Large-scale synthesis and microstructure of SnO2 nanowires coated with quantum-sized ZnO nanocrystals on a mesh substrate

Large-quantity single-crystal SnO(2) nanowires coated with quantum-sized ZnO nanocrystals (nc-ZnO/SnO(2) nanowires) were directly synthesized by thermal evaporation of SnO powder and a mixture of basic ZnCO(3) and graphite powders. A common stainless steel mesh was used to collect the products. The microstructure and possible growth mechanism of the nc-ZnO/SnO(2) nanowires were investigated. Results showed that tetragonal structured SnO(2) nanowires were obtained, whose surfaces were coated with single-layer ZnO nanocrystals with an average diameter of less than 5 nm. The nanowires had cross-rectangle section with width-to-thickness aspect ratio ranging from 2:1 to 5:1. The lengths of the nanowires were several tens of micrometers. ZnO nanocrystals were single crystalline wurtzite structures, which coated the whole nanowires and distributed uniformly. The possible growth mechanism of the composite nanowires may be enucleated that Zn atoms in the source vapor will replace the Sn atoms on the surface of the formed SnO(2) nanowires due to the higher reducibility of Zn than Sn. Two strong Raman scattering peaks at 626 and 656 cm(-1) appeared in the micro-Raman spectrum of nc-ZnO/SnO(2) nanowires. The origins of the peaks were discussed. Most importantly, the method can be extended to other composite oxide nanowires that are synthesized by oxidizing two kinds of metals, such as high reducibility elements Mg, Al, Zn, and Ti, and low reducibility elements In, Ge, Ga, etc.     

Ferrimagnetic Mn2SnO4 nanowires

Single-crystalline Mn2SnO4 nanowires were first synthesized by chemical vapor deposition; they consist of inverse spinel structure grown with the [111] direction; the nanowires have a ferrimagnetic phase below 46 K (T(C)) with large hysteresis; this ferrimagnetic transition is probably due to the presence of Mn3+ ions at octahedral sites.     

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.     

Sol-gel template synthesis and photoluminescence of n- and p-type semiconductor oxide nanowires.

A sol-gel template technique has been put forward to synthesize single-crystalline semiconductor oxide nanowires, such as n-type SnO2 and p-type NiO. Scanning electron microscopy and transmission electron microscopy observations show that the oxide nanowires are single-crystal with average diameters in the range of 100-300 nm and lengths of over 10 microm. Photoluminescence (PL) spectra show a PL emission peak at 401 nm for n-type semiconductor SnO2, and a PL emission at 407 nm for p-type semiconductor NiO nanowires, respectively. Correspondingly, the observed violet-light emission at room temperature is attributed to near-band-edge emission for SnO2 nanowires and the 3d(7)4s-->3d8 transition of Ni2+ for NiO nanowires.     

Size-controllable one-dimensional SnO2 nanocrystals: synthesis, growth mechanism, and gas sensing property

Single crystalline one-dimensional (1-D) SnO(2) nanocrystals with controllable sizes, including the diameter and the aspect ratio, were synthesized by modulating the precursor concentration, reaction time and temperature via a solution method. By regulating the growth in a kinetic regime, a higher temperature range (220-240 degrees C) was beneficial to the growth of SnO(2) nanowires, while reactions below 220 degrees C only resulted in nanorods or even nanoparticles. The aggregates of SnO(2) nanocrystals in the forms of hollow spheres and dendrites were observed as the intermediates for the nanowires. Based on the TEM and SEM observations, the growth mechanism is discussed from the viewpoints of the nature of the reverse micelles and the crystal habit of rutile SnO(2). CO gas sensing measurements were also carried out for SnO(2) nanocrystals with different assembly styles. The results indicate that the sensitivity had close correlation to the specific surface area of the nanocrystals.     

熔盐电解法制备纳米碳管及纳米线

以LiCl、LiCl+SnCl2等为熔盐电解质,采用电解石墨的方法制备了纳米碳管和纳米线,并运用TEM、XRD、EDS等分析手段对产物的形貌和结构进行了表征.结果表明,熔盐成分对电解产物的形态和性质有显著影响.在LiCl熔盐中可得到直径为75～100nm的纳米碳管;在LiCl+1.0%SnCl2熔盐中可生成β-Sn填充的纳米碳管.XRD测试表明,电解制备的β-Sn纳米线经氧化处理后在碳管内可转变为SnO2,其晶体结构为四方晶系,直径为20～50 nm.电解过程中Li+在石墨阴极上反应生成的LiC6化合物对纳米碳结构的形成具有重要作用.     

金催化一氧化碳氧化反应中锌锡复合氧化物的载体效应

氧化物负载的纳米金催化剂对CO氧化反应具有极高的活性,这不仅依赖于金的结构特性,也取决于氧化物载体的结构.近年来,除了氧化硅、氧化铝等惰性载体以及氧化钛、氧化铈、氧化铁等可还原性载体外,人们还致力于探索各类新型氧化物载体.另一方面,锡酸锌是具有反尖晶石结构的化合物,并且在透明导电氧化物、锂离子电池阳极材料、光电转换装置以及传感器等方面应用广泛.然而,迄今为止,锡酸锌仍未被用于负载纳米金催化剂,因此相关的构效关系作用研究也十分有限.基于此,本文采用氮气吸附-脱附实验、电感耦合等离子体原子发射光谱(ICP-AES)、X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和高分辨电镜(HRTEM)、高角环形暗场像-扫描透射电子显微镜(HAADF-STEM)、X射线吸收精细结构谱(XAFS)和氢气程序升温脱附(H2-TPD)等手段,系统研究了锡酸锌负载的纳米金催化剂在CO氧化反应中催化性能差异的原因.首先,利用水热法制备了锡酸锌(ZTO)载体,而其织构性质可由碱(N2H4·H2O)与金属离子(Zn2+)的比例在4/1(ZTO_1)、8/1(ZTO_2)和16/1(ZTO_3)之间进行调节.结果发现, ZTO_2具有最大的孔体积(0.223 cm3/g)和最窄的孔径分布.再采用沉积沉淀法将0.7 wt% Au负载于其上,得到金-锡酸锌(Au_ZTO)催化剂. ICP-AES测得样品中Au含量在0.57-0.59 wt%,与投料比接近. CO氧化反应结果显示, Au_ZTO_1和Au_ZTO_2的表观活化能相同,但后者的活性更高;而Au_ZTO_3在220°C以下没有活性,催化性能最差,与纯锡酸锌载体相当. XRD结果显示,反应过程中ZTO晶相、晶胞参数及晶粒尺寸变化不明显; TEM和HRTEM分析表明,载体ZTO在反应前后均为多面体形貌,平均颗粒尺寸在12-16 nm; XPS结果验证了Zn2+和Sn4+离子是新鲜和反应后样品中载体金属的存在形式; HAADF-STEM探测到所有样品中均含有1-2 nm的Au粒子; XAFS结果表明, Au以Au0形式存在,并且在Au_ZTO_3中Au平均粒径大于4 nm,而其它两样品约为2 nm. H2-TPR结果表明,金的引入对ZTO载体耗氢量影响不大,但还原峰温度向低温移动;金属-载体相互作用强弱与催化活性高低具有正相关性,即Au_ZTO_2> Au_ZTO_1>> Au_ZTO_3.这是由于不同织构性质的锡酸锌载体对于纳米金活性物种的稳定作用不同所致,具有最大孔体积和最窄孔径分布的ZTO_2负载的金纳米颗粒表现出最高活性.     

Electronic structure of the doped SnO_2

SnO2 doped with La, Ce, Sm, Zn, Ca, Al and Sb was prepared by sol-gel technique and characterized by TEM, BET, XPS and XAES. The effect of the dopants on the grain sizes of SnO2 was described and especially the effect of dopants on the distribution of the electronic state density (DESD) of Sn4d orbital was studied deeply by using X-ray-induced Auger electron spectros-copy (XAES). It was observed that the dopants could influence not only the grain sizes of SnO2 but also electronic structure of SnO2, as well as the stability of the doped SnO2 samples. The experiment results indicated that the structure and stability of SnO2 film could be improved by the chemical modification of the dopants.     

Growth Mechanism and Characterization of Single-crystalline Ga-doped SnO2 Nanowires and Self-organized SnO2/Ga2O3 Heterogeneous Microcomb Structures

Single-crystalline Ga-doped SnO2 nanowires and SnO2:Ga2O3 heterogeneous microcombs were synthesized by a simple one-step thermal evaporation and condensation method. They were characterized by means of X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). FE-SEM images showed that the products consisted of nanowires and microcombs that represent a novel morphology. XRD, SAED and EDS indicated that they were single-crystalline tetragonal SnO2. The influence of experimental conditions on the morphologies of the products is discussed. The morphology of the product showed a ribbon-like stem and nanoribbon array aligned evenly along one or both side of the nanoribbon. It was found that many Ga2O3 nanoparticles deposited on the surface of the microcombs. The major core nanoribbon grew mainly along the 110 direction and the self-organized branching nanoribbons grew epitaxially along 1110 or 1110 orientation from the (110) plane of the stem. A growth process was proposed for interpreting the growth of these remarkable SnO2:Ga2O3 heterogeneous microcombs. Due to the heavy doping of Ga, the emission peak in photoluminescence spectra has red-shifted as well as broadened significantly.     

Electrochemical insertion of lithium in mechanochemically synthesized Zn2SnO4

We studied the electrochemical insertion of Li in mechanochemically prepared Zn(2)SnO(4). The mechanism of the electrochemical reaction was investigated by using X-ray diffraction, nuclear magnetic resonance spectroscopy, and M?ssbauer spectroscopy. Changes in the morphology of the Zn(2)SnO(4) particles were studied by in situ scanning electron microscopy. The results were compared with mixtures of SnO(2) + ZnO and with Zn(2)SnO(4) prepared by conventional solid-state synthesis and showed that the mechanochemically prepared Zn(2)SnO(4) exhibits the best cyclic stability of these samples.     

氧化锡和氧化锌双层薄膜的XPS研究

用XPS法研究了SnO2 /ZnO及ZnO/SnO2 双层膜中锌和锡的扩散情况 ,结果表明 :锌在SnO2中的扩散比锡在ZnO中的扩散更容易。讨论了锌在SnO2 层中的扩散方式和扩散的结果。在ZnO层留下了较多的氧 ,并使部分的SnO2 还原为SnO。     

Incorporating Zn(2) SnO(4) Quantum Dots and Aggregates for Enhanced Performance in Dye-Sensitized ZnO Solar Cells

The performance of dye-sensitized ZnO solar cells was improved by a facile surface-treatment approach through chemical-bath deposition. After the surface treatment, the quantum dots of Zn(2) SnO(4) were deposited onto ZnO nanoparticles accompanied by the aggregations of Zn(2) SnO(4) nanoparticles. The ZnO film displayed a better resistance to acidic dye solution on account of the deposited Zn(2) SnO(4) nanoparticles. Meanwhile, the open-circuit photovoltage was greatly enhanced, which can be ascribed to the increased conduction-band edge of ZnO and inhibited interfacial charge recombination. Although the deposition of Zn(2) SnO(4) decreased the adsorption amounts of N719 dye, the aggregates of Zn(2) SnO(4) with a size of 350-450?nm acted as the effective light-scattering layer, thereby resulting in an improved short-circuit photocurrent. By co-sensitizing 10?μm-thick ZnO film with N719 and D131 dyes, a top efficiency of 4.38?% was achieved under the illumination of one sun (AM?1.5, 100?mW?cm(-2) ).     

Synthesis of silicon nanowires and nanoparticles by arc-discharge in water

Si nanowires of diameters 5-20 nm and nanoparticles of approximately 4 nm were synthesized by a simple arc-discharge method in water. The TEM analysis reveals that the growth direction of the observed Si nanowires is parallel to the {111} crystal planes.     

In-situ preparation and the characterization of Pt/SnO2

To enhance the cycling stability of Pt-based catalysts,the anti-corrosion property of support and the attachment of Pt with support should both get improved.For this purpose,a novel method is presented for in situ preparing Pt/SnO₂.The structure of Pt/ SnO₂ is characterized by X-ray diffraction（XRD） and transmission electron microscopy（TEM）,confirming the homogeneous deposition of Pt on SnO₂.The high resolution TEM（HRTEM） shows the large interfaces between Pt and SnO₂.The TEM photos recorded after accelerated durability tests with Pt/SnO₂ show that the agglomeration and size increment of Pt particles is not severe, indicating the good stability of Pt/SnO₂.The electrochemical active surface area（EAS） of Pt/SnO₂ keeps increasing during the 1000 cycles of cyclic voltammetric（CV） sweeping in H₂SO₄,while the EAS decayed by 35%when mixing Pt/SnO₂ with carbon nanotubes（CNTs）,indicating the superior anti-corrosion property of SnO₂ in contrast to CNTs.     

Zn_2SnO_4纳米材料制备及光致发光特性

以ZnO、SnO2和活性炭的混合物为原料,通过碳热还原热蒸发法无催化剂成功制备出Zn2SnO4纳米材料.借助X射线衍射仪(XRD)、拉曼光谱和扫描电子显微镜(SEM)对样品物相和形貌进行了表征,结果显示样品为面心立方结构的Zn2SnO4纳米链状棒,同时含有少量的ZnO物相.利用X射线光电子能谱(XPS)对Zn2SnO4样品表面各元素的化学状态及相互作用方式进行了测试,结果表明:样品中Zn和Sn分别是以+2价和+4价氧化态形式存在,其中Zn2p3/2电子有两个结合能,分别来自ZnO和Zn2SnO4,Zn2SnO4中Sn4+占据不同的格点位置.室温下光致发光谱(PL)结果显示,样品在紫外区域(320-450nm)和可见区域存在很强的发光带,其中紫外区域的宽发光带,经过高斯拟合可分为358和385nm两个发光峰,与同条件下制备得到的纯ZnO纳米材料发光谱比较,确认358nm发光峰是来自于Zn2SnO4的近带边复合发光.     

纳米SnO2@TiO2包覆催化剂的制备及表征

采用活性层包覆法在自制细SnO2胶体粒子表面包覆TiO2,制备出SnO2@TiO2包覆型复合催化剂,以其对有机磷农药DDVP的降解效果作为评价光催化活性的标准,对制备条件进行了优化,并用XRD、TEM和BET等手段对样品进行了表征,结果表明,SnO2胶体乙醇溶液含水量20％,钛酸丁酯质量分数为34.5％。灼烧温度680℃时制得TiO2含量56.45％的包覆样品SnO2@TiO2为纳米级粒子,且其光催化活性最佳。     

Synthesis and characterization of indium-doped ZnO nanowires with periodical single-twin structures

In-doped ZnO (IZO) nanowires have been synthesized by a thermal evaporation method. The morphology and microstructure of the IZO nanowires have been extensively investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). The products in general contain several kinds of nanowires. In this work, a remarkable type of IZO zigzag nanowire with a periodical twinning structure has been investigated by transmission electron microscopy (TEM). HRTEM observation reveals that this type of IZO nanowire has an uncommonly observed zinc blend crystal structure. These nanowires, with a diameter about 100 nm, grow along the [111] direction with a well-defined twinning relationship and a well-coherent lattice across the boundary. In addition, an IZO nanodendrite structure was also observed in our work. A growth model based on the vapor-liquid-solid mechanism is proposed for interpreting the growth of zigzag nanowires in our work. Due to the heavy doping of In, the emission peak in photoluminescence spectra has red-shifted as well as broadened seriously.     

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.     

纳米SnO2@TiO2的制备及其光催化性能

以SnCl4和Ti(OBu)4为原料,采用活性层包覆法制备了SnO2@TiO2包覆型复合光催化剂,并用XPS、IR、XRD、TEM和BET等手段进行了表征,以二甲基二氯乙烯基磷酸酯（简称DDVP）稀释液为模拟废水,考察了SnO2@TiO2的光催化活性及降解液初始浓度对反应动力学的影响.结果表明：包覆粒子由锐钛矿型TiO2和金红石型SnO2组成;与纯SnO2、TiO2相比,SnO2@TiO2包覆粒子的光催化活性明显提高,DDVP稀释液被光催化降解属于零级反应,但反应表观速率常数与降解液初始浓度成正比.     

纳米SnO_2@TiO_2的制备及其光催化性能

SnCl4和 Ti(OBu)4为原料,采用活性层包覆法制备了 SnO2@TiO2包覆型复合光催化剂,并用 XPS、 IR、 XRD、 TEM和 BET等手段进行了表征,以二甲基二氯乙烯基磷酸酯（简称 DDVP）稀释液为模拟废水,考察了 SnO2@TiO2的光催化活性及降解液初始浓度对反应动力学的影响 .结果表明：包覆粒子由锐钛矿型 TiO2和金红石型 SnO2组成;与纯 SnO2、 TiO2相比, SnO2@TiO2包覆粒子的光催化活性明显提高, DDVP稀释液被光催化降解属于零级反应,但反应表观速率常数与降解液初始浓度成正比 .