Surface characterisation of metal ions loaded TiO2 photocatalysts: structure–activity relationship
Abstract Transition metal loaded TiO 2 powders were characterised and tested for the photodegradation of some organic acids. Both Lewis and Bronsted surface acid sites were present in the samples containing large amounts of Mo, V and W. The Bronsted sites are associated to the presence of the transition metals as they do not exist in the unloaded support, and in particular to the presence of these metals in high oxidation states. The trend of the pzc values of the various powders matches rather well both with the surface acidity of the samples experimentally determined by NH 3 adsorption and with a scale of acidity/basicity for bulk binary oxides. XPS investigation indicates that only the p…
Surface properties of iron-titania photocatalysts employed for 4-nitrophenol photodegradation in aqueous TiO2 dispersion
Iron(III) doped specimens (0.01–5% atomic Fe ∶ Ti) have been prepared by impregnating polycrystalline “home prepared” TiO2 (mainly anatase) and have been studied for photocatalytic degradation of 4-nitrophenol in aqueous dispersions. Some structural and surface properties have been studied by X-ray diffraction, specific surface area and porosity measurements and FTIR monitoring of pyridine, ammonia and methanoic acid adsorption for surface acidity and basicity. Their surface properties were compared with a corresponding series of photocatalysts prepared by a coprecipitation method. Adsorption of pyridine and ammonia indicates the presence of surface acid Lewis sites, a low concentration of …
Preparation, Characterization and Photocatalytic Activity of TiO2 Impregnated with the Heteropolyacid H3PW12O40: Photo-assisted Degradation of 2-propanol in Gas-Solid Regime
Abstract Both commercial and home prepared TiO2 samples impregnated with tungstophosphoric acid (H3PW12O40) were prepared and used for the photo-assisted degradation of 2-propanol in gas–solid regime. The characterization results evidenced a good coverage of the polyoxometalate (POM) onto the surface of both types of TiO2 samples along with a marginal effect of the presence of ethanol or HCl during the POM impregnation step on the specific surface area, porosity, morphology, crystallinity and acidity of the samples. Propene was the main intermediate product found in 2-propanol photocatalytic degradation by using the samples containing POM as the photocatalyst, whereas propanone was mainly o…
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…
Zn,Al hydrotalcites calcined at different temperatures: Preparation, characterization and photocatalytic activity in gas–solid regime
Abstract Layered double hydroxides (LDH) containing zinc and aluminium within the brucite-like layers and carbonate as the interlayer anion have been used as precursors for the preparation of mixed metal oxides by calcination. Zinc oxide and the ZnAl 2 O 4 spinel were formed with different degree of crystallinity depending of two parameters, i.e., the Zn 2+ /Al 3+ molar ratio and the calcination temperature (500–800 °C) of the LDH precursor. A pure spinel phase was obtained to remove ZnO upon a basic post-treatment in NaOH solution of the samples calcined at 800 °C. All the samples were tested for the photodegradation of 2-propanol in gas–solid regime. All the samples resulted active as het…
Preparation and characterisation of TiO2 (anatase) supported on TiO2 (rutile) catalysts employed for 4-nitrophenol photodegradation in aqueous medium and comparison with TiO2 (anatase) supported on Al2O3
Abstract In this paper the preparation of two sets of polycrystalline photocatalysts prepared by supporting TiO2 (anatase) on TiO2 (rutile) or Al2O3 is reported. The powders were prepared by a wet impregnation method using titanium(IV) isopropylate. The impregnation was followed by thermal treatment and this procedure was repeated several times in order to obtain samples with progressively increasing amounts of TiO2 (anatase). The photocatalytic activity of all of the specimens was tested by carrying out the 4-nitrophenol photodegradation, used as a “probe” reaction, in aqueous medium and in different kinds of batch photoreactors. The solids were characterised by X-ray diffraction (XRD), sp…
Inorganic gels as precursors of TiO2 photocatalysts prepared by low temperature microwave or thermal treatment
Abstract A simple procedure for preparing active TiO2 photocatalysts is presented. The starting materials were unusual TiO2 gels formed from TiCl4. The use of microwaves for a very short time enhanced the TiO2 crystallinity preventing an increase of particle size and minimizing the decrease of specific surface area. This result makes this preparation very attractive. The formation of the gels was monitored through measurements of viscosity. All the samples were characterized by means of X-ray diffraction, diffuse reflectance spectroscopy and BET specific surface area measurements. The photoactivity of the samples was evaluated using the photodegradation of 4-nitrophenol in liquid–solid regi…
Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO2 systems. 1. Surface and bulk characterization
Polycrystalline ZnO/TiO2 solids have been prepared with four different methods using home prepared TiO2 (anatase) or TiO2 (rutile) as supports and Zn(NO3)2·6H2O or Zn(CH3COO)2·2H2O as precursors for ZnO. The bulk and surface properties of the samples were investigated by means of TG-DTA, XRD, TEM, SEM-EDAX, XPS, BET surface area determination, and porosity measurements. XRD and TEM results indicate that no significant defect structures exist in any of the samples. The ZnO crystallinity and its enrichment on the surface of TiO2 particles were dependent on the preparation method. The surface areas generally decrease by increasing the amount of ZnO except when ZnO from Zn(CH3COO)2·2H2O was sup…
Structural and surface characterization of the polycrystalline system CrxOy · TiO2 employed for photoreduction of dinitrogen and photodegradation of phenol
The polycrystalline system CrxOy-TiO2, used as a catalyst for photoreactions, was studied by X-ray diffractometric method, visible-ultraviolet diffuse reflectance and infrared spectroscopic methods, surface area determination, and porosimetry to characterize its structural and surface features. Two series of catalysts were prepared by two different methods, namely by coprecipitation and by impregnation. The first series was tested as photocatalysts for the dinitrogen photoreduction in a gas-solid regime and for the phenol photodegradation in a liquid-solid regime. The results indicate that the interaction of chromium ions with OH groups modifies the surface properties of the supports and co…
Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO2 systems. 2. Surface, bulk characterization, and 4-nitrophenol photodegradation in liquid-solid regime
Electron spin resonance spectroscopy (ESR), Fourier transform infrared spectroscopy (FTIR), and monitoring of pyridine (py) and boric acid trimethyl ester (BATE) adsorption for determining surface acidity and basicity, respectively, were used to carry out further characterization of mixed ZnO/TiO2 polycrystalline solids prepared by different methods. Moreover, the powders were tested in a batch photoreactor for a probe reaction, i.e., 4-nitrophenol photodegradation in aqueous medium. ESR results indicated the presence of signals attributable to Zn+ species in ZnO/TiO2 (anatase) solids, while in ZnO/TiO2 (rutile) samples the presence of zinc induced only the formation of signals probably due…
Tungstophosphoric acid supported on polycrystalline TiO2 for the photodegradation of 4-nitrophenol in aqueous solution and propan-2-ol in vapour phase
Abstract The present work reports the preparation of samples based on Millennium PC-500 TiO 2 loaded with different amounts of tungstophosphoric acid (up to 30% in weight) and their characterisation by means of different physicochemical techniques: powder X-ray diffraction, N 2 adsorption–desorption at −196 °C, transmission electron microscopy, UV–vis and FT-IR spectroscopies and thermogravimetric analyses. The acidity of samples was evaluated by FT-IR using pyridine as probe molecule, and the catalysts activity was tested for the photodegradation of 4-nitrophenol in aqueous solution and for the photo-oxidation of propan-2-ol in vapour phase. The results show a noticeable improvement (8 and…