Hierarchical ZnO microrods: synthesis,structure, optical and photocatalytic properties

Hierarchical ZnO microrods have been prepared by cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at low temperature. Sheetlike or fluffy ZnO nanostructures have been developed in a large density on the surface of the microrods. The ZnO cores grow preferentially along [001]; the nanosheets are single crystalline and grow in two dimensions along the [001] and [120] directions. The formation of hierarchical structures has been attributed to the presence of CTAB in the solution, which facilitates the secondary nucleation and growth. The nanosheet-covered hierarchical microrods have been analyzed by Raman and photoluminescence spectroscopy, and they exhibit a blue emission at 465 nm and a strong orange emission at 640 nm. Photocatalytic activities of the products have been examined, and the nanosheet-covered hierarchical microrods display the best activity in photodegradation of phenol due to their unique surface features and high surface area.     

纳米ZnO的表面化学修饰及其分析表征

采用水溶性羟丙基甲基纤维素HPMC对无机纳米ZnO粒子进行物理吸附处理 ,获得了核为无机纳米ZnO ,外壳为水溶性高分子HPMC的粒子。然后在其上进行了甲基丙烯酸甲酯的接枝聚合。采用红外光谱、差热分析的方法对复合粒子进行了表征 ,并采用透射电镜观察了粒子的形貌。红外光谱表明在纳米ZnO的表面吸附了HPMC并接枝了PMMA ,差热分析表明HPMC ,HPMC g PMMA和ZnO/HPMC g PMMA的热稳定性逐渐提高 ,透射电镜观察表明 ,在纳米ZnO的表面粘附了一层聚合物 ,成功地实现了纳米粒子的表面修饰。     

纳米Ag颗粒复合薄膜的制备及其吸收特性

利用磁控溅射分层制备Ag和SiO₂薄膜,通过快速热处理,使Ag颗粒富集在复合薄膜的表面.研究了Ag膜层厚度、退火时间、退火温度和退火方式对Ag颗粒形貌的影响,以及Ag颗粒致密度对其共振吸收的影响.结果表明:通过控制每层Ag膜的厚度,可有效控制Ag颗粒形貌.当每层金属为2 nm、退火温度为500 ℃时,形成的颗粒粒径大小均匀且致密度较高.通过间断退火可有效降低Ag颗粒的粒径.发现Ag颗粒表面等离子共振吸收并没有随颗粒粒径的减小而明显降低,甚至提高.这和以往的报道不同.通过深入研究金属颗粒表面等离子体产生机理,发现其表面等离子共振吸收增强的原因是致密度较高的颗粒表面能级与费米能级差值较大,Ag颗粒内部的电子向颗粒表面迁移越多,形成新的费米能级E'_F的电子数就越多,表面等离子共振吸收就越强.最终得出了金属颗粒共振吸收不单纯依赖于金属粒径、和颗粒的致密度也有很大关系的结论.     

SERS study on surface chain geometry of atactic poly (methyl methacrylate) film and nanosphere

The surface chain geometry of atactic poly (methyl methacrylate) (a‐PMMA) film and nanosphere (NS) was revealed by surface‐enhanced Raman scattering (SERS) spectra. The Ag nanoparticles and nanoplates were prepared by electrochemical deposition and chemical synthesis for SERS substrates. The experimental results suggested that the molecular chain axis of a‐PMMA film adopted a trans‐conformation on bonding to Ag surface ascribed to the short‐range chemical (CHEM) effect according to the SERS selection rules. However, for the well‐coated monolayer of a‐PMMA NSs, the α‐CH₃ in polymer chains stood vertically to the Ag surface due to the giant local electromagnetic effect, then the chain conformation presented in the interface between a‐PMMA NSs and Ag metal was adopted the opposite orientation compared with a‐PMMA film. The Raman enhancement of the Ag nanoparticles was more prominent than that of the Ag nanoplates due to the free energies of face‐centered cubic crystal faces in nanoparticles, but the single crystals with (111) plane of Ag nanoplates could improve the stability of SERS signals when the annealed temperature was above T_g of a‐PMMA NSs. The present work can provide some useful information of surface chain geometry and conformation of NSs for designing various materials with well‐defined structure via a‐PMMA NSs template. Copyright © 2013 John Wiley & Sons, Ltd.     

Luminescence enhancement of ZnO nanoparticles on metal surface

We have studied luminescence enhancement of zinc oxide (ZnO) nanoparticles with the average size of 30 nm on several metal surfaces at low temperatures. Bandedge luminescence originated from bound exciton (BE) annihilation is observed at 3.360 eV, and strongly depends on the kind and surface roughness of metal. The luminescence intensity is about 10 times larger for Ag surface than that for quartz surface. Furthermore, the luminescence increases remarkably when the roughness of Ag surface is almost the same as the particle size. The intensity ratio of the fast decay component to the slow one decreases for Ag surface compared with quartz. These results suggest that the luminescence enhancement is partially attributed to suppressing of the nonradiative recombination process in ZnO nanoparticles on metal surface.     

反相微乳液模板原位聚合制备纳米氯化银/聚甲基丙烯酸甲酯及其结构表征

用甲基丙烯酸甲酯 (MMA)作油相 ,反相胶束微乳液作为模板 ,制备了纳米氯化银 (AgCl)粒子 ,再进行原位聚合制备了纳米氯化银 /聚甲基丙烯酸甲酯 (AgCl/PMMA)复合材料 .透射电镜 (TEM )分析表明 ,纳米AgCl的尺寸为 2 0～ 80nm .扫描电镜 (SEM )测试表明纳米AgCl粒子均匀地存在于PMMA基材中 .红外分析证明 ,胶束中水和表面活性剂AOT的羰基在MMA聚合后微观环境发生变化 ,纳米粒子同聚合物之间有吸附行为 .动态力学 (DMTA)分析复合材料 ,发现纳米AgCl粒子与聚合物之间存在强烈相互作用 ,形成了中间相层 (interphaselayer) ,改变了聚合物的动态力学性能 .     

Preparation of Organic–Inorganic Multifunctional Nanocomposite Coating via Sol-Gel Routes

The inorganic–organic nanocomposite coatings are prepared on poly(methyl methacrylate) (PMMA) substrate by the spinning technique which involves incorporating homogeneously nanosized ZnO particle into the molecular inorganic–organic hybrid matrices. The hybrid matrices are derived from tetraethoxyasilane (TEOS) and 3-glycidoxypropyltrimethoxyailane (GLYMO). To avoid the destruction of the polymer structure caused by ZnO and modify the interface between nanoparticles and organic groups, ZnO was first surface-coated with SiO₂ from hydrolyzed TEOS using ammonia water as catalyst. The coatings thus obtained are dense, flexible, abrasion resistant and UV absorbent.     

Effect of some amines,dodecylamine (DDA) and hexadecyldimethylamine (DMHA), on the formation of ZnO nanorods synthesized by hydrothermal route

In this paper, we try to study the effect of two different ionic and nonionic amines dodecylamine (DDA) and hexadecyldimethylamine (DMHA) considered as weak bases and surfactant on the growth of ZnO nanorods using hydrothermal synthesis technique. The self-assembly of oriented attachment (OA) of ZnO nano- and microrods has been successfully obtained by this technique at temperatures greater than 150?°C. The ZnO nano/microrods were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman scattering spectroscopy, Fourier transform infrared (FTIR) and photoluminescence. The XRD measurements show that ZnO prepared by DDA amine presents small grain size in comparison to ZnO obtained from DMHA amine. From SEM characterization, we show that DDA amine has a great effect on the OA of several homogenous ZnO microrods building blocks. The growth process is explained by the formation of ZnO OA in microstructures scale which is depending on ionic character of amines. Optic measurements (Raman, FTIR and photoluminescence) are presented and commented.     

Quantum mechanics simulation and experimental study of adhesive interaction and aggregation of carbon-silicate nanoparticles—reinforcing fillers of polymer composites

Nanoparticles are widely used as polymer composite-reinforcing additives—fillers. Understanding the interaction mechanisms and regularities responsible for nanoparticle aggregation is of great significance for elucidating the nature of reinforcing of polymer composites. The paper reports on quantum mechanics calculations and full-scale experimental study of adhesive interaction of carbon and silicate adsorption complexes (nanomodels of active filler particles of polymer composites). The quantum mechanics approach allowed describing the adhesive properties of particle aggregates reasoning from nanoscopic structure of their surface. The quantum mechanics data were checked for adequacy on schungite—a natural mineral containing carbon and silicate. Schungite microparticles were milled to nanosizes by colloidal grinding in various disperse liquid media (alcohol, acetone, water) and the structure and properties of aggregated schungite micro- and nanoparticles were studied; fractal analysis of their surface was performed. It is found that smaller aggregates of silicate and carbon particles with higher surface fractal dimension are formed in colloidal grinding with small molecular sizes of disperse media (in our case, ethanol or methanol) and this agrees with the data predicted by quantum mechanics calculations.     

Pulsed laser deposition of polymer-metal nanocomposites

Different polymer-metal nanocomposites, metal clusters on a polymer surface and for the first time also polymer/metal multilayers, were pulsed laser deposited at a wavelength of 248 nm. Poly(methyl methacrylate) (PMMA) and Bisphenol A dimeth-acrylate (BisDMA), which strongly differ in their hardness of 3 and 180 N/mm², respectively, were taken as polymer components. Metals Ag and Cu were chosen because of their different reactivity to polymers. When depositing Ag on PMMA, spherical clusters are formed due to high diffusion and total coalescence. For Cu, much smaller grains with partially elongated shapes occur because of lower diffusivity and incomplete coalescence. Compared to the results on the soft PMMA, the clusters formed on the harder BisDMA are much larger due to higher diffusivity on this underlayer. In PMMA/Cu multilayers, wavy layered structures and buckling is observed due to relaxation of compressive stress in the Cu layers. Smooth Cu layers with higher thicknesses can only be obtained, when the hardness of the polymer is sufficiently high, as in the case of BisDMA/Cu multilayers.     

溅射法制备Ag/Ag2O超微粒子的分析

用Ｘ射线衍射、Ｘ射线光电子能谱、透射电子显微镜和差示扫描量热法对溅射法制备的Ａｇ超微粒子的晶体学结构、表面组成、微粒形态和热力学性质进行了分析。结果表明，所制备的微粒为内部为Ａｇ、表面为Ａｇ₂Ｏ的两相微粒，以及单一的Ａｇ₂Ｏ微粒，粒径在１０ｎｍ以上的微粒没有确定的外形，粒径在１０ｎｍ以下的微粒为球形。微粒有不同于块体金属Ａｇ的异常热效应。到４０天时，沉积在碳膜上的Ａｇ，Ａｇ₂Ｏ两相微粒有一部份还原形成了单一的金属Ａｇ超微粒子。 关键词：     

Template-free hydrothermal synthesis of ZnO microrods for gas sensor application

Zinc oxide microrods with controlled diameter were prepared without the addition of template and additive by a simple hydrothermal route only using Zn(CH₃COO)₂·2H₂O as a precursor. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and electron diffraction (ED). The crystal structure of prepared ZnO microrods is hexagonal phase polycrystalline with zincite structure. With the increase of the precursor concentration from 0.05 M to 0.6 M, the diameter of the ZnO microrods increased from 1 μm to 5 μm. A localized oriented attachment mechanism was prepared to account for the formation of ZnO microrods. The gas-sensing performance experiments indicated that the prepared ZnO microrods exhibited highly sensitive, selective gas-sensing properties, and good stability to acetone vapor. The response and recovery time of ZnO-based gas sensor to 100 ppm acetone vapor are 12 s and 18 s, respectively. The mechanism of the ZnO-based sensor was investigated.     

Effects of the embedding kinetics on the surface nano-morphology of nano-grained Au and Ag films on PS and PMMA layers annealed above the glass transition temperature

The morphology evolution of nano-grained Ag and Au films deposited on polystyrene (PS) and poly(methyl methacrylate) (PMMA) polymeric layers were studied, using the atomic force microscopy technique, when annealed above the polymers glass transition temperature. The main effects on the morphology changes were identified with those concerning the embedding kinetics of the Ag and Au nanoparticles in the PS or PMMA layers. The embedding process of the nanoparticles follows as a consequence of the long-range mobility of the polymeric chains above the glass transition temperature. In particular, the dependence of the nanoparticles mean height and surface density on the annealing time at various temperatures was quantified. The analyses of these behaviors allowed us: (1) to distinguish the overall embedding process in a first stage in which a thin wetting layer of the polymer coats the nanoparticles followed by a true embedding process of the nanoparticles into the polymer layer; (2) to evaluate the characteristic coating time for the Ag and Au nanoparticles in the PS and PMMA in the first stage; (3) to evaluate the characteristic embedding velocity for the Ag and Au nanoparticles in the PS and PMMA in the second stage; (4) to derive the activation energies for the embedding process of the Ag and Au nanoparticles in PS and PMMA; (5) to identify the embedding statistics of the Ag and Au nanoparticles in PS and PMMA with a “failure” Weibull statistics.     

高质量ZnO微米棒的制备及其光学性质

利用水热法制备ZnO微米棒。醋酸镁[Mg(CH3COO)2.4H2O]、醋酸锌[Zn(CH3COO)2.2H2O]和六次甲基四胺(C6H12N4)以一定比例配置成反应溶液,把反应溶液加热到90℃,反应时间为24h,能够在硅衬底上生长高质量的ZnO微米棒。用扫描电镜(SEM)和X射线衍射仪对ZnO微米棒的晶体结构和表面形貌进行了分析,结果表明,样品为细长条棒状结构,呈现六方纤锌矿结构,长径比可达10∶1,并且在[002]方向择优生长。在样品中并未发现镁离子,它有可能扮演着催化剂的角色。对ZnO微米棒的光致发光性能进行测量,由PL光谱分析可知,样品在384nm处有一个紫外发光峰,半峰全宽为13nm,紫外发光峰强度比可见发光峰强度大的多,样品的质量较好。     

Shuttle-like ZnO nano/microrods: Facile synthesis, optical characterization and high formaldehyde sensing properties

Shuttle-like ZnO nano/microrods were successfully synthesized via a low temperature (80 °C), “green” (without any organic solvent or surfactant) and simple hydrothermal process in the solution of zinc chloride and ammonia water. X-ray diffraction and Raman spectroscopy indicated that the ZnO nano/microrods are a well-crystallized hexagonal wurtzite structure. Yet photoluminescence analysis showed that abundant intrinsic defects (52.97% electron donor defects and 45.49% electron acceptor defects) exist on the surface of ZnO crystals. Gas sensors based on the shuttle-like ZnO nano/microrods exhibited high sensitivity, rapid response-recovery and good selectivity to formaldehyde in the range of 10-1000 ppm at an optimum operating temperature of 400 °C. Through applying linear fitting to the plot of sensitivity versus formaldehyde concentration in logarithmic forms, the chemisorbed oxygen species on the ZnO surface were found to be O²⁻ (highly active among O₂, O₂⁻ and O⁻ species). Notably, formaldehyde can be easily distinguished from acetaldehyde with a selectivity of about 3. The high formaldehyde sensitivity is mainly attributed to the synergistic effect of abundant electron donor defects (52.97%) and highly active oxidants (surface adsorbed O²⁻ species) co-existed on the surfaces of ZnO.     

Stabilisation of monometallic nanoparticles by polyamide 6

Monometallic metal nanoparticles (Pd, Pt, Ag and Ru) stabilised by polyamide 6 (PA6) have been prepared via a polyol process sustained by microwave irradiation. PA6 proved to be a good stabiliser, being spherical particles with little dimensional dispersion identified by transmission electron microscopy. Due to the inclusion of the metals in small amount (up to 3% w/w) into the macromolecular lattice, the polymer underwent changes in thermal behaviour, which, however, do not impair the possibility to process the material. The observed changes in differential scanning calorimetry curves indicated that metal containing PA6 materials are less crystalline and ordered than pure PA6. This was confirmed by diffuse reflectance infrared Fourier transform analysis, which indicated that the introduction of the metal nanoparticles lowered the conformational order of the polymer matrix and partly disrupted the hydrogen bond network of the polyamide.     

Solvothermal synthesis,photoluminescence and photocatalytic properties of pencil-like ZnO microrods

Pencil-like ZnO microrods was synthesized via a simple solvothermal process in an aqueous solution of ethylenediamine and ethanolamine. The as-prepared ZnO was characterized by X-ray powder diffraction, field-emission scanning electron microscopy, room temperature photoluminescence spectra and UV–vis absorption spectra. The results indicated that ZnO microrods had the length in the range of 1.3–25 μm. The photocatalytic activity was studied by degradation of methylene blue (MB) aqueous solution, which showed that the as-prepared ZnO microrods possessed a high photocatalytic activity. The formation mechanism of the pencil-like ZnO was also investigated based on the experimental results.     

银纳米颗粒阵列的表面增强拉曼散射效应研究

利用具有高密度拉曼热点的金属纳米结构作为表面增强拉曼散射(SERS)基底,可以显著增强吸附分子的拉曼信号.本文通过阳极氧化铝模板辅助电化学法沉积制备了高密度银(Ag)纳米颗粒阵列;利用扫描电子显微镜和反射谱表征了样品的结构形貌和表面等离激元特性;用1, 4-苯二硫醇(1, 4-BDT)为拉曼探针分子,研究了Ag纳米颗粒阵列的SERS效应.通过优化沉积时间,制备出高SERS探测灵敏度的Ag纳米颗粒阵列,检测极限可达10~(-13)mol/L;时域有限差分法模拟结果证实了纳米颗粒间存在强的等离激元耦合作用,且发现纳米颗粒底端的局域场增强更大.研究结果表明Ag纳米颗粒阵列可作为高效的SERS基底.     

常压化学气相沉积法在Ag/Si(111)模板上生长ZnO薄膜及其性能研究

在Si衬底上利用磁控溅射的方法沉积1.5 nm厚度的Ag膜用以阻挡Si衬底被氧化。采用常压金属有机化学气相沉积法(MOVCD),在Ag/Si(111)衬底上成功地生长出马赛克结构的ZnO薄膜。用光学显微镜观察表面形貌,结果显示有带晶向特征的微裂纹,裂纹密度为100 cm-1。依据X射线晶体衍射的结果,薄膜结晶质量良好,呈C轴高度择优取向。用双晶X射线衍射得到(002)面的ω扫描半峰宽为1.37°。温度10 K时光致发光谱(PL)观察到自由激子、束缚激子发射及它们的声子伴线。结果表明,金属有机化学气相沉积法方法在Si(111)衬底上制备ZnO薄膜时,Ag是一种有效的缓冲层。     

Automatic microcircuit formation based on gold-coated SU-8 microrods via dielectrophoresis

To explore the application of the characteristics of metallic microparticles, alternating current electric trapping of the SU-8 microrods coated with a thin gold layer by the chemical approach is investigated. Positive dielectrophoresis is used to absorb the gold-coated SU-8 microrods at the edge of the parallel electrodes, thereby forming chains to connect the electrodes. This is a fast automatic microcircuit formation process. Moreover, a non-charged molecule is modified on the surface of the gold-coated SU-8 microrod, and the modified microrods are controlled by the alternating electric field to form a number of chains. The different chains between the parallel electrodes consist of various parallel circuits. In order to compare these chains with different electric surfaces, the impedances of the metallic and modified microrods are measured and compared, and the results show that the gold-coated microrods act as pure resistors, while the microrods functionalized by a non-charged molecule behave as good capacitors.