A CTAB-assisted hydrothermal and solvothermal synthesis of ZnO nanopowders

ZnO nanopowders were synthesized by hydrothermal and solvothermal method by using CTAB as surfactant, and the effects of CTAB on the morphologies of ZnO nanopowders were investigated. The results showed that the presence of CTAB could greatly vary the shape of the ZnO crystals. ZnO nanorods were prepared from the hydrothermal system without CTAB and flowers-like ZnO nanostructures were produced from hydrothermal system with 0.4 M and 0.5 M CTAB. Low concentration of CTAB in ethanol was conducive to the formation of ZnO nanorods, but the concentration continued to increase, the morphology of sample transformed into hexagonal bipyramid, and then transformed into spherical. The synthesis mechanism of ZnO powders with different morphologies has been presented.     

Continuous synthesis of surface-modified zinc oxide nanoparticles in supercritical methanol

Continuous synthesis of surface-modified zinc oxide (ZnO) nanoparticles was examined using surface modifiers (oleic acid and decanoic acid) in supercritical methanol at 400 °C, 30 MPa and a residence time of ∼40 s. Wide angle X-ray diffraction (WAXD) analysis revealed that the surface-modified nanoparticles retained ZnO crystalline structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the surface modifiers changed drastically the size and morphology of the ZnO nanoparticles. When the molar ratio of oleic acid to Zn precursor ratio was 30, 10 nm size particles with low degree of aggregation were produced. The surface-modified ZnO nanoparticles had higher BET surface areas (29-36 m²/g) compared to unmodified ZnO particles synthesized in supercritical water (0.7 m²/g). Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA) indicated that aliphatic, carboxylate and hydroxyl groups were chemically attached on the surface of ZnO nanoparticles. Long-term (80 days) dispersion test using ultraviolet transmittance showed that the surface-modified ZnO particles had enhanced dispersion stability in ethylene glycol.     

Preparation of uniform 2D ZnO nanostructures by the ionic liquid-assisted sonochemical method and their optical properties

Uniform 2D ZnO nanostructures were successfully synthesized by a sonochemical method, using 1,4-diazabicyclo[2.2.2]octane (DABCO) and imidazolium-based ionic liquids in water as the solvent after 30 min. The effects of ionic liquids as template on the morphology and size of nanostructures were investigated. The structural and optical properties of ZnO nanostructures were studied by using XRD, SEM and UV–visible. The characteristic results revealed that using ionic liquids in water not only prevents a drastic increase in the crystallite size of the zinc oxide species but also provides suitable conditions for the oriented growth of primary nanoparticles with nanosheet morphology. SEM revealed that using the longer alkyl chain at position-1 of DABCO or dicationic ionic liquids causes a uniform nanosheet and nanoleaf. A possible mechanism was proposed to explain the formation of ZnO nanostructures with nanosheet morphology. Also band gap variation with particle size was investigated.     

Synthesis of ZnO nanoparticles by an aerosol process

Spherical nano-sized zinc oxide (ZnO) particles were produced by a spray pyrolysis method using the aerosol technique described in this study. The effects of reaction temperatures of 600, 800 and 1000 °C and collection locations of the particles, such as the flask collector and the tube exit, on the morphology and crystal structure of the ZnO particles were investigated. X-ray diffraction (XRD) studies showed that the crystallinity of the particles was increased by increasing the reaction temperature from 600 °C to 1000 °C. Fourier transform infrared spectroscopy (FTIR) measurements revealed that the particles were pure and similar to each other. Scanning electron microscopy (SEM) revealed that the synthesized nanoparticles had sizes between 200 nm and 400 nm, with uniform morphologies. A computational fluid dynamics (CFD) model of the horizontally positioned tube reactor was developed. Simulation results provided information about the residence time and the temperature distribution along the tube, which were found to be correlated to the particle morphology.     

Detection of trivalent-iron based on low-dimensional semiconductor metal oxide nanostructures for environmental remediation by ICP-OES technique

A large-scale synthesis of undoped low-dimensional semiconductor metal oxide nanostructures (ZnO nanoparticles, NPs) by simple wet-chemical method was performed using reducing agents at low temperature. The NPs were characterized in terms of their morphological, structural, and optical properties, and efficiently applied for the metal ions uptake. The detailed structural, compositional, and optical characterizations of the NPs were evaluated by powder X-ray diffraction pattern (XRD), Fourier-transform infra-red spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Electron dispersion spectroscopy (EDS), and UV–vis. spectroscopy, respectively which confirmed that the obtained NPs are well-crystalline undoped ZnO and possessed good optical properties. The ZnO NSs morphology was investigated by FESEM, which confirmed that the calcined materials were spherical shape in nano-level and growth in huge-quantity. The analytical efficiency of newly synthesized ZnO NPs was also investigated for a selective separation of trivalent iron [Fe(III)] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of ZnO NPs towards different metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II), Zn(II), and Zr(IV), was studied. Data obtained from the selectivity study suggested that that ZnO NPs phase was the most selective towards Fe(III). The static uptake capacity of Fe(III) was found to be ~79.80 mg g⁻¹. Moreover, adsorption isotherm data also provided that the adsorption process was mainly monolayer on a homogeneous adsorbent surface.     

Preparation and characterizations of highly transparent UV-curable ZnO-acrylic nanocomposites

A sol–gel chemical route was adopted to prepare the zinc oxide (ZnO) nanoparticles as small as 4 nm. UV-curable ZnO-acrylic nanocomposites were then prepared by employing 3-(trimethoxysilyl)propyl methacrylate (TPMA) as the surface modification agent of ZnO particles. UV–vis analysis revealed a high optical transparency (>95%) in visible light region for nanocomposite thin films with ZnO contents up to 20 wt.%. The addition of ZnO nanoparticles also enhanced the dielectric constants of nanocomposites and the dielectric constants greater than 4 in frequencies ranging from 1 to 600 MHz was obtained in the samples containing 10 wt.% of ZnO nanoparticles. A comparison of experimental results and theoretical calculation indicated that the interfacial polarizations in between ZnO nanoparticles and polymer matrix may play an important role in the enhancement of dielectric properties of nanocomposites.     

Preparation and characterization of UV-cured polyurethane acrylate/ZnO nanocomposite films based on surface modified ZnO

A series of polyurethane acrylate (PUA)/ZnO nanocomposite films with different ZnO contents were prepared via a UV-curing system. To ensure good dispersion in the PUA matrix, ZnO nanoparticles were modified with a silane coupling agent and confirmed by FT-IR analysis. The morphological structures, thermal properties, mechanical properties and water transfer properties of the prepared films were investigated as a function of their ZnO concentration. WAXD and SEM analyses showed that the surface-modified ZnO nanoparticles were homogeneously dispersed in the PUA matrix and the molecular ordering increased with increasing ZnO content. Compared with neat PUA, the hardness and elastic modulus in films increased from 0.03 to 0.056 GPa and from 2.75 to 3.55 GPa, respectively. Additionally, the water uptake and WVTR in the PUA/ZnO nanocomposite films decreased as the ZnO content nanoparticles increased, which may come from enhanced molecular ordering and hydrophobicity in films. UV light below approximately 450 nm can be efficiently absorbed by incorporating ZnO nanoparticles into a PUA matrix, indicating that these composite films exhibit good weather ability and UV-shielding effects. The enhanced physical properties achieved by incorporating modified ZnO nanoparticles can be advantageous in various applications, whereas the thermal stability of the composite films should be increased.     

Effects of ZnO nanoparticles on the mechanical and antibacterial properties of polyurethane coatings

Polyurethane-based coatings reinforced by ZnO nanoparticles (about 27 nm) were prepared via solution blending. The ZnO/PU films and coats were fabricated by a simple method of solution casting and evaporation. The mechanical properties of the films were investigated by a universal material test, and the abrasion resistance of the prepared coats was evaluated by a pencil-abrasion-resistance tester. It was found that significant improvement of the PU films in Young’s modulus and tensile strength was achieved by incorporating ZnO nanoparticles up to 2.0 wt%, and that the abrasion resistance of the PU coats was greatly enhanced due to the addition of ZnO nanoparticles. Moreover, the antibacterial property test was carried out via the agar dilution method and the result indicated that PU films doped with ZnO nanoparticles showed excellent antibacterial activity, especially for Escherichia coli.     

A simple electrochemical deposition route for the controllable growth of Ce-doped ZnO nanorods

Here we report that the various Ce⁴⁺-doped ZnO nanorods can be successfully synthesized by electrochemical deposition route, which represents a simple, quick and economical method for the controllable growth of Ce⁴⁺-doped ZnO nanorods. The high-resolution transmission electron microscopy (HRTEM) and the selected area electron diffraction (SAED) both proved that the prepared Ce⁴⁺-doped ZnO nanorods consisted of single crystal with preferential growth in the [0 0 0 1] direction. The morphology and size of the nanorods can be tailored by optimizing the synthetic parameters. Furthermore, the flowerlike Ce⁴⁺-doped ZnO nanorod clusters can also be successfully prepared. An obvious blue-shifted absorption peak of Ce⁴⁺-doped ZnO nanorod compared with that of the bulk ZnO phase was observed.     

ZnO nanosphere fabrication using the functionalized polystyrene nanoparticles for dye-sensitized solar cells

The nano-hollow spherical ZnO (NHS ZnO) photoelectrodes were prepared using functionalized polystyrene nanoparticles with flexible dimensional control of the particle diameter for dye-sensitized solar cells applications. NHS ZnO was formed by ZnO nanoparticles that accumulated on the surface of functionalized polystyrene with a high ionic strength. This method represents a one-step preparation method for an inorganic shell via polymerization between ZnO complexes. Even though NHS ZnO has a submicron size, it composed of nanoparticles that connect with each other, thereby implying good electron transfer properties, and has a high surface area. The submicron-sized diameter NHS ZnO has an enhanced light scattering capacity, which promotes the photons with more opportunities to be absorbed by the N719 dye molecules. Therefore, the ZnO films prepared from 600 nm to 1000 nm NHS ZnO possessed higher IPCE values over a wide range (from 400 nm to 750 nm) compared to films of the 300 nm ZnO due to the enhanced light scattering capacities of the film. In photocurrent-voltage measurements, the short-circuit current density of 300 nm and 600 nm NHS ZnO increases from 3.33 mA/cm² to 6.53 mA/cm² while the cell efficiency increases from 1.04% to 3.02% due to the light scattering efficiency. Electrochemical impedance spectroscopy showed that electrons in NHS ZnO with a larger particle size have a longer electron lifetime than NHS ZnO with a smaller particle size, as the latter hinders the electron transport in the NHS ZnO nanostructured films.     

Growth temperature dependent properties of ZnO nanorod arrays on glass substrate prepared by wet chemical method

In this work, ZnO nanorod arrays were grown on glass substrate by the wet chemical method, and the effect of synthesis temperature on the properties was investigated. The grown nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman and Photoluminescence (PL) measurements. XRD pattern showed that nanorod prepared at 80 °C and 90 °C has high crystallinity with wurtzite structure and orientated along the c-axis. However, nanorods were not formed at 60 °C and 70 °C due to less energy supply for the growth of the ZnO. FE-SEM results showed that the morphology and the size of ZnO can be effectively controlled. In particular, as the temperature increased, diameter of the nanorod was increased while length decreased. Raman scattering spectra of ZnO nanorod arrays revealed the characteristic E₂^high mode that is related to the vibration of oxygen atoms in the wurtzite ZnO. Room-temperature PL spectra of the ZnO nanorods revealed a near-band-edge (NBE) emission peak. The NBE (UV light emission) band at ~383 nm might be attributed to the recombination of free exciton. The narrow full-width at half-maximum (FWHM) of the UV emission indicated that ZnO nanorods had high crystallinity.     

Electrochemical performance and morphology evolution of nanosized ZnO as anode material of Ni-Zn batteries

Nanosized ZnO with prismatic form was prepared using homogeneous precipitation process and its electrochemical performance was investigated by the measurements of electrochemical cycle behaviors and passivation polarization curves. The discharge capacity delivered by nanosized ZnO still achieved about 600 mAh/g until the 250th cycle. Nanosized ZnO exhibited higher midpoint discharge voltage, better cycle stability and passivation toleration than commercial ZnO. Furthermore, nanosized ZnO showed the morphology evolution process differed slightly from that of the commercial ZnO, including morphology maintenance, orientation growth and the formation of Zn dendrites. The epitaxial growth, texture growth and crystal growth habit were put forward to illuminate the morphology evolution process.     

A novel mercury-media route to synthesize ZnO hollow microspheres

Zinc oxide (ZnO) hollow microspheres were prepared by templates of surfactant spheres in mercury-media for the first time. Field emission scan electron microscope (FESEM), X-ray diffraction (XRD), infrared spectra (IR) and N₂ adsorption–desorption analysis were used to characterize morphologies and structure features of the products. The obtained ZnO hollow microspheres are amorphous, 1–3 μm in diameter and 70–140 nm in wall thickness. After heat treatment at 500 °C for 2 h, the amorphous ZnO hollow spheres transform to hexagonal wurtzite structure ZnO, and retain hollow sphere morphologies. During the growth of ZnO hollow microspheres, Zn is oxidized at mercury/air interface and the formed ZnO nanoparticles are assembled on the surface of surfactant spheres. PEG plays an important role for the synthesis of ZnO hollow microspheres.     

Growth mechanism and pH-regulation characteristics of composite latex particles prepared from Pickering emulsion polymerization of aniline/ZnO using different hydrophilicities of oil phases

A Pickering emulsion polymerization of aniline, using different hydrophilicities of oil phases, was stabilized by ZnO nanoparticles and performed to synthesize composite latex particles of polyaniline/ZnO. Ammonium peroxydisulfate (APS) was used as an oxidizing agent. The morphologies and growth mechanisms of the resulted composite latex particles were studied. The pH-regulation capacity of the composite latex particles was discussed. When toluene was used as the oil phase, the composite latex particles showed hollow structure, irregular morphology, and hundreds of nanometer in size. It was ascribed to the polymerization of aniline on the interfaces of droplets/water. ZnO nanoparticles, with 50-100 nm in size, acted as surfactants to stabilize the emulsion. When THF was used as an oil phase, the composite latex particles showed spherical morphology and enwrapping ZnO nanoparticles. It was attributed to the homogeneous nucleation of polyaniline in the aqueous phase. ZnO nanoparticles acted as templates for the polyaniline particles. The stability of the Pickering emulsion polymerization was affected by the volume ratio of the oil phase to water. The aqueous solution with pH 3-9 could simply be regulated to about pH 7 by the composite latex particles. It was contributed by the dissolution of ZnO nanoparticles and doping-dedoping of polyaniline in the acidic and alkaline aqueous solutions.     

Filling behavior of ZnO nanoparticles into opal template via electrophoretic deposition and the fabrication of inverse opal

Combining colloidal crystal template (artificial opal) and electrophoretic deposition (EPD) process, well-ordered ZnO inverse opal can be formed by finding the optimum driving potential of EPD. Through providing the various driving potentials from −25 V, −10 V, −5 V to −2.5 V, the different mechanism of electrophoretically depositing ZnO nanoparticles into the colloidal crystal template was determined by the SEM observation of the filled templates. Because the nano-channels of colloidal crystal template are the network type, the results of surface jam, incomplete filling and perfect filling are found under specific applied voltages. The high-quality ZnO inverse opal can be only fabricated under the perfect nano-channel-filling condition. The filling behavior can be monitored dynamically by tracing the current transients, and the optimum conditions for filling the interstitial spaces of templates constructed from colloidal particles with 180 nm and 300 nm diameter can be obtained by applying a voltage of −5 V and −15 V, respectively. After the complete filling of ZnO nanoparticles into the colloidal crystal template consisting of 300 nm colloids, high-quality ZnO photonic crystal possessing an absorptive peak at the wavelength of 560 nm can be fabricated by removing the template. It is expected that the EPD can find extensive applications for preparing photonic crystals of various oxides only if their nanoparticles are available.     

Preparation and characterization of transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency

Transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency were reported in this paper. First, zinc oxide (ZnO) precursor was synthesized via the homogeneous precipitation method and ZnO nanoparticles were then made by calcination of the precursor at different temperature. The structural properties of the as-prepared ZnO nanoparticles were studied in detail using thermogravimetry (TGA), differential thermal analysis (DTA), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR) and transmission electron microscopy (TEM), respectively. Transparent ZnO/epoxy nanocomposites were subsequently prepared from transparent epoxy (EP-400) and as-prepared ZnO nanoparticles via in situ polymerization. Optical properties of ZnO/epoxy nanocomposites, namely visible light transparency and UV light shielding efficiency, were studied using an ultraviolet-visible (UV-vis) spectrophotometer. The optical properties of the as-obtained nanocomposites were shown to depend on ZnO particle size and content. The nanocomposite containing a very low content (0.07% in weight) of ZnO nanoparticles with an average particle size of 26.7 nm after calcination at 350 °C possessed the most optimal optical properties, namely high-visible light transparency and high-UV light shielding efficiency, that are desirable for many important applications.     

Growth and structural characteristics of perovskite-wurtzite oxide ceramics thin films

Wurtzite ZnO thin films were grown on single-crystal perovskite SrTiO₃(STO) (1 0 0) substrates at various temperatures. The ZnO/STO thin films thus formed exhibit a preferred (1 1 0)-orientation at a growth temperature of 600-700 °C. A high growth temperature enhances not only the (1 1 0)-texture of ZnO/STO thin films but also the crystalline quality of the film. (La_0.7Sr_0.3)MnO₃ (LSMO) thin films were subsequently grown on ZnO(1 1 0)/STO(1 0 0) substrates with various thicknesses, and were polycrystalline. A thicker LSMO film has a stronger (0 0 l)-preferred orientation than the thinner one. The lattice distortion of LSMO decreases as the LSMO thickness increases. Magnetization vs. temperature curves show that both crystalline quality and lattice distortion influence the magnetic properties of LSMO thin films. The physical properties of the manganite oxide can be modulated by forming a heterostructure with wurtzite ZnO.     

DC-field-induced synthesis of ZnO nanowhiskers in water-in-oil microemulsions

ZnO nanowhiskers were successfully fabricated using DC-field induced water-in-oil microemulsions method. Phase structure, morphology and microstructure of the product were investigated by X-ray diffraction and transmission electron microscopy. Parameters in preparation process such as electric field intensity and surfactant were discussed and the product formation mechanism was studied. XRD and TEM results showed that the obtained ZnO particle was hexagonal wurtzite-type with 1-3 nm in diameter and 20-70 nm in length, and morphology of the particles was shown to be correlated not only with the electric field intensity but also with the surfactant. There was a threshold when the electric field intensity was 80 V/mm. The morphology of the particles was basically spherical before the threshold, while L/D increased with the raise of electric field intensity. ZnO nanowhiskers were obtained under mixed surfactants but spherical particles were got with a single surfactant.     

Low-temperature solution synthesis of carbon nanoparticles, onions and nanoropes by the assembly of aromatic molecules

Graphitic carbon nanostructures were prepared in solution by two methods: solvothermal synthesis and hot injection. Small carbon nanoparticles with uniform diameters of 3-6 nm, carbon onion particles with larger diameters of 30-80 nm, and carbon nanoropes with a length of hundreds of nm and a width of 3-20 nm, were formed using commercial mesophase pitches as a carbon precursor through solution-phase synthesis below 200 °C. In the solvothermal synthesis, organic-organic assemblies of aromatic molecules from the pitches could be constrained into different stacking arrangements directed by varying the concentration of the block copolymer P123 template in toluene solution at 200 °C. In the hot injection method, when oleic acid was used as a solvent at 180 °C, the assemblies of the aromatic building blocks were controlled by varying the reaction time (5-30 min) or the concentration of H₂SO₄ catalyst (0.015-0.061 mol L⁻¹) in the nucleation and growth process.     

Electroless deposition of transparent conducting and 〈0 0 0 1〉-oriented ZnO films from aqueous solutions

Electroless ZnO deposition on a glass substrate from dissolved oxygen-free aqueous solutions containing Zn(NO₃)₂ and dimethylamineborane (DMAB) was examined to yield ZnO films applicable to a transparent conducting oxide (TCO). Concentration of Zn(NO₃)₂ was optimized in terms of crystal growth orientation and surface morphology using XRD and AFM, and that ranging from 0.065 to 0.075 M was found to provide well 〈0 0 0 1〉-oriented dense ZnO films. The polycrystalline ZnO films deposited with Zn(NO₃)₂ concentration of 0.07 M had a preferred 〈0 0 0 1〉 growth orientation and exhibited high visible transparency. Top-view and cross-sectional FE-SEM images revealed that hexagonal columnar ZnO grains with 200 nm in diameter and 290 nm in length grew almost vertically from a glass substrate. Heat treatment at 723 K under a reductive atmosphere was performed to increase the intrinsic carrier concentration in the ZnO film, and Hall effect measurements revealed low electrical resistivity of 4.7 × 10⁻³ Ω cm.