Nanocrystallinity and direct cross-linkage as key-factors for the assembly of gold nanoparticle-superlattices.

We report here how the crystallinity of AuNPs and the choice of binding sites of molecular cross-linkers control their aggregation. The combination of different binding moieties (N-oxides, ArF-I) and the reactivity of the particles' facets allow control over the organization and crystallinity of the AuNP assemblies.

Micro- and nano-spheres of low melting point metals and alloys, formed by ultrasonic cavitation.

Metals and alloys of low melting points (<430 °C) can be melted in hot silicone oil to form two immiscible liquids. Irradiation of the system with ultrasonic energy induces acoustic cavitation in the oil, which disperses the molten metals into microspheres that solidify rapidly upon cooling. This method has been applied to seven pure metals (Ga, In, Sn, Bi, Pb, Zn, Hg) and two eutectic alloys of gold (Au-Ge and Au-Si). The morphology and composition of the resulting microspheres were examined by SEM and EDS. Eutectic Au-Si formed also crystalline Au nanoparticles, which were separated and studied by HRTEM.

Nanocompression of individual multilayered polyhedral nanoparticles.

Inorganic layered materials can form hollow multilayered polyhedral nanoparticles. The size of these multi-wall quasi-spherical structures varies from 4 to 300 nm. These materials exhibit excellent tribological and wear-resisting properties. Measuring and evaluating the stiffness of individual nanoparticle is a non-trivial problem. The current paper presents an in situ technique for stiffness measurements of individual WS(2) nanoparticles which are 80 nm or larger using a high resolution scanning electron microscope (HRSEM). Conducting the experiments in the HRSEM allows elucidation of the compression failure strength and the elastic behavior of such nanoparticles under uniaxial compression.

Fullerene-like WS(2) nanoparticles and nanotubes by the vapor-phase synthesis of WCl(n) and H(2)S.

Inorganic fullerene-like (IF) nanoparticles and nanotubes of WS(2) were synthesized by a gas phase reaction starting from WCl(n) (n = 4, 5, 6) and H(2)S. The effect of the various metal chloride precursors on the formation of the products was investigated during the course of the study. Various parameters have been studied to understand the growth and formation of the IF-WS(2) nanoparticles and nanotubes. The parameters that have been studied include flow rates of the various carrier gases, heating of the precursor metal chlorides and the temperature at which the reactions were carried out. The best set of conditions wherein maximum yields of the high quality pure-phase IF-WS(2) nanoparticles and nanotubes are obtained have been identified. A detailed growth mechanism has been outlined to understand the course of formation of the various products of WS(2).

Structure and stability of molybdenum sulfide fullerenes.

MoS2 nanooctahedra are believed to be the smallest stable closed-cage structures of MoS2, i.e., the genuine inorganic fullerenes. Here a combination of experiments and density functional tight binding calculations with molecular dynamics annealing are used to elucidate the structures and electronic properties of octahedral MoS2 fullerenes. Through the use of these calculations MoS2 octahedra were found to be stable beyond nMo > 100 but with the loss of 12 sulfur atoms in the six corners. In contrast to bulk and nanotubular MoS2, which are semiconductors, the Fermi level of the nanooctahedra is situated within the band, thus making them metallic-like. A model is used for extending the calculations to much larger sizes. These model calculations show that, in agreement with experiment, the multiwall nanooctahedra are stable over a limited size range of 104-105 atoms, whereupon they are converted into multiwall MoS2 nanoparticles with a quasi-spherical shape. On the experimental side, targets of MoS2 and MoSe2 were laser-ablated and analyzed mostly through transmission electron microscopy. This analysis shows that, in qualitative agreement with the theoretical analysis, multilayer nanooctahedra of MoS2 with 1000-25 000 atoms (Mo + S) are stable. Furthermore, this and previous work show that beyond approximately 105 atoms fullerene-like structures with quasi-spherical forms and 30-100 layers become stable. Laser-ablated WS2 samples yielded much less faceted and sometimes spherically symmetric nanocages.

Shake and break--shaking-induced changes of size quantization in aggregated quantum dots.

We show how simple mechanical agitation of precipitated CdSe quantum dot aggregates causes partially reversible color changes (clearly visible to the eye) in the absorption spectrum of the CdSe (about 4 nm size). The color changes, which are due to changes in size quantization, are not accompanied by change in quantum dot size. This phenomenon is explained by partial deaggregation of the precipitates, leading to reduced charge overlap between neighboring dots. Shaking was shown to result in a looser aggregate structure. It is suggested that CdSO3 particles (an initial product of the CdSe formation reaction) act as weak bridges between CdSe quantum dots, mediating the interparticle interactions and allowing the deaggregation to occur on shaking.

A simple hydrothermal method for the growth of Bi2Se3 nanorods.

Bi2Se3 nanorods have been synthesized through a simple hydrothermal reduction approach. The nanorods formed were ≈10 nm in diameter and 100-200 nm in length. XRD characterization suggested that the product consisted of the hexagonal phase of pure Bi2Se3. EDX and XPS studies further confirmed the composition and purity of the product. A possible mechanism for the reaction is proposed, where Bi2Se3 microsheets are presumed to be the intermediate for the formation of the nanorods. The effect of solvent on the morphology of the final product is discussed, where, in the presence of aprotic solvent DMF, nanoparticle formation is observed. A bandgap of 2.25 eV is observed from the UV-visible absorption spectra.

Magnetization of small lead particles.

The magnetization of an ensemble of isolated lead grains of sizes ranging from 4 to 1000 nm is measured. A sharp disappearance of the Meissner effect with a lowering of the grain size is observed for the smaller grains. This is a direct observation by magnetization measurement of the occurrence of a critical particle size for superconductivity, which is consistent with Anderson's criterion.

Impact of molecular order in langmuir-blodgett films on catalysis

Catalytically active Langmuir-Blodgett films of a rhodium complex were prepared and characterized to determine the possible effect of the molecular order of metal complexes on catalytic activity. The hydrogenation of carbon-oxygen double bonds was used as a model reaction. The complex in solution exhibited low catalytic activity, whereas it was highly active in the film. The catalytic activity was found to be highly dependent on the orientation of the complex within the film. The reactions were also highly selective with regard to the substrate. These observations and the observed rate dependence on temperature strongly implicate the molecular order of a metal complex as an important dimension in catalysis.

Ice nucleation by alcohols arranged in monolayers at the surface of water drops.

Monolayers of aliphatic long-chain alcohols induced nucleation of ice at temperatures approaching 0 degrees C, in contrast with water-soluble alcohols, which are effective antifreeze agents. The corresponding fatty acids, or alcohols with bulky hydrophobic groups, induce freezing at temperatures as much as 12 degrees C lower. The freezing point induced by the amphiphilic alcohols was sensitive not only to surface area per molecule but, for the aliphatic series (C(n)H(2n + 1)OH), to chain length and parity. The freezing point for chains with n odd reached an asymptotic temperature of 0 degrees C for an upper value of n = 31; for n even the freezing point reached a plateau of -8 degrees C for n in the upper range of 22 to 30. The higher freezing point induced by the aliphatic alcohols is due to formation of ordered clusters in the uncompressed state as detected by grazing incidence synchrotron x-ray diffraction measurements. The diffraction data indicate a close lattice match with the ab layer of hexagonal ice.