微波诱导燃烧法合成类花状ZnO纳米材料及其晶体结构、荧光性质研究

以硝酸锌[Zn(NO3)2.6H2O]和尿素[CO(NH2)2]作前驱体,通过微波诱导燃烧技术可控合成具有不同形貌的ZnO纳米晶体,并用热重分析和差热分析进行了研究。对各种生长条件:微波功率,辐射时间和尿素/Zn2+物质的量的比对ZnO纳米晶体形貌的影响作了分析。结果表明:尿素/Zn2+物质的量的比对ZnO纳米材料的形貌具有显著影响。X衍射图表明合成的ZnO纳米结构呈六角形。傅里叶变换红外光谱图中400~500 cm-1处明显的峰为Zn-O的振动峰。ZnO纳米结构的发光光谱在366 nm的带边发射,因缺陷又由许多可见光发射峰组成。用扫描电子显微镜、透射电子显微镜、选区电子衍射研究了花状ZnO纳米结构的增长机理。本方法仅需几分钟就获得的了ZnO纳米结构。     

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。     

氧化锌纳米棒的水热合成及其光催化性能

以分析纯ZnO作为锌源、NaOH为矿化剂、盐酸为反应溶液pH调节剂,利用水热反应制备了花状ZnO纳米棒;采用扫描电子显微镜和X射线衍射仪分析了产物的形貌和结构,考察了水热温度以及Zn2+和OH-浓度比对产物形貌的影响;以甲基橙为目标降解物,采用紫外-可见分光光度计研究了ZnO纳米棒的光催化性能.结果表明,在水热反应温度80℃、Zn2+/OH-浓度比1∶7.5条件下所得ZnO纳米棒呈花状聚合,直径约为200nm,长度约为2μm,具有六方纤锌矿结构.当甲基橙初始浓度为30 mg.L-1、ZnO纳米棒的投放量为1.5g.L-1时,以300W紫外灯照射150min,甲基橙的降解率可达90%.     

Microwave-assisted solution synthesis and photocatalytic activity of Ag nanoparticles supported on ZnO nanostructure flowers

Ag nanoparticles supported on the surface of three-dimensional (3D) flower-like ZnO nanostructure were synthesized by a microwave-assisted solution method. The obtained products were characterized by X-ray diffraction analysis, field-emission scanning electron microscopy, Fourier-transform infrared spectroscopy, Raman spectrophotometry, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. The analytical results confirmed homogeneously distributed Ag nanoparticles supported on the surface of flower-like ZnO nanostructure. The photocatalytic effect of the heterostructure Ag/ZnO nanocomposites was investigated using photodegradation under ultraviolet (UV) light of methylene blue as model dye. The heterostructure Ag/ZnO nanocomposites exhibited much higher photocatalytic activity than pure ZnO flowers. The improved photocatalytic properties are attributed to formation of a Schottky barrier at the metal–semiconductor interface of the Ag/ZnO nanocomposites.     

Effect of 3D ZnO:Fe morphology on the photocatalytic activity under solar irradiation

Nanoparticles, microsphere, hedgehog sphere-like and flower-like ZnO:Fe photocatalysts were prepared by the hydrothermal method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet/visible absorption spectra (UV?CVis). The results show that the ZnO:Fe photocatalysts with different 3D morphologies are a hexagonal wurtzite structure with space group of p63mc. The pH value of the precursor has a great influence on various morphologies of ZnO:Fe photocatalysts. The flower-like and hedgehog sphere-like ZnO:Fe photocatalysts exhibit the high solar photocatalytic behavior on methylene blue (MB). The ZnO:Fe order of photocatalytic activity is as follows: flower?>?hedgehog sphere?>?microsphere?>?nanoparticle. The flower-like ZnO:Fe is optimal, which exhibits the highest degradation rate of 98% for light time of 5?h.     

咪唑类离子液体辅助水热法合成棒状微/纳米ZnO晶体

以醋酸锌和氢氧化钠为原料, 以水和含不同长度烷基链的咪唑类氯盐离子液体的混合物作为反应介质, 采用水热法合成出不同形貌的微/纳米ZnO晶体, 用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对合成的ZnO晶体进行表征. 研究了烷基链长度、 离子液体用量、 反应时间以及反应温度对形成棒状ZnO晶体形貌的影响. 实验结果表明, 所制备的棒状ZnO晶体样品均为六方晶系结构. 在棒状ZnO晶体的制备过程中, 控制反应温度, 选择不同的离子液体及其用量十分重要.     

Various shaped-ZnO nanocrystals via low temperature synthetic methods: Surfactant and pH dependence

ZnO nanocrystals, rod-, carnation-, and flower-like structures, have been synthesized in a high yield through low-temperature synthetic methods. Well-aligned ZnO nanorods having hexagonal wurtzite structure were grown on the ZnO thin films assembled by a spin-coating method. The morphologies of ZnO seed films are affected by pHs of sol–gel solutions, resulting smaller sizes and homogeneous roughness at higher pHs and higher number of spin-coating times. The carnation-like structures, average size of about 2–3 μm, were assembled by tens of uniform ZnO nanosheet petals of ∼50 nm in thickness when a different volume ratio of the precursory solution was used. ZnO nanocrystals on the facets of the compact ZnO nanorods have grown to linear nanorods having an average diameter of ∼500 nm and length of ∼2 μm. Furthermore, a noticeable difference in the growth of ZnO nanocrystals in the presence of various surfactants, polyvinylpyrrolidone, polyvinylsulphonic acid, and polyethyleneimine, has been observed and discussed.     

ZnO微晶的水热合成及形貌控制研究

以Zn(NH3)4(Ac)2为前驱体,不加任何模板剂和表面活性剂,低温下通过改变反应条件(如前驱体浓度、反应时间及反应温度),实现了对ZnO微晶形貌和尺度的有效控制.所得花状、蜂窝状、柱状ZnO用X射线衍射仪和扫描电镜进行了鉴定和表征,并初步探讨了不同形貌ZnO微晶的生长机理.     

Preparation and characterization of zinc oxide nanoflakes using anodization method and their photodegradation activity on methylene blue

In this work, we report the formation of leaf-like ZnO nanoflakes by anodization of zinc foil in a mixture of ammonium sulfate and sodium hydroxide electrolytes under various applied voltage and concentration of sodium hydroxide. The morphology and structure of ZnO nanoflakes were investigated by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. In addition, the photocatalytic activity of the prepared nanoflakes zinc oxide was evaluated in the photodegradation of organic dye methylene blue (MB) solution under UV irradiation. It was found that zinc oxide prepared under high concentration of sodium hydroxide and high voltage showed better performance in the photodegradation of methylene blue.     

三维花状ZnO纳米材料的制备及发光性质

常压下用溶胶凝胶和化学溶液生长两步法在3种不同的衬底上制备出三维花状ZnO纳米材料.采用X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)、选区电子衍射(SAED)、紫外吸收(UV)光谱和光致发光光谱(PL)对样品进行分析,结果表明,花状ZnO的组成单元为沿c轴方向生长的ZnO纳米棒,直径约为100 nm,...     

溶剂热法制备六角锥形ZnO及其光致发光性能

通过乙酸锌和醇溶液反应得到了六角锥形纳米ZnO颗粒, 反应过程中不使用碱溶液和表面活性剂. 利用透射电子显微镜(TEM)、选区电子衍射(SAED)及扫描电子显微镜(SEM)对其形貌和结构进行了表征分析. 结果表明, 此方法制备的ZnO颗粒为单晶, 而且六角锥形ZnO的室温光致发光谱(PL)在378 nm处显示出了单纯的紫外发射峰, 而不是通常报道的可见光区发射, 这也预示着这种特殊结构的纳米ZnO将会成为一种具有良好应用前景的光学材料.     

微观尺度高分子协同组装ZnO纳米片

以醇水混合体系作为反应介质,六水合硝酸锌和尿素为原料,聚乙烯吡咯烷酮(PVP)作为模板剂,经水热过程合成了由纳米片组装的花状微球碱式碳酸锌前驱体,经热处理得到相应的氧化锌(ZnO)产物。采用X射线衍射(XRD)和环境扫描电镜(SEM)对样品进行了表征,结果表明产物为六方纤维矿结构的ZnO,单分散花状微球直径约为2 μm,尺寸均一,组装成微球的纳米片构筑单元厚度为20 nm。红外分析表明PVP与Zn²⁺之间的化学配位作用发生在侧环的内酰基C=O键上的O位与Zn²⁺之间,研究表明PVP用量影响组装过程,在相同实验条件下,用聚乙二醇(PEG)代替PVP的模板作用,得到了粒径较大的纳米片组装的微球(φ～15 μm),在此基础上探讨了高分子结构对晶体生长和组装机制的影响。     

Hexagonal and prismatic nanowalled ZnO microboxes

We hereby report hydrothermal syntheses of new microstructures of semiconducting ZnO. Single-crystalline prismatic ZnO microboxes formed by nanowalls and hexagonal hollow microdisks closed by plates with micron-sized inorganic fullerene-like structures have been made in a base-free medium through a one-step hydrothermal synthesis with the help of n-butanol (NB). Structures and morphologies of the products were confirmed by results from powder X-ray diffraction and scanning electron microscopy. NB has been found to play a crucial role in the growth of these hollow structures. It is indicated that these hollow ZnO crystals were grown from redissolution of interiors. These ZnO microboxes exhibit a band emission in the visible range, implying the possession of a high content of defects.     

ZnO纳米管有序阵列与Cu2O纳米晶核壳结构的光电化学性能及全固态纳米结构太阳电池研究简

采用电化学方法在铟锡氧化物(ITO)导电玻璃基底上制备了高度有序的ZnO纳米管阵列,然后在ZnO纳米管阵列上电化学沉积Cu2O纳米晶颗粒,获得了一维有序Cu2O/ZnO核壳式纳米阵列结构,通过控制Cu2O纳米晶的沉积电量得到不同厚度的Cu2O壳层,并对该核壳式纳米阵列的形貌和结构进行了分析. 以Cu2O/ZnO一维核壳式纳米阵列结构为光电极组装全固态纳米结构太阳电池,研究了Cu2O壳层厚度对光电极光吸收性能、光电性能以及组装电池光伏性能的影响,优化了电池中对电极材料的喷金厚度. 结果表明,以Cu2O沉积电量为1.5 C的Cu2O/ZnO为光活性层,以4 mA电流下真空镀金20~25 min的铜基底为对电极组装的简易太阳电池最高可获得0.013%的光电转换效率.     

Self-assembled CuO nanoarchitectures and their catalytic activity in the thermal decomposition of ammonium perchlorate

CuO shuttle-like and flower-like nanocrystals were synthesized through a one-step, low-temperature solution-phase method in the presence of a cation surfactant, hexadecyl trimethyl ammonium bromide. These nanocrystals were studied as an additive for promoting the thermal decomposition of ammonium perchlorate (AP). With the addition of CuO shuttle-like and flower-like nanocrystals, the thermal decomposition temperature of AP decreased. The structure, particle size, and morphology of resulting CuO powders were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Thermogravimetric analysis technique was applied to investigate the thermal decomposition of mixtures of AP and as-prepared CuO nanocrystals.     

Spectroscopic characterization of zinc oxide nanorods synthesized by solid-state reaction

Well-crystallized zinc oxide nanorods have been fabricated by single step solid-state reaction using zinc acetate and sodium hydroxide, at room temperature. The sodium lauryl sulfate (SLS) stabilized zinc oxide nanorods were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and photoluminescence spectroscopy. The X-ray diffraction revealed the wurtzite structure of zinc oxide. The size estimation by XRD and TEM confirmed that the ZnO nanorods are made of single crystals. The growth of zinc oxide crystals into rod shape was found to be closely related to its hexagonal nature. The mass ratio of SLS:ZnO in the nanorods was found to be 1:10 based on the thermogravimetric analysis. Blue shift of photoluminescence emission was noticed in the ZnO nanorods when compared to that of ZnO bulk. FT-IR analysis confirmed the binding of SLS with ZnO nanorods. Apart from ease of preparation, this method has the advantage of eco-friendliness since the solvent and other harmful chemicals were eliminated in the synthesis protocol.     

Influence of pH on the synthesis ZnO nanorods and photocatalytic hydrogen production from glycerol solution

Photocatalytic oxidation of glycerol at ambient conditions has been investigated with the use of Zinc oxide photocatalysts. Zinc oxide nanorods were prepared via a simple hydrothermal method using zinc nitrate and sodium hydroxide in the solution pH of 7, 8 and 9. The samples prepared in this way were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), Brunauer-Emmett-Teller (BET) and ultraviolet–visible spectroscopy (UV–vis). The pH of the solution is 7, the sample contains zinc hydroxide nitrate hydrated. When the pH of solution was adjusted to 8 and 9, the samples consisted of pure hexagonal wurtzite ZnO without impurity detection. The influence of solution pH on hydrogen formation was investigated. The wurtzite ZnO nanorods synthesized in a solution with pH 9 are considered promising photocatalysts for hydrogen production under xenon radiation.     

Photocatalytic activity of ZNO with different morphologies synthesized by a sonochemical method

Different morphologies of ZnO structures were successfully synthesized in precursor solutions with the pH of 8, 9, 10, 11, and 12 by a sonochemical method at room temperature. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) and Raman spectroscopy. The photocatalytic activities of ZnO samples with different morphologies were evaluated via the degradation of methylene blue (C₁₆H₁₈ClN₃S). In this research, the flower-like ZnO sample of densely assembled nanoplates exhibited the highest photodegradation of 64% under UV light irradiation within 300 min.     

NiO@ZnO heterostructured nanotubes: coelectrospinning fabrication, characterization, and highly enhanced gas sensing properties

Novel NiO@ZnO heterostructured nanotubes (NTs) were fabricated by the coelectrospinning method, consisting of external hexagonal ZnO shell and internal cubic NiO NTs. They are carefully investigated by scanning electron microscopy, transmission electron microscopy, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy mapping, X-ray diffraction, and X-ray photoelectron spectroscopy techniques. A reasonable formation mechanism of the hierarchical NiO@ZnO NTs is proposed, which is discussed from the view of degradation temperature of different polymers and the amount of inorganic salts. They were then explored for fabrication of H(2)S gas sensors. The gas sensing test reveals that compared with the pure ZnO, NiO, and the ZnO-NiO mixed gas sensors, hierarchical gas sensor exhibits highly improved sensing performances to dilute hydrogen sulfide (H(2)S) gas. The response of the optimum NiO@ZnO NTs sensor to 50 ppm H(2)S increases as high as 2.7-23.7 times compared to the other sensors, whereas the response and recovery times also become shorter considerably. These enhanced gas sensing properties are closely related to the change of nanostructure and activity of ZnO and NiO nanocrystals as well as combination of homo- and heterointerfaces in the optimum gas sensor, which are confirmed by a series of well-designed experiments.     

Physicochemical Interaction of ZnO Fine Particles with 5‐Mono‐(4‐carboxyphenyl)‐10,15,20‐Triphenylporphyrin

This study deals with an investigation on the preparation and physicochemical interactions of ZnO nanoparticles with acid functionalized porphyrin [5‐mono‐(4‐carboxyphenyl)‐10,15,20‐triphenylporphyrin (CPTPP)] for photovoltaic applications in a detailed manner. Zinc acetate and sodium hydroxide were used as the starting materials for the synthesis of ZnO nanoparticles at 60 °C in an alcoholic medium. The freshly prepared fine particles were then functionalized with CPTPP. Both the virgin and pregnant ZnO particles were characterized by using UV‐Visible spectrophotometry (UV), fluorescence emission (PL), Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The band gap energy obtained for ZnO particles, having a value of 3.47 eV, shows significant quantum confinement effect and enhanced photophysical activity. FTIR analysis of the doped ZnO nanostructures showed the presences of some chemical species. SEM analysis revealed a clear change in the surface morphologies of undoped ZnO. The average crystallite size of nanoparticles, calculated from XRD peaks, was found in the nano regime. The lattice parameters calculated for ZnO nanocrystals were also found in good agreement with those given in the literature. From the enhancement in the red shift of the UV‐Vis spectra, it is concluded that hybridization of acid functionalized porphyrin can cause a significant expansion in the total absorption region of ZnO semiconductor for photovoltaic applications.