Ethylene glycol-assisted coating of titania on nanoparticles.

Coating titania shells onto sub-micron sized particles has been widely studied recently, with success mainly limited to objects with sizes above 50 nm. Direct coating on particles below this size has been difficult to attain especially with good control over properties such as thickness and crystallinity. Here we demonstrate that titanium-glycolate formed by reacting titanium alkoxide and ethylene glycol is an excellent precursor for coating titania on aqueous nanoparticles. The new coating method is particularly useful for its ability to coat materials lacking strong polymers or ligands which are frequently needed to facilitate typical titania coatings. We demonstrate the effectiveness of the process of coating titania on metal nanoparticles ranging from citrate-stabilized gold and silver spheres to gold nanorods and silver nanoplates, and larger particles such as SiO2 microspheres and polymer spheres. Further the thickness of these coatings can be tuned from a few nanometers to ∼40 nm through sequential coatings. These coatings can subsequently be crystallized into TiO2 through refluxing in water or by calcination to obtain crystalline shells. This procedure can be very useful for the production of TiO2 coatings with tunable thickness and crystallinity as well as for further study on the effect of TiO2 coatings on nanoparticles.

Magnetically tunable colloidal micromirrors.

Herein we demonstrate a method for decorating highly reflective 2D gold microplates with magnetic nanoparticles to produce an optical colloid that can be actuated using an applied magnetic field. These magnetic micromirrors can be rapidly rotated and exhibit a strong contrast in reflectance between the "on" and "off" states.

Templated synthesis of nanostructured materials.

Templating is one of the most important techniques for the controlled synthesis of nanostructured materials. This powerful tool uses a pre-existing guide with desired nanoscale features to direct the formation of nanomaterials into forms that are otherwise difficult to obtain. As a result, templated synthesis is capable of producing nanostructures with unique structures, morphologies and properties. In this review, we summarize the general principles of templated synthesis and cover recent developments in this area. As a wide variety of synthesis techniques are utilized to produce nanomaterials using template-based methods, the discussion is organized around the various types of common templates. We examine the use of both physical and chemical hard colloidal templates, soft templates, and other non-colloidal templates, followed by our perspective on the state of the field and potential future directions.

Monitoring the shape evolution of silver nanoplates: a marker study.

Out of the frame: A marker study using gold frames was designed to reveal that silver nanoplates undergo a shape transition during their seeded growth from triangular to circular to hexagonal plates before ultimately returning to triangular structures with an orientation 180° relative to that of the original triangular seeds (see picture, the original gold triangular frame is visible at the center of the silver nanoplate).

A systematic study of the synthesis of silver nanoplates: is citrate a "magic" reagent?

In this work we have carried out systematic studies and identified the critical role of hydrogen peroxide instead of the generally believed citrate in the well-known chemical reduction route to silver nanoplates. This improved understanding allows us to develop consistently reproducible processes for the synthesis of nanoplates with high efficiency and yields. By harnessing the oxidative power of H(2)O(2), various silver sources including silver salts and metallic silver can be directly converted to nanoplates with the assistance of an appropriate capping ligand, thus significantly enhancing the reproducibility of the synthesis. Contrary to the previous conclusion that citrate is the key component, we have determined that the group of ligands with selective adhesion to Ag (111) facets can be expanded to many di- and tricarboxylate compounds whose two nearest carboxylate groups are separated by two or three carbon atoms. We have also found that the widely used secondary ligand polyvinylpyrrolidone can be replaced by many hydroxyl group-containing compounds or even removed entirely while still producing nanoplates of excellent uniformity and stability. In addition to the general understanding of NaBH(4) as a reducing agent, it has also been found to act as a capping agent to stabilize the silver nanoparticles, prolong the initiation time required for nanoplate nucleation, and contribute to the control of the thickness as well as the aspect ratio of silver nanoplates. The improved insight into the specific roles of the reaction components and significantly enhanced reproducibility are expected to help elucidate the formation mechanism of this interesting nanostructure.

Role of salt in the spontaneous assembly of charged gold nanoparticles in ethanol.

This paper investigates the role of salt in the spontaneous linear assembly of charged gold nanoparticles in ethanol and attempts to clear up a misunderstanding on the role of ethanol in this process. Many prior reports have noted that the addition of ethanol to an aqueous solution of gold nanoparticles causes their aggregation into linear assemblies. It was therefore believed that ethanol plays the determining role during the assembly process. In this work, we carried out systematic studies which indicate that residual salt in conjunction with ethanol, instead of ethanol itself, induces the assembly of gold nanoparticles in ethanol. In the absence of salt, gold nanoparticles can be well dispersed in an ethanol solution. Furthermore, we find that the chainlike assemblies can disassemble upon dilution of the salt or the evaporation of ethanol if the gold nanoparticles are protected with a sufficiently strong ligand.

Epitaxial growth of shape-controlled Bi2Te3-Te heterogeneous nanostructures.

A one-pot solution process has been devised to synthesize colloidal Bi2Te3-Te heterogeneous nanostructures (HNs) that comprise Bi2Te3 nanoplates and Te nanorods. By controlling the reaction kinetics, the reaction of TeO3(2-) and Bi(3+) in the presence of hydrazine first produces uniform Te nanorods and then grows Bi2Te3 nanoplates on the tips and surfaces of these Te nanorods, forming various shapes including "nails", "barbells", "syringes", and "accordions". The specific topological arrangement realized arises from the peculiar anisotropic reactivity of the first formed Te nanorods, whose tips are subsequently exploited to seed the heterogeneous nucleation of Bi2Te3 as enabled by the similar crystal structure and the small lattice mismatch between Te and Bi2Te3. Three important processes, heterogeneous nucleation of Bi2Te3 on the tips and/or surface of Te nanorods, homogeneous nucleation of Bi2Te3, and the direct reaction of a Bi precursor and Te nanorods to form hollow structures via the Kirkendall Effect, occur under various conditions. The manipulation of these processes provides a robust means for the fine shape control of Bi2Te3-Te HNs. It is envisioned that the tailored synthesis of Bi2Te3-Te HNs may promise unique opportunities for producing thermoelectric materials with greatly enhanced performance.

Seeded growth of uniform Ag nanoplates with high aspect ratio and widely tunable surface plasmon bands.

Silver nanoplates with an extremely high aspect ratio (up to over 400) and a widely tunable surface plasmon resonance (SPR) band have been successfully synthesized by combining the concepts of selective ligand adhesion and seeded growth. Citrate ligands are used as the sole surfactant to effectively block overgrowth on the basal {111} facets and only allow growth in the lateral direction. By slowing down the reaction rate using Ag-citrate complex as precursor, the thin nature of Ag nanoplates is maintained with the edge length grown up to 4 µm, which ensures the high aspect ratio and the widely tunable SPR band. We also observe a size distribution focusing effect that helps to produce uniform nanoplates as well as narrow SPR bands over a wide range, which is important in many practical applications.

Control over the permeation of silica nanoshells by surface-protected etching with water.

We demonstrate a water-based etching strategy for converting solid silica shells into porous ones with controllable permeability. It overcomes the challenges of the alkaline-based surface-protected etching process that we previously developed for the production of porous and hollow silica nanostructures. Mild etching around the boiling point of water partially breaks the imperfectly condensed silica network and forms soluble monosilicic acid, eventually producing mesoscale pores in the silica structures. With the surface protection from poly(vinyl pyrrolidone) (PVP), it is possible to maintain the overall shape of the silica structures while at the same time to create porosity inside. By using bulky PVP molecules which only protect the near-surface region, we are able to completely remove the interior silica and produce hollow particles. Because the etching is mild and controllable, this process is particularly useful for treating small silica particles or core-shell particles with very thin silica shells for which the alkaline-based etching method has been difficult to control. We demonstrated the precise control of the permeation of the chemical species through the porous silica shells by using a model reaction which involves the etching of Ag encapsulated inside Ag@SiO(2) by a halocarbon. It is expected that the water-based surface-protected etching method can be conveniently extended to the production of various porous silica shells containing functional materials whose diffusion to outside and/or reaction with outside species can be easily controlled.

Magnetochromatic microspheres: rotating photonic crystals.

Magnetochromatic microspheres have been fabricated through instant assembly of superparamagnetic (SPM) colloidal particles inside emulsion droplets of UV curable resin followed by an immediate UV curing process to polymerize the droplets and fix the ordered structures. When dispersed in the liquid droplets, superparamagnetic Fe(3)O(4)@SiO(2) core/shell particles self-organize under the balanced interaction of repulsive and attractive forces to form one-dimensional chains, each of which contains periodically arranged particles diffracting visible light and displaying field-tunable colors. UV initiated polymerization of the oligomers of the resin fixes the periodic structures inside the droplet microspheres and retains the diffraction property. Because the superparamagnetic chains tend to align themselves along the field direction, it is very convenient to control the orientation of such photonic microspheres and, accordingly, their diffractive colors, by changing the orientation of the crystal lattice relative to the incident light using magnetic fields. The excellent stability together with the capability of fast on/off switching of the diffraction by magnetic fields makes the system suitable for applications such as color display, rewritable signage, and sensors. As a simple demonstration, we have fabricated a display unit that has on/off bistable states by embedding the magnetochromatic microspheres in a matrix that can thermally switch between solid and liquid phases.

Reconstruction of silver nanoplates by UV irradiation: tailored optical properties and enhanced stability.

The size and shape of it: The optical properties of Ag nanoplates can be precisely tuned in a wide range through a UV-light-induced reconstruction process in which the morphology of the nanoparticles is changed from thin triangular plates to thick round plates (see picture). This unconventional "backward tuning" strategy is a practical route to stable silver nanoplates that display a wide range of plasmon wavelengths.

Assembly of magnetically tunable photonic crystals in nonpolar solvents.

We have successfully assembled superparamagnetic colloids into ordered structures with magnetically tunable photonic properties in nonpolar solvents by establishing long-range electrostatic repulsive forces using charge control agents. Reverse micelles resulted from the introduction of charge control agents such as AOT molecules can enhance the charge separation on the surfaces of n-octadecyltrimethoxysilane modified Fe(3)O(4)@SiO(2) particles. The significantly improved long-range electrostatic repulsion can counterbalance the magnetically induced attraction and therefore allow ordering of superparamagnetic colloids in nonpolar solvents. This system possesses a fast and fully reversible optical response to the external magnetic fields, long-term stability in performance, and good diffraction intensity.