Fabrication & characterization of macroporous CdSe nanostructure via colloidal crystal templating with electrodeposition method

Large area ordered arrays of macroporous Cadmium Selenide (CdSe) nanostructure, which possesses high refractive index and negligible absorption in the visible spectrum critical for the realization of photonic band gaps, was prepared via colloidal templating by galvanostatic electrodeposition. This work investigates the effect of electrodeposition parameters on the macroporous CdSe nanostructure. Field Emission Scanning Electron Microscope (FESEM) images showed two and three dimensional porous structures, consisting of interconnected close-packed arrays of pores. For CdSe thin film of thickness less than 1/3 of the diameter of a polystyrene sphere, it showed a monolayer of circular pores. As for film thickness close to the diameter of the sphere, the pores adopted irregular rounded triangular shapes. When the film thickness was more than one layer of the colloidal polystyrene template, the pores were spherical and had the same diameter as the polystyrene spheres. X-ray Diffraction (XRD) showed that the CdSe films prepared had a cubic structure with nanometer grain size, which was smaller than the diameter of the template spheres as well as the diameter of the interconnected channels. A range of 45–70 nm thick CdSe films with > 90% optical transmittance showed that there was negligible absorption at wavelength of 750 nm. In addition, the CdSe thin film exhibited a band gap energy of 2.07 eV, blue-shifted from the characteristic 1.7 eV of CdSe. This blue-shift characteristic of the deposited CdSe film further indicated that it was nanocrystalline which is potentially useful in photonic applications.     

胶体晶体模板法制备三维有序排列的大孔SiO2材料

将粒径为480 nm的聚苯乙烯微球离心组装为胶体晶体模板,以正硅酸乙酯为硅源配制SiO₂溶胶并填充到模板间隙,原位形成凝胶,最后通过焙烧去除模板,得到三维有序大孔（3DOM）SiO₂。通过SEM检测,大孔以六方有序的方式排列,其孔径及孔径收缩率分别为360 nm和25％。大孔之间由小窗口连通,构成内部三维交联的大孔网络。低温N₂吸附测试表明,大孔孔壁上存在中孔孔隙,其中在3～4 nm有一集中的孔分布。XRD显示,制备的3DOM材料由无定形SiO₂组成。     

聚苯乙烯胶晶模板法制备三维有序大孔SiO2材料

以聚苯乙烯微球(polystyrene microsphere)自然沉积形成的胶体晶体作模板,将以正硅酸甲酯制备的SiO2溶胶填充到模板间隙中,原位形成凝胶,最后通过焙烧除去模板,得到三维有序大孔SiO2.通过SEM检测,观察到六方和四方2种有序的大孔排列方式.大孔孔径及孔径收缩率分别为240nm和19%.2种排列中,大孔之间由小窗口连通,构成三维有序大孔结构.XRD显示,制备的3DOM材料由无定形SiO2组成.     

以聚苯乙烯为模板制备有序大孔氧化铝

采用少皂乳液聚合法成功制备了单分散的聚苯乙烯微球,以微球自组装后的聚苯乙烯胶体晶体为大孔模板,铝溶胶为前驱体填充模板,干燥焙烧除去模板后制备了氧化铝载体。用激光粒度仪、扫描电镜、X射线衍射和氮气吸脱附对聚苯乙烯胶体晶体和氧化铝载体进行了表征。结果表明:少皂乳液聚合法制备的聚苯乙烯微球具有粒径较小(100~350 nm)、单分散性好(0.005)、收率高(约80%)等优点;自组装的胶体晶体呈规则有序排列,微球表面光滑洁净,并以此为模板成功制备了具有三维有序结构的、大孔孔径可调的氧化铝材料。     

Fabrication of egg-shell-roofed macroporous nickel films by a template-mediated electrodeposition process

Through an electrostatics-induced adsorption effect, nickel ions were found to be preferentially adsorbed onto the surface of colloidal particles at template top during the template-mediated electrodeposition process for preparing macroporous structures. This phenomenon results in the preferential reduction and growth of nickel on colloid surface on the template top, instead of filling into the channels among the colloids. After removing the template, an egg-shell-roofed macroporous nickel, consisting of macroporous film covered with monolayer of hollow spheres, can be created.     

Two modes in macroporous Cu2O growth through template-assisted electrodeposition method

Macroporous materials with three dimensional pores and channels are anticipated to exhibit improved performance in numerous applications such as photonic band gap crystals, battery electrodes and gas sensors due to their special structure. In this work, macroporous Cu₂O thin films were prepared by template-assisted electrodeposition method. The mechanism of electrodeposition infiltrating procedures indicated that the target architectures can basically maintain its original shape, and the fabrication of spherical-porous shaped Cu₂O controlled by crystalline structures is firstly studied systematically. The morphology of macroporous material along the (1 1 1) direction demonstrated that the target architecture can copy both the crystalline structures and the colloidal crystal template. Moreover, models are set up to discuss the evolution of the morphology (the shapes of the pore mouths and pore walls), which indicated that the pore mouths and pore walls were deeply influenced by the deposition depth.     

New Colloidal Lithographic Nanopatterns Fabricated by Combining Pre-Heating and Reactive Ion Etching

We report a low-cost and simple method for fabrication of nonspherical colloidal lithographic nanopatterns with a long-range order by preheating and oxygen reactive ion etching of monolayer and double-layer polystyrene spheres. This strategy allows excellent control of size and morphology of the colloidal particles and expands the applications of the colloidal patterns as templates for preparing ordered functional nanostructure arrays. For the first time, various unique nanostructures with long-range order, including network structures with tunable neck length and width, hexagonal-shaped, and rectangular-shaped arrays as well as size tunable nanohole arrays, were fabricated by this route. Promising potentials of such unique periodic nanostructures in various fields, such as photonic crystals, catalysts, templates for deposition, and masks for etching, are naturally expected.     

大孔二氧化硅膜上纳米碳纤维层结构化催化剂载体的制备

1 INTRODUCTION Fast gas-liquid phase reactions over solid cata- lysts easily cause concentration gradient in reactors and catalysts because of relatively slow diffusion as well as the frequent occurrence of low concentration when gasses are dissolved. Such concentration gradi- ent caused by the limitation of mass transfer influ- ences the reaction rate as well as selectivity. Conven- tional strategies for gas-liquid-solid phase catalytic reactions comprise slurry reactors and trickle bed r…     

高比表面积三维有序大孔炭材料的合成与表征

将粒径为540nm的SiO2胶体微球通过自然沉积组装为胶体晶体模板,以葡萄糖的水溶液为前体填充模板间隙,高温炭化后,以HF溶液溶去模板,得到三维有序大孔炭材料。根据SEM检测,大孔以六方有序的方式排列,其孔径及孔径收缩率分别为510nm和5.6%。大孔之间由小窗口连通,构成内部三维交联的大孔网络。低温N2吸附测试表明,大孔孔壁上存在2～10nm为主的中孔孔隙,同时由于前体的表面复制作用,使样品BET比表面积达到948m2/g。XRD表征显示,所制备的3DOM材料由无序石墨结构的炭质组成。     

PS/TiO2核壳型微球和空心TiO2微球有序排列的制备

利用纳米级二氧化钛（TiO₂）溶胶微粒与聚苯乙烯（PS）胶体颗粒的混合悬浮液,以垂直共沉积的方法制备了核壳型PS/TiO₂微球的有序排列。当利用煅烧的方法去除PS胶粒晶体模板后,可以形成空心TiO₂微球的三维有序排列。考察了混合悬浮液中两种胶体颗粒的体积比（PS∶TiO₂=R）对空心TiO₂微球有序排列形成的影响。实验结果表明,合适的R值（6∶1）对于空心微球有序排列的形成至关重要。与此同时,浸渍填充法对照实验的结果表明,煅烧过程中TiO₂纳米颗粒晶型转化引起的收缩是造成TiO₂空心球产生的主要原因。     

High-temperature stable inverse opal photonic crystals via mullite-sol-gel infiltration of direct photonic crystals

Three-dimensionally ordered macroporous materials for photonic or refractory applications have been developed by an innovative approach based on mullite sol-gel infiltration of direct photonic crystals followed by burn-out and calcination. Direct photonic crystals were obtained using polystyrene spheres templates either by vertical convective self-assembly or by drop casting. The samples were then infiltrated by spin coating with mullite sol-gels prepared with two different compositions (74 wt.% Al₂O₃, 26 wt.% SiO₂ and 80 wt.% Al₂O₃, 20 wt.% SiO₂). The inverse opal photonic crystals prepared with both sol-gels presented a highly ordered porosity and the high-alumina composition showed stability up to 1500°C. After inversion of the structure (polymeric template burn-out), the high-alumina composition showed roundness of the PS templated pores closer to an ideal sphere (Ø = 0.967) when compared to the low-alumina composition (Ø = 0.954). Although the inverse opal photonic crystals did not present a photonic bandgap, they showed structural stability at high temperatures, which enable their application as refractory materials.     

Creation of Controlled Defects Inside Colloidal Crystal Arrays with a Focused Ion Beam

In this work the reliability of the focused-ion-beam (FIB) patterning on polystyrene (PS) colloidal crystals at different scales is determined. Ordered arrays of PS spheres (465 nm) are successfully modified by selectively removing a single sphere. The water-vapor assisted FIB milling is crucial to obtain this result. Furthermore, isolated PS spheres are FIB drilled with or without chemically enhanced milling aiming at the exploration of the limits of such a technique. These controlled defects created using the FIB-assisted techniques may be helpful in preparing mockups of photonic crystals, sensors or as colloidal masks for diverse lithographic processes.     

Preparation and Characterization of Confined Atactic Polystyrene in Ordered Silica/Polystyrene Composites

Ordered silica/polystyrene composites were prepared via radical polymerization in silica colloidal crystal templates, and ordered macroporous polymers were accordingly obtained after removing the silica templates. The confinement effect of the templates on the polymers in the composites was investigated. NMR results indicated that the polystyrenes formed both inside and outside the template were atactic. The polystyrene inside the template possessed a higher molecular weight and a narrower molecular weight distribution than the bulk one outside the template. The glass transition temperature of the confined polystyrene increased significantly with decreasing silica sphere size of the templates, and so did the contraction of polymer pores. The smaller the silica sphere size of the templates, the more remarkable is the confinement, which could be explained by entropic confinement of the polymer chains within a fixed inorganic meso‐framework (T. P. Russell, Science 2001 , 293, 446).     

The fabrication of large-scale sub-10-nm core-shell silicon nanowire arrays

A combination of template-assisted metal catalytic etching and self-limiting oxidation has been successfully implemented to yield core-shell silicon nanowire arrays with inner diameter down to sub-10 nm. The diameter of the polystyrene spheres after reactive ion etching and the thickness of the deposited Ag film are both crucial for the removal of the polystyrene spheres. The mean diameter of the reactive ion-etched spheres, the holes on the Ag film, and the nanowires after metal catalytic etching exhibit an increasing trend during the synthesis process. Two-step dry oxidation and post-chemical etching were employed to reduce the diameter of the silicon nanowires to approximately 50 nm. A self-limiting effect was induced by further oxidation at lower temperatures (750°C ~ 850°C), and core-shell silicon nanowire arrays with controllable diameter were obtained.     

环糊精改性光子晶体分子印迹法检测诺氟沙星

首先合成顺丁烯二酸酐改性的β-环糊精,垂直沉积制备聚苯乙烯光子晶体模板。然后将改性环糊精与丙烯酸、过硫酸铵、N,N'-亚甲基双丙烯酰胺、诺氟沙星等混合的前驱液填入光子晶体模板中,引发交联聚合,得到蛋白石结构的凝胶光子晶体。再在二甲苯中超声除去聚苯乙烯光子晶体模板,用十二烷基硫酸钠的V(醋酸):V(甲醇)=1:9溶液除去分子印迹模板诺氟沙星,蒸馏水清洗后得到反蛋白石结构的分子印迹凝胶光子晶体。通过对比印迹凝胶光子晶体与非印迹凝胶光子晶体在同样条件下对诺氟沙星的响应性,发现印迹凝胶光子晶体能选择性地迅速响应溶液中的诺氟沙星,当诺氟沙星浓度从10^-9 mol/L递增到10^-4 mol/L时,其光子晶体的衍射峰位置从633 nm逐渐红移到722 nm,而非印迹凝胶光子晶体响应性很差。     

Preparation of ordered porous SnO2 films by dip-drawing method with PS colloid crystal templates

Ordered macroporous SnO₂ thin films were fabricated by using colloid crystal template of polystyrene (PS) spheres. Efficient dip-drawing method was used in both PS template assembly and the fabrication of porous structure. The PS templates were orderly assembled on clean glass substrates through colloid crystallization of monodisperse PS latex spheres, which were synthesized by an emulsion polymerization technique. The porous SnO₂ thin films were prepared through filling SnO₂ precursor sol into the spaces among the close-packed PS templates, and then annealing at 500 °C to remove the PS spheres and form SnO₂ crystal wall. The forming mechanism of PS templates through dip-drawing method was explained based on three driving forces existing in the assembly processes. The SnO₂ sol concentration and PS sphere size had important effects on formation of ordered porous structure The X-ray diffraction (XRD) spectra indicated the thin film was rutile structure and consisted of nanometer grains. The transmittance spectrum showed that optical transmittance kept above 80% beyond the wavelength of 440 nm. Optical band-gap of the porous SnO₂ film was 3.68 eV.     

Ordered Macro–Mesoporous nc-TiO2 Films by Sol–Gel Method Using Polystyrene Array and Triblock Copolymer Bitemplate

Ordered macro–mesoporous titania (TiO₂) film with a mesoporous anatase nanocrystalline wall was synthesized by simultaneous application of polystyrene (PS) array colloidal crystal and triblock copolymer P123 as templates, and tetrabutyl orthotitanate as titanium source. Mesoporous structure was optimized through solvent species, amount of P123, and the addition of hydrochloric acid. Permeation of mesoporous TiO₂ precursors into PS array template was examined by altering the sol concentration. The results show that the mesoporous anatase nanocrystalline titania (nc-TiO₂) formed has a Brunauer–Emmett–Teller surface area of 89.55 m²/g typically and an average mesoporous size of 5.67 nm. Sol concentration, characterized by viscosity, surface tension, and contact angle between the sol and PS template, dominates the perfection of macro–mesoporous structure. Optical transmittance for the mesoporous film keeps a high level (above 70%) beyond the wavelength of 400 nm, ∼10% higher than that of the macro–mesoporous film. The band gap of macro–mesostructure TiO₂ film is 3.00 eV, which is not only lower than the 3.25 eV of the mesoporous film, but is also lower than the 3.18 eV of P25 TiO₂, because of the defect level from the surface state of macroporous structure.     

Fabrication of Patterned Inverse Opal Structure Through Physical Confinement Assembly and Selective Electrochemical Deposition

We develop a chemical modification-free process for fabrication of patterned photonic crystals (PhCs) of inverse opal structure. This process, involving photolithography, colloidal assembly, and electrochemical deposition, is potentially applicable for fabrication of practical optical devices. Polystyrene (PS) spheres were self-assembled onto pre-patterned substrates to serve as the sacrificial template. This template was then converted into a patterned inverse opal structure with selective electrochemical deposition. The thickness of the inverse opal structure can be easily controlled by adjusting the time of electrodeposition. We demonstrated the process with fabrication of a T-shape structure surrounded by an inverse opal structure of titania. Titania was chosen here as a representative demonstration material, and the process can be readily applied to other materials of desired characteristics.     

三维有序大孔氧化物催化剂的制备及应用

三维有序大孔氧化物具有均匀有序的大孔孔道、较高的孔容以及骨架组成的多样性等。主要介绍了三维有序大孔氧化物的结构、制备过程及应用进展。详细阐述了单分散微球的制备及改性、胶体晶体模板的制备、前驱体的制备及填充以及胶体晶体模板的去除。简单综述了近年来三维有序大孔氧化物在环境催化、石油化工、光催化及生物催化领域的应用研究,并对未来三维有序大孔氧化物的发展做了总结和展望。     

三维有序大孔氧化钇稳定氧化锆的制备与表征

以聚苯乙烯(polystyrene, PS)胶体晶体为模板,采用柠檬酸凝胶方法制备氧化钇稳定氧化锆(yttria stabilized zirconia, YSZ)前驱体溶胶,采用浸渍-提拉方法向PS模板的空隙中填充YSZ溶胶,煅烧去除模板后成功地制备了三维有序大孔YSZ材料.研究前驱体溶胶不同浓度、浸渍次数以及煅烧条件等因素对大孔YSZ结构的影响.用扫描电子显微镜对YSZ的微观结构进行表征.结果表明:前驱体溶胶的浓度在0.3～0.4 mol/L的范围内,浸渍次数为1次或2次,煅烧温度为600℃时可以得到高度有序的大孔YSZ.