Synthesis and growth mechanism of ZnO rod‐like nanostructures by a microwave‐assisted low‐temperature aqueous solution route

A zinc oxide (ZnO) nanoarray (rod‐like nanostructure) was successfully synthesized through a low‐temperature aqueous solution and microwave‐assisted synthesis using zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and hexamethylenetetramine (HMTA) as raw materials, and using FTO glass as substrate. The effects of parameters in the preparation process, such as solution concentration, reaction temperature and microwave power, on the morphology and microstructure of ZnO nanoarray were studied. Phase structure and morphology of the products were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The results indicated that hexagonal wurtzite structure ZnO nanoarray with good crystallization could be prepared through a low‐temperature solution method. When the concentration of the mixed solution was 0.05 M, the reaction temperature was 95 °C, and the reaction time was 4 h, high‐density ZnO regular nanorods of 200 nm diameter were obtained. A possible mechanism with different synthesis methods and the influence of microwave processing are also proposed in this paper.     

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.     

Multi‐factors on photocatalytic properties of Y‐doped Bi2WO6 crystallites prepared by microwave‐hydrothermal method

Different contents of Y‐doped Bi₂WO₆ crystallites were synthesized by a microwave‐hydrothermal method. The photocatalytic properties with different contents of Y‐doped Bi₂WO₆ crystallites were studied. The Y‐doped Bi₂WO₆ crystallites were also characterized by XRD, EDX, SEM and UV‐vis DRS and the multi‐factors on photocatalytic properties of Y‐Doped Bi₂WO₆ crystallites were discussed. The results indicate that Y³⁺ replacing Bi³⁺ enters into the Bi₂WO₆ lattice, producing a degree of Bi₂WO₆ lattice distortion. It also has an impact on the crystallinity of Bi₂WO₆ and the band gap is from 2.49 eV to 2.71 eV. The photocatalytic results show that when the content of Y doping becomes 10%, the degradation rate of rhodamine B is above 90% after 40 min irradiation, which shows that doping the proper rare earth ions is conducive to the photocatalytic properties of Bi₂WO₆ crystallites.     

Relationship between morphology and structure of shape‐controlled CeO2 nanocrystals synthesized by microwave‐assisted hydrothermal method

The influence of synthesis conditions on morphology and structure of CeO₂ nanocrystals prepared by microwave‐assisted hydrothermal method were studied by XRD, TEM, Raman spectroscopy and photoluminescence measurements. Decisive effect of the OH^‐/Ce³⁺ molar ratio in the reaction mixture on the size and shape of CeO₂ nanocrystals was established and explained. Rise of the concentration of OH^‐ groups at the surface of growing CeO₂ nanocrystals promotes shape transformation from irregular (spheroidal) to cube and enables oriented attachment mode of particle growth. I was found that the unit cell parameter and intensity of Ce³⁺ defect related band in the luminescence and Raman spectra in ceria nanoparticles increase as follows: irregular shape nanocrystals < large cube < small primary cube shape particles. The reason is growing contribution of total subsurface volume under {100} faces, exposed by ceria nanocubes, where enhanced concentration of Ce³⁺ and oxygen vacancies occur.     

Shape‐controlled synthesis of ZnO architectures

Several ZnO nanoarchitectures have been selectively prepared through hydrothermal method including urchin‐shaped, flower‐shaped, butterfly‐shaped, and cacti‐shaped microstructures. The influence of reaction temperature and the concentration of amphiphilic copolymer on the morphologies and shapes of ZnO samples have been studied. The samples were characterized using XRD, TEM, and SEM. It was found that ZnO nanorods or their assemblies were fabricated at higher temperature, whereas ZnO nanosheet architectures were produced at lower temperature. These flower‐shaped architectures possess high BET surface area of 27.43 m²/g. Room temperature UV‐VIS and PL spectra of the as‐obtained ZnO nanoarchitectures have been examined. (© 2007 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)     

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)     

Surface‐morphology evolution of ZnO nanostructures grown by hydrothermal method

Surface‐morphology evolution of ZnO nanocrystals has been observed by the hydrothermal process. The effects of stirring time and ammonia content on the morphology evolution have been discussed, respectively. Extension of stirring time of the precursor results in morphology transformation from star‐like to wire‐like ZnO nanocrystals. ZnO nuclei aggregation and uniform Zn(OH)₂ precipitation can readily explain these two morphologies, respectively. By increasing the ammonia content in the solution, the morphology of ZnO crystals is transformed from an irregular shape to hexagon sheets to nanorods, and the side length of ZnO crystals is decreased accordingly. Hollow structures are realized at the subsequent solution aging process. Variation of zinc ammonic complex and minimum surface energy can well explain the morphology evolution of ZnO nanostructures.     

Ionic liquid‐assisted hydrothermal synthesis of γ‐Al2O3hierarchical nanostructures

The boehmite (Al₂O₃·H₂O) hierarchical nanostructure with spindle‐like morphology has been successfully synthesized via ionic liquid‐assisted hydrothermal synthetic method under mild condition using an ionic liquid 1‐butyl‐3‐dimethylimidazolium bromide ([Bmim][Br]) as a template. The proposed formation mechanism has been investigated and the hydrogen bond‐co‐π–π stack mechanism is used to be responsible for the present formation of the precursor hierarchical nanostructure. The γ‐Al₂O₃ hierarchical nanostructure was obtained by calcining the as‐synthesized precursor at 500 °C for 2 h, preserving the same morphology. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of dendritic‐like CdS by hydrothermal method and its photocatalytic performance

In this article, dendritic‐like CdS has been prepared by a hydrothermal method using thiourea as the sulfur source, and the effects of experimental conditions on the morphologies of CdS have been investigated. The performances of CdS have been analyzed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and the fluorescence and photodegradation properties of CdS have also been investigated. The XRD result indicates that the dendritic‐like CdS are of hexagonal phase and they are highly crystallized. Also, the FESEM results show that the ratio of raw material affects the yield of CdS, the reaction time affects the morphology of CdS. The best morphology of CdS is dendritic structures and the length is about 6 μm. The fluorescence spectrum shows three peaks at 470 nm, 513 nm and 547 nm, which indicates that the dendritic‐like CdS mainly emits green and blue fluorescence. Moreover, the dendritic‐like CdS exhibits good photocatalytic activity and its photodegradation rate to methylene blue can reach 92%. The growth mechanism for the formation of CdS with dendritic structure is also described.     

Morphology‐controlled CaMoO4 nanorods via a facile microwave‐assisted EDTA chelating agent process

This work reports on the shape‐controlled synthesis of CaMoO₄ nanorods via a high‐efficient microwave irradiation‐assisted chelating agent method. The phase and microstructure of these materials were systematically characterized by X‐ray diffraction and field‐emission scanning electron microscopy. It is noteworthy that EDTA plays pivotal roles as the complexing and capping agent in the oriented growth of uniform CaMoO₄ nanorods. The synthetic process gives the guidance to understand the morphological evolution of CaMoO₄ microstructures in microwave system, and provides a facile and designed strategy to fabricate functional one dimensional metallic molybdates.     

Vapour‐phase growth,purification and large‐area deposition of ZnO tetrapod nanostructures

Large‐yield zinc oxide (ZnO) nanosized tetrapods have been obtained by a standard vapour‐phase growth technique to which a few modifications have been added, such as the separation of the Zn source evaporation region from the Zn oxidation region inside the reactor setup. This modification allows to keep the growth conditions constant and continuous for a long time, thus favouring the obtainment of large amounts of ZnO tetrapod nanostructures. As some contaminations usually occur due to metallic Zn particles and/or different ZnO nanostructures, including not completely reacted ZnO_1‐x solid phases, they can be removed by a three‐step “purification” procedure as described in the article. Further to that, a deposition method from suitable liquid suspensions is also reported, which allows to produce homogeneous distributions of ZnO tetrapods on large substrate areas. The proposed procedures are expected to be particularly appropriate for a large production of samples for device use. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave hydrothermal synthesis and photocatalytic properties of ZnWO4 nanorods

Cd²⁺‐doped ZnWO₄ nanorods have been synthesized at 200 °C with microwave hydrothermal method, using Zn(NO₃)₂·6H₂O, Na₂WO₄·2H₂O and CdCl₂ as raw materials. The effects of Cd²⁺ doping contents on the structure and morphology of the product were studied. The results show that Cd²⁺ doping into the crystal lattice of ZnWO₄ nanopowder makes the powder orientationally grow along (010), (110) and (200) crystal planes to form the nanorods. The bigger Cd²⁺ doping contents are, the more obviously ZnWO₄ nanorods grow. Meanwhile, the nanopowder is gradually transformed from monoclinic phase into the orthogonal phase. As the charge transference medium between the interfaces, Cd²⁺ restrains the combination of holes and electrons. After doped, the photocatalytic properties of ZnWO₄ nanorods are increased. When Cd²⁺ doping content is 20%, the Cd²⁺‐doped ZnWO₄ nanorods showed the highest degradation rate up to 98% in 2 h.     

EDTA‐assisted synthesis of rose‐like ZnO architectures

Rose‐like ZnO nanostructures were prepared by a low‐temperature solution route with assistance of ethylenediaminetetraacetic acid disodium (EDTA‐2Na). The morphology of ZnO nanostructures was found to change from nanowire arrays to rose‐ and tower‐like architectures with increasing the molar ratio of EDTA‐2Na/Zn²⁺. Also, the shape evolution of ZnO nanostructures with time was observed from flat nanosheets to wrinkled nanosheets and to rose‐like nanostructures. EDTA‐2Na as a strong complexing agent was found to play a key role in the shape evolution. Photoluminescence spectra show that the rose‐like ZnO architectures have more defects than the nanowire arrays. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low‐temperature urea‐assisted hydrothermal synthesis of Bi2S3 nanostructures with different morphologies

Different morphologies of single‐crystalline orthorhombic phase bismuth sulfide (Bi₂S₃) nanostructures, including sub‐microtubes, nanoflowers and nanorods were synthesized by a urea‐assisted hydrothermal method at a low temperature below 120 °C for 12 h. The as‐synthesized powders were characterized by X‐ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM) and UV‐vis spectrophotometry. The experimental results showed that the sulfur sources had a great effect on the morphology and size of the resulting powders. The formation mechanism of the Bi₂S₃ nanostructures with different morphologies was discussed. All Bi₂S₃ nanostructures showed an appearance of blue shift relative to the bulk orthorhombic Bi₂S₃, which might be ascribed to the quantum size effect of the final products. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Phase‐manipulable synthesis of Cu‐based nanomaterials using ionic liquid 1‐butyl‐3‐methyl‐imidazole tetrafluoroborate

Using the ionic liquid (IL), 1‐butyl‐3‐methyl‐imidazole tetrafluoroborate, and the precursor Cu₇Cl₄(OH)₁₀·H₂O, series of phase‐manipulable Cu‐based nanomaterials were synthesized by hydrothermal and microwave assisted routes, respectively. The structural characters of the as‐prepared CuO, CuO/Cu₂O composites and pure Cu nanoparticles were investigated by XRD, SEM, TEM and HRTEM, and their surface photovoltaic properties were studied by surface photovoltage spectra. Via hydrothermal route Cu²⁺ ions were found to be reduced gradually into Cu⁺ and subsequently Cu⁰ with increasing the IL, and various phase ratio of CuO, Cu₂O and Cu composite nanosheets and pure Cu nanoparticles were obtained. This implies that the IL could function as both a reductant in the oxygen‐starved condition and a template for the nanosheet products. The ¹H‐NMR result of the IL supports it being a reductant. In microwave assisted route, however, only monoclinic single crystalline CuO nanosheets were obtained, which indicates the IL being a template only in oxygen‐rich condition. Therefore, the crystal phase, composition and morphology of the Cu‐based products could be controlled by simply adjusting the quantity of the IL and oxygen in solution routes. The molecular structure of the IL after oxidation reactions was investigated by ¹H‐NMR and a possible reaction mechanism was proposed. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication of hollow ZnO nanostructures by a CTAB‐assisted chemical bath deposition method

ZnO films consisted of hollow nanostructures were prepared by a CTAB‐assisted chemical bath deposition (CBD) method. ZnO rings, bowls and assemblies of hollow structures were successfully obtained on different substrates. Dense ZnO films consisted of sunken prisms can also be achieved by controlling the concentration of CTAB. The influences of reactant concentrations, types of the substrates and pre‐coated ZnO nanoparticles on the formation of ZnO films were examined. XRD patterns indicated the Wurtzite structure of ZnO and the preferred growth direction is [001]. The role of CTAB in CBD process was discussed and the evolution of different ZnO nanostructures was studied based on the observation of SEM. A plausible crystal growth mechanism was proposed for the formation of ZnO rings and bowls. The investigation of optical properties showed that high concentration of CTAB can improve the ultraviolet emission.     

Catalyst‐free thermally‐evaporated growth and optical properties of ZnO nanowires on Si,GaN and sapphire substrates

Vertically well‐aligned zinc oxide nanowires (NWs) with high density were successfully synthesized on Si, sapphire and GaN/sapphire substrates by thermal evaporation of zinc powders without catalysts or additives. The growth behavior of ZnO NWs was strongly dependent on the substrate materials. The effects of the substrate position on the structures and properties of ZnO NWs were primarily discussed. The morphology and crystallinity of the resultant NWs were studied by scanning electron microscope, transmission electronic microscope and X‐ray diffraction. The photoluminescence (PL) characteristics of the ZnO NWs on the different substrates were studied. The results showed that the as‐grown ZnO NWs exhibit a sharp and strong ultraviolet emission at 3.27 eV and a very weak green emission at around 2.48 eV, indicating that the a‐synthesized NWs have excellent PL properties with good crystalline quality and can be an ideal candidate for making luminescent devices. By comparison of PL spectra, we revealed that the green‐to‐UV emission intensity ratios were considerably dependent on the substrate materials, which was explained by the difference in the structural morphology of the produced nanowires.     

Controlled growth of ZnO torch‐like nanostructure arrays

Single‐crystal ZnO torch‐like nanostructure arrays were synthesized using a simple two‐step pressure controlled thermal evaporation method without any catalyst. The nanostructures had a hierarchical morphology, with well‐hexagonal faceted holders and needle‐like flames on them. The diameter of each single flame was about 20–40nm at the base and 10nm at the tip. Both the holders and flames were found to grow along the [0001] direction. The morphology of the structures could be effectively controlled by varying the growth temperature and vacuum pressure. The experimental results and analysis provided easy strategies to control the morphology of nanostructures and also enhanced the understanding of the growth mechanism. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)