Synthesis of nanosized TiO2/SiO2 particles in the microemulsion and their photocatalytic activity on the decomposition of p-nitrophenol

Nanosized pure TiO₂ particles were prepared by hydrolysis of TTIP in the sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles. TiO₂/SiO₂ nanoparticles were also prepared from TEOS as a silicon source and TTIP as a titanium source. These particles were characterized by TEM, XRD, FT-IR, BET, TGA and DTA. From thermal analysis and XRD analysis, the anatase structure of pure titania appeared in the 300–600 °C calcination temperature range and the rutile structure was showed above 700 °C. However, no rutile phase was observed for the TiO₂/SiO₂ particles up to 800 °C. The crystallite size decreased and the surface area of TiO₂/SiO₂ particles monotonically increased with an increase of the silica content. From FT-IR analysis, the band for Ti–O–Si vibration was observed and the band intensity for Si–O–Si vibration increased with an increase of the silica content. The micrographs of TEM showed that the TiO₂/SiO₂ nanoparticles had a spherical and a narrow size distribution. In addition, TiO₂/SiO₂ particles showed higher photocatalytic activity than pure TiO₂ and the TiO₂/SiO₂ (90/10) particles showed the highest activity on the photocatalytic decomposition of p-nitrophenol.     

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.     

Maya crude hydrodemetallization and hydrodesulfurization catalysts: An effect of TiO2 incorporation in Al2O3

Hydrotreating of Maya heavy crude oil over high specific surface area CoMo/TiO₂–Al₂O₃ oxide supported catalysts was studied in an integral reactor close to industrial practice. Activity studies were carried out with Maya crude hydrodesulfurization (HDS), hydrodemetallization (HDM), hydrodenitrogenation (HDN), and hydrodeasphaltenization (HDAs) reactions. The effect of support composition, the method of TiO₂ incorporation, and the catalyst deactivation are examined. Supported catalysts are characterized by BET specific surface area (SSA), pore volume (PV), pore size distribution (PSD), and atomic absorption. It has been found that sulfided catalysts showed a wide range of activity variation with TiO₂ incorporation into the alumina, which confirmed that molybdenum sulfided active phases strongly depend on the nature of support. The pore diameter and nature of the active site for HDS, HDM, HDN, and HDAs account for the influence of the large reactant molecules restricted diffusion into the pore, and/or the decrease in the number of active sites due to the MoS₂ phases buried with time-on-stream. The textural properties and hysteresis loop area of supported and spent catalysts indicated that catalysts were deactivated at the pore mouth due to the metal and carbon depositions. The atomic absorption results agreed well regarding the textural properties of spent catalysts. Thus, incorporation of TiO₂ with γ-Al₂O₃ alters the nature of active metal interaction with support, which may facilitate the dispersion of active phases on the support surface. Therefore, the TiO₂ counterpart plays a promoting role to HDS activity due to the favorable morphology of MoS₂ phases and metal support interaction.     

Local structure and photocatalytic activity of B2O3–SiO2/TiO2 ternary mixed oxides prepared by sol–gel method

The local structure and the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides (SiO₂ content was fixed as 30 at.% with respect to TiO₂) was investigated by using XRD, FT-IR, BET, UV-vis spectra, and electron paramagnetic resonance (EPR) measurement. In FT-IR analysis, boron was incorporated into the framework of titania matrix with replacing Ti---O---Si with Si---O---B or Ti---O---B bonds. Also, paramagnetic species such as O⁻ and Ti³⁺ defects were formed by the boron incorporation. In SiO₂/TiO₂ mixed oxides, a blue shift in the light absorption band was observed due to the quantization of band structure. All B₂O₃–SiO₂/TiO₂ samples had pure anatase phase and no rutile phase was formed even though the calcination temperature was over 900 °C. Incorporating boron oxides of more than 10% enlarges the grain size of anatase phase and causes a red shift of the light absorption spectrum. The surface area was monotonically decreased with increasing the content of boron content. As a result, the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides was greatly influenced by the content of boron oxide. The highest photoactivity (g moles/min l) was obtained when the boron content was 5% and seven times higher than that of silica/titania binary mixed oxide. In addition, the specific photoactivity (g moles/m² l) was maximum still at 5%. It was concluded that the large reduction of surface area, the change of band structure, and more formation of bulk Ti³⁺ sites are responsible for the deterioration in the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides when the content of boron is over 10%, although their crystallinity was enhanced by increasing the calcination temperature with keeping anatase phase.     

Niobium sulfide as a dopant for Mo/TiO2 catalysts

Mo/TiO₂ catalysts were modified with Nb by two different methods, sol–gel and surface deposition, in order to study the effect of Nb incorporation on the thiophene HDS activity. The results show that the formation of Nb–Ti mixed oxides leads to catalysts with poor HDS activity while the deposition of Nb oxide species on the surface of TiO₂ leads to catalysts with activities larger than those of Mo/Al₂O₃ and Mo/TiO₂. This increase in activity was attributed to the formation of a larger population of Mo sulfur anionic vacancies when Nb was surface deposited on the TiO₂.     

Mesostructured SiO2-doped TiO2 with enhanced thermal stability prepared by a soft-templating sol–gel route

Mesostructured SiO₂–TiO₂ mixed oxides have been prepared by a soft-templating sol–gel route, using a non-ionic triblock copolymer as structure-directing agent. Tetraethylorthosilicate (TEOS) and titanium tetraisopropoxide (TTIP) have been employed as Si and Ti sources, respectively. Using a prehydrolysis TEOS step allows mixed oxides to be produced with a homogeneous porosity and with no phase segregation, in a wide range of Si/Ti compositions. Both the hydrolysis molar ratio and the silicon content have been found to be important factors determining the final properties of these materials. For instance, mixed oxides containing low silicon concentrations exhibit N₂ physisorption isotherms typical of mesoporous materials, although with an important contribution of microporosity. On the other hand, increasing the hydrolysis molar ratio makes more difficult to reach a total dispersion of SiO₂ through the TiO₂ matrix. Even with low SiO₂ loadings, the thermal stability is effectively enhanced, when compared to the equivalent pure TiO₂ materials, as a consequence of a delay in the titania crystallization to anatase. Thus, after calcination at 300 °C for 3 h, mixed oxides containing low Si/Ti ratios (20/80) show BET surface area in the range 290–346 m²/g, while pure TiO₂ materials largely collapse under the same treatment and their BET surface area drop strongly to values around 125 m²/g. This synthesis route, therefore, provides mesoporous TiO₂-rich materials with enhanced stability and textural properties, which is of high interest for applications as catalysts and supports.     

Catalytic activities of Co(Ni)Mo/TiO2–Al2O3 catalysts in gasoil and thiophene HDS and pyridine HDN: effect of the TiO2–Al2O3 composition

The effect of the TiO₂–Al₂O₃ mixed oxide support composition on the hydrodesulfurization (HDS) of gasoil and the simultaneous HDS and hydrodenitrogenation (HDN) of gasoil+pyridine was studied over two series of CoMo and NiMo catalysts. The intrinsic activities for gasoil HDS and pyridine HDN were significantly increased by increasing the amount of TiO₂ into the support, and particularly over rich- and pure-TiO₂-based catalysts. It is suggested that the increase in activity be due to an improvement in reducing and sulfiding of molybdena over TiO₂. The inhibiting effect of pyridine on gasoil HDS was found to be similar for all the catalysts, i.e., was independent of the support composition. The ranking of the catalysts for the gasoil HDS test differed from that obtained for the thiophene test at different hydrogen pressures. In the case of gasoil HDS, the activity increases with TiO₂ content and large differences are observed between the catalysts supported on pure Al₂O₃ and pure TiO₂. In contrast, in the case of the thiophene test, the pure Al₂O₃-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also, in the thiophene test the difference in intrinsic activity between the pure Al₂O₃-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also in the thiophene test, the difference in intrinsic activity between the pure Al₂O₃- and pure TiO₂-based catalysts is relatively small and dependent on the H₂ pressure used. Such differences in activity trend among the gasoil and the thiophene tests are due to a different sensitivity of the catalysts (by different support or promoter) to the experimental conditions used. The results of the effect of the H₂ partial pressure on the thiophene HDS, and on the effect of H₂S concentration on gasoil HDS demonstrate the importance of these parameters, in addition to the nature of the reactant, to perform an adequate catalyst ranking.     

Activity and acidity of Nb2O5-MoO3 and Nb2O5-WO3 in the Friedel-Crafts alkylation

Nb₂O₅ loaded on the supports and mixed with oxides was studied to investigate the activity and acidity for Friedel-Crafts benzylation of anisole. From the study on the loaded catalysts, a preliminary conclusion for the selection of metal oxide was obtained; namely, such an acidic oxide as silica was suitable for the support of Nb₂O₅. Then, MoO₃ and WO₃ were mixed with Nb₂O₅, and prominent high catalytic activity and acidities were observed. Both oxides of Nb₂O₅-MoO₃ and Nb₂O₅-WO₃ showed almost similar behavior with respect to characterization and catalytic activity. Surface area increased, X-ray diffraction (XRD) and Raman bands were lost, acid sites, both Brønsted and Lewis characters generated, and surface acid site density was as high as 2–4 nm⁻². The acid sites were generated on the amorphous metal oxides consisting of Nb and Mo or W oxides, different in nature from those of Nb₂O₅ calcined and un-calcined, and active for Friedel-Crafts benzylation.     

Photodegradation of phenol and 4-chlorophenol by BaO–Li2O–TiO2 catalysts

The catalytic photodegradation of phenol and 4-chlorophenol with white and UV light over TiO₂, BaTi₄O₉ and Hollandite catalysts has been studied in our laboratories. BaTi₄O₉ and Hollandite catalysts were prepared by solid state reaction at 900°C and 1200°C, respectively. All the catalysts were characterized by different techniques such as surface area measurements by the BET method, atomic absorption spectroscopy and XRD. Photodegradation reaction experiments were monitored by HPLC analysis. The reaction intermediates: hydroquinone and 1,4-benzoquinone were identified by GC–MS analysis. The photocatalytic activities of these catalysts in the degradation of phenol and 4-chlorophenol were evaluated in comparison with titanium oxide. Experimental results showed that BaTi₄O₉ and Hollandite catalysts exhibit small photocatalytic activity as compared with TiO₂.     

C2H2 oxidation by plasma/TiO2 combination: Influence of the porosity, and photocatalytic mechanisms under plasma exposure

Plasma/catalyst combination is an active solution to reach high conversion rates at low energetic cost. TiO₂ is one of the catalysts frequently used in dielectric barrier discharges. Plasma/TiO₂ synergy was already exhibited but the mechanisms still have to be understood. This work distinguishes three main effects involved in the synergy: (a) effect of catalyst on the injected power, (b) the effect of porosity on C₂H₂ oxidation, and (c) the photocatalytic degradation of C₂H₂ on TiO₂ under plasma exposure. Different glass fibres-based catalytic materials coated with SiO₂ and/or TiO₂ nano-particles are used to separate these three contributions regarding to C₂H₂ conversion. It is reported that at constant voltage the injected power is mainly increased by the presence of glass fibres. C₂H₂ oxidation is mainly enhanced by the macroporosity of glass fibres and in a minor way by the nano-particles. The production of O atoms close to the surface is probably responsible for the higher C₂H₂ removal efficiency with porous material. The photocatalytic activity of TiO₂ is negligible in the plasma except if additional UV lamps are used to activate TiO₂. With external UV, photocatalytic activity is more efficient in the plasma phase than in a neutral gas phase. This plasma/photocatalysis synergy is due to the use of O atoms in photocatalytic mechanisms.     

Selective catalytic reduction of NOx with NH3 over a V2O5/TiO2 on silica catalyst

The catalytic properties of various supported and unsupported vanadium oxide based catalysts for the Selective Catalytic Reduction of NO_x with NH₃ (SCR) are investigated. It is concluded, that in order to achieve good selectivity in the SCR, the number of active sites favouring SCR has to be increased at the cost of sites favouring ammonia oxidation. This can be achieved by the application of the active vanadium oxide onto a suitable support. A specific catalyst preparation procedure is described which enables the application of vanadium oxide onto TiO₂-adlayered silica. The thus prepared catalyst is shown to exhibit the desired properties, that is, a high selectivity and good activity in the Selective Catalytic Reduction of NO_x with NH₃.     

Catalytic decomposition of chlorodifluoromethane (HCFC-22) over platinum supported on TiO2–ZrO2 mixed oxides

Sulfated and non-sulfated TiO₂–ZrO₂ were promoted with platinum and the activity and selectivity of the resulting catalysts for the hydrolytic decomposition chlorodifluoromethane in air was investigated. The addition of platinum reduced the specific surface area of the catalyst slightly and lowered the catalytic activity. On the other hand, the selectivity of the catalysts towards CO₂ formation was much improved. Metallic platinum was formed by the reduction of the platinum precursor with carbon monoxide produced during the hydrolysis of chlorodifluoromethane over the acidic mixed oxide and promoted the oxidation of CO. At the same time, platinum suppressed completely the formation of the fluorinated byproduct CHF₃, possibly by anchoring itself on the active sites responsible for the fluorination reaction. The platinum promoted non-sulfated TiO₂–ZrO₂ was stable and gave more than 90% of CHClF₂ conversion and 95% selectivity to CO₂ for over 60 h.     

Catalytic hydrolysis of dichlorodifluoromethane (CFC-12) on unpromoted and sulfate promoted TiO2–ZrO2 mixed oxide catalysts

The mixed oxide of zirconium and titanium was investigated for the catalytic hydrolysis of dichlorodifluoromethane. The mixed oxide was further promoted by doping with sulfate ions. It was found by both powder X-ray diffraction and Raman spectroscopy that addition of hydrogen peroxide to the methanol solution of ZrOCl₂ and TiCl₄ before gelation was induced by ammonia addition promoted the formation of the mixed oxide phase with the anatase structure in addition to the expected phase of columbite structure. This increased the surface area and activity of the mixed oxide. Promotion with sulfate enhanced the acidity and activity of the catalysts. When sulfate was added by treatment with sulfuric acid, phase transformation, depending on the concentration of the acid used, in addition to sulfate deposition on the oxide surface, occurred. The treatment with 96% sulfuric acid resulted in a catalyst with nearly entirely the anatase structure. This catalyst was found to be the most active, capable of complete conversion of CFC-12 and 100% selectivity to carbon dioxide at 280°C. Prolonged reaction of this catalyst at 280°C for 211 h resulted neither in reduction of activity nor reduction in CO₂ selectivity. The performance of this catalyst is among the highest reported in the literature.     

石墨烯/二氧化钛对PVC薄膜性能影响

以石墨粉和三氯化钛为原料,通过Hummers和水解法制备得石墨烯/二氧化钛(G/TiO₂),将G/TiO₂作为填料添加到聚氯乙烯(PVC)中,探究其对PVC薄膜性能的影响。结果表明,添加G/TiO₂提高了PVC薄膜的力学性能、抗静电性能和耐紫外老化性能。添加G/TiO₂的PVC薄膜的拉伸强度由纯PVC薄膜的12.79 MPa提升至22.74 MPa,提高了77.80%,断裂伸长率由77.73%提升至98.23%,提高了26.37%,表面电阻由大于1.034×10¹²Ω降低至8.156×10⁵Ω,达到抗静电材料要求;经过150 h紫外老化后,纯PVC薄膜的拉伸强度由12.79 MPa降低至8.49 MPa,下降了33.62%;添加G/TiO₂的PVC薄膜的拉伸强度由22.74 MPa降低至18.54 MPa,仅下降18.64%。     

Structure and photocatalytic performance of TiO2/clay nanocomposites for the degradation of dimethachlor

In the present study TiO₂/clay composites were synthesized by dispersion of TiO₂ on the surfaces of a natural montmorillonite and a synthetic hectorite in order to increase the sorption ability of TiO₂ and therefore its photocatalytic action. Six materials with different loading in TiO₂ (15, 30 and 55 wt%) were prepared and characterized by several analytical techniques including XRD, BET and SEM analysis. The synthetic procedure allows the development of delaminated layers for hectorite–TiO₂ samples, while in the case of montmorillonite–TiO₂ composites we have the formation of a more lamellar-like aggregation. It was found that, the greater the percentage of TiO₂, the greater the pore volume and the specific surface area of the montmorillonite–TiO₂ samples. On the contrary, in the case of hectorite–TiO₂ samples, as the content of TiO₂ increases, the surface area and pore volume decreases. The photocatalytic efficiency of the nanocomposite catalysts was evaluated using a chloroacetanilide herbicide (dimethachlor) in water as model compound. The primary degradation of dimethachlor followed pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. All supported catalysts exhibit good photodegradation efficiency and their overall removal efficiency per mass of TiO₂ was better than that of bare TiO₂ produced by the sol–gel method. In conclusion, together with their good sedimentation ability the composite materials could be considered as a promising alternative for the removal of organic water contaminants.     

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”.     

Catalytic wall reactor: Catalytic coatings of stainless steel by VOx/TiO2 and Co/SiO2 catalysts

Catalytic wall (structured) reactors and structured supports are suitable to study the catalytic properties of nanosized materials. The coating of metallic (aluminum and stainless steel) plates by thin layers of active phase is presented in two cases, VO_x/TiO₂ and Co/SiO₂, catalysts used in the oxidative dehydrogenation (ODH) of propane and in Fischer–Tropsch synthesis (FTS) of clean fuels, respectively. The preparation of coated plates and their characterisation by various methods of physicochemical analysis are described. Both chemical and physical methods were used for coating. VO_x/TiO₂ layers were obtained by grafting of Ti (on Al or stainless-steel plates) and V (on TiO₂) alkoxides and use of sol–gel media or suspension. A silica primer was deposited (on stainless-steel plate) by plasma-assisted chemical vapour deposition (PACVD) onto which Co oxide and silica were coprecipitated from sol–gel. The catalytic experiments in the respective reactions were carried out in special plate reactors and compared with those of catalytic powders. The study shows that the coating of a metallic substrate by a catalyst is not straightforward and requires specific studies dealing with both chemistry (chemical affinity between substrate and catalytic layers) and catalytic engineering (catalytic performance in taylor-made reactors).     

Reactivity of V2O5-WO3/TiO2 catalysts in the selective catalytic reduction of nitric oxide by ammonia

The physico-chemical characteristics and the reactivity of sub-monolayer V₂O₅-WO₃/TiO₂ deNO_x catalysts is investigated in this work by EPR, FT-IR and reactivity tests under transient conditions. EPR indicates that tetravalent vanadium ions both in magnetically isolated form and in clustered, magnetically interacting form are present over the TiO₂ surface. The presence of tungsten oxide stabilizes the surface V^IV and modifies the redox properties of V₂O₅/TiO₂ samples. Ammonia adsorbs on the catalysts surface in the form of molecularly coordinated species and of ammonium ions. Upon heating, activation of ammonia via an amide species is apparent. V₂O₅-WO₃/TiO₂ catalysts exhibits higher activity than the binary V₂O₅/TiO₂ and WO₃/TiO₂ reference sample. This is related to both higher redox properties and higher surface acidity of the ternary catalysts. Results suggest that the catalyst redox properties control the reactivity of the samples at low temperatures whereas the surface acidity plays an important role in the adsorption and activation of ammonia at high temperatures.     

TiO2–g-C3N4/BMMS光催化氧化脱硫催化剂

为了提高TiO₂的光催化氧化脱硫(PODS)活性,利用负载和复合的协同作用,将TiO₂与g-C₃N₄复合,并负载于双介孔二氧化硅(BMMS)上,制备了TiO₂–g-C₃N₄/BMMS。以含二苯并噻吩(DBT)的十二烷溶液为模拟油,评价了催化剂的催化性能;优化了反应条件并提出了催化反应机理。结果表明:TiO₂–g-C₃N₄/BMMS具有明显的双介孔结构,TiO₂与g-C₃N₄已实现复合并负载于BMMS上,TiO₂–g-C₃N₄活性组分在载体上分散良好,与单一TiO₂相比对光的吸收能力增强,催化活性有明显提高,优化后的反应条件为,催化剂用量3%(质量分数),O/S摩尔比为10:1,萃取剂与模拟油体积比为1:1,此时脱硫率可达96.6%,且重复使用8次后脱硫率仍保持85%以上,PODS过程中的主要活性中间物种是·O₂^–和h⁺。     

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.