以胶体粒子为模板制备核壳纳米复合粒子*

核壳纳米复合粒子具有许多不同于单组分胶体粒子的独特的光、电、磁、催化等物理与化学性质,是构筑新型功能复合材料的重要组元,在光子带隙材料、微波吸收材料、电磁流变液、催化剂和生物等领域有重要应用.本文从控制核壳复合粒子的微观结构及壳层均匀性与厚度的角度,详细评述了目前以胶体粒子为模板制备粒径从纳米到微米尺度的核壳复合粒子的方法.指出利用胶体粒子模板表面与壳层物质或其前驱物间的特殊相互作用(包括静电和化学相互作用),是完善现有制备方法和发展新方法来制备具有设定组成、结构和性能的核壳复合粒子的关键,同时也是将来的粒子表面纳米工程和获取有序的、先进纳米复合材料的主要方向。     

Pickering乳滴模板法制备超粒子结构有机/无机杂化微球

Pickering乳滴模板法制备有机/无机杂化的核壳微球越来越引起人们的关注,主要因为该方法制备出的微球具有以无机粒子为壳层的超粒子结构(supracolloidal structure),能够赋予微球独特的功能.胶体粒子在乳滴表面自组装形成有序的球面胶体壳,得到稳定Pickering乳液,固定乳滴表面的胶体粒子来制备核壳结构的微球或者以胶体粒子为壳层的微胶囊(colloidosome).本文综述了我们课题组以Pickering乳滴模板法制备超粒子结构有机/无机杂化微胶囊包括实心微球方面的工作.我们选择具有不同性能、种类的胶体粒子以及具有不同性质和功能的核材料,采用Pickering乳滴模板法,对吸附在乳滴表面的胶体粒子用不同的固定方法制备具有不同结构和性能的微球和微胶囊,利用基于多重Pickering乳液的聚合技术制备双纳米复合的超粒子结构多核聚合物微球.     

纳米碗阵列的制备与应用研究

纳米碗阵列具有周期性孔结构、大比表面积、弱对称性等特点。这些独特的纳米碗不仅提供了纳米孔结构,而且会导致许多特殊的物理和化学性质。近年来,由于其孔结构而使其具有新颖且增强的性能,纳米碗阵列引起了极大的关注。本文详细介绍了各种纳米碗阵列的制备方法,首先是制备胶体晶模板(通常是Si O2或者聚苯乙烯微球模板),然后通过物理气相沉积、化学或电化学沉积等技术在模板上沉积所需材料,最后采用溶解、高温处理等方法除去模板,得到纳米碗阵列。此外,本文还对纳米碗阵列的各种应用进行了综述,比如纳米碗阵列可以用作SERS增强基底、传感器,并且能够应用于催化和光学领域。还探讨了不同制备方法的优点和不足以及纳米碗阵列的应用前景及现存问题。     

磺化聚苯乙烯有序孔水凝胶的制备及其模板效应

有序大孔聚苯乙烯材料通过胶体晶模板技术合成, 再经过磺化处理制备得到有序大孔水凝胶体系. 研究了其化学组成和形态. 以溶胶/凝胶制备有序无机材料如二氧化钛对凝胶进行复型, 证明了有序大孔凝胶的形态特征, 同时显示了有序大孔水凝胶作为新型模板制备形态可控的介观尺度有序无机材料的潜力.     

有序介孔碳负载Fe、Co、Ni纳米晶的软模板合成及其表征

报道了在有序介孔碳基体中一步合成负载Fe、Co、Ni纳米晶的方法. 以间二苯酚和甲醛为碳源, F127为模板剂, Fe、Co、Ni的硝酸盐为前驱体, 通过软模板组装路线在酸性条件下合成了负载型有序介孔碳复合材料. 采用X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征. 结果表明: 合成的材料具有类似于SBA-15的有序介孔结构, 有序介孔碳负载Fe、Co、Ni纳米晶复合材料的比表面积分别为586、626和698 m²·g^-1. XRD和TEM表征结果证实了金属物种以高分散纳米晶的形式分布在介孔碳基体中.     

胶体晶体

简要综述胶体晶体的研究进展情况,主要介绍胶体粒子的简单自组装、模板引导下的自组装和二元胶体晶体组装等几类主要的胶体晶体制备技术,并概述胶体晶体在光子晶体、传感器、光子纸张、三维有序大孔材料、二维纳米结构阵列等方面的应用。     

三维有序金纳米壳结构的可控制备及其SERS性能

采用金种子原位生长法,以SiO_2胶体晶体为模板,H_2O_2为还原剂实现了三维有序金纳米壳(GNSs)结构的可控制备,并对其生长过程中表面增强拉曼光谱(SERS)性能进行了研究。实验结果表明,通过控制反应时间、反应温度、还原剂H_2O_2及生长液K_2CO_3-HAuCl_4的量等参数实现了三维有序GNSs阵列的可控批量制备,并可根据需要去除SiO_2内核得到中空有序GNSs结构。通过对其SERS性能的研究,发现SiO_2表面完全被Au纳米粒子覆盖的粗糙结构具有最佳的SERS性能,且对应的中空有序GNSs结构显示出更优异的SERS活性。     

两亲性嵌段共聚物导向合成有序介孔金属氧化物半导体材料

有序介孔材料作为一种结构稳定、高比表面积、孔径可调、孔壁易于修饰的新型纳米结构材料在基础研究与应用开发方面都引起了人们的关注.有关有序介孔材料的文献中,无定型介孔材料(如二氧化硅、碳材料等)报道占据了大约70%,主要是由于传统软模板剂(如小分子表面活性剂或者聚环氧乙烷-b-聚环氧丙烷基嵌段共聚物)能够胜任无定型介孔材料的合成.相比而言,常规软模板剂在合成具有独特物化性能(光、电、磁以及催化、气敏等特性)的晶态半导体金属氧化物介孔材料方面面临很大的挑战.近年来,随着学科交叉发展以及高分子界研究人员加入无机多孔材料领域,一系列新型嵌段共聚物模板剂(例如具有高残碳率、高玻璃化转变温度和络合能力的嵌段共聚物)相继被合成并用于合成新型多孔材料,特别是这些模板剂在诱导组装合成有序介孔金属氧化物材料方面的研究取得了突出进展.本文从聚合物模板剂的制备与组装出发,围绕金属氧化物前驱体与模板剂之间的相互作用,系统综述了两者组装的作用机理和组装行为.深入探讨并总结了常见的三大组装方式:金属无机盐-聚合物模板、金属簇化合物-聚合物模板、金属纳米晶-聚合物模板组装,详细阐述了聚合物模板在合成有序介孔金属氧化物中的组装机理以及微观结构调控规律,并分析了聚合物模板诱导合成有序介孔金属氧化物未来宏量制备面临的机遇与挑战.鉴于其丰富的物化特性和新颖的介孔结构,有序介孔金属氧化物将逐步成为纳米光电器件、纳米催化载体以及化学传感的核心材料.     

模板法制备高度有序的聚苯胺纳米纤维阵列

近年来,利用化学或物理方法制备多种材料的纳米有序阵列复合结构已成为学术界的研究热点．用具有纳米孔洞的模板(多孔阳极氧化铝、多孔硅以及聚碳酸脂膜)制备的金属、半导体、碳纳米管等材料的纳米有序阵列复合结构已在润滑、微电极、单电子器件、传感器、垂直磁记录、场致电     

气液界面胶体球刻蚀法制备二维有序多孔薄膜

作为一类重要的二维材料, 二维有序多孔薄膜受到人们的广泛关注. 气液界面胶体球刻蚀法是近些年发展起来的一种以漂浮在液面上的单层胶体晶体为模板来制备二维有序纳米结构的方法, 具有简单、高效、重现性好、适用范围广以及结构参数易调变等优点. 近年来, 我们课题组利用气液界面胶体球刻蚀法实现了包括多种无机物纳米网、纳米碗阵列和纳米网-纳米碗复合阵列在内的一系列自支撑二维有序多孔薄膜的可控制备, 考察了其二维光子晶体性质, 并研究了其在刻蚀掩膜、溶剂检测、生物传感、电阻开关器件、光电化学分解水等方面的应用. 本文在重点介绍我们课题组研究进展的同时, 也简要总结了该领域的整体发展状况并展望了该领域的今后发展方向.     

Recent Development on Controlled Synthesis of Metal Sulfides Hollow Nanostructures via Hard Template Engaged Strategy: A Mini‐Review

In this mini‐review, we highlighted the recent progresses in the controlled synthesis of metal sulfides hollow nanostructures via hard template technique. After a brief introduction about the formation mechanism of the inorganic hollow nanostructures via hard template technique, the discussions primarily focused on the emerging development of metal sulfides hollow nanostructures. Various synthetic strategies were summarized concerning the use of the hard template engaged strategies to fabricate various metal sulfides hollow nanostructures, such as hydrothermal method, solvothermal method, ion‐exchange, sulfidation or calcination etc. Finally, the perspectives and summaries have been presented to demonstrate that a facile synthetic technique would be widely used to fabricate metal sulfides hollow nanostructures with multi‐shells and components.     

Rational synthesis, self-assembly, and optical properties of PbS-Au heterogeneous nanostructures via preferential deposition

High-quality, monodisperse PbS-Au(1), PbS-Au(4), and PbS-Au(n) nanostructures have been synthesized via a facile and convenient solution chemistry approach. HRTEM images of these nanostructures showed good selectivity of gold deposition on the semiconductor in several spatially correlated directions. The formation of these regular nanostructures can be explained by the difference in polarity of crystal facets that led to the selective growth of metal on the semiconductor surface. Owing to their narrow size distribution and intrinsic high-symmetry, the resulting PbS-Au(4) and PbS-Au(n) heterogeneous nanostructures could spontaneously self-assemble into ordered arrays with different symmetries. From the results of the pump-probe measurements, the presence of Au in PbS-Au(4) nanostructures has substantially altered the nonlinear optical response of PbS nanocrystals.     

Rational Design of Mesoporous Metals and Related Nanomaterials by a Soft‐Template Approach

We review recent developments in the preparation of mesoporous metals and related metal‐based nanomaterials. Among the many types of mesoporous materials, mesoporous metals hold promise for a wide range of potential applications, such as in electronic devices, magnetic recording media, and metal catalysts, owing to their metallic frameworks. Mesoporous metals with highly ordered networks and narrow pore‐size distributions have traditionally been produced by using mesoporous silica as a hard template. This method involves the formation of an original template followed by deposition of metals within the mesopores and subsequent removal of the template. Another synthetic method is the direct‐template approach from lyotropic liquid crystals (LLCs) made of nonionic surfactants at high concentrations. Direct‐template synthesis creates a novel avenue for the production of mesoporous metals as well as related metal‐based nanomaterials. Many mesoporous metals have been prepared by the chemical or electrochemical reduction of metal salts dissolved in aqueous LLC domains. As a soft template, LLCs are more versatile and therefore more advantageous than hard templates. It is possible to produce various nanostructures (e.g., lamellar, 2D hexagonal (p6mm), and 3D cubic (Ia d)), nanoparticles, and nanotubes simply by controlling the composition of the reaction bath.     

Selective attachment of 1,4-benzenedimethanethiol on the copper mediated Si(111)-(7 x 7) surface through S-Cu linkage

The well-defined and patterned copper clusters formed on the Si(111)-(7 x 7) surface have been employed as a template for selective binding of 1,4-benzenedimethanethiol (HS-CH2-C6H4-CH2-SH, 1,4-BDMT), to form ordered molecular nanostructures. Scanning tunneling microscopic (STM) studies showed that each 1,4-BDMT molecule preferentially binds to two neighboring copper atoms within one copper cluster through the S-Cu interaction with its molecular plane parallel to the surface, whereas some 1,4-BDMT bond to individually adsorbed copper atoms, resulting in an upright configuration. Large-scale two-dimensional molecular nanostructures can be obtained using this patterned assembly technique. Our experiments demonstrate the feasibility for controllable growth of ordered molecular nanostructures on the Si(111)-(7 x 7) surface.     

Self-assembled template-directed synthesis of one-dimensional silica and titania nanostructures

Mineralized biological materials such as shells, skeleton, and teeth experience biomineralization. Biomimetic materials exploit the biomineralization process to form functional organic-inorganic hybrid nanostructures. In this work, we mimicked the biomineralization process by the de novo design of an amyloid-like peptide that self-assembles into nanofibers. Chemically active groups enhancing the affinity for metal ions were used to accumulate silicon and titanium precursors on the organic template. The self-assembly process and template effect were characterized by CD, FT-IR, UV-vis, fluorescence, rheology, TGA, SEM, and TEM. The self-assembled organic nanostructures were exploited as a template to form high-aspect-ratio 1-D silica and titania nanostructures by the addition of appropriate precursors. Herein, a new bottom-up approach was demonstrated to form silica and titania nanostructures that can yield wide opportunities to produce high-aspect-ratio inorganic nanostructures with high surface areas. The materials developed in this work have vast potential in the fields of catalysis and electronic materials.     

Controlled synthesis of 2-D and 3-D dendritic platinum nanostructures

Seeding and autocatalytic reduction of platinum salts in aqueous surfactant solution using ascorbic acid as the reductant leads to remarkable dendritic metal nanostructures. In micellar surfactant solutions, spherical dendritic metal nanostructures are obtained, and the smallest of these nanodendrites resemble assemblies of joined nanoparticles and the nanodendrites are single crystals. With liposomes as the template, dendritic platinum sheets in the form of thin circular disks or solid foamlike nanomaterials can be made. Synthetic control over the morphology of these nanodendrites, nanosheets, and nanostructured foams is realized by using a tin-porphyrin photocatalyst to conveniently and effectively produce a large initial population of catalytic growth centers. The concentration of seed particles determines the ultimate average size and uniformity of these novel two- and three-dimensional platinum nanostructures.     

Photoluminescence investigation based on laser heating effect in ZnO-ordered nanostructures

We synthesized ZnO-SiO2 composite opal and ZnO inverse opal by electrodeposition using SiO2-opal template and polystyrene (PS)-opal template, respectively. Compared with compact ZnO nanocrystal film also prepared by electrodeposition, ordered ZnO nanostructures exhibit more significant red-shift and broadening of the UV peak with increasing excitation power, which is due to a stronger local heating effect in ordered ZnO nanostructures. We developed a quantitative analytical method to investigate photoluminescence (PL) of ZnO based on laser heating effects. The experimental data agree well with fitting curves derived from the electron-phonon interaction model. Important parameters, such as electron-phonon coupling strength and thermal activation energy, can be obtained by fitting experimental data. The resonant Raman spectra provide further evidence that the analyses based on laser heating effects are feasible.     

Sustainable green catalysis by supported metal nanoparticles

The recent progress of sustainable green catalysis by supported metal nanoparticles is described. The template synthesis of metal nanoparticles in ordered porous materials is studied for the rational design of heterogeneous catalysts capable of high activity and selectivity. The application of these materials in green catalytic processes results in a unique activity and selectivity arising from the concerted effect of metal nanoparticles and supports. The high catalytic performances of Pt nanoparticles in mesoporous silica is reported. Supported metal catalysts have also been applied to biomass conversion by heterogeneous catalysis. Additionally, the degradation of cellulose by supported metal catalysts, in which bifunctional catalysis of acid and metal plays the key role for the hydrolysis and reduction of cellulose, is also reported. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 224–235; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900004     

General and Facile Syntheses of Metal Silicate Porous Hollow Nanostructures

Porous hollow nanostructures have attracted intensive interest owing to their unique structure and promising applications in various fields. A facile hydrothermal synthesis has been developed to prepare porous hollow nanostructures of silicate materials through a sacrificial‐templating process. The key factors, such as the concentration of the free metal cation and the alkalinity of the solution, are discussed. Porous hollow nanostructures of magnesium silicate, nickel silicate, and iron silicate have been successfully prepared by using SiO₂ spheres as the template, as well as a silicon source. Several yolk–shell structures have also been fabricated by a similar process that uses silica‐coated composite particles as a template. As‐prepared mesoporous magnesium silicate hollow spheres showed an excellent ability to remove Pb²⁺ ions in water treatment owing to their large specific surface and unique structures.     

Synthesis and optical properties of nanorattles and multiple-walled nanoshells/nanotubes made of metal alloys

The galvanic replacement reaction between silver and chloroauric acid has been exploited as a powerful means for preparing metal nanostructures with hollow interiors. Here, the utility of this approach is further extended to produce complex core/shell nanostructures made of metals by combining the replacement reaction with electroless deposition of silver. We have fabricated nanorattles consisting of Au/Ag alloy cores and Au/Ag alloy shells by starting with Au/Ag alloy colloids as the initial template. We have also prepared multiple-walled nanoshells/nanotubes (or nanoscale Matrioshka) with a variety of shapes, compositions, and structures by controlling the morphology of the template and the precursor salt used in each step of the replacement reaction. There are a number of interesting optical features associated with these new core/shell metal nanostructures. For example, nanorattles made of Au/Ag alloys displayed two well-separated extinction peaks, a feature similar to that of gold or silver nanorods. The peak at approximately 510 nm could be attributed to the Au/Ag alloy cores, while the other peak was associated with the Au/Ag alloy shells and could be continuously tuned in the spectral range from red to near-infrared.