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.     

Hydrothermal preparation and characterization of TiO2:AC composites

A new photocatalyst titania:activated carbon (TiO₂:AC) composite was prepared by impregnating anatase type TiO₂ nanoparticulates onto the activated carbon surface through a mild hydrothermal route. A varied ratio of TiO₂ to AC was considered for impregnation. As-prepared TiO₂:AC composite was characterized by various techniques such as powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), BET surface area and positron annihilation lifetime spectroscopy (PALS). Powder XRD results showed the persisting nature of anatase phase of TiO₂ deposited on the activated carbon surface. The BET, FTIR and PALS results revealed the impregnation threshold. The TiO₂ particulates were well adhered and uniformly dispersed on the carbon surface as confirmed by SEM.     

Preparation of N-methylaniline capped mesoporous TiO2 spheres by simple wet chemical method

Pure anatase mesoporous TiO₂ nanospheres were synthesized by simple wet chemical treatment and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet–visible spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (XRD). The results revealed that the surface morphology of the TiO₂ spheres could be controlled by adjusting the concentration of N-methylaniline and that the average diameter of the TiO₂ spheres was 600 nm. FTIR results confirmed the formation of N-methylaniline capped TiO₂ nanospheres.     

Synthesis of highly-active single-crystalline TiO2 nanorods and its application in environmental photocatalysis

Highly-active anatase TiO₂ nanorods have been successfully synthesized via a simple two-step method, hydrothermal treatment of anatase/rutile titanium dioxide nanoparticle powder in a composite-hydroxide eutectic system of 1:1 M KOH/NaOH, followed by acid post-treatment. The morphology and crystalline structure of the obtained nanorods were characterized using XRD, TEM, SEM/EDX and BET surface area analyzer. The obtained TiO₂ nanorods have a good crystallinity and a size distribution (about 4-16 nm); with the dimensions of 200-300 nm length and of 30-50 nm diameter. Compared with its precursor anatase/rutile TiO₂ nanoparticles and the titanate nanotubes, the pure anatase TiO₂ nanorods have a large specific surface area with a mesoporous structure. The photocatalytic performance of the prepared nanorods was tested in the degradation of the commercial Cibacrown Red (FN-R) textile dye, under UV irradiation. Single-crystalline anatase TiO₂ nanorods are more efficient for the dye removal.     

Preparation and characterization of Cu-doped TiO2 nanomaterials with anatase/rutile/brookite triphasic structure and their photocatalytic activity

Pure TiO₂ and Cu–doped TiO₂ containing different amounts of copper ions with anatase/rutile/brookite triphasic structure were successfully synthesized through a simple hydrothermal method. The obtained samples were characterized by X–ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), transmission electron microscope (TEM), X–ray photoelectron spectroscopy (XPS), UV?vis diffuse reflectance spectroscopy (UV-DRS), photoluminescence spectroscopy (PL) and Brunauer–Emmett–Teller surface area analyze (BET). Both pure and Cu–doped TiO₂ show relatively high photocatalytic activity owing to their considerable surface areas. Moreover, the three–phase coexisting structure and the conversion between Cu²⁺ and Cu⁺ ions facilitate the separation of photogenerated electrons and holes, which is favorable for photocatalytic performance. 1%Cu–TiO₂ exhibits the highest photocatalytic activity and the degradation degree of rhodamine B (RhB) reaches 93.5% after 30 min, which is higher than that of monophasic/biphasic 1%Cu–TiO₂. ·O₂^? radical is the main active species, and h⁺ and ·OH species are subsidiary in the degradation process.

     

Large-scale synthesis and characterization of fan-shaped rutile TiO2 nanostructures

Large-scale fan-shaped rutile TiO₂ nanostructures have been synthesized by means of a simple hydrothermal method using only TiCl₄ as titanium source and chloroform/water as solvents. The physicochemical features of the fan-shaped TiO₂ nanostructures are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), nitrogen absorption-desorption, diffuse reflectance ultraviolet-visible spectroscopy (UV-vis) and Fourier transform infrared spectroscopy (FTIR). Structural characterization indicates that the fan-shaped TiO₂ nanostructures are composed of several TiO₂ nanorods with diameters of about 5 nm and lengths of 300-350 nm. The average pore size and BET surface area of the fan-shaped TiO₂ nanostructures are 6.2 nm and 59 m²/g, respectively. Optical adsorption investigation shows that the fan-shaped TiO₂ nanostructures possess optical band gap energy of 3.11 eV.     

Synthesis and characterization of anatase and rutile TiO2 nanorods by template-assisted method

Well-aligned anatase and rutile TiO₂ nanorods and nanotubes with a diameter of about 80–130 nm have successfully been fabricated via sol-gel template method. The prepared samples were characterized by using thermogravimetric (TG) and differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). The XRD results indicated that the TiO₂ nanorods were crystallized in the anatase and rutile phases, after annealing at 400–800 °C for different periods of time from 0.2 to 10 h.     

Rapid synthesis of TiO2 hollow nanostructures with crystallized walls by using CuO as template and microwave heating

In this paper, TiO₂ hollow nanostructures with anatase walls have been rapidly fabricated by using CuO as template and microwave heating. These TiO₂ hollow nanostructures have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Experimental results showed that the TiO₂ shell transformed from amorphous to anatase phase in 3 min, induced by the hot CuO core under microwave irradiation. The diameter of TiO₂ hollow nanostructures is about 50-80 nm, and the length is about 200-300 nm. The thickness of the shell is about 3 nm. This method is promising to be used to synthesize other nanomaterials with a hollow nanostructure.     

Synthesis and characterization of pure anatase TiO<Subscript>2</Subscript> nanoparticles

Pure anatase TiO₂ nanoparticles were synthesized by microwave assisted sol–gel method and further characterized by powder X-ray diffraction (XRD), energy dispersive x-ray analysis (EDAX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV–Visible spectrophotometer, SEM images showed that TiO₂ nanoparticles were porous structure. The XRD patterns indicated that TiO₂ after annealed at 300 °C for 3 h was mainly pure anatase phase. The crystallite size was in the range of 20–25 nm, which is consistent with the results obtained from TEM images. Microwave heating offers several potential advantages over conventional heating for inducing or enhancing chemical reactions.     

Development of a novel fast-hydrothermal method for synthesis of Ag-doped TiO2 nanocrystals

Undoped and Ag-doped TiO₂ anatase nanocrystals were successfully prepared from titanium isopropoxide by a novel fast-hydrothermal method. The as-prepared TiO₂ nanocrystals were characterized by XRD, DRUV-VIS spectroscopy and SEM/EDX. The results show that the anatase TiO₂ has a particle size of around 4 nm from SEM and XRD results.     

Flame-made single phase Zn2TiO4 nanoparticles

Using zinc naphthenate and titanium tetra isopropoxide (1:1 mol.%) dissolved in ethanol as precursors, single phase Zn₂TiO₄ nanoparticles were synthesized by the flame spray pyrolysis technique. The Zn₂TiO₄ nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. The average diameter of Zn₂TiO₄ spherical particles was in the range of 5 to 10 nm under 5/5 (precursor/oxygen) flame conditions. All peaks can be confirmed to correspond to the cubic structure of Zn₂TiO₄ (JCPDS No. 25-1164). The SEM result showed the presence of agglomerated nanospheres with an average diameter of 10-20 nm. The crystallite sizes of spherical particles were found to be in the range of 5-18 nm from the TEM image. An average BET equivalent particle diameter (d_BET) was calculated using the density of Zn₂TiO₄.     

Growth of carbon nanotubes over Fe-Co and Ni-Co catalysts supported on different phases of TiO2 substrate by thermal CVD

The aim of this work is to examine the properties of CNTs formed on Fe-Co and Ni-Co bimetallic catalysts supported on different phases of TiO₂ (anatase and rutile) by wet impregnation method. The CNTs are grown from decomposition of acetylene via Thermal CVD at 700°C using the prepared catalysts. The nanomaterials were characterized by XRD, Xmap, BET, FESEM, TEM, and Raman spectroscopy. It was found that the catalyst samples supported on rutile TiO₂ have higher specific surface area, smaller catalytic nanoparticles with denser distribution and very more activity compared to anatase ones. Consequently, the CNTs nucleated from nanoparticles supported on rutile TiO₂ possess higher density, smaller average diameters and narrower diameter distribution compared to grown CNTs on anatase samples. Moreover, it was observed that the Fe-Co bimetallic catalysts regardless of TiO₂ support phase, possesses more catalytic activity and higher average growth rate of CNTs in compare with Ni-Co catalysts.     

Microstructures and photo-catalytic properties of B3+ and F− co-doped TiO2 films

The nano-crystalline B³⁺ and F^? co-doped titanium dioxide films were successfully prepared by the improved sol–gel process. The as-prepared specimens were characterised using X-ray diffraction (XRD), high-resolution field emission scanning electron microscopy (FE-SEM), the Brunauer–Emmett–Teller (BET) surface area, X-ray photo-electron spectroscopy, photoluminescence spectra and UV–Vis diffuse reflectance spectroscopy. The photo-catalytic activities of the films were evaluated by degradation of an organic dye in aqueous solution. The results of XRD, FE-SEM and BET analysis indicated that the TiO₂ films were composed of nano-particles. B³⁺ and F^? co-doping could obviously not only suppress the formation of brookite phase but also inhibit the transformation of anatase to rutile at high temperature. Diffuse reflectance measurements showed that co-doping could clearly extend the absorbance spectra of TiO₂ into visible region. Compared with pure TiO₂, B³⁺ doped or F^? doped TiO₂ film, the B³⁺ and F^? co-doped TiO₂ film exhibited excellent photo-catalytic activity. It is believed that the surface microstructure of the films and the doping methods of the two ions are responsible for improving the photo-catalytic activity.     

Microstructures and Photocatalytic Properties of S Doped Nanocrystalline TiO2 Films

The nanocrystalline S doped titanium dioxide films were successfully prepared by the improved sol-gel process. Here TiO(C₄H₉O)₄ and CS(NH₂)₂ were used as precursors of titania and sulfur, respectively. The as-prepared specimens were characterized using x-ray diffraction (XRD), x-ray energy dispersive spectroscopy (EDS), high-resolution field emission scanning electron microscopy (FE-SEM), Brunauer-Emmett-Teller (BET) surface area, and ultraviolet-visible diffuse reflectance spectroscopy. The photocatalytic activities of the films were evaluated by degradation of organic dyes in aqueous solution. The results of XRD, FE-SEM, and BET analyses indicated that the TiO₂ films were composed of nanoparticles. S doping could obviously not only suppress the formation of brookite phase but also inhibit the transformation of anatase to rutile at high temperature. Compared with pure TiO₂ film, S doped TiO₂ film exhibited excellent photocatalytic activity. It is believed that the surface microstructure of the modified films is responsible for improving the photocatalytic activity.     

Photocatalytic degradation of formaldehyde by nanostructured TiO2 composite films

Interest in the photocatalytic oxidation of formaldehyde from contaminated wastewater is growing rapidly. The photocatalytic activity of the nanocrystalline Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film for the degradation of formaldehyde solution under visible light was discussed in this study. The films were characterised by field emission scanning electron microscopy (FE-SEM) equipped with energy-dispersive spectroscopy, X-ray diffraction (XRD), BET surface area, UV–Vis absorption spectroscopy, and photoluminescence spectroscopy. The FE-SEM results revealed that the Fe³⁺/F^? co-doped TiO₂–SiO₂ film was composed of uniform round-like nanoparticles or aggregates with the size range of 5–10 nm. The XRD results indicated that only the anatase phase was observed in the film. Compared with a pure TiO₂ film and a singly modified TiO₂ film, the Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film showed the best photocatalytic properties due to its strong visible light adsorption and diminished electrons-holes recombination.     

Preparation of a high-activity ZnO/TiO2 photocatalyst via homogeneous hydrolysis method with low temperature crystallization

The nano-scale ZnO/TiO₂ coupled oxide photocatalyst was successfully synthesized by a two-step method, the homogeneous hydrolysis and low temperature crystallization. The resultant photocatalyst was characterized by ultraviolet-visible absorption spectroscopy (UV-vis), X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) techniques. The photocatalytic activity of coupled oxides was also evaluated by the degradation of methyl orange (MO) as a model compound. The experimental results showed that the prepared ZnO/TiO₂ at low hydrothermal crystallization temperature exhibited higher photocatalytic activity for the decomposition of MO than either pure phase ZnO or anatase TiO₂, and even higher than that of the Degussa P25 TiO₂.     

Alternative approaches to fabrication of gold-modified TiO2 nanotubes

Three approaches, impregnation–reduction, deposition and direct assembly, are used to fabricate gold-modified TiO₂ nanotubes. Prepared materials are characterized with powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), UV–visible absorption spectroscopy and BET, etc. The gold-modified TiO₂ nanotubes prepared via various procedures exhibit distinct difference in structure. By impregnation–reduction approach, gold-modified TiO₂ nanotubes with large gold particles are fabricated. The gold particles are either deposited on or encapsulated in TiO₂ nanotubes. However, by using gold hydrophilic colloidal dispersion as gold precursor, gold particles in the modified TiO₂ nanotubes are very small. Gold particles only adhere to the outer surface of TiO₂ nanotubes after deposition process, whereas adhere to not only the outer but also the inner walls of TiO₂ nanotubes after direct assembly process. A possible mechanism is proposed to illustrate the formation of gold-modified nanotubes that are prepared by direct assembly process.     

Combustion synthesized TiO2 for enhanced photocatalytic activity under the direct sunlight-optimization of titanylnitrate synthesis

Optimized synthesis of Ti-precursor ‘titanylnitrate’ for one step combustion synthesis of N- and C-doped TiO₂ catalysts were reported and characterized by using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), diffused reflectance UV–vis spectroscopy, N₂ adsorption and X-ray photoelectron spectroscopy (XPS). XRD confirmed the formation of TiO₂ anatase and nano-crystallite size which was further confirmed by TEM. UV-DRS confirmed the decrease in the band gap to less than 3.0 eV, which was assigned due to the presence of C and N in the framework of TiO₂ as confirmed by X-ray photoelectron spectroscopy. Degradation of methylene blue in aqueous solution under the direct sunlight was carried out and typical results indicated the better performance of the synthesized catalysts than Degussa P-25.     

Characterization and photoactivity of TiO2 sols prepared with triethylamine

Using triethylamine as a surface protective agent, a transparent and pale yellowish TiO₂ sol had been prepared at 90 °C. This method was very different from the traditional methods, which produced titanium dioxide nanoparticles with anatase crystalline structure either at high acid condition or high temperature. X-ray diffraction (XRD) and transmission electron spectroscopy (TEM) demonstrated that the as-prepared TiO₂ sol nanoparticles with anatase crystalline structure were uniformly distributed, and the average size was 3 nm. X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectra showed that triethylamine was adsorbed on TiO₂ sol particles surface. FTIR spectroscopy noted that TiO₂ sol particles had the similar spectra with Degussa P25. Photoactivity of the as-prepared TiO₂ sol was studied by investigating the photodegradation of methyl violet in hydrosol reaction system under visible light irradiation.     

Influence of high velocity oxy-fuel parameters on properties of nanostructured TiO<Subscript>2</Subscript> coatings

A liquid fuel high velocity oxy-fuel (HVOF) thermal spray process has been used to deposit TiO₂ nanostructured coatings utilizing a commercially available nanopowder as the feedstock. The coatings were characterized by means of X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. Photocatalytic activity was evaluated as a rate constant of decomposition reaction of methylene blue (MB) determined from the changes of relative concentration of MB with UV irradiation time. The results indicate that the sprayed TiO₂ coatings were composed of both TiO₂ phases viz. anatase and rutile, with different phase contents and crystallite sizes. A high anatase content of 80% by volume was achieved at 0·00015, fuel-to-oxygen ratio with nanostructure coating by grain size smaller than feedstock powder. Photocatalytic activity evaluation results indicated that all the TiO₂ coatings are effective to degradation MB under UV radiation and their activities differ in different spray conditions. It is found that fuel flow rate strongly influenced on phase transformation of anatase to rutile and by optimizing the rate which can promote structural transformation and grain coarsening in coating and improving photocatalytic activity.