Study of the effect of rutile/anatase TiO2 nanoparticles synthesized by hydrothermal route in electrospun PVA/TiO2 nanocomposites

Mixed rutile–anatase TiO₂ nanoparticles were synthesized by hydrothermal treatment under acidic conditions and incorporated into poly(vinyl alcohol) (PVA). These nanocomposites were electrospun to produce nanofibers of PVA/TiO₂, which were characterized by scanning electron microscopy, transmission electron microscopy, X‐ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The photocatalytic degradation of Rhodamine B and degradation of the polymer by UV‐C lamps were also investigated. The results showed that TiO₂ nanoparticles did not change the morphology and thermal behavior of the nanofiber polymer, but were effective in modifying the UV absorption of PVA without reducing its stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of photodegradable polypropylene/clay composites based on nanoscaled TiO2 immobilized organoclay

Photodegradable polypropylene (PP) composites were prepared via melting blending using PP and titanium dioxide (TiO₂) immobilized organically modified montmorillonite (organoclay). TiO₂ immobilized organoclay (TiO₂‐OMT) was synthesized by immobilizing anatase TiO₂ nanoparticles on organically modified clay via sol–gel method. The structure and morphology of TiO₂‐OMT were characterized by XRD and scanning electron microscope (SEM), which showed that anatase TiO₂ nanoparticles with the size range of 8–12 nm were uniformly immobilized on the surface of organoclay layers. Diffuse reflection UV–vis spectra revealed TiO₂‐OMT had similar absorbance characters to that of commercial photocatalyst, Degussa P25. The solid‐phase photocatalytic degradation of PP/TiO₂‐OMT composites was investigated by FTIR, DSC, GPC and SEM. The results indicated that TiO₂‐OMT enhanced the photodegradation rate of PP under UV irradiation. This was due to that immobilization of TiO₂ nanoparticles on organoclay effectively avoided the formation of aggregation, and thereby increased the interface between PP and TiO₂ nanoparticles. After 300 h irradiation, the average molecular weight was reduced by two orders of magnitude. This work presented a promising method for preparation of environment‐friendly polymer nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

The Assembly of TiO2 Nanoparticles into Micrometer‐Sized Structures,Photocatalytically Active Under UV and Vis Light

Micrometer‐sized structures consisting of TiO₂ nanoparticles were prepared using the sol–gel technique in combination with the structure‐directing agent triethanolamine (TEA). The interaction of the TEA with the hydrolyzed sol–gel products led to the formation of TEA titanate complexes, which then enabled the assembly of sol–gel‐precipitated nanosized powders. A subsequent thermal treatment of these powders resulted in the formation of micrometer‐sized structures consisting of TiO₂ anatase and rutile nanoparticles. To characterize the prepared powders, FTIR spectroscopy, XRD analysis, the Brunauer‐Emmett‐Teller method (s_BET), UV–Vis spectrometry and electron microscopy (FE‐SEM, and TEM) were employed. The photocatalytic degradation of the azo dye known as methylene blue was monitored under UV and Vis irradiation and showed that the micrometer‐sized structures consisting of TiO₂ nanoparticles exhibited a similar photocatalytic activity to submicrometer‐sized structures consisting of TiO₂ nanoparticles prepared without TEA.     

Fabrication of TiO2‒Ag nanocomposite thin films via one-step gas-phase deposition

In this work, TiO₂‒Ag nanocomposite thin films were fabricated for the first time via simultaneous plasma-enhanced chemical vapor deposition and physical vapor deposition of TiO₂ and Ag nanoparticles in the gas-phase, respectively. The presence of Ag nanoparticles in the prepared nanocomposites has been confirmed using transmission electron microscopy and energy dispersive X-ray spectrometry techniques. The obtained electron microscopy images showed that the average size of TiO₂‒Ag nanoparticles was larger than that of pristine TiO₂. Moreover, the temperature of the anatase transformation into the rutile phase was decreased due to the presence of Ag nanoparticles in the TiO₂ matrix, while the photocatalytic activity of the produced nanocomposite (estimated by studying the degradation of methylene blue aqueous solution under UV irradiation) was 35% greater than that of pristine TiO₂. Therefore, the addition of Ag nanoparticles into the TiO₂ matrix significantly affected the morphology, phase transformation temperature, and photocatalytic performance of the fabricated material.     

One-step preparation of size-defined aggregates of TiO2 nanocrystals with tuning of their phase and composition

One-step route based on the thermal decomposition of the double salt (NH₄)₂TiO(SO₄)₂ (ammonium titanyl sulfate, ATS) is presented to prepare size-defined aggregates of Ti-based nanoparticles with structural hierarchy. The component of Ti-based networks is tunable from anatase/rutile TiO₂, nitrogen-doped TiO₂, TiN_xO_1−x, to TiN depending on the atmospheres and reaction temperatures. The as-prepared Ti-based powders were characterized by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectra (DRS), and BET surface area techniques. It is found that TiO₂ in the predominant rutile phase could be achieved by the thermal decomposition of ATS in flowing Ar gas. Furthermore, the nitrogen-doped TiO₂, TiN_xO_1−x solid solution and TiN were prepared by the thermal decomposition of ATS in flowing NH₃ gas by varying the temperatures. The network of anatase TiO₂ with a specific surface area up to 64 m² g⁻¹ contains large mesopores with a mean diameter of ca. 15 nm, and the large pore size allows more accessible surface and interface available for the photocatalytic degradation of large-molecule dyes. The photocatalytic activity of the prepared TiO₂ and nitrogen-doped TiO₂ under UV–vis light irradiation is compared to Degussa P-25 using the photocatalytic degradation of methylene blue (MB) as a model reaction. The anatase TiO₂ nanoparticles derived from one-step route show the highly efficient photocatalytic activity for the degradation of MB in comparison with Degussa P-25. The presence of large-sized rutile in the TiO₂ powder decreases the specific surface area and thus the powder exhibits a lower photocatalytic activity.     

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.     

Preparation of CdS/TiO2 nanotube arrays and the enhanced photocatalytic property

In this paper, a series of CdS/TiO₂ NTs have been synthesized by SILAR method. The as-prepared CdS/TiO₂ NTs have been analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive spectrometer (EDS), and ultraviolet–visible (UV–vis). And their photocatalytic activities have been investigated on the degradation of methylene blue under simulated solar light irradiation. XRD results indicate that TiO₂ NTs were anatase phase, CdS nanoparticles were hexagonal phase. FESEM results indicate that low deposition concentration can keep the nanotubular structures. UV–vis results indicate that CdS can be used to improve the absorbing capability of TiO₂ NTs for visible light, and the content of CdS affects the band gap. Photocatalytic results indicate that CdS nanoparticles are conducive to improve the photocatalytic efficiency of TiO₂ NTs, and the highest degradation rate can reach 93.8%. And the photocatalytic mechanism of CdS/TiO₂ NTs to methylene blue is also described.     

UV-curable polyurethane acrylate–Ag/TiO2 nanocomposites with superior UV light antibacterial activity

Polyurethane acrylate (PUA)–Ag/TiO₂ nanocomposites were synthesized through in situ polymerization. The well-dispersed Ag/TiO₂ nanorods serve as photoinitiator. Meanwhile, the PUA–Ag/TiO₂ nanocomposite films exhibit superior activity toward the photocatalytic degradation of Escherichia coli under UV light. The excellent UV curing and antibacterial activities can be ascribed to the synergistic effect of Ag and TiO₂, which promotes the effective electron/hole separation and thus generates various reactive species. Thin films with these nanoparticles are more hydrophilic after UV illumination. And the antibacterial mechanism of the UV-curable PUA–Ag/TiO₂ nanocomposites was proposed.     

Preparation and photocatalysis of TiO2-fluoropolymer electrospun fiber nanocomposites

The preparation and photocatalytic properties of titanium dioxide (TiO₂)-fluoropolymer fiber nanocomposites were studied. The fluoropolymer nanofibers with carboxyl group were prepared by electrospinning. The complex was formed between carboxyl on fluoropolymer electrospun fiber surface and titanium ion, and then the TiO₂ nanoparticles were immobilized on the surface of fluoropolymer electrospun fibers through hydrothermal complex-precipitation. By controlling the reaction conditions, different sizes and numbers of TiO₂ nanocrystals can be obtained. The Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results reveal that an interaction exists between TiO₂ and fluoropolymer fibers. The degradation of methylene blue solution is performed by TiO₂-fluoropolymer fiber nanocomposites under UV irradiation. There may be an adsorption-migration-photodegradation process during the degradation of methylene blue by using TiO₂-fluoropolymer fiber nanocomposites as photocatalyst. The experimental results show that the TiO₂-fluoropolymer fiber nanocomposites have good photocatalytic ability, recycling and stability for the potential applicability in an environmental remediation.     

TiO2 nanofibers assembled on graphene-silver platform as a visible-light photo and bio-active nanostructure

The heterogeneous titanium oxide-reduced graphene oxide-silver (TiO₂/RGO/Ag) nanocomposites were successfully prepared by incorporation of two dimensional (2D) RGO nanosheets and spherical silver nanoparticles (NPs) into the 1D TiO₂ nanofibers. The novel TiO₂/RGO/Ag nanocomposites were synthesized by loading TiO₂ nanofibers, prepared via electrospinning technique, on the RGO/Ag platform. The resulting nanocomposites have been characterized using various techniques containing transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultra-violet-visible (UV–vis) spectroscopy. Microscopic studies clearly verified the existence of TiO₂ nanofibers with Ag NPs on the surface of RGO sheet and formation of TiO₂/RGO/Ag nanocomposites. Moreover, the results of UV–vis spectroscopy demonstrated that TiO₂/RGO/Ag nanocomposites extended the light absorption spectrum toward the visible region and significantly enhanced the visible-light photocatalytic performance of the prepared samples on degradation of rhodamine B (Rh. B) as a model dye. It was found that, incorporation of 50 µl RGO/Ag into the TiO₂ nanofibers lead to a maximum photocatalytic performance. Also, the improvement of the inactivation of Escherichia coli (E. coli) bacteria under visible-light irradiation was revealed by introduction of RGO/Ag into the TiO₂ matrix. The significant enhancement in the photo and bio-activity of TiO₂/RGO/Ag nanocomposites under visible-light irradiation can be ascribed to the RGO/Ag content by acting as electron traps in TiO₂ band gap.     

Preparation of TiO2/carbon nanotubes photocatalysts: The influence of the method of oxidation of the carbon nanotubes on the photocatalytic activity of the nanocomposites

A method for the preparation of efficient TiO₂/multi-wall carbon nanotubes nanocomposite photocatalysts by precipitation of anatase TiO₂ nanoparticles onto differently oxidized carbon nanotubes is presented. The precursor compound titanium(IV) bromide was hydrolyzed producing pure anatase phase TiO₂ nanoparticles decorated on the surface of the oxidized carbon nanotubes. The oxidative treatment of the carbon nanotubes influenced the type, quantity and distribution of oxygen-containing functional groups, which had a significant influence on the electron transfer properties, i.e., the photocatalytic activity of the synthesized nanocomposites. The results of C.I. Reactive Orange 16 photodegradation in the presence of all the synthesized nanocomposites showed their better photocatalytic activity in comparison to the commercial photocatalyst Degussa P-25.     

Surface modification of titanium dioxide nanoparticles by polyaniline via an in situ method

BACKGROUND: Nanoparticulate titanium dioxide (TiO₂) has the advantages of high chemical stability, high photocatalytic activity to oxidise pollutants in air and water, relatively low price and non‐toxicity. However, its high surface energy leads to the aggregation of nanoparticles. In addition, the wide band gap of TiO₂ (3.2 eV) only allows it to absorb ultraviolet (UV) light (<387 nm), which represents just a small fraction (3–5%) of the solar photons. These factors have limited its use in many fields. In this study, nanoparticulate TiO₂ was modified by polyaniline (PANI) in order to enhance its photoactivity under UV light and sunlight illumination. RESULTS: TiO₂ nanoparticles were modified by PANI via a chemical oxidative method. The introduction of small amounts of PANI enhanced the dispersion of TiO₂ nanoparticles and improved the photocatalytic activity under UV light. In addition, the band gap energies of all PANI/TiO₂ nanocomposites were lower than that of neat TiO₂ nanoparticles, so the PANI/TiO₂ nanocomposites can be excited to produce more electron–hole pairs under sunlight, which could result in higher photocatalytic activities. CONCLUSION: The modification of nanoparticulate TiO₂ by PANI can increase its photoactivity in the process of phenol degradation under UV light and sunlight illumination. Copyright © 2008 Society of Chemical Industry     

Hollow hybrid titanate/Au@TiO2 hierarchical architecture for highly efficient photocatalytic application

Hollow hybrid titanate/Au@TiO₂ hierarchical architecture consisting of titanate and anatase titanium dioxide (TiO₂) loaded with Au nanoparticles was prepared via a sol-impregnation method combined with a hydrothermal etching process. The titanate/Au@TiO₂ architecture possesses unique hollow spherical configuration with Au nanoparticles loaded in the middle of titanate and TiO₂ shells and allows to be used as a microreactor for photocatalytic application. The hybrid titanate/Au@TiO₂ photocatalyst shows significantly enhanced photocatalytic activity on degradation of methylorange (MO) under UV light irradiation due to the lower electron–hole pairs recombination rate arisen from the synergistic effect of titanate-Au-TiO₂ in hybrid hierarchical architecture.     

Synthesis of carbon quantum dots/TiO2 nanocomposite for photo-degradation of Rhodamine B and cefradine

Pure TiO₂ and carbon quantum dots (CQDs)-doped TiO₂ nanocomposite (CQDs/TiO₂ nanocomposite) were prepared by a sol-gel approach for photocatalytic removal of Rhodamine B and cefradine. Analyses by Transmission electronmicroscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), UV–visible spectroscopy and X-ray powder diffraction (XRD) confirmed the successful formation of CQDs/TiO₂ heterostructure. The as-prepared TiO₂ and CQDs/TiO₂ composite possessed small particles, spherical-like shape, and anatase crystal form. Meanwhile, Rhodamine B and cefradine were chosen to evaluate the photocatalytic activity of TiO₂ and CQDs/TiO₂ composite. Results revealed that with the facile decoration of CQDs, the absorption of photocatalyst was extended into visible light region and photocatalytic activity was improved in comparison with pure TiO₂. Furthermore, the mechanism for the improvement of the photocatalytic performance of the composites was discussed on the basis of the results. CQDs play an important role in the photocatalytic process, due to their superior ability to extend the visible absorption and produce more electrons and electron–hole pairs for the degradation of pollutants. In all, the paper offers further insights into the development of CQDs/TiO₂ nanocomposite as photocatalyst for the degradation of antibiotics.     

Effect of surfactant in a modified sol on the physicochemical properties and photocatalytic activity of crystalline TiO<Subscript>2</Subscript> nanoparticles

This study describes the effect of amphiphilic organic molecules (surfactants) in a sol on the physicochemical properties and photocatalytic activity of crystalline TiO₂ nanoparticles prepared via a simple sol–gel route at high temperatures from 400 to 800 °C. Addition of polyoxyethylenesorbitan surfactant and polyethylene oxide and polypropylene oxide triblock copolymer as particle size inhibitors and pore directing agents into a stable titania sol affected the physicochemical properties of TiO₂ nanoparticles such as their crystallographic structure, morphology, and defect structure. With the addition of the surfactants, the ratio of anatase and rutile crystal phases of TiO₂ was controlled and an active anatase crystal phase was maintained during heat treatment up to 800 °C. Decrease in the sintering rate and inhibition in crystal growth were also observed, which resulted in higher surface area and inhibition of crystallite aggregation. Bulk defects in TiO₂ were reduced while surface defects were increased as a result of the addition of surfactants. These physicochemical properties of TiO₂ nanoparticles were correlated with photocatalytic degradation of 4-chlorophenol in water. The results revealed that high crystallinity, anatase crystal phase, high specific surface area, surface defects, and segregated morphology of TiO₂ nanoparticles, which were induced by the addition of surfactants, were more advantageous for enhancing photocatalytic destruction of the model organic compound tested in the study.     

Green synthesis of TiO2 nanospheres from isolated Aspergillus eucalypticola SLF1 and its multifunctionality in nanobioremediation of C. I. Reactive Blue 194 with antimicrobial and antioxidant activity

For synthesis of titanium dioxide (TiO₂) nanoparticles (NPs), Green methods have been proven to be more efficient than several physiochemical methods. This article presents a non-toxic, ecofriendly, cost-effective and a facile route of green synthesis of TiO₂ NPs by an isolated fungus Aspergillus eucalypticola SLF1, which exhibits excellent photocatalytic, antimicrobial and antioxidant activity without structural modification done by physicochemical methods. The TiO₂ NPs are characterized by UV–Visible spectroscopy, XRD, FTIR, FE-SEM, DLS, TEM, BET, Raman spectroscopy and PL. The mesoporous, anatase phase, with a band gap 3.49 eV observed by BET, XRD. UV–Visible spectral analysis displayed sunlight driven photocatalytic performance against C. I. Reactive Blue 194 by advanced oxidation process. Decolourization and 99.70% degradation within 30 min exhibited pseudo first order kinetic with reaction rate constant 0.1935 min⁻¹ by linear method. These findings are superior physicochemical methods. Ecofriendly degradation was confirmed by UV–Vis. HPLC and LCMS etc and phytotoxic studies.     

Effects of carbon‐coated titanium dioxide nanoparticles as a photostabilizer on the photodegradation of rigid poly(vinyl chloride)

In this study, nanocomposites of rigid poly(vinyl chloride) (UPVC) using the synthesized carbon‐coated titanium dioxide (TiO₂) nanoparticles and commercial powder of titanium dioxide (with rutile structure) were prepared by melt blending. The presence of carbon‐coated TiO₂ nanoparticles with rutile structure in UPVC matrix led to an improvement in photo stability of UPVC nanocomposites in comparison with commercial UPVC. The photocatalytic degradation behavior of nanocomposites was investigated by measuring their structural changes, surface tension, and mechanical and morphological properties before and after UV exposure for 700 h. It was found that mechanical and physical properties of UPVC nanocomposites are not considerably reduced after UV exposure in the presence of carbon‐coated TiO₂ nanoparticles even in small percentage of nanoparticles in comparison with the presence of commercial TiO₂ particles. Therefore, it can be concluded that UPVC/TiO₂ nanocomposite with low content of carbon‐coated TiO₂ nanoparticles(0.25 wt %) illustrated high stability under light exposure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40228.     

Visible light photocatalytic activity of TiO2/heat‐treated PVC film

BACKGROUND: Semiconductor TiO₂ has been investigated extensively due to its chemical stability, nontoxicity and inexpensiveness. However, the wide band gap of anatase TiO₂ (about 3.2 eV) only allows it to absorb UV light. TiO₂ nanoparticles modified by conditional conjugated polymers show excellent photocatalytic activity under visible light. However, these conjugated polymers are not only expensive, but also difficult to process. Polyvinyl chloride (PVC) was heat‐treated at high temperature to remove HCl and a C?C conjugated chain structure was obtained. When TiO₂ nanoparticles were dispersed into the conjugated polymer film derived from PVC, this composites film exhibited high visible light photocatalytic activity. RESULTS: The photocatalytic activity of TiO₂/heat‐treated PVC (HTPVC) film was investigated by degrading Rhodamine B (RhB) under visible light irradiation. The photodegradation of RhB follows apparent first‐order kinetics. The rate constants of RhB photodegradation in the presence of the TiO₂/HTPVC films with different mass content of TiO₂ are 16–56 and 4–14 times that obtained in the presence of the pure HTPVC and TiO₂/polymethyl methacrylate (PMMA) composite film, respectively. The TiO₂/HTPVC film showed excellent photocatalytic activity and stability after 10 cycles under visible light irradiation. CONCLUSION: TiO₂/HTPVC film exhibits high visible light photocatalytic activity and stability. Copyright © 2012 Society of Chemical Industry     

Photoactive behavior of polyacrylonitrile fibers based on silver and zirconium co‐doped titania nanocomposites: Synthesis,characterization, and comparative study of solid‐phase photocatalytic self‐cleaning

Silver and zirconium co‐doped and mono‐doped titania nanocomposites were synthesized and deposited onto polyacrylonitrile fibers via sol–gel dip‐coating method. The resulted coated‐fibers were characterized by X‐ray diffraction (XRD), scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, thermogravimetric analysis, and BET surface area measurement. Photocatalytic activity of the TiO₂‐coated and TiO₂‐doped coated fibers were determined by photomineralization of methylene blue and Eosin Y under UV–vis light. The progress of photodegradation of dyes was monitored by diffuse reflectance spectroscopy. The XRD results of samples indicate that the TiO₂, Ag‐TiO₂, Zr‐TiO₂, and Ag‐Zr‐TiO₂ consist of anatase phase. All samples demonstrated photo‐assisted self‐cleaning properties when exposed to UV–vis irradiation. Evaluated by decomposing dyes, photocatalytic activity of Ag–Zr co‐doped TiO₂ coated fiber was obviously higher than that of pure TiO₂ and mono‐doped TiO₂. Our results showed that the synergistic action between the silver and zirconium species in the Ag‐Zr TiO₂ nanocomposite is due to both the structural and electronic properties of the photoactive anatase phase. These results clearly indicate that modification of semiconductor photocatalyst by co‐doping process is an effective method for increasing the photocatalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

TiO2 nanofibers doped with rare earth elements and their photocatalytic activity

In the present study rare earth doped (Ln³⁺–TiO₂, Ln = La, Ce and Nd) TiO₂ nanofibers were prepared by the sol–gel electrospinning method and characterized by XRD, SEM, EDX, TEM, and UV-DRS. The photocatalytic activity of the samples was evaluated by Rhodamine 6G (R6G) dye degradation under UV light irradiation. XRD analysis showed that all the synthesized pure and doped titania nanofibers contain pure anatase phase at 500 °C but at 700 °C it shows both anatase and rutile phase. XRD result also shows that Ln³⁺-doped titania probably inhibits the phase transformation. The diameter of nanofibers for all samples ranges from 200 to 700 nm. It was also observed that the presence of rare-earth oxides in the host TiO₂ could decrease the band gap and accelerate the separation of photogenerated electron–hole pairs, which eventually led to higher photocatalytic activity. To sum up, our study demonstrates that Ln³⁺-doped TiO₂ samples exhibit higher photocatalytic activity than pure TiO₂ whereas Nd³⁺-doped TiO₂ catalyst showed the highest photocatalytic activity among the rare earth doped samples.