Time-dependent control of hole-opening degree of porous ZnO hollow microspheres

Well-designed, monodispersed porous ZnO hollow microspheres with controlled hole-opening were successfully synthesized by a facile two-step solution route at low temperature. The hollow microspheres having average diameter of 3-4 μm showed time-dependent hole-opening, i.e. 4-100% for 15-75 min. The hole-opening percentage increases linearly with time until complete opening. The ZnO hollow microspheres also exhibited a high surface area (34 m(2) g(-1)), a large pore volume (0.19 cm(3) g(-1)) and an average pore diameter of 3.8 nm. A plausible growth mechanism for the formation of ZnO hollow microspheres was also proposed.     

金纳米粒子与聚吡咯纳米管的复合及其SERS效应研究

通过柠檬酸盐与HAuCl4水溶液在微沸状态下反应制备的金纳米粒子因其特殊的表面与界面效应在光学、生物学和催化化学领域得到了广泛应用,而聚吡咯(PPy)具有环境稳定性好、电导率高且变化范围大、容易合成等优点,聚吡咯纳米管可用作导电材料、酶封装材料、抗静电材料,也可用于制备传感器、传动器、固体电解质电容器等。     

Needle-like calcium carbonate assisted self-assembly of mesostructured hollow silica nanotubes

Mesostructured hollow silica nanotubes (MHSNTs) were successfully produced via the self-assembly of C₁₆TMABr and silica species on the surface of needle-like calcium carbonate nanoparticles in an alkaline medium at room temperature. The characterization of MHSNTs by transmission electron microscopy (TEM), scanning electron microscopy (SEM), pore size distribution (PSD) and Brunauer-Emmett-Teller (BET) indicated that MHSNTs had uniform tubular hollow structures with big openings, a length of 1.5-2.0 μm, an inner diameter of 150-200 nm at the open end and 50-60 nm at the closed end, and a wall thickness of 20-30 nm, as well as a narrow PSD around 2.3 nm in the shells and a BET surface area as high as ∼975.3 m²/g. By small-angle X-ray diffraction (XRD), BET and pore structure analysis, it was found that more uniformly structured mesopores could be formed by the method of removing the double templates simultaneously through a solvent extraction process, as compared to the separate removal of the double templates by calcinating and then etching in an acidic solution, and the amount of C₁₆TMABr affected the mesoporous structures of MHSNTs greatly. The formation processes of MHSNTs were also studied with XRD and FTIR.     

Catalytic activity and regeneration property of a Pd nanoparticle encapsulated in a hollow porous carbon sphere for aerobic alcohol oxidation

A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions.     

三维有序SiC空心球的制备及表征

以三维有序多孔碳为模板, 以聚甲基硅烷(PMS)为前驱体, 经过前驱体的渗入、交联和陶瓷转化以及多孔碳模板的烧除, 制备了长程三维有序SiC空心球. 所制备的SiC空心球的外径(135-896 nm)、 球壳厚度(14-79 nm)、 BET比表面积(50.8～5.0 m2/g)及微孔体积(0.265～0.038 cm3/g)受不同孔径的多孔碳模板(150-1 000 nm)或不同前驱体浓度的控制. 所制备的SiC空心球以hcp结构排列成长程三维有序的序列.     

Gold hollow nanospheres: tunable surface plasmon resonance controlled by interior-cavity sizes

Uniform gold hollow nanospheres with tunable interior-cavity sizes were fabricated by using Co nanoparticles as sacrificial templates and varying the stoichiometric ratio of starting material HAuCl4 over the reductants. The formation of these hollow nanostructures is attributed to two subsequent reduction reactions: the initial reduction of HAuCl4 by Co nanoparticles, followed by the reduction by NaBH4. In addition, a thick layer of silica was successfully coated onto the gold hollow nanospheres. These nanostructures are extensively characterized by TEM, XRD, HRTEM, SEM, electron diffraction, energy-dispersive X-ray analysis, and UV-visible absorption spectroscopy. It is evident that the SPR peak locations corresponding to these hollow nanospheres are shifted over a region of more than 100 nm wavelength due to changes of shell thickness, which make these optically active nanostructures of great interest in both fundamental research and practical applications.     

Facile preparation of Au nanoparticle-embedded polydopamine hollow microcapsule and its catalytic activity for the reduction of methylene blue

Abstract

Development of novel supported catalysts with high activity and stability is still a challenge. In this study, the Au-polydopamine (Au-PDA) hollow microcapsules with Au nanoparticles embedded into the PDA microcapsule shell have been synthesized through a simple template-induced covalent assembly method, where polystyrene (PS) nanospheres were used as templates to form core/shell structured PS/Au-PDA composites, followed by core removal through tetrahydrofuran etching. Their morphology and composition were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier transform infrared spectra (FT-IR), UV-Vis spectrophotometer and X-ray diffraction (XRD), respectively. Results showed that the Au-PDA microcapsules possessed well-fined hollow structure and uniform sizes with inner diameter of about 385?nm, shell thickness of about 30?nm, and Au nanoparticles with diameter of about 17?nm incorporated. The catalytic performance of Au-PDA hollow microcapsules was evaluated through the reduction of methylene blue (MB) dye with NaBH₄ as a reducing agent. Compared to PDA/Au composites with Au nanoparticles loaded on the surface of PDA microspheres, as-prepared Au-PDA hollow microcapsules show good stability and recyclability in the catalytic experiments as the Au nanoparticles were firmly wrapped in PDA matrix, which makes the Au-PDA hollow microcapsules a practicable catalyst candidate for advanced catalytic systems.     

Physical vapor deposition of one-dimensional nanoparticle arrays on graphite: seeding the electrodeposition of gold nanowires

One-dimensional (1D) ensembles of 2-15 nm diameter gold nanoparticles were prepared using physical vapor deposition (PVD) on highly oriented pyrolytic graphite (HOPG) basal plane surfaces. These 1D Au nanoparticle ensembles (NPEs) were prepared by depositing gold (0.2-0.6 nm/s) at an equivalent thickness of 3-4 nm onto HOPG surfaces at 670-690 K. Under these conditions, vapor-deposited gold nucleated selectively at the linear step edge defects present on these HOPG surfaces with virtually no nucleation of gold particles on terraces. The number density of 2-15 nm diameter gold particles at step edges was 30-40 microm-1. These 1D NPEs were up to a millimeter in length and organized into parallel arrays on the HOPG surface, following the organization of step edges. Surprisingly, the deposition of more gold by PVD did not lead to the formation of continuous gold nanowires at step edges under the range of sample temperature or deposition flux we have investigated. Instead, these 1D Au NPEs were used as nucleation templates for the preparation by electrodeposition of gold nanowires. The electrodeposition of gold occurred selectively on PVD gold nanoparticles over the potential range from 700-640 mV vs SCE, and after optimization of the electrodeposition parameters continuous gold nanowires as small as 80-90 nm in diameter and several micrometers in length were obtained.     

Narrow pore-diameter polypyrrole nanotubes

Bulk quantities of electrically conducting nanotubes of polypyrrole having narrow pore diameter (6 nm) can be synthesized rapidly by chemical oxidative polymerization of pyrrole in the presence of stoichiometric amounts of V2O5 nanofibers. The V2O5 nanofibers act as templates for polymerization and yield, as the initial product, polypyrrole nanotubes with pores filled with V2O5. The V2O5 dissolves readily in aq. 1.0 M HCl, yielding hollow polypyrrole nanotubes having conductivity of approximately 2 S/cm. As-synthesized polypyrrole nanotubes spontaneously reduce noble metal ions to the corresponding metal nanoparticles at room temperature without any capping or dispersing agents. For example, 3-5 nm size nanoparticles of Ag, Au, and Pd, etc., deposit readily on the surface of the tubes which then migrate spontaneously to the pore, and, in the case of Ag, coalesce in the core, yielding 4-8 nm diameter coaxial cables of Ag surrounded by a 20-30 nm thick polypyrrole fiber sheath.     

A general method for the rapid synthesis of hollow metallic or bimetallic nanoelectrocatalysts with urchinlike morphology

We have reported a facile and general method for the rapid synthesis of hollow nanostructures with urchinlike morphology. In-situ produced Ag nanoparticles can be used as sacrificial templates to rapidly synthesize diverse hollow urchinlike metallic or bimetallic (such as Au/Pt) nanostructures. It has been found that heating the solution at 100 degrees C during the galvanic replacement is very necessary for obtaining urchinlike nanostructures. Through changing the molar ratios of Ag to Pt, the wall thickness of hollow nanospheres can be easily controlled; through changing the diameter of Ag nanoparticles, the size of cavity of hollow nanospheres can be facilely controlled; through changing the morphologies of Ag nanostructures from nanoparticle to nanowire, hollow Pt nanotubes can be easily designed. This one-pot approach can be extended to synthesize other hollow nanospheres such as Pd, Pd/Pt, Au/Pd, and Au/Pt. The features of this technique are that it is facile, quick, economical, and versatile. Most importantly, the hollow bimetallic nanospheres (Au/Pt and Pd/Pt) obtained here exhibit an area of greater electrochemical activity than other Pt hollow or solid nanospheres. In addition, the approximately 6 nm hollow urchinlike Pt nanospheres can achieve a potential of up to 0.57 V for oxygen reduction, which is about 200 mV more positive than that obtained by using a approximately 6 nm Pt nanoparticle modified glassy carbon (GC) electrode. Rotating ring-disk electrode (RRDE) voltammetry demonstrates that approximately 6 nm hollow Pt nanospheres can catalyze an almost four-electron reduction of O(2) to H(2)O in air-saturated H(2)SO(4) (0.5 M). Finally, compared to the approximately 6 nm Pt nanoparticle catalyst, the approximately 6 nm hollow urchinlike Pt nanosphere catalyst exhibits a superior electrocatalytic activity toward the methanol oxidation reaction at the same Pt loadings.     

Fabrication of triple-shelled hollow spheres with optical properties via RAFT polymerization

<正>The triple-shelled hollow spheres with optical properties were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization.After removal the core templates of the poly(styrene),the hollow silica spheres were obtained.The coating process of poly(methyl methacrylate)(PMMA) on the hollow silica spheres surface via surface RAFT polymerization was performed subsequently.The polymers coated on the hollow spheres surfaces were end-functionalized by trithiocarbonate,and they were used as RAFT agent to proceed the chain extension polymerization using Tb complex as monomer.The samples were characterized by FT-IR,SEM and luminescence spectroscopy respectively.The results indicated that the triple-shelled hollow spheres had been prepared successfully and the average diameter of the hollow core was about 1μm.     

Novel drug delivery system of hollow mesoporous silica nanocapsules with thin shells: preparation and fluorescein isothiocyanate (FITC) release kinetics

Core-shell nanoparticles of Au@silica with a diameter of approximate 45–60 nm and wall thickness in range of 3–10 nm were synthesized by using 40 and 50 nm gold nanoparticles as the templates. The mesoporous particles are regulated by 3-aminopropyltrimethoxysilane addition. Hollow mesoporous silica nanocapsules (HMSNs) were prepared by using sodium cyanide to dissolve the gold cores. The characterization of Au@silica and HMSNs by transmission electronic microscope indicated that the silica shells were uniform and smooth, and also the porosity was proved by fluorescein isothiocyanate (FITC) release experiments. The ratio of hollow core to HMSNs is more than 70%. HMSNs were subsequently used as drug carrier to investigate FITC (as a model drug) release behaviors in vitro. Fluorescent spectrometry was performed to determine the release kinetics from the HMSNs. The release profiles are significantly different as compared with the control (free FITC), which show that HMSNs are good drug carriers to control drug release, and have high potential in therapeutic drugs delivery in future applications.     

以手性两亲小分子自组装体为模板制备介孔二氧化硅空心球

合成了手性阳离子型两亲性小分子化合物,利用圆二色谱分析了其在水中形成的自组装体的结构;以该化合物的自组装体为模板,在正丙醇和氨水的混合溶剂中制备得到了介孔二氧化硅空心球;利用扫描电镜、透射电镜、X射线衍射仪以及氮气吸附-脱附试验装置分析了二氧化硅空心球的形貌及孔结构.结果表明,两亲性小分子在水中形成的自组装体呈现手性堆积;合成的介孔二氧化硅空心球的直径约为600~800nm,壁厚约为100~150nm,其孔道垂直于球的表面,孔径约为3.0nm,比表面积约为306m2·g-1.正丙醇作为模板控制二氧化硅空心球的空腔尺寸和形貌,而两亲性小分子的自组装体作为模板控制放射状孔道的形貌和尺寸.     

Preparation, structure, and magnetic properties of mesoporous magnetite hollow spheres

Preparation of mesoporous Fe3O4 (magnetite) hollow spheres has been reported using hydrothermal synthesis and calcinations. The carboxyl-functionalized PS spheres were used as the templates coated by Fe3O4 particles and ethylene glycol (EG) as an organic structure directing agent. PS and EG were removed by calcinations method. The surface area after calcination at 500 degrees C is found to be 74 m(2) g(-1). The hollow spheres exhibited the weak ferromagnetism.     

第三次纳米自组装制备大孔主客体催化材料

本文提出了第三次纳米自组装的正向胶束、反向胶束法,并利用其制备了一种大孔主客体催化材料．以二次纳米自组装Al2O3为主体,根据压汞法,正向胶束法制备的催化材料孔容为0．62～0．80cm^3／g、比表面积为123～137mZ／g、平均孔径为20～23．3nm,孔径分布大于30nm范围的可达58．69％,堆积密度为0．43—0．55g／cm^3,活性金属负载量可达36．99％;由氮气吸附法,反向胶柬法制备的催化材料具有0．74cm^3／g的孔容、262m2／g的比表面积、11．8nm的平均孔径．结果显示,活性金属以球形或棒状的结晶态存在于主体表面,其中,正向胶束法中为直径2-3nm的微晶态纳米粒子,反向胶束法中为直径0．1μm、长1-2．5μm的棒状体．采用催化裂化柴油和催化裂化重循环油（1：2,体积比）混合而得油品对FA．Z20进行50h加氢评价实验,其单位体积活性金属的脱硫率、脱氮率、脱芳烃率（四环、五环）分别为参比剂的4．6、2．1和4．7倍,初活性良好,具有较强的抗结焦性能．     

Synthesis of poly(o-phenylenediamine) hollow spheres and nanofibers using different oxidizing agents

Poly(o-phenylenediamine) (PoPD) hollow spheres (ca. 800 nm in outer diameter) were synthesized by a simple solution route using ammonium persulfate (APS) as the oxidizing agent, whereas PoPD nanofibers (0.5-2 μm in width and more than 100 μm in length) and gold nanoparticles (200-500 nm) were obtained when changing the oxidizing agent of APS to chlorauric acid (HAuCl₄). The chemical structures of PoPD hollow spheres and nanofibers were characterized by FTIR and XRD spectra. When using HAuCl₄ as the oxidizing agent, the products of PoPD nanofibers and gold nanoparticles could be separated by chemical methods. The monomer droplets were proposed to act as template to the formation of polymer hollow spheres while the oriented growth of polymer nanofibers might be catalyzed by gold nanoparticles.     

Preparation of sterically stabilized gold nanoparticles for plasmonic applications

Plasmonic nanoparticles such as those of gold or silver have been recently investigated as a possible way to improve light absorption in thin film solar cells. Here, a simple method for the preparation of spherical plasmonic gold nanoparticles in the form of a colloidal solution is presented. The nanoparticle diameter is controlled in the range from several nm to tens of nm depending on the synthesis parameters with the size dispersion down to 14 %. The synthesis is based on thermal decomposition and reduction of the chloroauric acid in the presence of a stabilizing capping agent (surfactant) that is very slowly injected into the hot solvent. The surfactant prevents uncontrolled nanoparticle aggregation during the growth process. The nanoparticle size and shape depend on the type of the stabilizing agent. Surfactants with different lengths of the hydrocarbon chains such as Z-octa-9-decenylamine (oleylamine) with AgNO₃ and polyvinylpyrrolidone with AgNO₃ were used for the steric stabilization. Hydrodynamic diameter of the gold nanoparticles in the colloidal solution was determined by dynamic light scattering while the size of the nanoparticle metallic core was found by small-angle X-ray scattering. The UV-VIS-NIR spectrophotometer measurements revealed a plasmon resonance absorption in the 500–600 nm range. Self-assembled nanoparticle arrays on a silicon substrate were prepared by drop casting followed by spontaneous evaporation of the solvent and by a modified Langmuir-Blodgett deposition. The degree of perfection of the self-assembled arrays was analyzed by scanning electron microscopy and grazing-incidence small-angle X-ray scattering. Homogeneous close-packed hexagonal ordering of the nanoparticles stretching over large areas was evidenced. These results document the viability of the proposed nanoparticle synthesis for the preparation of high-quality plasmonic templates for thin film solar cells with enhanced power conversion efficiency, surface enhanced Raman scattering, and other applications.     

Elaboration of monodisperse spherical hollow particles with ordered mesoporous silica shells via dual latex/surfactant templating: radial orientation of mesopore channels

Monodisperse spherical hollow nanoparticles of mesoporous silica featuring mesopores with a radial orientation in the silica shell were synthesized via a dual-templating method. Specifically designed polystyrene latexes with anionic or cationic surface charges acted as the core templates, while cetyltrimethylammonium bromide served as a co-template to structure the mesopore formation during tetraethoxysilane hydrolysis/condensation. The particles were well-separated and presented homogeneous mesoporous silica shells. Average particle diameters were less than 200 nm, and the particles displayed high values of specific surface area and pore volume. The shell thickness and the hollow core diameter could be tuned independently while the radial pore structure was preserved. A detailed analysis of the nitrogen adsorption-desorption isotherms proved that the central cavity was completely isolated from the external medium, that is, only accessible through the radial mesopores of the shell. Consequently, our particles gather the advantages of a well-defined structure, straight penetrating channels across the silica shell, and a high accessible porous volume of the central core. These properties make them far better candidates than simple mesoporous particles for any storage and/or controlled release applications.     

Influence of Capping Ligands on the Self—organization of Gold Nanoparticles into Superlattices from CTAB Reverse Micelles

Gold nanoparticles with size 3-10nm (diameter) were prepared by the reduction of HAuCl4 in a CTAB/octane 1-butanol/H2O reverse micelle system using NaBH4 as the reducing agent.The as-formed gold nanoparticle colloid was characterized by UV/vis absorption spectrum and transmission electron microscopy(TEM).Various capping ligands,such as alkylthiols with different chain length and shape,trioctylphosphine(TOP),and pyridine are used to passivate the gold nanoparticles for the purpose of self-organization into superstructures.It is shown that the ligands have a great influence on the selforganization of gold nanoparticles into superlattices,and dodecanethiol C12H25SH is confirmed to be the best ligand for the self-organization.Self-organization of C12H25SH-capped gold nanoparticles into 1D,2D and 3D supperlattices has been observed on the carbon-coated copper grid by TEM without using any selective precipitation process.     

Control of TiO2 structures from robust hollow microspheres to highly dispersible nanoparticles in a tetrabutylammonium hydroxide solution

A new process for controlling the structure of TiO2 from hollow microspheres to highly dispersible nanoparticles has been developed by altering the concentration of tetrabutylammonium hydroxide (TBAH) in the solvothermal reaction of titanium isopropoxide. Robust and size-controllable hollow TiO2 microspheres, constructed by the assembly of 18 nm TiO2 nanoparticles, were synthesized at relatively high TBAH concentration. The diameters of hollow spheres, with a shell thickness of approximately 250 nm, were controlled to 1.5-4 microm by varying the concentration of TBAH in the range of 0.1-0.5 M. After calcination at 450 degrees C, the hollow microspheres were not appreciably deformed and were still floating on the surface of the water. However, highly dispersible TiO2 nanoparticles with an average diameter of 13 nm were obtained at a low TBAH concentration such as 9.2 mM. The colloidal particle size of TiO2 in an aqueous suspension at pH 2 was 12.5-13.5 nm, which indicates that the each nanoparticle is completely separated. The overall procedure is simple and highly reproducible, and large-scale synthesis is available at low cost.