Visible light photodegradation of dyes over mesoporous titania prepared by using chrome azurol S as template

Mesoporous TiO₂ with anatase crystalline structure (MTiO₂/CAS) has been synthesized by using chrome azurol S (CAS, 2″,6″-dichloro-3,3′-dimethyl-4′-hydroxy-3″-sulfofuchson-5,5′-dicarboxylic acid) as template. It was characterized by X-ray diffraction, nitrogen adsorption/desorption, diffuse reflectance UV–visible and FT-IR spectrometry, and transmission electron microscopy. It was found that MTiO₂/CAS had substantial photocatalytic activity in the degradation of methylthionine chloride, rhodamine B, gentian violet, safranin T, methyl violet, and fuchsine basic whereas Degussa P25 (P25) had negligible photodegradation yield (<6%) under visible light irradiation.     

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.     

Visible light-induced photocatalysis through surface plasmon excitation of platinum-metallized titania for photocatalytic bleaching of rhodamine B

Abstract  

Nanocomposites consisting of titania nanoparticles and metallic platinum were prepared via a soft chemical reduction method. The detailed structural, compositional, and optical characterization and physicochemical properties of the obtained products were analyzed by X-ray diffraction, nitrogen adsorption, Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, and FT-IR spectroscopy techniques. Employing photodegradation of rhodamine B as the model reaction, we found that the as-prepared Pt/TiO₂ nanocomposite showed an excellent photocatalytic oxidation activity under visible light irradiation. On the basis of these results, the intrinsic mechanism of visible light-induced photocatalytic oxidation of organic compounds on the platinized titania is proposed and discussed. The superior visible light-driven photocatalytic efficiency of the Pt/TiO₂ nanocomposite photocatalyst can be ascribed to the high efficiency of charge-pair separation due to the presence of deposited Pt serving as electron sinks to retard the rapid e⁻–h⁺ couple recombination; the good photoabsorption capacity in the visible light region; and the higher concentration of surface hydroxyl groups, which are able to effectively scavenge photogenerated valence band holes. Accumulation of the holes at the catalyst surface increases the probability of the formation of OH· as a reactive species that readily oxidizes the organic dye molecule.     

Liquid phase oxidation of p-chlorotoluene to p-chlorobenzaldehyde over cobalt-doped mesoporous titania with a crystalline framework

Cobalt-doped mesoporous titania with a crystalline framework synthesized by surfactant templating method presented highly selective (99%) and reasonable conversion rate (49%) of catalytic oxidation of para-chlorotoluene to para-chlorobenzaldehyde in acetic acid using aqueous hydrogen peroxide as oxidant for the first time. Recycling of the catalyst indicates that the catalyst can be used a number of times without losing its activity to a greater extent. By contrast, cobalt-doped mesoporous titania without a crystalline structure and cobalt doped the commercial titania, Degussa P25 prepared by impregnation method with the similar concentration of cobalt were found inactive. The effects of catalyst concentration, reaction time, reaction temperature, and solvents on the performance of the catalyst were also investigated.     

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.     

Visible light photoelectrocatalytic degradation of rhodamine B using a dye-sensitised TiO2 electrode

Titanium dioxide is a promising catalyst for application in the photodegradation of organic pollutants in water due to its powerful oxidising property and long-term photostability. This study presents the production of titanium dioxide using the sol-gel process, dye sensitisation of the TiO₂ electrode, and the performance of that cell. Sensitisation of titanium dioxide was performed using a dye, i.e., Fe(II)-polypyridyl complexes. The photoelectrocatalytic degradation of rhodamine B (RB) using ITO/TiO₂/dye as electrode was investigated via a series of potentials, from +1.0 V to ?1.0 V, and at various pH and NaCl concentration values (ITO is indium tin oxide conductive glass). The photoelectrocatalytic degradation of RB was performed with a visible light lamp. The change in the absorbance of RB with various potentials indicated that the absorbance of RB in solution systems with the sensitised TiO₂ electrodes decreased with increasing anodic potential bias. The degradation cell exhibited better performance when the positive anodic bias was applied. The pH values of RB in solution systems also influence the photoelectrodegradation process because of the different RB species present. NaCl concentration also affects the activity of RB photoelectrocatalytic degradation due to changes in the ionic strength character of the electrolyte.     

Immobilization of yttrium over crystalline titania

A co-precipitation method was adopted for the immobilization of yttrium radioactive waste over crystalline titania. A high uptake of⁹¹Y was observed over the preformed hydrous titania. Weighable quantity of Y was coprecipitated with Ti(IV) hydroxide and a maximum of 38 wt% was found to be adsorbed. Mixed masses were calcined separately at 800 and 1000°C for 20 hours, and soxhlet leach tests at 97°C, repeated 7 times at an interval of 24 hours, showed the release of yttrium in the order of 10^–1 and 10^–2 g·m^–2·d^–1, respectively. X-ray powder diffraction analysis revealed that the yttrium was immobilized in the titania crystal lattice which suffered some structural changes with the formation of new mineral phase Y₂Ti₂O₇ which is accompanied by rutile and little quantity of anatase form of titania at 800°C, and only rutile form of titania at 1000°C.     

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.     

Visible light induced photocatalytic reaction of rhodamine B dye via 12-tungstosilicic acid in water

Using 12-tungstosilicic acid (SiW124-) as the catalyst, rhodamine B (RhB) dye in an aerated aqueous solution can undergo an effective photocatalytic stepwise N-deethylation process under visible light irradiation, and dioxygen is reduced to hydrogen peroxide by the reducedSiW12 4-. This provides the potential for moving polyoxometalate-based photocatalytic processes from the near-UV into the visible region of the spectrum.     

Visible light driven photocatalytic hydrogen evolution over CdS incorporated mesoporous anatase TiO2 beads

Research on Chemical Intermediates - The synthesis of CdS incorporated mesoporous anatase TiO2 beads is reported in this work. The mesoporous structure, crystalline structure, morphology and...     

Synthesis of ordered mesoporous crystalline carbon-anatase composites with high titania contents

A direct-triblock-copolymer templating method is demonstrated to synthesize ordered mesoporous crystalline C-TiO(2) (MCT) composites using phenolic resins and acid-base pairs [acidic TiCl(4) and basic counterpart Ti(OC(4)H(7))(4)] as carbon and titanium sources, respectively. The composites possess highly crystalline anatase pore walls that are "glued" by amorphous carbon, ordered mesostructure, high surface areas (approximately 200 m(2)/g), and large pore volumes (approximately 0.15 cm(3)/g). The titania content is as high as 87 wt%. MCT composite favors the immobilization of proteins and enhances the electrocatalytic properties in relation to the reduction of hydrogen peroxide.     

Visible light induced CO2 reduction and Rh B decolorization over electrostatic-assembled AgBr/palygorskite

AgBr/palygorskite composite was prepared by an in situ electrostatic adsorption-deposition-precipitation method and characterized by field emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), UV-Vis diffuse reflection, and BET surface measurements techniques. The layer negative charge and larger specific surface area of palygorskite, along with the poor cation-exchange ability of tetra-n-butyl ammonium cation (N(CH(2)CH(2)CH(2)CH(3))(4)(+)) due to its larger ion radius, could mainly account for high dispersity of AgBr on the surface of fibrous palygorskite. The rate of Rh B decolorization and CO(2) reduction with H(2) as a proton donor and reductant over AgBr/palygorskite was about three and two times faster than that of the corresponding bare AgBr, respectively. The strategy reported in this work can be easily extended to synthesize other palygorskite-based heterostructure catalysts.     

Catalytic role of Ti dopant in boehmite for the photodegradation of rhodamine B

Research on Chemical Intermediates - Ti(IV) ions were introduced into the layered aluminum hydroxides via the precipitation of Al(NO3)3 solution and Ti(C2H5)4. Catalyst texture and structure were...     

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.     

Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO₂) nano-photocatalysts, with different phases, prepared using a modified sol?Cgel process were employed in the degradation of rhodamine at 10?mg?L^?1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450?°C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K _app) of 0.023?min^?1. The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024?min^?1 for 450, 500, 550 and 600?°C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017?min^?1, which is similar to that of the commercial titania.     

Preparation of mesoporous TiO2/CNT nanocomposites by synthesis of mesoporous titania via EISA and their photocatalytic degradation under visible light irradiation

Stabilized mesoporous TiO₂ was synthesized by evaporation induced self assembly (EISA) method and mechanically incorporated into single-walled carbon nanotubes (SWCNT) with different ratios. The physicochemical properties of the nanocomposites (mesoporous TiO₂/SWCNT) materials were investigated by Brunauer–Emmett–Teller (BET) measurement, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), photoluminescence (PL) and ultraviolet–visible (UV–Vis) spectroscopy measurements. The catalytic activity of mesoporous TiO₂ and nanocomposites were assessed by examining the degradation of rhodamine B as model aqueous solution under visible light. CNTs are facilitating the photocatalytic activity of mesoporous TiO₂ in the degradation of rhodamine B efficiently.     

Development of cation exchanger-based nano-CdS hybrid catalyst for visible-light photodegradation of rhodamine B from water

A new polymeric nanocomposite photocatalyst A15-CdS with large spherical beads (0.70-0.80 mm in diameter) was fabricated for efficient Rhodamine B (RhB) photodegradation with facile separation during cyclic runs,and photocorrosion,a congenital drawback of CdS,was successfully inhibited for A15-CdS.The nanocomposite catalyst was obtained by impregnating CdS nanoparticles within porous polymeric cation exchanger A15 through a facile inner-surface deposition.CdS nanoparticles (<20 nm) immobilized in A15 were deliberately distributed within an outside ring-like region of 40-50 m in depth,which is dominant for photoreaction because visible light is not expected to permeate through the inner region of nontransparent A15.As expected,efficient RhB photodegradation by A15-CdS was achieved under visible light irradiation,and large-size A15-CdS beads are expected to result in their facile separation from solution for repeated use.More significantly,negligible photocorrosion for the hybrid catalyst A15-CdS was demonstrated by the constant photodegradation efficiency and negligible CdS loss during five-cycle runs.The results indicated that nano-CdS immobilization within A15 would greatly improve the applicability of CdS nanoparticles in practical environmental remediation.     

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.