Electrospun polyamide‐6 membranes containing titanium dioxide as photocatalyst

Electrospun polyamide‐6 membranes containing titanium dioxide (TiO₂) photocatalyst were prepared and characterized. By tailoring the electrospinning parameters it was possible to obtain membranes having two different thicknesses, namely 5 and 20 µm, in which TiO₂ particles were homogeneously dispersed. As a comparison, hybrid films made with polyamide‐6 matrix and TiO₂ filler were successfully produced, with inorganic/organic ratios of 10 and 20 wt%. The photocatalytic activity of both hybrid systems was evaluated by following the degradation of methylene blue as a target molecule as a function of UV irradiation time. A smoother degradation was recorded for the electrospun membranes with respect to the hybrid films probably due to a less exposed surface because of the highly porous structure. Even if a longer photodegradation time was necessary, the degradation of the dye was successfully achieved. Copyright © 2010 Society of Chemical Industry     

Physical properties and enzymatic hydrolysis of poly(L‐lactide)–TiO2 composites

Amorphous poly(L ‐lactide) (PLLA) composite films with titanium dioxide (TiO₂) particles were prepared by solution‐casting using methylene chloride as a solvent, followed by quenching from the melt. The effects of surface treatment, volume fraction, size, and crystalline type of the TiO₂ particles on the mechanical properties and enzymatic hydrolysis of the composite films were investigated. The tensile strength of the PLLA composite films containing TiO₂ particles except for anatase‐type ones with a mean particle size of 0.3–0.5 μm was lowered and the Young's modulus became higher with increasing the content of TiO₂ particles. The tensile strength of the composite films containing anatase‐type TiO₂ with a mean particle size of 0.3–0.5 μm at contents of 20 wt % or less was almost the same as that of the pure PLLA film. The enzymatic hydrolysis of PLLA matrix was accelerated by the addition of the hydrophilic anatase‐type TiO₂ particles (nontreated or Al₂O₃ treated) with a mean particle size of 0.3–0.5 μm at relatively high contents such as 20 wt %. On the other hand, the enzymatic hydrolysis of PLLA matrix was inhibited by composite formation with the hydrophobic rutile‐type TiO₂ particles (Al₂O₃‐stearic acid treated, or ZrO₂‐Al₂O₃‐stearic acid treated). These results suggest that the mechanical properties and enzymatic hydrolyzability of the PLLA can be controlled by the kind and amount of the added TiO₂ particles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 190–199, 2005     

Photodegradation behavior of the polycarbonate/TiO2 composite films under the UV irradiation in ambient air condition

Photocatalytic degradation mechanism of the polycarbonate(PC)/TiO₂ composite films was studied under the ambient air condition in order to investigate the feasibility of the PC/TiO₂ composite as a photodegradable polymer. TiO₂ composition in the PC/TiO₂ composite was changed from 0 wt% to 4 wt%. Photodegradation behaviors of the composite films were compared with that of the pure PC films by performing the weight loss monitoring under UV irradiation, FTIR spectroscopy, color measurement analysis, SEM, and XPS analysis. The weight loss rate of the PC/TiO₂ composite film (33% weight loss after 300 h) with 4 wt% TiO₂ was twice as high as the pure PC films (14% weight loss after 300 h). The increase in the FTIR hydroxyl peak, and carbonyl peak intensity and the yellowing observation during the photodegradation were due to the formation of the photoproducts (aliphatic, aromatic chain‐ketones, aromatic, and OH radical) and the structural modification of polycarbonate. XPS analysis of composite film showed the photodegradation of the polymer surface and TiO₂ particles exposure on the surface of the composite films matrix. POLYM. COMPOS., 36:1462–1468, 2015. © 2014 Society of Plastics Engineers     

Niobium‐Doped Titania Photocatalyst Film Prepared via a Nonaqueous Sol‐Gel Method

Niobium‐doped Titanium dioxide (Nb:TiO₂) transparent films were successfully deposited on glass substrates using a non‐aqueous sol‐gel spin coating technique. The effect of Nb concentration on the structural and photocatalytic properties of Nb:TiO₂ films was studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV visible spectroscopy. The films with 12 at.% (atomic percent) Nb doped TiO₂ showed excellent photocatalytic activity through 97.3% degradation of methylene blue (MB) after 2 h of UV irradiation.     

Photocatalytic reactions of imazamox at TiO2, H2O2 and TiO2/H2O2 in water interfaces: Kinetic and photoproducts study

The photocatalytic transformation of imazamox, a herbicide of imidazolinone family, is investigated in aqueous solution containing titanium dioxide, hydrogen peroxide or the combination of TiO₂/H₂O₂ under simulated sunlight irradiation. The effect of parameters such as the amount of catalysts, the concentration of herbicide, and the pH were investigated by measurement of the rate constant of degradation. Experimental data obtained under different conditions describe the dependency of degradation rate on the above mentioned parameters. Consequently, kinetic parameters were experimentally determined and a pseudo-first-order kinetic was observed. Mulliken charge distributions calculated by the DFT method B3LYP/6–31+G(d) level of theory for key cationic, anionic and neutral structures of imazamox give interpretation for the dependency of photodegradation rate constant on pH. The degradation rate constants were always higher for the heterogeneous catalysis in reactions (TiO₂/UV, TiO₂/UV/H₂O₂) compared to the homogeneous systems (UV alone, H₂O₂/UV). In parallel, five photoproducts could be tentatively identified using Electrospray ionization Fourier transform ion cyclotron resonance mass spectroscopy based on precise chemical formula assignments.     

Enhanced photocatalytic activity of highly transparent superhydrophilic doped TiO2 thin films for improving the self-cleaning property of solar panel covers

Undoped and metal doped nanocrystalline TiO₂ transparent thin films were synthesized on glass substrates via sol-gel/dip-coating method. TiO₂ thin film coatings can be applied to the surfaces of solar panels to impart self-cleaning properties to them. The structural and optical properties of few nanometer-thick films were characterized by XRD, SEM, CA, AFM, XPS, and UV–Vis spectrophotometry techniques. The stoichiometric TiO₂ films crystallized in anatase phase, with a particle size of ～100 nm, which were uniformly distributed on the surface. The prepared films with a roughness of ～1–5 nm, increased the hydrophilicity of the glass surface. Reducing the amount of Ti precursor (X) favored the improvement of film quality. To improve the photocatalytic activity of the TiO₂ thin film, it was doped with Ni, Cd, Mo, Bi and Sr metal ions. The effect of metal doping on the photocatalytic activity of the films was investigated using the degradation process of methylene blue (MB) dye as the model contaminant. Among the prepared coatings, the Sr–TiO₂ film showed the highest efficiency for MB degradation. It increased the dye degradation efficiency of the films under both UV and Vis lights. The kinetic investigations also showed that the degradation of MB by TiO₂ and M ? TiO₂ films obeyed the pseudo-first order kinetics.     

Photocatalytic reactions of imazamox at TiO2, H2O2 and TiO2/H2O2 in water interfaces: Kinetic and photoproducts study

The photocatalytic transformation of imazamox, a herbicide of imidazolinone family, is investigated in aqueous solution containing titanium dioxide, hydrogen peroxide or the combination of TiO₂/H₂O₂ under simulated sunlight irradiation. The effect of parameters such as the amount of catalysts, the concentration of herbicide, and the pH were investigated by measurement of the rate constant of degradation. Experimental data obtained under different conditions describe the dependency of degradation rate on the above mentioned parameters. Consequently, kinetic parameters were experimentally determined and a pseudo-first-order kinetic was observed. Mulliken charge distributions calculated by the DFT method B3LYP/6–31+G(d) level of theory for key cationic, anionic and neutral structures of imazamox give interpretation for the dependency of photodegradation rate constant on pH. The degradation rate constants were always higher for the heterogeneous catalysis in reactions (TiO₂/UV, TiO₂/UV/H₂O₂) compared to the homogeneous systems (UV alone, H₂O₂/UV). In parallel, five photoproducts could be tentatively identified using Electrospray ionization Fourier transform ion cyclotron resonance mass spectroscopy based on precise chemical formula assignments.     

Synthesis,physical properties,and characterization of starch‐based blend films by adding nano‐sized TiO2/poly(methyl metacrylate‐co‐acrylamide)

The purpose of this study was to improve the physical properties and to expand the application range of starch‐based blend films added nano‐sized TiO₂/poly(methyl methacrylate‐co‐acrylamide) (PMMA‐co‐AM). Starch‐based blend films were prepared by using corn starch, polyvinyl alcohol (PVA), nano‐sized PMMA‐co‐AM, nano‐sized TiO₂/PMMA‐co‐AM particles, and additives, i.e., glycerol (GL) and citric acid (CA). Nano‐sized PMMA‐co‐AM was synthesized by emulsion polymerization and TiO₂ nanoparticles were also prepared by using sol–gel method. Nano‐sized TiO₂/PMMA‐co‐AM particles were synthesized by wet milling for 48 h. The morphology and crystallinity of TiO₂, nano‐sized PMMA‐co‐AM and TiO₂/PMMA‐co‐AM particles were investigated by using the scanning electron microscope (SEM) and X‐ray diffractometer (XRD). In addition, the functional groups of the TiO₂/PMMA‐co‐AM particles were characterized by IR spectrophotometry (FTIR). The physical properties such as tensile strength (TS), elongation at break (%E), degree of swelling (DS), and solubility (S) of starch‐based films were evaluated. It was found that the adding of nano‐sized particles can greatly improve the physical properties of the prepared films. The photocatalytic degradability of starch/PVA/nano‐sized TiO₂/PMMA‐co‐AM composite films was evaluated using methylene blue (MB) and acetaldehyde (ATA) as photodegradation target under UV and visible light. The degree of decomposition (C/C₀) of MB and ATA for the films containing TiO₂ and CA was 0.506 and 0.088 under UV light irradiation and 0.586 (MB) and 0.631 (ATA) under visible light irradiation, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

TiO2‐kaolin‐PE composite film: A study based on photocatalytic degradation and biodegradation

A novel photodegradable and biodegradable polyethylene (PE) film was prepared through a melt blending technique, where nano‐TiO₂ and common kaolin were used as the photocatalyst and biodegradable promoter showing improved degradable efficiency of the waste PE. The photo‐degradation of the composite film was investigated by weight loss monitoring, attenuated total reflection–fourier transformed infrared spectroscopy (ATR–FTIR), and scanning electron microscopy. The aerobic biodegradation of the residue films after photodegradation was investigated by analysis of evolved carbon dioxide of films in aquatic test systems according to the international standards (ISO 14852, 1999). The results showed that the weight loss of as‐prepared photo‐ and biodegradable composite film reached 26.8% after 240 h of UV light irradiation. The big cavities formed not only on the film surface but also inside the bulk film, together with the chalking phenomenon taking place. The biodegradation results revealed that the addition of kaolin enhanced the degradation of UV‐light treated TiO₂‐PE films. The prepared PE based composite films showed promising application as novel photo‐biodegradable environment‐harmless materials. In addition, a degradation mechanism for this composite film was also discussed. POLYM. COMPOS., 37:2353–2359, 2016. © 2015 Society of Plastics Engineers     

Photocatalytic functional coatings of TiO2 thin films on polymer substrate by plasma enhanced atomic layer deposition

We prepared photocatalytic TiO₂ thin films which exhibited relatively high growth rate and low impurity on polymer substrate by plasma enhanced atomic layer deposition (PE-ALD) from Ti(NMe₂)₄ [tetrakis (dimethylamido) Ti, TDMAT] and O₂ plasma to show the self-cleaning effect. The TiO₂ thin films with anatase phase and bandgap energy about 3.3 eV were deposited at growth temperature of 250 °C and the photocatalytic effects were compared with commercial Activ glass. From contact angles measurement of water droplet and photo-induced degradation test of organic liquid, TiO₂ thin films with anatase phases showed superhydrophilic phenomena and decomposed organic liquid after UV irradiation. The anatase TiO₂ thin film on polymer substrate showed highest photocatalytic efficiency after 5 h UV irradiation. We attribute the highest photocatalytic efficiency of TiO₂ thin film with anatase structure to the formation of suitable crystalline phase and large surface area.     

Investigation of surface modification of rutile TiO2 nanoparticles with SiO2/Al2O3 on the properties of polyacrylic composite coating

Surface modification and characterization of TiO₂ nanoparticles as an additive in a polyacrylic clear coating were investigated. For the improvement of nanoparticles dispersion and the decreasing of photocatalytic activity, the surface of nanoparticles was modified with binary SiO₂/Al₂O₃. The surface treatment of TiO₂ nanoparticles was characterized with FTIR. Microstructural analysis was done by AFM. The size, particle size distribution and zeta potential of TiO₂ nanoparticles in water dispersion was measured by DLS method. For the evaluation of particle size and the stability of nanoparticles in water dispersions with higher solid content the electroacoustic spectroscopy was made. To determine the applicability and evaluate the transmittance of the nano-TiO₂ composite coatings UV–VIS spectroscopy in the wavelength range of 200–800 nm was employed. The results showed that surface treatment of TiO₂ nanoparticles with SiO₂/Al₂O₃ improves nanoparticles dispersion and UV protection of the clear polyacrylic composite coating.     

Phorate degradation by TiO2 photocatalysis: Parameter and reaction pathway investigations

The photocatalytic degradation of phorate in aqueous suspensions was examined with the use of titanium dioxide (TiO₂) as a photocatalyst. About 99% of phorate was degraded after UV irradiation for 60 min. The photodegradation of phorate followed pseudo-first-order kinetics and parameters such as pH of the system, TiO₂ dosage, and presence of anions were found to influence the reaction rate. To obtain a better understanding of the mechanistic details of this TiO₂-assisted photodegradation of phorate with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) techniques. The probable photodegradation pathways were proposed and discussed. To the best of our knowledge, this is the first study that reports the degradation pathways of phorate. The electrical energy consumption per order of magnitude for photocatalytic degradation of phorate was also calculated and showed that a moderated efficiency (E_EO = 96 kWh/(m³ order)) was obtained in TiO₂/UV process.     

Colored films produced by electron beam deposition from nanometric TiO2 and Al2O3 pigment powders obtained by modified polymeric precursor method

Synthesis and the characterization of TiO₂:5%Co (green), TiO₃:5%Fe (brown-reddish), TiO₂:2%Cr (brown), Al₂O₃:5%Co (blue), Al₂O₃:5%Fe (brown-reddish) and Al₂O₃:2%Cr (light green) nanometric pigment powders using polymeric precursor (modified Pechini's method) is reported. Colored thick films were deposited on amorphous quartz substrates by electron beam physical vapor deposition (EB-PVD) using pellets of the pigment powders as target. The evaporation process was carried out in vacuum of 4 × 10⁻⁶ Torr and the amorphous quartz substrates were kept at 350 °C during deposition. The TiO₂-based pigment powders presented crystalline anatase phase and the Al₂O₃-based pigment powders showed corundum phase, investigated by X-ray diffraction (XRD). The average particle size of the pigment powders was about 20 nm, measured by scanning electron microscopy with field emission gun (SEM-FEG). Diffuse reflectance spectra and colorimetric coordinates L¹, a¹, b¹ using the CIE-L¹a¹b¹ method are shown for the pigment powders, in the 350–750 nm range. The colored thick films were characterized by transmittance (UV–Vis) and atomic force microscopy (AFM). The average film roughness was ∼5.5 nm and the average grain size obtained in the films was around 75 nm. Films with thickness from 400 nm to 690 nm were obtained, measured by talystep profiler. Transmission spectra envelop method has been used to obtain refractive index and thickness of the Al₂O₃ colored thick films.     

Self-cleaning performance of sol–gel-derived TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> double-layer thin films

The self-cleaning properties of the TiO₂/SiO₂ double-layer films prepared by sol–gel method were investigated. Thin films were prepared by spin coating onto glass and then thermally treated at different temperatures, and characterized using X-ray diffraction, atomic force microscopy, field emission scanning electron microscopy, and UV–visible spectroscopy. The cross-sectional structure of the films was observed by FESEM. The surface roughness of the films was characterized by AFM. The root mean square surface roughness of the thin films was below 2 nm, which should enhance their optical transparency. The photo-induced hydrophilicity of the films was evaluated by water contact angle measurement in air. The photocatalytic activity of the films was studied by the photocatalytic degradation of methylene blue under UV light irradiations. The TiO₂/SiO₂ double-layer thin films are plausibly applicable to developing self-cleaning materials in various applications such as windows, solar panels, cement, and paints.     

Effect of TiO2 surface treatment on the mechanical properties of cured epoxy resin

Mechanical properties of epoxy resin toughened with two different submicron particles of TiO₂ at different weight fractions (1, 3, and 5%, respectively) were investigated. The first TiO₂ particles are surface treated with Al₂O₃–SiO₂, and the second are surface treated with Al₂O₃–ZrO₂. The composites were characterized by tensile, flexural, pull off and abrasion tests, followed by X-ray photoelectron spectroscopy and scanning electron spectroscopy of the fracture surfaces. A small amount of TiO₂ (~1%) submicron particles improves the flexural, abrasion and pull-off strengths, while amounts up to 5% significantly enhance tensile properties only. TiO₂ particles surface treated with Al₂O₃–ZrO₂ produce an epoxy composite with higher strength and weight loss but lower pull off strength and more brittle than that prepared with Al₂O₃–SiO₂ particles. The TiO₂ particles surface treated with Al₂O₃–SiO₂ have a higher adherence to the epoxy composite matrix than the particles treated with Al₂O₃–ZrO₂ as shown by scanning electron spectroscopy.     

Preparation of titanium oxide,iron oxide,and aluminium oxide from sludge generated from Ti-salt,Fe-salt and Al-salt flocculation of wastewater

In this study, the settled floc (sludge) produced by aluminum sulfate (Al₂(SO₄)₃), ferric chloride (FeCl₃) and titanium tetrachloride (TiCl₄) flocculation was recycled with a novel flocculation process, which has a significant potential to the lower cost of waste disposal, protect the environment and public health and yield economically useful by-products. Three coagulants removed 70% of organic matter in synthetic wastewater. The settled floc was incinerated in the range from 100 °C to 1000 °C. Alumina (Al₂O₃), hematite (Fe₂O₃), titanium oxide (TiO₂) which are the most widely used metal oxides were produced from the wastewater sludge generated by the flocculation in wastewater with Al₂(SO₄)₃, FeCl₃ and TiCl₄, respectively. TiO₂ particles produced from the sludge consisted of the large amount of nano size particles. Hematite (Fe₂O₃) and grattarolaite (Fe₃ (PO₄)O₃ or Fe₃PO₇) included the majority of micro size (40%) particles. Alumina (Al₂O₃) also consisted of micro size (40%). Due to TiO₂ usefulness of the application, detailed characterisation of TiO₂ after calcination at different temperatures were investigated in terms of X-ray diffraction, energy dispersive X-ray, surface area and photoactivity.     

Photocatalytic degradation of poly(ethylene oxide) and polyacrylamide

The photocatalytic degradation of poly(ethylene oxide) (PEO) and polyacrylamide (PAM) was investigated using combustion synthesized nano‐sized TiO₂ catalyst (CSN‐TiO₂). The degradation was conducted with two different UV lamps of 125 and 80 W. Degradation of PEO was observed in both the cases, whereas PAM degraded only when exposed to lamp of higher power, even in the presence of catalyst. Gel permeation chromatography was used to determine the molecular weight distribution. Continuous distribution kinetics was applied to determine the kinetics of the photodegradation process. The degradation rate coefficients of the polymers in the presence of combustion synthesized TiO₂ were higher than the degradation rate coefficients obtained with commercially available TiO₂ (Degussa P‐25). The enhanced degradation rate of the polymers when catalyzed by CSN‐TiO₂ can be due to the nano‐size, high surface area, and the presence of hydroxyl groups on the surface of the catalyst. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3997–4003, 2006     

Bi and Al co-doped anatase titania for photosensitized degradation of Rhodamine B under visible-light irradiation

Although TiO₂ is a wide band gap semiconductor, it demonstrates photodegradation activity under visible light irradiation after dye sensitization. Compared with esterification between the surface hydroxyl group of TiO₂ and the carboxylic group of dyes, electrostatic interaction between TiO₂ and dye shows better photosensitized performance. In this work, Bi/Al co-doping anatase titania (Ti_1-xBi_2x/3Al_2x/3O₂ (0 ≤ x ≤ 0.3)) is designed to enhance the electrostatic interaction. The effect of Al ions is to enhance the solubility of Bi³⁺ into titania nanocrystals. A new band gap is generated after high concentration of Bi element doping, which not only promotes the absorption of visible light, but also improves the utilization of photogenerated carriers. Based on the results of transmission electron microscopy, light absorption, photodegradation activity and density functional theory calculations, it is found that bismuth dopant is the electron capture site. It first accumulates electrons through photocatalytic degradation reaction to enhance electrostatic adsorption between the catalyst and the positively charged dye molecules, and finally realizes high-efficiency photosensitization degradation of Rhodamine B. In addition, the sensitized titania has excellent photodegradation recyclability.     

Preparation of a layered hexaniobate–titania nanocomposite and its photocatalytic activity on removal of phenol in water

A nanocomposite photocatalyst of two photocatalytically active semiconductor oxides was prepared by flocculation of exfoliated layered hexaniobate K₄Nb₆O₁₇ with TiO₂ fine particles in presence of acid electrolyte, and evaluated as photocatalyst by using photodegradation of phenol as a test reaction. Disappearance of (0k0) peaks which correspond to the basal spacing in the X-ray diffraction (XRD) patterns of the nanocomposite suggested that the exfoliated niobate nanosheets were randomly hybridized with TiO₂ particles without restacking to the layered structure. Scanning electron microscopy revealed that the nanocomposite was an agglomerate of closely packed niobate nanosheets and TiO₂ particles. The nanocomposite is mesoporous and has a specific surface area larger than those of the original K₄Nb₆O₁₇ and TiO₂ as indicated by N₂ adsorption–desorption isotherms. The increase in surface area is ascribed to the porous structure constructed by the exfoliated niobate nanosheets and TiO₂ particles. The photocatalytic activity of the porous nanocomposite was superior to those of K₄Nb₆O₁₇ and TiO₂ in terms of degradation of phenol.     

Microwave photocatalysis III. Transition metal ion‐doped TiO2 thin films on mercury electrodeless discharge lamps: preparation,characterization and their effect on the photocatalytic degradation of mono‐chloroacetic acid and Rhodamine B

BACKGROUND: Mercury electrodeless discharge lamps (Hg‐EDLs) were used to generate UV radiation when exposed to a microwave field. EDLs were coated with doped TiO₂ in the form of thin films containing transition metal ions Mⁿ⁺ (M = Fe, Co, Ni, V, Cr, Mn, Zr, Ag). Photocatalytic degradation of mono‐chloroacetic acid (MCAA) to HCl, CO₂, and H₂O, and decomposition of Rhodamine B on the thin films were investigated in detail. RESULTS: Polycrystalline thin doped TiO₂ films were prepared by dip‐coating of EDL via a sol–gel method using titanium n‐butoxide, acetylacetone, and a transition metal acetylacetonate. The films were characterized by Raman spectroscopy, UV/Vis absorption spectroscopy, X‐ray photoelectron spectroscopy (XPS), electron microprobe analysis and by atomic force microscopy (AFM). The photocatalytic activity of doped TiO₂ films was monitored in the decomposition of Rhodamine B in water. Compared with the pure TiO₂ film, the UV/Vis spectra of V, Zr and Ag‐doped TiO₂ showed significant absorption in the visible region, and hence the photocatalytic degradation of MCAA had increased. The best apparent degradation rate constant (0.0125 min^?1), which was higher than that on the pure TiO₂ film by a factor of 1.7, was obtained with the Ag(3%)/TiO₂ photocatalyst. The effect of doping level of vanadium acetylacetonate on the photocatalytic efficiency of the V‐doped TiO₂ was determined. CONCLUSIONS: Transition metal ion‐doped TiO₂ thin films showed significant absorption in the visible region. The metal doped TiO₂ photocatalyst (with an appropriate amount of V, Zr and Ag) on the Hg‐EDLs increased the degradation efficiency of MCAA in a microwave field. Copyright © 2009 Society of Chemical Industry