Synthesis and Photocatalytic Activity of One-dimensional ZnO-Zn2SnO4 Mixed Oxide Nanowires

Mixed oxide photocatalysts, ZnO-Zn2SnO4 (ZnO-ZTO) nanowires with different sizes were prepared by a simple thermal evaporation method. The ZnO-ZTO nanowires were characterized with a scanning electron microscope, X-ray diffraction, high-resolution transmission electron microscopy, energy-dispersive spectrometer, and X-ray photoelectron spectrThe photocatalytic activity of the ZnO-ZTO mixed nanowires were studied by observing the photodegradation behaviors of methyl orange aqueous solution. The results suggest that the ZnO-ZTO mixed oxide nanowires have a higher photocatalytic activity than pure ZnO and Zn2SnO4 nanowires. The photocatalyst concentration in the solution distinctly affects the degradation rate, and our results show that higher photodegradation efficiency can be achieved with a smaller amount of ZnO-ZTO nanowire catalyst, as compared to the pure ZnO and ZTO nanowires. Moreover, the photocatalytic activity can also be enhanced by reducing the average diameter of the nanowires. The activity of pure ZnO and ZTO nanowires are also enhanced by physically mixing them. These results can be explained by the synergism between the two semiconductors.     

Preparation of ZnO Nanowires and Study of Surface‐adsorbate Interaction by Fourier‐Transform Infrared Spectroscopy

To study the surface‐adsorbate properties of ZnO nanowires, a hydrothermal method was modified to grow ZnO nanowires directly on ZnSe, which were then characterized by attenuated total reflection infrared (ATR‐IR) spectroscopy. To prepare ZnO nanowires directly on ATR sensing element of ZnSe, ZnO seed layers were first formed by annealing of ZnO seeds on ZnSe surfaces. The ZnO seed layers then were exposed to growth solution, forming ZnO nanowires directly on the ATR crystals. The interaction properties of the resulting surfaces were studied by an ATR‐IR method. The diameter, length and distribution of the ZnO nanowires can be tuned by adjusting the growth conditions, particularly the growing time and the concentrations of reagents. Two surfaces, namely Zn‐rich and Zn‐O ion‐pair surfaces were studied in detail for their adsorption properties toward compounds bearing different functional groups. By examination of several volatile organic compounds (VOCs), it was found that the Zn‐rich surface is less selective and interacts with compounds bearing the functional groups of amino and hydroxyl. The Zn‐O ion‐pair surface is more selective and a much stronger interaction was observed with non‐aromatic amino compounds. These results indicate that the improving of the selectivity of a ZnO‐based sensing device can be achieved by tuning the surface structure of the ZnO nanomaterials.     

Ag/ZnO/ZnSe三元异质结的合成及其可见光光催化性能

以Ag纳米线为模板,通过两步水浴法合成了Ag/ZnO/ZnSe三元异质结光催化材料。利用场发射扫描电子显微镜(FESEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)以及透射电子显微镜(FETEM)对样品的形貌和结构进行了表征。结果显示,Ag/ZnO/ZnSe三元异质结为蠕虫状的Ag/ZnO二元异质结外镶嵌着ZnSe小颗粒。在可见光下,对比纯Ag纳米线、纯ZnO纳米球、Ag/ZnO异质结对罗丹明B的可见光降解效率,结果发现Ag/ZnO/ZnSe异质结表现出了更高的光催化效率。其光催化性能的提高主要是由于Ag/ZnO/ZnSe异质结的作用促使电子空穴对的分离,降低了电子空穴对的复合机率,从而提高了材料的光催化效率。     

High surface-to-volume ratio ZnO microberets: low temperature synthesis, characterization, and photoluminescence

Novel hollow ZnO microstructures and ZnO microberets (ZMBs) with nanowires grown vertically on both the inner and outer surfaces of beret shells were synthesized on Si(100) substrates by simple thermal evaporation of pure zinc powder without any catalyst or template material at a relative low temperature of 490 degrees C. XRD, SAED, and HRTEM patterns show that the nanowires and shells of ZMBs are single-crystalline wurtzite structures. The growth mechanism of ZMBs is discussed in detail. The formation of these hollow microstructures depends on the optimum starting time of air introduction. It is a good way to grow well-aligned nanowires by using a nanoscale rough ZnO surface to realize a "self-catalyzed" vapor-liquid-solid process. The photoluminescence spectrum reveals a strong green emission related to the high surface-to-volume ratio of ZMBs. These types of special hollow high surface area structural ZMBs may find potential applications in functional architectural composite materials, solar cell photoanodes, and nanooptoelectronic devices.     

ZnO/ZnSe复合纳米结构的制备及可见光光催化性能

通过热水解法, 以氧化锌为模板, 成功制备出形貌均一的ZnO/ZnSe复合纳米结构. 为了对比不同O/Se比对光催化性能的影响, 保持其它反应参数不变, 调节还原剂水合肼的用量, 得到不同硒化程度的ZnO/ZnSe复合纳米结构. 采用场发射扫描电子显微镜、 X射线衍射仪和透射电子显微镜对样品的形貌及结构进行了表征, 通过测试该复合结构对亚甲基蓝的可见光催化降解评估了其光催化效率. 结果表明, 与纯ZnO比, ZnO/ZnSe复合结构在可见光区域和紫外光区域的光吸收范围变宽, 显示出较高的光催化效率. 原因在于ZnSe导带上的电子在扩散势能的作用下迁移到ZnO的导带上, 而空穴仍保留在ZnSe价带, 这样有助于光生电子和空穴对的分离, 降低其复合机率, 从而提高ZnO的光催化效率.     

Ag/ZnO/ZnSe三元异质结的合成及其可见光光催化性能

以Ag纳米线为模板,通过两步水浴法合成了Ag/Zn O/Zn Se三元异质结光催化材料。利用场发射扫描电子显微镜(FESEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)以及透射电子显微镜(FETEM)对样品的形貌和结构进行了表征。结果显示,Ag/Zn O/Zn Se三元异质结为蠕虫状的Ag/Zn O二元异质结外镶嵌着Zn Se小颗粒。在可见光下,对比纯Ag纳米线、纯Zn O纳米球、Ag/Zn O异质结对罗丹明B的可见光降解效率,结果发现Ag/Zn O/Zn Se异质结表现出了更高的光催化效率。其光催化性能的提高主要是由于Ag/Zn O/Zn Se异质结的作用促使电子空穴对的分离,降低了电子空穴对的复合机率,从而提高了材料的光催化效率。     

Epitaxial heterostructures: side-to-side Si-ZnS, Si-ZnSe biaxial nanowires, and sandwichlike ZnS-Si-ZnS triaxial nanowires

Epitaxial semiconducting heterostructures: side-to-side Si-ZnS, Si-ZnSe biaxial nanowires, and sandwichlike ZnS-Si-ZnS triaxial nanowires were grown via a simple two-stage thermal evaporation of mixed SiO and ZnS or SiO and ZnSe powders under a precise temperature control. Each nanowire had a uniform diameter of 40-120 nm and length ranging from several to several tens of micrometers. Subnanowires of Si, ZnS, and ZnSe within them had a diameter of 20-50, 40-60, and 20-50 nm, respectively. The optical property (nanoscale cathodoluminescence) was also investigated from these new structures. It is proposed that the Si nanowires formed through disproportionation of SiO to Si in the first evaporation stage and then served as one-dimensional nanoscale substrates (or templates) for an epitaxial growth of ZnS or ZnSe nanowires in the following thermal evaporation of ZnS or ZnSe powders. The present results suggest that the simple method might be useful for the synthesis of many other heterostructures containing Si and II-VI or III-V semiconducting composite nanowires to meet the growing demands of nanoscale science and technology.     

Luminescence Property and Synthesis of Sulfur-doped ZnO Nanowires by Electrochemical Deposition

"Sulfur-doped zinc oxide (ZnO) nanowires were successfully synthesized by an electric field-assisted electrochemical deposition in porous anodized aluminum oxide template at room temperature. The structure, morphology, chemical composition and photoluminescence properties of the as-synthesized ZnO:S nanostructures were investigated. X-ray diffraction and the selected area electron diffraction results reveal that the as-ynthesized products are single phase with hexagonal wurtzite structure with a highly preferential orientation in the (101) direction. Transmission electron microscopy observations indicate that the nanowires are niform with an average diameter of 70 nm and length up to several tens of micrometers. X-ray photoelectron pectroscopy further reveals the presence of S in the ZnO nanowires. Room-temperature photoluminescences observed in the sulfur-doped ZnO nanowires which exhibits strong near-band-edge ultraviolet peaks at 378 and 392 nm and weak green emissions at 533 and 507 nm. A blue emission at 456 nm and violet emissions at around 406, 420, and 434 nm were also observed in the PL spectrum for the as-synthesized ZnO:S nanowires. The PL spectrum shows that S-doping had an obvious effect on the luminescence property of typical ZnO nanowires."     

Synthesis and characterization of ZnO nanowires by thermal oxidation of Zn thin films at various temperatures

In this research high-quality zinc oxide (ZnO) nanowires have been synthesized by thermal oxidation of metallic Zn thin films. Metallic Zn films with thicknesses of 250 nm have been deposited on a glass substrate by the PVD technique. The deposited zinc thin films were oxidized in air at various temperatures ranging between 450 °C to 650 °C. Surface morphology, structural and optical properties of the ZnO nanowires were examined by scanning electron microscope (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX) and photoluminescence (PL) measurements. XRD analysis demonstrated that the ZnO nanowires has a wurtzite structure with orientation of (002), and the nanowires prepared at 600 °C has a better crystalline quality than samples prepared at other temperatures. SEM results indicate that by increasing the oxidation temperature, the dimensions of the ZnO nanowires increase. The optimum temperature for synthesizing high density, ZnO nanowires was determined to be 600 °C. EDX results revealed that only Zn and O are present in the samples, indicating a pure ZnO composition. The PL spectra of as-synthesized nanowires exhibited a strong UV emission and a relatively weak green emission.     

Three-dimensional type II ZnO/ZnSe heterostructures and their visible light photocatalytic activities

We report a method for synthesizing three distinct type II 3D ZnO/ZnSe heterostructures through simple solution-based surface modification reactions in which polycrystalline ZnSe nanoparticles formed on the surfaces of single-crystalline ZnO building blocks of 3D superstructures. The experimental results suggested a possible formation mechanism for these heterostructures. The formation of the ZnO/ZnSe heterostructures was assumed to result from a dissolution-recrystallization mechanism. The optical properties of the 3D ZnO/ZnSe heterostructures were probed by UV-vis diffuse reflectance spectroscopy. The 3D ZnO/ZnSe heterostructures exhibited absorption in the visible spectral region. The visible photocatalytic activities of 3D ZnO/ZnSe heterostructures were much higher than those of the 3D pure ZnO structures. The activities of the 3D ZnO/ZnSe heterostructures varied according to the structures under visible light. The morphologies and exposed crystal faces of pure ZnO building blocks prior to surface modification had a significant effect on the visible light photocatalytic processes of ZnO/ZnSe heterostructures after surface modification.     

ZnO纳米线的电化学制备研究

High-quality ZnO nanowires have been synthesized at relatively low temperature via one-step electrochemical anodization technique. In this method, Zn sheet acted as the anode and Pb sheet served as the counter electrode, and the complex solution of HF-C₂H₅OH-H₂O was used as electrolyte. ZnO nanowires were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED) and X-ray Diffraction (XRD). The results show that the nanowires were wurtzite crystalline ZnO, and the ZnO nanowires with the diameters of 70 nm and 30～40 nm were obtained by adjusting preparation conditions, respectively.     

Photovoltaic properties of oriented ZnO nanowires arrays decorated with TiO<Subscript>2</Subscript> shell layer for dye-sensitized solar cell application

Almost vertically aligned ZnO nanowires have been grown on Silicon substrates via a simple hydrothermal method. In order to improve the photoelectric conversion efficiency for fabricated dye-sensitized solar cells (DSSCs), an easily-operated immersing method was employed to fabricate a TiO₂/ZnO nanowires array heterojunction, which has advantage of high aspect ratio, low recombination rate and high absorption of visible light. The structure and surface morphology of the samples were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM), respectively. The photovoltaic properties of TiO₂/ZnO based DSCCs were measured by considering the power efficiency (η), photocurrent density (J_sc), open-circuit voltage (V_oc), and fill factor (FF). An efficiency of 0.559% is achieved for the composite cell, increasing 0.426 and 0.185% for the ZnO nanowires cell and TiO₂ cell, respectively. The short-circuit current and open-circuit voltage are also enhancing. The improvements are because of high surface are of TiO₂ shell layer, as well as fast electron transport and light scattering effect of ZnO nanowires.     

Synthesis and Characterization of ZnO Nanowires

Zinc oxide is a wide bandgap (3.37 eV) semiconductor with a hexagonal wurtzite crystal structure. ZnO prepared in nanowire form may be used as a nanosized ultraviolet light-emitting source. In this study, ZnO nanowires were prepared by vapor-phase transport of Zn vapor onto gold-coated silicon substrates in a tube furnace heated to 900 ?C. Gold serves as a catalyst to capture Zn vapor during nanowire growth. Size control of ZnO nanowires has been achieved by varying the gold film thickness…     

Synthesis and synchrotron light-induced luminescence of ZnO nanostructures: nanowires, nanoneedles, nanoflowers, and tubular whiskers

ZnO nanostructures, including single-crystal nanowires, nanoneedles, nanoflowers, and tubular whiskers, have been fabricated at a modestly low temperature of 550 degrees C via the oxidation of metallic Zn powder without a metal catalyst. Specific ZnO nanostructures can be obtained at a specific temperature zone in the furnace depending on the temperature and the pressure of oxygen. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD) studies show that ZnO nanostructures thus prepared are single crystals with a wurtzite structure. X-ray excited optical luminescence (XEOL) from the ZnO nanostructures show noticeable morphology-dependent luminescence. Specifically, ZnO nanowires of around 15 nm in diameter emit the strongest green light. The morphology of these nanostructures, their XEOL, and the implication of the results will be discussed.     

ZnO纳米线形态对其光致发光性能的影响

以多孔氧化铝膜为模板,电化学沉积出Zn纳米线,再通过高温氧化得到ZnO纳米线阵列。通过改变制备多孔氧化铝模板的工艺参数来改变模板纳米孔径,进而改变ZnO纳米线的直径,得到不同形态的ZnO纳米线阵列。应用X射线衍射仪、透射电子显微镜测试技术表征了ZnO纳米线的结构与形貌。结果发现,X射线衍射时会出现随ZnO纳米线直径增大衍射峰增多和增强的现象。采用荧光光谱仪测试样品的光致发光性能,通过Gaussian原理对谱峰的拟合分析了ZnO纳米线形态对其光致发光光谱的影响。结果表明,随着纳米线直径从30nm至60nm依次增大,其结晶性和化学计量比逐渐变好。近紫外区和蓝光区的发射峰随着纳米线直径的增大而蓝移,而纳米线直径为60nm的样品则出现随直径增大而红移的现象。结果可见,直径在55~60nm间的某点将是ZnO纳米线的结构和光致发光性能变化的临界点。     

Synthesis of europium-doped zinc oxide micro- and nanowires

Single crystalline Eu³⁺-doped wurtzite ZnO micro- and nanowires were synthesized by a chemical vapor deposition method (CVD). The nanostructures were grown by autocatalytic mechanism at walls of an alumina boat. The structure and properties of the doped ZnO is fully characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDX), scanning and transmission electron microscopy (SEM and TEM), and photoluminescence (PL) methods. The synthesis was carried out for 10 min giving vertically aligned nanowires with mean diameter of 50–400 nm and with length of up to several microns. The nanowires were grown along ±[0001] direction. The concentration of Eu³⁺ dopant in the synthesized nanowires was varied from 0.7 to 0.9 at %. The crystal structure and microstructures of the doped nanomaterials were discussed and compared with undoped ZnO. The photoluminescence spectra show that emission of doped samples were shifted towards orange-red region (2.02 eV) relative to undoped zinc oxide nanostructures (2.37 eV) due to Eu³⁺ intraionic transitions from ZnO/Eu.     

Zinc nanowires synthesized on a large scale by a simple carbothermal process

Metallic Zn nanowires have been synthesized by a new carbothermal reduction route in which ZnO and Eucalyptus sp. tar pitch were used as source materials. This simple practical procedure was capable of producing Zn nanowires in large quantities without reoxidation. This process was carried out in inert atmosphere, without vacuum or catalyst, at temperatures (800–900 °C) lower than those required in the carbothermal reduction of ZnO with graphite. A comparative study was performed using graphite that is traditionally used as a ZnO reducer, under the same experimental conditions, however, no reaction was observed. The new process involves the pyrolysis of biopitch to obtain a highly reactive coke and the reduction of ZnO with the release of Zn_(v) for the growth of Zn_(s) nanowires. The resulting Zn nanowires were characterized by X-ray diffractometry, energy-dispersive spectroscopy and scanning electron microscopy. Differential thermal analysis and thermogravimetric analysis coupled with infrared analysis techniques were used in an effort to understand the underlying mechanism and establish the best ratio biopitch/ZnO to be used. This paper presents the characterization of the as-synthesized nanowires and discusses the main reactions involved in their production.     

ZnO/CdS复合材料的合成与可见光催化性能

采用喷雾辅助气相沉积法在水热法合成的ZnO纳米线上沉积CdS纳米颗粒。采用X射线衍射仪（XRD）、激光拉曼仪（Raman）、扫描电镜（SEM）、透射电镜（TEM）、X射线光电子能谱分析谱（XPS）和紫外可见漫反射光谱等测试手段对复合光催化剂进行表征。结果表明,3~10 nm的CdS纳米粒子修饰在直径约为100 nm ZnO纳米线的表面。XPS和Raman表明复合材料中ZnO和CdS之间存在化学相互作用。可见光催化降解罗丹明B实验结果表明ZnO/CdS复合材料的催化性能优于单相CdS或ZnO,沉积时间为30 s合成的ZnO/CdS速率常数分别是CdS和ZnO的2.91和4.03倍,且具有较高的稳定性。ZnO/CdS复合材料光催化性能增强的可能原因为光吸收范围的拓展和光生载流子分离效率的提高。     

Tetraethylenepentamine-directed controllable synthesis of wurtzite ZnSe nanostructures with tunable morphology

A novel tetraethylenepentamine (TEPA)-directed method has been successfully developed for the controlled synthesis of ZnSe particles with distinctive morphologies, including nanobelts, nanowires, and hierarchically solid/hollow spheres. These structures, self-assembled from nanobelts and nanorods, have been synthesized by adjusting the reaction parameters, such as the solvent composition, reaction temperature, and the aging time. Results reveal that the volume ratio of H2O and TEPA plays a crucial role in the final morphology of ZnSe products. The mechanisms of phase formation and morphology control of ZnSe particles are proposed and discussed in detail. The products have been characterized by means of X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy (TEM), selected area electron diffraction, high-resolution TEM, Raman spectra and luminescence spectroscopy. The as-prepared ZnSe nanoparticles display shape- and size-dependent photoluminescent optical properties. This is the first time to report preparation of complex hollow structures of ZnSe crystals with hierarchy through a simple solution-based route. This synthetic route is designed to exploit a new H2O/TEPA/N2H4H2O system possibly for the preparation of other semiconductor nanomaterials.     

硫化锌与硫化锌/氧化锌异质结纳米线的化学气相沉积法制备与表征

介绍一种利用石墨还原快速制备大量硫化锌纳米线的方法,并分别合成了超晶格型、双轴型、核/壳型的硫化锌/氧化锌异质结纳米线。所合成的硫化锌纳米线存在六方纤锌矿和立方闪锌矿两种晶型,纳米线长度达几十微米,直径在20-50 nm,直径均匀且产量很高。在具有双轴型的硫化锌/氧化锌异质结中,首次发现具有超结构特征的氧化锌。HRTEM分析表明,硫化锌/氧化锌超晶格异质结界面为ZB-ZnS(111)∥ZnO(0001),而核/壳型异质结界面为W-ZnS(0001)∥ZnO(0001),这三个晶面分别为各自晶体的极性面,即所合成的硫化锌/氧化锌异质结中极性面相互平行。对ZnS 和ZnS/ZnO 异质结的生长机制进行了探讨,并对硫化锌纳米线与硫化锌/氧化锌异质结的光学性质进行了分析。