Reaction of perfluorobenzocycloalkenes with SiO<Subscript>2</Subscript>-SbF<Subscript>5</Subscript> and skeleton transformations of their carbonyl derivatives in SbF<Subscript>5</Subscript> medium

The reaction of perfluorinated benzocyclobutene and tetraline with SiO₂-SbF₅ led to the formation in a high yield of their mono- and further dicarbonyl derivatives. The monocarbonyl derivatives on heating with SbF₅ underwent disproportionation into the corresponding perfluorobenzocycloalkenes and diketones. Both mono- and diketones in the SbF₅ medium are liable to suffer skeleton rearrangements yielding five- and six-membered oxygen-containing heterocycles and/or products of the opening of the alicyclic fragment of the substrate, and from the perfluorobenzocyclobutenone compounds were also obtained with a number of carbon atoms greater than that of the initial ketone.     

Reaction of Perfluorobenzocyclobutene with Excess Pentafluorobenzene in SbF<Subscript>5</Subscript>

The reaction of perfluorobenzocyclobutene with excess pentafluorobenzene in SbF₅, followed by hydrolysis, gave a mixture of perfluoro-1,3,3-triphenyl-1,3-dihydro-2-benzofuran-1-ol, perfluoro-1,1,2-triphenylbenzocyclobuten- 5-one, and perfluoro-4-(2,2-diphenylbenzocyclobuten-1-ylidene)cyclohexa-2,5-dien-1- one. When the reaction mixture was treated for a long time with Olah’s reagent (HF–pyridine), isomeric perfluoro-9,10-diphenyl-1,4-, -1,10-, -2,9-, and -9,10-dihydroanthracenes were formed and were converted to perfluoro-9,10-diphenylanthracene by the action of SbF₅.     

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.     

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.     

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 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.     

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.     

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.     

Geometry and electronic structure of (SiO<Subscript>2</Subscript>)<Subscript>3</Subscript> clusters

Electronic structure of (SiO₂)₃ clusters was calculated by the density functional method. Charge states were determined using various functionals, bond lengths and total energies of clusters were estimated.     

Opening of the four-membered ring in perfluorinated 1-alkyl-2-phenyl- and 1-aryl-1,2-dihydrocyclobutabenzenes in the system I<Subscript>2</Subscript>-SbF<Subscript>5</Subscript>

Reactions of perfluorinated 1-phenyl-, 1-(2-ethylphenyl)-, 1-(4-ethylphenyl)-, 1-methyl-2-phenyl-, and 1-ethyl-2-phenyl-1,2-dihydrocyclobutabenzenes with iodine in antimony pentafluoride at 130°C, followed by hydroysis of the reaction mixture, resulted in the formation of perfluorinated 2-methyl-, 2-ethyl-2′-methyl-, 4-ethyl-2′-methyl-, 2-ethyl-, and 2-propylbenzophenones via opening of the four-membered ring in the initial cyclobutabenzene at the C¹–C² bond. The presence of hydrogen fluoride facilitates the process and promotes profound transformations leading to anthracene derivatives.     

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.     

Fabrication of gradient density SiO<Subscript>2</Subscript> aerogel

With tetraethoxysilane as the organic precursor, gradient density aerogels were fabricated by three different methods: layer-by-layer gelation, sol-co-gelation and continuous formation technics. Through layer-by-layer method, a 5-layer graded density silica aerogel whose density ranges from 50 to 200 mg/cm³ was obtained, but it existed a dense skin between adjacent layers which could result in density mutation in the interface. In order to optimize its interface character, sol-co-gelation technique was created to improve the interdiffusion and smooth out the density mutation via a self-built device. Finally, on the base of the device and sol-co-gelation technics, a continuous formation process was developed to fabricate the completely gradient density silica aerogel. Optical microscope and X-ray phase contrast method were used to characterize the samples prepared by three different technics and comparatively research their interface feature.     

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.     

Glasses in the CuNbOF<Subscript>5</Subscript>-BaF<Subscript>2</Subscript> and CuNbOF<Subscript>5</Subscript>-PbF<Subscript>2</Subscript> systems

Nonhygroscopic, colored glasses have been synthesized in the CuNbOF₅-BaF₂ and CuNbOF₅-PbF₂ systems proceeding from crystals of the complex compound CuNbOF₅ · 4H₂O. The glasses have been studied structurally and thermally. The crystallization resistance of the glasses has been studied as a function of glass composition. Lead difluoride glasses are more stable than barium difluoride glasses of the same composition. These glasses have lower glass-transition temperatures than the binary glasses formed in the NbO₂F-BaF₂ system. The glass structure is built of Nb(O,F)₆ polyhedra, which are linked in glass networks through oxygen bridges. Modifier cations influence both the structure of glass networks and the linkage of polyhedra.     

Microstructure and Photocatalytic Property of SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> Under Various Process Condition

Nanophase silica-titania particles were prepared by two different synthetic routes, namely, sol–gel and hydrothermal processing. The crystallinity and crystallographic phases, particle size and surface area of the materials were controlled by varying the calcination temperature, and/or the ratio of Si to Ti. It was determined by XRD that the crystallite sizes of SiO₂-TiO₂ prepared by sol–gel and hydrothermal processing decreased from 11 to 6 nm and 12 to 9 nm, respectively, as the mole fraction of silica was increased from 0.1 to 0.4. It is proposed that the presence of the amorphous silica suppresses the growth of anatase TiO₂ grains and their phase transformation to rutile. The photocatalytic decomposition rate of 1,4-dichlorobenzene (DCB) in aqueous solution with the sol–gel derived SiO₂-TiO₂ powder prepared at 750 °C was about 10 ± 5% higher than that observed with Degussa P25, whereas the SiO₂-TiO₂ samples prepared by hydrothermal processing at 250 °C showed a slightly lower decomposition rate than P25.     

Study on chemisorption of H<Subscript>2</Subscript>, O<Subscript>2</Subscript>, CO and C<Subscript>2</Subscript>H<Subscript>4</Subscript>on Pt-Ag/SiO<Subscript>2</Subscript>catalysts by microcalorimetry and FTIR

Adsorption microcalorimetry has been employed to study the interaction of ethylene with the reduced and oxidized Pt-Ag/SiO₂catalysts with different Ag contents to elucidate the modified effect of Ag towards the hydrocarbon processing on platinum catalysts. In addition, microcalorimetric adsorption of H₂, O₂, CO and FTIR of CO adsorption were conducted to investigate the influence of Ag on the surface structure of Pt catalyst. It is found from the microcalorimetric results of H₂and O₂adsorption that the addition of Ag to Pt/SiO₂leads to the enrichment of Ag on the catalyst surface which decreases the size of Pt surface ensembles of Pt-Ag/SiO₂catalysts. The microcalorimetry and FTIR of CO adsorption indicates that there still exist sites for linear and bridged CO adsorption on the surface of platinum catalysts simultaneously although Ag was incorporated into Pt/SiO₂. The ethylene microcalorimetric results show that the decrease of ensemble size of Pt surface sites suppresses the formation of dissociative species (ethylidyne) upon the chemisorption of C₂H₄on Pt-Ag/SiO₂. The differential heat vs. uptake plots for C₂H₄adsorption on the oxygen-preadsorbed Pt/SiO₂and Pt-Ag/SiO₂catalysts suggest that the incorporation of Ag to Pt/SiO₂could decrease the ability for the oxidation of C₂H₄.     

Crystal structure of KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> and KPb<Subscript>2</Subscript>Br<Subscript>5</Subscript>

The KPb₂Cl₅ and KPb₂Br₅ crystals are monoclinic (P2₁/c) with a microtwinned structure. X-ray analysis of chloride resulted in the parameters a = 8.854(2) Å, b = 7.927(2) Å, c = 12.485(3) Å; β = 90.05(3)°, d_calc = 4.78(1) g/cm³ (STOE STADI4, MoK_α, 2θ_max = 80°), R₁ = 0.0702 for 4094 F ≥ 4 σ(F) reflections. For bromide, a = 9.256(2) Å, b = 8.365(2) Å, c = 13.025(3) Å; β = 90.00(3)°, d_calc = 5.62(1) g/cm³ (Bruker P4, MoK_α, 2θ_max = 70°), R₁ = 0.0692 for 3076 F ≥ 4 (F) reflections.     

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).     

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.