Visible light photocatalyst: iodine-doped mesoporous titania with a bicrystalline framework

Iodine-doped (I-doped) mesoporous titania with a bicrystalline (anatase and rutile) framework was synthesized by a two-step template hydrothermal synthesis route. I-doped titania with anatase structure was also synthesized without the use of a block copolymer as a template. The resultant titania samples were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared, nitrogen adsorption, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible absorption spectroscopy. Both I-doped titania samples, with and without template, show much better photocatalytic activity than commercial P25 titania in the photodegradation of methylene blue under the irradiation of visible light (>420 nm) and UV-visible light. Furthermore, I-doped mesoporous titania with a bicrystalline framework exhibits better activity than I-doped titania with anatase structure. The effect of rutile phase in titania on the adsorptive capacity of water and surface hydroxyl, and photocatalytic activity was investigated in detail. The excellent performance of I-doped mesoporous titania under both visible light and UV-visible light can be attributed to the combined effects of bicrystalline framework, high crystallinity, large surface area, mesoporous structure, and high visible light absorption induced by I-doping.     

Study of photocatalytic activity of Cd-doped mesoporous nanocrystalline TiO2 prepared at low temperature

Mesoporous nanocrystalline Cd-doped titania was firstly prepared at low temperature by a modified sol–gel method, using dodecylamine as a template. The template could be easily removed by refluxing samples in nitric acid ethanol solution. The Fourier transform infrared spectrometer (FT-IR), low-angle and wide-angle X-ray diffraction (XRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and UV–visible diffuse reflectance spectroscopy were used for the characterization of catalysts. The characteristic results clearly showed that Cd²⁺ ions were doped into the titania lattice, and the mesoporous architecture of Cd-doped TiO₂ was composed of mixed-phase crystal textures of anatase and brookite. The samples displayed high visible-light photocatalytic activity for photodegradating 2,4-dichlorophenol (2,4-DCP) solution. The high activities of samples were attributed to the bicrystalline framework, large BET surface area, small crystallite size, and Cd-doping.     

Photocatalytic activity of a hierarchically macro/mesoporous titania

Light-harvesting macroporous channels have been successfully incorporated into a mesoporous TiO(2) framework to increase its photocatalytic activity. This bimodal porous material was characterized by X-ray diffractometry in both low-angle and wide-angle ranges, N(2) adsorption-desorption analysis, scanning and transmission electron microscopy, FT-IR, and diffuse reflectance spectroscopy. Ethylene photodegradation in gas-phase medium was employed as a probe reaction to evaluate the photocatalytic reactivity of the catalysts. The results reveal that sintering temperature significantly affects the structural stability and photocatalytic activity of titania. The catalyst which calcined at 350 degrees C possessed an intact macro/mesoporous structure and showed photocatalytic reactivity about 60% higher than that of commercial P25 titania. When the sample was calcined at 500 degrees C, the macroporous structure was retained but the mesoporous structure was partly destroyed. Further heating at temperatures above 600 degrees C destroyed both macro- and mesoporous structures, accompanied by a loss in photocatalytic activity. The high photocatalytic performance of the intact macro/mesoporous TiO(2) may be explained by the existence of macrochannels that increase photoabsorption efficiency and allow efficient diffusion of gaseous molecules.     

Aerosol-assisted fabrication of mesoporous titania spheres with crystallized anatase structures and investigation of their photocatalitic properties

We demonstrate practical aerosol-assisted approach to synthesize spherical mesoporous titania particles with high surface areas. Scanning electron microscopy observation of the spray-dried products clearly shows spherical morphology. To remove surfactants and enhance crystallinity, the spray-dried products are calcined under various temperatures. The crystalline structures inside the particles are carefully detected by wide-angle XRD measurements. With increase of the calcination temperatures, anatase crystal growth proceeds and transformation from anatase to rutile is occurred. The effect of various calcination temperatures on the mesostructures is also studied by using N₂ adsorption desorption isotherms. The mesoporous titania particles calcined at 350, 400, and 500 °C exhibit type IV isotherms with a capillary condensation step and shows a hysteresis loop, which is a characteristic of mesoporous materials. The reduction in the surface areas and the pore volumes is confirmed by increasing the calcination temperatures, while the average pore diameters are increased gradually. This is attributed to the distortion of the mesostructures due to the grain growth of the anatase phase and the transformation to the rutile phase during the calcination process. As a preliminary experimental photocatalytic activity, oxidative decomposition of acetaldehyde under UV irradiation is examined. The mesoporous titania calcined at 400 °C shows the highest photocatalytic activity, due to both high surface area and well-developed anatase crystalline phase.     

Visible light photodegradation of rhodamine B over VDF/CTFE copolymer-templated crystalline mesoporous titania

Mesoporous TiO₂ with anatase crystalline structure (MTiO₂/F₂₃₁₉) has been synthesized by using vinylidene fluoride/chlorotrifluoroethylene copolymer (1:9 in mole, F₂₃₁₉) as template. The synthesized mesoporous titania samples were characterized by a combination of various physicochemical techniques, such as X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, and N₂ adsorption/desorption. It was found that without any external doping, MTiO₂/F₂₃₁₉ exhibited significantly higher photocatalytic activities for the degradation of rhodamine B (RhB) dye than P25 TiO₂ under visible light irradiation. Furthermore, the UV-Vis absorption maximum of the dye solution exhibited a gradual hypsochromic shift due to de-ethylation and degradation of RhB dye.     

Photocatalytic activity of structured mesoporous TiO2 materials

Starting from colloidal TiO2 nanoparticles in combination with tetraethyl orthosilicate using neutral Pluronic or cationic cetyltrimethylammonium as templates, a series of structured mesoporous silicas has been obtained. The structure of the mesoporous titania was confirmed by isothermal gas adsorption, transmission electron microscopy, and X-ray diffraction. The pore diameter ranged between 3.8 and 10.9 nm, and the BET surface area varied from 99 to 584 m2 g(-1). The photocatalytic activity of these samples for the degradation of phenol in aqueous solution has been compared with that of standard P-25 TiO2. Even though the activity of these new mesostructured materials is lower that those found for P-25 TiO2, the turnover frequency of the photocatalytic activity (moles of phenol degraded per Ti atom present at initial reaction time) is much higher for the mesoporous titania, particularly with low titanium contents for those materials (mpTiO2-5 and TiO2SBA15-5).     

Characterization of mesoporous nanocrystalline TiO2 photocatalysts synthesized via a sol-solvothermal process at a low temperature

Nanocrystalline TiO₂ samples with mesoporous structure were prepared via a solvothermal treatment of surfactant-stabilized TiO₂ sols. The samples were obtained from media of different acidities including nitric acid, deionized water, and ammonia (denoted as HT-1, HT-2 and HT-3, respectively). These samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂-sorption (BET surface area), micro-Raman spectroscopy, infrared absorption spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were tested by the self-photosensitized degradation of an azo dye, Mordant Yellow 10 (MY), in aqueous solution under visible light irradiation. The results reveal that all three samples have high surface area and are pure anatase phase. The sample prepared in nitric acid medium possesses the most ideal mesoporous structure and also exhibits a blue shift in the Raman spectrum. All three samples show much higher photocatalytic activity than the commercial P-25. The activity order of the three samples is HT-1>HT-2>HT-3.     

Direct synthesis of mesoporous titania particles having a crystalline wall

In this study, we demonstrate a novel method for preparing crystallized mesoporous titania by using a low-temperature synthesis technique in the presence of cationic surfactant. XRD patterns showed that the titania particles obtained had both hexagonal structure and a wall with anatase crystalline structure. Transmission electron microscopy (TEM) observation and corresponding electron diffraction pattern confirmed that the calcined particles are crystallized mesoporous titania.     

New method to synthesize mesoporous titania by photodegradation of surfactant template

Mesoporous titania has been successfully synthesized by photodegradation removal of cetyltrimethylammonium bromide as the surfactant, after slow hydrolyzation of titanium(IV) isopropoxide. Fourier transform infrared spectra proved that photodegradation has successfully decreased the peak areas of the alkyl groups from the template. The nitrogen adsorption analysis showed that the pore size and the specific surface area of the mesoporous titania were 3.7 nm and 203 m² g⁻¹, respectively, proving the mesoporosity of the titania obtained with the existence of the interparticle mesoporosity which was confirmed by transmission electron microscopy. Based on X-ray diffraction results, the mesoporous titania obtained was in the form of crystalline anatase phase. Furthermore, results from the diffuse reflectance ultra violet-visible spectra showed that the composition of tetrahedral titanium(IV) was more than the octahedral titanium(IV). When the mesoporous titania obtained was used as a catalyst in the oxidation of styrene, an improvement in the conversion of styrene (38%) was observed when compared to those obtained using Degussa P25 TiO₂ (14%) as the catalyst.     

Synthesis and photocatalytic activity for water-splitting reaction of nanocrystalline mesoporous titania prepared by hydrothermal method

Nanocrystalline mesoporous TiO₂ was synthesized by hydrothermal method using titanium butoxide as starting material. XRD, SEM, and TEM analyses revealed that the synthesized TiO₂ had anatase structure with crystalline size of about 8 nm. Moreover, the synthesized titania possessed a narrow pore size distribution with average pore diameter and high specific surface area of 215 m²/g. The photocatalytic activity of synthesized TiO₂ was evaluated with photocatalytic H₂ production from water-splitting reaction. The photocatalytic activity of synthesized TiO₂ treated with appropriate calcination temperature was considerably higher than that of commercial TiO₂ (Ishihara ST-01). The utilization of mesoporous TiO₂ photocatalyst with high crystallinity of anatase phase promoted great H₂ production. Furthermore, the reaction temperature significantly influences the water-splitting reaction.     

Application of synthesized mesoporous titania microspheres for arsenic [(III) and (V)] uptake studies

The present work describes the application of radiotracer technique for studying uptake of arsenic on titanium hydroxide, commercial titanium dioxide (TiO₂) powder (anatase) and synthesized mesoporous titania beads in acidic, neutral, and alkaline conditions. Sol–gel templating method was used to prepare titania–polysaccharide composites, with different polymer contents. Mesoporous titania was obtained by heat treatment of the composite beads in a controlled environment. The synthesis process was optimized, using thermogravimetry analysis. X-ray diffraction patterns confirmed the formation of anatase pure phase titania (TiO₂) at 700 °C in different environments, and scanning electron microscopy studies confirmed uniform pore size distribution. The effect of surface area, polymer content and pH on uptake of arsenic(III) and (V) on the synthesized titania beads was also investigated. Arsenic(V) was found to be retained quantitatively on the titania beads synthesized from 0.8% polymer content titania–polymer composite precursor in neutral to alkaline conditions. Details of the results obtained are discussed.     

Anatase formation during the synthesis of mesoporous titania and its photocatalytic effect

Thermally stable mesoporous titania can be synthesized following different synthesis routes. In this paper, mesoporous titania was synthesized applying the evaporation-induced self-assembly (EISA) method. The mesostructured titania was treated with an NH(4)OH solution to increase the thermal stability. The influence of this postsynthesis treatment on the anatase formation was investigated using different initial synthesis conditions. Mesoporous titania was synthesized under both acidic and basic conditions, with hexadecylamine and cetyltrimethylammonium bromide as surfactants. The samples were investigated with FT-Raman to investigate when exactly anatase was formed during the synthesis. It will be shown that the anatase formation depends mainly on the initial synthesis conditions. This study shows that anatase can already be formed before calcination under certain circumstances. Furthermore, the accessibility of the anatase phase influenced the photocatalytic activity.     

Effect of calcination atmosphere on the structure and photocatalytic properties of titania mesoporous powder

In the work presented here, mesoporous titania (MTO) powders are synthesised by the sol?Cgel method using amphiphilic triblock copolymer as a template in two different calcination atmospheres, N₂ and air. Various techniques such as sequential thermal analysis (STA), small-angle X-ray diffraction (SAXRD), wide-angle X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet (UV)?Cvisible spectroscopy, high-resolution transmission electron microscopy (HRTEM) and N₂-adsorption/desorption analysis were utilised to study the prepared samples. Furthermore, the photocatalytic activities of the prepared samples were evaluated from the photo-degradation analysis of methylene blue (MB). For the sample calcined at N₂, the formation of an ordered mesostructure with a high specific surface area (172?m²?g^?1), mesoporosity (48%) and enhanced photocatalytic activity were obtained compared to that of the sample calcined in air. The observed increased MB degradation for the latter is mainly attributed to the formation of higher specific surface area and mesoporosity. The availability of highly ordered open-pore channels could provide increased contacts between reactants in the solution and the active sites on the surface of titania mesoporous particles. Considering the photoactivities of the samples, it is revealed that the photocatalytic activity is enhanced, together with an increase in the surface defects in N₂ atmosphere.     

Core-shell structure CdS/TiO2 for enhanced visible-light-driven photocatalytic organic pollutants degradation

CdS modified mesoporous titania core-shell spheres (CdS/CS-TiO₂) with enhanced visible-light activity were synthesized by an in situ method. This method included two steps: planting CdO into the framework of anatase TiO₂ core-shell spheres and then converting it to CdS by ion-exchange. The physicochemical properties of the obtained samples were investigated by X-ray diffraction, scanning electron microscopy, transmission electronic micrograph, UV–vis diffuse reflectance spectra and nitrogen sorption. The in situ strategy resulted in CdS quantum dots highly dispersed in CS-TiO₂ without destroying the mesoporous core-shell structure. Compared with CS-TiO₂, the as-synthesized samples exhibited stronger visible-light absorption capability and greatly enhanced photocatalytic activity toward the degradation of Rhodamine B and 4-chlorophenol aqueous solution under visible light irradiation (λ > 420 nm).     

Direct synthesis of Nd3+ doped mesoporous TiO2 and investigation of its photocatalytic performance

Nd³⁺ doped mesoporous TiO₂ samples with different molar ratio of Nd/Ti were synthesized by a sol?Cgel method. The textural and optical properties of the samples were systematical characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption?Cdesorption isotherms, Fourier transform infrared spectroscopy and UV?CVisible absorbance spectroscopy. It was revealed that Nd³⁺ doping inhibited the phase transformation from anatase to rutile after calcination, and the mesoporous structure of doped samples was still retained with the increase of Nd/Ti molar ratio. The surface area of the samples varied from 137 to 210 m²g^?1 and the average pore size of them ranged between 5.7 and 8.2?nm. The photocatalytic activities of all the samples were evaluated by degradation methyl orange (MO) in aqueous solution as a model reaction under UV light irradiation. The results showed that the doped samples demonstrated a higher photocatalytic activity than the mesoporous TiO₂, and the 3?mol% Nd³⁺ doped mesoporous TiO₂ exhibited the best photocatalytic performance. Meanwhile, a promotion effect of the H₂O₂ added was verified in the degradation of MO.     

硫和银共掺杂介孔TiO2的制备表征及光催化活性

以P123为模板,以钛酸四正丁酯、硝酸银和硫脲为原料采用模板法制备了一系列硫和银共掺杂介孔TiO2光催化材料。利用扫描电子显微镜（SEM）、X射线衍射（XRD）、BET和紫外-可见光谱（UV-Vis）等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征。以甲基橙溶液的光催化降解为模型反应, 考察了不同掺杂量的样品在紫外和可见光下的光催化性能。结果表明：用模板法制备的共掺杂介孔TiO2光催化材料在紫外和可见光条件下较纯介孔TiO2和单掺杂介孔TiO2对甲基橙溶液具有更好的光催化降解效果, 且硫和银的掺杂量及样品焙烧温度显著影响该材料的催化性能。当硫掺杂量为2%（mol）和银掺杂量为1%（mol）,在500℃焙烧2 h所得光催化材料的催化性能最佳, 4 h即可使甲基橙的降解率达98.8%,重复使用4次仍可使甲基橙的降解率保持在87.5%以上。因此, 以该模板合成法, 通过硫和银的共掺杂有望使TiO2成为一种低或无能耗、高活性的绿色环保型催化材料。     

Preparation and photocatalytic activity of multi-modally macro/mesoporous titania

Hierarchically disorder sponge-like macro/mesoporous titania was prepared by adding distilled water dropwise to a coating of tetrabutyl titanate. The results reveal that the un-calcined samples show obvious photocatalytic activity and multi-modal pore-size distribution. With increasing calcination temperatures, the photocatalytic activity and crystallinity increase. At 400°C, the calcined sample shows the highest photocatalytic activity. Further increasing the calcination temperatures results in the decrease of photocatalytic activity due to the drastic decrease of specific surface areas. However, the 600°C-calcined sample exhibits the highest specific photocatalytic activity due to high anatase crystallinity.     

Sonochemical fabrication of fluorinated mesoporous titanium dioxide microspheres

A sonochemical-hydrothermal method for preparing fluorinated mesoporous TiO₂ microspheres was developed. Formation of mesoporous TiO₂ and doping of fluorine was achieved by sonication and then hydrothermal treatment of a solution containing titanium isopropoxide, template, and sodium fluoride. The as-synthesized TiO₂ microspheres were characterized by X-ray diffraction (XRD), Fourier translation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, photoluminescence spectroscopy (PL), and BET surface areas. The P123 template was removed completely during the hydrothermal and washing steps, which was different from the conventional calcination treatment. The as- synthesized TiO₂ microspheres had good crystallinity and high stability. Results from the photocatalytic degradation of methylene blue (MB) showed that fluorination could remarkably improve the photocatalytic activity of titanium dioxide.     

Novel synthesis of high-surface-area ordered mesoporous TiO2 with anatase framework for photocatalytic applications

Ordered mesoporous TiO₂ materials with an anatase frameworks have been synthesized by using a cationic surfactant cetyltrimethylammonium bromide (C₁₆TMABr) as a structure-directing agent and soluble peroxytitanates as Ti precursor through a self-assembly between the positive charged surfactant S⁺ and the negatively charged inorganic framework I^? (S⁺I^? type). The low-angle X-ray diffraction (XRD) pattern of the as-prepared mesoporous TiO₂ materials indicates a hexagonal mesostructure. XRD and transmission electron microscopy results and nitrogen adsorption–desorption isotherms measurements indicate that the calcined mesoporous TiO₂ possesses an anatase crystalline framework having a maximum pore size of 6.9 nm and a maximum Brunauer–Emmett–Teller specific surface area of 284 m² g^?1. This ordered mesoporous anatase TiO₂ also demonstrates a high photocatalytic activity for degradation of methylene blue under ultraviolet irradiation.     

Samarium-doped mesoporous TiO2 nanoparticles with improved photocatalytic performance for elimination of gaseous organic pollutants

Mesoporous TiO₂ doped with different amounts of Sm were prepared via a sol-gel route with Pluronic P123 as template. The materials were characterized by X-ray diffraction, transmission electron microscopy, and N₂ sorption experiments, etc. The photocatalytic activity of the mesoporous TiO₂ was tested in elimination of gaseous methanol and acetone. The Sm doped mesoporous TiO₂ have higher activity than those of the commercial photocatalyst (Degussa, P25) and Sm doped TiO₂ counterparts without mesopore structure under ultraviolet light irradiation. A possible mechanism was proposed to account for the high photocatalytic activity of the Sm doped mesoporous TiO₂. The superior activity of the Sm doped mesoporous TiO₂ may be attributed to the synergic effect of the high surface area, mesopore structure and doped Sm species.