Characterization of superparamagnetic "core-shell" nanoparticles and monitoring their anisotropic phase transition to ferromagnetic "solid solution" nanoalloys

The structure, magnetism, and phase transition of core-shell type CoPt nanoparticles en route to solid solution alloy nanostructures are systematically investigated. The characterization of Co(core)Pt(shell) nanoparticles obtained by a "redox transmetalation" process by transmission electron microscopy (TEM) and, in particular, X-ray absorption spectroscopy (XAS) provides clear evidence for the existence of a core-shell type bimetallic interfacial structure. Nanoscale phase transitions of the Co(core)Pt(shell) structures toward c-axis compressed face-centered tetragonal (fct) solid solution alloy CoPt nanoparticles are monitored at various stages of a thermally induced annealing process and the obtained fct nanoalloys show a large enhancement of their magnetic properties with ferromagnetism. The relationship between the nanostructures and their magnetic properties is in part elucidated through the use of XAS as a critical analytical tool.     

Silica-metal core-shell nanostructures

Silica-metal nanostructures consisting of silica cores and metal nanoshells attract a lot of attention because of their unique properties and potential applications ranging from catalysis and biosensing to optical devices and medicine. The important feature of these nanostructures is the possibility of controlling their properties by the variation of their geometry, shell morphology and shell material. This review is devoted to silica-noble metal core-shell nanostructures; specifically, it outlines the main methods used for the preparation and surface modification of silica particles and presents the major strategies for the formation of metal nanoshells on the modified silica particles. A special emphasis is given to the St?ber method, which is relatively simple, effective and well verified for the synthesis of large and highly uniform silica particles (with diameters from 100 nm to a few microns). Next, the surface chemistry of these particles is discussed with a special focus on the attachment of specific organic groups such as aminopropyl or mercaptopropyl groups, which interact strongly with metal species. Finally, the synthesis, characterization and application of various silica-metal core-shell nanostructures are reviewed, especially in relation to the siliceous cores with gold or silver nanoshells. Nowadays, gold is most often used metal for the formation of nanoshells due to its beneficial properties for many applications. However, other metals such as silver, platinum, palladium, nickel and copper were also used for fabrication of core-shell nanostructures. Silica-metal nanostructures can be prepared using various methods, for instance, (i) growth of metal nanoshells on the siliceous cores with deposited metal nanoparticles, (ii) reduction of metal species accompanied by precipitation of metal nanoparticles on the modified silica cores, and (iii) formation of metal nanoshells under ultrasonic conditions. A special emphasis is given to the seed-mediated growth, where metal nanoshells are formed on the modified silica cores with deposited metal nanoparticles. This strategy assures a good control of the nanoshell thickness as well as its surface properties.     

Hybrid one-dimensional nanostructures: one-pot preparation of nanoparticle chains via directed self-assembly of in situ synthesized discrete Au nanoparticles

The fabrication of well-defined one-dimensional (1D) arrays is becoming a challenge for the development of the next generation of advanced nanodevices. Herein, a simple concept is proposed for the in situ synthesis and self-assembly of gold nanoparticles (AuNPs) into 1D arrays via a one-step process. The results demonstrated the formation of nanoparticle chains (NPC) with high aspect ratio based on discrete Au nanoparticles stabilized by short thiol ligands. A model was proposed to explain the self-assembly based on the investigation of several parameters such as pH, solvent, temperature, and nature of the ligand on the 1D assembly formation. Hydrogen bonding was identified as a key factor to direct the self-assembly of the hybrid organic-inorganic nanomaterials into the well-defined 1D nanostructures. This simple and cost-effective concept could potentially be extended to the fabrication of a variety of hybrid 1D nanostructures possessing unique physical properties leading to a wide range of applications including catalysis, bionanotechnology, nanoelectronics, and photonics.     

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...     

Applications of Non-precious Transition Metal Oxide Nanoparticles in Electrochemistry

Non-precious transition metal oxide nanomaterials offer numerous opportunities for various cost-effective electrochemical applications. This review article features the design and advancement of such nanomaterials with unique features applied for the fabrication of electrochemical devices. Also, it discusses various new syntheses of transition metal oxide nanoparticles (TMO NPs) via multiple chemicophysical and biological procedures. Further, the novel appliances of the TMO NPs with varying sizes and morphologies are appraised. The advantages and challenges of a number of investigations on the TMO NPs towards electrochemical applications are addressed with their standpoint of cost-effectiveness, applicability, and the efficiency of the introduced nanostructures for the industrial applications.     

Silica encapsulation and magnetic properties of FePt nanoparticles

Core-shell nanoparticles have emerged as an important class of functional nanostructures with potential applications in many diverse fields, especially in health sciences. We have used a modified aqueous sol-gel route for the synthesis of size-selective FePt@SiO2 core-shell nanoparticles. In this approach, oleic acid and olyel amine stabilized FePt nanoparticles are first encapsulated through an aminopropoxysilane (APS) monolayer and then subsequent condensation of triethoxysilane (TEOS) on FePt particle surface. These well-defined FePt@SiO2 core-shell nanoparticles with narrow size distribution become colloidal in aqueous media, and can thus be used as carrier fluid for biomolecular complexes. In comparison, the scarce hydrophilic nature of oleic acid monolayers on FePt particle surface yields an edgy partial coating of silica when only TEOS is applied for the surface modification. The synthesized core-shell nanoparticles were characterized by direct techniques of high resolution transmission electron microscopy (HRTEM), EDS and indirectly via UV-vis absorption and FTIR studies. The FePt@SiO2 nanoparticles exhibit essential characteristics of superparamagnetic behavior, as investigated by SQUID magnetometry. The blocking temperatures (T(B)) of FePt and FePt@SiO2 (135 and 80 K) were studied using zero field cooled (ZFC)/field cooled (FC) curves.     

Carbon nanoparticles as chromophores for photon harvesting and photoconversion

Carbon nanomaterials have generated a tremendous amount of attention in the scientific community. While most of the research and development efforts have been on fullerenes, carbon nanotubes, and graphene sheets, carbon nanoparticles (which are often considered as impurities or unwanted complications in the other carbon nanomaterials) have recently emerged as a unique class of highly fluorescent nano-dots. However, little or no attention has been paid to potential uses of carbon nanoparticles as chromophores in photochemical reactions or for photon harvesting and photoconversion in general. In the study reported herein we demonstrate the chromophore-equivalent functions of aqueous-suspended small carbon nanoparticles in harvesting visible photons for the reductive coating of the nanoparticles with silver and gold and, as a result, the preparation of unique carbon-noble-metal core-shell nanostructures.     

Multisegmented one-dimensional nanorods prepared by hard-template synthetic methods

In the science and engineering communities, the nanoscience revolution is intensifying. As many types of nanomaterials are becoming more reliably synthesized, they are being used for novel applications in all branches of nanoscience and nanotechnology. Since it is sometimes desirable for single nanomaterials to perform multiple functions simultaneously, multicomponent nanomaterials, such as core-shell, alloyed, and striped nanoparticles, are being more extensively researched. Nanoscientists hope to design multicomponent nanostructures and exploit their inherent multiple functionalities for use in many novel applications. This review highlights recent advances in the synthesis of multisegmented one-dimensional nanorods and nanowires with metal, semiconductor, polymer, molecular, and even gapped components. It also discusses the applications of these multicomponent nanomaterials in magnetism, self-assembly, electronics, biology, catalysis, and optics. Particular emphasis is placed on the new materials and devices achievable using these multicomponent, rather than single-component, nanowire structures.     

Core-shell nanorods of SnS-C and SnSe-C: synthesis and characterization

The straightforward, efficient, solventless, RAPET (reactions under autogenic pressure at elevated temperature) approach was explored for the fabrication of core-shell nanomaterials. Carbon-encapsulated SnS and SnSe nanorods were synthesized by a one-step thermal decomposition of tetramethyltin in the presence of either S or Se powder in a closed reactor at 700 degrees C for 40 min, under their autogenic pressure in an inert atmosphere. The powder X-ray diffraction measurements provided structural evidence for the formation of pure orthorhombic phases of SnS or SnSe particles. The Raman spectroscopy measurements ensured that the nature of the coated carbon was semigraphitic. The scanning electron micrographs verified the 1D morphology of the formed SnS and SnSe chalcogenides, and their stoichiometry was confirmed by EDAX measurements. The HR-TEM micrographs distinguished between core and shell morphologies. The nitrogen gas adsorption on the surface of core-shell nanostructures was determined by BET surface area analysis. The plausible mechanism for the creation of chalcogenide cores (SnS or SnSe) with a carbon shell was elucidated.     

表面展示肽在无机纳米材料的合成与组装中的应用

本文综述了表面展示肽在无机纳米材料合成与组装中的应用.表面展示肽是利用噬菌体、细胞等表面展示技术筛选出来的一类多肽,可以特异性地识别不同的无机物表面.一方面它们能够诱导不同种类无机纳米材料的合成,有助于我们进一步认识生物矿化的过程和基本原理;同时表面展示肽也可以用于无机纳米材料的组装,构建具有特定功能的纳米结构,从而为纳米器件的构造提供新的途径.     

Hollow and cage-bell structured nanomaterials of noble metals

Mastery of the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the synthesis of metal nanomaterials with hollow interiors or cage-bell structures based on the inside-out diffusion of Ag in core-shell structured nanoparticles. It begins with the synthesis of core-shell Ag-M or core-shell-shell M(A)-Ag-M(B) nanoparticles in an organic solvent. Ag is then extracted from the core or the inner shell by bis(p-sulfonatophenyl)phenylphosphane, which binds strongly with Ag(I)/Ag(0) to allow the complete removal of Ag in 24-48 h, leaving behind an organosol of hollow or cage-bell structured metal nanomaterials. Because of their relatively lower densities, which usually translate to a higher surface area than their solid counterparts, the hollow and cage-bell structured metal nanomaterials are especially relevant to catalysis. For example, cage-bell structured Pt-Ru nanoparticles were found to display outstanding methanol tolerance for the cathode reaction of direct methanol fuel cells (DMFCs) as a result of the differential diffusion of methanol and oxygen in the cage-bell structure.     

Transmetalation reaction between hydrophobic silver nanoparticles and aqueous chloroaurate ions at the air-water interface

The transmetalation reaction between a sacrificial nanoparticle and more noble metal ions in solution has emerged as a novel method for creating unique hollow and bimetallic nanostructures. In this report, we investigate the possibility of carrying out the transmetalation reaction between hydrophobic silver nanoparticles assembled and constrained at the air-water interface and subphase gold ions. We observe that facile reduction of the subphase gold ions by the sacrificial silver nanoparticles occurs resulting in the formation of elongated gold nanostructures that appear to cross-link the sacrificial silver particles. This transmetalation reaction may be modulated by the insertion of an electrostatic barrier in the form of an ionizable lipid monolayer between the silver nanoparticles and the aqueous gold ions that impacts the gold nanoparticle assembly. Transmetalation reactions between nanoparticles constrained into a close-packed structure and appropriate metal ions could lead to a new strategy for metallic cross-linking of nanoparticles and generation of coatings with promising optoelectonic behavior.     

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 and high-yield galvanic displacement approach to Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells and enhanced electrocatalytic performances

In this work, we utilize the galvanic displacement synthesis and make it a general and efficient method for the preparation of Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells, which consist of multilayer nanoparticles. The method is generally applicable to the preparation of Au-Au, Au-Pd, and Au-Pt core-shell nanostructures with typical porous shells. Moreover, the Au-Au isomeric core-shell nanostructure is reported for the first time. The lower oxidation states of Au(I), Pd(II), and Pt(II) are supposed to contribute to the formation of porous core-shell nanostructures instead of yolk-shell nanostructures. The electrocatalytic ethanol oxidation and oxygen reduction reaction (ORR) performance of porous Au-Pd core-shell nanostructures are assessed as a typical example for the investigation of the advantages of the obtained core-shell nanostructures. As expected, the Au-Pd core-shell nanostructure indeed exhibits a significantly reduced overpotential (the peak potential is shifted in the positive direction by 44?mV and 32?mV), a much improved CO tolerance (I(f)/I(b) is 3.6 and 1.63 times higher), and an enhanced catalytic stability in comparison with Pd nanoparticles and Pt/C catalysts. Thus, porous Au-M (M = Au, Pd, and Pt) core-shell nanostructures may provide many opportunities in the fields of organic catalysis, direct alcohol fuel cells, surface-enhanced Raman scattering, and so forth.     

Sensitive biosensing strategy based on functional nanomaterials

The first decade of the 21st century has been labeled as the sensing decade. The functional nanomaterials offer excellent platforms for fabrication of sensitive biosensing devices, including optical and electronic biosensors. A lot of works have fo- cused on the biofunctionalization of different nanomaterials, such as metal nanoparticles, semiconductor nanoparticles and carbon nanostructures, by physical adsorption, electrostatic binding, specific recognition or covalent coupling. These biofunc- tionalized ...     

Effects of organic ligands, electrostatic and magnetic interactions in formation of colloidal and interfacial inorganic nanostructures

This paper discusses effects of organic ligands, electrostatic and magnetic interactions involved in morphological control of chemically synthesized inorganic nanostructures including colloid and planar systems. The special attention was concentrated on noble metal (gold and palladium) nanoparticles and nanostructures formed at the gas-liquid interface. The analysis of experimental data showed that electrostatic and ligand-related interactions influence very strongly on the metal nanostructure morphology. The hydrophobicity of ligand, charge and binding affinity to inorganic phase are important factors influencing the morphology of inorganic nanostructures formed in a layer at the gas/liquid interface by the interfacial synthesis method. The important point of this method is the quasi two-dimensional character of reaction area and possibilities to realize ultimately thin and anisotropic dynamic monomolecular reaction system with two-dimensional diffusion and interactions of precursors, intermediates and ligands resulting in planar growth and organization of inorganic nanoparticles and nanostructures in the plain of Langmuir monolayer. The morphology of resulting inorganic nanostructures can be controlled efficiently by variations of growth conditions via changes in state and composition of interfacial planar reaction media with the same precursor, and by variations of composition of adjacent bulk phases. The extreme anisotropy and heterogeneity of two-dimensional interfacial reaction system allows creating conditions when growing inorganic particles floating on the aqueous phase surface interact selectively with hydrophobic water-insoluble ligands in interfacial monolayer or with hydrophilic bulk-phase ligands, or at the same time with ligands of different nature present in monolayer and in aqueous phase. The spatial anisotropy of interfacial reaction system and non-homogeneity of ligand binding to inorganic phase gives possibilities for growth of integrated anisotropic nanostructures with unique morphologies, in particularly those characterized by very high surface/volume ratio, high effective perimeter, and labyrinth-like structure. In a case of magnetic nanoparticles dispersed in colloids specific magnetic dipolar interactions can result in formation of chains, rings and more complex nanoparticulate structures or separated highly anisotropic nanoparticles. Theoretical considerations indicate to the importance of system dimensionality in relation to the energy balance which determines specific features of structure organization in planar charged metallic and magnetic nanostructures. For example, a requirement of Coulomb energy minimum, the possibility of free electron redistribution and strengthened attractive interactions between particles in metallic nanostructures can explain formation of very branchy systems with extremely high "effective perimeter". The obtained experimental and literature data show that system dimensionality, organic ligand nature along with electrostatic and magnetic interactions are most important factors of morphological control of chemically synthesized inorganic nanomaterials. The understanding and appropriate exploitation of these factors can be useful for further developments of efficient nanofabrication techniques based on colloidal and interfacial synthetic methods.     

Interfacially formed organized planar inorganic, polymeric and composite nanostructures

This paper discusses synthetic strategies for fabrication of new organized planar inorganic, polymeric, composite and bio-inorganic nanostructures by methods based on chemical reactions and physical interactions at the gas-liquid interface, Langmuir monolayer technique, interfacial ligand exchange and substitution reactions, self-assembling and self-organization processes, DNA templating and scaffolding. Stable reproducible planar assemblies of ligand-stabilized molecular nanoclusters containing definite number of atoms have been formed on solid substrate surfaces via preparation and deposition of mixed Langmuir monolayers composed by nanocluster and surfactant molecules. A novel approach to synthesis of inorganic nanoparticles and to formation of self-organized planar inorganic nanostructures has been introduced. In that approach, nanoparticles and nanostructures are fabricated via decomposition of insoluble metal-organic precursor compounds in a layer at the gas-liquid interface. The ultimately thin and anisotropic dynamic monomolecular reaction system was realized in that approach with quasi-two-dimensional growth and organization of nanoparticles and nanostructures in the plain of Langmuir monolayer. Photochemical and redox reactions were used to initiate processes of interfacial nucleation and growth of inorganic phase. It has been demonstrated that morphology of resulting inorganic nanostructures can be controlled efficiently by variations of growth conditions via changes in state and composition of interfacial planar reaction media, and by variations of composition of adjacent bulk phases. Planar arrays and chains of iron oxide and ultrasmall noble metal (Au and Pd) nanoparticles, nanowires and new organized planar disk, ring, net-like, labyrinth and very high-surface area nanostructures were obtained by methods based on that approach. Highly organized monomolecular polymeric films on solid substrates were obtained via deposition of Langmuir monolayer formed by water-insoluble amphiphilic polycation molecules. Corresponding nanoscale-ordered planar polymeric nanocomposite films with incorporated ligand-stabilized molecular metallic nanoclusters and interfacially grown nanoparticles were fabricated successfully. Novel planar DNA complexes with amphiphilic polycation monolayer were formed at the gas-aqueous phase interface and then deposited on solid substrates. Toroidal and new net-like conformations were discovered in those complexes. Nanoscale supramolecular organization of the complexes was dependent on cationic amphiphile monolayer state during the DNA binding. These monolayer and multilayer DNA/amphiphilic polycation complex Langmuir-Blodgett films were used as templates and nanoreactors for generation of inorganic nanostructures via metal cation binding with DNA and following inorganic phase growth reactions. As a result, ultrathin polymeric nanocomposite films with integrated DNA building blocks and organized inorganic semiconductor (CdS) and iron oxide quasi-linear nanostructures were formed. It has been demonstrated that interaction of deposited planar DNA/amphiphilic polycation complexes with bulk phase colloid inorganic cationic ligands (CdSe nano-rods) can result in formation of new highly organized hybrid bio-inorganic nanostructures via interfacial ligand exchange and self-organization processes. The methods developed can be useful for investigation of fundamental mechanisms of nanoscale structural organization and transformation processes in various inorganic and molecular systems including bio-molecular and bio-inorganic nanostructures. Also, those methods are relatively simple, environmentally safe and thus could prove to be efficient practical instruments of molecular nanotechnology with potential of design and cost-effective fabrication of new controlled-morphology organized planar inorganic and composite nanostructured materials. Possible applications of obtained nanostructures and future developments are also discussed.     

Construction of various nanostructures on carbon nanotube films

Construction of nanostructures on surfaces has appealed intensive attention due to its significant applications in diverse fields. Especially, engineering surface properties via surficial nanostructures is actually the creation of functional interface-based materials and slated to be the key aspect for the future of materials science. Although many efforts have been made, there are only a few reports about the construction of nanostructures on carbon nanotube film surfaces. The big challenge for constructing on carbon films is that these carbon assemblies are easy to be dispersed by immersion in a chemical solution. Here, in this paper, we have shown for the first time the fabrication of different kinds of nanostructures, i.e. nanoneedles, nanoparticles, nanospirals, on carbon nanotube films by using facile and cheap electrodeposition method and precise physical deposition method. We pretreat the films by an electrical method to strengthen the films to avoid dispersion during the electrodeposition process. These composite films are still very flexible after coating with nanostructures. Compared with those precise physical deposition methods, the facile electrodeposition method is more suitable for constructing nanostructures on carbon nanotube films, due to the low requirement for planeness of films. It is interesting to find that these nanostructures can endow superhydrophobicity or higher conductivity for these flexible composite films, which greatly broaden the potential applications for carbon nanotube films in the fields of battery, moisture self-cleaning, electrostatic energy harvesting, and enhancing condensation heat transfer for more efficiency of energy utilization, environmental, and thermal management.     

Synthesis of novel hierarchical porous polymers with a nanowire-interconnected network structure from core-shell polymer nanoobjects

Design and fabrication of the micro/nanostructures of the network units is a critical issue for porous nanonetwork structured materials. Significant progress has been attained in construction of the network units with zero-dimensional spherical shapes. However, owing to the limitations of synthetic methods, construction of porous building blocks in one dimension featuring high aspect ratios for porous nanonetwork structured polymer (PNSP) remains largely unexplored. Here we present the successful design and preparation of PNSP with a novel type of one-dimensional network unit, i.e., microporous heterogeneous nanowire. Well-defined core-shell polymer nanoobjects prepared from a gelable block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene are employed as building blocks, and facilely transformed into PNSP via hypercrosslinking of polystyrene shell. The as-prepared PNSP exhibits unique three-dimensional hierarchical nanonetwork morphologies with large surface area. These findings could provide a new avenue for fabrication of unique well-defined PNSP, and thus generate valuable breakthroughs in many applications.     

基于新型纳米传感材料的DNA生物传感器的应用

DNA是构建纳米技术和生物传感技术新设备的良好构建体.DNA生物传感器由于具有灵敏度高、选择性好等特点,近年来获得了飞速发展.研究发现,金属纳米粒子(MNPs)、碳基纳米材料等一系列纳米材料在传感器设计中提高了电化学DNA传感器的传感性能.本文侧重介绍了场效应晶体管、石墨烯、碳纳米管等新型纳米传感材料,以及基于这些材料...