Photocatalytic properties of porous TiO2/Ag thin films

In this study, nanocrystalline TiO₂/Ag composite thin films were prepared by a sol-gel spin-coating technique. By introducing polystyrene (PS) spheres into the precursor solution, porous TiO₂/Ag thin films were prepared after calcination at a temperature of 500 °C for 4 h. Three different sizes (50, 200, and 400 nm) of PS spheres were used to prepare porous TiO₂ films. The as-prepared TiO₂ and TiO₂/Ag thin films were characterized by X-ray diffractometry (XRD) and by scanning electron microscopy to reveal structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.When PS spheres of different sizes were introduced after calcination, the as-prepared TiO₂ films exhibited different porous structures. XRD results showed that all TiO₂/Ag films exhibited a major anatase phase. The photodegradation of porous TiO₂ thin films prepared with 200 nm PS spheres and doped with 1 mol% Ag exhibited the best photocatalytic efficiency where ∼ 100% methylene blue was decomposed within 8 h under UV exposure.     

Photocatalytic properties of Au/TiO2 thin films prepared by RF magnetron co-sputtering

Au/TiO₂ thin films with various Au doping contents were deposited on quartz substrates by radio frequency (RF) magnetron co-sputtering. The as-deposited Au/TiO₂ films were characterized by energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), XRD, and UV-vis techniques. Au doping and UV treatment enhanced the photocatalytic efficiency of TiO₂ thin films. The optimal RF power of the Au target and UV treatment time were 5 W and 1 h, respectively. The enhanced photoactivity of Au(5 W)/TiO₂ thin films with UV treatment is found to result from the increased hydroxyl concentration.     

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.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Preparation of anatase TiO2 thin films by vacuum arc plasma evaporation

Anatase titanium dioxide (TiO₂) thin films with high photocatalytic activity have been prepared with deposition rates as high as 16 nm/min by a newly developed vacuum arc plasma evaporation (VAPE) method using sintered TiO₂ pellets as the source material. Highly transparent TiO₂ thin films prepared at substrate temperatures from room temperature to 400 °C exhibited photocatalytic activity, regardless whether oxygen (O₂) gas was introduced during the VAPE deposition. The highest photocatalytic activity and photo-induced hydrophilicity were obtained in anatase TiO₂ thin films prepared at 300 °C, which correlated to the best crystallinity of the films, as evidenced from X-ray diffraction. In addition, a transparent and conductive anatase TiO₂ thin film with a resistivity of 2.6 × 10^− 1 Ω cm was prepared at a substrate temperature of 400 °C without the introduction of O₂ gas.     

Structural,morphological and photocatalytic characterisations of Ag-coated anatase TiO2 fabricated by the sol–gel dip-coating method

This study reports on the synthesis, characterisation and environmental applications of immobilised Titanium dioxide (TiO₂) as photocatalyst. Nanostructured thin films have been prepared on glass substrates using a layer-by-layer dip-coating method. The crystalline phase and surface morphology of the thin films were investigated by X-ray diffraction (XRD) pattern and scanning electron microscopy (SEM), respectively. The XRD results show that the TiO₂ thin films crystallise in anatase phase and we have found that the thin films consist of titanium dioxide nanocrystals. SEM shows that the nanoparticles are sintered together to form a compact structure and TiO₂ particles coated with silver nanoclusters were observed. Ag-coated TiO₂ films demonstrated photocatalysis performance when irradiated, and the Ag carrier further showed an electron-scavenging ability to mitigate electron–hole pair recombination, which can improve the photocatalytic efficiency. With the oxidisation and electron-scavenging ability of Ag and the photocatalysis ability of TiO₂, Ag-coated TiO₂ can decolour methyl orange (MO) more than bare TiO₂. It is a new approach to form Ag-coated TiO₂ nanoparticles with a simple system and non-toxic materials. The high photocatalytic effect of Ag-coated TiO₂ nanoparticles on pollutant (MO) suggests that it may have a promising future for water and wastewater treatments.     

High thermal stability thick wall mesoporous titania thin films

Mesoporous TiO₂ thin films were prepared by using tetrabutyl titanate as the inorganic precursor and triblock copolymer (Pluronic F127) as the structure directing agent. The obtained mesostructured TiO₂ thin film exhibits a high thermal stability, which can sustain 600 °C thermal treatment. The small angle XRD and wide angle XRD patterns indicate that the samples have mesoporous channel and are composed of anatase. The corresponding TEM images show that the homogeneous mesostructure and very thick pore walls (about 9–13 nm) are formed in the obtained thin films, which could be responsible for the high thermal stability of the framework. In addition, the samples have narrow pore diameter distribution and a mean pore size of 7.4 nm.     

Mesoporous Au/TiO2 composites preparation,characterization, and photocatalytic properties

In this work, mesoporous Au/TiO₂ composites have been synthesized and tested on photodegradation of methylene blue dye solution. Mesoporous TiO₂ prepared at 450 °C using triblock polymer F127 as structure-directing agent was applied as substrate, while various HAuCl₄ concentrations were used for Au loading through deposition-precipitation method using urea as precipitator and hydrogen reducing process. The influences of Au loading on the microstructures of mesoporous TiO₂ including degree of dispersion, particle size, surface area, light absorption, and band gap were studied with transmission electron microscopy (TEM), X-ray diffraction (XRD), diffuse reflection infrared Fourier transformed spectroscopy (DRIFT), N₂ adsorption–desorption isotherm analysis (BET), and UV–Vis diffuse reflectance spectra. With Au loading, the size of TiO₂ nanoparticles in Au/TiO₂ composites is similar as that of TiO₂ substrate. However, the degree of dispersion was greatly improved. Furthermore, an obvious surface plasmon resonance centered at 570 nm was found in UV–Vis diffuse reflectance spectra for Au/TiO₂ composites. Au loading also induced an obvious red shift of light absorption from UV region to visible region and strengthened both UV and visible light absorption in contrast to substrate. Photodegradation results verified that photocatalytic activity of mesoporous TiO₂ was improved by Au loading. 0.25%Au/TiO₂ composite showed the highest activity, which may be ascribed to its high surface hydroxyl content and the formed Schottky junction after Au loading. These results suggested that noble metal modification is a promising way to synthesize photocatalysts with both high activity and visible light sensitivity.     

Confined palladium colloids in mesoporous frameworks for carbon nanotube growth

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO₂ structured catalyst was considerably higher than that on 1 wt% Pd/TiO₂ thin films.     

Preparation and characterization of Co-doped TiO2 materials for solar light induced current and photocatalytic applications

Different amounts of Co-doped TiO₂ powders and thin films were prepared by following a conventional co-precipitation and sol–gel dip coating technique, respectively. The synthesized powders and thin films were subjected to thermal treatments from 400 to 800 °C and were thoroughly investigated by means of X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive analysis with X-rays, FT-infrared, FT-Raman, diffuse reflectance spectroscopy, ultraviolet–visible spectroscopy, BET surface area, zeta potential, flat band potential measurements, band-gap energy, etc. The photocatalytic ability of the powders was evaluated by methylene blue (MB) degradation studies. The thin films were characterized by photocurrent and ultraviolet–visible (UV–Vis) spectroscopy techniques. The characterization results suggest that the Co-doped TiO₂ powders synthesized in this study consist mainly anatase phase, and possess reasonably high specific surface area, low band gap energy and flat band potentials amenable to water oxidation in photoelectrochemical (PEC) cells. The photocatalytic degradation of MB over Co-doped TiO₂ powders followed the Langmuir–Hinshelwood first order reaction rate relationship. The 0.1 wt.% Co-doped TiO₂ composition provided the higher photocurrent, n-type semi-conducting behavior and higher photocatalytic activity among various Co-doped TiO₂ compositions and pure TiO₂ investigated.     

Low-temperature processing of thin films based on rutile TiO2 nanoparticles for UV photocatalysis and bacteria inactivation

Using a low-temperature, simple, and economic processing technique, TiO₂ nanoparticles (rutile phase) are immobilized in an inorganic matrix and then deposited on glass for bacteria inactivation in water. Using this low thermal budget method (maximum processing temperature of 220 °C), thin films of immobilized TiO₂ nanoparticles are obtained so that practical water decontamination after UV radiation is possible by avoiding the additional step of catalyst separation from treated water. In order to validate the photocatalytic activities of these TiO₂ nanoparticles (prepared as thin films), they were tested for bacteria inactivation in water under UV–A radiation (λ > 365 nm), while extensive characterizations by dynamic light scattering, X-ray diffraction, ultra violet–visible absorption spectroscopy, fourier-transform infra red spectroscopy, and profilometry were also carried out. Despite previous reports on the low or lack of photocatalytic activity of rutile-phase TiO₂, inactivation of Escherichia coli in water was observed when thin films of this material were used when compared with the application of UV radiation alone. Physical characterization of the films suggests that size and concentration-related effects may allow the existence of photocatalytic activity for rutile-TiO₂ as long as they are exposed under UV–A radiation, whereas no effect on bacteria inactivation was observed for thin films in the absence of TiO₂ or radiation. In brief, a low thermal budget process applied to thin films based on TiO₂ nanoparticles has shown to be useful for bacteria inactivation, while possible application of these films on widely available substrates like polyethylene terephthalate materials is expected.     

Study of the deposition parameters and Fe-dopant effect in the photocatalytic activity of TiO2 films prepared by dc reactive magnetron sputtering

The reactive magnetron sputtering method was used to prepare pure and Fe-doped titanium dioxide thin films. The films were deposited onto microscope glass slides and polycarbonate plates at different total pressure and Fe-doping concentrations. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-visible spectroscopy (UV). For glass substrates a polycrystalline TiO₂ structure was verified with X-ray diffraction, which showed typical characteristic anatase reflections. An iron phase appeared in the highly Fe-doped samples. The absorption edges of the Fe-doped TiO₂ films shifted to visible region with increasing concentration of iron. For the polycarbonate substrate an amorphous TiO₂ structure was revealed for all deposition conditions. The effects of different Fe-doping and total pressure levels on the photocatalytic activity were obtained by the degradation rates of Rhodamine-B (RoB) dye under UV light irradiation. For the deposition conditions considered in this study the highest photodegradation rates were achieved for films deposited on the polymer substrates. Of these overall highest rates was achieved for deposition at 0.4 Pa and without doping. However, for both substrates, films prepared at the particular total pressure of 0.5 Pa and a low iron concentration showed better photocatalytic activity than the pure TiO₂ films prepared under the same deposition parameters. On the contrary, the photocatalytic degradation rates of RoB on the highly Fe-doped TiO₂ films decreased strongly.     

Fabrication and characterization of nano TiO2 thin films at low temperature

Anatase TiO₂ thin films were successfully prepared on glass slide substrates via a sol–gel method from refluxed sol (RS) containing anatase TiO₂ crystals at low temperature of 100 °C. The influences of various refluxing time on crystallinity, morphology and size of the RS sol and dried TiO₂ films particles were discussed. These samples were characterized by infrared absorption spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission-scanning electron microscopy (FE-SEM) and UV–vis absorption spectroscopy (UV–vis). The photocatalytic activities of the TiO₂ thin films were assessed by the degradation of methyl orange in aqueous solution. The results indicated that titania films thus obtained were transparent and their maximal light transmittance exceeded 80% under visible light region. The TiO₂ thin films prepared from RS-6 sol showed the highest photocatalytic activity, when the calcination temperature is higher than 300 °C. The degradation of methyl orange of RS-6 thin films reached 99% after irradiated for 120 min, the results suggested that the TiO₂ thin films prepared from RS sol exhibited high photoactivities.     

Effect of porosity on the Seebeck coefficient of mesoporous TiO2 thin films

Mesoporous TiO₂ films were prepared by using titanium tetraisopropoxide as the titania precursor and triblock copolymer as the structure directing agent. The synthesized mesoporous TiO₂ film was confirmed to have the ordered pore structure with rutile phase by small angle and wide angle X-ray diffraction analyses. The mesoporous TiO₂ film has the porosity range from 21.6 to 35.6%, and its Seebeck coefficient was changed according to its porosity, up to −88.6 μV/K. From the obtained Seebeck coefficient, the ordered mesoporous TiO₂ film was found to be a good candidate of thermal sensing layer of thin film thermal sensor.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

Effect of TiO2 nanoparticles aggregation in silicate thin coating films on photocatalytic behavior for antifouling materials

Two types of disperser namely, a high speed agitation bead mill and a colloidal mill, were used for the dispersion behavior control of TiO₂ nanoparticles (20 nm in average primary diameter) in an aqueous suspension. A composite thin film raging in thickness from 90 to 400 nm was prepared from the coating suspension following the addition of a commercial ethyl silicate oligomer binder into the prepared suspension by means of a spray coating method. The mean aggregate size of TiO₂ nanoparticles in the aqueous suspension was found to be 80 nm and 290 nm in diameter, respectively, when using the agitated bead and colloidal milling methods. Large aggregates on the order of several hundred nanometers were found to remain in the suspension after colloidal milling. Further, a fine dispersion of TiO₂ nanoparticles in the thin film produced using the agitation bead milling process promoted the photocatalytic activity and enhanced transparency of the film for visible light. The aggregate structure of TiO₂ nanoparticles in an aqueous suspension was well maintained in the film prepared by a spray coating 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.     

Thermal evolution of morphological,optical, and photocatalytic properties of Au–Cu2O–CuO nanocomposite thin film

Plasmonic nanocomposite thin films find exciting applications in environmental remediation and photovoltaics. We report on thermal annealing driven development of morphology, structure and photocatalytic performance of Au–Cu₂O–CuO nanocomposite thin film. Nanocomposite thin film coatings of Au–Cu₂O–CuO, prepared by radio frequency (RF) magnetron co-sputtering, were annealed at different temperatures. Thermal annealing driven evolution of morphology of Au–Cu₂O–CuO nanocomposite was studied by field emission scanning electron microscopy (FESEM), which revealed significant growth in size of nanostructures from 10 nm to 69 nm upon annealing. X-ray diffraction (XRD) together with Raman studies confirmed the nanocomposite nature of Au–Cu₂O–CuO film. UV-visible diffuse reflectance spectroscopy (UV-vis-DRS) studies showed band gap variation from 2.44 eV to 1.8 eV upon annealing at 250 °C. Nanocomposite thin film annealed at 250 °C exhibited superior photocatalytic activity for organic pollutants [methylene blue (MB) and methyl orange (MO)] decomposition. The origins of thermal transformation of morphological, optical and photocatalytic behaviour of the Au–Cu₂O–CuO nanocomposite coating are discussed.

     

Improved photocatalytic activity of polymer-modified TiO2 films obtained by a wet chemical route

Porous TiO₂ films, exhibiting improved photocatalytic activity compared with commercial materials, have been deposited on glass. The films were dipcoated from a polymer-modified TiO₂ precursor solution, containing about 90 vol% water as solvent. The addition of water-soluble polymers such as polyethyleneglycol and polyvinylalcohol has produced TiO₂ films with different morphologies, exhibiting RMS roughnesses of up to 60 nm and increased porosity. We studied the effect of the polymers on the morphology and surface topography of a series of polymer-modified TiO₂ films and evaluated how their presence in the precursor influences the crystallinity, optical transmittance and most importantly, the photocatalytic activity of the films. X-ray diffraction analysis shows that all films exhibit the anatase crystal structure after calcining for 2 h at 500 °C. We find that the presence of polyethyleneglycol inhibits the crystallization of the TiO₂ films. Transmittance spectra show that most of the polymer-modified TiO₂ films obtained in this work are transparent although high polymer content can lead to opaque films because of increased porosity and surface roughness. The surface morphology of the films was studied by scanning electron microscopy and atomic force microscopy. Their photocatalytic efficiency was studied by following the decomposition of methylene blue under UV irradiation. The activity of the reference TiO₂ film obtained from a precursor without polymers is comparable to that of Saint-Gobain (SG) self-cleaning Bioclean glass, while some of the polymer-modified films show efficiencies that can be up to seven times higher.     

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.