Preparation and photocatalysis of TiO2 nanoparticles co-doped with nitrogen and lanthanum

Nanoparticles of TiO₂ powder co-doped with La and N were prepared using a coprecipitation method followed by being two hours calcinated at a temperature ranging from 500 to 600°C in NH₃/Ar atmosphere. Uniformly co-doped TiO₂ nanocrystalline was 5–15 nm with surface area 65–125 m²/g. Optical absorption along with the microstructural investigation for monodoped and co-doped catalyst provided that a part of O vacancy of Ti₅O₉ was occupied by N, which is responsible for the band-gap narrowing of TiO₂, while La³⁺ doping prevents the aggregation of powder in process of nitrification. Superior catalytic activity was observed in the co-doped TiO₂ under visible light (350 < < 450 nm). 20 mg/l methyl orange solution could be docomposed completely within 1 h using the 0.5 at.% La³⁺ doped TiO₂ calcinated in NH₃ for 2 h.     

Synthesis and photocatalytic properties of Zn doped anatase TiO2 nanofibers

Zn²⁺ doped TiO₂ nanofibers were prepared by electrospinning followed by calcination. The results of TGA, FE-SEM, XRD and XPS indicated that the obtained nanofibers with diameter in range of 50–150 nm were composed of anatase TiO₂ phase and Zn²⁺ doping in TiO₂ did not distort the pristine crystal structure of TiO₂. Besides methylene blue (MB) was employed to investigate photocatalytic properties of the obtained samples. The results revealed that Zn²⁺ doped TiO₂ nanofibers had excellent photocatalytic activity, which was symbolized by an optimum photodegradation efficiency of 96.1% under Zn²⁺ doping concentration of 2 at.%. The photocatalytic efficiency of 2 at.% Zn²⁺ doped TiO₂ nanofibers still exceeded 95% after using for five times.     

Effects of samarium dopant on photocatalytic activity of TiO<Subscript>2</Subscript> nanocrystallite for methylene blue degradation

Sm³⁺-doped TiO₂ nanocrystalline was synthesized by a sol–gel auto-combustion method and characterized by X-ray diffraction, Brunauer-Emmett-Teller method (BET), UV–vis diffuse reflectance spectroscopy (DRS), and also photoluminescence (PL) emission spectroscopy. The photocatalytic activity of Sm³⁺–TiO₂ catalyst was evaluated by measuring degradation rates of methylene blue (MB) under either UV or visible light. The results showed that doping with the samarium ions significantly enhanced the photocatalytic activity for MB degradation under UV or visible light irradiation. This was ascribed to the fact that a small amount of samarium dopant simultaneously increased MB adsorption capacity and separation efficiency of electron-hole pairs. The results of DRS showed that Sm³⁺-doped TiO₂ had significant absorption between 400 nm and 500 nm, which increased with the increase of samarium ion content. The adsorption experimental demonstrated that Sm³⁺–TiO₂ had a higher MB adsorption capacity than undoped TiO₂ and adsorption capacity of MB increased with the increase of samarium ion content. It is found that the stronger the PL intensity, the higher the photocatalytic activity. This could be explained by the points that PL spectra mainly resulted from surface oxygen vacancies and defects during the process of PL, while surface oxygen vacancies and defects could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions, so that the recombination of photoinduced electrons and holes could be effectively inhibited.     

Solar photocatalytic degradation of isoproturon over TiO2/H-MOR composite systems

The photocatalytic degradation and mineralization of isoproturon herbicide was investigated in aqueous solution containing TiO₂ over H-mordenite (H-MOR) photocatalysts under solar light. The catalysts are characterized by X-ray diffraction (XRD), UV–Vis diffused reflectance spectra (UV–Vis DRS), Fourier transform-infra red spectra (FT-IR) and scanning electron microscopy (SEM) techniques. The effect of TiO₂, H-MOR support and different wt% of TiO₂ over the support on the photocatalytic degradation and influence of parameters such as TiO₂ loading, catalyst amount, pH and initial concentration of isoproturon on degradation are evaluated. 15 wt% TiO₂/H-MOR composite is found to be optimum. The degradation reaction follows pseudo-first order kinetics and is discussed in terms of Langmuir–Hinshelwood (L–H) kinetic model. The extent of isoproturon mineralization studied with chemical oxygen demand (COD) and total organic carbon (TOC) measurements and 80% mineralization occurred in 5 h. A plausible mechanism is proposed based on the intermediates identified by liquid chromatography–mass spectroscopy (LC–MS).     

Preparation and characterization of N–I co-doped nanocrystal anatase TiO2 with enhanced photocatalytic activity under visible-light irradiation

N–I co-doped TiO₂ nanoparticles were prepared by hydrolysis method, using ammonia and iodic acid as the doping sources and Ti(OBu)₄ as the titanium source. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and ultraviolet–visible diffuse reflection spectroscopy (UV–vis DRS). XRD spectra show that N–I–TiO₂ samples calcined at 673 K for 3 h are of anatase structure. XPS analysis of N–I–TiO₂samples indicates that some N atoms replace O atoms in TiO₂ lattice, and I exist in I⁷⁺, I⁻ and I⁵⁺ chemical states in the samples. UV–vis DRS results reveal that N–I–TiO₂ had significant optical absorption in the region of 400–600 nm. The photocatalytic activity of catalysts was evaluated by monitoring the photocatalytic degradation of methyl orange (MO). Compared with P25 and mono-doped TiO₂, N–I–TiO₂ powder shows higher photocatalytic activity under both visible-light (λ > 420 nm) and UV–vis light irradiation. Furthermore, N–I–TiO₂ also displays higher COD removal rate under UV–vis light irradiation.     

Preparation and properties of antimony-doped SnO2 films by thermal decomposition of tin 2-ethylhexanoate

Transparent Sb-doped SnO₂ films were prepared at 600° C on glass substrates by thermal decomposition of tin 2-ethylhexanoate and antimony tributoxide. The films 100 to 300 nm thick, which are composed of fine particles, were very smooth. The films showed no preferred orientation. The minimum resistivity (2.1×10^–2 cm) was attained at a concentration of 8 at% Sb on the substrate precoated with SiO₂. The transmission of these films was about 80% over a wavelength range from 0.4 to 2.0 m.     

Sintering and properties of SrBi2(Ta1−x V x )2O9 ceramics

The effects of vanadium doping on the sintering, microstructure, dielectric properties, and ferroelectric properties of SrBi₂(Ta_1–x V _x )₂O₉ ceramics were investigated. The densification and grain-growth processes of the vanadium doped ceramics were shifted to a lower temperature range. For the ceramics with relative density 90%, the dielectric constant is 120–125 and 100–130 for the undoped and doped ceramics, respectively, and the dielectric loss tangent is below 1%. As compared with the undoped ceramics, the ferroelectric properties can be significantly improved by doping with an appropriate amount of vanadium and sintering at 1000°C. The variations of dielectric and ferroelectric properties are influenced by the incorporation of vanadium into crystal lattice and several microstructural factors.     

ZrO2–TiO2Materials

The magnetic, electrical, catalytic, and photocatalytic properties of ZrO₂–TiO₂materials were studied. The ZrO₂–TiO₂system was shown to contain ZrO₂-, TiO₂, and ZrTiO₄-based solid solutions. Procedures for the preparation of high-activity ZrO₂–TiO₂photocatalysts and photostable pigments were developed.     

Preparation,characterization and photocatalytic activity of TiO2 codoped with yttrium and nitrogen

Nanocrystalline photocatalysts of TiO₂ codoped with yttrium and nitrogen were prepared by the sol–gel method and investigated by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), the Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), respectively. Slight red-shifts of the Raman peak at 144 cm^?1 were observed in the doped samples after the incorporation of Y³⁺ and N^3? into the lattice of TiO₂. The N doping caused the improvement of visible light absorption because of the formation of the N 2p states isolated above the valence band maximum of TiO₂. Whereas, the absorption property of the pure or N doped TiO₂ was depressed after the introduction of Y. The photocatalytic activities of the samples were evaluated by monitoring the degradation of methylene blue (MB) solution. The codoped sample with N and 0.05 at.% Y exhibited an enhanced photocatalytic efficiency. It is suggested that the charge trapping due to the Y doping and the visible light response due to the N doping are responsible for the enhanced photocatalytic performance in this sample. However, the photocatalytic activity of the codoped TiO₂ was suppressed step by step as the Y doping level increased, which could be attributed to the formation of photogenerated charge carriers recombination centers at the Y substituting sites.     

Electrospinning preparation and characterization of a new kind of composite nanomaterials: One-dimensional composite nanofibers doped with TiO2 nanoparticles and Ru(II) complex

One-dimensional composite nanomaterials, PVP (poly(vinylpyrrolidone)) fibers with diameters in the range of 300–500 nm doped with RuL₂(NCS)₂ (L = 4,4′-Dicarboxy-2,2′-bipyridine) complex and TiO₂ nanoparticles (NPs), were prepared by electrospinning technique. The morphology of the composite nanofibers was systemically studied when the diameters of TiO₂ NPs, the concentrations of TiO₂ NPs and RuL₂(NCS)₂ in the PVP matrix were changed. A new kind of organic–inorganic composite nanomaterials which combine the advantages of one-dimensional nanostructures, organic materials and inorganic materials was obtained and it is desirable for low-weight and flexible photovoltaic devices, especially for dye-sensitized TiO₂ solar cells.     

NO treated TiO2 as an efficient visible light photocatalyst for NO removal

In this study, we report that nitrogen doped TiO₂ could be achieved via thermal treatment of Degussa P25 TiO₂ in NO atmosphere directly (P25-NO). The samples were characterized with XRD, XPS, and FT-IR. The characterization results suggested that nitrogen species were interstitially doped in P25-NO during the NO thermal treatment process. In comparison with P25, the P25-NO exhibited significantly enhanced photocatalytic activities under visible light irradiation (λ > 420 nm) for gaseous NO removal. On the basis of electronic band structure theory, we proposed a possible mechanism for the enhanced visible light driven photocatalytic oxidation process over the interstitial N doping P25-NO samples. This work could not only deepen understanding of the enhanced photoactivity originated from interstitial N doping in TiO₂, but also provide a facile route to prepare nitrogen doped TiO₂ for environmental and energy applications.     

Photocatalytic activities of Ion doped TiO2 thin films when prepared on different substrates

Pure and ion doped TiO₂ thin films were prepared by sol-gel dip coating process on metallic and non-metallic substrates. Test metal ion concentration ranged from 0.000002 to 0.4 at.%. The resulting films were annealed in air and characterized by optical spectroscopy and X-ray diffraction. The photodegradation of methyl orange under UV irradiation by pristine and ion-doped TiO₂ films was quantified in a photocatalytic reactor developed in this study. In general, both doped and undoped TiO₂ crystals appeared in anatase phase and the photocatalytic activities of the TiO₂ thin films varied with substrates, calcination temperature, doping ions and their concentrations. The best calcination temperature for different substrates ranged from 450 to 580 °C. Films prepared on the metallic substrates resulted in higher photocatalytic activities, while ion doping lowered their efficiencies. On the contrary, for non-metallic substrates except ceramic the photocatalytic efficiencies of undoped films were much lower (< 30%), while ion doping was shown to increase the photocatalytic efficiencies remarkably in some cases, e.g., Cr³⁺ with the tile substrate. Overall, ion doping affected the photocatalytic efficiency of TiO₂ films, and an optimal doping concentration of between 0.0002 and 0.002 at.%, close to an estimate by the Debye length equation, resulted in the highest efficiency for most substrates.     

Fabrication of the CN co-doped rod-like TiO2 photocatalyst with visible-light responsive photocatalytic activity

The CN co-doped TiO₂ nanorods were synthesized by the vapor transport method of water molecules, and urea was used as the carbon and nitrogen source. The samples were characterized by X-ray diffraction and photoelectron spectroscopy analysis. The scanning electron microscope images showed that as-prepared TiO₂ powders were nanorods, which were formed by the stacking of nanoparticles with a uniform size around 40 nm. The degradation of methylene blue with the prepared nanorods demonstrated the photocatalytic activities of TiO₂ under visible light are improved by doping with C and N elements. The main reasons were discussed: doping with C and N elements could enhance the corresponding visible-light absorption of TiO₂. On the other hand, doping C and N could create more oxygen vacancies in the TiO₂ crystals, which could capture the photogenerated electrons more effectively. Thus, more photogenerated holes could be left to improve the photocatalytic activity of TiO₂.     

Preparation,characterization and photocatalytic activities of holmium-doped titanium dioxide nanoparticles

Holmium-doped TiO₂ nanoparticles with high photocatalytic activities were prepared by sol–gel method and characterized by X-ray diffraction, transmission electron microscopy, ultraviolet–visible diffuse reflectance spectroscopy, and surface area measurement by nitrogen adsorption in this study. Experimental results indicated holmium doping could increase the surface area of TiO₂ nanoparticles, and inhibit the growth of crystalline size and the anatase-to-rutile phase transformation. The results of photodegrading methyl orange showed holmium doping improved the photocatalytic activity of TiO₂, and the reasons could be attributed to the synergetic effects of large surface areas, small crystallite size, lattice distortion and more charge imbalance of holmium-doped TiO₂. In our experiment, the optimal doped amount was 0.3 mol.% for the maximum photocatalytic degradation ratio when holmium-doped TiO₂ was calcined at 500 °C, and the optimal calcined temperature was 600 °C when the doped amount was 0.5 mol.%.     

Synthesis of novel Cu doped anatase TiO<Subscript>2</Subscript> catalysts and assessment of the influence of Nb concentration on the photocatalytic and electrochemical properties

In the present study, Cu doped (Ti_0.8Cu_xO_2?x/2) and (Cu, Nb) co-doped (Ti_0.8Cu_x?y Nb_yO_2?(x?y/2+y)) TiO₂ photocatalysts were fabricated by sol–gel method. The catalysts were polycrystalline in nature with preferential orientation along (101) plane answering to anatase phase of TiO₂. Higher Nb concentration results in the formation of secondary phase (Nb₂O₅). A decrease in average crystallite size was noticed with the addition of Nb concentration in Cu doped TiO₂ photocatalyst. The formation of anatase phase was also fixed by Raman spectra. The TEM photograph confirmed the co-doped TiO₂ photocatalyst in nanometer range of about 15 nm and the particles were in hexagonal shape. The doping of Nb⁵⁺ ions inspired a shift in the absorption threshold towards the visible spectral range (red shift) compared to Cu doped TiO₂ catalyst. The photocatalysts have direct bandgaps of 3.253 to 2.974 eV. Semiconducting properties were investigated through electrochemical impedance spectroscopy. The results indicate that the presence of Nb⁵⁺ ions into Cu doped TiO₂ has enhanced the efficiency of electrochemical conductivity. Photocatalytic performance was assessed from the sample degradation by illuminating methylene blue dye under visible light exposure. It is found that TCN3 photocatalyst bleaches MB much faster than all others. Also it exhibits great improvement of photocatalytic activity (96.86%) within 120 min. The photocatalytic degradation process is explained using the pseudo first order kinetics and it fits well with higher correlation coefficient. All these analyses elucidate that the incorporation of Nb⁵⁺ ions might tune the structural, optical, electrochemical and phocatalytic properties of Cu doped TiO₂ photocatalysts.     

Rapid electroplating of photocatalytically highly active TiO2-Zn nanocomposite films on steel

Nanocomposite films consisting of TiO₂ and Zn with thickness of 10–15 m (TiO₂-Zn) have been electrodeposited on steel plates by rapid plating from a ZnSO₄-based bath (I _d > 10 A dm^–2). Upon addition of NH₄NO₃ to the bath (<0.3 g L^–1), the uptake of TiO₂ in the film significantly increased. Glow discharge optical emission spectrometry clarified that TiO₂ particles were incorporated throughout the film and the loaded amount increased near the surface. The first-order rate constant (k/h^–1) for gas-phase CH₃CHO oxidation was employed as an indicator of the photocatalytic activity. The k value for the TiO₂-Zn film prepared at I _d = 12 A dm^–2 (0.20 h^–1) was comparable to that for the sample from a ZnCl₂-based bath at I _d = 4 A dm^–2 (0.27 h^–1). X-ray diffraction measurements indicated that a TiO₂-ZnO nanocomposite layer was generated on the surface by the heat treatment in air at 673 K for 6 h. Consequently, the photocatalytic activity was further improved (k = 0.29 h^–1); this effect was explained in terms of the synergy of TiO₂ and ZnO in photocatalysis.     

Enhanced H2 Generation of Au‐Loaded,Nitrogen‐Doped TiO2 Hierarchical Nanostructures under Visible Light

Hierarchical N‐doped TiO₂ nanostructured catalysts with micro‐, meso‐, and macroporosity are synthesized by a facile self‐formation route using ammonia and titanium isopropoxide precursor. UV–vis diffuse reflectance spectra confirm the red shift and band gap narrowing due to the doping of N species in the TiO₂ nanoporous catalyst. Hierarchical macroporosity with fibrous channel patterning is observed and well preserved even after calcination at 800 °C, indicating thermal stability, whereas micro‐ and mesoporosity are lost after calcination at 500 °C. The photocatalytic activity of hiearchical N doped TiO₂ catalysts loaded with Au is evaluated for H₂ production reaction in visible light. The enhanced photocatalytic activity is attributed to the combined synergetic effect of N doping for visible light absorption, micro‐ and mesoporosity for an increase of effective surface area and light harvestation, and hierarchical macroporous fibrous structure for multiple reflection and effective charge transfer.     

A facile decoration of anatase Fe3O4/TiO2 nanocomposite with graphene quantum dots: Synthesis,characterization, and photocatalytic activity

A combination of electron-rich graphene quantum dots (GQDs) with Fe₃O₄/TiO₂ nanocomposites may develop an efficient electron transfer for enhanced photocatalytic activity. In this report, a facile decoration of GQDs with maltose precursor was synthesized and loaded onto magnetic anatase TiO₂ nanocomposites under hydrothermal methods. The as-synthetized magnetic TiO₂/GQDs nanocomposite resulted in a specific surface area of 38.00 m²/g and a total pore volume of 0.186 cm³/g. The HRTEM images showed a lattice plane distance of 0.350 nm related to the interplanar spacing of the anatase TiO₂ (1 0 1) plane and that of 0.299 nm observed for the in-plane lattice part of GQDs. The effects of magnetic loading ratio and GQDs loading onto TiO₂, pH, photocatalyst dosage, and methylene blue (MB) concentration were thoroughly evaluated to find the optimum conditions of mineralization MB for getting the highest photocatalytic efficiency. The removal efficiency of around 86.08 ± 3.62% was obtained at pH11, photocatalytic dose 400 mg/100 mL, and MB concentration 10 mg/L. Moreover, the photogenerated electron transfers and MB degradation mechanism by the resulting Fe₃O₄/TiO₂/GQD_S under irradiation of UVA light are proposed. The as-synthesized material improved meaningfully greater photocatalytic efficiency for degrading MB under UVA light irradiation than merely pure anatase TiO₂. Also, the predominant mechanism of MB degradation was direct oxidative decomposition through the photogenerated holes. The photocatalytic destruction of MB complied with the apparent first-order models under UVA light irradiation.     

Effect of non-stoichiometry on the sintering of doped TiO2

The sintering of TiO₂ has been studied with respect to oxygen partial pressure ( ) and doping content. From the microstructural evolution, it is obvious that a decrease of the oxygen pressure promotes the densification with a comparatively smaller grain growth than in air sintering. This fact has been related with the influence of defects on the sintering. Both effects of and tantalum doping have been studied. They are interpreted on the basis of a model involving interstitial titanium, electron holes, titanium vacancies and complexes associating titanium vacancies with tantalum substituted titanium. This latter complex is probable according to previous microscopic studies of defects in TiO_2–x and may be important in highly doped compounds. The formation of such associates reduces the mobile defect concentration, however a decrease of the favour their dissociation. The titanium vacancies which are thus released allow the titanium ions to migrate, a necessary condition for the sintering.