Structural and photocatalytic properties of TiO2/SiOx/TiOx multi-layer prepared by electron-beam evaporation method

TiO₂/SiO_x/TiO_x multi-layers on quartz glass were prepared by electron-beam evaporation method and their structural and photocatalytic properties were investigated. The photocatalytic activity of the TiO₂/SiO_x/TiO_x multi-layer was evaluated by the photodecomposition of methylene blue in aqueous solution. As the thickness of the SiO_x inter-layer increased, the surface roughness of the TiO₂/SiO_x/TiO_x multi-layer increased but the anatase crystallite size decreased. The TiO₂/SiO_x(80 nm)/TiO_x multi-layer exhibited excellent photocatalytic activity resulting from higher surface roughness and more trap levels in the SiO_x(80 nm) inter-layer.     

Obtaining of Ni–P–TiO2 Composite Coatings with TiO2 Sol and Surfactants and Their Properties

The influence of surfactants and TiO₂ sol on mechanical, catalytic, and corrosive properties of electroless Ni–P coatings was investigated. Additives of the surfactants caused the decrease of internal stresses in the Ni–P coatings and smoothing of their surfaces. Incorporation of the TiO₂ particles facilitated the rise of microhardness of the Ni–P coatings from 545 ± 11 Hv up to 614 ± 17 Hv. Additives of the surfactants accelerated hydrogen evolution reaction on the composite Ni–P–TiO₂ coatings in acid and alkaline media, and increased photocatalytic activity in methylene blue decomposition. Incorporation of the TiO₂ particles and application of the surfactants resulted in an improvement in the corrosion resistance of original Ni–P coatings in 0.5 M H₂SO₄.     

Photocatalytic degradation of 2,4-dichlorophenol wastewater using porphyrin/TiO2 complexes activated by visible light

The use of TiO₂ as photocatalyst to degrade the organic compounds is an effective method of oxidation process and has been widely studied in environmental engineering. However, TiO₂ absorbed the UV light which is only small part of sunlight reaching earth surface to activate photocatalytic procedure effectively is a major disadvantage. Therefore, studies on the development of new TiO₂ wherein its photocatalytic activity can be activated by visible light which is the major part of sunlight will be valuable for field application. In this study, we evaluate the photocatalytic degrading efficiency of porphyrins/TiO₂ complexes on the organic pollutants under irradiation with visible light (λ = 419 nm). The results showed that the photodecomposition efficiency of 2,4-dichlorophenol (2,4-DCP) wastewater by using porphyrin/TiO₂ irradiated under visible light for 4 h was up to 42-81% at pH 10. These evidences reveal that the system of porphyrin/TiO₂ complexes has also significantly efficiency of photocatalytic degradation for some hazardous or recalcitrant pollutants under visible light irradiation.     

Visible-light photocatalysis in nitrogen-carbon-doped TiO2 films obtained by heating TiO2 gel-film in an ionized N2 gas

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO₂ films were obtained by heating a TiO₂ gel in an ionized N₂ gas. The as-synthesized TiO_2−x−yN_xC_y films have shown an improvement over titanium dioxide in optical absorption and photocatalytic activity such as photodegradation of methyl orange under visible light. The process of the oxygen atom substituted by nitrogen and carbon was discussed. Oxygen vacancy induced by the formation of Ti³⁺ species and nitrogen and carbon doped into substitution sites of TiO₂ have been proven to be indispensable for the enhance of photocatalytic activity, as assessed by UV-Vis Spectroscopy and X-ray photoemission spectroscopy.     

等离子体电解氧化法制备多孔TiO2/V2O5复合物膜层及其增强光催化产氢活性

较差的光催化产氢效率极大地阻碍了TiO₂光催化剂的工业化应用。为此,本文在含有NH₄VO₃的磷酸盐溶液中,采用等离子体电解氧化(PEO)法制备了多孔TiO₂/V₂O₅复合膜光催化剂,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、X射线光电子谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对其组成、结构及光吸收性质进行了表征,并采用气相色谱评价了薄膜催化剂的光催化产氢性能,研究了电解液中NH₄VO₃含量对膜的结构、组成和光催化产氢性能的影响。结果表明:复合膜催化剂主要由锐钛矿和金红石型TiO₂组成,具有微孔结构,V₂O₅主要以无定形形式存在于膜中,与TiO₂有很强的相互作用,影响TiO₂的晶面间距。研究发现,元素V抑制了TiO₂的结晶和金红石型TiO₂的形成,扩大了薄膜的光学吸收范围。针对Na₂S+ Na₂SO₃溶液中的光催化产氢性能的研究显示,在质量浓度为1 g/L NH₄VO₃的电解液中制备的TiO₂/V₂O₅薄膜的光催化活性最高,优于近年来报道的其他光催化剂。光催化重复实验表明,该复合膜催化剂具有较高的稳定性和较为恒定的光催化活性。     

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.     

Novel method for doping nano TiO2 photocatalysts by chemical vapour deposition

Highly active photocatalytic Fe-doped nano TiO₂ was successfully synthesised by chemical vapour deposition (CVD) method using FeCl₃ as Fe source. CVD was carried out by evaporating FeCl₃ at 350°C in nitrogen flow during 30–90?min. The amount of Fe incorporated into TiO₂ framework is adjusted by the amount of FeCl₃ used and the evaporation time. The obtained sample was characterised by X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), energy dispersive X-ray spectroscopy (EDS), UV-Vis, Fourier transform-infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). Photocatalytic activities of the samples were tested in photocatalytic decomposition of 2-propanol in liquid phase using visible light instead of UV light irradiation. Non-doped TiO₂ and high Fe loading TiO₂ samples showed very low photocatalytic activity, whereas the low Fe loading TiO₂ sample exhibited high photocatalytic activity under visible light. The high photocatalytic activity of this sample was rationalised by the existence of defects (Ti–OH groups) as the active sites.     

Bactericidal effect of blue LED light irradiated TiO2/Fe3O4 particles on fish pathogen in seawater

This study uses blue LED light (λ_max = 475 nm) activated TiO₂/Fe₃O₄ particles to evaluate the particles' photocatalytic activity efficiency and bactericidal effects in seawater of variable salinities. Different TiO₂ to Fe₃O₄ mole ratios have been synthesized using sol-gel method. The synthesized particles contain mainly anatase TiO₂, Fe₃O₄ and FeTiO₃. The study has identified TiO₂/Fe₃O₄'s bactericidal effect to marine fish pathogen (Photobacterium damselae subsp. piscicida BCRC17065) in seawater. The SEM photo reveals the surface destruction in bacteria incubated with blue LED irradiated TiO₂/Fe₃O₄. The result of this study indicates that 1) TiO₂/Fe₃O₄ acquires photocatalytic activities in both the freshwater and the seawater via blue LED irradiation, 2) higher photocatalytic activities appear in solutions of higher TiO₂/Fe₃O₄ mole ratio, and 3) photocatalytic activity decreases as salinity increases. These results suggest that the energy saving blue LED light is a feasible light source to activate TiO₂/Fe₃O₄ photocatalytic activities in both freshwater and seawater.     

Preparation,characterization and photocatalytic activity of Bi2O3–MgO composites

A series of Bi₂O₃–MgO composites were synthesized by solvent-thermal method. It was found that the Bi₂O₃–MgO composites perform much better than TiO₂ (P25), Bi₂O₃ and MgO in the photocatalytic degradation of rhodamine B (RhB) in the presence of HCl and under irradiation of visible light (λ > 400 nm). The effects of Bi/Mg molar ratio, crystallization temperature of Bi₂O₃–MgO and reaction conditions on photocatalytic activity were studied. The best performance was observed over the composite with Bi:Mg molar ratio equal to 2:1 that had been subject to crystallization at 120 °C for 20 h. In addition, the photocatalytic efficiency of the composite can be significantly enhanced by the presence of hydrochloric acid. The prepared samples were characterized by XRD and UV–vis DRS techniques. The relationships between the structure and photocatalytic performance of the as-prepared Bi₂O₃–MgO samples were also investigated.     

Enhancement of titania by doping rare earth for photodegradation of organic dye (Direct Blue)

Lanthanide ions (La³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, and Yb³⁺)/doped TiO₂ nanoparticles were successfully synthesized by sol–gel method. Their photocatalytic activities were evaluated using Direct Blue dye (DB53) as a decomposition objective. The structural features of TiO₂ and lanthanide ions/TiO₂ were investigated by XRD, SEM, UV-diffuse reflectance, and nitrogen adsorption measurements. Our findings indicated that XRD data characteristic anatase phase reflections and also XRD analysis showed that lanthanides phase was not observed on Lanthanide ions/TiO₂. The results indicated that Gd³⁺/TiO₂ has the lowest bandgap and particle size and also the highest surface area and pore volume (V_p) as well. Lanthanide ions can enhance the photocatalytic activity of TiO₂ to some extent as compared with pure TiO₂ and it was found that Gd³⁺/TiO₂ is the most effective photocatalyst. The photocatalytic tests indicate that at the optimum conditions; illumination time 40 min, pH ∼4, 0.3 g/L photocatalyst loading and 100 ppm DB53; the dye removal efficiency was 100%. Details of the synthesis procedure and results of the characterization studies of the produced lanthanide ions/TiO₂ are presented in this paper.     

Fabrication of photocatalytic heat-mirror with TiO2/TiN/TiO2 stacked layers

The photocatalytic heat-mirror based on TiO₂/TiN/TiO₂ stacked layers is prepared by reactive magnetron sputtering on quartz substrates under substrate-heating condition. We find that the addition of a thin Ti interlayer between the TiN and the outer TiO₂ layers drastically improves the heat-insulating performance. This type of stacked layer also exhibits higher photocatalytic activity for decomposition of acetaldehyde gas, compared with a TiO₂ single layer. The optical property of the TiN in TiO₂/TiN/TiO₂ stacked layers is the key not only revealing excellent heat-insulating effect but also improving the photocatalytic performance of the outer TiO₂ layers in the stacked layers.     

Surface properties of doped and undoped TiO2 thin films deposited by magnetron sputtering

In this work, transparent titanium dioxide (TiO₂) thin films were deposited onto microscope glass slides by means of the d.c. reactive magnetron sputtering method. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-visible spectroscopy (UV) and contact angle analysis using the Owens-Wendt method for the surface energy calculation. The photocatalytic activity of the films was tested by measuring the photodegradation of Rhodamine-B (RhB) dye under radiation of UV light. Iron-doped TiO₂ films were also prepared in order to study the Fe-doping effect on TiO₂ photocatalytic activity. The influences of different iron concentrations on the contact angle of the series of Fe-doped TiO₂ thin films, were investigated. The influences of total sputtering pressures on TiO₂ photocatalytic activity were also investigated. It was observed that the photocatalytic activity of the TiO₂ thin films was slightly improved by increasing the total sputtering pressure. Moreover, it was also observed that in general, iron-doping was detrimental for photocatalytic activity, nevertheless the films with low iron concentrations showed better photocatalytic activity than those with high iron concentrations. It was found that iron-doping has changed the wettability appetency of TiO₂ coated surfaces.     

Photocatalytic degradation of dyes and organic contaminants in water using nanocrystalline anatase and rutile TiO2

Nanocrystalline TiO₂ was synthesized by controlled hydrolysis of titanium tetraisopropoxide. The anatase phase was converted to rutile phase by thermal treatment at 1023 K for 11 h. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared absorption spectrophotometry (FT-IR) and N₂ adsorption (BET) at 77 K. This study compare the photocatalytic activity of the anatase and rutile phases of nanocrystalline TiO₂ for the degradation of acetophenone, nitrobenzene, methylene blue and malachite green present in aqueous solutions. The initial rate of degradation was calculated to compare the photocatalytic activity of anatase and rutile nanocrystalline TiO₂ for the degradation of different substances under ultraviolet light irradiation. The higher photocatalytic activity was obtained in anatase phase TiO₂ for the degradation of all substances as compared with rutile phase. It is concluded that the higher photocatalytic activity in anatase TiO₂ is due to parameters like band-gap, number of hydroxyl groups, surface area and porosity of the catalyst.     

Preparation of nitrogen co-doped SiO2/TiO2 thin films on ceramic with enhanced photocatalytic activity under visible-light irradiation

In this study, we have successfully deposited N-doped SiO₂/TiO₂ thin films on ceramic tile substrates by sol–gel method for auto cleaning purpose. After dip coating and annealing process the film was transparent, smooth and had a strong adhesion on the ceramic tile surface. The synthesised catalysts were then characterised by using several analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscope (AFM) and UV-vis absorption spectroscopy (UV-vis). The analytical results revealed that the optical response of the synthesised N-doped SiO₂/TiO₂ thin films was shifted from the ultraviolet to the visible light region. The nitrogen substituted some of the lattice oxygen atoms. The surface area of co-doped catalyst increased, and its photocatalytic efficiency was enhanced. The photocatalytic tests indicated that nitrogen co-doped SiO₂/TiO₂ thin films demonstrated higher than of the SiO₂/TiO₂ activity in decolouring of methylene blue under visible light. The enhanced photocatalytic activity was attributed to an increasing of the surface area and a forming of more hydroxyl groups in the doped catalyst.     

Glycine assisted synthesis of flower-like TiO2 hierarchical spheres and its application in photocatalysis

Flower-like anatase TiO₂ hierarchical spheres assembled by nanosheets were synthesized by glycine assistant via a simple hydrothermal approach and after-annealing process. These flower-like spheres are about 2 μm in diameter with sheet thickness about 20 nm. Results showed reaction time, temperature, solution pH and glycine dosage all played an important role in control of shape and size of the as-synthesized TiO₂ nanocrystals. The photocatalytic activity of this nano-TiO₂ was evaluated by the photocatalytic oxidation decomposition of methyl orange under sunlight illumination in the presence of hydrogen peroxide (H₂O₂). The photocatalytic activity of the obtained TiO₂ was higher than that of commercial TiO₂.     

Synthesis,Characterization and Photocatalytic Activity of TiO_2 Film/Bi_2O_3 Microgrid Heterojunction

TiO2 film modified by Bi2O3 microgrid array was successfully fabricated by using a microsphere lithography method.The structure and morphology of TiO2 film,Bi2O3 film and TiO2 film/Bi2O3 microgrid heterojunction were characterized through X-ray diffraction,atomic force microscopy and scanning electron microscopy.The optical transmittance spectra and the photocatalytic degradation capacity of these samples to rhodamine B were determined via ultraviolet-visible spectroscopy.The results indicated that the coupled system showed higher photocatalytic activity than pure TiO2 and Bi2O3 films under xenon lamp irradiation.The enhancement of the photocatalytic activity was ascribed to the special structure,which could improve the separation of photo-generated electrons and holes,enlarge the surface area and extend the response range of TiO2 film from ultraviolet to visible region.     

Determination of photo-catalytic activity of un-doped and Mn-doped TiO2 anatase powders on acetaldehyde under UV and visible light

Titanium dioxide (TiO₂) photocatalytic powder materials doped with various levels of manganese (Mn) were synthesized to be used as additives to wall painting in combating indoor and outdoor air pollution. The heterogeneous photocatalytic degradation of gaseous acetaldehyde (CH₃CHO) on Mn-TiO₂ surfaces under ultraviolet and visible (UV/Vis) irradiation was investigated, by employing the Photochemical Static Reactor coupled with Fourier-Transformed Infrared spectroscopy (PSR/FTIR) technique. Experiments were performed by exposing acetaldehyde (~ 400 Pa) and synthetic air mixtures (~ 1.01 × 10⁵ Pa total pressure) on un-doped TiO₂ and doped with various levels of Mn (0.1-33% mole percentage) under UV and visible irradiation at room temperature. Photoactivation was initiated using either UV or visible light sources with known emission spectra. Initially, the photo-activity of CH₃CHO under the above light sources, and the physical adsorption of CH₃CHO on Mn-TiO₂ samples in the absence of light were determined prior to the photocatalytic experiments. The photocatalytic loss of CH₃CHO on un-doped TiO₂ and Mn-TiO₂ samples in the absence and presence of UV or visible irradiation was measured over a long time period (≈ 60 min), to evaluate their relative photocatalytic activity. The gaseous photocatalytic end products were also determined using absorption FTIR spectroscopy. Carbon dioxide (CO₂) was identified as the main photocatalysis product. It was found that 0.1% Mn-TiO₂ samples resulted in the highest photocatalytic loss of CH₃CHO under visible irradiation. This efficiency was drastically diminished at higher levels of Mn doping (1-33%). The CO₂ yields were the highest for 0.1% Mn-TiO₂ samples under UV irradiation, in agreement with the observed highest CH₃CHO decomposition rates. It was demonstrated that low-level (0.1%) doping of TiO₂ with Mn results in a significant increase of their photocatalytic activity in the visible range, compared to un-doped TiO₂. This elevated activity is lost at high doping levels (1-33%). Finally, the photocatalytic degradation mechanism of CH₃CHO on 0.1% Mn-TiO₂ surfaces under visible irradiation leading to low CO₂ yields is different than that under UV irradiation resulting to high CO₂ yields.     

Photocatalytic degradation of dyes and organic contaminants in water using nanocrystalline anatase and rutile TiO2

Nanocrystalline TiO₂ was synthesized by controlled hydrolysis of titanium tetraisopropoxide. The anatase phase was converted to rutile phase by thermal treatment at 1023 K for 11 h. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared absorption spectrophotometry (FT-IR) and N₂ adsorption (BET) at 77 K. This study compare the photocatalytic activity of the anatase and rutile phases of nanocrystalline TiO₂ for the degradation of acetophenone, nitrobenzene, methylene blue and malachite green present in aqueous solutions. The initial rate of degradation was calculated to compare the photocatalytic activity of anatase and rutile nanocrystalline TiO₂ for the degradation of different substances under ultraviolet light irradiation. The higher photocatalytic activity was obtained in anatase phase TiO₂ for the degradation of all substances as compared with rutile phase. It is concluded that the higher photocatalytic activity in anatase TiO₂ is due to parameters like band-gap, number of hydroxyl groups, surface area and porosity of the catalyst.     

Investigation on solar photocatalytic activity of TiO2 loaded composite: TiO2/Eggshell, TiO2/Clamshell and TiO2/CaCO3

The TiO₂/Eggshell, TiO₂/Clamshell and TiO₂/CaCO₃ loaded composites were prepared by sol-gel method and characterized by XRD and SEM. Their photocatalytic activities were measured through the degradation of Acid Red B under solar light irradiation. The influences of TiO₂ loaded content, heat-treated temperature and time on the photocatalytic activities were reviewed. The effects of irradiation time and dye initial concentration on the photocatalytic degradation were also investigated. The results showed that the photocatalytic activity can be greatly enhanced by appropriate TiO₂ loaded content.     

Photocatalytic performance of very thin TiO2/SnO2 stacked-film prepared by magnetron sputtering

TiO₂/SnO₂ stacked-layers are synthesized by reactive sputter deposition on the glass substrate. Very thin TiO₂/SnO₂ bilayer-photocatalysts exhibited a very high photocatalytic activity for a degradation of gaseous acetaldehyde. Both the control of an electronic structure of TiO₂ overlayer in the near-surface region and the interfacial separation of photogenerated electrons/holes in the TiO₂/SnO₂ stacked-layer are keys to improve the photocatalytic performance.