Preparation N-F-codoped TiO2 nanorod array by liquid phase deposition as visible light photocatalyst

An efficient method for the preparation of N-F-codoped visible light active TiO₂ nanorod arrays is reported. In the process, simultaneous nitrogen and fluorine doped TiO₂ nanorod arrays on the glass substrates were achieved by liquid phase deposition method using ZnO nanorod arrays as templates with different calcination temperature. The as-prepared samples were characterized by Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectra measurements. It was found that calcination temperature is an important factor influencing the microstructure and the amount of N and F in TiO₂ nanorod arrays samples. The visible light photocatalytic properties were investigated using methylene blue (MB) dye as a model system. The results showed that N-F-codoped TiO₂ nanorod arrays sample calcined at 450 °C demonstrated the best visible light activity in all samples, much higher than that of TiO₂ nanoparticles and P25 particles films.     

Preparation of Fe-doped TiO2 nanotube arrays and their photocatalytic activities under visible light

Fe-doped TiO₂ nanotube arrays have been prepared by the template-based liquid phase deposition method. Their morphologies, structures and optical properties were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and UV-vis absorption spectroscopy. Their photocatalytic activities were evaluated by the degradation of methylene blue under visible light. The UV-vis absorption spectra of the Fe-doped TiO₂ nanotube arrays showed a red shift and an enhancement of the absorption in the visible region compared to the undoped sample. The Fe-doped TiO₂ nanotube arrays exhibited good photocatalytic activities under visible light irradiation, and the optimum dopant amount was found to be 5.9 at% in our experiments.     

Nonaqueous sol-gel synthesis and growth mechanism of single crystalline TiO2 nanorods with high photocatalytic activity

In this paper, we report on a nonaqueous synthesis of single crystalline anatase TiO₂ nanorods by reaction between TiCl₄ and benzyl alcohol at a low temperature of 80 °C. The resulting samples were characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscopy, nitrogen adsorption, X-ray photoelectron spectrometry and UV-vis diffuse reflectance spectroscopy. We proposed that the TiO₂ nanorods were formed through an oriented attachment mechanism. More importantly, these single crystalline anatase TiO₂ nanorods exhibited significantly higher photocatalytic activities than commercial photocatalyst P25. This study provides an environmentally friendly and economic approach to produce highly active TiO₂ photocatalyst.     

Hydrothermal synthesis, characterization, photocatalytic activity and dye-sensitized solar cell performance of mesoporous anatase TiO2 nanopowders

Mesoporous anatase TiO₂ nanopowder was synthesized by hydrothermal method at 130 °C for 12 h. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), HRTEM, and Brunauer-Emmett-Teller (BET) surface area. The as-synthesized sample with narrow pore size distribution had average pore diameter about 3-4 nm. The specific BET surface area of the as-synthesized sample was about 193 m²/g. Mesoporous anatase TiO₂ nanopowders (prepared by this study) showed higher photocatalytic activity than the nanorods TiO₂, nanofibers TiO₂ mesoporous TiO₂, and commercial TiO₂ nanoparticles (P-25, JRC-01, and JRC-03). The solar energy conversion efficiency (η) of the cell using the mesoporous anatase TiO₂ was about 6.30% with the short-circuit current density (Jsc) of 13.28 mA/cm², the open-circuit voltage (Voc) of 0.702 V and the fill factor (ff) of 0.676; while η of the cell using P-25 reached 5.82% with Jsc of 12.74 mA/cm², Voc of 0.704 V and ff of 0.649.     

Synthesis and enhanced photocatalytic activity of tin oxide nanoparticles coated on multi-walled carbon nanotube

A nanocomposite of SnO₂ nanoparticles coated on multi-walled carbon nanotube (MWNT@SnO₂) was synthesized and characterized by thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, nitrogen physisorption measurements, photoluminescence. The results show that the SnO₂ nanoparticles with a narrow size of 4 nm are uniformly deposited on MWNT. The photocatalytic activity of the nanocomposite was studied using methyl orange as a model organic pollutant. MWNT@SnO₂ exhibits much higher photocatalytic activity than that of commercial TiO₂ (P-25). The promotion is mainly contributed from electron transfer between SnO₂ and MWNT.     

Fabrication of TiO2 nanotube arrays by electrochemical anodization in an NH4F/H3PO4 electrolyte

Highly ordered TiO₂ nanotube arrays were fabricated by electrochemical anodization of titanium in an NH₄F/H₃PO₄ electrolyte. A TiO₂ crystal phase was identified by X-ray diffraction, and the morphology, length and pore diameter of the TiO₂ nanotube arrays were determined by field-emission scanning electron microscopy (FE-SEM). The anodization parameters including the rate of magnetic stirring, F⁻ concentration, calcination temperature, anodization voltage and anodization time were investigated in detail. The results show that the as-prepared TiO₂ nanotube arrays possessed good uniformity, a well-aligned morphology with a length of 750 nm and an average pore diameter of 62 nm at a 150 rpm rate of magnetic stirring for 120 min at 20 V in an electrolyte mixture of 0.2 M H₃PO₄ and 0.3 M NH₄F with a 500 °C calcination to obtain 100% anatase phase. The adsorption of N-719 dye at different tube lengths was determined by UV-vis analysis and found to increase with increasing tube length. We also discuss the formation mechanism of the TiO₂ nanotube arrays. The findings indicate that the formation of the TiO₂ nanotube arrays proceeds by the combined action of the electrochemical etching and chemical dissolution.     

Efficient growth of aligned SnO2 nanorod arrays on hematite (α-Fe2O3) nanotube arrays for photoelectrochemical and photocatalytic applications

SnO₂ nanorod arrays were fabricated on hematiete nanotube arrays by an efficient hydrothermal method. The hematiete nanotube arrays were prepared by anodization of pure iron foil in an ethylene glycol solution. SnO₂ nanorod arrays grew from the bottom of hematite nanotubes and were firmly combined with the iron foil substrate. The morphology and microstructure of SnO₂ nanorod arrays are investigated by field-emission scanning electron microscopy, grazing incidence X-ray diffraction and UV–Vis absorbance spectra. The sample presented typical SnO₂ nanorod arrays (reacted for 2 h) generally of 400 nm in length and 50 nm in side width showed the best photocatalytic activity and photoelectrochemical response under the UV illumination. It should be attributed to the effective electron–hole separation and the excellent electron transfer pathway along the 1D SnO₂ nanorod arrays and hematiete nanotube arrays.     

Structural, electrical and optical properties of ITO films with a thin TiO2 seed layer prepared by RF magnetron sputtering

Tin-doped indium oxide (ITO) films were deposited by RF magnetron sputtering on TiO₂-coated glass substrates (the TiO₂ layer is usually called seed layer). The properties of ITO films prepared at a substrate temperature of 300 °C on bare and TiO₂-coated glass substrates have been analyzed by using X-ray diffraction, atomic force microscope, optical and electrical measurements. Comparing with single layer ITO film, the ITO film with a TiO₂ seed layer of 2 nm has a remarkable 41.2% decrease in resistivity and similar optical transmittance. The glass/TiO₂ (2 nm)/ITO film achieved shows a resistivity of 3.37 × 10⁻⁴ Ω cm and an average transmittance of 93.1% in the visible range. The glass/TiO₂ may be a better substrate compared with bare glass for depositing high quality ITO films.     

Preparation and characterization of nanostructured MWCNT-TiO2 composite materials for photocatalytic water treatment applications

Nanoscale composite materials containing multi-walled carbon nanotubes (MWCNT) and titania were prepared by using a modified sol-gel method. The composites were comprehensively characterized by thermogravimetric analysis, nitrogen adsorption-desorption isotherm, powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis absorption spectroscopy. The analysis revealed the presence of titania crystallites of about 7.5 nm aggregated together with MWCNT in particles of 15-20 nm of diameter. The photoactivity of the prepared materials, under UV or visible irradiation, was tested using the conversion of phenol from model aqueous solutions as probe reaction. A synergy effect on the photocatalytic activities observed for the composite catalysts was discussed in terms of a strong interphase interaction between carbon and TiO₂ phases by comparing the different roles of MWCNT in the composite materials.     

Facile synthesis of mesoporous core-shell TiO2 nanostructures from TiCl3

The present study reports the synthesis and formation process of mesoporous core-shell TiO₂ nanostructures by employing a glucose-assisted solvothermal process using water-ethanol mixture as solvent and subsequent calcination process at 550 °C for 4 h. X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption analysis were used to investigate the structural properties of these nanostructures. By optimizing the preparation conditions, especially the contents of water and ethanol in the mixture solvent, mesoporous core-shell TiO₂ nanostructures were obtained. These mesoporous nanostructures have anatase phase and exhibit the superior photocatalytic activity. This synthesis route is facile due to the usage of stable and low-cost Ti precursor such as TiCl₃ and is thus applicable for large-scale production.     

Synthesis and characterization of large area well-aligned carbon nanotubes by ECR-CVD without substrate bias

Large area, well-aligned carbon nanotubes (CNTs) were synthesized on porous silicon by electron cyclotron resonance chemical vapor deposition (ECR-CVD). No bias was applied on the substrate in this experiment. CH₄ and H₂ were used as source gases and Fe₃O₄ nanoparticles as the catalyst. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), and Raman spectrum were used to evaluate the structure and composition. The results show that these CNTs have varying outer diameters from 10 to 90 nm and uniform length over 10 μm. They display hollow tubular and chain structures. The possible formation mechanism of aligned CNTs is discussed.     

Rapid synthesis, characterization and optical properties of TiO2 coated ZnO nanocomposite particles by a novel microwave irradiation method

A novel and rapid microwave method was used to prepare TiO₂ coated ZnO nanocomposite particles. The resulted particles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). Results show that ZnO nanoparticles were coated with 6-10 nm amorphous TiO₂ layers. In addition, zeta potential analysis demonstrated the presence of TiO₂ layer on the surface of ZnO nanoparticles. Photoluminescence (PL) spectroscopy and UV-visible spectroscopy were used to investigate the optical properties of the nanoparticles. Compared to uncoated ZnO nanoparticles, the TiO₂ coated ZnO nanoparticles showed enhanced UV emission. The UV-visible diffuse reflectance study revealed the significant UV shielding characteristics of the nanocomposite particles. Moreover, amorphous TiO₂ coating effectively reduced the photocatalytic activity of ZnO nanoparticles as evidenced by the photodegradation of Orange G with uncoated and TiO₂ coated ZnO nanoparticles under UV radiation.     

Synthesis and optical properties of single-crystalline GaN nanorods

Single-crystalline GaN nanorods were successfully synthesized on Si(1 1 1) substrates through ammoniating Ga₂O₃/Mo films deposited on the Si(1 1 1) substrate by radio frequency magnetron sputtering technique. The as-synthesized nanorods are confirmed as single-crystalline GaN with wurtzite structure by X-ray diffraction (XRD), selected-area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM). Scanning electron microscopy (SEM) displays that the GaN nanorods are straight and smooth with diameters in the range of 100-200 nm and lengths typically up to several micrometers. X-ray photoelectron spectroscopy (XPS) confirms the formation of bonding between Ga and N. The representative photoluminescence spectrum at room temperature exhibits a strong and broad emission band centered at 371.1 nm, attributed to GaN band-edge emission. The growth process of GaN nanorod may be dominated by vapor-solid (VS) mechanism.     

Third-order nonlinear optical properties of Bi2S3 nanocrystals doped in sodium borosilicate glass studied with Z-scan technique

The third-order nonlinear optical properties of Bi₂S₃ nanocrystals doped in sodium borosilicate glass are measured by Z-scan technique. The microstructures of the glass are characterized by means of X-ray diffraction, transmission electron microscopy, scanning transmission electron microscopy, energy dispersion X-ray spectra, and high-resolution transmission electron microscopy. The results show that the Bi₂S₃ nanocrystals ranging from 10 to 30 nm are determined to be of the orthorhombic crystalline phase, and the third-order optical nonlinear refractive index γ, absorption coefficient β, and susceptibility χ⁽³⁾ of the glass are determined to be 2.56 × 10⁻¹⁶ m² W⁻¹, 4.13 × 10⁻¹⁰ mW⁻¹, and 1.43 × 10⁻¹⁰ esu, respectively.     

Preparation and characterization of the TiO2 ultrafine particles by detonation method

Utilizing the raw materials of TiOSO₄, NaOH, NH₄NO₃ and RDX, the TiO₂ ultrafine particles were prepared under high pressure and high temperature by detonation method. The structure, composition and size distribution of the TiO₂ ultrafine particles were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results indicated the as-prepared TiO₂ ultrafine particles exhibited spherical-like grains and that the average size of particles was 25 ± 5 nm. After being heated at 700 °C for 1 h, TiO₂ particles have entirely completed the anatase-rutile phase transition, which means that detonation method can effectively enhance the anatase-rutile phase transition by lowering the transition temperature. The size of TiO₂ nanoparticles can be effectively controlled because the as-prepared nanoparticles do not have enough time to grow to large and perfect crystallites during the detonation process.     

Visible light photocatalytic degradation of paraoxon and parathion pesticides on carbon-doped TiO<Subscript>2</Subscript> nanorod thin films

In the present work the nanostructured carbon-doped TiO₂ thin films with nanorod morphology were deposited on glass substrate by a combination of ultrasonic and chemical vapor deposition methods, and for the first time were applied for the photocatalytic degradation of paraoxon and parathion organophosphorus pesticides under visible light irradiation. X-ray Diffraction, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, and scanning electron microscopy techniques were used for characterization of the prepared thin films. Obtained results show that presence of carbon element and also special nanorod morphology of the thin films remarkably improve the optical properties of TiO₂ in visible light region and results in the good visible light photocatalytic activity of the thin films for degradation of the pesticides. The photonic efficiencies of the prepared thin films were also examined based on the international ISO-10678:2010 standard protocol for photocatalytic degradation of methylene blue under UV light irradiation. The results show a maximum photonic efficiency of 0.0312% for the carbon-doped TiO₂ thin film with 570 nm thickness, which compared to a reference standard TiO₂ films indicates a 30% improvement in photonic efficiency.     

Room temperature synthesis of nearly monodisperse rodlike rutile TiO2 nanocrystals

A new method was developed to synthesize uniform rodlike rutile TiO₂ nanocrystals by the hydrolysis of tetrabutyl titanate [Ti(OC₄H₉)₄] in hydrochloric acid-alcohol aqueous solutions at room temperature. The hydrolytic sol-gel reaction generated 44 nm (diameter) × 200 nm (length) sized rutile TiO₂ nanocrystals. Transmission electron microscopic images showed that the particles have a uniform shape and narrow size distribution. X-ray diffraction and electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the rodlike TiO₂ nanoparticles prepared at room temperature were crystalline rutile structure grown along the [001] direction. The morphology and photocatalytic activity of the TiO₂ nanocrystals formed at different urea concentrations were showed. The rutile TiO₂ nanocrystals formed in the absence of urea exhibited higher photocatalytic activity than the commercial photocatalyst P25 on the photocatalytic degradation of Rhodamine B.     

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.%.     

Fabrication of TiO2/ZnO composite nanofibers by electrospinning and their photocatalytic property

TiO₂/ZnO composite nanofibers with diameters in the range of 85–200 nm were fabricated via the electrospinning technique using zinc acetate and titanium tetra-isopropoxide as precursors, cellulose acetate as the fiber template, and N,N-dimethylformamide/acetone 1:2 (v/v) mixtures as the co-solvent. After treated with 0.1 mol/L NaOH aqueous solution, TiO₂/zinc acetate/cellulose acetate composite nanofibers were transformed into TiO₂/Zn(OH)₂/cellulose composite nanofibers. TiO₂/ZnO composite nanofibers were obtained by calcinating the hydrolyzed composite fibers at 500 and 700 °C for 5 h. The structure and morphology of composite nanofibers were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. With the blending of ZnO into TiO₂, a new crystallite ZnTiO₃ was formed in addition to the ZnO and TiO₂ crystallites, and the ultraviolet light absorption efficiency was enhanced according to the UV–vis diffuse reflectance spectroscopy. The photocatalytic activity of TiO₂/ZnO composite nanofibers toward the decomposition of Rhodamine B and phenol was investigated. Almost 100% Rhodamine B and 85% phenol were decomposed in the presence of TiO₂/ZnO composite nanofibers under mild conditions. The results demonstrated that the blending of ZnO in the TiO₂/ZnO composite nanofibers increased the photocatalytic efficiency. The optimum ZnO content in the TiO₂/ZnO composite nanofibers was 15.76 wt% to reach the most efficient photocatalytic activity. A schematic diagram of photocatalytic mechanism of TiO₂/ZnO composite nanofibers was also presented.     

Fabrication and photocatalytic property of ZnO nanorod arrays on Cu2O thin film

ZnO nanorod arrays were fabricated on Cu₂O thin film by a simple low-temperature liquid-phase-deposition method. The samples were characterized by X-ray powder diffraction (XRD) and field emission scanning electron microscopy (FESEM). The UV-Vis spectroscopy showed that the obtained sample was able to absorb a large part of visible light (up to 650 nm). Their photocatalytic activities were investigated by degradation of dye methylene blue (MB) under UV-Vis and visible light irradiation. It was found that the photocatalytic activity of the ZnO/Cu₂O NRs was higher than the ZnO/ZnO NRs under UV-Vis light. In a word, Cu₂O played an important role in enhancing the photocatalytic activity of the ZnO/Cu₂O NRs.