Catherine Amiens

Novel, Spongelike Ruthenium Particles of Controllable Size Stabilized Only by Organic Solvents

Soluble ruthenium nanoparticles of uniform size (see picture) with a porous spongelike structure were obtained by the reaction of [Ru(C(8)H(10))(C(8)H(12))] with H(2) in methanol or THF/methanol. The particle size can be controlled in the range 15-100 nm by varying the MeOH/THF ratio. The particles catalyze benzene hydrogenation without modification of their size or structure. Their formation is proposed to occur in the droplets of a nanosized emulsion, which act as nanoreactors.

Chemisorption on nickel nanoparticles of various shapes: Influence on magnetism

Nanoparticles of nickel have been obtained in solution through reaction of an organometallic precursor, Ni(COD)2 (COD=cycloocta-1,5-diene), with dihydrogen, in the presence of various stabilizing agents. X-ray diffraction studies evidence a face-centered-cubic structure for all samples. Spherical isolated superparamagnetic nanoparticles (d∼4.5 nm) are produced in the presence of poly(N-vinylpyrrolid-2-one). They display a magnetization value comparable to that of bulk nickel, as determined from superconducting quantum iinterference device (SQUID) measurements. Exposure of the surface of the nanoparticles to CO, leading to CO coordination as monitored by infrared spectroscopy, or to methanol, strongly reduces their magnetization. This reduction corresponds respectively to one or two magnetically inactive layers of nickel atoms at the nanoparticles surface. The production of elongated nanoparticles was favored when either trioctylphosphineoxide or hexadecylamine (HDA) were used as stabilizing agents. In this case, SQUID measurements show that only HDA preserves the magnetization of the surface. This stabilizing agent was selected for the production of nickel nanorods. The influence of ligands on the effective anisotropy is discussed.Nanoparticles of nickel have been obtained in solution through reaction of an organometallic precursor, Ni(COD)2 (COD=cycloocta-1,5-diene), with dihydrogen, in the presence of various stabilizing agents. X-ray diffraction studies evidence a face-centered-cubic structure for all samples. Spherical isolated superparamagnetic nanoparticles (d∼4.5 nm) are produced in the presence of poly(N-vinylpyrrolid-2-one). They display a magnetization value comparable to that of bulk nickel, as determined from superconducting quantum iinterference device (SQUID) measurements. Exposure of the surface of the nanoparticles to CO, leading to CO coordination as monitored by infrared spectroscopy, or to methanol, strongly reduces their magnetization. This reduction corresponds respectively to one or two magnetically inactive layers of nickel atoms at the nanoparticles surface. The production of elongated nanoparticles was favored when either trioctylphosphineoxide or hexadecylamine (HDA) were used as stabilizing agents. In thi...

Organometallic approach for the synthesis of nanostructures

Nanostructures are considered as chemical systems of high potential owing to their unusual properties at the interface of those of molecular species and bulk metals. Consequently, they are promising candidates for application in different domains such as catalysis, magnetism, medicine, opto-electronics or sensors. The control of the characteristics of nanostructures is a fundamental prerequisite if one envisages exploring their physical or chemical properties since they vary dramatically with size, shape and surface state. Thus, the development of efficient methods leading to reproducible nanostructures is presently one of the main objectives in the nanochemistry community. Although organometallic chemistry has been early involved, it arises only marginally in the field. Nevertheless, the concepts and techniques of organometallic chemistry appear to be well-adapted for the growth of well-controlled nanostructures. This will be discussed through recent advances in the synthesis of metal and metal oxide nanoparticles in terms of size dispersion, chemical composition, surface state, shape or organization, pointing out the role of ligands. Moreover their characterization at a molecular level and the development of their chemical/physical properties towards applications will be described. This review reflects more than 20 years of efforts of our team to achieve these goals.

Experimental evidence of structural evolution in ultrafine cobalt particles stabilized in different polymers—From a polytetrahedral arrangement to the hexagonal structure

Ultrafine cobalt particles have been reproducibly synthesized by decomposition of an organometallic precursor in the presence of a stabilizing polymer. The size of the stable monodisperse colloids thus obtained is seen to strongly depend on the nature of the polymer: around 4.2 nm diameter in polyphenylenoxide (PPO) and around 1.4 nm diameter in polyvinylpyrrolidone (PVP). Investigations by wide angle x-ray scattering (WAXS) and high-resolution transmission electron microscopy (HRTEM) give evidence for a size dependence of the structural organization, and hence for a close relationship between structure and synthesis conditions. Co/PPO particles exhibit a hexagonal compact structure with the metal–metal bond length of the bulk material while Co/PVP ones display an original structure. We show that the unusual features of the experimental data in Co/PVP clearly point to a nonperiodic polytetrahedral structure. Successful simulations of the HRTEM and WAXS results have been obtained using models built on the ...

Ultrasmall iron nanoparticles: Effect of size reduction on anisotropy and magnetization

Stable iron nanoparticles have been synthesised by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen pressure. Those conditions lead to a system of monodisperse and metallic nanoparticles which diameter is less than 2nm and stabilized by HN[Si(CH3)3]2. The magnetization is found to be MS=1.92μB∕at., i.e., 10% lower than the bulk value. The Mossbauer spectrum is fitted by two contributions of metallic iron. The magnetic anisotropy energy constant increases up to 5.2×105J∕m3, i.e., ten times the bulk one.

Quantitative magnetization measurements on nanometer ferromagnetic cobalt wires using electron holography

The magnetic remanent states of 4-nm-diameter single-crystalline Co nanowires are characterized using off-axis electron holography. Measurements are obtained from isolated wires, as well as from bundles of wires and “multibranch” wires joined by 15-nm-diameter nodes of Co. The fraction of magnetically active moments in a single 4-nm-diameter wire is measured to be 1.01±0.19, indicating that, to within experimental error, the wire is fully magnetized throughout its diameter.

Magnetic nanoparticles through organometallic synthesis: evolution of the magnetic properties from isolated nanoparticles to organised nanostructures.

Co and NiFe nanoparticles (2.7 to 3.3 nm mean diameter) of narrow size distribution have been obtained through the decomposition of organometallic precursors in organic solutions of long alkyl chain ligands, namely oleic acid and hexadecylamine. Materials of various volume fractions were produced. The particles have been structurally characterised by WAXS. Both adopt the bulk structure: HCP in the case of cobalt; a mixture of FCC and BCC for NiFe. Their aptitude to self-assemble either on flat supports or in bulk solid state has been investigated by means of TEM and SAXS. This study suggests the crystallisation of the nanoparticles upon solvent evaporation, especially a local FCC arrangement was observed for the NiFe material. Magnetic measurements (SQUID) confirm this tendency. The blocking temperature depends on the metal volume fraction, i.e. on the anisotropy generated by the dipolar couplings (Ki). We show that, for dense samples, the particles of high intrinsic anisotropy, Ku, (Co) still display an individual behaviour while the soft ones (NiFe) display a collective behaviour.

Tailoring the magnetic anisotropy in CoRh nanoalloys

CoRh alloy nanoparticles (NPs) show nontrivial correlations between chemical and magnetic order that lead to a remarkable nonmonotonous dependence of the magnetic anisotropy energy as a function of composition. Combining experiment and theory we demonstrate how the induced 4d moments and the 3d−4d interfaces control the magnetoanisotropic behavior. New possibilities of tailoring the magnetic characteristics of NPs are thus opened.

ORGANOMETALLIC SYNTHESIS OF NANOPARTICLES

Nanoparticles can be synthesized from metal-organic or organometallic precursors, either by classical thermal decomposition, ultrasound activation, photolysis as well as hydrogenation or hydrolysis reactions. The size, size distribution and more importantly surface state of these nanoparticles are much better controlled than when they are produced by chemical or electrochemical reduction of metal salts. Hence, metal or oxide nanoparticles can be obtained that are suitable for fundamental physics at the nanoscale, especially for magnetic studies. This is currently of particular interest as many applications require systems of still smaller sizes, the properties of which are not yet fully understood.

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).