Combined TiO2/SiO2 mesoporous photocatalysts with location and phase controllable TiO2 nanoparticles

Combined TiO₂/SiO₂ mesoporous materials were prepared by deposition of TiO₂ nanoparticles synthesised via the acid-catalysed sol–gel method. In the first synthesis step a titania solution is prepared, by dissolving titaniumtetraisopropoxide in nitric acid. The influences of the initial titaniumtetraisopropoxide concentration and the temperature of dissolving on the final structural properties were investigated. In the second step of the synthesis, the titania nanoparticles were deposited on a silica support. Here, the influence of the temperature during deposition was studied. The depositions were carried out on two different mesoporous silica supports, SBA-15 and MCF, leading to substantial differences in the catalytic and structural properties. The samples were analysed with N₂-sorption, X-ray diffraction (XRD), electron probe microanalysis (EPMA) and transmission electron microscopy (TEM) to obtain structural information, determining the amount of titania, the crystal phase and the location of the titania particles on the mesoporous material (inside or outside the mesoporous channels). The structural differences of the support strongly determine the location of the nanoparticles and the subsequent photocatalytic activity towards the degradation of rhodamine 6G in aqueous solution under UV irradiation.     

Removal of cyanides in wastewater by supported TiO2-based photocatalysts

Titania supported samples on different types of silica have been prepared through a sol–gel method followed by hydrothermal processing. The photocatalytic activity of the samples was tested for free cyanides photo-oxidation. As compared to commercial TiO₂ all the synthesised materials showed not only similar photocatalytic efficiencies but improved recovery properties. The degradation of iron(III) cyanocomplexes was also studied in the absence or presence of titania catalyst. In all cases, a photoinduced CN⁻ released from the complex takes place through a homogeneous process. The further oxidation of those cyanides ions to cyanate species is significantly enhanced in the presence of the catalyst in which mesostructured SBA-15 silica is used as support.     

A simple route for the preparation of anatase titania-coated magnetic porous carbons with enhanced photocatalytic activity

A method is described for the production of a magnetically separable photocatalyst, which consists of porous activated carbon, iron oxide particles and anatase titania particles. The prepared samples were characterized by XRD, TEM, SEM and vibrating sample magnetometry. The photocatalytic activity of the samples was determined by degrading model contaminated water, a phenol aqueous solution. The results were compared with a commercial titania, Degussa P25, and enhanced photocatalytic activities were obtained with all the samples prepared here. An additional advantage of these composite photocatalyst is their recyclability, because it can be easily magnetically separated by an external magnetic field. The degradation rate of phenol by a titania-coated magnetic activated carbon with an Fe content of 20% and a calcination temperature for the support of 450 °C, was still higher than 85% after the photocatalyst was used for 5 cycles.     

Ethidium bromide binding to DNA cryogels

The interaction of the classical intercalator ethidium bromide (EtBr) with the double helical network strands of DNA cryogels was investigated. The cryogels were prepared starting from aqueous solutions of DNA (about 2000 base pairs long) at ?18 °C using 1,4-butanediol diglycidyl ether crosslinker under various reaction conditions. In contrast to the solubilization of DNA hydrogels in aqueous EtBr solutions, DNA cryogels remain stable even after complete saturation of their EtBr binding sites. The total binding capacity of the cryogels is 0.6 ± 0.1 EtBr per nucleotide, which is close to the theoretical maximum number of EtBr molecules that can bind to DNA. Even in very dilute solutions (down to 3 μM), cryogels remove EtBr from aqueous solutions with an efficiency of 90%. The equilibrium binding constant and the maximum number of EtBr binding sites of the cryogels almost coincide with the reported values for the secondary binding process of EtBr by DNA in aqueous solutions. At low mole ratios of bound EtBr to DNA, the cryogels swell with increasing amount of bound EtBr, most likely caused by the lengthening of DNA due to the intercalated EtBr. The response of DNA cryogels to changes in EtBr concentration between 3 and 300 μM also suggests that they can be used to detect DNA binding substrates in aqueous solutions.     

Photoactivity of anatase–rutile TiO2 nanocrystalline mixtures obtained by heat treatment of homogeneously precipitated anatase

Nanosized titanium dioxide photocatalysts with varying amount of anatase and rutile phases have been synthesized. Homogeneous precipitation of aqueous solutions containing TiOSO₄ with urea was used to prepare porous spherical clusters of anatase TiO_2. Photoactive titania powders with variable amount of anatase and rutile phases were prepared by heating of pure anatase in the temperatutre range 800–1150 °C. The structure evolution during heating of the starting anatase powders was studied by XRD analysis in overall temperature range of phase transformation. The morphology and microstucture characteristics were also obtained by HRTEM, BET and BJH. The spherical particle morphology of TiO₂ mixtures determined by SEM was stable in air up to 900 °C. The photocatalytic activity of the sample titania TIT85/825 heated to 825 °C in air, contained 77.4% anatase and 22.6% rutile was higher than that nanocrystalline anatase powder. Titania sample TIT85/825 reveals the highest catalytic activity during the photocatalyzed degradation of 4-chlorophenol in aqueous suspension.     

Structural peculiarities of TiO2 and Pt/TiO2 catalysts for the photocatalytic oxidation of aqueous solution of Acid Orange 7 Dye upon ultraviolet light

TiO₂ (anatase) with different microstructure was synthesized by thermal hydrolysis of the titanyl sulfate and studied by X-ray powder diffraction, high resolution transmission electron microscopy and UV–vis diffuse reflectance spectroscopy. The effect of titanium dioxide structure, regular or distorted, on the photocatalytic degradation of Acid Orange 7 Dye (AO7) in water upon ultraviolet light was studied. It was found that synthesized TiO₂ possesses a relatively high reactivity when illuminated but also show different adsorption in the dark. The relationship between these behaviors depends on the real structure of the catalysts. Catalysts with a perfect structural ordering formed after heating at temperature higher than 500 °C show better photocatalytic performance. Small amount of Pt added into the TiO₂ structure was found to improve further the catalyst reactivity. Pt-modified titania catalysts oxidize AO7 more efficiently than P-25 Degussa TiO₂. Doping effect of Pt on the structural and photocatalytic properties of the samples is discussed.     

Synthesizing and Comparing the Photocatalytic Properties of High Surface Area Rutile and Anatase Titania Nanoparticles

Rutile titania nanocrystalline particles with high specific surface areas were directly prepared by thermal hydrolysis of titanium tetrachloride aqueous solution. The as-prepared rutile titania powder was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area analysis, and Fourier transform Raman and IR spectroscopies. Neither anatase nor amorphous titania could be detected in this titania powder by XRD, Raman spectroscopy, and high-resolution TEM. In the phenol degradation reaction, the rutile titania powder with an initial crystalline size of 7 nm was found to have higher photocatalytic activity than that of anatase titania with the same specific surface area. The rutile titania powders calcined at 300° and 450°C also showed a relatively high photocatalytic property. The high activity of the as-prepared rutile titania was attributed to the abundance of hydroxy groups in the powder, as was proven by thermogravimetric analysis data, which provided more active sites for the degradation reaction.     

Photocatalytic degradation of chlorinated pyridines in titania aqueous suspensions

The photocatalytic degradation of 3-chloropyridine was studied using different titania-based catalysts, its disappearance followed a zero-order kinetics. In our conditions, complete mineralization of 100 ppm of 3-chloropyridine occurred within ca. 480 min of UV-radiation on bare-titania systems. Doping of titania with metals was detrimental for photocatalysis. Some reaction intermediates were identified by SPME–GC–MS and a tentative degradation pathway was proposed implying two parallel routes with hydroxylation and ring opening prior to or after the release of chloride ions. Unlike 3-chloropyridine, 2-chloropyridine degradation follows a first-order kinetics. Competitive reactions on solutions containing 3-chloropyridine and 2-chloropyridine evidenced the stronger adsorption of the latter compound. Finally, in a similar way as described for 3-chloropyridine, photocatalytic degradation of 2,3-dichloropyridine followed a zero-order kinetics. Moreover, detection of coupling products containing 3 chlorine atoms evidenced the existence of a radical mechanism.     

Efficient gas phase photodecomposition of acetone by Ru-doped Titania

Nanocrystalline titania particles doped with ruthenium oxide have been prepared by homogenous hydrolysis of TiOSO₄ in aqueous solutions in the presence of urea. The synthesized particles were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HRTEM), Selected Area Electron Diffraction (SAED) and surface area (BET) and porosity determination (BJH). The photocatalytic activity of Ru-doped titania samples was determined in the gas phase by decomposition of acetone during irradiation at 365 nm and 400 nm. The Ru-doped titania samples demonstrated enhanced photocatalytic activity under visible light. Ruthenium oxide causes the anatase to rutile transformation to occur at lower temperatures and decreasing of band-gap energy of Ru-doped samples.     

TIO2-photocatalyzed degradation of phenol and ortho-substituted phenolic compounds

The photocatalytic degradation of phenol, guaiacol, 2-chlorophenol and catechol in aqueous suspensions of TiO₂ under different experimental conditions has been investigated. The photodegradation of the different organics follows a Langmuir–Hinshelwood kinetics, showing rate constants that decrease in the order: guaiacol>2-chlorophenolphenol>catechol. A similar trend is also observed, except for catechol, for the stability of the σ-complexes that may be formed between the aromatic ring and the OH√ radical. From different analytical techniques (HPLC, GC/MS and HPLC/MS), various hydroxylated intermediate compounds have been reported and different mechanisms of degradation of the starting compounds have been proposed. From experiments performed using aqueous solutions containing the four organics, it is observed that the competitive Langmuir–Hinshelwood kinetics for the degradation of each one of the phenolic compounds is obeyed.     

Photocatalytic degradation of phenol on MWNT and titania composite catalysts prepared by a modified sol–gel method

Multi-walled carbon nanotubes (MWNT) and nanocrystalline titania composite catalysts were prepared by a modified sol–gel method. Thermogravimetric analysis, N₂ adsorption–desorption isotherm measurements, powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, transmission electron microscopy and UV–vis spectra were carried out to characterize the composite catalysts with different MWNT contents. The results suggest that the presence of MWNT embedding in the composite catalysts matrix prevents TiO₂ particle agglomeration. Additionally, a correlation exists between the MWNT content and the changes in the UV–vis absorption properties. The photocatalytic degradation of phenol was chosen as a model reaction to evaluate the photocatalytic activities of the composite catalysts. An optimum of the synergetic effect was found for a weight ratio MWNT/TiO₂ equal to 20%. The effects induced by MWNT on the composite catalysts may be explained in terms of a strong interphase interaction between MWNT and TiO₂ in the composite catalysts.     

Influence of the acid–base/redox properties of TiOx-sepiolite supported vanadium oxide catalysts in the gas-phase selective oxidation of toluene

Catalytic behaviour in the selective oxidation of toluene of a series of vanadium systems supported on TiO_x-coated sepiolite (6, 12 and 25 wt.% TiO₂) with a vanadia loading around the theoretical monolayer (10 wt.%) has been investigated. The surface acid–base/redox properties of the solids were also evaluated by using 2-propanol conversion and pyridine chemisorption. The reducibility of surface vanadia species was studied by H₂-TPR. Surface properties of vanadia species and, consequently, their catalytic behaviour were influenced by titania loading on sepiolite. Thus, the vanadium systems with the highest titania loading were the most active and selective in toluene oxidation. Furthermore, this behaviour seems to be mainly related to the density of the active sites capable of being reduced and producing propanone in the vanadium systems.     

NiO掺杂InVO4光催化降解甲酸水溶液产氢的研究

以有机污染物为电子供体可达到制氢与治污的双重目标.通过高温固相法制备了新型NiO/InVO4复合光催化剂.采用XRD,SEM,UV-VIS,BET等测试手段对复合光催化剂的物理和光学性质进行了表征,考察了NiO/InVO4复合光催化剂降解甲酸水溶液制氢的光催化反应.结果表明:NiO/InVO4复合光催化剂为正交晶相结构...     

Comparative photocatalytic behavior of Ta catalysts prepared by d.c.-sputtering, sol–gel and grafting in acetone degradation

Ta-doped photocatalysts were prepared using three different techniques: reactive d.c.-magnetron sputtering, sol–gel and grafting of tantalum on MCM-41 and TiO₂. The composition of the catalysts prepared by reactive d.c.-magnetron sputtering consisted in tantalum and titania, while that of sol–gel and grafted catalysts of Ta–titania–silica mixed oxides. The characterization of these catalysts was carried out using the adsorption-desorption isotherms of N₂ at 77 K, X-ray diffraction (XRD) patterns, small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), XPS, TEM, and ²⁹Si- and ¹⁸¹Ta-CP/MAS NMR spectra. The behavior of these photocatalysts was checked in acetone degradation. The photocatalytic tests indicate that, depending on the preparation conditions and tantalum content, an enhancement of the activity occurs as compared with pure titania. Sol–gel and Ta-grafted MCM and TiO₂ catalysts exhibited a rather poor activity, which was correlated with the lack of crystallinity of titania.     

Hydrothermal synthesis of titanium dioxides from peroxotitanate solution using different amine group-containing organics and their photocatalytic activity

Nanosized TiO₂ particles were prepared by hydrothermal method of the amorphous powders which were precipitated in an aqueous peroxotitanate solution using different amine group-containing organics. The physical properties of prepared nanosized TiO₂ particles were investigated. We also examined the activity of TiO₂ particles as a photocatalyst for the decomposition of orange II. The TiO₂ particles calcined at 400 °C were shown to have a stable anatase phase which has no organic compounds. The particles size of titania particles decreased from 15 to 10 nm as the carbon chain length increased. The titania nanoparticles were shown to have a polygonal shape prepared using NH₄OH and tetramethylammonium hydroxide (TMAOH) as additives, however, the micrographs showed the spherical and narrow size distribution prepared using tetraethyl-ammonium hydroxide (TEAOH) and tetrabutylammonium hydroxide (TBAOH). The titania particles prepared using TEAOH as an amine group-containing organic showed the highest activity on the photocatalytic decomposition of orange II. In addition, the titania particles calcined at 500 °C showed the highest activity on the photocatalytic decomposition of orange II.     

Synthesis of TiO2 particles by reverse microemulsion method using nonionic surfactants with different hydrophilic and hydrophobic group and their photocatalytic activity

TiO₂ nanoparticles were prepared using hydrolysis of titanium tetraisopropoxide in W/O microemulsions consisting of water, nonionic Brij series surfactants with different hydrophilic and Tween series surfactants with different hydrophobic group, and cyclohexane. The properties of these particles were characterized by TEM, XRD, FT-IR, TGA and DTA. The photocatalytic degradation of p-nitrophenol has been studied in order to compare the photocatalytic activity of prepared nanosized titania. TiO₂ particles calcined at 500 °C have a stable anatase phase which has no organic surfactants and the product completely transforms into the anatase phase above 300 °C and the rutile phase begins to appear at 600 °C regardless of surfactants. The particles are shown to have a spherical shape and have an uniform size distribution but the shape becomes distorted with a decrease of hydrophilic group chain length according to rapid hydrolysis of water and titanium alkoxide. In addition, the crystallite size and crystallinity increase with a decrease of hydrophilic and hydrophobic group chain length and an increase of calcination temperature. The photocatalytic activity increases with an increase of hydrophilic and hydrophobic group length and the titania calcined at 500 °C shows the highest activity on the photocatalytic degradation of p-nitrophenol regardless of surfactants.     

颜料二氧化钛光催化特性评价

采用悬浆外照式光催化反应器,研究了在紫外光照下低活性颜料二氧化钛光催化降解罗丹明B的反应动力学特性。考察了二氧化钛浓度、罗丹明B浓度、紫外线波长及光强对光催化反应速率的影响,确定了适合颜料二氧化钛光催化特性评价的优化检测条件。研究表明,颜料二氧化钛光催化降解罗丹明B具有一级反应动力学特性。确定颜料二氧化钛光催化特性检测方法的优化操作条件为二氧化钛浓度约为4 g·L^-1、罗丹明B浓度为2~10 mg·L^-1、紫外光源主发射波长为254 nm。实验检测了表面包硅二氧化钛样品的光催化特性,表明该检测方法能够对颜料二氧化钛及包膜二氧化钛的光催化特性进行快速定量的评价。     

Photocatalytic degradation of imazapyr in water: Comparison of activities of different supported and unsupported TiO2-based catalysts

Photocatalytic oxidation in aqueous phase of imazapyr, a systemic herbicide characterized by its high persistence and mobility in soils, has been investigated using two different titania photocatalysts: commercial Degussa P-25 and industrial Millennium PC-500. Despite potentially better textural and crystalline properties of PC-500, its photocatalytic activity is smaller than that of P-25 for that reaction. A less efficiency of PC-500 powders absorbing the irradiated photons, as well as a low substrate adsorption capacity, has been attributed as the main responsible for such behaviour. Variables such as concentration of imazapyr, amount of catalyst and the physical state of TiO₂ (as a powder or deposited on an Ahlstrom paper) have been studied to elucidate their influence on the efficiency of the photocatalyzed degradation of imazapyr. It has been determined that both adsorption capacities of the catalyst and the reaction rates are strongly affected by the above mentioned parameters. They are even able to modify both the mechanism and kinetic order of the process, by affecting the interfacial substrate–TiO₂ interactions.     

Influence of low concentration Sm doping on optical and catalytic performance of titania

The work focuses on exploring the effect of the concentration of Sm dopant (0.2–0.6 at.%) on structural, optical and photocatalytic properties of the spin coated titania based thin films annealed at different temperatures. The optical interpretation involves the influence of Sm doping on optical constants and luminescence behaviour of the samples. The comprehensive work on optical bandgap, Urbach energy and electron-phonon interaction strength was conducted for Sm doped samples. The optical band gap was found to increase with the increasing concentration of Sm, but decreased with high temperature annealing. Using ellipsometry measurement, refractive index of the samples was obtained. The orbital level information was gathered using X-Ray Photoelectron Spectroscopy (XPS) study with a special emphasis on the evolution of physico-chemical properties as function of Sm doping. The XPS study confirms the presence of Sm in the titania host material and it helped in estimating defects induced by Sm doping. The photocatalytic study of Sm doped titania thin films was carried out by using methylene blue (MB) and Rhodamine B (RhB) dye and we have found an enhanced photocatalytic activity for the 0.4 at.% Sm doped samples.     

Preparation of cerium and nitrogen co-doped titania hollow spheres with enhanced visible light photocatalytic performance

N,Ce-codoped titania hollow spheres were prepared using carbon spheres as template and using N,Ce-codoped titania nanoparticles as building blocks. The N,Ce-codoped titania nanoparticles were synthesized at low temperature. The prepared hollow spheres were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and UV-Vis diffuse reflectance spectrum (DRS). The effect of N and Ce content on the physical structure and photocatalytic properties of the as-prepared hollow sphere samples was investigated. The mechanism of photocatalytic degradation of dyes under visible light irradiation was also discussed.