Effect of a side reaction involving structural changes of the surfactants on the shape control of cobalt nanoparticles.

Cobalt nanoparticles with different sizes and morphologies including spheres, rods, disks, and hexagonal prisms have been synthesized through the decomposition of the olefinic precursor [Co(η(3)-C8H13)(η(4)-C8H12)] under dihydrogen, in the presence of hexadecylamine and different rhodamine derivatives, or aromatic carboxylic acids. UV-vis spectroscopy, X-ray diffraction, low and high resolution transmission electron microscopy, and electron tomography have been used to characterize the nanomaterials. Especially, the Co nanodisks formed present characteristics that make them ideal nanocrystals for applications such as magnetic data storage. Focusing on their growth process, we have evidenced that a reaction between hexadecylamine and rhodamine B occurs during the formation of these Co nanodisks. This reaction limits the amount of free acid and amine, usually at the origin of the formation of single crystal Co rods and wires, in the growth medium of the nanocrystals. As a consequence, a growth mechanism based on the structure of the preformed seeds rather than oriented attachment or template assisted growth is postulated to explain the formation of the nanodisks.

On the use of amine-borane complexes to synthesize iron nanoparticles.

The effectiveness of amine-borane as reducing agent for the synthesis of iron nanoparticles has been investigated. Large (2-4 nm) Fe nanoparticles were obtained from [Fe{N(SiMe3)2}2]. Inclusion of boron in the nanoparticles is clearly evidenced by extended X-ray absorption fine structure spectroscopy and Mössbauer spectrometry. Furthermore, the reactivity of amine-borane and amino-borane complexes in the presence of pure Fe nanoparticles has been investigated. Dihydrogen evolution was observed in both cases, which suggests the potential of Fe nanoparticles to promote the release of dihydrogen from amine-borane and amino-borane moieties.

Organometallic control at the nanoscale: a new, one-pot method to decorate a magnetic nanoparticle surface with noble metal atoms.

A novel cascade of reactions is designed to control in situ the deposition of noble metal islands (e.g. Rh) on top of nanoparticles of a 3d metal (e.g. Fe, Co).

NiFe nanoparticles: a soft magnetic material?

Polytetrahedral NiFe nanoparticles with diameters of (2.8+/-0.3) nm have been obtained by hydrogenation of Ni[(COD)(2)] (COD=1,5-cyclooctadiene) and Fe[{N(SiMe(3))(2)}(2)] at 150 degrees C using stearic acid and hexadecylamine as stabilizing ligands. The nanoparticles are superparamagnetic at room temperature and display a blocking temperature of 17.6 K. Their anisotropy (2.7x10(5)J m(-3)) is determined to be more than two orders of magnitude higher than that of the bulk NiFe alloy (10(3)J m(-3)) and is close to that determined for Fe nanoparticles of the same size. Still, they display a magnetization of (1.69+/-0.05) mu(B) per metallic atom, identical to that of the bulk NiFe alloy. Combining the results from X-ray absorption and Mössbauer studies, we evidence a progressive enrichment in iron atoms from the core to the surface of the nanoparticles. These results are discussed in relation to both size and chemical effects. They show the main role played by the enriched Fe surface on the magnetic properties and address the feasibility of soft magnetic materials at the nanoscale.