溶胶-凝胶法设计与制备金属及合金纳米材料的研究进展

溶胶-凝胶法是常见的制备金属氧化物的方法之一。在溶胶-凝胶法中,各种反应物能达到分子级的均匀混合,因此能制备成份复杂的氧化物材料。目前,溶胶-凝胶法也应用于设计与制备金属纳米材料,特别是合金纳米颗粒。例如,溶胶-凝胶法能应用于制备CoPt、FePt等磁性纳米合金材料以及CoCrCuNiAl高熵合金纳米材料,以及物相结构为有序相的Cu3Pt合金纳米材料。本文综述溶胶-凝胶法设计制备金属纳米材料的研究进展,包括溶胶-凝胶法实施的基本步骤、该方法在制备金属纳米材料方面的具体应用,并着重论述采用热力学计算设计金属及化合物的基本原理。该基本原理包括计算金属氧化物与还原性气体如氢气的还原反应的吉布斯自由能的变化量、金属氧化物的标准电极电位(不同于金属离子的标准电极电位)。最后探讨溶胶-凝胶法设计制备金属纳米材料存在的问题以及后续可能的发展方向。     

聚合物-二氧化硅复合基材中CdS纳米晶的合成

本文报道在Sol-gel基材中制备由聚合物稳定的CdS纳米晶的新方法， 即通过甲基丙烯酸镉与甲基丙烯酸羟乙酯共聚合合成了含有Cd 2+的聚合物微凝胶, 在聚合物微凝胶网络中原位聚合正硅酸乙酯形成聚合物互穿的Sol-gel复合基材. 再向该聚合物/二氧化硅复合基材中通入H2S气体得到CdS纳米晶. 在聚合物网络中原位聚合正硅酸乙酯可以降低纯二氧化硅材料的脆性; 另一方面, 二氧化硅可以作为增强剂增加聚合物材料的强度. 因此, 在我们合成的聚合物/二氧化硅复合基材中制备的CdS纳米晶将具有很好的应用前景.     

Sulfide Gels and Films: Products of Non-Oxide Gelation

The preparation of concentrated sols and transparent stiff gels of II-VI semiconductors nanocrystals is reported. A two-step process for the production of cadmium sulfide is reported. Sol stabilization and gelation control are achieved through successive passivation and depassivation of the surface of the nanocrystals which are complexed with thiols. The mechanisms driving the aggregation and the gelation are explained on the basis of NMR and SAXS experiments. Thin films as well as monoliths can be produced. The general principles of the method presented are not restricted to chalcogenide systems and thus enlarge the domain of application of the inorganic sol-gel process.     

Single crystal manganese oxide multipods by oriented attachment

Nonhydrolytic sol-gel processes in organic solvents have become very popular for the synthesis of metal oxide NCs. We report an affordable, high-yield, shape-control synthesis of MnO multipod nanocrystals with a quick reaction time. The reaction yields exclusively multipods; two to six pod nanocrystals are synthesized. The mechanism leading to this hierarchical nanostructure is studied in relation with an oriented attachment mechanism; all nanocrystals are found to be single crystals. The study is completed by high-resolution TEM, X-ray powder diffraction, and magnetic measurements.     

溶胶-凝胶法可控制备氧化锡纳米晶包覆碳纳米管

采用溶胶-凝胶法制备了氧化锡纳米晶包覆的碳纳米管。自由Sn4+离子从稳定的Sn柠檬酸配合物中缓慢释放出来,迁移到碳纳米管上,并在碳纳米管上沉积形成了SnO2纳米晶,沉积过程完全为异相成核方式,在碳纳米管外并没有发现单独的SnO2纳米晶。这种溶胶-凝胶方法还可以用来制备无氯离子污染的、低团聚的纯SnO2纳米晶。     

Synthesis of monodisperse spherical nanocrystals

Much progress has been made over the past ten years on the synthesis of monodisperse spherical nanocrystals. Mechanistic studies have shown that monodisperse nanocrystals are produced when the burst of nucleation that enables separation of the nucleation and growth processes is combined with the subsequent diffusion-controlled growth process through which the crystal size is determined. Several chemical methods have been used to synthesize uniform nanocrystals of metals, metal oxides, and metal chalcogenides. Monodisperse nanocrystals of CdSe, Co, and other materials have been generated in surfactant solution by nucleation induced at high temperature, and subsequent aging and size selection. Monodisperse nanocrystals of many metals and metal oxides, including magnetic ferrites, have been synthesized directly by thermal decomposition of metal-surfactant complexes prepared from the metal precursors and surfactants. Nonhydrolytic sol-gel reactions have been used to synthesize various transition-metal-oxide nanocrystals. Monodisperse gold nanocrystals have been obtained from polydisperse samples by digestive-ripening processes. Uniform-sized nanocrystals of gold, silver, platinum, and palladium have been synthesized by polyol processes in which metal salts are reduced by alcohols in the presence of appropriate surfactants.     

Synthesis and Characterization of ZnS：Ag Nanocrystals Surface-capped with Thiourea

Ag^＋ -doped ZnS nanocrystals surface-capped with thiourea （expressed as ZnS： Ag/thiourea） were synthesized through sol-gel method with thiourea as a surface modifier and characterized by X-ray diffraction（XRD）, transmission electron microscope（TEM）, X-ray fluorescence spectrum（XRF）, infrared spectrum （IR）, UV-Vis absorption spectrum（ UV-Vis）, and photoluminescence spectrum（PL）. The results show that Ag^＋ ions are doped in ZnS nanocrystals, and the sulfur atoms in thiourea molecules coordinate with metal ions on the surface of the nanocrystals. The spherical ZnS： Ag/thiourea nanocrystals with an average diameter of 5 nm have good fluorescent characteristics, and therefore have great potential for use in molecular assembly and novel luminescence materials.     

Photochromism of spiropyran nanocrystals embedded in sol-gel matrices

Spectroscopic and kinetic properties of a new photochromic medium, consisting of nanocrystals of spyropyran molecules (1,3-dihydro-1,3,3,5',6',pentamethyl-spiro[2H-indole-2,2'-[2H]pyrano [3,2-b]pyridinium] iodide) embedded in an organo-silicate sol-gel film, are presented and compared to microcrystals obtained by slow evaporation of a solvent. High photoconversion efficiencies for both kinds of crystals have been observed. In microcrystals, the photomerocyanine form absorbs at 570 nm with a fading rate of 5 h, in nanocrystals the photomerocyanine form absorbs at 535 nm with a fading rate of 41 h. Therefore, the crystalline structure of nanocrystals is different from the microcrystal one.     

掺杂CuInS2纳米晶玻璃的三阶非线性光学性质

采用溶胶-凝胶法结合气氛控制制备了CuInS2纳米晶玻璃. 利用X射线粉末衍射仪(XRD)和透射电子显微镜(TEM)对CuInS2纳米晶在玻璃中的形貌和微结构进行了表征, 并利用飞秒Z扫描技术对该玻璃的三阶非线性光学性质进行了研究. 结果表明, 在钠硼硅玻璃中形成了尺寸分布为10 nm左右的均一的CuInS2四方晶系纳米晶. 该玻璃体现出优良的三阶非线性光学性能, 其三阶非线性光学折射率γ、吸收系数β和极化率χ(3)分别为8.57×10-16 m2/W, 3.74×10-8 m/W和1.95×10-17 m2/V2.     

Synthesis of highly luminescent glasses incorporating cdte nanocrystals through sol-gel processing

Highly photoluminescent glass was prepared by embedding water-soluble nanocrystals in a glass matrix using a novel sol-gel process. Thiol-stabilized CdTe nanocrystals and aminopropyltrimethoxysilane were found to be the best combination in the preparation. The synthesis process had to be optimized to avoid nanocrystal agglomeration. The nanocrystals thus embedded in the glass matrix did not show any deterioration of the surface condition. The obtained glass combines excellent optical properties of nanocrystals with the high stability of glass; it emits light of various colors with narrow emission spectra and high photoluminescent efficiency (41%).     

Effects of thermal annealing on the structural and optical properties of Mg(x)Zn(1-x)O nanocrystals

Mg(x)Zn(1-x)O ternary alloy nanocrystals with hexagonal wurtzite structures were fabricated by using the sol-gel method. X-ray diffraction patterns, UV-vis absorption spectra, and photoluminescence spectra were used to characterize the structural and optical properties of the nanocrystals. For as-prepared nanocrystals, the band gap increases with increasing Mg content. Weak excitonic emission with strong deep-level emission related to oxygen vacancy and interface defects is observed in the photoluminescence spectra at room temperature. Thermal annealing in oxygen was used to decrease the number of defects and to improve the quality of the nanocrystals. In terms of XRD results, the grain sizes of nanocrystals increase with increasing annealing temperature and the lattice constants of alloy are smaller than those of pure ZnO. The band gap becomes narrower with increasing annealing temperature. For Mg(x)Zn(1-x)O nanocrystals (x=0.03-0.15) annealed at temperatures ranging from 500 to 1000 degrees C, intense near-band-edge (NBE) emissions and weak deep-level (DL) emissions are observed. Consequently, the quality of Mg(x)Zn(1-x)O nanocrystals can be improved by thermal annealing.     

一种提高SiO2凝胶玻璃中ZnSe纳米晶稳定性的方法

半导体纳米品材料具有很大的应用潜力，然而非氧化物半导体纳米晶在空气中通常不稳定．因此其应用受到限制．纳米品不稳定主要是因为其表面原子配位不足，存在大量的悬空键，d使其很容易与环境中的物质发生反应而逐渐变质．人们通常采用惰性介质包覆的方法来提高纳米晶的稳定性，     

Optical Gas Sensing Properties of Silica Film Doped with Cobalt Oxide Nanocrystals

SiO₂ sol-gel films doped with cobalt oxide nanocrystals have been fabricated. The nanocrystals precipitate in the glass film at 500_°C, while the film is still porous. The nanocomposite films showed a reversible change in the optical transmittance when exposed to CO in the 250 < < 850 nm range. The effects of the residual porosity and testing temperature have been studied. The gas sensing properties of the cobalt oxide nanocrystals doped films are compared with those of nickel oxide nanocrystals doped silica film, previously reported.     

Preparation and Characterization of N-4-Nitrophenyl-L-prolinol Nanocrystals in Sol-Gel Matrices

Organic nanocrystals of N-4-nitrophenyl-l-prolinol (NPP) have been grown in sol-gel matrices prepared from silicon alkoxide precursors. Our process is based on the control of the nucleation and growth kinetics of the dye in the pores of dense gels. Nanocomposites gel-glasses are obtained with a high optical quality due to the small size of the nanocrystals (10-20 nm). Differential scanning calorimetry experiments evidenced clearly the melting point of NPP nanocrystals, which is registered 51°C above that of NPP powder. Micro-Raman and solid state NMR spectroscopies allowed us to demonstrate that our nanocrystallization process does not chemically modify NPP molecules. We specified also the nature of interactions existing between the NPP nanocrystals and the xerogels. These strong interactions, which explain the important increase of the melting point of the nanocrystals in comparison to the NPP powder, are hydrogen bonds between nitro groups of NPP and uncondensed silanol functions of the silicate network.     

SiO_2基底中MnFe_2O_4纳米晶的制备与表征

在N,N-二甲基甲酰胺(DMF)存在下,以溶胶-凝胶技术成功地制备了无定形二氧化硅基底中均匀分布的MnFe_2O_4纳米晶.由粉末X射线衍射和电子衍射确证了MnFe_2O_4纯相的生成. 由粉末X射线衍射和红外吸收光谱研究了MnFe_2O_4纳米晶形成过程.尖晶石结构的MnFe_2O_4在800℃时开始形成,900℃时基本完成.磁性质测量表明在烧结到900℃的样品中,MnFe_2O_4纳米晶室温具有超顺磁性,78K时为软磁性.1000℃ 和1100℃下得到的样品室温和78K时都具有软磁性.     

室温光致发光含钒硅胶的制备和研究

钒掺杂的硅胶显示出有广阔应用前景的催化和光催化特性,引起了人们在其催化机理和应用方面的研究热潮[1-6]。硅胶中氧化钒的微观分子结构和电子状态与它的催化特性密切相关,而荧光谱和磷光谱是研究分子结构,电子状态和光反应的重要工具,目前关于发光机制的研究已经取得巨大进展     

钛酸锌的制备及其对高氯酸铵热分解的催化性能

ZnTiO₃ nanocrystals were prepared by sol-gel method, using Zn(NO₃)₂ and Ti(C₄H₉O)₄ in the topic. The as-prepared ZnTiO₃ nanocrystals were characterized by XRD, FTIR and TEM, and the catalytic performance of ZnTiO₃ nanocrystals of different contents for the ammonium perchlorate(AP)decomposition was investigated by thermal analysis. The results indicate that ZnTiO₃ with pure cube structure can be synthesized at 600 ℃ by this procedure,which was spheroid with particle size of about 60~100 nm. The results expressed that the low temperature decomposition peaks of AP is advanced by 17 ℃ and the high temperature decomposition peaks of AP is advanced by 24 ℃ when adding 5% nanoparticle ZnTiO₃ powder. The catalytic effects of ZnTiO₃ powders on the high temperature decomposition of AP are less than that of nanometer metal powders, but all the micron metal powders decrease the low decomposition temperature of AP.     

溶胶-凝胶法合成硅溶胶包覆型均分散纳米β分子筛

在系统考察铝源、反应体系硅铝比、钠离子、反应温度等对分子筛粒度影响的基础上,优化合成条件合成出了粒径为100 nm左右的β分子筛。利用XRD和TEM对所合成样品进行了表征。采用溶胶凝胶法研究了硅溶胶包覆的均分散纳米β分子筛复合材料的合成,结果表明合成产物为纳米β分子筛均匀分散于硅溶胶基质中的微孔-介孔双孔复合材料。     

Role of urea in the preparation of highly porous nanocomposite aerogels

The preparation of highly porous CoFe2O4-SiO2 nanocomposite aerogels was successfully achieved by a novel sol-gel procedure involving urea-assisted co-gelation of the precursor phases. This method allows fast gelation, giving rise to an aerogel with 97% porosity. The formation of CoFe2O4 nanocrystals homogeneously distributed within the matrix occurs after calcination at 750 degrees C and is complete at 900 degrees C. Despite the high temperature required for the formation of the CoFe2O4 nanocrystals, the high porosity typical of aerogels is still retained.     

肼溶胶-凝胶法制备高比表面积纳米氮化钛粉体的研究

以无水肼作氮源, 采用肼溶胶-凝胶技术(HSG)成功地制备了TiN粉体, 研究了不同钛源、处理气氛及焙烧温度对TiN粉体晶化过程的影响, 并对其形成机理进行了讨论. 与氨气氮化法相比, 该方法所需温度低、TiN的粒径小、比表面积大, 并且分散均匀.