A phase-transfer identification of core-shell structures in Ag-Pt nanoparticles

Ag-Pt nanoparticles with a confirmed core-shell structure could only be formed by the successive reduction method using Ag nanoparticles as the seeds. The core-shell structure could be conveniently inferred from the transferability of the particles from water to toluene. Independent measurements by UV-vis spectroscopy, transmission electron microscopy, energy-dispersive X-ray analysis, and X-ray photoelectron spectroscopy were used to validate the experimental results. The reverse order of synthesis using Pt nanoparticles as the seeds did not result in any core-shell product. Instead a physical mixture of Ag nanoparticles and the original Pt seeds was obtained under the same experimental conditions.     

Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction

Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.     

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.     

PMMA纳米球的制备及其银膜包覆技术

采用无皂乳液聚合法制备了单分散、直径为170 nm左右的聚甲基丙烯酸甲酯(PMMA)纳米球, 然后利用3-甲基丙烯酰氧基丙基三甲氧基硅烷(MATS)和3-巯丙基三甲氧基硅烷(MPTMS)对PMMA纳米球进行表面改性, 在其表面包覆一层均匀的巯基, 通过巯基与银离子之间的相互作用, 使银在PMMA纳米球表面成核长大, 从而合成PMMA/Ag纳米球壳粒子. 通过扫描电子显微镜、投射电子显微镜和紫外-可见吸收光谱测试技术对产物性能进行了表征, 研究结果表明, 制备的PMMA/Ag纳米球壳粒子的分散性好、包覆均匀.     

Synthesis of bimetallic nanoshells by an improved electroless plating method

In the Letter, we demonstrate an improved electroless plating method for the synthesis of bimetallic shell particles. The procedure involves a combination of surface reaction, seeding growth, and removal of supporting cores. We modified ammonical AgNO3 in ethanol with a controlled amount of HCHO in the seeding process and a uniform and relatively dense coverage of silver nanoparticle seeds on colloid cores was achieved. Following the second kind of metal plating, we extended this method to prepare continuous bimetallic core-shell and hollow particles with a submicrometer diameter. The morphologies of the bimetallic Cu/Ag and Pt/Ag particles were studied with transmission electron microscopy and scanning electron microscopy, and their crystallinity and chemical composition were confirmed by X-ray diffraction. The prepared materials may be of applied value in areas such as catalysis, optics, and plasmonics.     

Size-dependent morphology of dealloyed bimetallic catalysts: linking the nano to the macro scale

Chemical dealloying of Pt binary alloy precursors has emerged as a novel and important preparation process for highly active fuel cell catalysts. Dealloying is a selective (electro)chemical leaching of a less noble metal M from a M rich Pt alloy precursor material and has been a familiar subject of macroscale corrosion technology for decades. The atomic processes occurring during the dealloying of nanoscale materials, however, are virtually unexplored and hence poorly understood. Here, we have investigated how the morphology and intraparticle composition depend on the particle size of dealloyed Pt-Co and Pt-Cu alloy nanoparticle precursor catalysts. To examine the size-morphology-composition relation, we used a combination of high-resolutionscanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), electron energy loss (EEL) spectroscopy, energy-dispersive X-ray spectroscopy (EDS), and surface-sensitive cycling voltammetry. Our results indicate the existence of three distinctly different size-dependent morphology regimes in dealloyed Pt-Co and Pt-Cu particle ensembles: (i) The arrangement of Pt shell surrounding a single alloy core ("single core-shell nanoparticles") is exclusively formed by dealloying of particles below a characteristic diameter d(multiple cores) of 10-15 nm. (ii) Above d(multiple cores), nonporous bimetallic core-shell particles dominate and show structures with irregular shaped multiple Co/Cu rich cores ("multiple cores-shell nanoparticles"). (iii) Above the second characteristic diameter d(pores) of about 30 nm, the dealloyed Pt-Co and Pt-Cu particles start to show surface pits and nanoscale pores next to multiple Co/Cu rich cores. This structure prevails up to macroscopic bulklike dealloyed particles with diameter of more than 100 nm. The size-morphology-composition relationships link the nano to the macro scale and provide an insight into the existing material gap of dealloyed nanoparticles and highly porous bulklike bimetallic particles in corrosion science.     

Core-shell Ag–Pt nanoparticles: A versatile platform for the synthesis of heterogeneous nanostructures towards catalyzing electrochemical reactions

Heterogeneous nanostructures that are defined as a hybrid structure consisting of two or more nanoscale domains with distinct chemical compositions or physical characteristics have attracted intense efforts in recent years. In this review, we focus on the introduction of a number of heterogeneous nanostructures derived using core-shell Ag–Pt nanoparticles as starting materials, including hollow, dimeric and composite structures and also highlight their application in catalyzing electrochemical reactions, e.g., methanol oxidation reaction and oxygen reduction reaction. This review not only shows the capability of core-shell Ag–Pt nanoparticles in producing various heterogeneous nanostructures as starting templates, but also highlights the structural design or electronic interaction that endows the heterogeneous nanostructures with enhanced catalytic properties either in methanol oxidation or in oxygen reduction. Further, we also make some perspectives for more heterogeneous nanostructures that may be prepared by using core-shell Ag–Pt particles or their derivatives so as to offer the readers the opportunities and challenges in this field.     

Synthesis and utilization of monodisperse hollow polymeric particles in photonic crystals

We developed a process to fabricate 150-700 nm monodisperse polymer particles with 100-500 nm hollow cores. These hollow particles were fabricated via dispersion polymerization to synthesize a polymer shell around monodisperse SiO(2) particles. The SiO(2) cores were then removed by HF etching to produce monodisperse hollow polymeric particle shells. The hollow core size and the polymer shell thickness, can be easily varied over significant size ranges. These hollow polymeric particles are sufficiently monodisperse that upon centrifugation from ethanol they form well-ordered close-packed colloidal crystals that diffract light. After the surfaces are functionalized with sulfonates, these particles self-assemble into crystalline colloidal arrays in deionized water. This synthetic method can also be used to create monodisperse particles with complex and unusual morphologies. For example, we synthesized hollow particles containing two concentric-independent, spherical polymer shells, and hollow silica particles which contain a central spherical silica core. In addition, these hollow spheres can be used as template microreactors. For example, we were able to fabricate monodisperse polymer spheres containing high concentrations of magnetic nanospheres formed by direct precipitation within the hollow cores.     

Characterization of Ag/Pt core-shell nanoparticles by UV-vis absorption, resonance light-scattering techniques

The water-soluble Ag/Pt core-shell nanoparticles were prepared by deposition Pt over Ag colloidal seeds with the seed-growth method using K2PtCl4 with trisodium citrate as reduced agent. The Ag:Pt ratio is varied from 9:1 to 1:3 for synthesizing Pt shell layer of different thickness. A remarkable shift and broadening of Ag surface plasmon band around 410 nm was observed. The contrast of TEM images of Ag/Pt colloids has been obtained. Various techniques, such as transmission electron microscopy (TEM), UV-vis absorption and resonance light-scattering spectroscopy were used to characterize nanoparticles. The data of TEM, UV-vis and resonance light-scattering spectrum all confirm formation of Ag/Pt core-shell nanoparticles. Resonance light-scattering and emission spectrum show the Ag and Ag/Pt core-shell nanoparticles have a nonlinear light-scattering characteristic.     

Cation exchange: a simple and versatile route to inorganic colloidal spheres with the same size but different compositions and properties

This paper describes a cation exchange approach to the synthesis of metal chalcogenide core-shell particles with the same size but a number of different compositions. This method begins with the preparation of colloidal spheres of amorphous Se (a-Se), followed by their reaction with Ag atoms to form Se@Ag2Se spheres. These core-shell spheres are then converted into Se@MSe (M = Zn, Cd, and Pb) via cation exchange with Zn2+, Cd2+, and Pb2+. All the colloidal spheres prepared using this method are monodispersed in size and characterized by a spherical shape and a smooth surface. Starting from the same batch of Se@Ag2Se, the resultant Se@MSe samples were essentially the same in size. Furthermore, these core-shell colloidal spheres can be easily made superparamagnetic by incorporating Fe3O4 nanoparticles into the a-Se cores. This synthetic approach provides a simple and versatile route to magnetoactive core-shell spheres with the same size but a range of different compositions. This study also implies that it is feasible to further increase the diversity of cations that can be used in the cation exchange of a colloidal system to produce multifunctional core-shell spheres with a variety of properties.     

核壳纳米粒子与牛血清白蛋白表面增强拉曼光谱的研究

本文用表面增强拉曼光谱(SERS)系统地研究了牛血清白蛋白(BSA)与Ag/Pt核壳纳米粒子的相互作用,特别是核壳纳米粒子与被吸附的牛血清白蛋白分子之间的界面作用,并用紫外可见光谱、圆二色光谱(CD)作为辅助手段进一步证实了BSA与核壳纳米粒子的作用状况.通过紫外光谱研究发现,核壳纳米粒子的特征吸收峰的消失表明纳米粒子完全被牛血清白蛋白包覆.用近紫外CD光谱探讨了血清白蛋白的芳基氨基酸(苯丙氨酸、酪氨酸)残基微环境的变化.为探讨牛血清白蛋白与Ag/Pt核壳纳米粒子的作用机理及纳米尺寸的生物效应奠定了理论基础.     

纳米碳材料负载铂催化剂在环己烷脱氢反应中的催化性能研究

制备了纳米碳材料负载铂的催化剂,通过N₂吸附、TEM、XRD技术分别对载体的BET比表面积和催化剂结构、形貌和粒径大小进行了表征。考察了不同催化剂在环己烷脱氢反应中的催化性能以及温度对纳米碳颗粒负载铂催化剂活性的影响。结果表明,锚定在不同碳载体上的铂有较好的分散性,粒径较小,粒度分布范围较窄并且具有相同的晶型结构。孔状纳米碳颗粒负载铂催化剂的活性高于碳纳米管和高比表面的活性炭负载铂催化剂,并且在低温条件下已经显示了较高的活性,尤其是中空碳颗粒负载铂催化剂在环己烷脱氢反应中显示了好的活性和稳定性。     

Pt@Au/Al2O3核壳纳米粒子的制备和表征及其在催化氧化甲苯中的应用

Customizing core-shell nanostructures is considered to be an efficient approach to improve the catalytic activity of metal nanoparticles. Various physiochemical and green methods have been developed for the synthesis of core-shell structures. In this study, a novel liquid-phase hydrogen reduction method was employed to form core-shell Pt@Au nanoparticles with intimate contact between the Pt and Au particles, without the use of any protective or structure-directing agents. The Pt@Au core-shell nanoparticles were prepared by depositing Au metal onto the Pt core; AuCl⁴⁻ was reduced to Au(0) by H₂ in the presence of Pt nanoparticles. The obtained Pt@Au core-shell structured nanoparticles were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), high-resolution TEM, fast Fourier transform, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and H₂-temperature programmed reduction (H₂-TPR) analyses. The EDX mapping results for the nanoparticles, as obtained from their scanning transmission electron microscopy images in the high-angle annular dark-field mode, revealed a Pt core with Au particles grown on its surface. Fourier transform measurements were carried out on the high-resolution structure to characterize the Pt@Au nanoparticles. The lattice plane at the center of the nanoparticles corresponded to Pt, while the edge of the particles corresponded to Au. With an increase in the Au content, the intensity of the peak corresponding to Pt in the FTIR spectrum decreased slowly, indicating that the Pt nanoparticles were surrounded by Au nanoparticles, and thus confirming the core-shell structure of the nanoparticles. The XRD results showed that the peak corresponding to Pt shifted gradually toward the Au peak with an increase in the Au content, indicating that the Au particles grew on the Pt seeds; this trend was consistent with the FTIR results. Hence, it can be stated that the Pt@Au core-shell structure was successfully prepared using the liquid-phase hydrogen reduction method. The catalytic activity of the nanoparticles for the oxidation of toluene was evaluated using a fixed-bed reactor under atmospheric pressure. The XPS and H₂-TPR results showed that the Pt₁@Au₁/Al₂O₃ catalyst had the best toluene oxidation activity owing to its lowest reduction temperature, lowest Au 4d & 4f and Pt 4d & 4f binding energies, and highest Au⁰/Au^δ+ and Pt⁰/Pt²⁺ proportions. The Pt₁@Au₂Al₂O₃ catalyst showed high stability under dry and humid conditions. The good catalytic performance and high selectivity of Pt@Au/Al₂O₃ for toluene oxidation could be attributed to the high concentration of adsorbed oxygen species, good low-temperature reducibility, and strong interaction.     

Facile fabrication of AgCl@polypyrrole-chitosan core-shell nanoparticles and polymeric hollow nanospheres

A one-step sequential method for preparing AgCl@polypyrrole-chitosan core-shell nanoparticles and subsequently the formation of polypyrrole-chitosan hollow nanospheres is reported. The formation of the core and the shell is performed in one reaction medium almost simultaneously. Transmission electron microscopy (TEM) images show the presence of core-shell nanoparticles and hollow nanospheres. Ultraviolet-visible (UV-vis) studies reveal that AgCl was formed first followed by polypyrrole. X-ray diffration (XRD) and UV-vis studies show that AgCl was present in the core-shell nanoparticles and could be removed completely from the core.     

壳层可控导电聚吡咯/聚苯乙烯复合微球及聚吡咯中空微胶囊的制备

在导电聚合物含量较小时,含核壳结构的导电聚合物复合粒子就可以具有和本体相当的导电率,且加工性好,近年来这种核壳结构微粒的制备已引起了科学家们的广泛关注．Armes等[制备了导电聚吡咯、导电聚苯胺包覆聚苯乙烯的核壳结构胶体粒子及聚苯胺和二氧化硅的纳米复合物．刘正平等用改进的方法在粒径为116nm的单分散聚苯乙烯乳胶粒子上包覆聚吡咯,     

Core-shell and hollow nanocrystal formation via small molecule surface photodissociation; Ag@Ag2Se as an example

Metallic Ag nanoparticles have been converted to Ag2Se nanoparticles at ambient temperature and open atmosphere by UV photodissociation of adsorbed CSe2 on the Ag core surface. The photolysis could be prevented at any stage yielding Ag@Ag2Se core-shell structures of different thickness. Depending on the initial Ag nanoparticle size, either hollow or filled nanocrystals of Ag2Se could be prepared. The Kirkendall effect has been proposed to account for the formation of hollow nanoparticles. A coated-sphere Drude model has been used to explain the redshift of the Ag plasmon band as a function of the Ag2Se shell thickness as well as to provide the first estimates of the wavelength-dependent dielectric function of Ag2Se. This photochemical method might be especially promising for carrying out a direct room-temperature phototransformation of metallic into semiconductor nanostructures already assembled on surface templates.     

TEM-induced structural evolution in amorphous Fe oxide nanoparticles

Exposure to the high energy electron beam of a TEM changes the morphology of amorphous Fe oxide nanoparticles from solid spheres to hollow shells. Amorphous Fe oxide nanoparticles prepared via high-temperature methods using hexadecylamine and trioctylphosphine oxide surfactants were compared to crystalline gamma-Fe2O3 particles of similar size. Both sets of particles are fully characterized via SQUID magnetometry, X-ray powder diffraction, BET surface analysis, EPR spectroscopy, high-resolution transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS). Time-resolved TEM images reveal that the amorphous Fe oxide particles evolve from solid spheres into hollow shells in <2 min, whereas crystalline gamma-Fe2O3 are unaffected by the electron beam. The resulting nanocrystalline Fe oxide shells bear striking resemblance to core-shell nanocrystals, but are a result of a morphology change attributed to restructuring of particle voids and defects induced by quasi-melting in the TEM. These results thus imply that caution is necessary when using TEM to analyze nanoparticle core-shell and heterostructured nanoparticles.     

Au/Ag核一壳结构复合纳米粒子形成机制的研究

在已制备好的Au纳米粒子表面,通过化学还原的方法沉积生长Ag包覆层,通过 控制Au, Ag的比列,制备了粒度均匀且粒径可控的Au/Ag核-壳结构纳米粒子。利用 UV-vis吸收光谱和透射电子显微镜（TEM）对SAu, Ag摩尔比为1：10的复合纳米粒 子的光学性质和形态进行随时监测,直接观察了核-壳结构纳米粒子的生长过程： 一部分Ag+在Au核表面还原生长,溶液中其余Ag+还原形成银的纳米团簇向粒子表面 的继续沉积生长,壳层增厚。     

A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles

A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles has been developed. The core-shell nanostructures with NH4Cl as core and TiO2·xH2O-NH4Cl as shell were prepared in nonaqueous system by the deposition on the surface of the aggregated NH4Cl crystals, which could be transformed into mesoporous anatase nanoparticles or hollow nanospheres by calcination at 500℃ or extraction with methanol, respectively. The hierarchical mesoporous nanostruc...     

制备核-壳结构聚合物纳米微球和空心球的原位聚合方法的普适性研究

采用原位聚合制备核-壳结构聚合物纳米微球和空心球的新方法, 利用甲基丙烯酸2-羟丙酯(HPMA)和乙酸乙烯酯(VAc)两种单体, 在类似的反应条件下, 成功地制备了以聚(ε-己内酯)(PCL)为核, 分别以交联PHPMA和PVAc为壳的纳米微球; 将微球的核酶解后, 分别得到了对应的交联PMAA空心球和交联PVA空心球. 结果表明, 原位聚合制备核-壳结构聚合物微球的新方法具有一定的普适性, 适用于单体可溶于水而生成的聚合物不溶于水的体系.