lasers.     

Preparation and characterization of poly(phthalazinone ether ketone)/SiO<Subscript>2</Subscript> hybrid composite thin films with low friction coefficient

Organic–inorganic poly(phthalazinone ether ketone) (PPEK)/SiO₂ hybrid composite thin films were prepared by the dip-coating method on pre-cleaned glass substrates. The covalent bonds between organic and inorganic phases were introduced by an in-situ O-acylation reaction of isocyanatopropyltriethoxysilane (ICPTES) with the borohydride-reduced PPEK forming a polymer bearing triethoxysilyl groups. Theses groups were subsequently hydrolyzed with tetraethoxysilane (TEOS) and allowed to form a network via a sol–gel process. The polymer hybrid composite exhibited good thermal stability and a higher glass transition temperature as compared with the pure resin. Atomic force microscope, water contact angle measurement and scanning electron microscope were used to characterize the polymer hybrid thin films. The tribological experiment showed that the films have very low friction coefficient (about 0.1) and good anti-wear properties, without failure even after sliding for 18,000 s under modest loads. The improved tribological properties of the modified substrate were attributed to good adherence of PPEK/SiO₂ hybrid films on the substrate and synergy of both PPEK matrix and silica particles.     

SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> nanoparticles in Aerosol OT reverse microemulsions: Synthesis and characterization

Stable SiO₂ and TiO₂ organosols were prepared by hydrolyzing tetraethyl orthosilicate (TEOS) in the presence of 6–12 M NH₃ and titanium(IV) isopropylate (TTIP) in reverse microemulsions of 0.12–0.25 M bis(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT) in n-decane with the aqueous pseudophase content of 2–3 vol %, 0.018–0.090 M TEOS, and 0.15–0.55 vol %, 0.003–0.025 M TTIP. The degree of hydrolysis was monitored by IR spectroscopy (for TEOS) and spectrophotometry (for TTIP). Oxide nanoparticles were characterized by photon-correlation spectroscopy (PCS) (D _h = 8–100 nm) and laser electrophoresis (ζ-potential = 7.4–11.6 mV). The occurrence of surface potential made it possible to separate the oxides from the excess of surfactant by nonaqueous electrophoresis and to determine particle sizes (7–40 nm) by means of transmission electron microscopy (TEM).     

Preparation and characterization of the Ti/IrO<Subscript>2</Subscript>/WO<Subscript>3</Subscript> as supercapacitor electrode materials

WO₃ films have been prepared onto IrO₂-coated Ti substrate by electro-deposition, and as-deposited and annealed films have been characterized by using Raman spectroscopy. It was found that the asdeposited film consists of orthorhombic WO₃ · H₂O phase, which transforms to amorphous WO₃ by annealing at 250°C and to monoclinic phase by annealing at and above 350°C. All electrochemical experiments were carried on Ti/IrO₂/WO₃ annealed at 450°C. The open-circuit potential could change significantly due to the hydration of the coating film. However this process is fairly slow. Reproducible voltammograms could be obtained quickly, further revealing high electrochemical stability of the Ti/IrO₂/WO₃ electrode. And the shapes of CV show the approximate rectangular mirror image, showing the typical characteristic of capacitive behavior. The specific capacitance obtained at a scan rate of 50 mV s⁻¹ is 46 F g⁻¹.     

Porphyrins incorporated to SiO<Subscript>2</Subscript> gels as fluorescent materials and efficient catalysts in biomimetic photocatalytic systems

Two types of porphyrins (water-soluble and water-insoluble) were encapsulated in transparent monolithic silica gels. Their properties in solutions and at various steps of the sol–gel process were studied by absorption and emission electron spectroscopy. A photocatalytic system containing porphyrins immobilized in powdered silica gel for α-pinene biomimetic oxidation to pinocarveol, pinocarvone and myrtenol is reported. The impact of several parameters (visible light irradiation time, organic solvent, the presence of an electron acceptor/donor, and substrate concentration) on this biotransformation process was investigated and optimized. It was established that photochemical excitation of sol–gel immobilized metal-free porphyrins is crucial for catalyzed oxidation of monoterpenes.     

Synthesis and characterization of MF-4SK + SiO<Subscript>2</Subscript> hybrid membranes modified with tungstophosphoric heteropolyacid

Composites based on MF-4K perfluorinated cation-exchange membranes doped with hydrous silica nanoparticles, which were precipitated under various conditions, and with tungstophosphoric heteropolyacid nanoparticles were synthesized. The proton conductivity of the composites was studied as a function of temperature and relative ambient humidity. As a result of modification, the water content and ion conductivity of the membranes in low humidities increase by 2.5 orders of magnitude compared to unmodified MF-4SK membranes and the material is rendered less water-dependent.     

Microstructure and electrical properties of lead zirconate titanate thin films deposited by sol-gel method on La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>/SiO<Subscript>2</Subscript>/Si substrate

(La_0.7Sr_0.3)MnO₃ thin films were deposited on SiO₂/Si substrates by a metal-organic decomposition (MOD) method, and then Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were grown on (La_0.7Sr_0.3)MnO₃-coated SiO₂/Si substrates by a sol-gel method. The effects of annealing temperature on the crystalline phases, microstructures and electrical properties of the PZT films were investigated. X-ray diffraction analysis results indicated that the PZT films with a perovskite single phase could be obtained by annealing at 650°C. The dielectric constant and the remnant polarization of the PZT films increased with increasing annealing temperature. The remnant polarization and the coercive field of the films annealed at 650°C were 18.3 μC/cm² and 35.5 kV/cm, respectively, whereas the dielectric constant and loss value measured at 1 kHz were approximately 1100 and 0.81, respectively.     

Modeling the active centers of V<Subscript>2</Subscript>O<Subscript>5</Subscript>/SiO<Subscript>2</Subscript> and V<Subscript>2</Subscript>O<Subscript>5</Subscript>/TiO<Subscript>2</Subscript> supported catalysts. DFT theoretical analysis of optical properties

Within the framework of the density functional theory (DFT), the electronic structure of monooxodioxovanadium functional groups in tetrahedral coordination, which model the active centers (ACs) of fine supported catalysts V₂O₅/SiO₂ and V₂O₅/TiO₂, has been analyzed. The optimal structures of three ACs as possible models of monomeric and polymeric oxovanadium forms on the carriers with low vanadium content were determined. The modified DFT method involving the time dependence of Kohn-Sham equation (TDDFT) was used for the adopted AC models to calculate the energies of the excited states, and optical spectra of the absorption in 25000–60000 cm^?1 region were reconstructed on their base. The spectrum in this region is due to O → V charge transfer. The features of electronic spectra with the charge transfer for V₂O₅/SiO₂ and V₂O₅/TiO₂ catalysts and the vibrational spectra of three AC models corresponding to the monomeric and dimeric oxovanadium forms of the supported catalysts V₂O₅/SiO₂ and V₂O₅/TiO₂ were defined. The detailed interpretation of normal vibration frequencies is given. The frequencies typical of the monomeric and dimeric oxovanadium forms on the carrier surface were identified.     

Permeation studies on transparent multiple hybrid SiO<Subscript>2</Subscript>-PMMA coatings-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> barriers on PEN substrates

In this work we report the performance of permeation barriers based on organic/inorganic multilayer stacks. We have used PMMA-SiO₂ (poly methyl methacrylate-silica) hybrid films synthesized through a sol–gel route as organic–inorganic components, whereas Al₂O₃ thin films were used as the inorganic component. The hybrid layers were deposited by dip coating and the Al₂O₃ by atomic layer deposition (ALD), films were prepared on polyethylene naphthalene (PEN) substrates. The permeability of the films and stacks is evaluated using helium as the diffusion gas in a custom made ultra-high vacuum system. The results show that permeability for PEN is reduced from 5 × 10⁻³ g/m²-day to about 9 × 10⁻⁵ g/m²-day for the best multiple barrier evaluated. Increased barrier properties are due to the increasing in the path and hence the lag-time of the permeating gas. In particular, we report the surface roughness of the different layers and its impact on the barrier performance. The hybrid layers reduced notably the roughness of the bare PEN substrate improving the quality of the Al₂O₃ layer in the barrier. The optical transmittance of the barriers in the visible region is higher than 80% in all the studied cases.     

Mechanical and optical properties of SiO<Subscript>2</Subscript> thin films deposited on glass

The optical and mechanical properties of amorphous SiO₂ films deposited on soda-lime silicate float glass by reactive RF magnetron sputtering at room temperature were investigated in dependence of the process pressure. The densities of the films are strongly influenced by the process pressure and vary between 2.38 and 1.91 g cm^?3 as the pressure changes from 0.27 to 1.33 Pa. The refractive indices of the films shift between 1.52 and 1.37, while the residual compressive stresses in the deposited films vary in the range from 440 to 1 MPa. Hardness and reduced elastic modulus values follow the same trend and decline with the increase of process pressure from 8.5 to 2.2 GPa and from 73.7 to 30.9 GPa, respectively. The abrasive wear resistance decreases with the density of the films.