合成ZnO纳米阵列及刺突状CuO/ZnO异质结

采用低温水热法在掺氟SnO₂ (FTO)导电玻璃表面制备ZnO纳米阵列, 研究了前驱体溶液浓度摩尔配比对ZnO纳米阵列形貌、光学性能及其生长机理的影响. 研究发现, 随着前驱体溶液浓度摩尔配比的增加, ZnO纳米阵列形貌及光学性能也随之变化. ZnO纳米阵列高度逐渐降低, ZnO纳米阵列直径和光学带隙值大体上出现先增大后降低的趋势. 而当前驱体溶液(Zn(NO₃)₂:环六亚甲基四胺(HMT, C₆H₁₂N₄))浓度摩尔配比为5:5时, 其光学禁带值(3.2 eV)接近于理论值. 结果显示制备ZnO纳米阵列的最优浓度摩尔配比为5:5. 随后选用最优浓度摩尔配比下制备的ZnO纳米阵列为基底, 通过一种两步溶液法成功在其表面制备刺突状CuO/ZnO异质结.从场发射扫描电镜(FE-SEM)结果中可以清楚看见, 大量的CuO纳米粒子沉积在ZnO纳米阵列表面形成刺突状异质结结构.研究发现该CuO/ZnO纳米异质结相对于纯ZnO纳米阵列在紫外光下光催化性能明显增加. 最后, 讨论了CuO/ZnO纳米异质结光催化机理.     

一维ZnO纳米棒阵列的水热合成

以锌片为衬底,用硝酸锌和氨水为原材料,在90 ℃时由水热法合成了有序生长的ZnO纳米棒阵列。 纳米棒长度为500～800 nm,直径约为100 nm,SEM图片显示该纳米棒顶部截面是六边形。 XRD谱表明,ZnO纳米棒为六方纤锌矿结构。 考察了制备温度、时间和物料比对合成的材料形貌和结构的影响。     

ZnO纳米环的可控合成

以六次甲基四胺(Hexamethylenetetramine, C6H12N4)和水合硝酸锌[Zn(NO3)2·2H2O]为原料, 表面活性剂聚丙烯酰胺-氯化二烯丙基二甲基铵[poly(acrylamide-co-diallyldimethylammonium chloride, 缩写为PAM-CTAC]为形貌控制剂, 采用液相沉淀法合成了ZnO纳米环. 产物的结构与形貌经X射线粉末衍射(XRD)和扫描电子显微镜(SEM)表征. 研究了不同实验条件(如表面活性剂的浓度、反应物浓度、反应温度和反应时间等)对产物形貌与尺寸的影响. 讨论了PAM-CTAC作用下ZnO纳米环可能的形成机理. 结果表明, 合成产物为六方Wurtzite型结构的ZnO纳米环, 环内径约为220 nm, 壁厚约为70 nm. 反应物浓度、反应温度对ZnO纳米环的形成以及纳米环的尺寸都有一定的影响, 但起关键作用的是PAM-CTAC. 通过改变PAM-CTAC的浓度, 能有效地实现ZnO纳米环的可控合成. 室温荧光光谱显示, ZnO纳米环的紫外发射峰具有较窄的半高宽(FWHM)(约7 nm), 表明合成产物具有较窄的尺寸分布.     

氨水溶液制备ZnO纳米晶阵列的研究

以氨水和硝酸锌为前躯体，采用低温水溶液法在涂敷ZnO晶种层的玻璃衬底上外延生长了ZnO纳米棒晶阵列。应用SEM、TEM、SAED和XRD表征了ZnO纳米晶的形貌和结构。讨论了该组成体系水溶液法纳米棒外延生长的机理及其对棒晶形貌的影响。通过对水溶液pH值的原位二次调整，制备出了ZnO纳米管和表面绒毛状的棒晶阵列，基于生长机理探讨了它们的形成原因，为实现不同形貌ZnO纳米晶阵列的优化控制提供了可能的技术途径。结果表明，不同形貌的ZnO均属沿c轴择优取向的六方纤锌矿结构。     

不规则形ZnO纳米棒的制备及其光催化性能研究

本文采用溶剂热法,以Zn(NO3)2,NaAc为原料,聚乙二醇-10000为表面活性剂,制备了不规则形的ZnO纳米棒。并用X-射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)、荧光光谱、紫外-可见分光光度计对其进行了表征。考察了硝酸锌用量、聚乙二醇-10000用量、反应时间和反应温度等对氧化锌粒子形貌和大小的影响,初步讨论了氧化锌纳米棒的可能形成机理。以ZnO纳米棒作为光催化剂,考察了其光催化降解龙胆紫的性能。研究了催化剂用量、龙胆紫的初始浓度对光催化降解率的影响。     

Cu、Ni共掺杂ZnO光催化性能及机理

以自制的Gemini表面活性剂为软模版,硝酸锌为锌源、硫酸铜为铜源、硝酸镍为镍源,采用水热法制备Cu、Ni共掺杂ZnO。用XRD、SEM-EDX、UV-Vis DRS和PL对样品进行表征。以罗丹明B为模拟污染物,研究了水热时间,水热温度,煅烧时间,煅烧温度,Cu、Ni掺杂量对光催化性能的影响。结果表明:Cu和Ni均掺入到了ZnO晶格中,光催化实验表明,当水热时间8h、水热温度130℃、煅烧温度500℃、煅烧时间3 h,0.8 mg·L~(-1)的1.0%Cu-3.0%Ni/ZnO在250 W高压汞灯灯光照射90 min后对10 mg·L~(-1)罗丹明B溶液的降解率达到96.9%。     

近二维结构的六边形金属镍纳米片的水热合成

片状二维镍纳米材料具有较高的形状各异性,在催化、磁记录以及生物探测方面具有重要的应用价值,因此寻找一种简单,成本低的方法制备表面无活性剂的片状镍纳米材料显得尤为重要。在没有有机表面活性剂和形貌控制剂的条件下,在氟掺杂氧化铟锡(FTO)导电玻璃表面,通过水热制备得到金属镍纳米薄片。系统地研究了反应条件对产物形貌的影响,发现镍源、氢氧化钠、氨水的浓度以及反应温度对纳米镍的形貌有较大的影响。只有在合适的氨水和氢氧化钠浓度共同存在下,才能获得具有较大的特征长度以及较薄的近二维结构的六边形镍金属钠米薄片。经过条件优化,制备得到的厚度约为10 nm,横向特征长度超过1μm金属镍纳米薄片。经过分析认为,体系的p H值及温度影响了反应速度,最终导致产物的形貌受到影响,在p H值约为10的条件下,氨水对镍离子的络合作用对镍纳米薄片的二维生长具有一定的促进作用。     

纳米ZnO对白僵菌孢子的紫外保护及与孢子的生物相容性

用沉淀法制备经油酸表面修饰的纳米ZnO,测定其紫外吸收性能及对油悬浮剂型白僵菌孢子的抗紫外保护效率;用扫描电子显微镜观察纳米ZnO与孢子的混合状态,通过对含纳米ZnO的白僵菌制剂在贮存期间孢子萌发率差异显著性的分析,确定其与白僵菌孢子的生物相容性.结果表明：制备的纳米ZnO的平均粒径为27nm,其对波长200nm～370nm范围的紫外光具有良好的吸收性能.含纳米ZnO质量分数为1.0%、2.0%和5.0%的油悬浮剂型白僵菌,紫外灯照射8h,对孢子保护效率均大于60%,不含纳米ZnO为9.7％. 纳米ZnO被吸附包覆于孢子表面,屏蔽紫外线,保护孢子免受紫外线的杀伤.含0.5%、1.0%和2.0%纳米ZnO的油悬浮剂型白僵菌制剂室温贮存10个月,其孢子萌发率与不含纳米ZnO的差异不显著;纳米ZnO与白僵菌孢子生物相容性好.油悬浮剂型白僵菌制剂中纳米ZnO的适宜含量为1.0%～2.0%.     

杨桃状ZnO纳米片微球的制备及气敏性能的研究

以六水合硝酸锌和尿素为原料,水为反应介质,油酸作为表面活性剂,经水热过程合成了由纳米片组装的碱式碳酸锌微球前驱体,经煅烧后得到形貌一致的氧化锌(ZnO)纳米片组装的杨桃状微球。采用X射线衍射仪(XRD)和环境扫描电镜(SEM)对样品进行表征,结果表明产物为六方纤维矿结构的ZnO,微球尺寸比较均一,直径约为20μm,组装单元扇形ZnO纳米片均匀排列,单元之间存在均匀空隙,BET测试显示纳米片呈现多级介孔结孔结构,比表面积为18.9m2·g-1,室温下的光致发光性能表明其结构表面存在大量氧空位,对产物ZnO气敏元件进行了乙醇和丙酮气体敏感性测试。     

Cu、Ni共掺杂ZnO光催化性能及机理

以自制的Gemini表面活性剂为软模版,硝酸锌为锌源、硫酸铜为铜源、硝酸镍为镍源,采用水热法制备Cu、Ni共掺杂ZnO。用XRD、SEM-EDX、UV-Vis DRS和PL对样品进行表征。以罗丹明B为模拟污染物,研究了水热时间,水热温度,煅烧时间,煅烧温度,Cu、Ni掺杂量对光催化性能的影响。结果表明：Cu和Ni均掺入到了ZnO晶格中,光催化实验表明,当水热时间8 h、水热温度130℃、煅烧温度500℃、煅烧时间3 h,0.8 mg·L^-1的1.0% Cu-3.0% Ni/ZnO在250 W高压汞灯灯光照射90 min后对10 mg·L^-1罗丹明B溶液的降解率达到96.9%。     

Sol‐Gel Synthesis of Polycrystalline ZnO and ZnS Fibers

ZnO fibers with wurtzite structure have been prepared by a sol‐gel method using zinc nitrate hexahydrate and glucose as starting materials. The ZnO fibers with the diameter in the order of 3–5 µm are composed of ZnO nanoparticles with the size of 40～100 nm. The evolution of gel fibers to ZnO fibers was characterized by TG, XRD, FT‐IR, TEM, and SEM techniques in details. In addition, the transformation of ZnO fibers to ZnS fibers also was investigated.     

Controlled growth of well-aligned ZnO nanorod array using a novel solution method

A simple method of synthesizing nanomaterials and the ability to control the size and position of them are crucial for fabricating nanodevices. In this work, we developed a novel ammonia aqueous solution method for growing well-aligned ZnO nanorod arrays on a silicon substrate. For ZnO nanorod growth, a thin zinc metal seed layer was deposited on a silicon substrate by thermal evaporation. Uniform ZnO nanorods were grown on the zinc-coated silicon substrate in aqueous solution containing zinc nitrate and ammonia water. The growth temperature was as low as 60-90 degrees C and a 4-in. wafer size scale up was possible. The morphology of a zinc metal seed layer, pH, growth temperature, and concentration of zinc salt in aqueous solution were important parameters to determine growth characteristics such as average diameters and lengths of ZnO nanorods. We could demonstrate the discrete controlled growth of ZnO nanorods using sequential, tailored growth steps. By combining our novel solution method and general photolithography, we selectively grew ZnO nanorod arrays on a patterned silicon substrate. Our concepts on controlled ZnO nanorod growth using a simple solution method would be applicable for various nanodevice fabrications.     

Flow-injection determination of inorganic forms of nitrogen by gas diffusion and conductimetry

A flow-injection—conductimetric method was applied to the determination of ammonia, nitrate and nitrite at concentrations down to 5, 20 and 20 ng ml^?1, respectively. Ammonia was determined by merging the injected sample with an alkaline solution (NaOHEDTA) and passing the mixture through a diffusion cell. The ammonia released was collected by a flowing stream of deionized water that passed through a conductance flow cell. Nitrate and nitrite concentrations were determined after reduction to ammonia in alkaline medium using a column filled with metallic zinc. The ammonia produced was then measured as described above. About 60 samples per hour can be processed with a relative standard deviation of about 1%. Satisfactory agreement was observed between results for ammonia in samples of natural water and nitrate in tap and mineral water determined by the proposed method and by standard spectrophotometric procedures. Speciation can be achieved by adding sulphanilic acid to remove nitrite from the sample and determining the ammonia without the use of the column.     

氧化锌薄膜的电化学沉积和表征

以透明导电玻璃(TCO)为衬底，用硝酸锌水溶液作为电解液，研究了阴极还原沉积ZnO薄膜的反应机理和电化学行为. 通过改变工艺条件来控制ZnO的生长速率， 得到了粒径为10～15 nm的纳米ZnO薄膜. XRD分析显示纳米ZnO薄膜纯度高， 呈纤锌矿结构. 光学测试结果表明，在可见光区其透光度高达90%，禁带宽度为3.37 eV.     

Aqueous solution fabrication of large-scale arrayed obelisk-like zinc oxide nanorods with high efficiency

Two-dimensional (2D) arrays of obelisk-like zinc oxide nanorods were successfully synthesized with high efficiency on quartz and glass substrate on a large scale through a simple aqueous solution deposition method with zinc nitrate, ammonia, and ammonium chloride as the precursors. Characterized by XRD, EDS, TEM and SEM, the as-grown zinc oxide rods had a single crystalline obelisk-like hexagonal wurtzite structure with diameters of about 300-400 nm and length up to 5 μm. Both XRD and SEM studies revealed the orientation of ZnO rods, and the orientation of ZnO rods can be controlled easily by temperature, pH of the reaction system and the concentration of reactants.     

图案化锥形氧化锌纳米带的原位热氧化法制备与发光性质

采用光刻技术制备出图案的锌膜,所得锌膜与纯氧在700℃氧化反应10 min,在锌膜的表面上原位生长出具有图案的锥形ZnO纳米带阵列,实现了ZnO纳米带生长位置的可控生长。锌膜上得到的锥形ZnO纳米带为单晶六方纤锌矿结构,长度在1～4μm,纳米带根部和顶部的宽度分别在300～700 nm和100～300 nm。提出了锥形ZnO纳米带的可能生长机理。在波长为300nm光的激发下,发现了锌膜上锥形ZnO纳米带具有发光峰位于395 nm弱的紫外光发光和510 nm强的蓝绿光发光,它们分别起源于ZnO宽带隙的激子发射以及表面上离子化氧空位中的电子与价带中光激发的空穴之间的复合。     

Investigation of the growth parameters of hydrothermal ZnO nanowires for scale up applications

Zinc oxide nano-wires (ZnO NWs) are synthesized reproducibly with high yield via a low temperature hydrothermal technique. The influence of the growth duration time, growth temperature, zinc precursor and base concentration of Na₂CO₃ on the morphology of NWs is investigated. The growth products are characterised using scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). SEM analysis shows that the optimum growth temperature is 140 °C and finds that length and diameter of ZnO NWs have a relationship with growth duration time and base concentrations of Na₂CO₃. In addition, it is reported that a high (～90%) yield of ZnO NWs can be synthesised via using any of three different precursors: zinc chloride, zinc acetate and zinc nitrate. TEM and XRD results indicate the high purity and the single crystalline nature of the ZnO NWs. XPS confirms the absence of sodium contaminants on the surface and indicates a near flat band surface condition. PL shows a large visible band in the yellow part of the spectrum, and a small exciton emission peak, indicating a large defect concentration, which is reduced after annealing in air.     

Electrochemistry-assisted self-assembly of oriented zinc oxide and long-chain alkyl amine surfactant multilamellar nanostructures

Highly oriented ZnO-surfactant multilamellar nanostructures were fabricated by Electrochemistry-Assisted Self-Assembly on silicon substrates from the solution containing zinc nitrate and dilute surfactant hexadecylamine at 60 °C. The co-absorption of inorganic ions with surfactant on the electrode surface implied that the unique growth mechanism depended strongly on the environmental change of cathodic electrode area under the electric field. The ZnO nanosheets (～2.3 nm) were produced. Comparing with pure ZnO film by electrodeposition, the multilamellar nanostructures consisting of the dielectric organic barriers and the semiconducting inorganic well layers give rise to 2-dimensional quantum confinement. This kind of organic–inorganic hybrid materials may be a potential candidate in practical applications.