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.     

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.     

Synthesis and characterization of the water-soluble silica-coated ZnS:Mn nanoparticles as fluorescent sensor for Cu ions

Silica-coated ZnS:Mn nanoparticles were synthesized by coating hydrophobic ZnS:Mn nanoparticles with silica shell through microemulsion. The core–shell structural nanoparticles were confirmed by X-ray diffraction (XRD) patterns, high-resolution transmission electron microscope (HRTEM) images and energy dispersive spectroscopy (EDS) measurements. Results show that each core–shell nanoparticle contains single ZnS:Mn nanoparticle within monodisperse silica nanospheres (40 nm). Photoluminescence (PL) spectroscopy and UV–vis spectrum were used to investigate the optical properties of the nanoparticles. Compared to uncoated ZnS:Mn nanoparticles, the silica-coated ZnS:Mn nanoparticles have the improved PL intensity as well as good photostability. The obtained silica-coated ZnS:Mn nanoparticles are water-soluble and have fluorescence sensitivity to Cu²⁺ ions. Quenching of fluorescence intensity of the silica-coated nanoparticles allows the detection of Cu²⁺ concentrations as low as 7.3 × 10⁻⁹ mol L⁻¹, thus affording a very sensitive detection system for this chemical species. The possible quenching mechanism is discussed.     

Synthesis of ZnS Nanospheres in Microemulsion Containing Cationic Gemini Surfactant

The reverse microemulsion containing cationic gemini surfactant trimethylene‐1,3‐bis(dodecyldimethyl ammonium bromide) (12‐3‐12, 2Br^?) is applied to synthesize ZnS nanospheres. Narrow size distributed ZnS nanospheres with controllable size and uniform morphology are successfully fabricated by direct reaction of ZnCl₂ and Na₂S in the reverse microemulsion systems. Except for the appearance of large aggregates owing to quantum size effects when the incubation time is 2 h, with increasing the incubation time from 12 to 48 h, the diameter of the ZnS nanosphere can be controlled as 20–25 nm and 140 nm, respectively. X‐ray diffraction (XRD), transmission electron microscopy (TEM), and UV‐visible absorption spectroscopy are applied to characterize the resulting ZnS nanoparticles. In the system used in the present study uniform nanosphere morphology can be synthesized, with the incubation time as an important factor in controlling the size of as‐prepared products.     

单分散ZnS纳米球与纳米梭之间的形貌转换及光学性能研究

利用平平加作为表面活性剂, 正戊醇作为助表面活性剂, 环己烷作为油相, 以硫化钠(Na₂S)和醋酸锌(Zn(Ac)₂)作为反应物, 通过控制反应条件在反相胶束体系中合成出单分散的ZnS纳米球与纳米梭. 采用XRD和TEM对产物的结构和形貌进行表征, 结果表明产物均为六方相ZnS, 晶胞参数为a＝0.3823 nm, c＝56.2 nm, 纳米球直径约为50 nm, 纳米梭直径约为60 nm, 长度约为110 nm. 采用UV-Vis(紫外可见吸收光谱)和PL(荧光光谱)研究了产物的光学性能. 纳米球的紫外可见光谱的吸收峰出现在288 nm处, 而纳米梭在305 nm处有强吸收峰, 与块体材料相比, 分别有约60和50 nm的蓝移. 当激发波长为270 nm时, 纳米球和纳米梭产物分别能够发出波长为408和303 nm的紫外光.     

Facile route to synthesize multiwalled carbon nanotube/zinc sulfide heterostructures: optical and electrical properties

A simple method to decorate the multiwalled carbon nanotubes (MWCNTs) with ZnS nanospheres has been developed. The method involves ultrasonic pretreatment and heat treatments of MWCNTs, zinc chloride, and thiourea in ethanol. The heterostructures have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Comparative experiments show that both ultrasonic treatment and heat treatment are necessary for synthesizing the MWCNTs/ZnS heterostructures. Moreover, a photoluminescence spectrum shows that the MWCNTs/ZnS heterostructures feature a broad blue emission at about 430 nm, indicating that there exists significant ground-state interaction between ZnS nanospheres and MWCNTs. Meanwhile, the current-voltage characteristic of the MWCNTs/ZnS exhibits clear rectifying behavior, revealing charge transfer between MWCNTs and ZnS nanospheres.     

Surfactant-assistant and facile synthesis of hollow ZnS nanospheres

Small and monodisperse ZnS hollow nanospheres with outer diameter ranging from 60 to 70 nm and wall thickness of 15-20 nm were fabricated in a large scale by a simple surfactant polyethylene glycol (PEG) assisted method. The diameter and the wall thickness of the hollow nanospheres could be controlled by manipulating the amount of PEG and the aging time, respectively. Moreover, the wall of these hollow nanospheres is very compact. The product was characterized by X-ray power diffraction (XRD), transmission electron microscopy (TEM), UV-vis spectrum and fluorescence spectroscopy. The photocatalytic activity of as-prepared ZnS hollow nanospheres was also evaluated by using methyl orange (MO) as a model organic compound and the result revealed that their photocatalytic activity is a little lower than that of Degussa P25 TiO(2) but better than that of ZnS nanocrystals prepared by literature method. Furthermore, a rational mechanism to the formation and evolution of the products is proposed.     

Synthesis of ZnS hollow nanospheres with holes using different amine templates

ZnS hollow nanospheres with holes were prepared by reacting ZnSO₄ with H₂S, the sulfide source formed in the reaction of CS₂ with ethylenediamine, 1,3-propylenediamine, butylamine or 2-(2-aminoethylamino) ethanol, which also acted as a template agent, at 50°C under agitation. The shape, particle size of about 100–850 nm and hole size of about 150–600 nm of ZnS hollow nanospheres with holes were shown by SEM and TEM images. These ZnS nanospheres with β cubic ZnS phase and composed of 2–5 nm nanocrystals were characterized by XRD and HRTEM. The blue shift of maximum absorption in UV-vis displayed the effect of quantum size. The two amino groups of amine templates reacted favorably with Zn²⁺ to form uniform and relatively smooth ZnS nanospheres with holes, while hydroxyethyl played a disadvantageous role. A reasonable mechanism of hole formation by H₂S rushing out is suggested. __________ Translated from Journal of Jinan University (Natural Science), 2007, 28(1): 92–95 [译自: 暨南大学学报(自然科学版)]     

Templating CdSe tetrapods at the air/water interface with POPC lipids

ZnS nanoparticles were precipitated in aqueous dispersions of cationic surfactant cetyltrimethylammonium bromide (CTAB). The sphere radii of ZnS nanoparticles calculated by using band-gap energies steeply decreased from 4.5 nm to 2.2 nm within CTAB concentrations of 0.4-1.5 mmol L(-1). Above the concentration of 1.5 mmol L(-1), the radii were stabilized at R=2.0 nm and increased up to R=2.5 nm after 24 h. The hydrodynamic diameters of CTAB-ZnS structures observed by the dynamic light scattering (DLS) method ranged from 130 nm to 23 nm depending on CTAB concentrations of 0.5-1.5 mmol L(-1). The complex structures were observed by transmission electron microscopy (TEM). At the higher CTAB concentrations, ZnS nanoparticles were surrounded by CTA(+) bilayers forming positively charged micelles with the diameter of 10nm. The positive zeta-potentials of the micelles and their agglomerates were from 16 mV to 33 mV. Wurtzite and sphalerite nanoparticles with R=2.0 nm and 2.5 nm covered by CTA(+) were modeled with and without water. Calculated sublimation energies confirmed that a bilayer arrangement of CTA(+) on the ZnS nanoparticles was preferred to a monolayer.     

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.     

A new solid-phase nanoparticle FRET assays based on GO/CS/ZnS nanocomposite film and developed in sensing for bromonium ion

Composite thin films consisting of nano-sized ZnS particles dispersed in chitosan/GO films have been prepared by in-situ method. The films obtained were characterized by FTIR and UV–Vis spectroscopy. The ZnS nanoparticles with 90 nm in diameter were dispersed uniformly in the film matrix. Optical absorption peak due to the size of ZnS particles was observed around 350 nm. The fluorescence emission at 430 nm of the GO/CS/ZnS nanocomposite films is very sensitive to the presence of bromonium ion from aqueous solutions. New solid-phase nanoparticles FRET assays are firstly immobilized on the substrate and then interacted with functionalized acceptor molecules in the solution to trigger the FRET effect to detect Br^–.     

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.     

Influence of cobalt concentration on structural and optical properties of ZnS quantum dots

ZnS and Co-doped ZnS nanoparticles have been prepared by simple chemical precipitation method. Zinc acetate, sodium sulfide, and cobalt nitrate have been used as precursors for the preparation of Co-doped ZnS quantum dots. The X-ray diffraction results revealed that the undoped and Co-doped ZnS quantum dots exhibit hexagonal structure. The average grain size of quantum dot was found to lie in the range of 2.6–3.8 nm. The surface morphology has been studied using scanning electron microscope. The compositional analysis results confirm the presence of Co, Zn and S in the sample. The optical properties of undoped and Co-doped ZnS quantum dots have been studied using absorption spectra. TEM results show that undoped and Co-doped ZnS nanoparticles exhibit a uniform size distribution with average size of 2.5–3.4 nm.     

仿生支撑液膜法制备硫化锌自组装纳米球链

采用了一种全新的化学仿生方法——载体支撑液膜法制备ZnS纳米球链. 常温常压条件下, 利用含邻菲罗啉载体的支撑液膜(SLM)反应体系选择性传输Zn^2＋至膜另一侧, 在SLM模板作用下, 控制结晶位点, 定向结合阴离子, 加上局部过饱和及界面成核的影响, 成功制备出由8～30 nm纳米粒子自组装的直径范围为250～300 nm ZnS球链. 由XRD和TEM的结果显示, 其结构为立方闪锌矿, 晶格常数为α＝0.5390 nm. 本文还对其荧光性质及产物形成机理进行了初步探讨.     

Synthesis of Ag nanospheres particles in ethylene glycol by electrochemical-assisted polyol process

The synthesis of monodispersed Ag nanosphere particles from silver nitrite in ethylene glycol at room temperature essentially promoted with the use of an electrochemical method was demonstrated. Poly(N-vinylpyrrolidone) (PVP) behaves electrochemically stable and facilitates the formation of well-defined Ag nanospheres of average size in the range of 11 nm. Further characterization by high-resolution transmission electron microscopy (HRTEM) image and nano-beam electron diffraction (NBED) pattern indicate that the growth direction of Ag nanosphere particles is the 1 1 1 direction. The time evolution of absorption spectra by UV–Vis spectroscopy illustrates that silver nanoparticles in the electrolyte increase rapidly upon electrochemical process.     

Nanosilica-supported polyethoxyamines as low-cost, reversible carbon dioxide sorbents

Nanoparticles capped with amine ligands with different steric properties, dodecylamine and oleylamine, respectively, are investigated in the solid state as well as in solution. A combined X-ray diffraction, small angle X-ray scattering and electron microscopy investigation showed that the nanoparticles exhibit the sphalerite modification of ZnS as crystal phase with a diameter of 3-5 nm. A close packing of the monocrystalline nanoparticles in the solid state is observed. However, in the dodecylamine sample, besides spherical particles, a fraction of the nanoparticles is elongated. The nanoparticles are readily resoluble in apolar solvents like hexane. Dynamic light scattering (DLS) and SAXS investigations of the solutions reveal that the nanoparticles are dissolved as singular particles. In the case of oleylamine-capped ZnS, a defined core-shell structure with a ZnS core with a diameter of 4 nm and an organic shell with a thickness of approximately 2 nm have been found. Dodecylamine-capped nanoparticles slightly tend to form agglomerates with a diameter of approximately 40 nm.     

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.     

Mesoporous cadmium bismuth niobate (CdBi_2Nb_2O_9) nanospheres for hydrogen generation under visible light

Herein, we report visible light active mesoporous cadmium bismuth niobate(CBN) nanospheres as a photocatalyst for hydrogen(H_2) generation from copious hydrogen sulfide(H_2S). CBN has been synthesized by solid state reaction(SSR) and also using combustion method(CM) at relatively lower temperatures.The as-synthesized materials were characterized using different techniques. X-ray diffraction analysis shows the formation of single phase orthorhombic CBN. Field emission scanning electron microscopy and high resolution-transmission electron microscopy showed the particle size in the range of ~0.5–1 μm for CBN obtained by SSR and 50–70 nm size nanospheres using CM, respectively. Interestingly, nanospheres of size 50–70 nm self assembled with 5–7 nm nanoparticles were observed in case of CBN prepared by CM.The optical properties were studied using UV–visible diffuse reflectance spectroscopy and showed band gap around ~3.0 eV for SSR and 3.1 eV for CM. The slight shift in band gap of CM is due to nanocrystalline nature of material. Considering the band gap in visible region, the photocatalytic activity of CBN for hydrogen production from H_2S has been performed under visible light. CBN prepared by CM has shown utmost hydrogen evolution i.e. 6912 μmol/h/0.5 g which is much higher than CBN prepared using SSR.The enhanced photocatalytic property can be attributed to the smaller particle size, crystalline nature,high surface area and mesoporous structure of CBN prepared by combustion method. The catalyst was found to be stable, active and can be utilized for water splitting.     

Solution-phase synthesis of spherical zinc sulfide nanostructures

A facile solution-phase method has been developed to synthesize specially hollow and solid ZnS nanospheres. High-resolution TEM images on the nanospheres suggest their formation via the oriented aggregation of the primary ZnS nanocrystals. The morphology and size of the ZnS nanospheres can also be tuned easily by controlling the experimental conditions. These special spherical structures are very easily encapsulated within a uniform silica layer without any surface modification, suggesting potential applications in biochemistry and biodiagnostics.     

Preparation and characterization of ZnS nanoparticles deposited on montmorillonite

ZnS nanoparticles were prepared and deposited on montmorillonite (MMT) in the presence of cetyltrimethylammonium (CTA). UV spectrometry and transmission electron microscopy (TEM) proved the formation of nanoparticles with diameters ranging from 3 nm to 5 nm. Selected-area electron diffraction (SAED) patterns revealed the presence of romboedric ZnS. The band gap energy of nanosize ZnS was estimated at 3.89 ± 0.03 eV. Photoluminescence spectra exhibited a strong emission band between 300 nm and 600 nm explained by the vacant ZnS nanostructure. The prepared ZnS-montmorillonite nanocomposite (ZnS-MMT) was used for the photocatalytic reduction of CO(2) providing a considerably high efficiency that exceeded 5-6-fold the results of commercial TiO(2) Degussa P25. The main reaction products were hydrogen and methane. Methanol and carbon oxide were also observed in about 7-fold lower amounts. The stability of ZnS against oxidation was confirmed by the determination of sulphate using capillary isotachophoresis.