传感器用镓掺杂氧化锌纳米盘/纳米花状结构催化剂的制备及表面表征

采用简便的旋涂过程和一步水热法在压电基片上制备了Ga掺杂的ZnO纳米薄膜(GZO)。在水热处理过程中,通过添加不同的聚合物可形成纳米盘和纳米花状形貌的薄膜。采用场发射扫描电镜(Fe-SEM)、X射线衍射(XRD)和Raman光谱表征了样品的形貌、微结构和组成。 XRD和FE-SEM结果证明,在AlN/Si压电基片上形成的纳米盘、纳米棒和纳米花状GZO均为纤维锌矿相。采用浸渍法进一步在所制GZO样品上固定了绿色的荧光蛋白质(GFP)。运用原子力显微镜和荧光光谱分析了GFP与GZO表面结合的性质,考察了其用于传感器和生物成像技术的可行性。痕量GFP的固定使该材料产生荧光响应,表明其用于紫外光传感器时具有较好活性。     

Structural stability and phase transitions in WO3 thin films

Tungsten oxide (WO3) thin films have been produced by KrF excimer laser (lambda = 248 nm) ablation of bulk ceramic WO3 targets. The crystal structure, surface morphology, chemical composition, and structural stability of the WO3 thin films have been studied in detail. Characterization of freshly grown WO3 thin films has been performed using X-ray diffraction (XRD), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy (RS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) measurements. The results indicate that the freshly grown WO3 thin films are nearly stoichiometric and well crystallized as monoclinic WO3. The surface morphology of the resulting WO3 thin film has grains of approximately 60 nm in size with a root-mean-square (rms) surface roughness of 10 nm. The phase transformations in the WO3 thin films were investigated by annealing in the TEM column at 30-500 degrees C. The phase transitions in the WO3 thin films occur in sequence as the temperature is increased: monoclinic --> orthorhombic --> hexagonal. Distortion and tilting of the WO6 octahedra occurs with the phase transitions and significantly affects the electronic properties and, hence, the electrochemical device applications of WO3.     

不同形貌WO3的水热合成及其在水处理中的应用研究

三氧化钨(WO₃)以其较窄的带隙,成为继二氧化钛(TiO₂)之后颇具发展潜力的n型半导体光催化剂.本文采用水热合成法,通过调控反应参数,如原料组成、沉淀时间等,合成了不同形貌和晶型的WO₃;采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FT-IR)、氮气吸附-脱附(N₂ adsorption-desorption)等表征了所合成的WO₃产品,发现原料组成、沉淀时间等条件对WO₃的晶型和形貌都有影响;研究了所合成的WO₃产品去除水中亚甲基蓝染料污染物的性能,结果表明,所制备的WO₃对水中亚甲基蓝具有较好的去除效果,去除率可达97%.     

Polymer nanodisks by collapse of nanocapsules

It is an important challenge to make disk-like polymeric nanostructures. Herein we report a facile method for preparing polymer nanodisks by self-collapse of nanocapsules self-assembled from a statistical copolymer after partial hydrolysis. We find that partial hydrolysis of the statistical copolymer is crucial for the formation of nanodisks as it affords a suitable rigidity for the membrane of nanocapsules. The nanodisk structure has been confirmed by transmission electron microscopy(TEM), scanning electron microscopy(SEM) and atomic force microscopy(AFM) studies with a thickness of 6.3±0.2 nm. Overall, our results demonstrated a new method for making disk-like nano-objects.     

Highly sensitive WO3 hollow-sphere gas sensors

In this paper, we describe how WO(3) hollow spheres have been synthesized in solution phase by the controlled hydrolysis of WCl(6) using novel carbon microspheres as the templates. All of the products were characterized by X-ray powder diffraction (XRD), scanning electronic microscopy (SEM), and transmission electron microscopy (TEM). The as-synthesized spheres had large diameters of about 400 nm and thin shells of about 30 nm composed of numerous small nanocrystals. Prompted by the porous structure and small crystal size of the shell wall, we constructed WO(3) hollow-sphere gas sensors and found that these sensors had good sensitivity to alcohol, acetone, CS(2), and other organic gases.     

Low-voltage anodized TiO<Subscript>2</Subscript> nanostructures studied by alternate current electrochemical microscopy and photoelectrochemical measurements

This paper presents the characterization of TiO₂ nanostructures obtained by low-voltage anodization using alternate current electrochemical microscopy (AC-SECM) and photoelectrochemical (PEC) measurements. TiO₂ nanostructures were obtained from the exposure of titanium foils to several aqueous acidic solutions of hydrofluoric acid + phosphoric acid at potentials of 1 to 3 V. Scanning electron microscopy, X ray diffraction, and atomic force microscopy studies evidence the formation of a thin porous amorphous layer (<600 nm) with pore size in the range of 200–1,000 nm. By AC-SECM studies at different bias, we were able to confirm the unambiguous semiconducting properties of as-obtained porous titania films, as well as differences in surface roughness and conductivity in specimens obtained at both potentials. The difference in conductivity persists in air annealed samples, as demonstrated by electrochemical impedance spectroscopy and PEC measurements. Specimens obtained at 3 V show lower photocurrent and dark current than those obtained at 1 V, regardless of their larger conductivity, and we proposed it is due to differences on the oxide layer formed at the pore bottom.     

Solventless synthesis of monodisperse Cu2S nanorods, nanodisks, and nanoplatelets

Cu(2)S nanocrystals with disklike morphologies were synthesized by the solventless thermolysis of a copper alkylthiolate molecular precursor. The nanodisks ranged from circular to hexagonal prisms from 3 to 150 nm in diameter and 3 to 12 nm in thickness depending on the growth conditions. High resolution transmission electron microscopy (HRTEM) revealed the high chalcocite (hexagonal) crystal structure oriented with the c-axis ([001] direction) orthogonal to the favored growth direction. This disk morphology is thermodynamically favored as it allows the extension of the higher energy [100] and [110] surfaces with respect to the [001] planes. The hexagonal prism morphology also appears to relate to increased C-S bond cleavage of adsorbed dodecanethiol along the more energetic [100] facets relative to [001] facets. Monodisperse Cu(2)S nanodisks self-assemble into ribbons of stacked platelets. This solventless approach provides a new technique to synthesize anisotropic metal chalcogenide nanostructures with shapes that depend on both the face-sensitive thermodynamic surface energy and the surface reactivity.     

WO3/TiO2 复合纤维的制备及储能光催化性能

以钛酸正丁酯为前驱体, 采用静电纺丝技术制得了纯锐钛矿TiO2纤维, 并以其为基质, 通过水热法制备了具有异质结构的WO3/TiO2复合纤维. 利用X射线衍射仪(XRD)、 扫描电子显微镜(SEM)、 能量色散光谱仪(EDS)、 透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)等对样品的结构和形貌进行了表征. 以罗丹明B的脱色降解为模型反应, 考察了样品的光催化性能和储能光催化性能. 结果表明, 花状WO3微球包裹在TiO2纤维上, 得到了具有异质结构的WO3/TiO2复合纤维光催化剂. WO3与TiO2复合有利于光生载流子的输运和分离, 增强了体系的量子效率, 提高了光催化活性. WO3/TiO2 复合纤维经光照处理后, 在黑暗条件下显示出储能光催化特性.     

Large-scale synthesis of tungsten oxide nanofibers by electrospinning

We show in this communication that large-scale synthesis of orthorhombic WO3 nanofibers can be obtained via a simple electrospinning method. The morphology and the crystal structure are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), FTIR, X-ray diffraction patterns (XRD) and X-ray photoelectron spectra (XPS) spectra. SEM and TEM images showed that the diameter of the obtained WO3 nanofibers is between 100 and 500 nm. The structure of the obtained WO3 nanofibers was characterized by FTIR, XRD, and XPS spectra. The photoluminescence of the obtained WO3 nanofibers were also investigated.     

海藻酸锌纤维热降解法制备氧化锌纳米结构

采用天然高分子海藻酸钠为原料, 以氯化锌水溶液为凝固浴, 通过湿法纺丝技术成功制备了海藻酸锌(Alg-Zn)纤维.通过在空气中不同温度下对所得海藻酸锌纤维进行热处理, 得到了多种ZnO纳米结构. 利用热失重分析(TG)、X射线衍射(XRD)、电子能量损失谱(EELS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)等手段对产物的组成、形貌和微观结构进行了详细表征. 结果表明, 焙烧温度和时间对所得ZnO纳米结构的尺寸和形貌具有重要影响; 800 ℃下热处理24 h以上可以得到直径约为120 nm的ZnO纳米棒. 通过仔细考察不同热处理时间得到的ZnO纳米结构, 提出了在焙烧条件下ZnO纳米棒的生长机理.     

Fabrication of symmetric hierarchical hollow PbS microcrystals via a facile solvothermal process

Symmetric hierarchical hollow PbS structures consisting of nanowalls were successfully fabricated by a facile solvothermal process in ethylenediamine at 120 degrees C for 12 h, employing lead acetate trihydrate and dithizone as precursors; the thickness of the nanowalls is about 80 nm. No surfactants or other templates were used in the process. The synthesized product was characterized by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), ultraviolet-visible spectrometer (UV-vis), near-infrared absorption spectroscopy (near-IR), and fluorescence spectrophotometer. The effect of the reaction conditions on the size and morphologies of PbS structures was investigated. The results show that the temperatures, solvent, and sulfur sources are crucial factors on the morphologies and sizes of the symmetric hierarchical hollow PbS microcrystals. A possible growth mechanism of hierarchical hollow PbS structures is presented. UV-vis absorption spectrum holds a weak peak at 253 nm; the near-infrared absorption spectrum of PbS microcrystals has the two absorption peaks centered at 9613 cm(-1) (1040 nm) and 6771 cm(-1) (1477 nm), showing a blue shift compared with the bulk PbS (approximately 3020 nm). And the fluorescence spectrum of PbS microcrystals consists of an emission peak with a maximum at 305 nm. These PbS microcrystals may have potential applications in the fundamental study of nanostructures as well as fabricating nanodevices.     

General solution route for nanoplates of hexagonal oxide or hydroxide

A citric acid (CA)-assisted hydrothermal process was used to prepare Fe2O3 hexagonal nanoplates with a lateral size of about 100 nm. In addition, the hexagonal nanoplates of Co(OH)2, MnCO3, and Ni(OH)2 were also synthesized by this route, indicative of the universality of the solution route presented herein. The morphologies and structures of the synthesized platelike nanostructures have been characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), and X-ray diffraction (XRD). Furthermore, the mechanism for the formation of the platelike nanostructures has been preliminarily discussed. It is believed that the capping molecule of CA, which inhibits crystal growth along the <001> direction due to its chelating effect, plays a critical role in the hydrothermal formation of the nanoplates.     

微波热解法制备Cu/Cu2O纳米材料

在二乙二醇溶剂体系中利用微波介电加热分解醋酸铜前体,进一步还原得到Cu2O和Cu纳米粒子以及Cu/Cu2O核壳结构。 采用X射线衍射、透射电子显微镜、扫描电子显微镜和紫外吸收光谱测试技术对产物的形貌、结构和组成进行了研究,结果表明,得到的Cu/Cu2O核壳结构直径为500 nm左右。 对比实验研究了不同聚合度乙二醇系列溶剂、反应时间以及表面活性剂或配位剂对产物形貌、组成的影响,表明低聚合度乙二醇和长的反应时间有利于醋酸铜还原形成铜。     

G1 dendrimers-mediated evolution of silver nanostructures from nanoparticles to solid spheres

With the control of G1 poly(amidoamine) (PAMAM), an evolutionary course of stable colloidal silver from discrete nanoparticles to solid spheres through ultraviolet irradiation reduction of silver nitrate solutions was observed by transmission electron microscopy (TEM). The morphologies of the products depend on the Ag+ concentration. A mechanism of globular assembly was put forward to interpret the evolution of the nanostructures. Powder X-ray diffraction (XRD), electron diffraction (ED) patterns, and X-ray photoelectron spectroscopy (XPS) indicate the presence of cubic symmetry silver. XPS and Fourier transform infrared (FT-IR) spectroscopy confirm that dendrimers have participated in the stabilization and control of Ag nanostructures. In the UV-vis spectra, the intense surface plasmons are centered at 425 and 430 nm corresponding to the shapes of dots and solid spheres, respectively. The solid spheres exhibit excellent catalytic efficiency on the reduction of 2,7-dicholoroflurescein (DCF).     

Straight and thin ZnO nanorods: hectogram-scale synthesis at low temperature and cathodoluminescence

A novel seed-assisted chemical reaction at 95 degrees C has been employed to synthesize uniform, straight, thin, and single-crystalline ZnO nanorods on a hectogram scale. The molar ratio of ZnO seed and zinc source plays a critical role in the preparation of thin ZnO nanorods. At a low molar ratio of ZnO seed and zinc source, javelin-like ZnO nanorods consisting of thin ZnO nanorods with a diameter of 100 nm and thick ZnO nanorods with a diameter of 200 nm have been obtained. In contrast, straight ZnO nanorods with a diameter of about 20 nm have been prepared. Dispersants such as poly(vinyl alcohol) act spatial obstructors to control the length of ZnO nanorods. The morphology, structure, and optical property of the ZnO nanostructures prepared under different conditions have been characterized by transmission electron microscopy, field emission scanning electron microscopy, X-ray powder diffraction, high-resolution transmission electron microscopy, and cathodoluminescence. The formation mechanisms for the synthesized nanostructures with different morphologies have been phenomenologically presented.     

A novel tungsten trioxide (WO3)/ITO porous nanocomposite for enhanced photo-catalytic water splitting

Hybrid nanocomposite films of ITO-coated, self-assembled porous nanostructures of tungsten trioxide (WO(3)) were fabricated using electrochemical anodization and sputtering. The morphology and chemical nature of the porous nanostructures were studied by Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS), respectively. The photoelectrochemical (PEC) properties of WO(3) porous nanostructures were studied in various alkaline electrolytes and compared with those of titania nanotubes. A new type of alkaline electrolyte containing a mixture of NaOH and KOH was proposed for the first time to the best of our knowledge and shown to improve the photocurrent response of the photoanodes. Here, we show that both the WO(3) nanostructures and titania nanotubes (used for comparison) exhibit superior photocurrent response in the mixture of NaOH and KOH than in other alkaline electrolytes. The WO(3) porous nanostructures suffered from surface corrosion resulting in a huge reduction in the photocurrent density as a function of time in the alkaline electrolytes. However, with a protective coating of ITO (100 nm), the surface corrosion of WO(3) porous nanostructures reduced drastically. A tremendous increase in the photocurrent density of as much as 340% was observed after the ITO was applied to the WO(3) porous nanostructures. The results suggest that the hybrid ITO/WO(3) nanocomposites could be potentially coupled with titania nanotubes in a multi-junction PEC cell to expand the light absorption capability in the solar spectrum for water splitting to generate hydrogen.     

不同形貌ZnO纳米结构的电子显微分析

控制实验合成条件,利用溶胶-凝胶法和化学溶液生长法制备出不同形貌的ZnO纳米结构。采用X射线衍射仪(XRD)、扫描电子显微镜( SEM) 以及透射电子显微镜(TEM)等多种测试手段对ZnO纳米结构的微观形态及晶相进行了分析。结果表明:3种ZnO纳米结构形貌虽不同,但均具有Z nO六方纤锌矿晶相结构。ZnO纳米棒和花状ZnO纳米结构为单晶,生长方向均沿(0001)方向。ZnO纳米球则为多晶。     

Pear fruit extract-assisted room-temperature biosynthesis of gold nanoplates

In this paper, a single-step room-temperature biosynthetic route for producing gold nanostructures using pear fruit is reported. The alkaline conditions of the pear fruit extract induced gold nanoparticles with plate-like morphologies. Successfully biosynthesized triangular and hexagonal nanoplates were observed, elegantly assembled with hexagonal gold nanoparticles. Nanostructure size, crystal nature, purity and morphologies were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS) and energy dispersive X-ray analysis (EDAX). The edge lengths of the nanostructures ranged from 200 to 500 nm. Using AFM analysis, the nanohexagons were observed to have a thickness ranging from 12 to 20 nm. The XRD patterns showed a (1 1 1) preferential orientation of the nanostructures. The XPS and EDAX analysis also confirmed the presence of pure-phase Au without any substantial impurities. The preparation of nanostructured gold particles using pear fruit provides an environmentally friendly option, as compared to currently available chemical and/or physical methods.     

Electroless gold island thin films: photoluminescence and thermal transformation to nanoparticle ensembles

Electroless gold island thin films are formed by galvanic replacement of silver reduced onto a tin-sensitized silica surface. A novel approach to create nanoparticle ensembles with tunable particle dimensions, densities, and distributions by thermal transformation of these electroless gold island thin films is presented. Deposition time is adjusted to produce monomodal ensembles of nanoparticles from 9.5 +/- 4.0 to 266 +/- 22 nm at densities from 2.6 x 1011 to 4.3 x 108 particles cm-2. Scanning electron microscopy and atomic force microscopy reveal electroless gold island film structures as well as nanoparticle dimensions, densities, and distributions obtained by watershed analysis. Transmission UV-vis spectroscopy reveals photoluminescent features that suggest ultrathin EL films may be smoother than sputtered Au films. X-ray diffraction shows Au films have predominantly (111) orientation.     

Zn3(OH)2V2O7·2H2O纳米片的水热制备

采用硝酸锌、五氧化二钒和氢氧化钠作为反应物,通过一个简单的CTAB辅助的水热方法制备了Zn3(OH)2V2O7·2H2O纳米片.运用XRD,ICP-AES,FTIR,HRTEM,EDS,FE-SEM对产物的晶相和形貌进行了表征.结果表明CTAB在控制产物的形貌、尺寸分布和自组装过程中起着关键作用.同时我们研究了产物的晶体生长行为和自组装过程.