Hybridized synergy effect among TiO2, Pt and graphite silica on photocatalytic hydrogen production from water–methanol solution

The photocatalytic production of hydrogen gas from aqueous methanol solution was performed using powdered mixtures of graphite silica (GS) and platinized TiO₂ (Pt/TiO₂) or those of GS, Pt and TiO₂. The addition of GS to Pt/TiO₂ resulted in the decrease of the amount of H₂ gas, whereas the addition of GS to mixtures of TiO₂ and Pt led to the incremental production of H₂ gas. This effect is attributed to the aggregation of GS, TiO₂ and Pt in suspension. The new additional electron transfer process of TiO₂ → Pt → GS caused the increment of the amount of hydrogen gas.     

Enhanced photocatalytic decomposition of 4-nonylphenol by surface-organografted TiO2: a combination of molecular selective adsorption and photocatalysis

n-Octyl-grafted TiO₂ (C8-TiO₂) was prepared as a model of a photocatalyst with high molecular adsorption selectivity, and its photocatalytic activity for the decomposition of dilute 4-nonylphenol (an endocrine disrupter, ca. 2 ppm) in water was investigated. The catalyst was highly active in the presence of concentrated phenol (1000 ppm), and the 4-nonylphenol was decomposed in 180 min, while pristine TiO₂ (P-25) under the same conditions showed much lower activity. The high C8-TiO₂ activity was ascribed to the molecular selective adsorption of the organic molecules on the alkyl-grafted hydrophobic surface. Infrared spectra showed that the grafted alkyl groups were gradually decomposed under photoirradiation. The model catalyst demonstrated that molecular selective adsorption is important for removal of low-concentration contaminants in the presence of other, more concentrated compounds.     

Enhancement of photoinduced hydrogen production from irradiated Pt/TiO2 suspensions with simultaneous degradation of azo-dyes

The production of hydrogen from aqueous Pt/TiO₂ suspensions illuminated with UV–vis light has been examined in the absence and in presence of azo-dyes in solution. The effects of operational variables, including dye concentration, solution pH and temperature, on the rate of hydrogen production were investigated. It has been found that deposition of Pt (0.5 wt.%) on the semiconductor surface results in an increase of the H₂ production rate, which goes through a maximum with time of irradiation and then drops to steady-state values comparable to those obtained over bare TiO₂. Both, maximum and steady-state rates obtained over Pt/TiO₂ suspensions were found to increase with increasing solution pH and temperature. Addition of small quantities of azo-dyes in solution results in significantly enhanced rates of H₂ production for a period which depends on dye concentration, solution pH and, to a lesser extent, solution temperature. It is proposed that the dye acts as a scavenger of photogenerated oxidizing species while it is degraded toward CO₂ and inorganic ions. When complete mineralization is achieved, oxygen can no longer be removed from the photocatalyst surface and the rate drops to steady-state values, comparable to those obtained in the absence of azo-dye in solution. The amount of additional H₂ produced is directly proportional to the amount of dye added in the solution. The rate increases with increasing solution pH, where dye degradation is faster, indicating that the process is limited by the rate of consumption of photogenerated oxygen. It is concluded that, under certain experimental conditions, it is possible to obtain significantly enhanced rates of photoinduced hydrogen production from Pt/TiO₂ suspensions with simultaneous mineralization of azo-dyes. The process could be used for combined production of fuel H₂ and degradation of organic pollutants present in water.     

Electrochemical response of a composite Pt/TiO2 layer formed potentiodynamically on titanium surfaces

By potentiodynamic polarization of mechanically polished titanium in a diluted aqueous solution of hexachloroplatinic acid, nearly spherical Pt microparticles were grown, embedded into the simultaneously formed TiO₂ film. The real surface of platinum may be easily controlled by the number of potentiodynamic cycles, and roughness factors exceeding 100 were obtained. Within the potential region of both hydrogen and oxygen underpotential deposition, in both acidic and alkaline solutions, the electrode displayed an excellent electrochemical response characteristic of smooth polycrystalline platinum, unlike to highly dispersed platinum electrodes produced by other methods. The preparation method applied in this work presents an easy way to obtain an electrode surface combining the behaviour of smooth polycrystalline platinum with the behaviour of microdisc arrays. Its high electrocatalytic effectiveness was demonstrated for oxygen reduction and bromide ion adsorption/oxidation.     

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.     

A comparative study of the water-gas shift activity of Pt catalysts supported on single (MOx) and composite (MOx/Al2O3, MOx/TiO2) metal oxide carriers

The water-gas shift (WGS) activity of platinum catalysts dispersed on a variety of single metal oxides as well as on composite MO_x/Al₂O₃ and MO_x/TiO₂ supports (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, Tm) has been investigated in the temperature range of 150–500 °C, using a feed composition consisting of 3% CO an 10% H₂O. For Pt catalysts supported on single metal oxides, it has been found that both the apparent activation energy of the reaction and the intrinsic rate depend strongly on the nature of the support. In particular, specific activity of Pt at 250 °C is 1–2 orders of magnitude higher when supported on “reducible” compared to “irreducible” metal oxides. For composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts, it is shown that the presence of MO_x results in a shift of the CO conversion curve toward lower reaction temperatures, compared to that obtained for Pt/Al₂O₃ or Pt/TiO₂, respectively. The specific reaction rate is in most cases higher for composite catalysts and varies in a manner which depends on the nature, loading, and primary crystallite size of dispersed MO_x. Results are explained by considering that reducibility of small oxide particles increases with decreasing crystallite size, thereby resulting in enhanced WGS activity. Therefore, evidence is provided that the metal oxide support is directly involved in the WGS reaction mechanism and determines to a significant extent the catalytic performance of supported noble metal catalysts. Results of catalytic performance tests obtained under realistic feed composition, consisting of 3% CO, 10% H₂O, 20% H₂ and 6% CO₂, showed that certain composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts are promising candidates for the development of active WGS catalysts suitable for fuel cell applications.     

Pathways of solar light-induced photocatalytic degradation of azo dyes in aqueous TiO2 suspensions

The photocatalytic degradation of aqueous solutions of Acid Orange 7 in TiO₂ suspensions has been investigated with the use of a solar light simulating source. The photoreaction was followed by monitoring the degradation of the dye and the formation of intermediates and final products, as functions of time of irradiation, both in solution and on the photocatalyst surface. It has been found that the dye adsorbs on TiO₂ and undergoes a series of oxidation steps, which lead to decolorization and formation of a number of intermediates, mainly aromatic and aliphatic acids. These molecules are further oxidized toward compounds of progressively lower molecular weight and, eventually, to CO₂ and inorganic ions, such as sulfate, nitrate and ammonium ions. A TiO₂-mediated photodegradation mechanism for Acid Orange 7 is proposed on the basis of quantitative and qualitative detection of intermediate compounds.     

A quantitative evalution of the photocatalytic performance of TiO2 slurries

This paper reports the results of a comparison between two TiO₂ photocatalysts that differ for particle size and absorption/scattering optical properties. The catalyst with larger particles and lower surface area performed better in the degradation of phenol than the specimen with smaller particles and larger surface area. Following carefully designed experiments, it is possible to assess the relative role of light absorption/scattering properties and catalyst-related efficiency by means of a basic kinetic model for the rate of photocatalytic reactions. Explicit relationships are derived in the framework of the steady-state approximation for the quantum yield as a function of one a-dimensional number collecting surface kinetic constants for charge carrier reactions at the interface, absorbed light and surface substrate concentrations. The dimensionality change to volume-defined quantities allows derivation of the explicit dependence of the quantum yield on substrate concentration and partition constants, catalyst concentration, and the rate of volumetric light absorption. Following this approach, the rate expression for slurry systems, valid in the absence of back reactions, is directly derived. Some further simplification of the rate equation for the case of low quantum yield regime leads to analytical relationships able to account for the dependence of the rate on catalyst concentration and absorbed light in the case of stirred and unstirred conditions. The reported properly designed experiments allow the estimation of catalyst-specific micro-kinetic constants.     

The kinetics of photocatalytic degradation of trichloroethylene in gas phase over TiO2 supported on glass bead

In this investigation, a packed bed filled with coated titanium dioxide glass beads to study the kinetics of photocatalytic degradation of trichloroethylene under irradiation of 365 nm UV light. In the range of 100–500 ml/min of flowrate, the reaction rate for 6 μM TCE increased with an increasing flowrate upto 300 ml/min, while was not affected by the flowrate at the values higher than 300 ml/min. For moisture in the range of 9.4–1222.2 μM, the reaction rate of TCE was decreased with an increasing humidity. The adsorbed water on the catalyst surface could compete with the adsorption of TCE on the sites. The reaction rate of 6 μM TCE increased as the light intensity increased, and was proportional to the 0.61 order of the light intensity. Among the three L–H bimolecular form models, the experimental data had the best fit for one of models:

     

Tubular V-free and V-doped TiO2 derived from H2Ti12O25 hollow spheres: Vapour-thermal synthesis,morphology evolution,and photocatalytic performance

Vanadium (V)-free and V-doped H₂Ti₁₂O₂₅ hollow spheres (HTOHSs) were first synthesised via vapour-thermal method at 290?°C using common chemicals and solvents, over super-critical temperature (243?°C) of ethanol (vapour source). Then, they were annealed at 600?°C under different processing conditions to obtain titanium dioxide (TiO₂) photocatalysts. All catalysts were characterised by means of XRD, SEM, TEM, XPS, UV–vis DRS, FT-IR, N₂ adsorbtion-desorbtion and fluorescence lifetime. Results indicated that after the treatment in air, V-free HTOHSs were transformed into open-ended hollow tubes with uniform length of ~5?µm and diameter of ~1?µm, and walls of hollow tubes consisted of aggregated nanosheets. Furthermore, HTOHS crystallised into anatase TiO₂ (white) phase. The treatment in N₂ atmosphere led to the breaking of longer tubes into shorter ones. In contrast, after the treatment in N₂ atmosphere or by reduction using NaBH₄ as a reductant, V-doped HTOHS resulted in the formation of anatase TiO₂ (black) samples and consisted of fewer tubes and more deformed spheres. In this study, fluorescence lifetime (τ) of photo-generated carriers corresponded well with the ratio of oxygen vacancy, indicating that oxygen vacancy dominates the lifetime even though it is very sensitive to many factors. The evolution of structure and morphology and photocatalytic mechanism were analysed and discussed.     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2

A visible-light-active TiO₂ photocatalyst was prepared through carbon doping by using glucose as carbon source. Different from the previous carbon-doped TiO₂ prepared at high temperature, our preparation was performed by a hydrothermal method at temperature as low as 160 °C. The resulting photocatalyst was characterized by XRD, XPS, TEM, nitrogen adsorption, and UV–vis diffuse reflectance spectroscopy. The characterizations found that the photocatalyst possessed a homogeneous pore diameter about 8 nm and a high surface area of 126 m²/g. Comparing to undoped TiO₂, the carbon-doped TiO₂ showed obvious absorption in the 400–450 nm range with a red shift in the band gap transition. It was found that the resulting carbon-doped TiO₂ exhibits significantly higher photocatalytic activity than the undoped counterpart and Degussa P25 on the degradation of rhodamine B (RhB) in water under visible light irradiation (λ > 420 nm). This method can be easily scaled up for industrial production of visible-light driven photocatalyst for pollutants removal because of its convenience and energy-saving.     

Study on the photocatalytic activities of TiO2 films prepared by reactive RF sputtering

Titanium oxide (TiO₂) films were deposited on non-alkali glass by reactive radio frequency (RF) magnetron sputtering using a Ti metal target in this study. The deposition parameters employed to realize the photocatalytic activities of TiO₂ films include RF power, deposition time, argon–oxygen ratio (O₂/(Ar + O₂)) and substrate temperature. The orthogonal array and analysis of variance (ANOVA) were adopted to determine the effect of the deposition variables on characteristic properties and the optimal conditions. The results indicated that a higher photocatalytic activity of TiO₂ films could be achieved under RF power of 150 W, deposition time of 3 h, argon–oxygen ratio of 40% and substrate temperature of 80 °C. RF power and argon–oxygen ratio had a higher effect on the methylene blue (MB) absorbance. The validation experiments show an improved photocatalytic activities of 5% when the Taguchi method is used.     

Direct synthesis of TiO2 nanoparticles by using the solid-state precursor TiH2 powder in a thermal plasma reactor

We attempt the direct synthesis of TiO₂ by using the solid state precursor TiH₂ powder with oxygen in a thermal plasma reactor. Nanocrystalline titanium dioxide powder has been synthesized by using thermal plasma synthesis in a non-transferred arc thermal plasma reactor. The thermal plasma-synthesized powder product consists of nano-sized particles of anatase and rutile phases of titanium dioxide. Particle compositions were observed on collecting powder from different positions of the reactor and varying the amount of flow rate of reactive gases (O₂). The characteristics of the powder such as particle size, size distribution and phases were analyzed using various techniques such as XRD, SEM, TEM, XPS, EDS and particle size analyzer. UV–visible reflection spectroscopy of the plasma-synthesized TiO₂ powders showed the absorbance in the visible region leading to effective photocatalytic activity, which is clearly confirmed from the XPS analysis. XPS analysis reveals the presence of –OH bonds on the surface of nanoparticles, which is the significant evidence of better quality of powders in comparison to other methods. Also, we have investigated the phase transformation phenomenon of anatase to rutile. At 1000 °C, complete transformation of the anatase to rutile occurs. Powders prepared in this procedure are white in colour and their diameter varies from 10 nm to 150 nm. Average particle size distributes in the range of 20–50 nm. The unique property about the plasma-synthesized powders is high resistance to heat treatment, with enhanced photocatalytic activity.     

The photocatalytic destruction of the cyanotoxin, nodularin using TiO2

Titanium dioxide (TiO₂) photocatalysis has been used to initiate the destruction of nodularin, a natural hepatotoxin produced by cyanobacteria. The destruction process was monitored using liquid chromatography–mass spectrometry analysis which has also enabled the identification of a number of the photocatalytic decomposition products. The reduction in toxicity following photocatalytic treatment was evaluated using protein phosphatase inhibition assay, which demonstrated that the destruction of nodularin was paralleled by an elimination of toxicity.     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

FTIR study of gas-phase alcohols photocatalytic degradation with TiO2 and AC-TiO2

In this paper the degradation of gaseous alcohols (methanol, ethanol, 1-propanol and 1-butanol) has been studied in a continuous reaction system. Methanol and ethanol, but not 1-propanol and 1-butanol, have caused the catalyst bare-TiO₂ to become deactivated. The catalyst containing activated carbon, AC-TiO₂, has not shown almost deactivation in any experiment.

To explain this behaviour variation, a thorough FTIR study concerning the interaction of gaseous alcohols with the catalyst surface and the effect of light on the process was performed. Thus, the interaction of the different catalysts with the selected alcohols, the formed species and the hydroxyl group evolution under irradiation was studied.     

Photocatalytic reduction of carbon dioxide into gaseous hydrocarbon using TiO2 pellets

It has been shown that CO₂ could be transformed into hydrocarbons when it is in contact with water vapour and catalysts under UV irradiation. This paper presents an experimental set-up to study the process employing a new approach of heterogeneous photocatalysis using pellet form of catalyst instead of immobilized catalysts on solid substrates. In the experiment, CO₂ mixed with water vapour in saturation state was discharged into a quartz reactor containing porous TiO₂ pellets and illuminated by various UV lamps of different wavelengths for 48 h continuously. The gaseous products extracted were identified using gas chromatography. The results confirmed that CO₂ could be reformed in the presence of water vapour and TiO₂ pellets into CH₄ under continuous UV irradiation at room conditions. It showed that when UVC (253.7 nm) light was used, total yield of methane was approximately 200 ppm which was a fairly good reduction yield as compared to those obtained from the processes using immobilized catalysts through thin-film technique and anchoring method. CO and H₂ were also detected. Switching from UVC to UVA (365 nm) resulted in significant decrease in the product yields. The pellet form of catalyst has been found to be attractive for use in further research on photocatalytic reduction of CO₂.