One-dimensional ZnS-based Hetero-,Core/shell and Hierarchical Nanostructures

A focus of the current nanotechnology has shifted from routine fabrication of nanostructures to designing functional electronic devices and realizing their immense potentials for applications. Due to infusion of multi-functionality into a single system, the utilization of hetero-, core/shell and hierarchical nanostructures has become the key issue for building such devices. ZnS, due to its direct wide bandgap, high index of refraction, high transparency in the visible range and intrinsic polarity, is one of the most useful semiconductors for a wide range of electronics applications. This article provides a dense review of the state-of-the-art research activities in one-dimensional （1D） ZnS-based hetero-, core/shell and hierarchical nanostructures. The particular emphasis is put on their syntheses and applications.

Hierarchical Carbon Microtube@Nanotube Core-Shell Structure for High-Performance Oxygen Electrocatalysis and Zn-Air Battery

Zinc-air batteries(ZABs)hold tremendous promise for clean and efficient energy storage with the merits of high theoretical energy density and environmental friendliness.However,the performance of practical ZABs is still unsatisfactory because of the inevitably decreased activity of electrocatalysts when assembly into a thick electrode with high mass loading.Herein,we report a hierarchical electrocatalyst based on carbon microtube@nanotube core-shell nanostructure(CMT@CNT),which demonstrates superior electrocatalytic activity for oxygen reduction reaction and oxygen evolution reaction with a small potential gap of 0.678 V.Remarkably,when being employed as air-cathode in ZAB,the CMT@CNT presents an excellent performance with a high power density(160.6 mW cm^−2),specific capacity(781.7 mAhgZn^−1)as well as long cycle stability(117 h,351 cycles).Moreover,the ZAB performance of CMT@CNT is maintained well even under high mass loading(3 mg cm−2,three times as much as traditional usage),which could afford high power density and energy density for advanced electronic equipment.We believe that this work is promising for the rational design of hierarchical structured electrocatalysts for advanced metal-air batteries.

Synthesis and Characterization of Fluorine-containing Polyacrylate Emulsion with Core-Shell Structure

包含氟的符号的 polyacrylate 共聚物乳剂被一个种子乳剂聚合方法，在甲基， methacrylate (MMA ) 和丁基 acrylate (BA ) 作为包含氟的符号的单体被用作主要单体和 hexafluorobutyl methacrylate (HFMA ) 综合。结构和性质被 Fourier 变换描绘红外线的光谱(英尺红外) ，传播电子显微镜学(TEM ) ，粒子尺寸分析， X 光检查光电子光谱学(XPS ) ，接触角度(CA ) ，微分扫描热量测定(DSC ) 和 thermogravimetry (TG ) 分析。FTIR 和 TEM 结果证明 HFMA 有效地涉及乳剂 copolymerization，并且形成的乳剂粒子让核心壳结构和一个狭窄的粒子缩放分发。XPS 和 CA 分析表明氟的符号的坡度集中在富于氟的符号和在一个方面恐水病的更多的包含氟的符号的乳剂电影的深度侧面存在。DSC 和 TG 分析也证明清楚的核心壳结构在包含氟的符号的乳剂粒子存在，并且他们的电影比没有氟的符号的乳剂的显示出更高热的稳定性。

Photochemical synthesis of bimetallic Au-Ag nanoparticles with “core-shell” type structure by seed mediated catalytic growth

The colloidal Au core/Ag shell structure composite nanoparticles were synthesized in PEG-acetone solution by photochemical route. The monodispersed Au nanoparticles with average diameter of 3.9 nm were used as growth seeds. The optical property of colloids and the sizes of composite nanoparticles were characterized when the molar ratio of Au to Ag ranges from 4∶1 to 1∶4. The results show that a composite nanoparticle structure similar to strawberry shape is formed at the molar ratio of Au to Ag from 4∶1 to 1∶1; the composite nanoparticles consisting of a core of Au and shell of Ag were generated at the 1∶4 molar ratio, having a striking feature of forming (interconnected) network structure.

Synthesis of Ag@Al_2O_3 Core-shell Structure Nanoparticles and Their Enhancement Effect on Dielectric Properties for Ag@Al_2O_3/Polyimide Nanocomposites

A novel core-shell structure Ag@Al2O3 nano-particles were synthesized and doped into polyimide as conductive fillers to prepare the composite films with high dielectric properties and low dielectric loss. The morphology and structures of the Ag@Al2O3 nano-particles were characterized by transmission electron microscopy （TEM）, X-ray diffraction （XRD）, and UV-visible spectroscopy. All the results proved that the Ag@Al2O3 nano-parficles had a typical core-shell structure, for the Ag particles were coated by Al2O3 shell and the average sizes ofAg@Al2O3 particles were between 30 to 150 nm. The as-prepared Ag@Al2O3 nanoparticles were doped into the polyimide with different mass fractions to fabricate the Ag@Al2O3/PI composite films via in-situ polymerization process. SEM analysis of composite films showed that the Ag@Al2O3 nano- particles homogeneously dispersed in polyimide matrix with nanoseale. As dielectric materials for electronic packaging systems, the Ag@Al2O3/PI composites exhibited appropriate mechanical properties and erthaneed dielectric properties, including greatly enhanced dielectric constant and just a slight increase in dielectric loss. These improvements were attributed to the core-shell structure of fillers and their fine dispersion in the PI matrix.

Effect of milling process on the core-shell structures and dielectric properties of fine-grained BaTiO_3-based X7R ceramic materials

Fine-grained BaTiO3-based X7R ceramic materials were prepared and the effects of milling process on the core-shell structures and dielectric properties were investigated using scanning electron microscope, transmission electron microscope, and energy dispersive spectroscopy （EDS）. As the milling time extends, the dielectric constant of the ceramics increases, whereas the temperature coefficient of capacitance at 125℃ drops quickly. The changes in dielectric properties are considered relevant to the microstructure evolution caused by the milling process. Defects on the surface of BaTiO3 particles increase because of the effects of milling process, which will make it easier for additives to diffuse into the interior grains. As the milling time increases, the shell region gets thicker and the core region gets smaller; however, EDS results show that the chemical inhomogeneity between grain core and grain shell becomes weaker.

Core-shell structured 1,4-benzoquinone@TiO_2 cathode for lithium batteries

Organic carbonyl compounds are considered as promising candidates for lithium batteries due to theirhigh capacity and environmental friendliness, However, they suffer from serious dissolution in the elec-trolyte, leading to fast capacity decay. Here we report core-shell structured 1,4-benzoquinone@titaniumdioxide （BQ@TiO2） composite as cathode for lithium batteries. The composite cathode can deliver a highdischarge capacity of 441.2 mA h/g at 50 mA/g and a high capacity retention of 80.7% after 100 cycles. Thegood cycling performance of BQ@TiO2 composite can be attributed to the suppressed dissolution of BQ,which results from the physical confinement effect of Ti02 shell and the strong interactions between BQand Ti02. Moreover, the combination of ex situ infrared spectra and density functional theory calculationsreveals that the active redox sites of BQ are carbonyl groups. This work provides an alternative way tomitigate the dissolution of small carbonyl compounds and thus enhance their cycling stability.

Shell-driven Fine Structure Transition of Core Materials in Co@Au Core-shell Nanoparticles

Co@Au core shell nanoparticles(NPs) of different shell thicknesses were fabricated by a combination of the displacement process and the reduction-deposition process in a microfluidic reactor. The effect of the shell thickness on the fine structures(local atom arrangement) of core materials was investigated by X-ray Absorption Near Edge Structure(XANES) and Extended X-ray Absorption Fine Structure(EXAFS).The results indicate that the shell thickness affects the fine structure of the core materials by causing atomic re-arrangement between the hexagonal close pack(hcp) and the face centered cubic(fcc) structure, and forming Co-Au bonds in the core-shell interface.

Immobilization of metalloporphyrins on CeO_2@SiO_2 with a core-shell structure prepared via microemulsion method for catalytic oxidation of ethylbenzene

Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

Reduced-temperature ordering of FePt nanoparticle assembled films by Fe30Pt70/Fe3O4 core/shell structure

In this paper, Fe30Pt70/Fe3O4 core/shell nanoparticles were synthesized by chemical routine and the layered polyethylenimine （PEI）-Fe30Pt70/Fe3O4 structure was constructed by molecule-mediated self-assembly technique. The dimension of core/shell structured nanoparticles was that of 4nm core and 2 nm shell. After annealing under a flow of forming gas （50%Ar2＋30%H2） for 1 h at or above 400℃, the iron oxide shell was reduced to Fe and diffused to Pt-rieh core, which leaded to the formation of L1. phase FePt at low temperature. The x-ray diffraction results and magnetic properties measurement showed that the chemical ordering temperature of Fe30Pt70/Fe3O4 core/shell nanoparticles assembly can be reduced to as low as 400℃. The sample annealed at 400℃ showed the eoereivity of 4KOe with the applied field of 1.5T. The core/shell structure was suggested to be an effective way to reduce the ordering temperature obviously.

Application of Monodisperse Thermo-Responsive Composite Microgels with Core-Shell Structure Based on Au@Ag Bimetallic Nanorod as Core in Surface Enhanced Raman Spectroscopy Substrate

The monodisperse Au@Ag bimetallic nanorod is encapsulated by crosslinked poly( N-isopropylacrylamide)( PNIPAM) to produce thermo-responsive composite microgel with well-defined core-shell structure( Au@ Ag NR@ PNIPAM microgel)by seed-precipitation polymerization method using butenoic acid modified Au @ Ag NRs as seeds. When the temperature of the aqueous medium increases from 20℃ to 50℃,the localized surface plasmon resonance( LSPR) band of the entrapped Au @ Ag NR is pronouncedly red-shifted because of the decreased spatial distances between them as a result of shrinkage of the microgels,leading to their plasmonic coupling. The temperature tunable plasmonic coupling is demonstrated by temperature dependence of the surface enhanced Raman spectroscopy( SERS) signal of 1-naphthol in aqueous solution. Different from static plasmonic coupling modes from nanostructured assembly or array system of noble metals,the proposed plasmonic coupling can be dynamically controlled by environmental temperature. Therefore, the thermo responsive hybrid microgels have potential applications in mobile LSPR or SERS microsensors for living tissues or cells.

Raman scattering in In/InOx core-shell structured nanoparticles

The properties of Raman phonons are very important due to the fact that they can availably reflect some important physical information. An abnormal Raman peak is observed at about 558 cm-1 in In film composed of In/InOx core-shell structured nanoparticles, and the phonon mode stays very stable when the temperature changes. Our results indicate that this Raman scattering is attributed to the existence of incomplete indium oxide in the oxide shell.

Preparation of Core-shell Structured Particles and Their Nucleation in Polyester:I. Preparation of Monodisperse SiO_2/PS Core-shell Composite Particles

To enhance the nucleation and crystallization properties of polyester (e.g., polyethylene terephthalate, PET), core-shell structured particles are used to improve these properties by controlling the inorganic dispersion properties in the polymers. In the paper, monodisperse particles of silica/polystyrene (PS) are prepared with both dispersion and emulsion polymerization techniques. The monodisperse silicon dioxide particles are first prepared with the seed growth method and modified by the coupling agents. Silica is properly modified with KH-570, and its size deviation is 3.0% or so. The modified silica then reacts with the mixture of ethanol, water medium, and monomer of styrene under dispersion polymerization. Results show that the dispersion polymerization technique is more suitable for monodisperse core-shell SiO2/PS particles than that of the emulsion. The morphology and molecular structure of the core-shell particles are investigated with the transmission electron microscope (TEM), and fourier transform infra-red spectroscopy (FTIR). The results show that the modified silica particles are successfully encapsulated with polystyrene. The average number of silica particles encapsulated into each polystyrene sphere decreases when the size of silica particles increases from 50 nm to 600 nm, and will approach one when the silica is greater than 380nm in size. The mass ratio for silica/PS particles in emulsion polymerization is 4.7/1, lower than that of 6.8/1 for dispersion polymerization, which is the first reported optimized data for preparing the similar monodisperse composite particles. Thus, the PS shell in the former is thinner than that in the latter.

Fabrication of the Core-Shell Structured ZSM-5@Mg(Al)O and Its Catalytic Application in Propane Dehydrogenation

In this study, a novel core-shell structure of ZSM-5@Mg(Al)O(abbreviated as Z@MA) was designed by using the sol-gel method, and the influence of different weight ratios of Mg(Al)O/ZSM-5 on the structure and catalytic performance was investigated. The as-obtained materials were characterized by XRD, N_2-physisorption, SEM, FT-IR, NH_3-TPD and XPS analyses. The results showed that, with the increase of the weight ratio of Mg(Al)O/ZSM-5, the thickness of Mg(Al)O shell was improved, and the pore structure and physiochemical properties of core-shell materials were directly modified. After introduction of Mg(Al)O, the acidity properties of different materials were significantly suppressed. Meanwhile, more Sn oxide species in Z@MA could facilitate the anchoring of Pt on the support. By effectively employing these modifications, the capacity of the catalysts to accommodate coke was significanty improved and the carbon deposits were migrated from active metal to the carrier. When the weight ratio was equal to 3, the catalyst PtSnNa/Z@MA showed a highest conversion and high selectivity in propane dehydrogenation.

A Comparative Study on the Selected Area Electron Diffraction Pattern of Fe Oxide/Au Core-shell Structured Nanoparticles

The selected area electron diffraction （SAED） pattern of magnetic iron oxide core/gold shell nanoparticles has been studied. For the composite particles with mean size less than 10 nm, their SAED pattern is found to be different from either the pattern of pure Fe oxide nanoparticles or that of pure Au particles. Based on the fact that the ring diameters of these composite particles fit the characteristic relation for the fcc structure, the Au atoms on surfaces of the concerned particles are supposed to pack in a way more tightly than they usually do in pure Au nanoparticles. The driving force for this is the coherency strain which enables the shell material at the heterostructured interface to adapt the lattice parameters of the core.

The Magnetic Field Effects on Radially Symmetric Core-Shell-Shell Structure

In this paper, we modeled a core/shell/shell structure with cylindrical Schrodinger-Poisson coupled equation when a magnetic field is (and is not) applied along its axis. We showed the electron density is peaked near the outer surface of the channel when the magnetic field is applied. Therefore one may make a nano-device which its electrons move only on its outer surface. Also we applied a gate voltage to the device and showed a higher threshold voltage (to turn on the device) is necessary when a magnetic field is applied. This is because of the increase in the lowest energy level similar to the size quantization. i.e a device with longer channel looks like a device with shorter channel if it is placed in a magnetic field parallel to its axis.

Core-shell structured Ru-Ni@SiO_2: Active for partial oxidation of methane with tunable H_2/CO ratio

This study demonstrated that a Ru-Ni bimetallic core-shell catalyst（0.6%Ru-Ni）@Si O2with a proper surface Ru concentration is superior in achieving better catalytic activity and tunable H2/CO ratio at a comparatively lower reaction temperature（700℃）.Compared to the impregnation method,the hydrothermal approach leads to a highly uniform Ru distribution throughout the core particles.Uniform Ru distribution would result in a proper surface Ru concentration as well as more direct Ru-Ni interaction,accounting for better catalyst performance.Enriched surface Ru species hinders surface carbon deposition,but also declines overall activity and H2/CO ratio,meanwhile likely enhances Ni oxidation to certain degree under the applied reaction conditions.Over the current（m%Ru-Ni）@Si O2catalyst,the formation of fibrous carbon species is suppressed,which accounts for good stability of catalyst within a TOS of 10 h.

Preparation and upconversion luminescence properties of LaF_3:Yb^(3 +),Er^(3 +) /SiO_2 nanocomposites with core /shell structure

LaF_3:Yb^(3 +),Er^(3 +) nanoparticles were successfully synthesized using solvothermal treatment,and LaF_3:Yb^(3 +),Er^(3 +) /SiO_2 core /shell nanoparticles were also prepared with reverse microemulsion technique.The crystal structure,morphology and photoluminescence properties of as-prepared core /shell nanoparticles were investigated by X-ray diffraction,transmission electron microscopy and fluorescence spectrophotometer.The results showed that LaF_3:Yb^(3 +),Er^(3 +) nanoparticles are of hexagonal structure and SiO_2 shell is amorphous.The size of LaF_3:Yb^(3 +),Er^(3 +) nanoparticles is 13 nm and the LaF_3:Yb^(3 +),Er^(3 +) /SiO_2 nanoparticles present clearly a core /shell structure with 12 nm shell thickness.The solubility of LaF_3:Yb^(3 +),Er^(3 +) nanocrystals in water and the biocompatibility are both improved by the SiO_2 shell.The upconversion luminescence spectra suggested that the SiO_2 shell has small effect on the upconversion luminescence properties of the LaF_3:Yb^(3 +),Er^(3 +) nanocrystals.The core /shell structure LaF_3:Yb^(3 +),Er^(3 +) /SiO_2 nanoparticles are expected to be used in biological applications.

核壳结构C-TiO_(2)纳米复合材料用于高效光催化降解有机染料

化工、纺织印染与农药化肥等产业的蓬勃发展推动着人类社会的进步,但同时也给环境治理带来了巨大难题。目前,光催化降解局限于在特定波长下针对单一有机污染物进行降解,然而现实中的情况往往更复杂。因此,开发一种多功能光催化材料用于光催化降解不同有机污染物显得尤为重要。采用一步无模板溶剂热法合成了核壳结构的C-TiO_(2)复合材料前驱体,并在氩气气氛下煅烧得到高结晶度的C-TiO_(2)复合光催化材料。运用SEM、TEM、XRD和TG等表征手段对材料进行表征,结论如下:550℃煅烧时的样品为包含少量碳的高结晶度的锐钛矿相TiO 2,且550℃煅烧时的样品依然保持了完整的核壳结构。此外,C-TiO_(2)复合材料的比表面积高达85.69 m 2·g^(-1),平均孔径为16.4 nm以及孔体积为0.423 m 3·g^(-1)。在UV-Vis光照射下,C-TiO_(2)复合材料分别对罗丹明B(RhB)、亚甲基蓝(MB)和刚果红(CR)3种染料显示出增强的光催化降解活性。