Electrospun nanofibers of ZnO‐TiO2 hybrid: characterization and potential as an extracellular scaffold for supporting myoblasts

One‐dimensional nanofibers have attracted tremendous attention because of their potential applications. Electrospinning technology enables industrial production of these nanofibers. This study aims to fabricate one‐dimensional ZnO doped TiO₂ by electrospinning and to characterize these hybrid nanofibers. The nanocomposite was prepared using colloidal gel composed of zinc nitrate, titanium isopropoxide and polyvinyl acetate. X‐ray diffraction, energy dispersive x‐ray analysis and transmission electron microscopy analysis confirmed the purity and crystalline nature of this material, whereas the diameter of these nanofibres estimated from scanning electron microscope (SEM), field emission SEM and transmission electron microscopy are between 200 and 300 nm. Cell counting with Kit‐8 assay at regular time intervals and phase‐contrast microscopy data revealed that C2C12 cells proliferated well on ZnO/TiO₂ nanofibers between 1 and 10 µg/ml, and cellular attachments are visible by SEM. The nanostructured ZnO/TiO₂ hybrid nanofibers show higher cell adhesion, proliferation and spreading behavior compared with the titanium substrate and control. Our study suggests that ZnO/TiO₂ nanofibers could potentially be used in tissue engineering applications. The scalability, low cost, reproducibility and high‐throughput capability of this technology is potentially beneficial to examine and optimizing a wide array of cell‐nanofiber systems prior to in vivo experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Coaxial Electrospinning Method for the Preparation of TiO2@CdS/PVA Composite Nanofiber Mat and Investigation on its Photodegradation Catalysis

TiO₂/PVA composite nanofiber mat was prepared via an electrospinning technology. SH‐TiO₂‐SiO₂ hybrid particles and PVA solution were injected through a coaxial syringe, yielding a composite nanofiber mat. The as‐prepared SH‐TiO₂‐SiO₂/PVA composite nanofiber mat was immersed in Cd²⁺ cation solution and S^2? anion solution in turn. Thus, yellow TiO₂@CdS/PVA composite nanofiber mats were prepared. By adjusting the number of times a mat was immersed in the Cd²⁺ and S^2? solutions, different amounts of CdS particles attaching to the mats were obtained. Both SH‐TiO₂‐SiO₂/PVA and TiO₂@CdS/PVA composite nanofiber mats were employed to catalyze the photodegradation of a model dye, methylene blue. The photodegradation performance could be greatly enhanced by the introduction of CdS particles anchoring onto TiO₂ particles. The photodegradation efficiency reached 99.2% within 180 min. Also, the nanofiber mat could be recycled and reused at least 10 times. The photodegradation efficiency of TiO₂@CdS/PVA composite nanofiber mats remained 68.8% for 10 cycles.     

CdS‐Encapsulated TiO2 Nanotube Arrays Lidded with ZnO Nanorod Layers and Their Photoelectrocatalytic Applications

A novel TiO₂ nanotube array/CdS nanoparticle/ZnO nanorod (TiO₂ NT/CdS/ZnO NR) photocatalyst was constructed which exhibited a wide‐absorption (200–535 nm) response in the UV/Vis region and was applied for the photoelectrocatalytic (PEC) degradation of dye wastewater. This was achieved by chemically assembling CdS into the TiO₂ NTs and then constructing a ZnO NR layer on the TiO₂ NT/CdS surface. Scanning electron microscopy (SEM) results showed that a new structure had been obtained. The TiO₂ NTs looked like many “empty bottles” and the ZnO NR layer served as a big lid. Meanwhile the CdS NPs were encapsulated between them with good protection. After being sensitized by the CdS NPs, the absorption‐band edge of the obtained photocatalyst was obviously red‐shifted to the visible region, and the band gap was reduced from its original 3.20 eV to 2.32 eV. Photoelectric‐property tests indicated that the TiO₂ NT/CdS/ZnO NR material maintained a very high PEC activity in both the ultraviolet (UV) and the visible region. The maximum photoelectric conversion efficiencies of TiO₂ NT/CdS/ZnO NR were 31.8 and 5.98 % under UV light (365 nm) and visible light (420–800 nm), respectively. In the PEC oxidation, TiO₂ NT/CdS/ZnO NR exhibited a higher removal ability for methyl orange (MO) and a high stability. The kinetic constants were 1.77×10^?4 s^?1 under UV light, which was almost 5.9 and 2.6 times of those on pure TiO₂ NTs and TiO₂ NT/ZnO NR, and 2.5×10^?4 s^?1 under visible light, 2.4 times those on TiO₂ NT/CdS.     

Ammonia Gas Sensor Using Polypyrrole‐Coated TiO2/ZnO Nanofibers

Highly porous polypyrrole (PPy)‐coated TiO₂/ZnO nanofibrous mat has been successfully synthesized. The core TiO₂/ZnO nanofibers have an average diameter of ca. 100 nm and the shell of ultrathin PPy layer has a thickness of ca. 7 nm. The NH₃ gas sensor using the as‐prepared material exhibited a fast response over a wide dynamic range and high sensitivity with a detection limit of 60 ppb (S/N=3). Compared to conventional pristine PPy film, the improved performance in NH₃ detection can be attributed to the free access of NH₃ to PPy and a minimized gas diffusion resistance through the ultrathin PPy layer.     

Fabrication and characterization of electrospun silk fibroin/TiO2 nanofibrous mats for wound dressings

Silk fibroin (SF) nanofibrous mats were fabricated via electrospinning process. These fibers were blended with TiO₂ nanoparticles (TiO₂ NPs). The influence of TiO₂ NPs on the nanofibrous matrices was investigated by scanning electron microscopy (SEM), transmission electron microscopy, energy‐dispersive X‐ray, and thermogravimetric analysis. The SEM images revealed that the average diameter of the SF/TiO₂ fibers was 385 ± 63 nm when the concentration of SF was up to 10% (w/v). Infrared spectra showed that the β‐sheet structure of the silk fibroin increased after acetone treatment. These SF/TiO₂ nanofibrous mats exhibited higher equilibrium water content and water vapor transmission rate than hydrocolloid dressing. The hemocompatibility and cytocompatibility of SF/TiO₂ nanofibrous mats were evaluated by complete blood count, cell attachment, and the spreading of L929 fibroblasts. These SF/TiO₂ nanofibrous mats exhibited antibacterial activity against Escherichia coli under UV irradiation. Thus, these novel nanocomposite mats may be used for biomedical applications such as wound dressing. Copyright © 2011 John Wiley & Sons, Ltd.     

UV-protection and photocatalytic properties of electrospun polyacrylonitrile nanofibrous mats coated with TiO<Subscript>2</Subscript> nanofilm via sol–gel

UV radiation causes serious damage to skin, and a protective system capable of absorbing or reflecting UV radiation is required to protect skin. This paper describes the UV protection and photocatalytic properties of TiO₂ nanofilm coated electrospun polyacrylonitrile (PAN) nanofibrous mats with various nanofiber diameter and area density. The mats were coated by sol–gel process. The results of this research showed that sol–gel is capable of coating porous nanofibrous mats with a weight increase as low as 0.8%. The TiO₂ nanofilm coated on the nanofibrous mats has a considerable effect on its UV protection. The UV protection factor (UPF) of the mats increases with decreasing nanofiber diameter. In fact decreasing the diameter of nanofibers of the TiO₂ nanofilm coated PAN nanofibrous mats increases their photocatalytic activity. Moreover, this research showed that TiO₂ nanofilm produced through sol–gel process on the PAN nanofibers has a crystalline structure. The UPF of the nanofibrous mat coated with a TiO₂ nanofilm via sol–gel process can be classified as excellent.     

Facile Fabrication of Porous ZnS and ZnO Films by Coaxial Electrospinning for Highly Efficient Photodegradation of Organic Dyes

Porous ZnS and ZnO nano‐crystal films were fabricated via a three‐step procedure. First, Zn(CH₃COO)₂/Silk Fibroin nanofiber mats were prepared by coaxial electrospinning. Second, Zn(CH₃COO)₂/Silk Fibroin mats were immersed in NaS solution to react with S²⁻ to obtain ZnS/Silk Fibroin nanofiber mats. Finally, ZnO porous films were prepared by calcination of ZnS/Silk Fibroin composite mat at 600°C in air atmosphere. When ZnS/Silk Fibroin mats were calcinated in nitrogen, ZnS/Carbon composite mats were obtained accordingly. The resulting porous films were fully characterized. The ZnO porous films were the aggregation of ZnO nano‐crystal with hexagonal wurtzite structure. The seize of ZnO was estimated in the range of 10–20 nm. Both of the ZnS and ZnO nano‐crystal films exhibited high photocatalytic activities for the photodegradation of Methylene blue and Rhodamine B. It was also found that ZnO porous films are better than ZnS/Carbon nanofiber mats. In addition, photocatalysis of a real wastewater sample from a printing and dyeing company was conducted. The ZnO porous films exhibited excellent performance to treat the real samples. Moreover, the porous ZnO nano‐crystal photocatalyst could easily be recycled without notable loss of catalysis ability.     

Photodegradation of Rhodamine B on Sulfur Doped ZnO/TiO2 Nanocomposite Photocatalyst under Visible-light Irradiation

Sulfur doped ZnO/TiO₂ nanocomposite photocatalysts were synthesized by a facile sol‐gel method. The structure and properties of catalysts were characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), UV‐vis diffusive reflectance spectroscopy (DRS) and N₂ desorption‐adsorption isotherm. The XRD study showed that TiO₂ was anatase phase and there was no obvious difference in crystal composition of various S‐ZnO/TiO₂. The XPS study showed that the Zn element exists as ZnO and S atoms form SO^2?₄. The prepared samples had mesoporosity revealed by N₂ desorption‐adsorption isotherm result. The degradation of Rhodamine B dye under visible light irradiation was chosen as probe reaction to evaluate the photocatalytic activity of the ZnO/TiO₂ nanocomposite. The commercial TiO₂ photocatalyst (Degussa P25) was taken as standard photocatalyst to contrast the prepared different photocatalyst in current work. The improvement of the photocatalytic activity of S‐ZnO/TiO₂ composite photocatalyst can be attributed to the suitable energetic positions between ZnO and TiO₂, the acidity site caused by sulfur doping and the enlargement of the specific area. S‐3.0ZnO/TiO₂ exhibited the highest photocatalytic activity under visible light irradiation after Zn amount was optimized, which was 2.6 times higher than P25.     

Superior Photostability and Photocatalytic Activity of ZnO Nanoparticles Coated with Ultrathin TiO2 Layers through Atomic‐Layer Deposition

Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO₂ layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO₂ layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO₂ nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO₂ coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO₂ coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO₂, and the photocatalytic activity to that of pure ZnO.     

Synthesis and characterization of conductive polyaniline/TiO2 composite nanofibers

Fibrillar conductive polyaniline/TiO₂ (PANI/TiO₂) nanocomposites with different TiO₂ amount were synthesized with a template-free in situ polymerization method and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and conductivity measurement. The morphology determination shows that the PANI/TiO₂ composite nanofibers are relatively uniform with the diameter and length in the range of 20–40 nm and 390–420 nm respectively. It also shows that the TiO₂ of the composite is rutile crystalline and PANI has some degree of crystallinity. The IR measurement indicates that there is a strong interaction between the PANI and TiO₂ nanoparticles, and it has a beneficial effect on the thermal stability of the composite nanofiber. The conductivity of PANI/TiO₂ composites changes with TiO₂ amount and reaches an optimum value of 2.86 S/cm at 11.1 wt% TiO₂. Translated from Journal of Northwest Normal University (Natural Science), 2006, 42(4): 67–70 (in Chinese)     

Electrochemical deposition of nano-structured ZnO on the nanocrystalline TiO2 film and its characterization

One-dimensional structure of ZnO nanorod arrays on nanocrystalline TiO₂/ITO conductive glass substrates has been fabricated by cathodic reduction electrochemical deposition methods in the three-electrode system, with zinc nitrate aqueous solution as the electrolyte, and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and photoluminescence (PL) spectra. The effects of film substrates, electrolyte concentration, deposition time, and methenamine (HMT) addition on ZnO deposition and its luminescent property were investigated in detail. The results show that, compared with on the ITO glass substrate, ZnO is much easily achieved by electrochemical deposition on the TiO₂ nanoparticle thin films. ZnO is hexagonally structured wurtzite with the c-axis preferred growth, and further forms nanorod arrays vertically on the substrates. It is favorable to the growth of ZnO to extend the deposition time, to increase the electrolyte concentration, and to add a certain amount of HMT in the system, consequently improving the crystallinity and orientation of ZnO arrays. It is demonstrated that the obtained ZnO arrays with high crystallinity and good orientation display strong band-edge UV (375 nm) and weak surface-state-related green (520 nm) emission peaks.     

Improved performance of dye sensitized ZnO nanorod solar cells prepared using TiO2 seed layer

Zinc oxide (ZnO) nanorods of different structures have been grown on indium-doped tin oxide substrates by using TiO₂ as seed layer. The ZnO nanorods have been prepared using TiO₂ seed layers annealed at different temperatures via a simple sol–gel method. The X-ray diffraction result indicates that the prepared samples are of wurtzite structure. Dye sensitized solar cells have been fabricated using the prepared ZnO nanorods. The open circuit voltage, short circuit current density, fill factor, and power conversion efficiency of the ZnO nanorod based dye sensitized solar cells prepared using TiO₂ seed layers annealed at different temperatures have been determined. The improvement in power conversion efficiency may be due to the flower like structured ZnO nanorods with smaller diameter and large specific surface area which paves way for the efficient electron transfer in hybrid solar cells.     

Influence of solvents properties on morphology of electrospun polyurethane nanofiber mats

Segmented polyurethane (SPU) nanofiber mats were prepared by electrospinning technique using the combination of four different solvents viz. tetrahydrofuran, N,N′‐dimethyl formamide, N,N′‐dimethyl acetamide, and dimethyl sulfoxide. Morphology of the electrospun nanofibers was examined by field emission scanning electron microscope. Experimental results revealed that the morphologies of polyurethane nanofiber mats have been changed significantly with the solvent selection for the electrospinning. It was observed that the diameters and morphology of the SPU nanofibers were influenced greatly by the use of combination of solvents. The uniform polyurethane nanofibers without beads or curls could be prepared by electrospinning through the selection of combination of good conductive and good volatile solvent viz. 7.5 wt/v% of SPU in N,N′‐dimethyl formamide/tetrahydrofuran (30 : 70 v/v) solutions at 20 kV applied voltages and volume flow rate of 1 ml/min. On the basis of the results obtained from this investigation, it has been established that solvent selection is one of the driving factors for controlling the morphology of the polyurethane electrospun nanofiber mats. The well‐controlled morphology of electrospun polyurethane nanofiber mats could be useful for many potential industrial applications such as in biomedical, smart textiles, nanofiltration, and sensors. Copyright © 2013 John Wiley & Sons, Ltd.     

ZnO纳米棒阵列在TiO2介孔薄膜上的生长及其表征

通过低温水热法成功地将ZnO纳米棒阵列定向生长在了介孔锐钛矿TiO2纳米晶薄膜上,并主要利用X射线衍射、场发射扫描电子显微镜和光致发光光谱等对其进行了表征。所制备的纳米棒具有六边形的端面,纳米棒的尺寸及端面边长分布范围窄,并且沿c轴方向(002)表现出了明显的择优化生长。此外,相比于玻璃基底或TiO2纳米颗粒薄膜,生长在介孔TiO2薄膜上的ZnO纳米棒阵列表现出了较好的取向生长,表明基底的表面结构和组成对ZnO纳米棒阵列的生长有显著的影响。根据基底有序的多孔结构,讨论了纳米棒阵列可能的生长机理。所得到的ZnO纳米棒阵列在室温下分别表现出了以370 nm为中心的强近紫外光和以530 nm为中心的弱绿光两条荧光谱带。     

Fabrication of Highly Photoluminescent TiO2/PPV Hybrid Nanoparticle‐Polymer Fibers by Electrospinning

In this study, we have synthesized highly photoluminescent TiO₂/poly (phenylene vinylene) (PPV) hybrid nanoparticle‐polymer fibers by electrospinning a PPV precursor added to a TiO₂ sol‐gel solution. The diameters of the hybrid fibers ranged from 100–300 nm and the average size of TiO₂ nanoparticles within the fibers was 10–60 nm. FT‐IR analysis indicated that a new band around 1 632 cm⁻¹ assigned to the Ti O C vibration appeared, which resulted in the stronger luminance of the fluorescence of the TiO₂/PPV hybrid fibers compared to free standing PPV nanofibers.

     

Visible Light Photocatalyst Anatase Phased TiO2 Nanoparticles for Enhanced Antibacterial Performance

This study reports the development of anatase TiO₂ synthesized by facile photon-induced method (PIM) at various reaction times of 6 days, 8 days, 10-day samples. The 10 days TiO₂ sample shows stable anatase phase, whereas 100% rutile phase at the same temperature was observed for standard TiO₂. Mainly, the PIM was used to tuning the properties of visible light absorbance TiO₂ photocatalyst used for improving antibacterial performance. The antibacterial activity of TiO₂ against Staphylococcus aureus and Escherichia coli was determined by the agar disc diffusion method. Anatase TiO₂ nanoparticles demonstrated excellent antibacterial activity against extracellular S. aureus with 80% and E. coli with 82% killing efficacy at concentrations as low as 100 μg/mL, which is 100% faster than the standard and other pure TiO₂ reported earlier. The obtained undoped anatase Titania with enhanced chemical reactivity has great potential for antibacterial properties. Moreover, the smaller crystallite size (25 nm) and narrowing bandgap (2.96 eV) TiO₂ nanoparticles were more effective in killing bacteria compared with standard TiO₂. Therefore, this work indicated that anatase phased TiO₂ under visible light absorbance has good potential with excellent clinical applications.

     

Controllable Fabrication of TiO2 1D‐Nano/Micro Structures: Solid,Hollow, and Tube‐in‐Tube Fibers by Electrospinning and the Photocatalytic Performance

The solid, hollow, and tube‐in‐tube porous nanofiber structures of TiO₂ are synthesized successfully by a simple non‐coaxial electrospinning method without using a complicated coaxial jet head, combined with adjusting the concentration of the TiO₂ precursor and the pinhole diameter of the jet head and by final calcination. The formation mechanisms of different structured TiO₂ fibers are discussed in detail. This method is facile and effective, and easy to scale up. Furthermore, it is a versatile method for constructing tube‐in‐tube fibers of other metal oxides such as ZrO₂, SiO₂, SnO₂, and In₂O₃. The photocatalytic activity of tubular TiO₂ nanofibers for the degradation of 2‐chlorophenol and 2,4‐dichlorophenol under UV or visible‐light irradiation is better than the one of commercial available TiO₂ powder, rutile, and anatase TiO₂ fibers.     

Electrochemical Properties of Fiber‐in‐Tube‐ and Filled‐Structured TiO2 Nanofiber Anode Materials for Lithium‐Ion Batteries

Phase‐pure anatase TiO₂ nanofibers with a fiber‐in‐tube structure were prepared by the electrospinning process. The burning of titanium‐oxide‐carbon composite nanofibers with a filled structure formed as an intermediate product under an oxygen atmosphere produced carbon‐free TiO₂ nanofibers with a fiber‐in‐tube structure. The sizes of the nanofiber core and hollow nanotube were 140 and 500 nm, respectively. The heat treatment of the electrospun nanofibers at 450 and 500 °C under an air atmosphere produced grey and white filled‐structured TiO₂ nanofibers, respectively. The initial discharge capacities of the TiO₂ nanofibers with the fiber‐in‐tube and filled structures and the commercial TiO₂ nanopowders were 231, 134, and 223 mA h g^?1, respectively, and their corresponding charge capacities were 170, 100, and 169 mA h g^?1, respectively. The 1000th discharge capacities of the TiO₂ nanofibers with the fiber‐in‐tube and filled structures and the commercial TiO₂ nanopowders were 177, 64, and 101 mA h g^?1, respectively, and their capacity retentions measured from the second cycle were 89, 82, and 52 %, respectively. The TiO₂ nanofibers with the fiber‐in‐tube structure exhibited low charge transfer resistance and structural stability during cycling and better cycling and rate performances than the TiO₂ nanofibers with filled structures and the commercial TiO₂ nanopowders.     

Synthesis of ZnO and TiO2 nanoparticles

We report on the synthesis of ZnO and TiO₂ nanoparticles by solution-phase methods, with a particular focus on the influence of experimental parameters on the kinetics of nucleation and coarsening. The nucleation rate of ZnO from the reaction between ZnCl₂ and NaOH in ethanol was found to increase with increasing precursor concentration, while the coarsening rate is independent of precursor concentration up to a threshold concentration. The nucleation rate of ZnO from Zn(OOC-CH₃)₂ and NaOH in n-alkanols was found to decrease with decreasing chain length, which is explained by the increase of the dielectric constant of the solvent. Due to the larger solubility of ZnO, nucleation is significantly slower than that observed in the case of TiO₂. TiO₂ nanoparticles coarsen according to the Lifshitz-Slyozov-Wagner model for Ostwald ripening. We also show that using amorphous titania as a base material, pure anatase and brookite nanoparticles can be synthesized.     

Parameters controlling the photocatalytic performance of ZnO/Hombikat TiO2 composites

Commercial TiO₂ (Hombikat, UV-100) was impregnated with different loadings of zinc nitrate solution and subsequently calcined at different temperatures in order to obtain a stable homogeneous solid composite of ZnO/TiO₂. The prepared samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), UV-vis and Raman spectroscopy, inductively coupled plasma mass spectroscopy (ICP), X-ray photoelectron spectroscopy (XPS) as well as N₂ adsorption and desorption measurements. Results show that ZnO was incorporated within the TiO₂ crystals and did not form a separate bulky phase or metallic zinc. Moreover, the calcination temperature dramatically modifies the texture properties of the prepared samples compared with original Hombikat TiO₂. The photocatalytic performance of the prepared samples was evaluated by monitoring the degradation of methyl orange dye under black light illumination. Three main parameters were studied; ZnO loading, surface area and initial pH of the methyl orange solution. The variation in ZnO loading appears to have less influence on the catalytic activity than either the surface area or the pH.