0000000000382693
AUTHOR
A. Di Paola
Preparation and photoactivity of nanocrystalline TiO2 powders obtained by thermohydrolysis of TiOSO4
Nanocrystalline TiO2 photocatalysts were synthesized in mild conditions by thermohydrolysis of TiOSO4 in water at 100 °C and post-calcination treatment at various temperatures. The TiO2 powders were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, specific surface area determinations, scanning electron microscopy and electron paramagnetic resonance measurements. The photoactivity of the samples was tested employing the photodegradation of 4-nitrophenol in liquid–solid regimen and the photooxidation of gaseous 2-propanol. The best results were obtained with the powder calcined at 600 °C for 10 h. Surprisingly, the not calcined sample was the most active for the abatement…
Coupled Semiconductor Systems for Photocatalysis. Preparation and Characterization of Polycrystalline Mixed WO3/WS2 Powders
Mixed WO3/WS2 powders were prepared by oxidation of WS2. The physical properties of the samples were characterized by X-ray diffraction, diffuse reflectance spectroscopy, and scanning electron microscopy; they were strongly dependent upon the time and temperature of oxidation. The chemical state and the elemental distribution of the sample surface were investigated by X-ray photoelectron spectroscopy. The photocatalytic results have showed that the aqueous suspensions of the mixed WO3/WS2 systems have significantly higher activities than pure WS2 and WO3 for the photodegradation of phenol. The enhanced performance can be related to the presence of heterojunctions WO3/WS2 on the single parti…
Photocatalytic behavior of mixed WO3/WS2 powders
Polycrystalline mixed WO3/WS2 powders have been prepared by different methods. The samples have been characterized by bulk and surface techniques and tested as catalysts for the photodegradation of phenol. The results have indicated that the coupling of WO3 and WS2 leads to an enhanced rate of disappearance of the organic substrate. The effect is explained as the result of the simultaneous electron transfer from WS2 to WO3 and hole transfer from WO3 to WS2. The efficiency of the mixed WO3/WS2 systems strongly depends on the relative amounts of WO3 and WS2 in the various samples. A maximum of photoactivity is obtained when the surface WS2 and WO3 molar fraction is about 0.5.
Photocatalytic degradation of organic compounds in aqueous systems by transition metal doped polycrystalline TiO2
Abstract Some probe catalytic photooxidation reactions with aliphatic and aromatic organic compounds having different acid strengths, i.e. methanoic acid, ethanoic acid, benzoic acid and 4-nitrophenol, were carried out in aqueous systems by using polycrystalline TiO2 powders doped with various transition metal ions (Co, Cr, Cu, Fe, Mo, V and W). The Co-doped powder showed to be more photoactive than the bare TiO2 for methanoic acid degradation while the behaviour of TiO2/Cu and TiO2/Fe was similar to that of the support. TiO2/W was the most efficient sample for the photodegradation of benzoic acid and 4-nitrophenol, TiO2 the most active powder for ethanoic acid. A tentative explanation is p…
Preparation in mild conditions of photocatalytically active nanostructured TiO2 rutile
Abstract Nano structured TiO 2 rutile samples were prepared in mild conditions by hydrolysis of TiCl 4 in different solutions. The powders revealed a fair photoactivity for the photoeatalytic degradation of 4-nitrophenol. The influence of preparation procedure, pH and presence of Cl − and N 3 − anions on the physicochemical features and photocatalytic activity of the powders was investigated.
Preparation of N-doped TiO2: characterization and photocatalytic performance under UV and visibile light
Nanocrystalline N-doped TiO(2) samples were prepared by using TiCl(4) or TiOSO(4) as precursors. The powders were characterized by X-ray diffraction, BET specific surface area measurements, scanning electron microscopy, diffuse reflectance spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was tested using the photodegradation of 4-nitrophenol under UV and visible light.Some samples were more active than commercial Degussa P25. A shift of the absorption edge to a lower energy and a stronger absorption in the visible light region were observed in the samples obtained from TiCl(4). Two absorption edges were observed in the samples derived from T…
Tools for quality assurance and assessment of Agricultural Engineering programmes, TUNING subject-area lines and disappearing/rare knowledge in Italy
The quality assurance process applied by Italian State University institutions, in order to achieve some level of internal quality control or assessment for the offered study programmes, is established in the funding criteria of the Ordinary Financing Fund (FFO), decided by the National Committee for the Evaluation of the University System (CNVSU). In most Italian Universities the quality assurance and assessment procedure of the study programmes starts with a report, written by a specific committee, that carries out an internal assessment, by which the strong and weak points of the study programme and the related causes are focused. The quality assurance and assessment procedure appoints t…
Anodic oxide films on tungsten—I. The influence of anodizing parameters on charging curves and film composition
Abstract The formation of anodic films on tungsten has been studied in 1N solutions of H 2 PO 4 , H 2 SO 4 , HNO 3 , HClO 4 and HCl at different temperatures. The shape of the anodic charging curves depends on the electrolyte composition and on the temperature. The chemical composition of the films is strongly influenced by the working temperature. The first step of the anodization is the formation of a barrier film of amorphous WO 3 . The thickening of the oxide layer occurs on account of the WO 3 dissolution and following precipitation of sparingly soluble oxides on the electrode surface.
Complete characterization of low-noise devices at microwave frequencies: two alternative procedures for HEMTs
Fast and efficient procedures for determining the microwave noise parameters of HEMT's at decreasing temperatures
Noise parameters are an electrical representation of the noise performance of transistors which is widely used in reliability studies as well as in the design of low-noise microwave amplifiers. Such parameters are usually determined by employing a complex indirect (standard) procedure based on multiple noise figure measurements and appropriate data processing techniques. We report here two altemative and rapid methods used to perform the complete noise characterization of HEMT's at decreasing temperatures over the 6 to 18 GHz frequency range. The results show a very satisfactory agreement.among the different procedures thus assessing the inherent consistency of the global approach to the pr…
Preparation and Characterization of Tungsten Chalcogenide Photocatalysts
Tungsten chalcogenides powders have been prepared by sulfidation of WO3 with gaseous H2S. Different mixed WS2/WO3 systems have been obtained by varying the amount of initial WO3 powder, the time, o...
Photocatalytic activity of TiO2/SiO2 systems
Silica-supported TiO(2) powders were synthesized by a wet method under mild conditions. The aim of the work was the preparation of TiO(2)/SiO(2) additives for photocatalytic cements. Three types of commercial SiO(2) were used as supports: Cabot, Axim and Fly Ash. Cabot silica was ultra-pure whereas the other two silica contained different percentages of various oxides. The TiO(2)/SiO(2) samples, denoted TiO(2)/Cabot, TiO(2)/Axim and TiO(2)/Fly Ash, were prepared by boiling suspensions obtained by addition of silica to a solution of TiCl(4) in water (volume ratio 1:10). The photocatalytic activity was evaluated in a gas-solid system both in batch and in continuous reactors using 2-propanol a…
Photoactivity of Nanostructured TiO2 Catalysts in Aqueous System and their Surface Acid-Base, Bulk and Textural Properties
This work reports on the characterisation and determintion of the photocatalytic activity of some TiO2 catalysts prepared using TiCl4 as precursor. The samples, consisting of suspensions, dispersions or powders of nanonstructured anatase or rutile phases, were obtained in very mild conditions, i.e., by boiling the solution obtained after hydrolysis of TiCl4 at atmospheric pressure: it is worth noting that no calcination was necessary to obtain photoactive phases. The samples were characterised by X-ray diffraction (XRD), determination of the BET specific surface area (SSA), scanning electron microscopy (SEM) observations and diffuse reflectance spectroscopy (DRS). FT-IR spectroscopy was use…
ChemInform Abstract: Preparation and Characterization of Tungsten Chalcogenide Photocatalysts.
Tungsten chalcogenides powders have been prepared by sulfidation of WO3 with gaseous H2S. Different mixed WS2/WO3 systems have been obtained by varying the amount of initial WO3 powder, the time, o...
TiO2 photocatalysts prepared by thermohydrolysis of TiCl4 in aqueous solutions
Abstract Nanostructured TiO 2 photocatalysts were synthesized by thermohydrolysis of TiCl 4 at 100 °C in various aqueous solutions. Anatase or rutile, binary mixtures of anatase and rutile or anatase and brookite, and ternary mixtures of anatase, brookite and rutile were obtained depending on the hydrolysis solution. The most efficient catalysts consisted of ternary mixtures of the three polymorphic TiO 2 phases.
Study on a photocatalytic membrane reactor for water purification
Abstract Some results obtained in a photocatalytic membrane reactor, to be used for degradation of toxic organic species dissolved in water, are reported. The catalyst, TiO 2 P25 Degussa, was immobilised by means of a flat sheet polymeric membrane and 4-Nitrophenol (4-NP) was used as a model molecule to evaluate the reactor performance. A preliminary investigation of the stability, under UV irradiation, of some eligible polymeric membranes was carried out by using scanning electron microscopy (SEM), optical microscopy (OM), determinations of water permeation flux (WPF) and total organic carbon (TOC). These tests showed that commercial membranes made of fluoride + PP (FS 50 PP-Dow), polysulp…
Photocatalytic behaviour of metal-loaded TiO2 aqueous dispersions and films
Abstract Titanium dioxide nanoparticles loaded with Ce, Co, Eu, Sm, W and Yb species were prepared by coprecipitation in mild conditions using TiCl 4 as precursor with the aim to enhance the photocatalytic activity, especially under visible light irradiation. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SSA) determination and UV–Vis diffuse reflectance spectroscopy. The photocatalytic activity of the powders of pure and loaded TiO 2 was investigated by employing the photodegradation of 4-nitrophenol as probe reaction in a liquid–solid system. Loading with suitable amounts of W, Co and Sm resulted in a significan…
Preparation of Photocatalytic Nanostructured TiO<sub>2</sub> Thin Films
Photoactive films consisting of pure anatase, brookite or rutile were deposited on glass slides by a dip coating process from water dispersions or solutions obtained by using TiCl4 as the precursor. The films were characterized by X-ray diffraction, scanning electron microscopy and atomic force microscopy. The photocatalytic activity of the various samples was evaluated by using the photooxidation of 2-propanol in gas solid regime as probe reaction. Brookite and anatase films showed a good photoactivity degrading the substrate and the propanone produced during the reaction.
Photocatalytic thin films of TiO2 formed by a sol-gel process using titanium tetraisopropoxide as the precursor
Abstract Thin TiO 2 films were prepared with the dip-coating technique by using sols deriving from titanium tetraisopropoxide. TiO 2 films were formed on glass substrates previously covered by a SiO 2 layer obtained from a tetraethylortosilicate sol. The films, after a thermal treatment at 673 K, mainly consisted of TiO 2 anatase. The samples were characterised by X-ray diffraction, UV–Vis spectroscopy, scanning electron microscopy and atomic force microscopy. The photoactivity of the various films was tested by using as probe reaction the photo-oxidation of 2-propanol in gas-solid regime. The photoreactivity results indicated that the TiO 2 films were efficient for degrading 2-propanol und…
Up to Date Version of a Computer-Driven Noise Figure Measuring System for the Simultaneous Determination of Noise, Gain and Scattering Parameters of Microwave Transistors
The complete characterization of microwave transistors in terms of (four) noise, (four) gain and scattering parameters sets ({N), {G) and [SI, respectively) vs. frequency and bias conditions (and also vs. decreasing temperature, if required) is the first and most important step to design low noise amplifiers (LNAs). The characterization of the device under test (DUT) in terms of [SI is friendly by means of commercial Automatic Network Analyzer; then the { G) set may be determined by computation.
Heterogeneous photocatalytic degradation of nitrophenols
The photocatalytic degradation of 2-, 3- and 4-nitrophenol has been investigated in oxygenated aqueous suspensions containing TiO2. The organic reaction intermediates have been determined by high performance liquid chromatography. The results indicate the complete mineralisation of the substrates and the formation of both nitrate and ammonium ions. The degradation pathways involve a rapid opening of the aromatic ring followed by a slower oxidation of the aliphatic compounds. The hydroxyl radicals are responsible for the primary attack of the nitrophenols with formation of dihydroxynitrobenzenes. The ring hydroxylation occurs in the positions activated by the contemporaneous presence of phen…
Preparation of photocatalytic brookite thin films
Pure brookite films were deposited from a brookite dispersion obtained by peptizing a mixture brookite–rutile prepared by thermolysis of TiCl4 in a HCl solution. The films were characterised by X-ray diffraction and Raman spectroscopy. The photoactivity of the samples was tested by using the photo-oxidation of 2-propanol in gas–solid regime as a probe reaction. The brookite films efficiently degraded 2-propanol under UV illumination.
Photocatalytic activity of TiO2 thin films prepared in the presence of organic and inorganic additives
Three Different Methods for Determining the Microwave Noise Parameters of HEMT's at Decreasing Temperatures
The noise characteristics of any transistor are usually represented by means of four parameters which are frequency-, bias- and temperature-dependent, similarly to the scattering parameters. The noise parameters are determined by a standard indirect procedure based on multiple noise figure measurements and appropriate data processing techniques requiring a complex instrumentation set-up and skilled operators. As an alterative way, we have shown that the noise parameters of packaged HEAMT's can be computed with very good accuracy from the analysis of a noisy circuit model derived from the scattering parameters plus a single noise figure measurement. A third way exists for the determination o…
Preparation of Sm-loaded brookite TiO2 photocatalysts
Abstract Pure and Sm-loaded brookite nanoparticles and thin films were prepared using TiCl4 as precursor of TiO2. The samples were characterized by X-ray diffraction (XRD), specific surface area (SSA) determination, diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) measurements. The photocatalytic activity of the powders was investigated by employing the photodegradation of 4-nitrophenol in a liquid–solid system whilst the photoreactivity of the films was tested by evaluating the rate of degradation of 2-propanol in a gas–solid system. Loading with Sm resulted in a significant improvement of the photoreactivity of brookite and the beneficial effect was attributed to an incre…
Anodic oxide films on tungsten—II. The morphology and dissolution of the films
Abstract Scanning electron microscopy was used to investigate the morphology of anodic oxide films on tungsten, obtained in various conditions of anodization. Studies were made of the growth of porous films, whose thickness increases with time and depends upon the current density. Temperature and electrolyte composition influence the film morphology. Gravimetric measurements of film dissolution at 70°C show that after a transient time, the rate of metal dissolution and that of film formation coincide. The porous films thicken because tungsten dissolves as WO 2 2+ and precipitates as WO 3 .H 2 O.
Effect of the TiO2 crystalline structure on the photocatalytic production of hydrogen
Removal of drugs in aqueous systens by photoassisted degradation
Aqueous solutions of tetracycline, lincomycin and ranitidine were irradiated with UV light in homogeneous and heterogeneous systems. Two commercial polycrystalline TiO2 powders (Degussa P25 and Merck) were used as photocatalysts. After 5A h, an appreciable photolytic degradation of tetracycline and ranitidine was observed while the degradation of lincomycin was noticeably lower. As far as the mineralization is concerned, a small decrease of the TOC values was measured in the case of tetracycline whereas negligible variations were found for lincomycin or ranitidine. The presence of the photocatalysts greatly enhanced the degradation rates of the drugs with respect to those observed during th…
ChemInform Abstract: Coupled Semiconductor Systems for Photocatalysis. Preparation and Characterization of Polycrystalline Mixed WO3/WS2 Powders.
Mixed WO3/WS2 powders were prepared by oxidation of WS2. The physical properties of the samples were characterized by X-ray diffraction, diffuse reflectance spectroscopy, and scanning electron microscopy; they were strongly dependent upon the time and temperature of oxidation. The chemical state and the elemental distribution of the sample surface were investigated by X-ray photoelectron spectroscopy. The photocatalytic results have showed that the aqueous suspensions of the mixed WO3/WS2 systems have significantly higher activities than pure WS2 and WO3 for the photodegradation of phenol. The enhanced performance can be related to the presence of heterojunctions WO3/WS2 on the single parti…
A novel noise figure and gain test set for microwave devices
A new instrument for the measurement of noise and gain of microwave devices is presented. It differs from the commercial ones in the accomplishment of the gain measurement and is also useful for measuring mismatched devices such as transistors, The instrument is driven via HP-IB by a PC and a user-friendly virtual panel is designed to perform all the required operations. Also included is the possibility of removing the second-stage noise contribution and correcting various sources of error (source ENR variations, temperature variations, etc.). The test set provides a very good accuracy for both matched and mismatched devices, usually limited by source ENR accuracy and step attenuator repeat…
Photochemical and photocatalytic isomerization of trans -caffeic acid and cyclization of cis -caffeic acid to esculetin
Abstract The photoisomerization of trans-caffeic acid to cis-caffeic acid has been studied in the presence of N2 in homogeneous aqueous solutions and in suspensions of various TiO2 catalysts. The results supported the hypothesis of an energy transfer process from TiO2 to the substrate due to the recombination of the photogenerated electron–hole pairs. The differences among the measured photostationary [cis]/[trans] ratios have been attributed to the different physico-chemical properties of the catalysts. In particular, the lowest ratio measured in the presence of Merck TiO2 was ascribed to the very low adsorption of trans-caffeic acid onto the surface of this sample. In the presence of O2 a…
Preparation and photoactivity of samarium loaded anatase, brookite and rutile catalysts
Abstract Pure and samarium loaded anatase, brookite and rutile nanopowders were synthesized by thermohydrolysis of TiCl 4 . The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SSA) determination, UV–vis diffuse reflectance spectroscopy (DRS), atomic force microscopy (AFM), contact angle (CA) measurements and photoluminescence (PL) spectroscopy. The photocatalytic activity of pure and Sm-loaded TiO 2 polymorphs was investigated by employing the photodegradation of 4-nitrophenol as probe reaction in a liquid-solid system. Loading with Sm resulted in an improvement of the photoreactivity of the three TiO 2 polymorphs. The benefi…
The Multi-frequency Robotic facility REM: first results
The REM Observatory, recently installed and commissioned at la Silla Observatory Chile, is the first moderate aperture robotic telescope able to cover simultaneously the visible-NIR (0.45-2.3 microns) wavelength range. Due to its very fast pointing and its full robotization REM is conceived for fast transients observation. The high throughput Infrared Camera (REMIR) and the Visible imaging spectrograph (ROSS), simultaneously fed by a dichroic, allow to collect high S/N data in an unprecedented large spectral range on a telescope of this size. The REMobservatory is an example of a versatile and agile facility necessary complement to large telescopes in fields in which rapid response and/or t…
A tensiostatic study of the anodic behaviour of tungsten in acid solutions
Abstract Tensiostatic anodization of tungsten has been studied in 1 N solutions of H 2 SO 4 , HClO 42 , HNH 2 SO 3 and HCl at 25 °C. For several voltage values, the curves of current vs . time and open-circuit voltage vs . time have been obtained. All results indicate that the oxide films produced during the polarization are slowly dissolved in the acid solutions. The HCl, and to a lesser extent the HNH 2 SO 3 solutions, show a more aggressive behaviour. For values of the applied voltage above about 50 V, gas evolution begins. In the case of HCl solutions, the gas is Cl 2 and the electrode is rapidly corroded.
The role of water in the photocatalytic degradation of acetonitrile and toluene in gas-solid and liquid-solid regimes
Photocatalytic degradation of acetonitrile and toluene was carried out both in gas-solid and in liquid-solid regimes by using commercialTiO2samples (Merck and Degussa P25). The investigation was mainly aimed to study the influence of water present in the reaction environment on the mechanism and degradation rate of two probe molecules. In gas-solid regime, the reacting mixture consisted of toluene or acetonitrile, oxygen, nitrogen, and water vapour. The main degradation product of toluene wasCO2with small amounts of benzaldehyde. In the presence of water vapour, the activity ofTiO2Merck remained stable but greatly decreased if water was absent.TiO2Degussa P25 continuously deactivated, even …
Comparison between two measuring methods for complete characterization of low-noise HEMTs at microwaves
The good performances of a set-up for the complete characterization of HEMTs up to 40 Ghz in terms of noise and scattering parameters through noise figure measurements only are shown by many experimental results. Because of some inconveniences in practice the use of the method is suggested for research laboratories only. For industrial applications an alternative symplified method is proposed whose performances are shown to be in surprising agreement with the ones of the standard method.
Kinetics of coloration of anodic electrochromic films of WO3·H2O
Polycrystalline layers of WO3·H2O are obtained by anodization of tungsten in 1 N H2SO4 at 70° C. The cathodic reduction of these layers in acid solutions causes the formation of blue WO3−x·H2O (0<x⩽:0.12) oxides. The kinetics of coloration are investigated by galvanostatic and potentiostatic techniques. The experimental results are compared with the theoretical data obtained by solving the diffusion equation for a constant flow of oxygen vacancies and for a time-dependent surface vacancy concentration. Except in the initial stage of coloration, the process controlling rate can be ascribed to the diffusion of oxygen vacancies from the oxide-electrolyte interface into the bulk of the layers. …
Preparation of polycrystalline TiO2 photocatalysts impregnated with various transition metal ions : characterization and photocatalytic activity for the degradation of 4-nitrophenol
A set of polycrystalline TiO2 photocatalysts loaded with various ions of transition metals (Co, Cr, Cu, Fe, Mo, V, and W) were prepared by using the wet impregnation method. The samples were characterized by using some bulk and surface techniques, namely X-ray diffraction, BET specific surface area determination, scanning electron microscopy, point of zero charge determination, and femtosecond pump-probe diffuse reflectance spectroscopy (PP-DRS). The samples were employed as catalysts for 4-nitrophenol photodegradation in aqueous suspension, used as a probe reaction. The characterization results have confirmed the difficulty to find a straightforward correlation between photoactivity and si…