Fabrication of hollow spheres of metal oxide using fructose-derived carbonaceous spheres as sacrificial templates

In this report, fructose-derived carbonaceous spheres were utilized as sacrificial templates for the fabrication of metal oxide hollow spheres (MOHSs) by a facile hydrothermal approach. Hollow spheres of a series of crystalline metal oxides (α-Fe₂O₃, Cr₂O₃, Co₃O₄, NiO, and ZnO) have been fabricated, utilizing the metal chloride as the oxide precursors. Heating of an aqueous solution of the metal chloride and fructose to moderate temperature in an autoclave affords a spherical composite consisting of a metal precursor shell sheathing a carbonaceous core. Subsequent removal of the interior carbonaceous cores by thermal treatment through oxidation in air produces free-standing crystalline oxides hollow spheres. The MOHSs were characterized by means of SEM, TEM, XRD, IR spectroscopy, energy dispersive X-ray (EDX) and sorption measurements. The results show convincingly that using fructose as a sacrificial template after application of a hydrothermal synthesis route could be a favourable sacrificial template for the fabrication of various MOHSs.     

Metal oxide and sulfide hollow spheres: layer-by-layer synthesis and their application in lithium-ion battery

A novel layer-by-layer approach has been developed to synthesize polycrystalline SnO(2) hollow spheres with tunable shell thickness and size using SiO(2) spheres as a template. The surface of the SiO(2) spheres has been first modified by the polyelectrolyte, and subsequently, the compact SnO(2) layer has deposited on the surface of the SiO(2) spheres through a redox reaction because of the electrostatic attraction between the charged species. After HF etching treatment, the uniform SnO(2) hollow spheres have been obtained. The approach presented herein has been extended to synthesize other metal oxide and sulfide hollow spheres such as In(2)O(3) and ZnS. Moreover, the as-synthesized SnO(2) hollow spheres have been applied in lithium-ion battery and show improved performance compared with SnO(2) nanoparticles. The high surface area and stable hollow structure of the SnO(2) hollow spheres may be responsible for the improved performance.     

One-step synthesis of SnO2 and TiO2 hollow nanostructures with various shapes and their enhanced lithium storage properties

A versatile one-step method for the general synthesis of metal oxide hollow nanostructures is demonstrated. This method involves the controlled deposition of metal oxides on shaped α-Fe(2)O(3) crystals which are simultaneously dissolved. A variety of uniform SnO(2) hollow nanostructures, such as nanococoons, nanoboxes, hollow nanorings, and nanospheres, can be readily generated. The method is also applicable to the synthesis of shaped TiO(2) hollow nanostructures. As a demonstration of the potential applications of these hollow nanostructures, the lithium storage capability of SnO(2) hollow structures is investigated. The results show that such derived SnO(2) hollow structures exhibit stable capacity retention of 600-700?mA h g(-1) for 50?cycles at a 0.2?C rate and good rate capability at 0.5-1?C, perhaps benefiting from the unique structural characteristics.     

TiO2/SnO2复合空心球在染料敏化太阳能电池中的应用

采用模板辅助法制备了SnO2/TiO2复合空心球,样品直径为1.5~4.0μm,比表面积达到了92.9 m^2·g^-1,复合空心球表现出优越的光散射性能.以这种复合空心球作为染料敏化太阳能电池的光阳极,电池的光电转换效率可达到7.72%,高于SnO2微米球(2.70%)和TiO2微米球(6.26%).此外,以锐钛矿型TiO2纳米晶作为底层,SnO2/TiO2复合空心球作为光散射层制备的双层结构光阳极,电池光电转换效率进一步提升至8.43%.     

二氧化锡中空微球用于快速灵敏检测硫化氢

以氨基酚醛树脂球作模板,通过一种简单的模板法制备了具有中空微球(HMS)结构的二氧化锡;将其涂覆于氧化铝陶瓷管金电极表面,制得一种新型薄膜式硫化氢传感器.采用X射线衍射(XRD)及透射电子显微镜(TEM)表征了材料的微观结构和形貌,并考察了二氧化锡中空微球(Sn O2HMS)的气敏性能.结果表明,二氧化锡中空微球对硫化氢气体表现出良好的气敏特性.在最佳工作温度(200℃)下,所制作的传感器对142.6 mg/m3硫化氢的响应值高达97.13%,响应时间为22 s.该传感器对硫化氢的响应线性范围为0.2852~142.6 mg/m3,相关系数为0.9931,检出限达到0.1549 mg/m3,且几乎不受环境湿度和温度的影响,具有良好的重现性和选择性.对养殖场中硫化氢气体连续监测10个月后,传感器响应信号衰减了5.4%,表明该传感器具有长期稳定的使用寿命,可实现远程监测的实际应用.     

Facile synthesis of hollow Co3O4 microspheres and its use as a rapid responsive CL sensor of combustible gases

The hollow Co(3)O(4) microspheres (HCMs) were prepared by the carbonaceous templates, which did not need the surface pretreatment. The chemiluminescence (CL) and catalytic properties for CO oxidation over these hollow samples were evaluated. The samples were characterized by scanning electron microscopy (SEM), energy disperse spectra (EDS), transmission electron microscopy (TEM), selected area electron diffraction (ED), X-ray diffraction (XRD), temperature-programmed desorption (TPD) and N(2) adsorption. The influences of filter' band length, flow rate of gas, test temperature, and particle structure on CL intensities were mainly investigated. It was found that compared with the solid Co(3)O(4) particles (SCPs), HCMs had a stronger CL intensity, which was ascribed to its hollow structure; and that CL properties of the catalysts were well correlated with their reaction activities. Moreover, HCMs were used to fabricate a highly sensitive gas detector, which is a rapid and effective method for the selection of catalysts or the detection of environmental deleterious gases.     

SnO_2纳米棒负载Pd-Cu空心球催化剂的制备及其对乙醇氧化电催化性能研究

本文通过简单溶剂热反应合成棒状SnO2,然后以谷氨酸为添加剂,乙二醇为分散剂和还原剂,溶剂热合成SnO2纳米棒负载的Pd-Cu球形空壳催化剂.透射电镜结果表明Pd-Cu空心球粒径大约100 nm,并且分布均匀.电化学测试结果表明,该催化剂对乙醇氧化表现出较高的电催化活性和稳定性,其中电流密度可达119.4 mA cm?2,研究表明,合适的金属氧化物的引入可使催化剂释放更多的活性位点从而提高催化剂的电催化活性.     

Polyvinylpyrrolidone-assisted ultrasonic synthesis of SnO nanosheets and their use as conformal templates for tin dioxide nanostructures

Single crystalline SnO nanosheets with exposed {001} facets have been prepared by an ultrasonic aqueous synthesis in the presence of polyvinylpyrrolidone, which hinders the spontaneous formation of the truncated bipyramidal SnO microcrystals and exfoliate them into layer-by-layer hierarchical structures and further into separate SnO nanosheets. The SnO nanosheets have been used as conformal sacrificial templates converted into polycrystalline SnO(2), as well as layered SnO/SnO(2) nanostructures, by calcination in air. The concept of fabrication of two-dimensional tin oxide nanostructures demonstrated here may be relevant for the crystal design of layered materials, in general.     

Photochemical preparation of CdS hollow microspheres at room temperature and their use in visible-light photocatalysis

CdS hollow microspheres have been successfully prepared by a photochemical preparation technology at room temperature, using polystyrene latex particles as templates, CdSO₄ as cadmium source and Na₂S₂O₃ as both sulphur source and photo-initiator. The process involved the deposition of CdS nanoparticles on the surface of polystyrene latex particles under the irradiation of an 8 W UV lamp and the subsequent removal of the latex particles by dispersing in dichloromethane. Photochemical reactions at the sphere/solution interface should be responsible for the formation of hollow spheres. The as-prepared products were characterized by X-ray diffraction, transmission electron microscopy and scanning electron microscopy. Such hollow spheres could be used in photocatalysis and showed high photocatalytic activities in photodegradation of methyl blue (MB) in the presence of H₂O₂. The method is green, simple, universal and can be extended to prepare other sulphide and oxide hollow spheres.     

General and Facile Syntheses of Metal Silicate Porous Hollow Nanostructures

Porous hollow nanostructures have attracted intensive interest owing to their unique structure and promising applications in various fields. A facile hydrothermal synthesis has been developed to prepare porous hollow nanostructures of silicate materials through a sacrificial‐templating process. The key factors, such as the concentration of the free metal cation and the alkalinity of the solution, are discussed. Porous hollow nanostructures of magnesium silicate, nickel silicate, and iron silicate have been successfully prepared by using SiO₂ spheres as the template, as well as a silicon source. Several yolk–shell structures have also been fabricated by a similar process that uses silica‐coated composite particles as a template. As‐prepared mesoporous magnesium silicate hollow spheres showed an excellent ability to remove Pb²⁺ ions in water treatment owing to their large specific surface and unique structures.     

Preparation and up-conversion luminescence of hollow La2O3:Ln (Ln = Yb/Er, Yb/Ho) microspheres

Hollow La(2)O(3):Ln (Ln = Yb/Er, Yb/Ho) microspheres with up-conversion (UC) luminescence properties were successfully synthesized via a facile sacrificial template method by employing carbon spheres as hard templates followed by a subsequent heating process. The structure, morphology, formation process, and fluorescent properties are well investigated by various techniques. The results indicate that the hollow La(2)O(3):Ln microspheres can be well indexed to the hexagonal La(2)O(3) phase. The hollow La(2)O(3):Ln microspheres with uniform diameter of about 270 nm maintain the spherical morphology and good dispersion of the carbon spheres template. The shell of the hollow microspheres consists of numerous nanocrystals with the thickness of approximately 40 nm. Moreover, the possible formation mechanism of evolution from the carbon spheres to the amorphous precursor and to the final hollow La(2)O(3):Ln microspheres has also been proposed. The Yb/Er and Yb/Ho codoped La(2)O(3) hollow spheres exhibit bright up-conversion luminescence with different colors derived from different activators under the 980 nm NIR laser excitation. Furthermore, the doping concentration of the Yb(3+) is optimized under fixed concentration of Er(3+)/Ho(3+). This material may find potential applications in drug delivery, hydrogen and Li ion storage, and luminescent displays based on the uniform hollow structure, dimension, and UC luminescence properties.     

General Synthesis of Multi‐Shelled Mixed Metal Oxide Hollow Spheres with Superior Lithium Storage Properties

Complex hollow structures of transition metal oxides, especially mixed metal oxides, could be promising for different applications such as lithium ion batteries. However, it remains a great challenge to fabricate well‐defined hollow spheres with multiple shells for mixed transition metal oxides. Herein, we have developed a new “penetration–solidification–annealing” strategy which can realize the synthesis of various mixed metal oxide multi‐shelled hollow spheres. Importantly, it is found that multi‐shelled hollow spheres possess impressive lithium storage properties with both high specific capacity and excellent cycling stability. Specifically, the carbon‐coated CoMn₂O₄ triple‐shelled hollow spheres exhibit a specific capacity of 726.7 mA h g^?1 and a nearly 100 % capacity retention after 200 cycles. The present general strategy could represent a milestone in design and synthesis of mixed metal oxide complex hollow spheres and their promising uses in different areas.     

Synthesis of novel tantalum oxide sub-micrometer hollow spheres with tailored shell thickness

Sub-micrometer-sized hollow tantalum oxide (Ta2O5) spheres with tunable shell thickness and void size have been fabricated exploiting beta-diketone-functionalized polystyrene (PS) beads as sacrificial templates in a sol-gel process. First, a controlled precipitation of Ta2O5 nanoparticles was carried out on the template surface by hydrolyzing tantalum ethoxide (Ta(OEt)5) at room temperature, and subsequently, the polymer core was removed either via chemical treatment with toluene or calcination at 650 degrees C. The thickness of the tantala shell precipitated on the PS core during the coating process was tuned between 100 and 142 nm by varying the concentration of tantala precursor in the reaction media. The obtained Ta2O5-coated PS particles and hollow microspheres were characterized by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. Due to the unique optical and dielectric properties, these nanostructured materials are envisaged to be used in applications such as novel building blocks for the fabrication of advanced materials, surface coatings, catalysts, and drug delivery systems.     

Optical and gas sensing properties of mesoporous hollow ZnO microspheres fabricated via a solvothermal method

Mesoporous,hollow Zn O microspheres were synthesized via a hydrothermal method,using glycerol and zinc acetate as the starting materials.XRD and FESEM analysis showed that the surface morphology of the spheres with a Wurtzite structure could be reasonably adjusted by varying the weight ratio(Rw) of Zn(CH3COO)2 2H2O:H2O:C3H8O3.The responses of the gas sensor based on the spheres to 100 ppm ethanol and 100 ppm acetone are 18.9 and 10.4,respectively.The response and recovery times of the sensor to ethanol and acetone are 2 s and 3 s,3 s and 5 s,respectively.The hollow spheres show an intense UV emission at 392 nm and a broad blue-green emission at 488 nm.Interestingly,a light trapping phenomenon is revealed by UV emission and scattering measurements on the microspheres,which can be attributed to the mesoporous shell and hollow structure of the microsphere.     

中空TiO_2微球的制备及对聚丙烯酸酯薄膜性能的影响

采用阳离子聚苯乙烯微球作为模板,钛酸四丁酯为钛源,氨水为催化剂,制备了中空TiO_2微球.采用X射线衍射、扫描电镜及比表面测定仪对其形貌和结构进行了表征,并考察了模板粒径、钛源用量以及催化剂用量对中空TiO_2微球形貌的影响.通过物理共混法将其引入至聚丙烯酸酯乳液中并成膜,研究了复合薄膜的保温性能、抗紫外性能及力学性能.结果表明,锐钛矿相中空TiO_2微球模板粒径、钛源用量以及催化剂用量影响中空TiO_2微球的空心尺寸、壁厚及壳层致密性.中空TiO_2微球可显著提升聚丙烯酸酯薄膜的保温性能、抗紫外性能和力学性能.采用不同粒径的模板制备的中空TiO_2微球对复合薄膜的各项性能均有影响,其中模板粒径为140 nm时复合薄膜性能最优,光反射率提升63%,导热系数降低27%,且在波长小于360 nm范围内,紫外透过率几乎为0,抗张强度增加100%,断裂伸长率提升62%.     

Porous tin oxide nanostructured microspheres for sensor applications

We have sought to enhance the sensitivity of conductometric gas microsensors through the design and fabrication of porous, three-dimensional tin oxide nanoparticle structures. Electrostatically controlled layer-by-layer processing in aqueous solutions was used to decorate sacrificial latex microspheres with Sb:SnO2 nanoparticles. To evaluate their sensing performance, these structures were then deposited as films, via micropipetting, on MEMS micro-hot-plate platforms with interdigitated electrodes. Prior to gas testing, rapid heating of the micro-hot-plates was used to remove the sacrificial latex templates, thereby revealing a 3-D structure composed of interconnected spherical tin oxide nanoparticle shells with porous ultrathin walls. Changes in film conductance, caused by exposure to test gases (methanol, carbon monoxide, benzene, water) in a dry air background, were measured at different temperatures. Hollow nanoparticle microsphere films exhibited partial selectivity for these different gases, good dynamic range at different temperatures and gas concentrations, and good repeatability and stability over long runs. These films also yielded approximately 3-fold and 5-fold increases in sensitivity to methanol when compared to SnO2 polycrystalline chemical vapor deposition films and Sb:SnO2 microporous nanoparticle films, respectively. Gains in sensitivity are attributed to the multiscale porous architecture of the hollow microsphere films. This architecture promotes gas diffusion and increases the active surface area.     

Easy method for preparing nanocrystalline CdS hollow spheres using miniemulsion droplets as templates

CdS hollow spheres with well-controlled morphology and uniform size were successfully prepared using a miniemulsion technique, in which miniemulsion droplets of isooctane prepared with dodecylmercaptane as a co-stabilizer were employed as templates. The SH groups of dodecylmercaptane generated S(-) ions under alkaline conditions, and further reacted with Cd(2+) ions to form cadmium thiolate around the droplets. The cadmium thiolate then reacted with S(2-) ions, stemming from Na(2)S9H(2)O, to directly form CdS hollow spheres owing to the evaporation of isooctane during the reaction and/or the subsequent drying process. No additional dissolution, calcination or additional surface modification of the templates was needed. The size of the hollow spheres could be tuned by altering the molar ratio of the anionic and non-ionic surfactants, while their shell thickness could be adjusted by changing the amount of co-stabilizer.     

A solution-phase, precursor route to polycrystalline SnO2 nanowires that can be used for gas sensing under ambient conditions

This paper describes a solution-based, precursor method for the facile synthesis of uniform nanowires containing rutile SnO2 nanocrystallites. In a typical procedure, nanowires of approximately 50 nm in diameters and up to 30 mum in length were obtained as a white precipitate by refluxing SnC2O4.2H2O and poly(vinylpyrrolidone) in ethylene glycol. Structural analyses by XRD, FT-IR, and TGA indicate that these highly anisotropic nanostructures were formed in an isotropic medium through the aggregation of chainlike precursors that were, in turn, formed via polyol-mediated oligomerization. These nanowires could be further converted to polycrystalline SnO2 by calcination in air at 500 degrees C. The resultant nanowires of SnO2 were highly porous and could be used for gas sensing with improved sensitivity and reversibility under ambient conditions. We have also demonstrated that this new approach could be extended to generate polycrystalline nanowires of other metal oxides such as In2O3 and anatase TiO2.     

Interplay between O2 and SnO2: oxygen ionosorption and spectroscopic evidence for adsorbed oxygen.

Tin dioxide is the most commonly used material in commercial gas sensors based on semiconducting metal oxides. Despite intensive efforts, the mechanism responsible for gas-sensing effects on SnO(2) is not fully understood. The key step is the understanding of the electronic response of SnO(2) in the presence of background oxygen. For a long time, oxygen interaction with SnO(2) has been treated within the framework of the "ionosorption theory". The adsorbed oxygen species have been regarded as free oxygen ions electrostatically stabilized on the surface (with no local chemical bond formation). A contradiction, however, arises when connecting this scenario to spectroscopic findings. Despite trying for a long time, there has not been any convincing spectroscopic evidence for "ionosorbed" oxygen species. Neither superoxide ions O(2)(-), nor charged atomic oxygen O,(-) nor peroxide ions O(2)(2-) have been observed on SnO(2) under the real working conditions of sensors. Moreover, several findings show that the superoxide ion does not undergo transformations into charged atomic oxygen at the surface, and represents a dead-end form of low-temperature oxygen adsorption on reduced metal oxide.     

Single‐Crystal‐like Nanoporous Spinel Oxides: A Strategy for Synthesis of Nanoporous Metal Oxides Utilizing Metal‐Cyanide Hybrid Coordination Polymers

Development of a new method to synthesize nanoporous metal oxides with highly crystallized frameworks is of great interest because of their wide use in practical applications. Here we demonstrate a thermal decomposition of metal‐cyanide hybrid coordination polymers (CPs) to prepare nanoporous metal oxides. During the thermal treatment, the organic units (carbon and nitrogen) are completely removed, and only metal contents are retained to prepare nanoporous metal oxides. The original nanocube shapes are well‐retained even after the thermal treatment. When both Fe and Co atoms are contained in the precursors, nanoporous Fe?Co oxide with a highly oriented crystalline framework is obtained. On the other hand, when nanoporous Co oxide and Fe oxide are obtained from Co‐ and Fe‐contacting precursors, their frameworks are amorphous and/or poorly crystallized. Single‐crystal‐like nanoporous Fe?Co oxide shows a stable magnetic property at room temperature compared to poly‐crystalline metal oxides. We further extend this concept to prepare nanoporous metal oxides with hollow interiors. Core‐shell heterostructures consisting of different metal‐cyanide hybrid CPs are prepared first. Then the cores are dissolved by chemical etching using a hydrochloric acid solution (i.e., the cores are used as sacrificial templates), leading to the formation of hollow interiors in the nanocubes. These hollow nanocubes are also successfully converted to nanoporous metal oxides with hollow interiors by thermal treatment. The present approach is entirely different from the surfactant‐templating approaches that traditionally have been utilized for the preparation of mesoporous metal oxides. We believe the present work proves a new way to synthesize nanoporous metal oxides with controlled crystalline frameworks and architectures.