Preparation,characterization and enhanced photocatalytic activity of Ni<Superscript>2+</Superscript> doped titania under solar light

Anatase TiO₂ was prepared by sol-gel method through the hydrolysis of TiCl₄. Ni²⁺ was doped into the TiO₂ matrix in the concentration range of 0.02 to 0.1 at.% and characterized by various analytical techniques. Powder X-ray diffraction revealed only anatase phase for all the samples, while diffuse reflectance spectral studies indicated a red shift in the band gap absorption to the visible region. The photocatalytic activities of these photocatalysts were probed for the degradation of methyl orange under natural solar light. The photocatalyst with optimum doping of 0.08 at.% Ni²⁺, showed enhanced activity, which is attributed to: (i) effective separation of charge carriers and (ii) large red shift in the band gap to visible region. The influence of crystallite size and dopant concentration on the charge carrier trapping — recombination dynamics is investigated.     

Synthesis of Zn doped black TiO2 nanoparticles for degradation of 2, 4, 6 tri-chloro-phenol under visible light

A modified sol-gel method was used for synthesis of zinc doped black TiO₂ nanoparticles. The modified sol-gel synthesised catalyst was utilised for degradation of 2, 4, 6 tri-chloro-phenol under visible light irradiation. The catalyst was characterized using XRD, SEM, TEM, BET and DRS analysis. The nanoparticles were crystalline in nature and in anatase phase. The size of zinc doped black TiO₂ nanoparticles was 5 nm. The synthesised nanoparticles were mesoporous in nature and the specific surface area was found to be 34.15 m²/g. The band gap energy of zinc black TiO₂ nanoparticles was found to be 2.73 eV. The point of zero charge of zinc doped black TiO₂ nanoparticles was 6.7. The maximum degradation of 2, 4, 6 tri-chloro-phenol using 2 mol% zinc doped black TiO₂ was found to be 95%.     

Transition metals Fe3+, Ni2+ modified titanium dioxide (TiO2) film sensors fabricated by CPT method to sense some toxic environmental pollutant gases

The present investigation deals synthesis of undoped TiO₂, Ni²⁺ doped TiO₂, and Fe³⁺ doped TiO₂ nanoparticles by low-cost co-precipitation (CPT) method. The thick film sensors of all the fabricated modified TiO₂ nanoparticles were designed by a screen printing strategy. The prepared thick film sensors were characterized by various sophisticated techniques. The structural parameters of undoped TiO₂ and modified TiO₂ film sensors were characterized by X-Ray Diffraction (XRD) which confirmed anatase phase of TiO₂ lattice. The surface morphological properties of all the prepared materials were confirmed by means of scanning electron microscope (SEM). The energy dispersive spectroscopy (EDS) confirms the elemental composition of all the prepared materials. High-Resolution Transmission Electron Microscopy (HR-TEM) was utilized to investigate the crystal lattice of fabricated TiO₂ material. The HR-TEM results revealed the anatase phase crystal morphology of prepared material. The prepared TiO₂ materials were also characterized by means of X-Ray photoelectron spectroscopy (XPS) to confirm the surface doping, specific biding energies, chemical states and elemental composition of modified TiO₂ materials. The Brunauer–Emmett–Teller (BET) study was carried to investigate the specific surface area of all the prepared sensors. The Fe³⁺ doped TiO₂ sensor found with enhanced surface area (83.10 ​m²/g) in comparison to Ni²⁺ doped TiO₂ and bare TiO₂ (67.34 ​m²/g). All the prepared materials were investigated for gas sensing characteristics. The NO₂, SO₂, and CO₂ gases were investigated for all the prepared sensors. The reusability test confirms that the Fe³⁺ doped TiO₂ is reproducible and stable sensor for long time repeated sensing of SO₂ and NO₂ vapors. Importantly, Fe³⁺ doped TiO₂ sensor showed rapid response and recovery towards SO₂ and NO₂ vapors.     

Synthesis of TiO<Subscript>2</Subscript> using different hydrolysis catalysts and doped with Zn for efficient degradation of aqueous phase pollutants under UV light

In this work, various TiO₂ and TiO₂ doped with 0.1, 1.0, and 5.0 mol% of Zn were prepared by the sol–gel method varying different hydrolysis catalysts (HNO₃, OHAc, H₃PO₄) in order to be used as photocatalysts for environmental applications. The X-ray diffraction results showed that the different TiO₂ samples have presented the anatase as main phase, However, the acid nature has played an important role in the superficial and optical properties. The N-physisortion analysis has revealed that the specific surface area of calcined TiO₂ samples prepared using H₃PO₄, HOAc, and HNO₃ was 245, 100, and 90 m² g⁻¹, respectively, while the spectroscopic UV analysis, the band gap energy has shifted by 3.3–3.0 eV. In order to improve the optical properties of TiO₂, the last preparation was doped with different zinc concentrations. The result showed that, as the Zn concentration increase by 0.1–5.0 mol%, the surface area increased from 90 to 120 m² g⁻¹. Nevertheless, the E _g returned from 3.0 to 3.32. The SEM analyses have not revealed important morphological changes between no doped and doped materials. The catalytic activity of the composite was studied on the photocatalytic degradation of 2,4-Dichlorophenoxyacetic acid (2,4-D) and the activity results showed that small Zn concentrations decrease the t _1/2 in 28 min.     

Preparation, characterization and photocatalytic activity of visible light driven chlorine-doped TiO2

A novel chlorine-doped titanium dioxide catalyst with visible light response was prepared by hydrolysis of tetrabutyl titanate in hydrochloric acid. The catalyst samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS). Results showed that the doped element of Cl lowered the temperatures of phase transformation of TiO₂ from amorphous to anatase and from anatase to rutile. The absorption edge of chlorine-doped TiO₂ calcined at 300°C shifted to visible light region. X-ray photoelectron spectroscopy results proved that chlorine existed in the TiO₂ crystal lattice as anion. The photocatalytic degradation of phenol showed that under visible light (λ > 400 nm) irradiation, the chlorine-doped TiO₂ calcined at 300°C displayed the best performance, the degradation ratio of phenol was 42.5% after 120 min. Translated from Chinese Journal of Catalysis, 2006, 27(10): 890–894 [译自: 催化学报]     

Photocatalytic activity of nitrogen and copper doped TiO2 nanoparticles prepared by microwave-assisted sol-gel process

Cu and N-doped TiO₂ photocatalysts were synthesized from titanium (IV) isopropoxide via a microwave-assisted sol-gel method. The synthesized materials were characterized by X-ray diffraction, UV-vis diffuse reflectance, photoluminescence (PL) spectroscopy, SEM, TEM, FT-IR, Raman spectroscopy, photocurrent measurement technique, and nitrogen adsorption–desorption isotherms. Raman spectra and XRD showed an anatase phase structure. The SEM and TEM images revealed the formation of an almost spheroid mono disperse TiO₂ with particle sizes in the range of 9-17 nm. Analysis of N₂ isotherm measurements showed that all investigated TiO₂ samples have mesoporous structures with high surface areas. The optical absorption edge for the doped TiO₂ was significantly shifted to the visible light region. The photocurrent and photocatalytic activity of pure and doped TiO₂ were evaluated with the degradation of methyl orange (MO) and methylene blue (MB) solution under both UV and visible light illumination. The doped TiO₂ nanoparticles exhibit higher catalytic activity under each of visible light and UV irradiation in contrast to pure TiO₂. The photocatalytic activity and photocurrent ability of TiO₂ have been enhanced by doping of the titania in the following order: (Cu, N) - codoped TiO₂ > N-doped TiO₂ > Cu-doped TiO₂ > TiO₂. COD result for (Cu, N)-codoped TiO₂ reveals ∼92% mineralization of the MO dye on six h of visible light irradiation.     

Photocatalytic Activity of High Aspect Ratio TiO2 Nanorods

In this article, TiO₂ nanorods (aspect ratio >20) were prepared through a polyol process and doped with metal ions (Cu²⁺, Ni²⁺, Fe³⁺, and Cr³⁺). Compared with TiO₂ nanoparticles, the TiO₂ nanorods displayed relatively higher photocatalytic activity for the degradation of copper sulfophthalocyanine. Moreover, the photocatalytic activity was greatly enhanced when the metal ions were doped in the TiO₂ nanorods.     

Preparation and Characterization of Room-temperature Ferromagnetic Ni-doped TiO2 Nanobelts

Ni-doped anatase TiO₂ nanobelts (NBs) with different Ni²⁺ contents were simply prepared by combining ion-exchange with hydrothermal treatment. They were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), and magnetic measurement techniques. The results showed that Ni²⁺ cations doped into the TiO₂ lattice and no metallic nickel clusters or nanoparticles could be found. The magnetic results demonstrated that the prepared Ni-doped TiO₂ samples had complex magnetic mechanism including room-temperature ferromagnetic and paramagnetic behaviors, and with the increase of Ni²⁺ content, the magnetization also increased under the same applied field owing to uniform distribution of Ni²⁺ ions in TiO₂ nanobelts.     

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.     

Efficient decomposition of liquid waste containing EDTA by advanced oxidation nanotechnology

Degradation of ethylenediaminetetraacetic acid (EDTA) present in the liquid waste was demonstrated by photocatalytic oxidation route by using nanoparticles of anatase titania. Nano sized titania photocatalyst was synthesized using sol–gel method coupled with ultrasonication mode and characterized using X-ray diffraction, transmission electron microscope, BET, Fourier transform infrared spectroscopy and TG–DTA. A cylindrical photoreactor was employed for the degradation studies. Five milligram of the nano anatase TiO₂ + 0.5 ml of 30% H₂O₂ were employed as catalysts for the degradation studies of 1,000 mg/L EDTA. EDTA degradation was followed by a complexometric titration method. Complete degradation of 1,000 mg/L EDTA could be achieved in 90 min and the photocatalytic efficiency of the synthesized titania photocatalyst was higher than that of P-25 TiO₂ for EDTA degradation. The influence of pH on the degradation of EDTA follow the order acidic > neutral > alkaline. More than ten fold increases in the decontamination factors were obtained for the chemical precipitation step for the liquid waste containing degraded EDTA compared to liquid waste without EDTA degradation.     

Preparation of nanocrystalline TiO<Subscript>2</Subscript> powders for photocatalytic oxidation of phenol

Nanocrystalline TiO₂ powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl₄ solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m²/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO₂ nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic mixed-phase TiO₂ powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO₂ (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated that rutile TiO₂ crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after the photocatalytic process over the rutile TiO₂ photocatalysts of larger crystallite size.     

Thermal and hydrothermal stability of flame hydrolytically synthesized SiO2/TiO2 mixed oxides

The phase stability of the two TiO₂ modifications (anatase and rutile) in fumed SiO₂/TiO₂ nano-composites (0–24.8 wt-% silica) under thermal and hydrothermal conditions was investigated by X-ray powder diffraction, transmission electron microscopy (TEM) and gas adsorption methods (BET). The results show that the phase transformation from anatase to rutile type of structure and the growth of anatase crystallites are significantly retarded by mixing small amounts of SiO₂ into TiO₂, while the specific surface area is maintained. The SiO₂/TiO₂-composites reveal a remarkable shift in the anatase to rutile transformation temperature from approx. 500 °C (pure TiO₂) to approx. 1000 °C (samples with SiO₂ contents of more than 10%). The rate of phase transformation from anatase to rutile is enhanced under hydrothermal conditions compared to conventional thermal treatment, e.g. pure titania (AEROXIDE^® TiO₂ P25) annealed under hydrothermal conditions (100 g/m³ absolute humidity, 4 h at 600 °C) had a rutile content of 85%, while the same specimens annealed in absence of humidity contained only 46% rutile. However, the difference in rate of phase transformation became less pronounced when the silica content in SiO₂/TiO₂-composites was further increased.TEM results showed that the surface of the anatase crystallites was covered with silica. This averts coalescence of anatase crystallites and keeps them under a critical size during the annealing process. When the crystal domains grew larger, a rapid conversion to rutile took place. The critical size of anatase crystallites for the phase transformation was estimated to be 15–20 nm.     

X-ray induced photocatalysis on TiO2 and TiO2 nanotubes: Degradation of organics and drug release

The photocatalytic activity of titanium dioxide under X-ray radiation is of great interest for biomedical applications. In the present work we explore the use of compact TiO₂ layers and TiO₂ nanotubes for X-ray induced photocatalysis, in particular the degradation of organics and monolayer chain scission for drug release. The radiation was done with a conventional X-ray source and doses up to 50 × 10^?3 J/kg. The results show the feasibility of X-ray catalysis on TiO₂ and X-ray induced monolayer chain scission by the release of surface attached Zn–porphyrin molecules. Furthermore, a higher efficiency for anatase films and nanotubes is obtained than for amorphous morphologies.     

Dye degradation studies of Mo‐doped TiO2 thin films developed by reactive sputtering

TiO₂ thin films with various Mo concentrations have been deposited on glass and n‐type silicon (100) substrates by this radio‐frequency (RF) reactive magnetron sputtering at 400°C substrate temperature. The crystal structure, surface morphology, composition, and elemental oxidation states of the films have been analyzed by using X‐ray diffraction, field emission scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy, respectively. Ultraviolet‐visible spectroscopy has been used to investigate the degradation, transmittance, and absorption properties of doped and undoped TiO₂ films. The photocatalytic degradation activity of the films was evaluated by using methylene blue under a light intensity of 100 mW cm⁻². The X‐ray diffraction patterns show the presence of anatase phase of TiO₂ in the developed films. X‐ray photoelectron spectroscopy studies have confirmed that Mo is present only as Mo⁶⁺ ions in all films. The Mo/TiO₂ band gap decreases from ~3.3 to 3.1 eV with increasing Mo dopant concentrations. Dye degradation of ~60% is observed in Mo/TiO₂ samples, which is much higher than that of pure TiO₂.     

Solar active nano-TiO2 for mineralization of Reactive Red 120 and Trypan Blue: 1st Nano Update

Nano-TiO₂ was synthesized by sol–gel method. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) images, transmission electron microscope (TEM), BET surface area measurement and DRS analysis. The formation of anatase phase nano-TiO₂ was confirmed by XRD measurements and its crystalline size is found to be 15.2 nm. SEM images depict the crystalline nature of prepared TiO₂. The BET surface area of prepared TiO₂ is found to be 86.5 m² g^?1 which is higher than that of commercially available TiO₂–P25. The photocatalytic activity of prepared anatase phase TiO₂ has been tested for the degradation of two azo dyes: Reactive Red 120 (RR 120) and Trypan Blue (TB) using solar light. The photocatalytic activity of nano-TiO₂ is higher than TiO₂–P25 under solar light. The mineralization of dyes has been confirmed by chemical oxygen demand (COD) measurements.     

Preparation of nanocrystalline Fe-doped TiO<Subscript>2</Subscript> powders as a visible-light-responsive photocatalyst

Nanocrystalline Fe-doped TiO₂ powders were prepared using TiOSO₄, urea, and Fe(NO₃)₃ · 9H₂O as precursors through a hydrothermal method. The as-synthesized yellowish-colored powders are composed of anatase TiO₂, identified by X-ray diffraction (XRD). The grain size ranged from 9.7 to 12.1 nm, calculated by Scherrer’s method. The specific surface area ranged from 141 to 170 m²/g, obtained by the Brunauer–Emmett–Teller (BET) method. The transmission electron microscopy (TEM) micrograph of the sample shows that the diameter of the grains is uniformly distributed at about 10 nm, which is consistent with that calculated by Scherrer’s method. Fe³⁺ and Fe²⁺ have been detected on the surface of TiO₂ powders by X-ray photoelectron spectroscopy (XPS). The UV–Vis diffuse reflection spectra indicate that the light absorption thresholds of the Fe-doped TiO₂ powders have been red-shifted into the visible light region. The photocatalytic activity of the Fe-doped TiO₂ was evaluated through the degradation of methylene blue (MB) under visible light irradiation. The Fe-doped TiO₂ powders have shown good visible-light photocatalytic activities and the maximum degradation ratio is achieved within 4.5 h.     

Synthesis and Studies of the Visible‐Light Photocatalytic Properties of Near‐Monodisperse Bi‐Doped TiO2 Nanospheres

Near‐monodisperse Bi‐doped anatase TiO₂ nanospheres with almost uniform diameters in the range of 117 to 87 nm were prepared simply by introducing different amounts of bismuth nitrate pentahydrate into the reaction system and subsequent calcinations. X‐ray diffraction, UV‐visible diffuse reflectance spectra, and X‐ray photoelectron spectroscopy confirm that the doped ions substitute some of the lattice titanium atoms, and furthermore, Bi³⁺ and Bi⁴⁺ ions coexist. All the Bi‐doped TiO₂ samples show much better photocatalytic activity than pure TiO₂ in the degradation of rhodamine B (RhB) under the irradiation of visible light (λ>420 nm), and, interestingly, it was found that the degradation mechanism is different from the conventional one, which has already been reported elsewhere. The detailed mechanism is discussed in this article.     

Effect of annealing temperatures and of high content of the iron ion (Fe<Superscript>3+</Superscript>)-doping on transition anatase–rutile phase of nanocrystalline TiO<Subscript>2</Subscript> thin films prepared by sol–gel spin coating

Titanium dioxide doped with iron (III) was prepared by sol–gel Spin Coating method. The phase structures, morphologies, particle size of the doped TiO₂ have been characterized by X-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM) and ultraviolet–visible (UV–Vis) spectrophotometer. The XRD and Raman results show that the 10% Fe³⁺-doped TiO₂ thin films crystallize in anatase phase between 600 and 800 °C, and into the anatase–rutile phase at 1,000 °C, and further into the rutile phase when the content of Fe³⁺ increases (20%). The grain size calculated from XRD patterns shows that the crystallinity of the obtained anatase particles increased from 39.4 to 43.4 nm as the temperature of annealing increase, whereas the size of rutile crystallites increases, with increasing Fe³⁺ concentrations from 36.9 to 38.1 nm. The AFM surface morphology results confirmed that the particle size increases by increasing the annealing temperature and also with an increasing of Fe³⁺ content. The optical band gap (E _g) of the films was determined by the UV–Vis spectrophotometer. We have found that the optical band gap decreased with an increasing of annealing temperatures and also with an increasing of Fe³⁺ content.     

Photocatalytic hydrogen evolution over mesoporous TiO2/metal nanocomposites

Na⁺ complex with the dibenzo-18-crown-6 ester was used as a template to synthesize mesoporous titanium dioxide with the specific surface area 130–140 m²/g, pore diameter 5–9 nm and anatase content 70–90%. The mesoporous TiO₂ samples prepared were found to have photocatalytic activity in Cu^II, Ni^II and Ag^I reduction by aliphatic alcohols. The resulting metal–semiconductor nanostructures have remarkable photocatalytic activity in hydrogen evolution from water–alcohol mixtures, their efficiency being 50–60% greater than that of the metal-containing nano-composites based on TiO₂ Degussa P25.The effects of the thermal treatment of mesoporous TiO₂ upon its photocatalytic activity in hydrogen production were studied. The anatase content and pore size were found to be the basic parameters determining the photoreaction rate. The growth of the quantum yield of hydrogen evolution from TiO₂/Ag⁰ to TiO₂/Ni⁰ to TiO₂/Cu⁰ was interpreted in terms of differences in the electronic interaction between metal nanoparticles and the semiconductor surface. It was found that there is an optimal metal concentration range where the quantum yield of hydrogen production is maximal. A decrease in the photoreaction rate at further increment in the metal content was supposed to be connected with the enlargement of metal nanoparticles and deterioration of the intimate electron interaction between the components of the metal–semiconductor nanocomposites.     

Hydrothermal synthesis of mesostructured nanocrystalline TiO2 in an ionic liquid–water mixture and its photocatalytic performance

Anatase mesostructured TiO₂ nanocrystalline was prepared in a mixture of 1-butyl-3-methyl-imidazolium tetrafluoroborate (BMIM⁺BF₄⁻) ionic liquid and water by a low temperature hydrothermal method. The obtained materials were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and N₂ adsorption–desorption. The existence of BMIM⁺BF₄⁻ enhanced the polycondensation and crystallization rate, which encouraged the formation of anatase crystal. The TiO₂ particles were thermally very stable and thus resistant to anatase-rutile phase transformation during calcination at high temperatures. The anatase TiO₂ showed high photocatalytic activity in the degradation of p-chlorophenol than that of the commercially available TiO₂, Degussa P25. After 2 h reaction under the UV-irradiation of 250 W, the removing rate of p-chlorophenol was up to 96.3%.