Anodic oxidation of pentachlorophenol at Ti/SnO<Subscript>2</Subscript> electrodes

The electrochemical oxidation of dilute aqueous solutions of pentachlorophenol (PCP) using Ti/SnO₂ as an electrocatalytic material has been investigated. The studies were carried out in a two-compartment electrochemical cell at three different current density values (10, 30 and 50 mA cm^–2) at 25 °C and using 20 mg L^–1 of PCP in 0.1 M NaOH (pH 10) as supporting electrolyte. The PCP concentration and the by-products of the oxidized solution were monitored during the oxidation process using UV and HPLC techniques. For the three current densities investigated it was found that the rate of PCP elimination depends only on the specific electrical charge. Likewise, the oxidation mechanism was proved to occur through the participation of adsorbed hydroxyl radicals (·OH) formed on the SnO₂ surface, whatever the current density used. However, as the applied current density was increased, a current efficiency lower than 2% was obtained, which is due to mass transfer limitations. In addition, it was observed that the PCP was mineralized to CO₂ with conversion percentages as high as 92% and at current density values as low as 10 mA cm^–2. The PCP degradation produces two other by-products of oxidation (<10%), namely carboxylic acids, which are non-toxic compounds. Electronic Publication     

Electrochemical determination of 5-hydroxytryptamine using mesoporous SiO<Subscript>2</Subscript> modified carbon paste electrode

A mesoporous SiO₂ was synthesized according to the published work, and then used to modify the carbon paste electrode (CPE). The electrochemical behaviors of 5-hydroxytryptamine (5-HT) at the bare CPE and the mesoporous SiO₂ modified CPE were compared. Owing to the huge surface area, unique mesopores and strong adsorptive ability, the oxidation signal of 5-HT at the mesoporous SiO₂ modified CPE greatly increased, compared with that at the bare CPE. This clearly suggests that the mesoporous SiO₂ modified electrode shows efficient and remarkable enhancement effect towards 5-HT. Based on this, a sensitive, rapid and convenient electrochemical method was developed for the determination of 5-HT after optimizing the experimental parameters such as supporting electrolyte, content of mesoporous SiO₂ as well as accumulation time. The linear range is from 2.0 × 10⁻⁷ to 1.5 × 10⁻⁵ mol/l, and the limit of detection is as low as 8.0 × 10⁻⁸ mol/l after 2-min accumulation. The relative standard deviation (RSD) for 10 mesoporous SiO₂ modified CPEs is evaluated to be 6.7%. Finally, this novel method was successfully used to determine 5-HT in human blood serums.     

Impedance of the SnO<Subscript>2</Subscript>|liquid crystal ZhK-440|SnO<Subscript>2</Subscript> system

The SnO₂|ZhK-440|SnO₂ system, where the ZhK-440 is a liquid crystal mixture consisting of 2/3 parts of p-butyl-p'-methyloxyazoxybenzene and 1/3 part of p-butyl-p'-heptanoyloxyazoxybenzene, was studied by impedance spectroscopy. The impedance spectrum of the system contained the contributions from electric conductivity and bulk and electrode polarizations. The models of bulk and electrode impedance were discussed.     

Solution,Solid-State Two Step Synthesis and Optical Properties of ZnO and SnO<Subscript>2</Subscript> Nanoparticles and Their Nanocomposites with SiO<Subscript>2</Subscript>

Nanostructure luminescent ZnO and SnO₂ materials are prepared by a two-step solid-state method based on the solution preparation of the macromolecular precursors ZnCl₂·Chitosan and SnCl₂·Chitosan having different ratios (1:1, 1:5 and 1:10), their pyrolysis under air at 800 °C. The pyrolytic ZnO and SnO₂ nanomaterials show a dependence of the particle size, morphology and luminescent properties with the ratio [metal/polymer] in the MCl₂·Chitosan precursors. Thus, ZnO semiconductor materials exhibit luminescence spectra with several emission at 440 nm corresponds to a radiative transition of an electron from the shallow donor level of oxygen vacancies, and the zinc interstitial, to the valence band. On the other hand, the photoluminescence spectrum of the nanostructured SnO₂ shows an intense blue luminescence at a wavelength of 420 nm which may be attributed to oxygen-related defects that have been introduced during the growth process of the nanoparticles. Additionally, whereas SnO₂ was successfully incorporated into SiO₂ structure (SnO₂//SiO₂) by pyrolysis of solid-state mixtures of the precursors SnCl₂·Chitosan in the presence of SiO₂, the same reaction carried out with ZnCl₂·Chitosan precursors led to a mixture of Zn₂SiO₄ and SiO₂. Thus, this new methodology yields nanostructured semiconductor materials, ZnO and SnO₂, suitable for optoelectronic and sensor solid-state devices.     

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.     

FePO<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> Catalysts for Propylene Glycol Oxidation

FePО₄/SiO₂ supported catalysts with a different content of iron phosphate are prepared. The properties of the catalyst are changed by the introduction of alkali metal compounds (Na or Cs) on its surface. The samples obtained are characterized by X-ray diffraction, low-temperature nitrogen adsorption, temperatureprogrammed reduction by hydrogen, and temperature-programmed desorption of ammonia. The catalytic properties are investigated in the reaction of gas-phase propylene glycol oxidation. It is shown that the selectivity of methylglyoxal formation on the unmodified catalysts is determined by the state of the supported active component and by its reduction–oxidation ability under the action of a reaction mixture.     

Comparing the electrochemical properties of pure phase Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> and composite Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/C

Compound Zn₂SnO₄ was synthesized by a hydrothermal method in which SnCl₄ · 5H₂O, ZnCl₂ and N₂H₄ · H₂O were used as reactants. Composite Zn₂SnO₄/C was then synthesized through a carbothermic reduction process using the as-prepared Zn₂SnO₄ and glucose as reactants. Comparing to the pure Zn₂SnO₄, some improved electrochemical properties were obtained for composite Zn₂SnO₄/C. When doped with 15% glucose, the composite Zn₂SnO₄/C showed the best electrochemical performance. Its first discharge capacity was about 1500 mA h g⁻¹, with a capacity retain of 500 mA h g⁻¹ in the 40th cycle at a constant current density of 100 mA/g in the voltage range of 0.05–3.0 V. There were also some differences displayed in their cyclic voltammogram.     

Sol-gel synthesis of mesoporous mixed oxides in the ZrO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> system

Simple and convenient method was proposed for synthesis of mixed oxides in the system ZrO₂-SiO₂ (10–60 mol% zirconium dioxide). Starting substances were tetraethylorthosilicate and zirconium chloride octahydrate. The surface properties of the synthesized samples were studied and the degree of their homogeneity and the strength of acid centers were determined.     

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.     

Phase formation in mixed TiO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> oxides prepared by sol-gel method

Pure titania, zirconia, and mixed oxides (3–37 mol.% of ZrO₂) are prepared using the sol-gel method and calcined at different temperatures. The calcined samples are characterized by Raman spectroscopy, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption porosimetry. Measurements reveal a thermal stability of the titania anatase phase that slightly increases in the presence of 3–13 mol.% of zirconia. Practically, the titania anatase-rutile phase transformation is hindered during the temperature increase above 700°C. The mixed oxide with 37 mol.% of ZrO₂ treated at 550°C shows a new single amorphous phase with a surface area of the nanoparticles double with respect to the other crystalline samples and the formed srilankite structure (at 700°C). The anatase phase is not observed in the sample containing 37 mol.% of ZrO₂. The treatment at 700°C causes the formation of the srilankite (Ti_0.63Zr_0.37O_x) phase.     

Conductivity of SnO<Subscript>2</Subscript>-In<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystalline composite films

The conductivity of films consisting of a mixture of SnO₂ and In₂O₃ nanocrystals at 200–500°C was studied. Based on the experimental data, it was assumed that in films containing less than 20 wt % In₂O₃, the current flows along SnO₂ nanocrystals. A model of conductivity in these films is presented; it includes an electron transfer from In₂O₃ to SnO₂, which forms positively charged In₂O₃ nanocrystals that contact the negatively charged SnO₂ nanocrystals. In the presence of In₂O₃ nanocrystals, the activation energy of the electron transfer between SnO₂ nanocrystals decreased substantially because of a decrease in the barrier of electron transfer between SnO₂ crystals under the action of the negative charge. As a result, a percolation cluster of charged SnO₂ crystals formed. At high contents of In₂O₃ (over 20 wt %), the conductivity increased dramatically. The curve of the temperature dependence of conductivity changed because of the appearance of a percolation cluster of In₂O₃ nanocrystals, in which the current passed. The conductivity of a mixed film of this kind differed from that of the nanocrystalline film of pure In₂O₃.     

Synthesis and study of solid acid materials SnO<Subscript>2</Subscript>/B<Subscript>2</Subscript>O<Subscript>3</Subscript>

SnO₂/B₂O₃ samples were produced by a reaction between SnCl₄, H₃BO₃, and (NH₂)₂CO in a boiling aqueous solution. The Sn: B molar ratio in these samples was 1: 1, 1: 2, and 1: 3. The phase composition and degree of crystallinity of these materials was studied. The surface acidity of the samples was analyzed by the method based on a temperature-programmed reaction of dehydration of 2-methyl-3-butyn-2-ol. Thermal transformations of SnO₂/B₂O₃ samples were examined by means of differential-thermal analysis.     

Phase relationships in the SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> system

Phase equilibria in a miscibility gap of the SiO₂-TiO₂ system were studied. A visual polythermal analysis and annealing of samples were performed in a Galakhov microfurnace. The microstructure and composition of the obtained samples were investigated by scanning electron microscopy and electron probe microanalysis. A critical analysis of the experimental data was made. Thermodynamically optimized based on the sub-regular solution model, a phase diagram of the SiO₂-TiO₂ system was constructed.     

Nano particles of iron oxides in SiO<Subscript>2</Subscript> glass prepared by ion implantation

Quartz (SiO₂) glass was implanted with 5 × 10^{16 57}Fe ions/cm² at a substrate temperature of 500 °C, and annealed at temperatures between 700 and 950 °C. The implanted and annealed plates were characterized by conversion electron Mössbauer spectroscopy (CEMS), and measured by a Kerr effect magnetometer or a vibration sample magnetometer. Kerr effect measurement of as-implanted SiO₂ glass showed ferromagnetism at room temperature. CEM spectrum of the as-implanted glass consisted of magnetic relaxation peaks of finely dispersed metallic Fe species, and paramagnetic doublets of Fe³⁺ and Fe²⁺ species. The sample heated at 700 °C contained large grains of metallic Fe and a lot of oxidation products of Fe²⁺ species. After oxidation at temperatures higher than 800 °C, the samples showed also ferromagnetism, which was attributed mainly to ferromagnetic ε-Fe₂O₃ precipitated in SiO₂ matrix. Small amounts of α-Fe₂O₃ were produced at 950 °C. The results suggest that ion implantation and oxidation make a transparent ferromagnetic glass possible.     

Template-free synthesis of hierarchical porous SnO<Subscript>2</Subscript>

Hierarchical porous tin dioxide has been successfully prepared through a fast one-pot template-free synthesis route. The boiling of the mixture of alcohol and glycerol can be utilized to generate nanopores in the SnO₂ monolith. Polycrystalline hierarchical SnO₂ with well proportioned composition has also been obtained in the pore walls of tin dioxide.     

Preparation and performance of potassium-based sorbent using SnO<Subscript>2</Subscript> for post-combustion CO<Subscript>2</Subscript> capture

Potassium-based sorbents using γ-Al₂O₃ or TiO₂ as a support or an additive material have disadvantages in terms of their thermal stability and cyclic CO₂ capture. To overcome the shortcomings of these sorbents, a novel potassium-based sorbent (KSnI30) using SnO₂ was developed in this study. The KSnI30 sorbent formed only K₂CO₃ and SnO₂ phases without any inactive alloy species even after calcination at high temperatures (500–700 °C), indicating the good thermal stability of the KSnI30 sorbent regardless of the calcination temperature. Furthermore, the KSnI30 sorbent has an excellent regeneration property (above 98 %), as well as high CO₂ capture capacities (89–94 mg CO₂/g sorbent). Its excellent regeneration property is due to the formation of a KHCO₃ phase without by-products during CO₂ sorption. These results of the present study demonstrate that the SnO₂ shows promise as a new support or an additive material to replace TiO₂ and γ-Al₂O₃ in the preparation of a regenerable potassium-based sorbent for post-combustion CO₂ capture with good thermal stability and excellent regeneration property.     

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.     

Catalytic properties of SnO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> compositions in total methane oxidation

Tin and titanium dioxides and their compositions were studied as catalysts for the reaction of complete oxidation of methane. The catalytic activity of the test samples was compared in terms of first-order reaction rate constants with reference to the unit surface area of a catalyst. The crystal structures and specific surface areas of the obtained compositions were characterized. The thermal stability of SnO₂ was investigated. Data on the temperature-programmed reduction of SnO₂ and the composition Sn_0.70Ti_0.30O₂ in hydrogen were given.     

Synthesis of BaSnO<Subscript>3</Subscript>/SnO<Subscript>2</Subscript> Nanocomposites as Heterogeneous Additive for Composite Solid Electrolytes

Method of differential thermal analysis was used to study the thermolysis of a mixture of barium oxalate hydrate and α-SnO₂·H₂O, produced by precipitation from hydrochloric solutions. The methods of X-ray diffraction analysis, electron microscopy, and low-temperature nitrogen adsorption were used to examine the reaction products formed at various heating temperatures and determine their phase composition. The nanocomposite BaSnO₃/SnO₂ is the final product of thermolysis and subsequent heating to 950°C. The nanocomposite was used as a heterogeneous oxide additive for obtaining a CsNO₂–BaSnO₃/SnO₂ composite solid electrolyte. The conductivity of the composite exceeds that of the starting salt by more than order of magnitude.     

Stabilization of Oil-in-Water Emulsions with SiO<Subscript>2</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles

Stabilization of oil-in-water Pickering emulsions with SiO₂ and Fe₃O₄ nanoparticles has been studied. Emulsions containing three-dimensional gel networks formed by aggregated nanoparticles in the dispersion media have been shown to be stable with respect to flocculation, coalescence, and creaming. Concentration ranges in which emulsions are kinetically stable have been determined. Stabilization with mixed Ludox HS-30 and Ludox CL SiO₂ nanoparticles leads to the formation of stable emulsions at a weight ratio between the nanoparticles equal to 2 and pH 6.7. In the case of stabilization with Ludox CL and Fe₃O₄ nanoparticles, systems resistant to aggregation and sedimentation are obtained at pH 8. The use of mixed Ludox HS-30 and Fe₃O₄ nanoparticles has not resulted in the formation of emulsions stable with respect to creaming, with such emulsions appearing to be resistant only to coalescence at pH 2–6.