TiO2 deactivation during gas-phase photocatalytic oxidation of ethanol

The deactivation of TiO₂ Degussa P25 during the gas-phase photocatalytic oxidation of ethanol has been studied. Water vapor plays a clear competitive role for surface sites adsorption, thus hampering the ethanol photo-oxidation. Dark adsorption of ethanol on a fresh catalyst shows a Langmuirian behavior with the formation of a monolayer of adsorbate. Dark adsorption in a TiO₂ surface that has been used in consecutive photocatalytic experiments of ethanol degradation gives non-Langmuirian isotherms, indicating the existence of noticeable changes of the catalyst surface structure. After several irradiations the catalyst activity decreases. Such deactivation has been investigated, observing that the rate constant of ethanol and acetaldehyde (its main degradation product) oxidation decreases with irradiation time. Several surface treatments have been studied in order to find suitable procedures for catalytic activity recovery, but regular decay of activity is always observed after every treatment.     

Gas-phase photocatalytic degradation of trichloroethylene on pretreated TiO2

This paper reports the effects of preillumination, prechlorination and prehydroxylation of TiO₂ glass fiber cloth (TiO₂-GFC) on the photocatalytic degradation (PCD) reaction of trichloroethylene (TCE) in gas–solid regime. The reaction was monitored in situ by FT-IR spectroscopy at room temperature (298 K). Product analysis by gas chromatography–mass spectrometry (GC–MS) revealed the formation of a new by-product, 1,1-dichloroethane (1,1-DCE) in significant amount along with other known by-products. The photocatalytic activities of TiO₂-GFC and the mineralization of TCE were dependent on preillumination, prehydroxylation and prechlorination while the product yield was significantly influenced by prehydroxylation and prechlorination of TiO₂-GFC. Prechlorination increased the yields of phosgene (COCl₂) and pentachloroethane (C₂HCl₅) while prehydroxylation decreased the yield of COCl₂ with corresponding increases in the yield of oxalyl chloride (COClCOCl) and the mineralization of TCE, suggesting a possible surface-mediated hydrolysis of phosgene to COClCOCl in the latter case. Reaction schemes have been proposed to account for the formation of 1,1-DCE and COClCOCl. The photocatalytic activity of TiO₂-GFC and the mineralization of TCE have been found to correlate with the concentration of HCl employed for the prechlorination of TiO₂-GFC.     

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:

     

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.     

Influence of the methods of TiO2 incorporation in monolithic catalysts for the photocatalytic destruction of chlorinated hydrocarbons in gas phase

Three different methods of fixing titanium dioxide on a monolithic, natural magnesium silicate matrix, onto-the-wall extrusion, wash-coating and sol–gel, are compared. Photo-assisted oxidation tests with chlorinated hydrocarbons, trichloroethylene (TCE) alone and in mixtures with perchloroethylene (PCE) were carried out with the monolithic photocatalysts.

Results show that the use of extruded titania monoliths provides significant advantages for best stability of anatase, porosity and resistance to loss of active phase due to erosion. Catalysts obtained by the sol–gel method maybe a good option for this application, but the coating method must still be improved.     

TiO2 coating types influencing the role of water vapor on the photocatalytic oxidation of methyl ethyl ketone in the gas phase

Four TiO₂-based materials, named A, B, C and D, are used to investigate the influence of water vapor on the gas–solid adsorption and heterogeneous photocatalytic oxidation of gaseous methyl ethyl ketone (MEK). Two of the photocatalysts (A and B) are constituted of powdered TiO₂ deposited onto two different supports (ordinary glass and non-woven cellulose fibers). The other ones (C and D) are composed of a thin film of TiO₂ coated on glass substrates. The effect of water vapor on MEK initial conversion rates is studied for the four photocatalytic materials using the Langmuir–Hinshelwood model at the initial time. On the concentrations range where the model hypotheses are verified, adsorption constants K and kinetics constants k are calculated for experiments under both dry and humid atmosphere. When the relative humidity is increased, the evolution of these constants shows that water vapor acts differently depending on the form of deposited TiO₂ (powder and film).     

TiO2光催化降解亚硝酸钠的研究

采用溶胶-凝胶法制备了TiO2光催化剂,以紫外光照射下的光催化降解亚硝酸钠为模型反应,以盐酸萘乙二胺显色法测定样品的吸光度,进而得出亚硝酸钠的转化率,并采用BET、XRD和IR对催化剂进行了表征。结果表明,500℃焙烧的TiO2催化剂比表面积为42.5 m2/g,平均孔径为5.8 nm,热稳定性好。400℃焙烧2 h的TiO2尚存在一定量的无定形相TiO2,500℃焙烧的TiO2完全转变为锐钛矿型TiO2,700℃时完全转化为金红石相。本实验最佳的反应条件为:TiO2(500℃,2 h)催化剂0.2 g,100 mL 0.125μg/mL亚硝酸钠溶液中,紫外光降解150 min,亚硝酸钠的降解率为100%;添加适量浓度的H2O2溶液,可促进亚硝酸钠溶液的转化。     

Role of the support on the activity of silica-supported TiO2 photocatalysts: Structure of the TiO2/SBA-15 photocatalysts

Immobilization of TiO₂ on silica materials has been commonly proposed in order to make easier the separation of the catalyst after the photocatalytic reactions in aqueous systems. The main drawback of the supported photocatalysts is that they usually show lower activities in comparison with powdered TiO₂ materials. The aim of this work is to elucidate the structure of some silica-supported TiO₂ photocatalysts recently developed as well as to evaluate the role that the porous structure of the support can play in the observed photocatalytic activities. In comparison with the use of an amorphous silica support, the use of the mesostructured silica SBA-15 produces an ordered structure in which TiO₂ crystals of similar sizes, independently of titania loading, are located inside the mesoporous channels of the support. The photocatalytic treatment of several cyanide-containing compounds is analyzed and the results are explained in terms of the structure of every catalyst. Depending on the model compound, the characteristic structure of the TiO₂/SBA-15 materials allows increasing up to eight times the activity achieved by the Degussa P25 TiO₂. The main conclusion of this work is the strong influence of the textural properties of the support on the catalytic activity of immobilized TiO₂ photocatalysts.     

Characterization and photocatalytic activity of transition-metal-supported surface bond-conjugated TiO2/SiO2

TM/TiO₂/SiO₂ photocatalysts were prepared by the photodeposition method using transition metal salts (TM=Fe³⁺, Co²⁺, Ni²⁺ and Cu²⁺) as precursors and the surface bond-conjugated TiO₂/SiO₂ as supporter in N₂ atmosphere, and were characterized by XRD, XPS, UV-Vis diffuse reflection and zeta-potential. Their photocatalytic activities were evaluated using reactive brilliant red K-2G (K-2G) and cationic blue X-GRL (CBX) showing different adsorption behavior on the oxides. Fe, Cu supported TiO₂/SiO₂ can efficiently extend the light absorption to the visible region. XPS analysis verified that the introduction of transition metal lead to the changes of the electronic environmental of Ti cations and the zeta-potential of oxides. As a result, K-2G has higher adsorption on the modified TiO₂/SiO₂ than that on the baked one, while the adsorption of CBX has a little change on the both oxides. At the same time, for the photodegradation of K-2G, Fe³⁺, Co²⁺, Ni²⁺-modified catalysts show that their photoactivities are 3.3–2.2 times higher than the bare one. On the contrast, all transition-metal-supported catalysts have no significant activity improvement except that Fe/TiO₂/SiO₂ shows 1.68 times higher activity for the photodegradation of CBX. The results indicate that the photoactivity could be increased in photodegradation of dyes by changing the performances of adsorption to dyes and absorption to light of photocatalyst.     

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.     

水基纳米TiO_2路径制备有序介孔TiO_2-SiO_2及其可见光催化性能

在多巴胺修饰的水基TiO_2纳米微粒(TiO_2NPs)悬浮液中,以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,分别采用碱性水热方法或酸性溶胶-凝胶方法,制备了有序介孔TiO_2-SiO_2(TiO_2NPs/MCM-41或TiO_2NPs/SBA-3)。采用XRD、TEM、ICP和N2吸附-脱附实验对样品进行表征。结果表明,制备的介孔TiO_2-SiO_2在TiO_2高负载质量分数(23.98%TiO_2NPs/MCM-41、17.27%TiO_2NPs/SBA-3)时,仍能保持长程有序的介孔氧化硅结构。TiO_2NPs随机地嵌入在有序介孔氧化硅孔道所组成的网络结构中。在可见光下催化甲基橙降解反应中,反应时间120 min时,在P25上甲基橙相对浓度降为57%,在TiO_2NPs/MCM-41上降为33%,而在TiO_2NPs/SBA-3上降为5.7%。     

Enhancement of the photocatalytic activity of pelletized TiO2 for the oxidation of propene at low concentration

In a previous study we have shown that the pelletization of titanium dioxide, a convenient step for gas phase applications, causes an important activity lost. Such activity lost can be partially recovered pelletizing in presence of carbon materials. Porosity, as well as carbon conductivity of the selected carbon material, is important. Based on these previous results, we analyze the pelletization of TiO₂ in presence of “white additives”, such as MCM-41, zeolites, metal–organic framework, SiO₂, Al₂O₃, glass wool and quartz wool. Our results show that the activities of these composite photocatalytic pellets are higher than that of 100% TiO₂-pellets. Pellets containing MCM-41, precipitated SiO₂, glass wool and quartz wool present the highest propene conversions. Attention has been paid to the effect of porosity and UV-absorbance on the resulting photocatalytic activity. Although it is difficult to find a correlation between the porosity of these “white additives” and the photocatalytic activity of the TiO₂-based materials, additives with no porosity or with some mesoporous contribution seem to be desired to maximize the activity. The different catalytic activities for the studied photocatalysts could not be explained on basis of their UV-absorption and further research is currently being performed trying to deep into the reasons for such behaviour. Comparison of the photocatalytic activities for pellets containing the above-mentioned “white additives” with those of a TiO₂/carbon photocatalyst having the highest porosity and conductivity among all those studied highlights the superior performance of the samples containing “white additives”.     

Carbon-modified TiO2 photocatalyst by ethanol carbonisation

The new photocatalysts based on commercially available titanium dioxide powders: Tytanpol A11 (Police, Poland), pure anatase and P-25 (Degussa, Germany) containing about 20% rutile were modified by carbon via ethanol carbonisation. Titanium dioxides were heated at different temperature from 150 to 400 °C for 1 h in an atmosphere of ethanol vapour. The photocatalytic activity of carbon-modified TiO₂ was studied by oxidation of phenol in water under UV and artificial solar light irradiation. With increasing of carbon content in TiO₂ photocatalysts the activity for phenol decomposition under UV light was decreasing but that under visible light was stable. Turbidity of the slurry solution decreased with increasing of carbon content for all prepared photocatalysts because of the change of their surface character from hydrophilic to hydrophobic.     

Role of Cu in the Cu-TiO2 photocatalytic degradation of dihydroxybenzenes

The photocatalytic degradation of three dihydroxybenzenes (hydroquinone, catechol and resorcinol) by TiO₂ and Cu-TiO₂ has been studied. Degradation rates depend on the molecule catalyst surface interaction type. FTIR studies have shown that Cu presence modifies the organics interactions with the catalysts surface. Therefore, catalysts have shown different types of behaviour with each compound.

Resorcinol interaction with Cu-TiO₂ may produce a hydroxyphenolate thus reducing the number of activating centres in the aromatic ring. However, catechol interaction provides a catecholate bidentate which virtually deactivates the aromatic ring, hence reducing its degradation by OH radicals attacks. Hydroquinone interaction with Cu-TiO₂ occurs by means of a hydrogen bond, while with TiO₂ this interaction is established through the formation of a hydroxyphenolate monodentate. This justifies the improved catalytic behaviour of Cu-TiO₂.

Studies in presence of H₂O₂ have shown the existence of similar degradation mechanisms, but degradation rates have been notably higher.     

Effects of Sn dopant on the photoinduced charge property and photocatalytic activity of TiO2 nanoparticles

In this paper, Sn-doped TiO₂ nanoparticles were prepared by a sol–gel method, and also were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectrum (IR), ultraviolet–visible diffuse reflection spectrum (UV–vis DRS), photoluminescence spectrum (PL), surface photovoltage spectroscopy (SPS) and electrical field induced surface photovoltage spectroscopy (EFISPS). The sample activity was evaluated by photocatalytic oxidation reactions of phenol solution. The effects of thermal treatment temperature and Sn amount on photoinduced charge property, mainly involving charge separation and bound excitons resulting from surface states, and photocatalytic activity of TiO₂ nanoparticles were principally investigated. The results show that an appropriate calcination temperature and Sn dopant amount can greatly enhance the SPS responses of TiO₂ nanoparticles related not only to the band–band transitions but also to the bound excitons, and obviously weaken the PL signal, while the photocatalytic activity remarkably raises. These demonstrate that the separation rate of photoinduced charges of TiO₂ nanoparticles can be effectively improved by doping Sn, which is responsible for the obvious increase in the photocatalytic activity. Moreover, the existence of bound excitons related to surface states also favor the photocatalytic activity. In addition, it can be found that the SPS responses related to the bound excitons could easily exhibit in the TiO₂ sample consisting of much of anatase and little of rutile, which is possibly ascribed to the heterojunction between the anatase and rutile phase.     

Study of the synergic effect of sulphate pre-treatment and platinisation on the highly improved photocatalytic activity of TiO2

An important improvement of the photocatalytic activity of sol–gel prepared TiO₂ has been achieved by sulphate pre-treatment, calcination at high temperature and further platinisation of the samples.

The presence of sulphuric acid clearly stabilised TiO₂ surface area against sintering, maintaining at the same time anatase phase until higher calcination temperatures than in non-sulphated samples. Platinisation of the samples with different nominal amounts of platinum (from 0.5 to 2.5 wt%) was performed and the influence of sulphate treatment on the dispersion and deposit size of platinum on the TiO₂ surface was studied.

Characterisation results and photocatalytic activity of these catalysts were compared with those of unmodified TiO₂. Simultaneously sulphated and platinised TiO₂ samples were highly active for phenol degradation, used as model reaction for the photocatalytic studies, having higher activities than only platinised or only sulphated samples. The activity of these samples were several orders of magnitude higher than that of the commercial TiO₂ Degussa P25 (platinised or unmodified) as well, with independence of the nominal amount of platinum of the samples.

A wide characterisation of the samples was performed and correlations between characterisation results and activity properties are reported.     

Preparation of photocatalytic TiO2 coatings by gel-dipping with polysaccharides

Commercial tiles are being produced in vast quantities. The main properties of tiles are well established but there is an increasing interest in producing ceramics with tailored-properties and advanced functionalities. One way of adding value to commercial tiles is to deposit a photocatalytic coating to obtain ‘smart’ tiles for environmental reasons, e.g. for the (photo) degradation of organic pollutants in air or in a liquid. Here, we show the manufacture of ‘smart’ tiles by formation of TiO₂ coatings onto commercial tiles by a colloidal processing route based on the immersion of the substrate into a homogeneous aqueous ceramic suspension and its consolidation by agar thermogelation. The effect of the processing parameters (withdrawal rate, solid loading and gelling agent content) and the grain size on the photocatalytic activity of the final coated tiles is reported and discussed. Final coatings properties depend on the viscosity of the suspension, particle size, withdrawal rate, solid loading and gelling agent content, and hence, this dependence affects the photocatalytic activity of the coatings.     

Dye sensitized artificial photosynthesis in the gas phase over thin and thick TiO2 films under UV and visible light irradiation

Perylene diimide based organic sensitizers capable of electron generation under illumination were used to initiate gas phase photo reduction reactions on TiO₂ thin and thick film surfaces. For comparison [Ru(Bpy)₃]²⁺ dye sensitizers were also studied. The photo reduction of CO₂ was carried out under static conditions in the gas phase. TiO₂ films were coated on hollow glass beads via a sol–gel procedure. Pt was incorporated on the films either by adding the precursor salt in the sol, Pt(in), or by wet impregnation of calcined film with an aqueous solution of the precursor salt, Pt(on). Organic sensitizers were incorporated on the films by wet impregnation of the film from an aqueous solution. Under UV illumination, the methane yields of platinized TiO₂ thin films decreased in the following order: Pt(on)·TiO₂ > Pt(in)·TiO₂ > TiO₂. The presence of organic sensitizers inhibited the catalytic activity of pure and platinized TiO₂ thick films under UV illumination. The relative enhancement of the reaction yields in the presence of the organic sensitizer under visible light illumination depended on the presence of Pt as well as the incorporation method of Pt in the TiO₂ structure. The reaction yields were better when Pt was impregnated on the TiO₂ film than when Pt was incorporated in the Ti sol. On the other hand, pure or platinized TiO₂ under visible light illumination was totally inactive indicating the role of the organic dye in generating catalytically active electrons under visible light.     

ESR study of the initial stages of the photocatalytic oxidation of toluene over TiO2 powders

In the present work, the initial stages of the photocatalytic oxidation of toluene over two commercial TiO₂ powders were investigated at the molecular level by ESR spectroscopy. UV-irradiation of the TiO₂ samples, which present different phase composition and surface area, gave rise to several oxygenated radicals like O⁻, O₂⁻ and O₃⁻, as well as Ti³⁺ centers. The proportion of these species generated depends on the gaseous environment (vacuum or oxygen), and the structural and morphological characteristic of the TiO₂ samples. In contrast, co-adsorption of toluene and oxygen on any of the TiO₂ samples studied yields upon UV illumination slightly different ESR signals, which have been assigned to the formation of benzylperoxy radicals, Ph-CH₂OO, adsorbed on the semiconductor. Such species are only detected when TiO₂ is exposed to toluene–oxygen mixtures enriched in the organic, and under these conditions neither of the other oxygenated radicals is formed. The reasons for this behavior are discussed on the basis of the mechanism for the photocatalytic oxidation of toluene.