Synthesis of silica–titania composite oxide via “green” aqueous peroxo-route

The preparation procedure of silica–titania composite oxide using novel solution/sol single precursor containing titanium peroxocomplex and silicic acid has been described. Pechini-type sol–gel process has been used to prepare oxides from the aqueous precursor. Some structural, morphological and textural characteristics of the prepared material have been presented. Composite SiO₂/TiO₂ has high surface area (c.a. 300 m²/g), and it is composed of anatase nanoparticles with the mean diameter of 5 nm embedded in amorphous silica, then TiO₂ prepared via similar method is presented as a mixture of anatase and rutile phases. The proposed synthetic procedure meets the requirements of “green chemistry”.     

Application of synthesized mesoporous titania microspheres for arsenic [(III) and (V)] uptake studies

The present work describes the application of radiotracer technique for studying uptake of arsenic on titanium hydroxide, commercial titanium dioxide (TiO₂) powder (anatase) and synthesized mesoporous titania beads in acidic, neutral, and alkaline conditions. Sol–gel templating method was used to prepare titania–polysaccharide composites, with different polymer contents. Mesoporous titania was obtained by heat treatment of the composite beads in a controlled environment. The synthesis process was optimized, using thermogravimetry analysis. X-ray diffraction patterns confirmed the formation of anatase pure phase titania (TiO₂) at 700 °C in different environments, and scanning electron microscopy studies confirmed uniform pore size distribution. The effect of surface area, polymer content and pH on uptake of arsenic(III) and (V) on the synthesized titania beads was also investigated. Arsenic(V) was found to be retained quantitatively on the titania beads synthesized from 0.8% polymer content titania–polymer composite precursor in neutral to alkaline conditions. Details of the results obtained are discussed.     

Sustainable fabrication of silver-titania nanocomposites using goji berry (Lycium barbarum L.) fruit extract and their photocatalytic and antibacterial applications

Silver-titania nanocomposites (Ag-TiO₂ NCs) have unique functional attributes due to their photocatalytic and antibacterial properties. In this study, titania nanoparticles (TiO₂-NPs) were successfully in-situ decorated with silver nanoparticles (Ag-NPs) using the aqueous extract of goji berries (Lycium barbarum L.) as a bioreducing and stabilizing agent. Different Ag-TiO₂ NCs were synthesized by treating different concentrations of silver nitrate with a specific concentration of TiO₂-NPs in the presence of fruit extract. The green-synthesized NCs were characterized using several techniques viz., ultraviolet–visible spectrophotometry, X-ray diffractometry (XRD), scanning electron microscopy, field-emission transmission electron microscopy (FE-TEM), Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. XRD analysis revealed the formation of face-centered cubic (fcc) crystals, and FE-TEM analysis revealed the embedment of Ag-NPs throughout the surface of TiO₂-NPs. The average size of Ag-NPs on TiO₂-NPs increased from 11.2 ± 3.05 nm to 16.4 ± 4.5 nm with an increase in the concentration of silver ions, and the morphology of Ag-NPs was predominantly quasi-spherical and hexagonal. These NCs exhibited an excellent photocatalytic degradation of an azo dye, methylene blue (MB). The synthesized Ag-TiO₂ NCs (3:1) showed higher photocatalytic degradation efficiency of ∼ 93.4% for MB in 130 min under visible light irradiation. Ag-TiO₂ NC_S also exhibited good antibacterial activities towards Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative). Therefore, the formation of Ag-NPs on the surface of TiO₂-NPs to form Ag-TiO₂ NCs exhibits eco-friendly photocatalytic degradation of azo dye contaminants as well as antibacterial activity.     

Hierarchical‐Structured Anatase‐Titania/Cellulose Composite Sheet with High Photocatalytic Performance and Antibacterial Activity

Bulk hierarchical anatase‐titania/cellulose composite sheets were fabricated by subjecting an ultrathin titania gel film pre‐deposited filter paper to a solvo‐co‐hydrothermal treatment by using titanium butoxide as the precursor to grow anatase‐titania nanocrystallites on the cellulose nanofiber surfaces. The titanium butoxide specie is firstly absorbed onto the nanofibers of the cellulose substance through a solvothermal process, which was thereafter hydrolyzed and crystallized upon the subsequent hydrothermal treatment, leading to the formation of fine anatase‐titania nanoparticles with sizes of 2–5 nm uniformly anchored on the cellulose nanofibers. The resulting anatase‐titania/cellulose composite sheet shows a significant photocatalytic performance towards degradation of a methylene blue dye, and introduction of silver nanoparticles into the composite sheet yields an Ag‐NP/anatase‐titania/cellulose composite material possessing excellent antibacterial activity against both Gram‐positive and Gram‐negative bacteria.     

High activity of novel Pd/TiO2 nanotube catalysts for methanol electro-oxidation

Electro-oxidation of methanol in sulfuric acid solution was studied using palladium well-dispersed on titanium nanotubes, in relation to methanol oxidation processes in the direct oxidation methanol fuel cell. Pd dispersed on titania nanotubes, which leads to high surface area substrates, showed excellent catalytic activities compared to those of pure Pd and Pd-TiO₂ nanoparticles. TEM results show a narrow distribution of TiO₂ nanoparticles whose particle size is about 10 nm, and uniform nano-sized TiO₂ nanotubes with 10 nm in diameters are seen from HRTEM . A homogeneous structure in the composite nanomaterials is indicated by XRD analysis. The composite electrode activities were measured by cyclic voltammetry (CV) and at 25 °C it was found that 3 wt% Pd in titania nanotubes had the best activity for methanol oxidation.     

Transparent poly(methyl methacrylate)/TiO<Subscript>2</Subscript> nanocomposites for UV-shielding applications

Transparent poly(methyl methacrylate) (PMMA)/TiO₂ nanocomposites have been prepared by solution mixing PMMA with organically soluble titania xerogel. The organically soluble titania xerogel in the form of amorphous phase has been synthesized via a simple sol-gel method, involving hydrolysis of tetrabutyl titanate (TBT) in trifluoroacetic acid (TFA) and gelation. The obtained PMMA/TiO₂ nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), thermogravimetry (TG) and ultraviolet-visible (UV-vis) absorption spectroscopy. The results showed that the interaction between titania nanoparticles and PMMA macromolecular chains led to a homogeneous dispersion of TiO₂ in PMMA matrix. The resulting PMMA/TiO₂ nanocomposites showed improved thermal stability, high transparency and high UV-shielding efficiency with a small amount of titania xerogel (≤3.0 wt %). The present work is of interest for developing a series of transparent UV-shielding nanocomposites.     

Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO₂) nano-photocatalysts, with different phases, prepared using a modified sol?Cgel process were employed in the degradation of rhodamine at 10?mg?L^?1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450?°C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K _app) of 0.023?min^?1. The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024?min^?1 for 450, 500, 550 and 600?°C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017?min^?1, which is similar to that of the commercial titania.     

Synthesis,characterization and evaluation of nanocrystalline anatase titania for the degradation of dibutyl phosphate

Degradation of dibutyl phosphate (DBP) in aqueous solution was successfully demonstrated in this paper using nanoparticles of anatase titania. Nanocrystalline anatase titania employed for the degradation study was synthesized in house by solgel route under stirring mode using titanium ethoxide precursor. The catalyst was characterized using XRD, DRS, BET, TEM, TG–DTA and Raman spectroscopy to establish the catalytic activity and surface morphology. A cylindrical photoreactor was used for the photocatalytic experiments. 10 mg of nano anatase titania and 0.5 mL of 30 % H₂O₂ were used as catalysts for the degradation of 1,000 mL of 240 mg/L DBP. Ion chromatographic procedure was used for following the DBP degradation. More than 95 % of DBP degradation could be in less than 45 min and the kinetics of DBP was found to follow pseudo first order. It was demonstrated that the photocatalytic efficiency of the synthesized titania was better than P-25 titania.     

Hierarchical,Titania‐Coated,Carbon Nanofibrous Material Derived from a Natural Cellulosic Substance

Hierarchical, titania‐coated, nanofibrous, carbon hybrid materials were fabricated by employing natural cellulosic substances (commercial filter paper) as a scaffold and carbon precursor. Ultrathin titania films were firstly deposited by means of a surface sol–gel process to coat each nanofiber in the filter paper, and successive calcination treatment under nitrogen atmosphere yielded the titania–carbon composite possessing the hierarchical morphologies and structures of the initial paper. The ultrathin titania coating hindered the coalescence effect of the carbon species that formed during the carbonization process of cellulose, and the original cellulose nanofibers were converted into porous carbon nanofibers (diameters from tens to hundreds of nanometers, with 3–6 nm pores) that were coated with uniform anatase titania thin films (thickness ≈12 nm, composed of anatase nanocrystals with sizes of ≈4.5 nm). This titania‐coated, nanofibrous, carbon material possesses a specific surface area of 404 m² g^?1, which is two orders of magnitude higher than the titania–cellulose hybrid prepared by atomic layer deposition of titania on the cellulose fibers of filter paper. The photocatalytic activity of the titania–carbon composite was evaluated by the improved photodegradation efficiency of different dyes in aqueous solutions under high‐pressure, fluorescent mercury‐lamp irradiation, as well as the effective photoreduction performance of silver cations to silver nanoparticles with ultraviolet irradiation.     

Ag nanoparticles deposited onto silica,titania, and zirconia mesoporous films synthesized by sol–gel template method

A variety of Ag nanoparticles/oxide mesoporous films with templated silica, titania, and zirconia was synthesized by sol–gel method at glass, aluminum, and silicon substrates using metal alkoxides (tetraethoxysilane, titanium tetraisopropoxide, and zirconium tetrapropoxide) and AgNO₃ as precursors of oxide films and Ag nanoparticles, respectively, and Pluronic P123 as a template agent. Oxide films alone and Ag/oxide composites were characterized using hexane adsorption, X-ray diffraction (XRD), Raman and ultraviolet (UV)/vis spectroscopies, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods. The distribution of Ag nanoparticles within the films, their sizes, intensity, and position of surface plasmon resonance (SPR) absorbance band at λ = 400 nm, as well as the textural and structural characteristics of whole films depend on treatment temperature, types of substrates and oxide matrices, oxide crystallization, and Ag content. Ag nanoparticles form preferably on the outer surface of the films under lower sintering temperatures if the amount of loaded silver is low. Oxide crystallization (e.g., TiO₂) promotes silver embedding into the outer film layer. At higher silver content (≥10 at.%) and higher calcination temperature (873 K), silver nanoparticles could be entrapped more uniformly along the film profile because of more intensive evaporation of silver droplets from the outer surface of the films on heating.     

Aerosol-assisted synthesis of mesoporous titania nanoparticles with high surface area and controllable phase composition

Mesoporous titania nanoparticles (denoted as MTN) with high surface area (e.g., 252 m² g⁻¹) were prepared using tetrapropyl orthotitanate (TPOT) as a titania precursor and 10–20 nm or 20–30 nm silica colloids as templates. Co-assembly of TPOT and silica colloids in an aerosol-assisted process and immediate calcination at 450 °C resulted in anatase/silica composite nanoparticles. Subsequent removal of the silica colloids from the composite by NaOH solution created mesopores in the TiO₂ nanoparticles with pore size corresponding to that of silica colloids. Effects of silica colloids’ contents on MTN porosity and crystallites’ growth at a higher calcination temperature (e.g., 1000 °C) were investigated. Silica colloids suppressed the growth of TiO₂ crystallites during calcination at a higher calcination temperature and controllable contents of the silica colloids in precursor solution resulted in various atomic ratios of anatase to rutile in the calcinated materials. The mesostructure and crystalline structure of these titania materials were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), differential thermal analysis (DTA)-thermo-gravimetric analysis (TGA), and N₂ sorption.     

Preparation of antibacterial polyimide films containing silver nanoparticles

Polyimide/silver composite films were successfully prepared by in situ polymerization. A precursor, AgNO₃ was used as the source of the silver nanoparticles. The structure and morphology of resulting films were characterized by FTIR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Consequently, the silver nanoparticles were well dispersed in polyimide matrix. Meanwhile, thermal properties from thermal gravimetric analyses (TGA) and mechanical properties from tensile test which confirmed composites were kept good performance as compared to pure polyimide. In addition, the antimicrobial activity of polyimide/silver composite films against three different bacteria, B. subtilis, S. aureus, and E. coil, illustrated excellent activity. This composite is potential useful as antimicrobial material with good thermal performance in a wide variety of biomedical and general use applications.     

Preparation and characterization of nanocomposites in system as: SnO<Subscript>2</Subscript>–xTiO<Subscript>2</Subscript> (where <Emphasis Type="Italic">x</Emphasis> = 25, 50 and 75 mol%)

Nanocomposite samples containing various molar compositions of tin and titanium oxides were synthesized by a sol–gel method using octadecylamine as controlling template agent. The structural and the crystalline features of the samples were investigated with Fourier Transformer Infra-red, X-ray diffraction, Transmission electron microscope (TEM) where the surface area was estimated by BET analysis. The crystalline parameters and the particle size were estimated by Rietveld quantitative phase analysis. It is interesting to mention that a reduction in the lattice parameters was detected upon introduction of various molar compositions of titanium oxide revealing that a part of titania is incorporated into the SnO₂ lattice forming Ti_1−xSn_xO₂ solid solution. The quantitative analysis claims that part of titanium oxide is incorporated substitutionally in the crystal lattice of SnO₂, forming a solid solution and other parts are either segregated as separate rutile titania phase or dispersed as amorphous phase on the grain boundary of SnO₂. The results show a remarkable reduction in particle size from 42 to 5 nm and increasing in the specific surface area up to 176 m²/g upon introduction of various content of titania implying the role of titania particles in preventing SnO₂ crystallites from further growing up during the progress of calcination. TEM images show that pure tin oxide particles arranged in large aggregation in wormhole like structure, while the existence of titanium oxide are successfully creates spherical nanoparticles system organized in a definite structure. The optical absorbance spectra indicate a red shift and band gap narrowing upon introduction of titania which increase with increasing in titania contents.     

Comprehensive evolved gas analysis (EGA) of amorphous precursors for S-doped titania by in situ TG–FTIR and TG/DTA–MS in air: Part 2. Precursor from thiourea and titanium(IV)-n-butoxide

Thermal decomposition of an amorphous precursor for sulfur-doped titania (S:TiO₂) nanopowders, prepared by controlled sol–gel hydrolysis-condensation of titanium(IV) tetrabutoxide and thiourea in aqueous butanol, has been studied in situ up to 850 °C in flowing air by simultaneous thermogravimetric and differential thermal analysis coupled online with quadrupole mass spectrometer (TG/DTA–MS) and FTIR spectrometric gas cell (TG–FTIR) for analysis of gases and their evolution dynamics in order to explore and simulate thermal annealing processes of fabrication techniques aimed S:TiO₂ photocatalysts with photocatalytic activities under visible light.The studied S-doped precursor's decomposition course remembers to that of non-doped xerogel from Ti(IV)-n-butoxide, which seems to retard a considerable amount of organics in the solid phase even at high temperature, probably in polymeric forms, proven by evolution of CO₂ in several temperature regions of decomposition stages. The incorporation form of thiourea in the original xerogel seems to be chemically bounded, resulting lower decomposition temperature than that of pure thiourea, and producing evolution of carbonyl sulfide (COS) already between 120 and 190 °C. Nevertheless, evolution of SO₂, and that of CO₂ is also observed above 500 °C by both EGA detection methods. The latter observation implies that the blackish grey samples obtained even at 750 °C might be simultaneously S- and C-doped ones.     

Preparation of polyimide/BaTiO3/Ag nanocomposite films via in situ technique and study of their dielectric behavior

Triphase polyimide nanocomposite films were fabricated using barium titanate （BaTiO3） with high dielectric constant and silver （Ag） with high conductivity as fillers. In situ method was utilized to obtain the homogeneous dispersion of nanoparticles. The in situ polymerization of polyimide precursor-poly（amic acid） was performed in the presence of BaTiO3 particles. Silver compound 1,1,1-trifluoro-2,4-pentadionato silver（I） was added into the BaTiO3 containing poly（amic acid） solution to achieve silver nanoparticles via in situ self metallization technique. The thermally induced reduction converted silver （I） to metallic silver with concomitant imidization of poly（amic acid） to polyimide. Both BaTiO3 and silver nanoparticles were uniformly dispersed in the polyimide substrate. The dependence of dielectric behavior on the BaTiO3 and Ag contents was studied. The incorporation of small amount of silver nanoparticles greatly increased dielectric constant of composite films.     

Multiscale characterization of antimicrobial poly(vinyl butyral)/titania nanofibrous composites

Titania nanofillers were used to reinforce nanofibers in composite mats produced by electrospinning of poly(vinyl butyral) with two different concentrations of polymers. The titania nanoparticles and titania nanotubes were added into an acetic acid/ethanol solution in different contents of 3 and 1 wt%, respectively. The effect of the processing system on the morphology of the produced fibers was analyzed. The antimicrobial poly(vinyl butyral) composite fibers with titanium dioxide nanoparticles and titanium dioxide nanotubes were produced by single and multineedle electrospinning systems. This study reports fabrication of composite nanofibrous mats with significant mechanical and antimicrobial properties at a high production speed, which is promising for commercial applications (health care, photocatalysis, protective clothing, etc.). The reported result revealed an outstanding correlation between values of elastic modulus derived from nanoindentation and dynamic mechanical techniques. Copyright © 2017 John Wiley & Sons, Ltd.     

Decrement of magnetic spin effect in films of polymer composites with rubrene: Interaction of excited states with magnetic nanoparticles

For films of poly(alkane etherimide) composites containing rubrene microcrystals, the effect of Cu–Ni magnetic nanoparticles (MNP) with a reduced Curie temperature T _C (40–60°C) on luminescence and photoconductivity, as well as on the magnetic spin effect, has been observed and studied. It has been shown that this effect depends on the excitation intensity and weak heating (up to T < T _C°C). The assumption has been made that the excited states of the microcrystals (or charge carriers) interact with the MNP surface, leading to a change in their magnetic characteristics.     

Annealing Behavior of Silica Gel Powders Modified with Silver Crystalline Aggregates

The annealing behaviour of silica powders added with silver, prepared by the sol-gel method, was studied using X-ray diffraction. Partial crystallization of amorphous SiO₂ samples as low as 600°C has been observed. For that, silver needed to be added to the precursor solution in such a way that it formed aggregates. Silica xerogel samples were prepared using a molar ratio ethanol/H₂O/TEOS of 4:11.6:1 and loaded with silver in three different ways: in the form of silver nitrate, silver chloride, or chemically synthesised silver fine particles. The microstructure of the silica xerogel powders was studied as a function of annealing temperature. Attention was paid to the evolution of the glass matrix as well as the silver aggregates in the SiO₂ matrix. Partial crystallization of the glass matrix was achieved at temperatures much lower than those specified by the phase diagram, independently of preparation method of the silver aggregates.     

Preparation of nano-silver-supported activated carbon using different ligands

In this study, we investigated the effect of water soluble ligands [i.e., sodium borohydride (NaBH₄), polyvinyl alcohol, glucose and galactose] on the preparation of nano-silver-supported activated carbon (AC). Ligand-stabilized Ag nanoparticle dispersion characteristics were also compared with those of ligand-free Ag nanoparticles. The nanoparticle distribution was investigated using a scanning electron microscope (SEM) which enabled a qualitative analysis of ligand-dependent nanoparticle adsorption onto AC. Silver nanoparticles with average sizes ranging from 7 to 20 nm were synthesized with different coatings. In particular, silver nanoparticles reduced and stabilized by NaBH₄ were found to have a dense and homogenous dispersion of sizes in the range of 100–400 nm on the AC surface. These particles also seemed to remain on the AC surface after rinsing with water. The distribution of silver nanoparticles prepared in the presence of NaBH₄/PVA was not as good as the one prepared with NaBH₄. Their aggregate size varied from 300 to 600 nm on the AC surface and particles greater than 500 nm were eliminated from the AC surface upon rinsing with water. Glucose- and galactose-stabilized silver nanoparticles did not display an extensive adsorption and their adsorption seemed to be poor. However, glucose-stabilized silver nanoparticles could still be detectable to some extent after rinsing, while galactose-stabilized ones could not. Antimicrobial studies showed that all silver-containing carbons studied in this study inhibit bacterial growth and act as bacteriostatic agents.     

Synthesis of highly stable silver nanoparticles using imidazolium-based ionic liquid

Highly stable, aqueous dispersions, and hydrophilic ionic liquid-capped silver nanoparticles with positive surface charge were synthesized by in situ reduction of AgNO₃ with NaBH₄ in the presence of an imidazolium-based ionic liquid, viz., 1-dodecyl-3-methylimidazolium chloride ([C₁₂mim][Cl]) at room temperature. Prepared silver nanoparticles were characterized by UV–vis spectra, transmission electron microscopy (TEM), and zeta potential. UV–visible spectrum of the aqueous medium peaked at 407 nm corresponding to the plasmon absorbance of silver nanoparticles. TEM analysis revealed the spherical shape of the particles with sizes about 9 nm and low polydispersed. The surface charge of the synthesized silver nanoparticles was determined as +5.0 mV. The ionic liquid ([C₁₂mim][Cl]) capped silver nanoparticles were stable for at least 8 months.