Effect of surface fluorination on the photocatalytic and photo-induced hydrophilic properties of porous TiO2 films

Porous surface-fluorinated TiO₂ (F-TiO₂) films were prepared through PEG modified sol-gel method and surface fluorination. The as-prepared films were characterized with XRD, FTIR, AFM, XPS and UV-vis DRS. The effects of surface fluorination on the photocatalytic activity and hydrophilicity of porous TiO₂ film were studied by photocatalytic degradation of rhodamine B (RhB) as well as water contact angle (CA) on porous TiO₂ film. The results showed that the surface fluorination increased the adsorption of RhB on the porous TiO₂ film and enhanced the photocatalytic degradation of RhB. The concentration and pH of NaF solutions affected much the photocatalytic activity of porous TiO₂ film. Porous F-TiO₂ film prepared in 40 mM NaF solution at pH 4.0 showed the highest photocatalytic activity. Because of its porous structure, the porous F-TiO₂ film had original water CA of 22.7°, which is much smaller than that of normal F-TiO₂ film. Under UV light irradiation, the water CA of porous F-TiO₂ film decreased to 5.1° in 90 min.     

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO₂ sol-gels with various Ag/TiO₂ molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO₂ thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO₂ nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO₂ sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO₂ sol-gel, four types of the TiO₂ thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO₂), TA (bottom layer was pure TiO₂, surface layer was Ag modified), TT (pure TiO₂ thin film) and AA (TiO₂ thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I_ph). LSV confirmed the existence of Ag⁰ state in the TiO₂ thin film. SEM and XRD experiments indicated that the sizes of the TiO₂ nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO₂ thin film.     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.     

Effect of N2 ion flux on the photocatalysis of nitrogen-doped titanium oxide films by electron-beam evaporation

Nitrogen-doped titanium oxide (TiO_xN_y) films were prepared with ion-assisted electron-beam evaporation. The nitrogen (N) incorporated in the film is influenced by the N₂ flux modulated by the N₂ flow rate through an ion gun. The TiO_xN_y films have the absorption edge of TiO₂ red-shifted to 500 nm and exhibit visible light-induced photocatalytic properties in the surface hydrophilicity and the degradation of methylene blue. The structures and states of nitrogen in the films are investigated by X-ray diffraction patterns (XRD), and X-ray photoelectron spectroscopy (XPS) and related to their visible light-induced photocatalytic properties. The results indicate that the substitutional N in anatase TiO₂ can induce visible light photocatalysis. The substitutional N is readily doped by the energetic nitrogen ions from the ion gun. The best photocatalytic activity is obtained at the largest N loading about 5.6 at.%, corresponding to the most substitutional N in anatase TiO₂. The film exhibits the degradation of methylene blue with a rate-constant (k) about 0.065 h⁻¹ and retaining 7° water contact angle on the surface under visible light illumination.     

Synthesis and photocatalytic properties of porous TiO2 films prepared by ODA/sol-gel method

Porous TiO₂ films were deposited on SiO₂ pre-coated glass-slides by sol-gel method using octadecylamine (ODA) as template. The amount of ODA in the sol played an important role on the physicochemical properties and photocatalytic performance of the TiO₂ films. The films prepared at different conditions were all composed of anatase titanium dioxide crystals, and TiO₂ crystalline size got larger with increasing ODA amount. The maximum specific surface area of 41.5 m²/g was obtained for TiO₂ powders prepared from titanium sol containing 2.0 g ODA. Methyl orange degradation rate was enhanced along with increasing ODA amount and reached the maximal value at 2.0 g addition of ODA. After 40 min of UV-light irradiation, methyl orange degradation rate reached 30.5% on the porous film, which was about 10% higher than that on the smooth film. Porous TiO₂ film showed almost constant activity with slight decrease from 30.5% to 28.5% after 4 times of recycles.     

Characterization of N,C-codoped TiO2 films prepared by reactive DC magnetron sputtering

Titanium dioxide (TiO₂) films are deposited by codoping nitrogen and carbon on indium tin oxide-coated substrates as visible light (Vis)-enabled catalysts. The X-ray diffraction peak intensity of the preferential orientation in (2 1 1) plane declines when the topmost 1.0 μm layer of the film is ground off. The decrease in the crystallite size and the crystallinity of anatase TiO₂ film is also evidenced by a shift towards the high wave number and broadening of the Raman spectra. Low doping concentrations of N (1.3%) and C (1.8%) are estimated by X-ray photoelectron spectroscopy (XPS) which displays an N 1s peak at 396.8 eV and a C 1s peak at 282.1 eV, respectively. This is attributed to the substitution of the oxygen sites with nitrogen and carbon, which is believed to be responsible for the Vis photocatalytic activity into a wavelength of >500 nm. The cross-sectional transmission electron microscopy images show larger pores at the grain boundaries and in larger columnar crystals than in the undoped TiO₂ film. All of these results indicate that porosity, crystallinity and shift in the preferential orientation are more pronounced close to the surface than close to the bottom of the sample. Wettability upon measurement of the water contact angle, methylene blue degradation and radical formation tests under both ultraviolet and Vis irradiation demonstrate that the topmost surface renders not only a larger reactive surface area but also a better carrier transport route than the rest of the film, improving its photocatalytic activity. These results show that surface porosity of the film is dominant than the tailoring of the photocatalytic activities of N,C-codoped TiO₂ catalysts.     

Preparation and photocatalytic activity of CeO2/TiO2 interface composite film

The CeO₂/TiO₂ and TiO₂/CeO₂ interface composite films were prepared on glass substrates by the sol-gel process via dip-coating and calcining technique. The scanning electron microscopy (SEM) revealed that the TiO₂ layer has a compact and uniformity glasslike surface with 200 nm in thickness, and the CeO₂ layer has a coarse surface with 240 nm in thickness. The X-ray diffractometer (XRD) analysis showed that the TiO₂ layer is made up of anatase phase, and the CeO₂ layer is structured by cubic fluorite phase. Through a series of photo-degradation experiments, the relationship of the photocatalytic activity with the constituents of the films was studied. In virtue of the efficient interfacial charge separation via the process of electron transfer from TiO₂ to CeO₂, the photocatalytic activity of the CeO₂/TiO₂ composite film is high. Contrarily, the photocatalytic activity of the TiO₂/CeO₂ composite film is low, due to its inert surface made up of CeO₂ with broad bandwidth. Apart from the effect of the film structure, the effect of film thickness on photocatalytic activity was also discussed.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

Role of reactive gas in atmospheric plasma for cell attachment and proliferation on biocompatible poly ?-caprolactone film

This paper reports the surface modification of a biocompatible poly ?-caprolactone (PCL) film treated by atmospheric cold plasma (ACP) with reactive gases. The change in wettability and surface morphology of the PCL film after the plasma treatment with the reactive gases (Ar, H₂, N₂ and O₂) were determined using contact angle and surface roughness measurements. The chemical bonding states and molecular vibration modes of the activated organic groups on the polymer surface were examined by X-ray photoelectron spectroscopy and Fourier-transformation infrared techniques. The surface of the ACP-treated PCL films was also examined for their in vitro cell attachment and proliferation using human prostate epithelial cells (HPECs). The increase in the hydrophobicity of the Ar + H₂ plasma-treated PCL film resulted in a lower cell loading in the initial step of cell culture as well as a decrease in the level of cell attachment and proliferation compared with the pristine film. However, the hydrophilic properties of the Ar + N₂, Ar and Ar + O₂ plasma-treated PCL film improved the adhesion properties. Therefore, the Ar + N₂, Ar and Ar + O₂ plasma-treated PCL films showed a better cell distribution and growth than that of the pristine PCL film. The ACP-treated PCL film is potentially useful as a suitable scaffold in biophysics and bio-medical engineering applications.     

Photocatalytic and superhydrophilicity properties of N-doped TiO2 nanothin films

Pure TiO₂ and nitrogen doped titanium dioxide (N-TiO₂) thin films were prepared by sol-gel method through spin coating on soda lime glass substrates. TiCl₄ and urea were used as Ti and N sources in the sol. XRD results showed nitrogen doping has retarded anatase to rutile phase transformation. The doping also leads to a decrease in roughness of the samples from 4 nm (TiO₂) to 1 nm (N-TiO₂). However, surface analysis by statistical methods reveals that both surfaces have self-affine structure. Optical band gap of thin films was shifted from 3.65 eV (TiO₂) to 3.47 eV (N-TiO₂). Hydrophilic conversion and photocatalytic degradation properties of thin films were investigated and exhibited that N-TiO₂ thin film has more preferable hydrophilicity and photocatalytic properties under UV illumination.     

Studies on wettability of medical poly(vinyl chloride) by remote argon plasma

The paper studies surface modification of medical poly(vinyl chloride) (PVC) by remote argon plasma and characterized surface structure, performance of treated PVC by the water contact angle measurement, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Results show that the remote argon plasma makes the surface of the PVC film higher hydrophilic than the direct argon plasma and does not give remarkable degradation on the PVC film surface. The hydrophilicity depends on sample position as well as the RF power and the plasma exposure time. The remote argon plasma contributes more effectively to the dechlorination (Cl/C = 0.01) from the PVC film than the direct argon plasmas (Cl/C = 0.03) and more effectively to the formation oxygen functionalities on the PVC film surface. These experimental results show the possibility that remote argon plasma treatment can enhance interaction reactions with argon radicals relative to those with electron and argon ions.     

Photo(electro)catalytic Activity of Cu-Modified TiO2 Nanorod Array Thin Films under Visible Light Irradiation

In the present study, a two-step method was applied to synthesise Cu²⁺-modified TiO₂ nanorod array thin films for photocatalytic processes. TiO₂ nanorod array thin films were synthesised by a hydrothermal method and then modified with an ultrasonic-assisted sequential cation adsorption method. The samples were characterised by X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (DRS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and inductively coupled plasma mass spectroscopy (ICP-MS) analysis. The photoelectrochemical properties of the samples were evaluated by linear sweep voltammetry and Mott–Schottky analysis; photocatalytic activities were tested by methylene blue degradation under visible light. The photocurrent density of the TiO₂/FTO sample modified with 50 mM Cu²⁺ solution was 26 times higher than that of the unmodified TiO₂/FTO sample. Additionally, methylene blue degradation efficiency under visible light was increased 40% with respect to the efficiency of the unmodified sample. The mechanism of the photocatalytic activity enhancement of Cu²⁺-modified TiO₂ nanorod films was discussed.     

Preparation and characterization of patterned copper sulfide thin films on n-type TiO2 film surfaces

Micro-arrayed patterns of p-type copper sulfide (Cu_xS) thin films with positive and negative features were deposited onto the surfaces of n-type TiO₂ semiconductor films via a selective nucleation and growth process from aqueous solution. The surface functional molecules of the UV photo-oxidised patterned SAMs were utilized to direct the nucleation and growth of Cu_xS crystallites. The resultant Cu_xS/TiO₂ composite films with negative and positive Cu_xS patterns on the TiO₂ film surface were investigated using SEM, XRD, XPS and a 3D Surface Profiler. It is demonstrated that regular and compact patterned films of Cu₂S crystallites had been deposited onto the n-type TiO₂ surface, with sharp edges demarcating the boundaries between the patterned Cu₂S region and the TiO₂ film region. The UV-vis spectra for three Cu₂S/TiO₂ films exhibit a wide absorption between 300 nm and 450 nm. The maximum wavelength differences in the spectra of Cu₂S/TiO₂ films and TiO₂ film were attributed to the added absorption of Cu₂S films at 302 nm and the unchanged adsorption of TiO₂ films. The absorption intensities of the Cu₂S/TiO₂ films could be varied in the UV-vis range using the Cu₂S patterned features (positive, negative).     

Nanostructure of photocatalytic TiO2 films sputtered at temperatures below 200 °C

The article reports on correlations between the process parameters of reactive pulsed dc magnetron sputtering, physical properties and the photocatalytic activity (PCA) of TiO₂ films sputtered at substrate surface temperature T_surf ≤ 180 °C. Films were deposited using a dual magnetron system equipped with Ti (Ø50 mm) targets in Ar + O₂ atmosphere in oxide mode of sputtering. The TiO₂ films with highly photoactive anatase phase were prepared without a post-deposition thermal annealing. The decomposition rate of the acid orange 7 (AO7) solution during the photoactivation of the TiO₂ film with UV light was used for characterization of the film PCA. It was found that (i) the partial pressure of oxygen pO₂ and the total sputtering gas pressure p_T are the key deposition parameters influencing the TiO₂ film phase composition that directly affects its PCA, (ii) the structure of sputtered TiO₂ films varies along the growth direction from the film/substrate interface to the film surface, (iii) ∼500 nm thick anatase TiO₂ films with high PCA were prepared and (iv) the structure of sputtered TiO₂ films is not affected by the substrate surface temperature T_surf when T_surf < 180 °C. The interruption of the sputtering process and deposition in long (tens of minutes) pulses alternating with cooling pauses has no effect on the structure and the PCA of TiO₂ films and results in a decrease of maximum value of T_surf necessary for the creation of nanocrystalline nc-TiO₂ film. It was demonstrated that crystalline TiO₂ films with high PCA can be sputtered at T_surf ≤ 130 °C. Based on obtained results a phase zone model of TiO₂ films was developed.     

Preparation and characterization of amine-functionalized SiO2/TiO2 films for formaldehyde degradation

This paper investigated the gaseous formaldehyde degradation by the amine-functionalized SiO₂/TiO₂ photocatalytic films for improving indoor air quality. The films were synthesized via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and 3-aminopropyltrimethoxysilane (APTMS). The physicochemical properties of prepared photocatalysts were characterized with N₂ adsorption/desorption isotherms measurement, X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FT/IR). The effect of amine-functional groups and the ratio of MTMOS/APTMS precursors on the formaldehyde adsorption and photocatalytic degradation were investigated. The results showed that the formaldehyde adsorption and photocatalytic degradation of the APTMS-functionalized SiO₂/TiO₂ film was higher than that of SiO₂/TiO₂ film due to the surface adsorption on amine sites and the relatively high of the specific surface area of the APTMS-functionalized SiO₂/TiO₂ film (15 times higher than SiO₂/TiO₂). The enhancement of the formaldehyde degradation of the film can be attributed to the synergetic effect of adsorption and subsequent photocatalytic decomposition. The repeatability of photocatalytic film was also tested and the degradation efficiency was 91.0% of initial efficiency after seven cycles.     

Visible-light photocatalysis of nitrogen-doped TiO2 nanoparticulate films prepared by low-energy ion implantation

Nitrogen-doped TiO₂ (N-TiO₂) films were prepared by low-energy implantation of nitrogen ions into pulsed laser deposited anatase TiO₂ films. The anatase phase of the films was not changed by the implantation with very low energy of 200 eV. XPS measurements revealed that the implanted nitrogen species were mainly interstitial ones. The nitrogen concentration was increased with increasing ion flux which could be controlled by adjusting the gas flow rate of the ion source. All the produced N-TiO₂ films exhibited visible-light photocatalytic activities in degradation of methylene blue in aqueous solutions, indicating that interstitial nitrogen could also be responsible for the photocatalysis in visible region. Higher visible-light photocatalytic efficiency was achieved with higher implanted nitrogen concentration.     

Low-temperature preparation of F-doped TiO2 film and its photocatalytic activity under solar light

A novel and simple method for preparing F-doped anatase TiO₂ (defined as FTO) film with high photocatalytic activity was developed using titanium-n-butoxide and NH₄F as TiO₂ and fluorine precursors under mild condition, i.e. low temperature (lower than 373 K) and ambient pressure. The prepared samples were characterized by XRD, SEM, X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectrum (DRS), photoluminescence spectrum (PL) and TG-DSC analysis. The photocatalytic activity was evaluated by decomposing X-3B under artificial solar light. The results showed that the crystallinity of TiO₂ was improved by F-doping. F⁻ ions can prevent the grain growth, and the transformation of anatase to rutile phase was also inhibited. The doped fluorine atoms existed in two chemical forms, and the ones incorporated into TiO₂ lattice might take a positive role in photocatalysis. Compared with surface fluorination samples, FTO film exhibited better photocatalytic activity. The high photocatalytic activity of FTO may due to extrinsic absorption through the creation of oxygen vacancies rather than the excitation of the intrinsic absorption band of bulk TiO₂. Furthermore, the FTO can be recycled with little photocatalytic activity depression. Without any further treatment besides rinsing, after 6 recycle utilization, the photocatalytic activity of FTO film was still higher than 79%.     

Photocatalytic thin films containing TiO2:N nanopowders obtained by the layer-by-layer self-assembling method

In this work, TiO₂-N powders were synthesized by high-energy ball milling, using commercial titanium dioxide (TiO₂) in the anatase phase and urea to introduce nitrogen into TiO₂ in order to enhance their photocatalytic properties in the visible spectral region. Several samples were prepared by milling a mixture of TiO₂-urea during 2, 4, 8, 12 and 24 h and characterized by spectroscopic and analytical techniques. X-ray diffraction (XRD) results showed the coexistence of anatase and high-pressure srilankite TiO₂ crystalline phases in the samples. Scanning electron microscopy (SEM) revealed that the grain size of the powder samples decreases to 200 nm at 24 h milling time. UV-Vis diffuse reflectance spectroscopic data showed a clear red-shift in the onset of light absorption from 387 to 469 nm as consequence of nitrogen doping in the samples. The photocatalytic activity of the TiO₂-N samples was evaluated by methylene blue degradation under visible light irradiation. It was found that TiO₂-N samples had higher photocatalytic activity than undoped TiO₂ samples, which could be assigned to the effect of introducing N atoms and XPS results confirm it. Using polyethylenimine (PEI), transparent thin films of TiO₂-N nanoparticles were prepared by layer-by-layer self assembly method. UV-visible spectrophotometry was employed in a quantitative manner to monitor the adsorbed mass of TiO₂ and PEI after each dip cycle. The adsorption of both TiO₂ and PEI showed a saturation dip time of 15 min.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Photocatalytic activity enhancement of TiO2 films by micro and nano-structured surface modification

Titanium oxide thin films were deposited by spin coating using a precursor solution of titanium oxide (IV) acetylacetonate. To increase the contact surface area of the films, TiO₂ microspheres were added to the surface of the films. These spheres were 2 μm in diameter and formed agglomerates on the surface. They did not spread uniformly across the substrate, creating different roughnesses and morphologies along the surface of films. Photocatalytic properties of the samples were tested by the degradation of a methyl orange solution. The degradation performance was compared between plain films, films with microspheres and films covered with commercial TiO₂ P25 powder. The results indicate that the samples that were surface modified with TiO₂ microspheres present a photodegradation reaction rate 62 times higher than that obtained for plain TiO₂ films. The rate of reaction of the samples covered with P25 was 2 times greater than that obtained for the samples with microspheres, but the adhesion to the film was better in the case of microspheres. Moreover, samples with microspheres could be reused several times maintaining the same structural and photocatalytic properties.