Facile synthesis and characterization of hierarchical CuO nanoarchitectures by a simple solution route

The controlled synthesis of hierarchical CuO nanomaterials in a solution phase has been realized with high yield at low temperature using copper acetate hydrate and NaOH as starting materials with the assistance of surfactant under hydrothermal conditions. X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet‐visible spectroscopy (UV‐Vis) were used to characterize the products. It was shown that the hierarchical CuO nanoarchitectures were formed through aggregation of tiny single‐crystal CuO nanorods. Experiments demonstrated that the morphology of CuO products was significantly influenced by hydrothermal temperature and reaction time. A rational growth mechanism based on oriented attachment was proposed for the selective formation of the hierarchical CuO nanoarchitectures. Our work demonstrated the growth of hierarchical CuO nanoarchitectures built from one‐dimentional nanorods through a one‐step solution‐phase chemical route under controlled conditions. In addition, The UV‐Vis spectrum of the hierarchical CuO nanoarchitectures showed large blue shift because of the quantum size effect. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Leaf‐like copper oxide nanocrystals synthesized by a gas‐liquid diffusion method at room temperature

The leaf‐like copper oxide (CuO) nanocrystals have been synthesized by a gas‐liquid diffusion method in pure aqueous solution at room temperature. The structure, morphologies and related properties of the as‐prepared crystals were characterized with X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), selected area electron diffraction (SAED) and thermogravimetric analysis (TG). The influence of copper concentration was investigated, which plays an important role in the formation of nanostructured CuO crystals. Only when the copper concentration was low enough (0.005 M) that the leaf‐like CuO could be obtained directly. Additionally, a growth mechanism of CuO was also proposed based on the observed results.     

Synthesis and self‐assembled mechanism of CuO peony‐flowers by a composite hydroxide‐mediated approach at low temperature

A composite‐hydroxide mediated (CHM) method was utilized for the synthesis of CuO peony‐flower nanostructures under temperatures ranging between 25 and 160 °C. The CHM mechanism was confirmed through X‐ray Powder Diffraction (XRD) and a Thermo‐Gravimetric Differential Scanning Calorimeter (TG‐DSC). Cu(NO₃)₂ was shown to transform into Cu(OH)₂ in the mixed alkalis (NaOH/KOH); the reaction was facilitated by the solvent properties of the mixed alkalis. Cu(OH)₂ subsequently consumed H₂O in the adsorption of the mixed alkalis at 25∼65 °C. At higher reaction temperatures (>65 °C), the Cu(OH)₂ was seen to decompose at an accelerated rate. Therefore, crystalline CuO could be obtained not only above 65 °C but also at 25 °C. The crystal morphology and structure of CuO were examined through Filed Emission Scanning Electron Microscopy (FE‐SEM) and Transmission Electron Microscopy (TEM). It was determined that the CuO peony‐flower had a polycrystalline structure composed of single crystalline CuO petals. Using the Selected Area Electron Diffraction (SAED) results, the rings were indexed as (002), (111), (112), (202) and (−113), which was in agreement with the XRD results. With increasing temperature, the CuO flower petals self‐assembled through random aggregation and gathered CuO nanorod parts, which led to incomplete CuO flower petals through orientated aggregation. Prolonged reaction time led to the growth of CuO flower petals in the direction of [001]. An ideal CuO flower structure was observed through TEM observation.     

Preparation of CuO mesocrystals via antlerite intermediate for photocatalytic applications

CuO mesocrystals were synthesized by thermal decomposition of antlerite (Cu₃(OH)₄SO₄) formed as an intermediate by the reaction between CuSO₄.5H₂O and urea under specific experimental conditions. Antlerite possessing spindles of sea urchin‐like morphology was obtained via controlled hydrolysis process using ethylene glycol as a co‐solvent. Antlerite and CuO mesocrystals were characterized by X‐ray diffraction (XRD), fourier transform‐infrared spectrum (FT‐IR), thermo gravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and energy dispersive spectroscopy (EDS). A probable mechanism for formation of such morphologies has been proposed. The photocatalytic and optical properties of CuO mesocrystals were also evaluated.     

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.     

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)     

One‐step green synthesis by organic molten salt method and optical properties of CdS nanosheets

Cadmium sulfide (CdS) nanosheets were synthesized by an environment friendly, “green” organic molten salt (OMS) method at 220 °C. The as‐synthesized products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS), respectively. The XRD results reveal that the as‐synthesized CdS nanosheets are of the hexagonal wurtzite structure and the CdS nanosheets grow along the c‐axis. The SEM results indicate that the diameters and thickness of the CdS nanosheets are about 20–40 nm and 5–10 nm, respectively. The optical properties of the CdS nanosheets were investigated by ultraviolet–visible (UV‐Vis) spectroscopy and photoluminescence (PL) spectroscopy. The ultraviolet–visible spectrum exhibits two excitonic peaks with a step‐like absorption and the photoluminescence spectrum shows a green emission peak centered at around 524 nm. A possible growth mechanism of CdS nanosheets was discussed.     

Optical and Photocatalytic properties of Mn‐doped CuO nanosheets prepared by hydrothermal method

Mn‐doped CuO nanosheets were prepared through a hydrothermal method to enhance their photocatalytic property. The structural and morphological features were monitored by using X‐Ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) with energy dispersive spectroscopy (EDS). UV‐vis absorption spectra showed the enhance absorption performance both in UV and visible light region. The band gaps were also calculate and the minimum value was 1.25 eV. The photocatalytic activity was investigated by the degradation of methylene blue (MB), which indicated that the photoactivity of samples depended on the amount of Mn²⁺ incorporated into the CuO lattice. The improved performance of photocatalysts can be attributed to enhanced light absorption and lower electron‐hole recombination.     

Synthesis of nanoflakes‐based self‐assembling crossed structure of stannous oxide and photocatalysis property

Self‐assembling nanoflakes‐based crossed architectures of stannous oxide (SnO) were successfully synthesized via template‐free hydrothermal growth method by using SnCl₂·2H₂O and KOH as precursors. Crystal structures, morphology, chemical composition and optical properties were examined by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FESEM), energy dispersive X‐ray analysis, and Raman spectroscopy, respectively. The results indicate that the as‐synthesized product belongs to tetragonal phase SnO with crossed morphology self‐assembled by nanoflakes. Furthermore, UV‐vis spectrophotometry was used to determine optical band gap of the SnO nanostructures and the direct band gap of 2.90 eV was obtained. The photocatalysis of the product has been evaluated with methyl orange and the high degradation ratio of 87% is obtained in 240 minutes under the measuring condition which is attributed to the wide band gap and large specific surface area of the nanoflakes‐based crossed SnO architectures. A possible growth mechanism is proposed in the end.     

Ethylenediamine inducing growth of {100} facets exposed PbS nanosheets

A simple ethylenediamine‐assisted hydrothermal method was developed for the synthesis of sheet‐like PbS nanostructures. Studies show that ethylenediamine not only provides a weakly basic environment for the reaction system, but also acts as a capping reagent to control the growth habit of cubic PbS. A reasonable growth mechanism for the PbS nanosheet structure has been proposed on the basis of the experimental studies. The structure, morphology, and composition of the nanosheets have been characterized by X‐ray powder diffraction, field‐emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy.     

Facile synthesis of low dimensional CuO nanostructures and their gas sensing applications

A simple and cost effective hydrothermal method has been employed to synthesis morphology controlled pure and Cr doped (4 and 8 at. %) CuO nanostructures. Crystalline purity and structure of the nanostructures were validated by X‐ray diffraction and Retvield analyses. Field emission scanning electron microscopy revealed the evolution of rod‐like, sheet‐like and boat‐like morphologies for pure, 4 and 8 at. % Cr doped CuO nanostructures respectively. The optical band gap estimated using the K‐M function plot from diffused reflectance spectroscopy showed a shift in band gap from 1.68 to 1.90 eV with respect to Cr concentration. The synthesized CuO nanostructures were investigated for the efficient room temperature gas sensing of ammonia, ethanol and methanol vapours under different concentrations (100‐600 ppm). The 8 at. % Cr doped CuO nano‐boats showed enhanced gas sensitivity than other CuO nanostructures owing to their typical morphology, larger surface area and related properties.     

Crystal growth,quality characterization and THz properties of DAST crystals

4‐N, N‐diethylamino‐4’‐N’‐methyl‐stilbazolium tosylate (DAST) crystals were grown by slope nucleation method (SNM). The crystal structure of grown DAST crystals was characterized by single crystal X‐ray diffraction with demonstrating X‐ray diffraction main peaks. The crystal defects were analyzed by the synchrotron radiation X‐ray topography. It was found that the unbalanced temperature gradient, the Teflon groove and the super saturation fluctuation were primary causes of crystal defects. Furthermore, widely tunable THz waves ranging from 1.16 to 16.71 THz were generated from 1 mm‐thick DAST crystal using the optical parametric oscillator (OPO). It was obtained that the THz output energy was 27.4 nJ (peak power of 2.74 W) and the highest conversion efficiency was 1.37 × 10⁻⁵ at 3.8 THz.     

Conversion from ZnO nanospindles into ZnO/ZnS core/shell composites and ZnS microspindles

The formation process of ZnO/ZnS core/shell microcomposites and ZnS microspindles prepared by the reaction of ZnO colloids and thioacetamide under hydrothermal conditions was investigated in detail by X‐ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy and selected‐area electron diffraction techniques. The precursors of spindlelike ZnO colloids were prepared by a hydrothermal method with the help of a surfactant. A growth mechanism was proposed to account for the formation of ZnO/ZnS core/shell microcomposites and ZnS microspindles. Luminescence measurement revealed that ZnO/ZnS core/shell microcomposites integrated the luminescence effect of ZnO and ZnS. The blue and green emissions were dramatically enhanced, while the orange emission disappeared. The results provide a good approach to tune the visible emission of the ZnO nanostructures by ZnS coating. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Highly efficient photocatalytic degradation of methyl orange and Rhodamine B by hierarchical BiOBr microspheres

Hierarchical BiOBr microspheres were successfully synthesized via a solvothermal method by using the diethylene glycol(DEG) as the solvent and soft‐template. The as‐obtained products were characterized by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), high resolution transmission electron microscopy (HRTEM), N₂ adsorption–desorption and UV–Vis diffuse reflectance spectroscopy(DRS) techniques. The formation mechanism for the growth of hierarchical BiOBr microspheres has been studied. The possible mechanism of photocatalysis has been discussed. Remarkably, the as‐prepared BiOBr microspheres has a large specific surface area, which can reach a maximum surface area of 55.9307 m²/g. In addition, the superior enhanced photocatalytic activities of BiOBr microspheres were evaluated by the photodegradation of methyl orange (MO) and Rhodamine B (RhB) under visible‐light illumination, which presented the efficiency up to 98.10% just within 50 min and 98.64% within 30 min, respectively. BiOBr microspheres can be a promising candidate as highly efficient photocatalyst for decompositing of organic contaminants for environmental remediation.     

BaMoO4 thin films prepared by electrochemical method at room temperature

Highly crystallized BaMoO₄ films were prepared on molybdenum substrates in Ba(OH)₂ solutions by electrochemical method at room temperature. The deposition conditions (reaction temperature and current density) during electrochemical formation were researched. The films were characterized by using the X‐ray Diffraction (XRD), Scanning Electronic Microscopy (SEM) and X‐ray Photoelectron Spectroscopy (XPS) analyses. The XRD analyses show that the films are good crystalline with single scheelite‐type tetragonal structure; the SEM photographs show that the films are densely deposited with double tetragonal tapers in shape; and the XPS analyses reveal that the composition of the BaMoO₄ films (embodied Ba²⁺, Mo⁶⁺ and O^2‐) is in agreement with stoichiometry. The optimum electrochemical conditions for BaMoO₄ films formation are the lower reacting temperature (near room temperature) and the feasible current density (about 1mA/cm²)     

Controllable one‐step synthesis of CuO,Cu2O and Cu

In the present report, CuO, Cu₂O and Cu have been successfully synthesized through a facile, one‐step hydrothermal method at a relative low temperature by controlling only the concentration of citric acid. Compared with other synthetic methods, the present method is mild, high‐efficient and nontoxic. The crystal structure and morphology of the as prepared samples were characterized by X‐ray diffraction and scanning electron microscopy, respectively. The mechanism for the crystal phase and morphological changes with different citric acid concentrations were discussed. The possible reaction process of the synthesis was also studied on the basis of the experimental results. We hope that this facile, one‐step hydrothermal method could be used in controlling synthesis of other metals and metal oxides under appropriate experimental conditions.     

Synthesis of ZnO nanorods by the thermal reduction process of a mixture of ZnO and Al powder

Single‐crystalline Zinc oxide (ZnO) nanorods were firstly synthesized on gold‐coated Si substrate via a simple thermal reduction method from the mixture of ZnO and Al powder. The growth process was carried out in a quartz tube at different temperature (550‐700 °C) and at different oxygen partial pressure. Their structure properties were investigated by X‐ray diffraction (XRD), scanning electron microscope (SEM), X‐ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The length of the as‐prepared ZnO nanorods was up to several micrometers and their diameters were about 130 nm. The X‐ray diffraction patterns, transmission electron microscopic images, and selective area electron diffraction patterns indicate that the one‐dimensional ZnO nanorods are a pure Single‐crystal and preferentially oriented in the [0001] direction. The reaction mechanism of ZnO nanorods was proposed on the basis of experimental data. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Morphology control of CuO micro‐particles using Zn2+ ion and ultrasonic treatment

Novel tomato‐shaped copper oxide crystals has been prepared by a simple hydrothermal method with the presence of Zn²⁺ ion. The ultrasonic pretreatment has proved to be the key factor during the synthesis process. Scanning electron microscope, energy dispersive X‐ray spectrometry and powder X‐ray diffraction were used to characterize the microstructure and morphology of the as‐prepared products. The obtained tomato‐shaped CuO particles were constructed by nanorods with the diameter of about 20 nm. The possible growth mechanism was proposed based on the experimental results. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mixed metal oxide nanocomposites derived from layered double hydroxides as photocatalysts for C.I. Basic Blue 3 degradation under UV light

In this research we report synthesis of the heterostructure Mg‐Al‐Zn mixed metal oxide (ZnO/MMO) nanocomposite photocatalysts derived from Zn(OH)₂/Mg‐Al‐layered double hydroxides (ZLDHs) precursors. The obtained samples were characterized by the X‐ray diffraction (XRD), FT‐IR, BET surface area, ICP and TG/DTG methods. The chemical compositions and morphology of the synthesized materials were investigated by the energy dispersive X‐ray analysis (EDX) and the transmission electron microscopy (TEM). The results reveal that at the reaction time 96 h, ZLDH has the highest crystalinity which was confirmed by the X‐ray diffraction spectra. The calcined samples at 500, 600 and 700 °C for 4 h show that the crystallinity of the nanocomposite improves with the increase of calcination temperature. The photocatalytic activities of synthesized nanocomposites were compared for the degradation of C. I. Basic Blue 3 (BB3) dye under UV illumination in aqueous solution. Among the synthesized nanocomposites, ZnO/MMO calcined at 700 °C shows the highest efficiency towards the removal of dye. The effect of UV illumination on the stability of ZnO in ZnO/MMO nanocomposite and pure ZnO was also investigated. The results showed that the photostability of ZnO in ZnO/MMO nanocomposite is increased compared to the pure ZnO.     

Solvothermal synthesis of flower‐like lanthanum tartrate and lanthanum oxide microspheres in ethanol‐water mixed system

Monodispersed lanthanum tartrate microspheres with flower‐like shape were synthesized by a mild solvothermal method using ethanol‐water mixed system as the solvent. Lanthanum oxide with reserved spherical shape was subsequently fabricated by a following calcination process. X‐ray diffraction analyses (XRD), X‐ray spectroscopy (EDS), scanning electron microscopy (SEM), thermogravimetry‐differential thermal analysis (TG‐DTA) were employed to characterize the composition, structure, and morphology of the products. The lanthanum tartrate microspheres were aggregated by nanosheets as petals. Size of the aggregation and thickness of the petal vary with the vol.% of ethanol. As the vol.% of ethanol increases the degree of aggregation and the thickness of the petal decrease, and other properties such as the size distribution, dispersion are also modulated. These alterations can be interpreted by the changing dielectric constant of mixed solvent. Such lanthanum tartrate can be applied to fabricate micro‐sphereshaped lanthanum oxide after calcination. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)