Miguel A. Correa-Duarte

Stabilization of CdS semiconductor nanoparticles against photodegradation by a silica coating procedure

Abstract Nanometre-sized CdS semiconductor particles were synthesized in the presence of sodium citrate, and subsequently surrounded by a homogeneous silica shell. The coating procedure makes use of 3-(mercaptopropyl) trimethoxy silane (MPS) as a surface primer to deposit a thin silica shell in water. The dispersion is then transferred into ethanol, where thicker shells can be grown. The citrate-stabilized particles are slowly degraded through photochemical oxidation in the presence of dissolved oxygen. This destabilizing process is suppressed when a homogeneous, microporous silica shell is built up around the particles, through a limited access of O 2 molecules to the CdS surface.

Layer-By-Layer Assembly of Core-Shell Magnetite Nanoparticles: Effect of Silica Coating on Interparticle Interactions and Magnetic Properties

Monodisperse PS spheres were synthesized and packed into colloidal crystals by centrifugation as described previously [6]. Sphere diameters in various batches ranged from 420 ‐ 50 nm to 660 ‐ 30 nm. To prepare macroporous nickel oxide, nickel(II) acetate (2 g) was dissolved in either acetic acid (5 mL) or a mixture of H2O (5 mL)and ethanol (5 mL) at 60 C. After cooling to room temperature, any undissolved solid was removed by filtration. Centimeter-scale, close-packed, colloidal polystyrene crystals (1 g) were soaked in this solution for 3‐5 min. Excess solution was removed from the impregnated colloidal crystals by vacuum filtration. The samples were dried at 60 C for 2 h. The dried composites were soaked in 10 mL of a saturated solution of oxalic acid in ethanol (ca. 25‐30 g in 100 mL) for 3‐5 min. After additional vacuum filtration and drying, the PS spheres were removed by calcination in flowing air at 360‐575 C for 7‐10 h (heating rate: 1 C/ min). Macroporous Ni was prepared by heating macroporous NiO in flowing H2 at 300 C for 2‐5 h (heating rate: 1 C/min) or by heating the nickel oxalate/PS composite in flowing nitrogen at 450‐500 C for 10 h. Preparation of partially reduced samples containing both NiO and Ni was possible by decreasing the reduction time or temperature, or by carrying out a fast calcination, for example at 360 C for 1 h in fast flowing air. Electrochemical tests were performed in two electrode cells using 1 M aqueous KOH as the electrolyte and nickel pellets as both electrodes. Pellets were made by pressing a mixture of 10 wt.-% poly(vinylidene fluoride) binder with 90 wt.-% nickel to 1500 psi for 30 s. An SEM of the material indicated that a porous structure was still maintained. No carbon powder was needed to enhance the pellet conductivity. Impedance analysis was performed using a Solartron 1260 Impedance/Gain-Phase Analyzer along with a Solartron 1287 Electrochemical Interface. Other product characterization was carried out as described previously [6].

Design of SERS-Encoded, Submicron, Hollow Particles Through Confined Growth of Encapsulated Metal Nanoparticles

The synthetic architectures of complex inorganic nanostructures, including multifunctional hollow capsules, are expected to play key roles in many different applications, such as drug delivery, photonic crystals, nanoreactors, and sensing. Implementation of novel strategies for the fabrication of such materials is needed because of the infancy of this knowledge, which still limits progress in certain areas. Herein we report a straightforward synthetic approach for the development of multifunctional submicron reactors comprising catalytic gold nanoparticles (2-3 nm) confined inside hollow silica capsules. Additionally, the confined growth of encapsulated metal nanoparticles was carried out to evidence the usefulness and functionality of these reactors in catalytic applications and as an approach for the development of novel complex nanostructures. Their potential and multifunctionality have been pointed out by fabrication of SERS-encoded submicrometer particles with shape and size uniformity for use in antigen biosensing; this was accomplished via codification of gold nanoparticle islands grown onto their inner surfaces.

Carbon nanotubes as templates for one-dimensional nanoparticle assemblies

We present a simple, generally applicable procedure for the assembly of nanoparticles on carbon nanotubes in aqueous solution. The method makes use of polyelectrolytes for wrapping carbon nanotubes and providing them with adsorption sites for electrostatically driven nanoparticle deposition. The method is exemplified by the assembly of gold nanoparticles which results in single, optically labelled carbon nanotubes.

Hollow‐Shelled Nanoreactors Endowed with High Catalytic Activity

Hollow-shelled nanoreactors have emerged as efficient structures to maximize the potential of nanoparticles in the field of catalysis. In this Concept article, we underline the importance of both the morphology of the active nanoparticles as well as the composition and porosity of the shell for the catalytic performance of the overall nanocomposite. Different configurations are discussed, with a focus on preparative methods and applications in organic synthesis. Perspectives on future designs that may offer new opportunities to improve the selectivity of the catalyzed transformations and add additional features are also addressed, in order to illustrate the potential of these unique nanostructures.

Loading of Exponentially Grown LBL Films with Silver Nanoparticles and Their Application to Generalized SERS Detection

Feature film: Thin films made by exponential layer-by-layer growth display high diffusivity and can be readily infiltrated with inorganic nanoparticles. They can sequestrate molecular systems from solution as a function of the composition of their layers, while providing intense surface-enhanced Raman scattering (SERS) signals (see picture).

Highly Active Nanoreactors: Nanomaterial Encapsulation Based on Confined Catalysis**

It happens inside: highly active nanoreactors are prepared by encapsulating dendritic Pt nanoparticles (NPs) grown on a polystyrene template inside hollow porous silica capsules. The catalytic activity of these Pt NPs is preserved after encapsulation and template removal. Different metals, such as Ni, can thus be reduced inside the capsules, thereby leading to the formation of composites with tunable magnetic properties.

Highly transparent and conductive films of densely aligned ultrathin Au nanowire monolayers.

The combination of low electrical resistance and high optical transparency in a single material is very uncommon. Developing these systems is a scientific challenge and a technological need, to replace ITO in flexible electronic components and other highly demanding applications. Here we report a facile method to prepare single layers of densely aligned ultrathin Au-nanowires, homogeneous over cm(2) areas. The as-deposited films show an electrical/optical performance competitive with ITO and graphene-based electrodes. Moreover, the Au-films show a good stability under ambient conditions, and the large aspect ratio of the ultrathin nanowires makes them perfect for deposition in flexible substrates.

Synthesis and Stabilization of Subnanometric Gold Oxide Nanoparticles on Multiwalled Carbon Nanotubes and Their Catalytic Activity

Small gold nanoclusters in a very narrow size distribution (1.1 ± 0.5 nm) have been stabilized onto multiwalled carbon nanotubes (MWCNT). Theoretical studies supported by XPS and (16)O(2)/(18)O(2) isotopic exchange experiments have shown that, on small gold nanoparticles (0.9-1.5 nm), dissociation of molecular O(2) and formation of a surface oxide-like layer is energetically favorable and occurs at room temperature, while O(2) recombination and desorption involves a larger activation barrier. CO titration experiments and theoretical studies demonstrate that the reactivity of the oxidized particles toward CO does not only depend on particle size but also on oxygen coverage. The oxidation-reduction process described is reversible, and the oxidized nanoparticles are active in the epoxidation of styrene with air.

Macroscale Plasmonic Substrates for Highly Sensitive Surface-Enhanced Raman Scattering

The fabrication of macroscale optical materials from plasmonic nanoscale building blocks is the focus of much current multidisciplinary research. In these macromaterials, the nanoscale properties are preserved, and new (metamaterial) properties are generated as a direct result of the interaction of their ordered constituents.1 These macroscale plasmonic assemblies have found application in a myriad of fields, including nanophotonics, nonlinear optics, and optical sensing.2 Owing to their specific requirements in terms of size and shape, their fabrication is not trivial and was until recently restricted to the use of lithographic techniques, especially those based on electron- or ion-beam patterning.3 However, these techniques are not only expensive, time-consuming, and demanding but are also restricted to small simple and solid geometries, which are good for proof of concepts but less suitable for real-life applications. Approaches based on colloidal chemistry are gaining relevance as an alternative. During the past few years, several examples of the fabrication of organized particles have been reported, including the preparation of complex colloidal particles4 and the use of preformed colloids to create large crystalline organized entities known as supercrystals.5 The latter approach provides optical platforms with unprecedented plasmonic properties that can be exploited for the design of cheap ultrasensitive and ultrafast sensors with surface-enhanced Raman scattering (SERS)6 spectroscopy as the transducer.