纳米颗粒的模板自组装

纳米颗粒具有优异的物理化学性质,是各种超结构材料最为重要的构造基元。作为一种"自下而上"的制备方法,模板自组装技术可以控制纳米颗粒在自组装超结构材料中的位置和排列顺序,尤其适用于制备规整、多组分、结构复杂的自组装体系。介绍了纳米颗粒自组装方法中常用的模板,以及利用这些模板实现纳米颗粒自组装的一般过程。强调了纳米颗粒与模板之间的物理、化学作用,从本质上阐明模板自组装方法,为制备功能性复杂纳米颗粒自组装材料提供了有益的借鉴。     

相转移过程中贵金属纳米颗粒的自组装行为

采用湿化学法制备了系列贵金属纳米颗粒（Ag、Au、Pt和Rh）,并通过相转移过程实现了贵金属纳米颗粒的自组装,首先将水相中制备的贵金属溶胶与十二胺的乙醇溶液混合,然后将十二胺稳定的金属颗粒从极性的水相中转移到非极性的有机相中。这种方法不仅能实现金属纳米颗粒在基底上的自组装,而且有望应用于纳米颗粒自组装膜的制备中。     

静电自组装纳米复合膜及其应用

对静电自组装方法制备的纳米复合膜的组成,结构及其在发光二极管、高容量电池、等方面的潜在应用进行了综述。     

纳米态电极催化材料Au-Pt/半胱氨酸/Au电极的制备及性能研究

利用自组装技术制备了纳米态Au-Pt/半胱氨酸/Au电极,TEM、ED、XPS等研究表明双金属纳米粒子为Au合金,粒子的平均粒径＜10nm;通过组装时间可以控制双金属纳米颗粒组装的数量.对组装电极的电化学性能进行了测试,通过SEM对其表面结构进行了表征.结果表明,利用自组装方法可以制备纳米态Au-Pt/半胱氨酸/Au电极,该电极具有良好的电催化性能.     

自组装技术在特殊形貌无机纳米材料制备中的作用

目前无机纳米材料的研究主要集中于低维无机纳米材料的制备,如纳米颗粒、纳米纤维等,其制备方法已相当成熟,而对高维特殊形貌无机纳米材料的研究相对较少。近年来,具有特殊形貌的高维无机纳米材料因独特的结构和表面性质在催化、太阳能电池、传感器、微波吸收、医学等领域展现出优于低维纳米材料的性能,但制备出的材料种类少,形貌不均一,可控性较差。因此,研究者们致力于特殊形貌无机纳米材料生长机理的研究,为材料制备提供有效的理论依据。制备无机纳米材料的方法有微乳液法、溶胶-凝胶法、电化学法、水/溶剂热法等。其中水/溶剂热法制备的无机纳米材料具有晶粒发育完整、粒度分布均匀、颗粒之间少团聚、原料价格较便宜的优点,因此被广泛应用于特殊形貌无机纳米材料的制备。自组装技术作为超分子领域的新概念,在制备特殊形貌的材料中发挥着重要作用,其主要作用是将低维的纳米结构单元通过氢键、范德华力、静电力等非共价键作用力进行连接而组装成各种复杂的层级结构。现已通过自组装技术合成了片状、棒状、花状、海绵状、树枝状等特殊形貌无机纳米材料。其中片状材料的生长过程如下:第一步是纳米颗粒的奥斯特瓦尔德熟化过程,第二步是熟化的纳米颗粒定向附着自组装成片状材料。棒状材料的生长过程出现了两种情况,第一种与片状形成过程相同,第二种则是先形成片状,然后片状发生卷曲形成棒状材料,棒状材料再定向附着自组装成长径比不同的棒状材料。花状、海绵状、树枝状等复杂形貌的形成则是基于片状或棒状材料,通过氢键自组装而成。自组装过程会受到表面活性剂或模板剂、溶剂、沉淀剂、酸碱度等因素的影响。研究者们发现利用水热法制备纳米材料时,引入合适的表面活性剂或模板剂,能够促使低维纳米结构单元进行有序自组装而形成结晶度好、尺寸均匀的特殊形貌纳米材料。通过改变表面活性剂或模板剂、溶剂、沉淀剂的种类和剂量及酸碱度等因素,影响纳米颗粒的生长方向、生长速率及颗粒之间的作用力,进而控制产品的形貌和尺寸。本文对近年来国内外利用自组装技术制备特殊形貌无机纳米材料的研究成果进行了介绍,分析讨论了自组装过程的影响因素,并对自组装制备特殊形貌无机纳米材料的发展方向和应用前景进行了展望,以期为制备性能优越的特殊形貌纳米材料提供参考。     

有机-无机杂化一维磁性自组装聚合物纳米链的研究进展

随着纳米科技的发展,有机-无机杂化一维磁性自组装聚合物纳米链的设计合成与应用成为新的研究热点。综述了有机-无机杂化一维磁性自组装聚合物纳米链的磁场诱导自组装、模板诱导自组装和偶极诱导自组装等制备方法,并介绍了其在光学、生物医学和水处理等领域的应用。最后指出有机-无机杂化一维磁性自组装聚合物纳米材料制备技术存在的不足,并对其应用前景进行展望。     

C_(60)自组装新型碳材料的制备与应用研究进展

C_(60)自组装新型碳材料不同于常规碳材料,具有新颖的结构和形貌,包括C_(60)纳米颗粒、纳米棒、纳米片和纳米管等。由于具有优异的物理和化学性质,在众多领域里显示出潜在的应用价值,如应用于催化、光能转化和电化学等领域。因此,C_(60)自组装的碳材料及其应用研究迅速成为材料研究领域的研究热点之一。综述了C_(60)自组装碳材料的制备以及应用的研究进展,探讨了C_(60)自组装碳材料应用于实际需要解决的问题以及今后的研究趋势和发展前景。     

丝网印刷法制备染料敏化太阳能电池光电性能的研究

采用水热法制备TiO2纳米颗粒,将获得的TiO2纳米颗粒制备成胶体,采用丝网印刷法在FTO表面刷涂制备染料敏化太阳能电池（DSSC）光阳极,通过扫描电子显微镜对电极表征和电池光电性能测试,探讨印刷层数及入射光强对DSSC光电性能的影响,实验结果表明,将制备的光阳极组装成电池后具有较好的光电性能,当印刷层数为8层、光强为80W／m2时,电池取得最好的光电性能。     

铁氧化物纳米晶自组装空心微球的制备、表征及其应用

铁氧化物纳米材料和纳米结构空心微球分别代表了材料研究中组分和结构的研究热点. 而由铁氧化物纳米晶自组装形成的空心微球的研究则是二者相结合, 具有重要的科学意义和良好的应用前景. 虽然已发展了多种方法制备各种单质及化合物的空心微球, 但铁氧化物纳米晶自组装空心微球的制备方法报道较少. 本文简要介绍了近几年发展起来的多种铁氧化物纳米晶自组装空心微球的一些制备方法, 利用上述方法, 制备出了多种不同组成单元、不同尺寸、不同空心程度的铁氧化物纳米晶自组装空心微球, 对所制备的铁氧化物纳米晶自组装空心微球进行了表征, 并初步介绍了所制备的铁氧化物纳米晶自组装空心微球在药物缓释和环境领域中的应用.     

静电自组装膜研究进展

由静电自组装技术来制备功能型薄膜是发展迅速的新研究领域。本文着重阐述了静电自组装聚电解质-聚电解质复合膜、静电自组装聚电解质-无机纳米粒子复合膜、静电自组装聚合物-半导体纳米粒子复合膜、静电自组装其他多层膜体系制备方法和特点,展望了静电自组装在渗透分离膜、基因传输、传感器系统、光伏设备等领域的应用前景。     

One-step approach for the synthesis and self-assembly of silver nanoparticles

This study demonstrates a facile approach for one-step synthesis and self-assembly of silver nanoparticles at ambient conditions. It was found that pyrogallol acid (PYA) can play multiple roles in the proposed synthesis, including a reducing agent, a stabilizer, and a linking agent for assembly. Silver ions can be readily reduced by PYA at room temperature due to its powerful reducing capability. The capability in shape and size control can be evidenced by TEM images. A third function of PYA in this case is to link the generated silver particles into chains through the action of hydrogen bonding, which leads to a new plasmon resonance emerges in the longer wavelength region centered at approximately 650 nm. These results may be useful for shape-controlled synthesis and self-assembly of other metallic nanoparticles. The self-assembly structures would be imposed more functional applications in the areas of optics, plasmonics, biomedicine labeling and ionic sensing.     

氧化石墨烯/壳聚糖层层自组装复合膜的制备及其在环保领域中的应用

利用层层自组装技术将氧化石墨烯与壳聚糖进行自组装,制备出一种新型的氧化石墨烯/壳聚糖复合膜,并利用原位合成的方法引入纳米银粒子。采用紫外可见光谱(UV-Vis)、红外光谱(FTIR)、X射线衍射(XRD)和原子吸收等分析方法对复合膜的自组装行为和催化性能进行了研究。实验结果表明,氧化石墨烯与壳聚糖可通过层层自组装技术制备出新型复合膜,这种复合膜可包裹纳米银粒子,膜内纳米银粒子对4-硝基苯酚的催化活性较高,并且可实现循环使用。此外,在稳定性实验中,复合膜不会释放纳米银粒子或银离子,避免了给水体带来二次污染。因此,这种材料在水处理等环保领域中可能具有巨大的潜在实用价值。     

Correlating self-assembly of block copolymers for their application in synthesis of gold nanoparticles

We report the role of self-assembly of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) block copolymers for the synthesis of gold nanoparticles from hydrogen tetrachloroaureate (III) hydrate (HAuCl4 x 3H2O) in aqueous solution. The synthesis has been carried out using three different block copolymers P85 [EO26PO39EO26], F88 [EO103PO39EO103] and P105 [EO37PO56EO37], which not only have varying molecular weight but also differ in hydrophobicity to hydrophilicity ratio. The formation of gold nanoparticles is confirmed by the UV-Visible Spectroscopy. Transmission electron microscopy (TEM) provides the sizes of the nanoparticles formed in these systems. Small-Angle Neutron Scattering (SANS) and Dynamic Light Scattering (DLS) techniques are used to correlate the self-assembly of block copolymer to their propensity to form gold nanoparticles. The yield is found to be in the order P105 > P85 > F88 and is related to the higher tendency of block copolymer to self-assemble to give greater yield of gold nanoparticles. For all the block copolymers, SANS and DLS results suggests that the yield in the synthesis does not always increases with the salt concentration and is limited due to the fact that most of the block copolymers remain unassociated with the gold nanoparticles. By making use of these unassociated block copolymers, we propose two methods (i) step addition method and (ii) additional reductant method, where the synthesis yield of gold nanoparticles can be enhanced by manifold.     

纳米/微米结构粒子合成技术进展

介绍了近年来纳米/微米结构粒子的合成技术进展,将纳米单元(纳米棒、纳米带、纳米片、纳米颗粒)自组装为各种尺度的有序结构会产生更优异的整体协同性质,这对纳米/微米结构粒子的性能研究有重要意义。主要介绍了表面活性剂法、水热法和模板诱导法等。表面活性剂由于具有多种特殊、优异的性能,包覆在纳米粒子表面可使其组装成具有新颖结构的聚集体,是目前研究热点。水热法所得粒子具有纯度高、分散性好、晶形可控,生产成本低等特点已被广泛采用。     

Hierarchical nanoparticle assemblies formed by decorating breath figures

The combination of two self-assembly processes on different length scales leads to the formation of hierarchically structured nanoparticle arrays. Here, the formation of spherical cavities, or 'breath figures'-made by the condensation of micrometre-sized water droplets on the surface of a polymer solution-that self-assemble into a well-ordered hexagonal array, is combined with the self-assembly of CdSe nanoparticles at the polymer solution-water droplet interface. Complete evaporation of the solvent and water confines the particle assembly to an array of spherical cavities and allows for ex situ investigation. Fluorescence confocal, transmission electron and scanning electron microscope images show the preferential segregation of the CdSe nanoparticles to the polymer solution-water interface where they form a 5-7-nm-thick layer, thus functionalizing the walls of the holes. This process opens a new route to fabricating highly functionalized ordered microarrays of nanoparticles, potentially useful in sensory, separation membrane or catalytic applications.     

Functionalized gold nanoparticles self-assemblies with efficient nonlinear optical properties

Satellite-patterns aggregate structures of gold nanoparticles were fabricated by the inducing pi-pi stacking interactions. The self-assembly process of satellite-patterns was tuned by the controlling ligand exchange on the surface of spherical gold nanoparticles, which provide a novel concept and an efficient method for controlling self-assembly of gold nanoparticles. With increasing the porphyrin alkanethiol ratio (r) of gold nanoparticles, the self-assembly induces to form the larger satellite-structures. The study indicates that exchange process of tetra-n-octylammonium bromide molecules and porphyrin alkanethiol molecules results in the formation of satellite-pattern structures with topological features. Nonlinear optical properties of porphyrin alkanethiol capped gold nanoparticles of toluene solution were measured using the Z-scan technique, and its third-order nonlinear optical susceptibility (chi(3)) is calculated as 0.9 x 10(-13) esu, presented the third-order nonlinear optical properties. The well-ordered assembly of gold nanoparticles exhibits controlled the third-order nonlinear optical properties, which can be enhanced with the increasing of the porphyrin alkanethiol ratio in systems.     

Controlled self-assembly of metal-organic frameworks on metal nanoparticles for efficient synthesis of hybrid nanostructures

We report a novel approach for synthesizing inorganic nanoparticle/metal-organic frameworks (MOFs) heterostructured nanocomposites by self-assembly of MOFs on nanoparticles. This approach involves the synthesis of Au nanoparticles and preferential growth of [Cu(3)(btc)(2)](n) frameworks consisting of Cu(2+) ions and benzene-1,3,5-tricarboxylate (btc) on nanoparticles. Aggregates consisting of 11-mercaptoundecanoic acid (MUA)-stabilized Au nanoparticles linked by Cu(2+) ions were necessary for preferential self-assembly of [Cu(3)(btc)(2)](n) frameworks on the aggregates, resulting in the formation of Au nanoparticles/[Cu(3)(btc)(2)](n) nanocomposites. The present approach was confirmed to be applicable for other hybrids consisting of Au nanoparticles and tetragonal [Cu(2)(ndc)(2)(dabco)](n) frameworks.     

Synthesis and self-assembly of colloidal nanoparticles

We describe recent developments in the synthesis of semiconductor nanoparticles, which lead to a substantial improvement of the luminescence quantum efficiency. Concerning a theoretical model for the growth of an ensemble of nanoparticles, the highest quantum efficiencies are achieved in particles that grow under conditions of a rapid exchange of monomers at the particle surface, leading to a smooth surface structure. Selective etching, core-shell formation and doping of nanoparticles are also discussed as fluorescence-enhancing preparative techniques. Examples of self-assembly of almost-uniformly-sized nanoparticles are given, which result in two-dimensional and three-dimensional superlattices, colloidal crystals and crystalline structures built-up from particles of different sizes. Finally, the self-assembled oriented attachment of quasi-spherical ZnO nanoparticles onto single-crystalline nanorods is presented.     

Formation of nanoparticle arrays on S-layer protein lattices

Crystalline bacterial cell surface layers (S-layers) composed of identical protein units have been used as binding templates for well-organized arrangements of nanoparticles. Isolated S-layer proteins were recrystallized into monomolecular arrays on solid substrates (such as silicon wafers and SiO2-coated grids) and in suspension forming so-called self-assembly products. These S-layer assemblies were studied by atomic force microscopy and transmission electron microscopy (TEM). The orientation of the S-layer lattice, exhibiting anisotropic surface properties, on the solid surface and on the self-assembly products, was compared with the orientation on the bacterial cell. On both bacterial cells and SiO2 surfaces the outer face of the S-layer protein was exposed. On the self-assembly products occasionally the inner face was also visible. Metal- and semiconductor nanoparticles 2 to 10 nm in mean diameter were covalently or electrostatically bound to the solid-supported S-layers and self-assembly products. TEM studies reveal that upon activation of carboxyl groups in the S-layer lattice with 1-ethyl-3,3'(dimethylaminopropyl)carbodiimide (EDC), a close-packed monolayer of 4-nm amino-functionalized CdSe nanoparticles could be covalently established on the S-layer lattice. Because of electrostatic interactions, anionic citrate-stabilized Au nanoparticles (5 nm in diameter) formed a superlattice at those sites where the inner face of the S-layer lattice was exposed. In contrast, cationic semiconductor nanoparticles (such as amino-functionalized CdSe particles) formed arrays on the outer face of the solid-supported S-layer lattices.