Vladimir Blaskov

Visible light photocatalytic activity of TiO2 deposited on activated carbon

Four photocatalyst samples, prepared from beech sawdust, were synthesized by an original method, combining pyrolysis and impregnation — two of them: TiO2 + activated carbon and other two — only activated carbon. The pyrolysis process has been carried out at two different temperatures — 680°C and 830°C. The prepared samples were characterized by a series of methods — XRD, BET, SEM and DTA/TG. The most important result was achieving visible light photocatalytic activity with an azo dye pollutant for both materials. The TiO2/AC-680°C sample demonstrated higher activity under visible light illumination than the TiO2/AC-830°C sample. The visible light activity was attributed to the active carbon component in the composite materials, which was evidenced by the photocatalytic tests with bare carbon (without any TiO2) manifesting visible light activity. The AC-680°C carbon was superior to the AC-830°C under visible illumination probably due to its higher specific surface area and porous texture. UV-light testing of the photocatalytic activity revealed that the TiO2/AC-680°C sample was higher than that of the TiO2/AC-830°C under polychromatic UV-A illumination (320–400 nm with a maximum at l = 365 nm). The TiO2/AC-680°C sample was also more efficient with the monochromatic UV-C illumination (l = 254 nm).Graphical abstract

Sprayed nanostructured TiO2 films for efficient photocatalytic degradation of textile azo dye

Spray pyrolysis procedure for preparation of nanostructured TiO(2) films with higher photocatalytic effectiveness and longer exploitation life is presented in this study. Thin films of active nanocrystalline TiO(2) were obtained from titanium isopropoxide, stabilized with acetyl acetone and characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The activity of sprayed nanostructured TiO(2) is tested for photocatalytic degradation of Reactive Black 5 dye with concentrations up to 80 ppm. Interesting result of the work is the reduction of toxicity after photocatalytic treatment of RB5 with TiO(2), which was confirmed by the lower percentage of mortality of Artemia salina. It was proved that the film thickness, conditions of post deposition treatment and the type of the substrate affected significantly the photocatalytic reaction. Taking into account that the parameters are interdependent, it is necessary to optimize the preparation conditions in order to synthesize photocatalytic active films.

Effect of the mechanical activation of the reagents on the solid phase synthesis of iron (III) molybdate

Abstract The solid phase synthesis of iron (III) molybdate (Fe 2 (MoO 4 3 ) has been investigated, The synthesis temperature has been lowered by intensive mechanical treatment of the reagents: iron (111) oxide-hydroxide (FeO(OH)) and ammonium paramolybdate ((NH 4 6 (Mo 7 O 24 · 4H 2 O). A decrease of the synthesis temperature by more than 200 K has been demonstrated by a study of the products of interaction between the same nonactivated reagents, After intensive mechanical treatment of the reagents in a centrifugal planetary mill, the synthesis of Fe 2 (MoO 4 ) 3 has been carried out at 673 K, The products of the interaction have been investigated by DTA/TG analysis, XRD, Mossbauer spectroscopy and BET method, The product obtained after mechanical treatment of the reagents is practically single-phase and it is suitable for the needs of heterogeneous catalysis.

Microwave-assisted and conventional sol-gel preparation of photocatalytically active ZnO/TiO2/glass multilayers

AbstractFor the first time a combination of microwaves and/or the conventional treatment method was used to dry and heat multilayered sol-gel ZnO/TiO2/glass structures. Compact or porous TiO2 films were deposited as a bottom layer, covered with a ZnO film.The structures were characterized by X-ray Diffraction (XRD), Energy Dispersive X-ray Spectroscopy (EDX) and Scanning Electron Microscopy (SEM). Only peaks of wurtzite ZnO crystalline phase were registered on the X-Ray diffractograms.The microwave irradiation leads to a formation of poorly crystallized multilayers with very small crystallites and enhanced surface roughness. This results in a better photocatalytic activity of these structures than the structures of the samples treated conventionally.It was established that the morphology of the bottom titania layer affects the reaction of photocatalytic degradation of Malachite Green dye (MG). The structures with the compact bottom TiO2 films showed higher activities than those on porous TiO2 films.This study offers an energy saving method of producing ZnO/TiO2/glass multilayered structures of various morphologies and pronounced photocatalytic properties. The method does not involve any calcination step, normally applied to achieve a good degree of crystallization. This makes the method suitable for protecting substrates of low thermal stability.

Synthesis and Catalytic Activity of Silver-Coated Perlite in the Reaction of Ozone Decomposition

Samples of Bulgarian perlite mineral deposit (natural alumino-silicate glass) in the Rhodope mountain were coated with Ag particles via a spray pyrolysis method. This method allows uniform distribution of the silver particles on the outer shell surfaces. SEM, XPS, FT-IR, and XRD methods were applied for characterization of the samples. The XRD investigations of the pristine samples revealed the formation of metallic silver and a small quantity of Ag2O3 phase. The presence of silver was also confirmed by XPS analysis. It was established that Ag/perlite composite prepared by spray pyrolysis is a promising catalyst for ozone decomposition. The high catalytic activity is preserved during the complete course of the catalytic reaction. After the catalytic activity test some structural and phase changes in the samples were observed. The XRD patterns of the ozonated samples proved the presence of metallic silver, AgO and Ag2O3 phases. The FT-IR analyses revealed that some bands, assigned to Si-O-Si stretching modes, were shifted to lower frequencies after the ozone decomposition test. In general, the spray pyrolysis method turned out to be a very suitable technique for preparation of highly active silver-coated perlite catalyst for efficient ozone removal.

Study of the selectivity of a V2O5−ZrO2 catalyst for partial oxidation ofo-xylene at high temperatures

It has been established that at high temperatures (above 450°C) the V2O5−ZrO2 catalyst exhibits a higher selectivity in the oxidation ofo-xylene to phthalic anhydride than does the conventional V2O5−TiO2(a) catalyst. The catalyst selectivity is found to increase with respect to partial oxidation ofo-xylene, the valuable by-product maleic anhydride being obtained. Studies by different physicochemical methods have shown that V2O5−ZrO2 undergoes no significant phase and structural changes under high-temperature conditions.

Behaviour of Cu(II) hydroxide during mechanical treatment

Abstract It has been established that Cu(II) hydroxide (Cu(OH) 2 ) can be decomposed mechanochemically to CuO. After dry grinding, Cu(OH) 2 is dehydrated for 3 h, while wet grinding (in a cyclohexane medium) for the same period of time cannot ensure that the decomposition process will be completed. During mechanical treatment, the samples are activated, which is confirmed by the broadening of the X-ray lines, the decrease in the temperature of thermal decomposition of Cu(OH) 2 , and the appearance of additional exothermic peaks on the differential thermal analysis curve. The CuO obtained by mechanochemical decomposition is reduced more easily than CuO produced by thermal decomposition of Cu(OH) 2 , regardless of the fact that Cu(OH) 2 has a larger specific surface area.

Effect of post-synthesis acid activation of TiO2 nanofilms on the photocatalytic efficiency under visible light

Nanosized TiO2 films were deposited by spray pyrolysis and thermally treated at 400oC. Then the films were dipped in 1M aqueous solution of HCl. The activated samples were divided into two parts - one part was dried (A) and another was annealed (AT) in air. The photocatalytic degradation of Reactive Black (RB5) textile dye under visible light was tested. The following instrumental methods: X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were applied for the phase and surface characterization of obtained samples. According to Raman and XRD analyses all films are anatase. The XRD showed that activated films are better crystallized than non activated TiO2 film. The presence of chlorine at 200.3 eV was registered for acid activated samples by X-Ray photoelectron spectroscopy. The acidic activated films exhibited higher rate of dye photodegradation than that of the reference TiO2 sample. The photocatalytic efficiency decreases in the order A > AT> non activated TiO2 films. The degradation rate constant for acid activated films is two times higher than those of the reference film. The hydroxyl content in TiO2 acidic activated films is greater than that of the non- activated films, which results in significant increase in the photocatalytic activity. In addition, the presence of chlorine may also lead to enhancement in efficiency.

MANGANESE-DOPED ZINC OXIDE NANOPOWDERS FOR PHOTOCATALYTIC DECOLORATION OF REACTIVE BLACK 5 TEXTILE DYE

Zinc oxide photocatalysts doped with manganese (0.04‐1 at.%) were synthesized via precipitation technique. Their characteristics were studied by Xray diraction (XRD) and BET analysis. The calculated mean size of the crystallites was in the range of 31‐45 nm. Manganese doping of ZnO samples results in slight decrease in crystalline size. Increasing the Mn content in ZnO powders results in a lower photocatalytic activity. The pure ZnO nanopowders decolorate Reactive Black 5 dye under ultraviolet light to almost 92% for 2 h.

Mechanochemically activated synthesis of nanostructured NiFe2O4

Powdery NiFe2O4 has been obtained by mechanothermal treatment. Nickel and iron hydroxides are used as initial compounds. For comparison the initial compounds are calcinated without mechanical treatment (samples obtained by direct heating). The characterization of the samples is carried out by XRD analysis and Mössbauer spectroscopy. It is established that single phase NiFe2O4 is formed after mechanical activation (5 h) and calcination at 773 K. The ferrite synthesized at this temperature contains a smaller quantity of Fe3+ ions in tetrahedral position (31%) than is the case of conventional nickel ferrite (50%). The number of tetrahedrally coordinated iron ions increases with enhancement of the synthesis temperature, approaching the distribution of the tetrahedral and octahedral positions typical of conventional NiFe2O4. The samples obtained by direct heating contain unreacted NiO and α-Fe2O3 even after calcinations at 1073 K.