多种形貌勃姆石纳米材料制备的研究进展

不同形貌的勃姆石纳米材料广泛应用于各个领域,也是制备Al2O3的重要前驱体。具有特殊形貌的氧化铝因独特的孔道结构和表面性质,显示出比传统的氧化铝更加优越的吸附和催化性能,被广泛用作特种陶瓷、催化剂载体、催化剂和吸附材料等。因勃姆石在煅烧过程中原有的微观形貌保持不变,可通过煅烧不同形貌的勃姆石得到特定形貌的氧化铝纳米微晶。因此,制备不同形貌的勃姆石纳米材料是一个非常有价值的课题。对近年来国内外运用不同方法制备多种形貌勃姆石的研究结果做了综合评述和展望。     

多元醇介导还原的银纳米线的形貌与结构调控

以硝酸银为银源、乙二醇为还原剂，采取溶剂热反应途径，制备了高长径比的银(Ag)纳米线，通过聚乙烯吡咯烷酮(PVP)的选择性晶面吸附、乙二醇的介导和无机离子的辅助作用，对Ag纳米线的物相和形貌结构进行了有效调控。详细地考察了PVP加入量、无机离子助剂摩尔配比、反应时间和温度等因素对Ag纳米线产物形貌的影响。结果表明：将PVP浓度控制在44g/L,调节等摩尔离子(Fe³⁺、Cu²⁺)助剂的总浓度为0.24mmol/L,在408K温度下进行5h溶剂热反应，可获得平均线径70nm、平均长度高于40μm的Ag纳米线，非线性副产物(如微纳米Ag晶粒)占比不超过5%,且Ag纳米线产物的纯度高、结晶度良好。     

热蒸发锌粉法制备半导体氧化锌纳米线的研究

采用热蒸发锌(Zn)粉的方法,制备出高产量的由半导体氧化锌纳米线组成的蒲公英花状和四角锥状纳米结构.利用SEM、TEM和X射线衍射对产物的形貌及结构进行了分析.结果表明,所生成的是具有六方结构的单晶ZnO纳米线.纳米线长约5-10μm,根部直径较粗,约110-120nm;梢部较细,约25-30nm,其生长机制为气-固(VS)机制.     

磁控溅射法可控制备有序碲纳米线阵列

采用磁控溅射法在较低基底温度下(200 ℃)制备了有序碲纳米线阵列, 并利用X射线衍射、扫描电镜和透射电镜对所制备薄膜进行了相、形貌和微观结构分析。结果表明, 所制备的纳米线阵列由单晶碲纳米线组成, 单根碲纳米线具有针状形貌, 并沿[101]晶向生长, 平均直径和长度分别为100 nm和1 μm。氩气压力和基底温度均对碲纳米线阵列的形成具有重要影响, 以平衡碲原子沿[101]晶向和(101)晶面方向的扩散和生长。提出了碲纳米线阵列的生长机制, 包括吸附、结合、成核和生长等过程。     

苯甲酸铵导向合成线状纳米结构CePO_4和Ce_(0.95)PO_4∶Tb_(0.05)及其发光性能

采用水热法通过苯甲酸铵(简写为L)导向控制合成了六方相CePO_4和Ce_(0.95)PO_4∶Tb_(0.05)纳米线。用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)及透射电镜(TEM)分析产物的相结构、晶粒尺寸及微观形貌。实验结果表明,随着配体L的增加,CePO_4的微观形貌由纳米棒逐渐转变成纳米线再生长成纳米颗粒。当n(Ce3+)∶n(L)=1.0∶1.0时,所合成的CePO_4纳米线长径比大且分散较均匀,直径为20~30nm、长约1~2μm。发现苯甲酸铵对产物的尺寸及长径比具有导向合成作用。荧光光谱分析表明n(Ce3+)∶n(L)=1.0∶1.0时所合成的CePO_4纳米线荧光强度最强,相同方法合成的Ce_(0.95)PO_4∶Tb_(0.05)纳米线具有较强的荧光性能。     

水热合成Sb_2Se_3纳米线及其对Bi_2Te_3纳米粉末热电性能的影响

以SbCl3和Se粉为原料,水合肼(N2H4·H2O)为还原剂,采用水热法在150℃下,分别保温不同的时间合成Sb2Se3纳米粉末.通过X射线衍射(XRD)、场发射电子扫描电镜(FESEM)、透射电镜(TEM)以及高分辨透射电镜(HRTEM)等分析方法对产物的物相成分和微观形貌等进行了表征,实验结果表明保温时间达到24h时,获得产物为单相Sb2Se3纳米线晶体.根据实验结果还研究了水热合成Sb2Se3纳米线晶体可能的反应及生长机理,结果表明一维纳米线沿[001]方向生长,纳米线的形成与其独特的层状晶体结构有关.最后采用放电等离子体快速热压烧结法将水热合成的Bi2Te3纳米粉末与不同含量Sb2Se3纳米线进行复合,分析了Sb2Se3纳米线对Bi2Te3纳米材料热电性能的影响,发现复合约1at%Sb2Se3纳米线可以使Bi2Te3纳米材料热电性能有一定提高.     

SOI基上制备CuO纳米线

在SOI基上制备光电纳米器件具有良好的光电集成应用前景,通过铜膜生长法在SOI基上制备了形貌为类针状的Cu(OH)2前驱体纳米线,并采用热处理法600℃条件下成功制备了CuO纳米线。通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射测试(XRD)对样品结构、形貌进行了表征。SEM、TEM测试结果表明,Cu(OH)2前驱体纳米线结构一致,尺寸均匀,表面光滑。在Cu(OH)2前驱体纳米线上二次生长的CuO纳米线具有类蒲草状细长光滑的结构,CuO纳米线直径约为80~100nm,长度约为10μm,CuO纳米线结晶性良好。     

核壳结构SiC/SiO2纳米线的低温合成与表征

以酚醛树脂(PF)作为碳源, 纳米SiO₂为硅源, 在1300℃氩气气氛下通过碳热还原反应, 制备出具有核壳结构的SiC/SiO₂纳米线。采用X射线分析衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨率透射电子显微镜(HRTEM)、拉曼光谱(Raman)对产物的组成、形貌、微观结构等进行了表征。结果表明; SiC/SiO₂纳米线长可达数毫米, 单根SiC/SiO₂纳米线由直径30 nm的β-SiC晶体为内核和厚度约12 nm的无定形SiO₂壳层组成; 室温下SiC/SiO₂纳米线的PL发光峰与β-SiC单晶的发光特征峰相比有蓝移。最后, 讨论了核壳结构SiC/SiO₂纳米线的生成机制。     

L-半胱氨酸诱导单晶银纳米线的快速合成及表征

采用化学还原法,以聚乙烯砒咯烷酮(PVP)为稳定剂和形貌控制剂,乙二醇为还原剂,在L-半胱氨酸诱导下,由硝酸银快速制备了银纳米线。采用紫外-可见吸收光谱、X射线衍射、扫描电子显微镜、选区电子衍射和透射电子显微镜手段对所得产物进行表征,结果表明利用L-半胱氨酸诱导可在15min内制备直径为100nm左右,长度约几百微米的银纳米线,并具有单晶结构,根据实验结果提出了可能的银纳米线快速合成机理。     

表面活性剂对超细BaTiO3纳米颗粒制备的影响

以钛酸四丁酯为钛源,醋酸钡为钡源,采用改进的水热法(即溶剂热法)在低温条件下合成钙钛矿结构的超细钛酸钡纳米颗粒,重点研究表面活性剂对产物的影响,探讨了不同表面活性剂影响产物形貌和种类的作用机理.通过扫描电子显微镜(SEM)、X射线衍射(XRD)及能谱(EDS)对产物进行表征,结果表明加入不同的表面活性剂时,制备的产物不同,其产物的形貌分别为超细纳米线、纳米棒(直径约几十纳米)和纳米颗粒(尺寸约50～100nm).通过调节反应过程中的表面活性剂,可以实现从线状钡的硫酸盐到纯相的超细钛酸钡纳米颗粒的转变.此方法为尺寸小于20nm的钛酸钡颗粒的制备及铁电材料尺寸限制效应的研究提供了重要参考.     

Metal organic chemical vapour deposition of vertically aligned ZnO nanowires using oxygen donor adducts

Vertically aligned zinc oxide (ZnO) nanowires (NWs) have been grown by liquid injection Metal Organic Chemical Vapour Deposition, using oxygen donor adducts of Me2Zn. The growth and characterisation of the nanowires grown using [Me2Zn(L)] where L = monodentate ethers, tetrahydrofuran (C4H8O) (1), tetrahydropyran (C5H10O) (2), furan (C4H4O) (3) and the bidentate ethers, 1,2-dimethoxyethane (C4H12O2,) (4) 1,4-dioxane (C4H8O2) (5) and 1,4-thioxane (C4H8SO) (6) is discussed. Single crystal X-ray structures of (4), (5), (6) have been established and are included here. The ZnO NWs were deposited in the absence of a seed catalyst on Si(111) and F-doped SnO2/glass substrates over the temperature range 350-600 degrees C. X-ray diffraction (XRD) data shows that the nanowires grown from all adduct precursors were deposited in the wurtzitic phase.     

Solid-phase low temperature steam-assisted synthesis of thermal stable alumina nanowires

A simple steam-assisted solid phase synthesis method was developed for synthesis of boehmite nanowires in the presence of TEAOH surfactant. The boehmite nanowires had uniform diameters (12-16 nm) and length up to 1-2 microm. The morphology of the nanostructured wires was well preserved after being converted to pure gamma-Al2O3 by thermal treatment at 600 degrees C for 5 h. The nanowires of Al2O3 exhibited excellent thermal stability by retarding the phase transformation and maintaining the wires-like nanostructure after being aged up to 1300 degrees C by preventing sintering between particles at high temperatures. The surface areas of Al2O3 nanowires could be maintained as high as 68 m2/g at 1300 degrees C while the surface areas of Al2O3 micropowder shrank to 0.89 m2/g after same thermal treatment. Both in-situ XRD and 27Al NMR results indicated that the crystal structure of gamma-Al2O3 nanowires was not transformed to alpha-Al2O3 at 1300 degrees C whereas micropowder Al2O3 was fully converted to alpha-Al2O3 at 1100 degrees C.     

Growth and properties of aligned ZnO nanowires and their applications to n-ZnO/p-Si heterojunction diodes

Aligned n-ZnO nanowires were synthesized via simple thermal evaporation process by using metallic zinc powder in the presence of oxygen on p-silicon (Si) substrate. The as-synthesized aligned ZnO nanowires were characterized in terms of their structural and optical properties by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction process (XRD) and room-temperature photoluminescence (PL) properties. The detailed structural and optical studies revealed that the as-grown nanowires are single crystalline with the wurtzite hexagonal phase and exhibit good optical properties. From application point of view, the as-grown aligned n-ZnO nanowires on p-Si substrates were used to fabricate heterojunction diodes. The fabricated heterojunction diodes exhibited good electrical (I-V) properties with the turn-on voltage of approximately 1.0 V. A temperature-dependant (from 25 degrees C approximately 130 degrees C), I-V characteristics for the fabricated device was also demonstrated in this paper. The presented results demonstrate that the simply grown aligned n-ZnO nanowires on p-Si substrate can be efficiently used for the fabrication of efficient heterojunction devices.     

One-dimensional TiO2 nanomaterials: preparation and catalytic applications

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.     

Uniaxial alignment of liquid-crystalline conjugated polymers by nanoconfinement

We demonstrate the uniaxial alignment of a liquid-crystalline conjugated polymer, poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) by means of nanoconfinement during nanoimprinting. The orientation of the conjugated backbones was parallel to the nanolines imprinted into the polymer film. Polarized UV-vis absorption and photoluminescence spectra were measured to quantify the degree of alignment, showing that the polarization ratio and uniaxial molecular order parameter were as high as 66 and 0.97, respectively. The aligned F8BT film was used as the active layer in a PLED, which resulted in polarized electroluminescence with a polarization ratio of 11. Ambipolar PFET in a top-gate configuration with aligned F8BT as the active semiconducting layer showed mobility enhancement when the chains were aligned parallel to the transport direction. Mobility anisotropies for hole and electron transport were 10-15 and 5-7, respectively, for current flow parallel and perpendicular to the alignment direction.     

One-pot template-free synthesis of mesoporous boehmite core-shell and hollow spheres by a simple solvothermal route

Uniform-sized and monodispersed boehmite core-shell and hollow spheres have been successfully synthesized using a template-free solvothermal route. The experimental parameters such as reaction duration, the trisodium citrate amounts and solvents are shown to play important roles in the formation of the AlOOH core-shell and hollow spheres. X-ray diffraction, Fourier transform IR, thermal gravimetric analysis, N₂ adsorption/desorption, scanning electron microscopy, transmission electron microscopy, and high-resolution TEM were used to characterize the products. The results show that the prepared polycrystalline hollow spheres are composed of well-aligned AlOOH nanowires and have an orthorhombic structure. Finally, a dissolution-renucleation mechanism was proposed for the formation of boehmite hollow structures.     

Template-free solvothermal synthesis of hierarchical boehmite hollow microspheres with strong affinity toward organic pollutants in water

Three-dimensional hierarchical boehmite hollow microspheres with a very high yield at low cost were successfully synthesized via a one-pot template-free solvothermal route using aluminum chloride hexahydrate as precursor in a mixed ethanol–water solution with assistance of trisodium citrate. The as-synthesized products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption/desorption techniques. The results show that Cl⁻ and addition amount of trisodium citrate have significant effect on the morphologies of the resultant products, and 6–8 mmol of trisodium citrate is optimal for the synthesis of boehmite hollow microspheres assembled from randomly interconnecting and aligned nanorods with solvothermal time no less than 15 h. A synergistic mediation mechanism of citrate ions and Cl⁻ to form boehmite hollow spheres via self-assembly morphology evolution was proposed based on the experimental results. Interestingly, the typical boehmite hollow microspheres with a surface area of 102 m² g⁻¹, pore volume of 0.37 cm3 g⁻¹, and the average pore size of 14.6 nm show superb adsorption properties for Congo red with maximum capacity of 114.7 mg g⁻¹ which is higher than that of a commercial boehmite. This simple synthetic route is a very promising way for the design and synthesis of new functional hierarchical nanostructured materials with desired adsorptive properties.     

Vertically aligned ZnO/amorphous-Si core-shell heterostructured nanowire arrays

We report the synthesis of vertically aligned ZnO/a-Si core-shell nanowire arrays (ZnO nanowires coated with amorphous silicon) through chemical vapor deposition. The core-shell heterostructured nanowires possessed uniform morphology and the thickness of the amorphous silicon shells could be controlled easily by tuning the deposition duration and temperature. The core-shell heterostructured nanowires exhibited enhanced antireflection and absorption performance as well as tunable PL properties. Because the individual ZnO/a-Si nanowires showed p-type characteristics and the ZnO cores were n-type semiconductors, the core-shell nanowires formed p-n junctions naturally.     

Bottom-up growth of carbon nanotube multilayers: unprecedented growth

An unusual growth phenomenon, with no precedent in vapor-phase thin film growth, is described here, for the case of the growth of stacked multiple layers of vertically aligned carbon nanotubes(1-6) on solid substrates. As multiple layers of ordered nanotubes are sequentially deposited from the vapor onto the substrate, each layer nucleates and grows from the original substrate surface at the bottom of the existing multiple stacks of nanotubes. In contrast to conventional understanding of thin film deposition,(7) the mechanism here has similarities to porous oxide film formation on surfaces.(8) The stacked layers of aligned nanotubes act as fully permeable membranes for the downward diffusion of growth precursor vapors, allowing growth to occur at the buried solid interface. The preexisting multiple nanotube stacks lift up to accommodate the vertical growth of fresh layers, allowing the formation of nanotube towers extending in millimeter lengths. Our results provide evidence for a new growth phenomenon, characterized by selective, interface-driven, bottom-up growth of self-assembled nanowires at buried interfaces, covered with weakly adhering thick porous membranes.     

Solvothermal Synthesis of Boehmite and γ-Alumina Nanorods

Boehmite nanorods were synthesized by a solvothermal method using AICl3·6H2O in mixed solvents of water and aniline. The solvothermal time, heating temperature and the concentration of aniline have effects on the morphology of boehmite. γ-alumina nanorods were prepared by a simple thermal transformation of boehmite nanorods. A rational mechanism based on the oriented attachment is proposed for the formation of boehmite nanorods. The products were characterized by X-ray powder diffraction （XRD） and transmission electron microscopy （TEM）. Photoluminescence （PL） spectrum of the boehmite nanorods was also investigated.