A simple one-step solvothermal synthesis of hierarchically structured ZnO hollow spheres for enhanced selective ethanol sensing properties

A simple one-step solvothermal method, using ethanolamine as solvent without any additives except zinc source, has been employed to synthesize hierarchically structured ZnO hollow spheres consisting of numerous orderly and radical nanorods with diameter of several tens nanometers and length of 2–3 μm. The ethanolamine and the solvothermal process play the critical role in the synthesis of the ZnO hollow spheres by the primary formation of ZnO crystal nucleus and subsequent transformation into nanorods, which self-assemble into hollow spheres. The morphology and structure of the spheres have been characterized by transmission electron microscopy, field emission scanning electron microscopy, X-ray powder diffraction, high-resolution transmission electron microscopy, and Brunauer–Emmett–Teller N₂ adsorption–desorption analyses. The results also indicate that the sensor based on the prepared ZnO hollow spheres exhibit good ethanol sensing performance, which can be attributed to its structural defects and high surface-to-volume ratio that significantly facilitate the absorption of oxygen species and diffusion of target gas. Besides, the sensor shows high selectivity to ethanol because ZnO as a basic oxide is favored for dehydrogenation of ethanol.     

Highly efficient decomposition of organic dye by aqueous-solid phase transfer and in situ photocatalysis using hierarchical copper phthalocyanine hollow spheres

The hierarchical tetranitro copper phthalocyanine (TNCuPc) hollow spheres were fabricated by a simple solvothermal method. The formation mechanism was proposed based on the evolution of morphology as a function of solvothermal time, which involved the initial formation of nanoparticles followed by their self-aggregation to microspheres and transformation into hierarchical hollow spheres by Ostwald ripening. Furthermore, the hierarchical TNCuPc hollow spheres exhibited high adsorption capacity and excellent simultaneously visible-light-driven photocatalytic performance for Rhodamine B (RB) under visible light. A possible mechanism for the "aqueous-solid phase transfer and in situ photocatalysis" was suggested. Repetitive tests showed that the hierarchical TNCuPc hollow spheres maintained high catalytic activity over several cycles, and it had a better regeneration capability under mild conditions.     

Rambutan-like hierarchically heterostructured CeO<Subscript>2</Subscript>-CuO hollow microspheres: Facile hydrothermal synthesis and applications

Hierarchically heterostructured hollow spheres are of great interest for a wide range of applications owing to their unique structural features and properties.However,the fabrication of well-defined hollow spheres with highly specific morphology for mixed transition metal oxides on a large scale remains challenging.In this work,uniform rambutan-like heterostructured CeO2-CuO hollow microspheres with numerous copper-ceria interfacial sites and nanorods and nanoparticles as building blocks are prepared via a facile hydrothermal method followed by calcination.Importantly,this approach can be readily scaled up and is applicable to the synthesis of various CuO-based mixed metal oxide complex hollow spheres.The as-prepared CeO2-CuO hollow rambutans exhibit superior performance both as electrode materials for supercapacitors and as Cu-based catalysts for the Rochow reaction,mainly due to the small primary nanopartide constituents,high surface area,and formation of numerous interior heterostructures.     

Preparation and photocatalytic activity of hollow ZnO and ZnO-CuO composite spheres

ZnO and ZnO-CuO composite hollow spheres were fabricated by using colloidal carbon spheres as templates. The morphology, structure and chemical composition of the as-prepared samples were investigated using field emission scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The photocatalytic activity of the hollow spherical products was evaluated by photocatalytic degradation of methylene blue (MB) aqueous solution at ambient temperature. The results indicated that the ZnO-CuO composite hollow spheres display higher photocatalytic efficiency than pure hollow ZnO products. The related photocatalytic mechanism was discussed based on the microstructure and properties of the ZnO and ZnO-CuO composite hollow spheres. The facile strategy for the preparation of ZnO-CuO hollow nanostructures can be applicable to the synthesis of other composite hollow spheres.     

Fabrication of hollow silver spheres by MPTMS-functionalized hollow silica spheres as templates

In this study, we provide a strategy to prepare the hollow silver spheres by accumulating the silver nanoparticles on the surface of 3-mercaptopropyltrimethoxysilane (MPTMS)-functionalized silica as templates, which was accomplished by the chemisorption between silver nanoparticles and thiol groups. Then, the resulting hollow silver spheres were obtained through the chemical wet etching process with 10 M HF solution. In conventional method, the fabrication of hollow silver spheres from core-shell spheres was not easy due to the difficulties in retaining the shell structures during core removal. The method in this paper could overcome this limitation. The major focus of study is on understanding the mechanism of formation of the hollow silver spheres through the self-assembly behavior by chemisorption between silver nanoparticles and thiol groups. The silver-coated silica and hollow silver spheres were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), and X-ray photoelectron spectroscopy (XPS).     

亚微级氧化锌空心球的制备及其光催化性能研究进展

亚微级ZnO空心球由于具有密度低、比表面积大、结构规整、尺寸可控等优点及众多优异的物理化学性能,引起科研工作者的广泛关注。因此,探索简单易行、经济高效的亚微级ZnO空心球的制备方法成为关注的热点。结合课题组在亚微级ZnO空心球方面的研究进展和国内外在其制备过程中涌现出的新方法,如水热法、声化学法、超声辅助水热法、静电纺丝法和微波辐射法等,对中空ZnO的制备新技术进行了综述。同时,对这些方法的基本原理、特点、应用情况等进行了总结,并对中空ZnO的光催化性能进行了综述。最后,在此基础上对亚微级ZnO空心球的发展方向和前景进行了展望。     

Synthesis of hollow spheres with mesoporous silica nanoparticles shell

Hollow spheres with mesoporous silica nanoparticles shell were synthesized with the use of cetyltrimethylammonium bromide (CTAB) and polystyrene (PS) hollow spheres as dual templates. The key to this study is that the uneven surface of the template provides nucleation sites for mesoporous nanoparticles, resulting in the formation of hollow spheres with mesoporous silica nanoparticles shell. The final products with hierarchical mesopores can be obtained through a simple one-step approach.     

Bi_2MoO_6空心球的水热沉淀法制备及其光催化性能

以葡萄糖为前躯体,采用水热法制备胶体碳球,以其为模板通过水热沉淀法制备C/Bi2MoO6核壳结构,然后在350℃空气中煅烧,获得了具有良好光催化性能的Bi2MoO6空心球.通过SEM、XRD、FT-IR和BET等测试方法对该催化剂进行了表征;并对其形成机理及反应过程进行了初步探讨,以亚甲基蓝作为被降解物质,研究了其光催化活性。结果表明,Bi2MoO6空心球是由纳米晶粒组成的,壁厚约为30～50nm,平均直径约为0.6～0.8μm,采用胶体碳球作模板时制得的Bi2MoO6空心球比表面积为11.315m2/g,而直接合成的粉体比表面积为3.378m2/g。在黑管灯照射下,2.5h亚甲基蓝的降解率达到了91.95%。     

A simple approach for facile synthesis of Ag,anisotropic Au and bimetallic (Ag/Au) nanoparticles using cruciferous vegetable extracts

We present a simple and straightforward approach for the synthesis and stabilization of relatively monodisperse Ag, Au and bimetallic (Ag/Au) nanoparticles by using cruciferous vegetable (green/red) extracts by simply adjusting the pH environment in the aqueous medium. The vegetable extracts act both as reducing and capping agents. The monometallic and bimetallic nanoparticles of Ag and Au so obtained were characterized by UV–visible spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM). It is shown that red cabbage extract can be used for the preparation of anisotropic Au nanoparticles. The formation of Au anisotropic nanoparticles was found to depend on a number of environmental factors, such as the pH of the reaction medium, reaction time, and initial reactant concentrations. Additionally, it is shown that these extract-stabilized Au and Ag nanoparticles can be used as a seed for preparation of bimetallic Au/Ag nanoparticles. For bimetallic alloy nanoparticles the absorption peak was observed between the two maxima of the corresponding metallic particles. The surface plasmon absorption maxima for bimetallic nanoparticles changed linearly with increasing Au mole ratio content in various alloy compositions. It has been shown that the formation of hollow Au spheres depends on the experimental conditions.     

One-pot synthesis of ZnO/Ag nanospheres with enhanced photocatalytic activity

ZnO/Ag composite nanospheres with an average diameter of about 440 nm, were synthesized through a facile one-pot solvothermal reaction, using a kind of biomolecular sodium alginate as template, H₂O and diethanolamine as solvents, followed by the assembly of ZnO and Ag nanoparticles in-situly produced. The composite spheres were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy disperse X-ray spectrum. Moreover, the results showed that the as-made ZnO/Ag assembled nanospheres exhibited better photocatalytic performance than the pure ZnO nanoparticles and this one-pot synthesis method has great potential to be extended for the synthesis of other metallic oxide/metal spheres.     

Large scale synthesis of porous ZnO hollow structures with tunable diameters and shell thicknesses

Hollow and porous nanostructures have attracted a great deal of attention because of their widespread potential applications, and nanostructures with tunable size are desirable to optimize their properties. Therefore, simple and high yield methods for preparation of nanostructures with tunable sizes have been regarded as pursuing objects. Herein, we report a novel simple method for large scale synthesis of porous ZnO hollow structures with tunable diameters and shell thicknesses. The novel synthesis strategy involves oxidizing Zn spheres and polyhedrons in solid state to form a thin ZnO layer on the surface under low temperature, followed by removal of the Zn cores upon heating. Noticeably, not only can the diameter and shell thickness be respectively tuned, but also the shell thickness can be also easily controlled because of its slow oxidation rate in a solid-phase diffusion process under low temperature. It is obvious that this novel simple method involved here can readily be extended to other metal oxide systems.     

Fast synthesis of cerium oxide nanoparticles and nanorods

The microwave-hydrothermal method has been investigated for the fast synthesis of rare earth cerium oxide (CeO2) nanoparticles and nanorods. This approach combines the advantages of both hydrothermal and microwave heating techniques. It is facile, rapid, energy-saving, and environmentally-benign and leads to high-yields. The average sizes of the obtained CeO2 nanoparticles could be adjusted from approximatrly 1.6 nm to approximately 20 nm. Moreover, by changing cerium source and adjusting the amount of the added ammonia water, CeO2 nanorods could be synthesized under microwave-assisted conditions for the first time. No calcination process or surfactant is required in our experiments for both CeO2 nanoparticles and nanorods. The ultraviolet and visible (UV-vis) spectra show the obvious size-dependence of the position of the absorbance peak. The Brunaur Emmett Teller (BET) nitrogen adsorption indicates that these nanoparticles and nanorods have high specific surface areas, which are needed for potential applications in many fields. Compared with conventional hydrothermal method, microwave-assisted hydrothermal method shows its advantages of rapidity, convenience and perhaps cost-effectiveness and could be extended to the synthesis of other nanoparticles and nanorods.     

Improved photocatalytic activity of surface charge functionalized ZnO nanoparticles using aniline

Functionalization of aniline molecules on zinc oxide(ZnO)nanoparticles is reported using a simple impregnation technique.Functionalized ZnO samples were systematically characterized based on mor-phology,surface and optical properties,and photocatalytic performance towards methyl orange(MO).Aniline functionalization increased the surface charge of the modified ZnO.Compared to pristine ZnO,the aniline-functionalized ZnO yielded faster photodegradation of MO,degrading 98.29％ of MO in 60 min and superoxide radicals were the major species during the MO photodegradation reaction.These results indi-cate that the improvement of photocatalytic degradation could be attributed to opposite charge-induced surface adsorption.Hence,protonated amine as a positively charged molecule was expected to increase the surface adsorption of MO(as an anionic dye)on ZnO nanoparticles surfaces,thereby increasing their photocatalvtic degradation performance.     

氧化锌空心球的制备及其气敏性能研究

以新制的碳球为模板在溶液相中制备了氧化锌空心球,并制成气敏元件,进行了气敏性能测试。结果表明,氧化锌空心球气敏元件对乙醇、丙酮和三乙胺有很好的敏感性。尤其是对三乙胺和乙醇分别在175℃和400℃表现出高的灵敏度和快的响应特性。     

Hydrothermal synthesis of PbS hollow spheres with single crystal-like electron diffraction patterns

PbS hollow spheres were successfully prepared by a sodium citrate-assisted hydrothermal process at 120 degrees C for 12 h, employing lead acetate trihydrate, thiourea and sodium citrate as precursors. The diameter of PbS hollow spheres is 200-400 nm, which is composed of about 50-80 nm nanoparticles. The synthesized product was characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), Fourier transform-infrared (FT-IR) spectroscopy, ultraviolet-visible spectrometer (UV-vis) and near-infrared absorption spectrometer (NIR). The effects of the reaction conditions on morphologies of PbS structures were investigated. Star-shaped and flat PbS crystals were obtained by changing some experiment conditions. The results show that temperature, sodium citrate concentration, sulfur sources and solvent play key roles on the final morphologies formation of PbS crystals. Especially, ED result indicates that PbS hollow spheres hold single crystal-like electron diffraction patterns. And the possible formation mechanism of hollow spheres was proposed.     

Template-free fabrication of TiO2 hollow spheres and their photocatalytic properties

Submicrometer-sized anatase TiO(2) hollow spheres were fabricated through a template-free solvothermal route using TiCl(4) as a raw material and a mixture of alcohols-acetone as solvent. Control of the hollow spheres' size was achieved by adjusting the ratio of alcohols to acetone. Products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM, X-ray photoelectron spectra (XPS), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and thermogravimetric (TG) analysis. It was found that the formation process of the TiO(2) hollow spheres might include the hydrolysis of Ti(IV) with the water formed from the solvothermal etherification reaction, the aggregation of the anatase TiO(2) nanoparticles, and the Ostwald ripening. Furthermore, the as-prepared TiO(2) hollow nanostructures exhibited good photocatalytic activity for the degradation of phenol.     

Bio-inducing growth of ZnO hollow spheres in lotus root

In this paper, ZnO hollow spheres are prepared via an antitoxic bio-inducing process in lotus roots. FESEM images indicate that the tannin cells coated with ZnO are spherical with diameters ranging from 1.5 microm to 3 microm. The spheres with approximately the same size aggregate on the surface of vessels in short-range. The new bio-inducing process for formation of oxides hollow spheres might exist for long time in nature. It is proved that plant antitoxic function is the key factor to induce these structures formation. And moreover, it could be predicted that this bio-inducing phenomenon is an ideal way for preparation of materials with special structures.     

One-pot template-free synthesis of mesoporous boehmite core-shell and hollow spheres by a simple solvothermal route

Uniform-sized and monodispersed boehmite core-shell and hollow spheres have been successfully synthesized using a template-free solvothermal route. The experimental parameters such as reaction duration, the trisodium citrate amounts and solvents are shown to play important roles in the formation of the AlOOH core-shell and hollow spheres. X-ray diffraction, Fourier transform IR, thermal gravimetric analysis, N₂ adsorption/desorption, scanning electron microscopy, transmission electron microscopy, and high-resolution TEM were used to characterize the products. The results show that the prepared polycrystalline hollow spheres are composed of well-aligned AlOOH nanowires and have an orthorhombic structure. Finally, a dissolution-renucleation mechanism was proposed for the formation of boehmite hollow structures.     

Synthesis, structural and optical properties of Ni-doped ZnO micro-spheres

Ni doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Ni:Zn atomic ratio from 0 to 5 %. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and nickel acetate tetrahydrate followed by heat treatment at 65 °C under refluxing using methanol as a solvent. X-ray diffraction analysis reveals that the Ni-doped ZnO crystallizes in a wurtzite structure with crystal size of 4–11 nm. These nanocrystals self-aggregated themselves into hollow spheres of size of 600–170 nm. High resolution transmission electron microscopy image shows that each sphere is made up of numerous nanoparticles of average diameter 4 nm. The XRD patterns, Scanning electron microscopy and transmission electron microscopy micrographs of doping of Ni in ZnO are confirmed the formation of micro-spheres. Furthermore, the UV–vis. spectra and photoluminescence spectra of the Ni-doped ZnO nanoparticles were also investigated. The band gap of the nanoparticles can be tuned in the range of 3.55–3.36 eV by the use of the dopants. The observed red shift in the band gap from UV–visible analysis and near band edge UV emission with Ni doping may be considered to be related to the incorporation of Ni ions into the Zn site of the ZnO lattice.     

Synthesis and optical properties of ZnS hollow spheres from single source precursor

A facile one-pot synthesis of ZnS hollow spheres has been carried out via a chemical transformation induced inside-out Ostwald ripening process from a single source precursor. The size and shell thickness of the ZnS hollow spheres can be controlled by adjusting the reaction temperature and reaction time, respectively. Photoluminescence spectra show a dominant emission peak at 470 nm accompanied by several weaker peaks. UV-vis measurement reveals that the obtained ZnS hollow spheres exhibit “hollow effect”. The formation process of ZnS hollow spheres has been discussed.