Template‐free synthesis of hierarchical zinc oxide with improved photocatalytic properties

Novel hierarchical nano materials possess tremendous latent force in many applications. In this paper, hierarchical flower‐like, spherical and bowl‐like zinc oxide was successfully synthesized by altering solvent ratio (absolute ethanol and diethylene glycol) via a simple and template‐free solvothermal synthetic route. The solvent ratio also plays a vital role in deciding the structure, crystalline, band gap energy and specific surface area of the as‐synthesized samples. The preparation mechanism of ZnO in mixed alcohols was discussed. The obtained samples were characterized by energy dispersive spectroscopy(EDS), X‐ray diffraction (XRD), field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM), N2 adsorption‐desorption, UV–vis diffuse reflectance spectroscopy (DRS). Photocatalytic activity of the as‐prepared ZnO nanocrystals was evaluated by the degradation of MB under UV irradiation. Among, the most effective photocatalyst was synthesized when the diethylene glycol was 10 ml.     

Optical properties of flower‐like CdS prepared by a hydrothermal method with SDBS as surfactant

In this article, flower‐like CdS structures have been prepared by a hydrothermal method with SDBS as surfactant. The influences of different experimental conditions on the morphologies, UV‐Vis and fluorescence properties of CdS have been investigated. The performances of CdS have been analyzed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet‐visible (UV–Vis) and room‐temperature photoluminescence (PL). The XRD result indicates that the flower‐like CdS structures are of hexagonal phase. The FESEM results indicate that the main role of SDBS is to make the CdS crystals assemble together to form the flower‐like structures. The UV–Vis results show CdS has a strong absorption in the ultraviolet region and visible‐light region. The PL results show CdS has two emission peaks, respectively at 461 nm and 553 nm. The growth mechanism for the formation of flower‐like CdS structures is also described.     

Morphology‐photocatalytic properties‐growth mechanism for ZnO nanostructures via microwave‐assisted hydrothermal synthesis

ZnO nanostructures with various morphologies including rod‐like, sheet‐like, needle‐like and flower‐like structures were successfully synthesized via a fast and facile microwave‐assisted hydrothermal process. Reaction temperature, reaction time and the addition of NaOH were adjusted to obtain ZnO with different morphologies. Scanning electron microscopy(SEM), transmission electron microscope(TEM), X‐ray diffraction (XRD) and ultraviolet spectrophotometer (UV) were used to observe the morphology, crystal structure, ultraviolet absorption and photocatalytic activity of the obtained ZnO. The results indicated that growth rate of ZnO nanostructure along [001] direction was more sensitive to temperature compared with those along [101] and [100] directions. The competition between anionic surfactant and OH⁻ played an important role in the formation of ZnO with various morphologies. Flower‐like ZnO had better ultraviolet absorption property and excellent photocatalytic activity than ZnO in the other morphologies. On the basis of the above results, a possible growth mechanism for the formation of ZnO nanostructures with different morphologies was described.     

The influence of annealing atmosphere on the optical properties of flower‐like ZnO

The influence of annealing atmosphere on the optical properties of flower‐like ZnO is investigated. The flower‐like ZnO is composed of nanosheets. Annealing at 500°C results in the increase of the thickness of nanosheets and the enhancement of UV emission. PL spectra results show that the annealing atmosphere affects the visible emission band, which is sensitive to intrinsic and surface defects in the flower‐like ZnO. The vibrational properties of the flower‐like ZnO annealing in different atmospheres are characterized by Raman spectra. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Controlled synthesis of various morphologies of nanostructured zinc oxide: flower,nanoplate, and urchin

Nanoplates, flower‐like nanostructure of ZnO were successfully synthesized by employing ZnSO₄·7H₂O, NaOH as the starting materials at 120°C under hydrothermal condition. Keeping the same parameters, ZnO urchin shape was obtained by addition of vitamin C at 190°C. Characterizations were carried out by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) at room temperature. Selected area electron diffraction (SAED) pattern confirms that the product is single crystalline nature. The possible formation mechanisms for synthesized ZnO nanosturcture with various morphologies have also been proposed. PL spectrum from the ZnO flower‐like structures reveals weak UV emission and strong green emission. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of radial‐like ZnO structure by hydrothermal method with ZnSO4·7H2O and Zn(CH3COO)2·2H2O as zinc sources

Radial‐like ZnO structures were prepared using zinc sulfate (ZnSO₄·7H₂O) and zinc acetate [Zn(CH₃COO)₂·2H₂O] as zinc sources by a facile template‐free hydrothermal method in this paper. Structural and optical properties of radial‐like ZnO structures are characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), UV‐vis spectrophotometer and photoluminescence measurement (PL). It has been found that the distinct surface morphologies of radial‐like ZnO structures grown by different zinc sources. Slim radial‐like ZnO with a hexagonal wurtzite structure is grown by using ZnSO₄·7H₂O as zinc sources, whereas coarse radial‐like ZnO with zincite structure is achieved by zinc acetate. The UV‐vis absorption spectra of them both display an obvious and significant absorption in the ultraviolet region. The room temperature PL spectra of ZnO structures grown by two different zinc sources possess a common feature that consists of a strong ultraviolet (UV) peak and visible emission band.     

Facile morphology‐controlled hydrothermal synthesis of flower‐like self‐organized ZnO architectures

Flower‐like self‐organized crystalline ZnO architectures were obtained through a facile and controlled hydrothermal process. As‐synthesized products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), electron diffraction and UV‐Vis spectroscopy. XRD and electron diffraction results confirmed the obtained materials are pure wurtzite ZnO. The effects of different ratios of starting materials and solvent on the morphologies of ZnO hydrothermal products were also evaluated by SEM observations. It is suggested that the use of water, rather than ethanol as the solvent, as well as employing a precursor of Zn(Ac)₂ and 2NaOH (v/v) in hydrothermal reactions are responsible for the generation of specific flower‐like self‐assembled ZnO structures. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of highly‐ordered hierarchical ZnO nanostructures and their application in dye‐sensitized solar cells

In order to improve the performance of ZnO‐based solar cells, highly‐ordered hierarchical ZnO nanostructures were design and fabricated. The hierarchical nanostructures were grown on FTO (fluorine doped tin oxide, SnO₂:F) glass substrates via a facile, low‐temperature, and low‐cost chemical route. The morphology and structure of the obtained products has been confirmed by field‐emission scanning electron microscopy and X‐ray diffraction measurements. The performance investigation of the prepared dye‐sensitized solar cells (DSSCs) demonstrates that the hierarchical ZnO nanostructure‐based solar cell shows a higher short‐circuit current density compared with the ZnO nanowire counterpart. The enhanced current density may be due to the fact that the surface area of the hierarchical nanostructures is increased. These results indicate that hierarchical ZnO nanostructures are more suitable for the application as photoelectrode of DSSCs. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

PbS crystals with clover‐like structure: Preparation,characterization, optical properties and influencing factors

A new and simple route to synthesize Lead sulfide (PbS) crystals with the clover‐like structure was described in the current paper. PbS was prepared in a simple aqueous solution employing (CH₃COO)₂Pb and thiourea as the initial materials under 130 W microwave irradiation. No any surfactant or template including organic polyamines with N‐chelation property was needed. The phase and composition of the product were identified by X‐ray powder diffraction (XRD) and X‐ray photoelectron spectra (XPS). TEM observation showed that the product with the six‐petal flower‐shaped structures was obtained, but SEM observation confirmed the clover‐like structure of the product; and the six‐petal flowers were formed via the overlap of two clovers revolved 60° around the center of the flower. Some factors affected the shape of the final product were studied and the optical properties of PbS crystals with the clover‐like structure were measured. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydrothermal synthesis of anatase flower‐like nanostructures for photocatalytic degradation of dye

Flower‐like hierarchical nanostructures of titanium dioxide (TiO₂) have been synthesized in large scale by a facile and controlled hydrothermal and after annealing process. The morphologies of flower‐like hierarchical nanostructures are formed by self‐organization of several tens of radially distributed thin flakes with a thickness of several nanometers holding a larger surface area. The materials are characterized by Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The ultraviolet photocatalytic degradation of R6G dyes has been studied over this flower‐like hierarchical nanostructures and the activity is compared with that of commercial P25 TiO₂ under same conditions. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydrothermal conversion of ZnO2 to ZnO flowers: A mechanistic investigation and characterization

In this article, we report a novel but simple method for the phase transformation of ZnO₂ to flower‐like ZnO microstructures hydrothermally at 90 °C with and without the assistance of hexadecylamine as surfactant. The generation of zincate ion ZnO$^{2-}_{2}$ as a growth unit from the reaction between ZnO₂ and peroxide ion O$^{2-}_{2}$ in situ plays a key role in the phase transformation of ZnO₂ to ZnO. The morphology, structure, and composition of the products have been investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Powder X‐ray diffraction (PXRD) and energy dispersive X‐ray analysis (EDX). It has been demonstrated that the as‐fabricated ZnO flowers are composed of self‐assembled brooms and rods in the presence and absence of hexadecylamine respectively. On the basis of experimental results, a possible reaction mechanism and the growth processes involved in the formation of flower‐like ZnO microstructures are discussed.     

Low temperature synthesis of spindle‐like ZnO nanostructures under microwave irradiation

A simple and general microwave route is developed to synthesize nanostructured ZnO using Zn(acac)₂·H₂O (acac = acetylacetonate) as a single source precursor. The reaction time has a great influence on the morphology of the ZnO nanostructures and an interesting spindle‐like nanostructure is obtained. The microstructure and morphology of the synthesized materials are investigated by X‐ray diffraction (XRD), scanning electron microscopy (SEM), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). It is found that all of them with hexagonal wurtzite phase are of single crystalline structure in nature. Ultraviolet–visible (UV‐vis) absorption spectra of these ZnO nanostructures are investigated and a possible formation mechanism for the spindle‐like ZnO nanostructures is also proposed.     

Synthesis from zinc oxalate,growth mechanism and optical properties of ZnO nano/micro structures

We report the synthesis of various morphological micro to nano structured zinc oxide crystals via simple precipitation technique. The growth mechanisms of the zinc oxide nanostructures such as snowflake, rose, platelets, porous pyramid and rectangular shapes were studied in detail under various growth conditions. The precursor powders were prepared using several zinc counter ions such as chloride, nitrate and sulphate along with oxalic acid as a precipitating agent. The precursors were decomposed by heating in air resulting in the formation of different shapes of zinc oxide crystals. Variations in ZnO nanostructural shapes were possibly due to the counter ion effect. Sulphate counter ion led to unusual rose‐shape morphology. Strong ultrasonic treatment on ZnO rose shows that it was formed by irregular arrangement of micro to nano size hexagonal zinc oxide platelets. The X‐ray diffraction studies confirmed the wurzite structure of all zinc oxide samples synthesized using different zinc counter ions. Functional groups of the zinc oxalate precursor and zinc oxide were identified using micro Raman studies. The blue light emission spectra of the various morphologies were recorded using luminescence spectrometer. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Facile fabrication of porous ZnO by a template free method

In this paper, a template free method has been employed to fabricate porous ZnO. Brick shaped precursor was first synthesized by a mild hydrothermal process. Accompanied with the decomposition of the precursor during the subsequent annealing treatment, porous ZnO with the inherited morphology of the precursor was obtained. The as‐prepared products were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). It exhibited that the porous hierarchical frame consists of nano‐sheets with wurtzite‐type. The size of the pores as well as the size of the particles varied with the annealing temperature. Mechanism speculation showed that the crystal‐aggregation in the growth process of the precursor is the key to the establishment of pore structure. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Graphene oxide used as a surfactant to induce the flower‐like ZnO microstructures: growth mechanism and enhanced photocatalytic properties

In this paper, graphene oxide (GO) was used as a temple to induce the formation of flower‐like ZnO microparticals compared with surfactants, such as cetyltrimethylammonium bromide (CTAB) and dodecyl dimethyl betaine (BS‐12). The zinc hydroxide carbonate ((Zn₄(CO₃)(OH)₆,ZHC)) was produced by a hydrothermal reaction. The flower‐like ZnO microparticals were gained by calcining ZHC. In the GO medium, the microparticals were assembled by numerous porous nanosheets from one point (initial nucleus) to flower‐like microparticals finally. The nanosheets of graphene oxide and functional groups were likely to contribute to the formation of the precursor, and some nanosheets were retained in the complex. The growth mechanism of ZHC was also proposed in this paper. The photocatalytic activity of the flower‐like ZnO microparticals was evaluated by photo degradation reaction of rhodamine B (RhB). The peony‐like porous ZnO/rGO compounds showed high photocatalytic activity and better than ZnO microparticals formed in the CTAB and BS‐12. These results indicated that GO could be widely used as a surfactant to induce composite materials with special morphology and photoelectric properties, etc.     

Facile synthesis of pencil‐like ZnO nanostructures at low temperature

Pencil‐like ZnO nanostructure was synthesized by directly oxidizing granular Zn films, which was thermal deposited in a nitrogen atmosphere from Zn powder in a horizontal tube furnace. The formation of the pencil‐like structure, including a hexagonal rod and a sharp tip with diameter about 60 nm, highly depend on the thickness of the initial zinc film and the temperature of the oxidizing process. ZnO nanorods were formed in a relatively low temperature, while thicker zinc film was apt to form a dense ZnO film with tubular structures. The different structured ZnO materials showed distinguishing optical properties which indicate the intrinsic defects forming in the different growth conditions. The pencil‐like ZnO structures exhibit a relatively strong green emission attributed to the high concentrations of oxygen vacancies and its taper tip has great prospects in field‐emission devices.     

Facile solvothermal synthesis,growth mechanism and thermoelectric property of flower‐like Bi2Te3

Hierarchical flower‐like Bi₂Te₃ was synthesized through a facile solvothermal method. The crystal structure and morphology of the as‐prepared samples were characterized by X‐ray diffraction (XRD), filed emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and high resolution TEM. The reaction parameters such as reaction time, the amount of glucose, concentration of NaOH and the reaction temperature were systematically investigated. Based on the FESEM observations, a possible mechanism defined as a self‐assembly process accompanied by anisotropic growth mechanism was proposed. Moreover, the thermoelectric properties were measured at the temperature range of 300–600 K. The hierarchical flower‐like Bi₂Te₃ presented good thermoelectrical properties. The maximum ZT value reached up to 0.6 at 600 K, which was higher than that of Bi₂Te₃ nanoparticles.     

A direct suppression of green band emission of ZnO particles by adjusting the volume fraction of ethanol in reaction solutions

ZnO particles were successfully prepared by one step CTAB‐assisted hydrothermal method with different volume fraction of ethanol‐water mixture solution. The formed thorn‐ball like ZnO particles have an average size of 1 ∼ 2 μm in diameter. XRD result shows a hexagonal wurtzite structure and higher crystallinity. Room‐temperature photoluminescence shows a strong and dominated peak at ∼383 nm with a green emission at ∼510 nm. The intensity ratio between the UV and green emission increased from 1.31 to 7.53 when the volume fraction of ethanol was changed from 0% to 50%, which shows a direct suppression of structural defects just by adjusting the ethanol fraction in reaction solutions. The possible growth and luminescence mechanisms for thorn‐ball like ZnO particles are discussed.     

Morphology‐controllable synthesis of ZnO nano‐/micro‐ structures by a solvothermal process in ethanol solution

Flower‐like ZnO nanostructures assembled by nanorods with bimodal size distribution have been synthesized by a solvothermal process in NaOH‐Et system. Various effects of the solvothermal parameters and assistant additives on the morphologies of ZnO nanostructures have been investigated. The directing effect of chloride ions have been observed in the formation of highly symmetrical 3D ZnO nanostructures. A possible mechanism has been proposed to explain the formation of ZnO nanoflowers in NaOH‐Et system. A strong near‐UV emission band centered at around 396 nm is observed in the photoluminescence spectrum of flower‐like ZnO nanostructures, indicating of their high crystal quality.     

Synthesis,transformation to octahedron‐like crystals,and gas‐sensing property of six‐horned nanospheres of Cu2O

Single‐crystal six‐horned nanospheres of Cu₂O with a diameter of 760 nm in average were prepared in aqueous solution of CuCl₂and NaOH by using ascorbic acid as the reductant in the presence of sodium dodecyl benzenesulfonate (SDBS) at room temperature. The horn grows along the <100> direction, which is consistent with the protuberant direction of an apex of octahedron. The formation process of six‐horned nanospheres included two steps: the formation of Cu₂O nanospheres via Ostwald ripening process, and the appearance of horns on the surface of nanospheres under low concentration of SDBS. As increasing the concentration of SDBS, the six‐horned nanospheres could be transformed into octahedron‐like Cu₂O. And at the same concentration of SDBS, keeping the volume ratio of water and ethanol in mixed solutions as 1:1, Cu₂O octahedra were obtained. Moreover, gas‐sensing property showed that six‐horned nanospheres of Cu₂O had higher sensitivity compared with Cu₂O nanospheres and Cu₂O octahedra to ethanol gas (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)