Facile Synthesis of Uniform Zinc-blende ZnS Nanospheres with Excellent Photocatalytic Activity toward Methylene Blue Degradation

Uniform and well-dispersed Zn S nanospheres have been successfully synthesized via a facile chemical route. The crystal structure, morphology, surface area and photocatalytic properties of the sample were characterized by powder X-ray diffraction(XRD), scanning electron microscopy(SEM), Brunauer-Emmett-Teller(BET) and ultraviolet-visible(UV-vis) spectrum. The results of characterizations indicate that the products are identified as mesoporous zinc-blende ZnS nanospheres with an average diameter of 200 nm, which are comprised of nanoparticles with the crystallite size of about 3.2 nm calculated by XRD. Very importantly, photocatalytic degradation of methylene blue(MB) shows that the as-prepared Zn S nanospheres exhibit excellent photocatalytic activity with nearly 100% of MB decomposed after UV-light irradiation for 25 min. The excellent photocatalytic activity of ZnS nanospheres can be ascribed to the large specific surface area and hierarchical mesoporous structure.     

Preparation of PdCo Bimetallic Hollow Nanospheres and its Electrocatalytic Activity for Oxidation of Formic Acid

The performance of the direct formic acid fuel cell (DFAFC) is considerably higher than the direct methanol fuel cell (DMFC) because of some characteristics of formic acid1. For example, formic acid is non-toxic. Formic acid has two orders of magnitude smaller crossover flux through a Nafion membrane than methanol2. In DFAFC, the concentration of formic acid can be as high as 20 mol/L, while the best concentration of methanol in DMFC is only about 2 mol/L3. Thus, the power density of …     

The synthesis of ZnS hollow nanospheres with nanoporous shell

ZnS hollow nanospheres with nanoporous shell were successfully synthesized through the evolvement of ZnO nanospheres which were synthesized by hydrothermal method with poly (sodium-p-styrene sulfonate) (PSS) as surfactant at low temperature. The as-synthesized samples were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), UV/vis spectrum and N₂ adsorption. The results showed that the shell of as-synthesized ZnS hollow structure was composed of many fine crystallites and had a nanoporous structure with pore diameter about 4 nm demonstrated by N₂ adsorption/desorption isotherm. The sample possessed efficiency of photocatalytic degradation on X-containing (X=Cl, Br, I) organic pollutants.     

三元添加剂水溶液体系合成亚微米硫化锌空心球

利用仿生合成方法,通过加入一定量的引发剂使甲基丙烯酸原位聚合,在聚乙二醇(PEG)、聚甲基丙烯酸(PMAA)和十二烷基硫酸钠(SDS)的三元添加剂混合溶液体系中控制了合成硫化锌晶体,提出了一种简单易行的合成硫化锌空心球的新方法.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线粉末衍射(XRD)及紫外吸收光谱等手段对合成样品的形貌、结构及性能进行了表征.TEM结果显示,ZnS空心球的直径约为300～400nm,其壳层的厚度约为50nm.SEM结果显示,空心球的外壳是由初级纳米粒子定向熔合排列形成的蠕虫状结构紧密组装而成.由于相应的胶束结构的改变,表面活性剂SDS浓度的变化明显改变了ZnS产物的形貌,在较高浓度的SDS溶液中得到了ZnS片状晶体的球形聚集体.利用核-壳机理初步解释了空心球结构的形成过程.     

A novel method for the templated synthesis of homogeneous samples of hollow carbon nanospheres from cellulose chars

A novel method for the production of homogeneous samples of hollow carbon nanospheres is reported from cellulose, an inexpensive and renewable precursor. The nanospheres are of diameter 50 nm, graphitic wall thickness 5-10 nm, and can easily be produced in several hundred milligram batches. The nanospheres are derived from the laser pyrolysis of a nickel chloride templated cellulose char via open Ni-core shells.     

硫化锌纳米空心球：合成及光学性质研究

Cubic ZnS hollow nanospheres have been prepared by a simple and template-free solvothermal method. The reaction was accomplished between Zn powder and the in-situ prepared S8. The results of X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) show that the ZnS hollow spheres are composed of ultrafine nanoparticles. The average diameters of the hollow nanospheres are about 100 nm. Their photoluminescence (PL) spectra indicate that they have excellent optical properties.     

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.     

ZnO hollow nanospheres via Laux-like oxidation of Zn0 nanoparticles

Zinc oxide hollow nanospheres were obtained via a Laux-like oxidation of zinc nanoparticles using nitrobenzene as oxidizing agent. The ZnO hollow nanospheres exhibit an outer diameter of 10.4 ± 1.3 nm and a well crystallized sphere wall with a thickness of 2.9 ± 0.4 nm. Laux-like oxidation and formation of the ZnO hollow nanospheres were performed instantaneously after sodium naphthalenide ([NaNaph]) driven reduction of ZnCl₂ to Zn⁰ nanoparticles in the liquid phase without any separation of the intermediate Zn⁰ nanoparticles. The diameter of the resulting ZnO hollow nanospheres (10.4 ± 1.3 nm) reflects the diameter of the intermediate Zn⁰ nanoparticles (10.1 ± 2.3 nm). In accordance with the small diameter of the ZnO sphere wall, quantum-size effects occur with a band gap that is blue-shifted by 0.2 eV in comparison to bulk-ZnO.     

Solvothermal synthesis of hollow ZnS spheres

Mono-dispersed semiconductor ZnS hollow spheres with the diameter of 300-500 nm and the shell thickness of about 100-150 nm have been synthesized successfully by solvothermal method from ethanol solution in the presence of a special surfactant-quaternary ammonium salt of 2-undecyl-1-dithioureido-ethyl-imidazoline (SUDEI) made in our lab. The mono-dispersed ZnS hollow spheres are characterized by XRD, size distribution investment, UV-vis, TEM, and SEM, respectively. The UV-vis measurement indicates that there is a broad absorption at 210-280 nm, which is likely to be caused by "hollow-effect." A growth mechanism of ZnS hollow spheres has also been put forward and discussed.     

One-step synthesis of hollow UO2 nanospheres via radiolytic reduction of ammonium uranyl tricarbonate

Black precipitates were successfully obtained by radiolytic reduction of ammonium uranyl tricarbonate in the aqueous solution of HCOONH_4 by one step.TEM,SAED,EDS,and XRD analysis indicated that the precipitates consist of hollow UO_2 nanospheres(φ:30-50 nm,wall thickness:8-15 nm,and cavity diameter:10-20 nm).The effect of HCOONH_4 concentration,irradiation time and dose rate on the morphology,and size of nanospheres was investigated.Then,a gas-bubble template mechanism was proposed.     

PAMAM树形分子为模板低温制备纳米硫化锌空心球

Hollow ZnS spheres have been prepared in the presence of generation 3.5 poly (amidoamine) dendrimers with surface ester groups (G3.5-COOCH3 PAMAM dendrimer) as synthetic matrix template. The products obtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-Vis absorption. TEM studies show that the hollow spheres with diameters ranging from 80 to 100 nm are prepared. The range of wall thickness was estimated to be about 20～30 nm. It was found that the concentration of PAMAM dendrimer had a significant influence on the formation of hollow ZnS spheres. The possible formation mechanism of the hollow spherical structure is also discussed.     

dl‐Aspartic Acid‐Mediated Hydrothermal Synthesis of β‐ZnS Microspheres and Their Optical Properties

ZnS hollow microspheres were synthesized by a dl ‐aspartic acid mediated hydrothermal route. dl ‐aspartic acid plays an important role as crystal growth soft template, which regulates the release of Zn²⁺ ions for the formation of ZnS hollow spheres. The formation of these hollow spheres was mainly attributed to an Ostwald ripening process. The products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), electron diffraction (ED), UV/Vis spectroscopy (UV), and photoluminescence (PL). The shells of the microspheres were composed of ZnS quantum dots (QDs) with the average size of 2.31 nm. The average microspheres diameter is 0.5–3.5 μm. The shell thickness of the hollow sphere is ≈?300 nm. The optical bandgap energy increased significantly compared to the bulk ZnS material due to the strong quantum confinement effect. Two strong emissions at ≈?425 nm and ≈?472 nm in the photoluminescence (PL) spectrum of ZnS hollow microspheres indicate strong quantum confinement because of the presence of QDs.     

Template-free synthesis of CdS hollow nanospheres based on an ionic liquid assisted hydrothermal process and their application in photocatalysis

Polycrystalline CdS hollow nanospheres with diameter of about 130 nm have been successfully synthesized in high yield by an ionic liquid (IL) assisted template-free hydrothermal method for the first time. Both the molar ratios of Cd/S precursor in the solution and the reaction temperature play important roles in the formation of the CdS hollow nanospheres. The concentrations of capping agent hexamethylenetetramine (HMT) and polyvinylpyrrolidone (PVP) are also crucial for the morphology and size of the final product. IL was found to be a key component in the formation of CdS hollow structures, because solid spheres were obtained in the absence of IL. A subsequent growth mechanism of hollow interior by localized Ostwald ripening process has been further discussed. Such hollow structures show high photocatalytic ability in the photodegradation of methylene blue.     

同轴静电纺丝法在纳米中空TiO2纤维中填充Ag的应用

以聚乙烯吡咯烷酮(PVP)溶胶/钛酸四正丁酯和PVP溶胶/银颗粒为前驱体, 以共轴静电纺丝法制备了银填充的TiO2中空纳米纤维. 将双组分纤维在200 ℃下热处理去除乙醇与表面吸附水后, 继而在空气气氛中焙烧至600 ℃, 可以得到在内表面上沉积银颗粒的TiO2纳米管, 银颗粒的直径为5-40 nm, TiO2纳米管的外径150-300 nm, 管臂厚10-20 nm. 用红外吸收光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等测试手段对超细纤维进行了表征. 中空纤维的直径和管壁可以通过改变电纺参数来调节. 与Ag-TiO2纳米纤维、TiO2纳米中空纤维、TiO2纳米纤维及TiO2纳米粉体相比较, Ag颗粒填充的TiO2纳米中空纤维在光分解亚甲基蓝上表现出了更好的光催化性能.     

负载钯纳米粒子聚电解质空心微球的制备及其还原对硝基苯酚的催化活性

用表面引发原子转移自由基聚合法(SI-ATRP)在二氧化硅纳米粒子表面接枝聚碘化甲基丙烯酸三甲基胺基乙酯(PMETAI),原位还原静电吸附的PdCl62-后刻蚀除去二氧化硅模板,成功制备了Pd纳米粒子复合聚电解质空心微球(air@PMETAI@Pd)。 用透射电子显微镜(TEM)、红外光谱仪(FTIR)、能谱仪(EDX)、热重分析仪(TGA)等技术手段对所制备的空心微球进行表征。 结果表明,Pd纳米粒子均匀负载在聚电解质微球上,其直径约为(1.5±0.2) nm。 将负载Pd纳米粒子的微球作为催化剂应用于硼氢化钠还原4-硝基苯酚反应,显示出很好的催化效果且具有较好的回收利用性。     

同轴静电纺丝法在纳米中空Ti02纤维中填充Ag的应用

以聚乙烯吡咯烷酮(PVP)溶胶,钛酸四正丁酯和PVP溶胶,银颗粒为前驱体,以共轴静电纺丝法制备了银填充的TiO2中空纳米纤维.将双组分纤维在200℃下热处理去除乙醇与表面吸附水后,继而在空气气氛中焙烧至600℃.可以得到在内表面上沉积银颗粒的TiO2纳米管,银颗粒的直径为5-40 nm,TiO2纳米管的外径150-300 nm.管臂厚10-20 nm.用红外吸收光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等测试手段对超细纤维进行了表征.中空纤维的直径和管壁可以通过改变电纺参数来调节.与Ag-TiO2纳米纤维、TiO2纳米中空纤维、TiO2纳米纤维及TiO2纳米粉体相比较,Ag颗粒填充的TiO2纳米中空纤维在光分解亚甲基蓝上表现出了更好的光催化性能.     

Synthesis of hollow CaCO3 nanospheres templated by micelles of poly(styrene-b-acrylic acid-b-ethylene glycol) in aqueous solutions

An asymmetric triblock copolymer, poly(styrene-b-acrylic acid-b-ethylene glycol) (PS-b-PAA-b-PEG), was synthesized via reversible addition-fragmentation chain transfer controlled radical polymerization. Micelles of PS-b-PAA-b-PEG with PS core, PAA shell, and PEG corona were then prepared in aqueous solutions, followed by extensive characterization based on dynamic light scattering, zeta-potential, and transmission electron microscopy (TEM) measurements. The well-characterized micelles were used to fabricate hollow nanospheres of CaCO(3) as a template. It was elucidated from TEM measurements that the hollow nanospheres have a uniform size with cavity diameters of ca. 20 nm. The X-ray diffraction analysis revealed a high purity and crystallinity of the hollow nanospheres. The hollow CaCO(3) nanospheres thus obtained have been used for the controlled release of an anti-inflammatory drug, naproxen. The significance of this study is that we have overcome a previous difficulty in the synthesis of hollow CaCO(3) nanospheres. After mixing of Ca(2+) and CO(3)(2-) ions, the growth of CaCO(3) is generally quite rapid to induce large crystal, which prevented us from obtaining hollow CaCO(3) nanospheres with controlled structure. However, we could solve this issue by using micelles of PS-b-PAA-b-PEG as a template. The PS core acts as a template that can be removed to form a cavity of hollow CaCO(3) nanospheres, the PAA shell is beneficial for arresting Ca(2+) ions to produce CaCO(3), and the PEG corona stabilizes the CaCO(3)/micelle nanocomposite to prevent secondary aggregate formation.     

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.     

铂纳米空球的制备及其对甲醇氧化的电催化性能

以粒径为100nm的硒球作模板,在室温下批量合成了粒径约110nm、壳厚约5 nm的铂空球.采用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、高分辨透射电子显微镜（HR-TEM）、选区电子衍射（SAED）、X射线衍射（XRD）、能量色散X射线谱（EDX）等检测技术表征了其形貌与结构;以甲醇为探针分子研究了铂纳米空球修饰玻碳电极对甲醇电氧化的催化性能.结果表明,由铂原子簇团构筑的多孔铂空球粒径均匀、分散性好、结构稳定、比表面积大、传质性能好,是甲醇氧化的理想催化材料.循环伏安（CV）结果表明:当甲醇氧化的电流密度0.10 mA·cm^-2,正扫时,铂纳米空球的氧化电位与实心铂纳米粒子及铂黑相比,分别负移了约110和64mV;负扫时,前者比后两者分别负移了约51与13 mV.经800圈循环伏安扫描后,正扫时,甲醇在铂纳米空球上氧化峰的电流密度为实心铂纳米粒子及铂黑上的13和15倍;负扫时,前者为后两者的19和38倍.表明铂纳米空球对甲醇氧化具有较好的催化活性和稳定性.     

Preparation of BiVO4 Hollow Spheres and its Photocatalytic Degradation of Methylene Blue

Monoclinic BiVO₄ hollow nanospheres were successfully prepared via template-free method using citric acid (C₆H₈O₇) as chelating agent and characterized by X-ray diffraction patterns, transmission electron microscope, UV-Vis DRS, and TG-DTA technique. C₆H₈O₇ played an important role in the formation of hollow spheres. Morphology observations revealed that when appropriate amount ofC₆H₈O₇ was introduced, the cavity with the diameter of 40 nm was obtained in BiVO₄ nanospheres. UV-Vis diffuse reflectance spectra indicated that the samples had absorption in both UV and visible light region. The photocatalytic activities were evaluated by the degradation of methylene blue under Xe lamp irradiation. Hollow spheres endow BiVO₄samples with greatly improved photocatalytic activity. A possible formation mechanism of hollow spheres was proposed.