Bruno Chaudret

Ruthenium Nanoparticles inside Porous [Zn4O(bdc)3] by Hydrogenolysis of Adsorbed [Ru(cod)(cot)]: A Solid-State Reference System for Surfactant-Stabilized Ruthenium Colloids

The gas-phase loading of [Zn4O(bdc)3] (MOF-5; bdc = 1,4-benzenedicarboxylate) with the volatile compound [Ru(cod)(cot)] (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene) was followed by solid-state (13)C magic angle spinning (MAS) NMR spectroscopy. Subsequent hydrogenolysis of the adsorbed complex inside the porous structure of MOF-5 at 3 bar and 150 degrees C was performed, yielding ruthenium nanoparticles in a typical size range of 1.5-1.7 nm, embedded in the intact MOF-5 matrix, as confirmed by transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (PXRD), and X-ray absorption spectroscopy (XAS). The adsorption of CO molecules on the obtained Ru@MOF-5 nanocomposite was followed by IR spectroscopy. Solid-state (2)H NMR measurements indicated that MOF-5 was a stabilizing support with only weak interactions with the embedded particles, as deduced from the surprisingly high mobility of the surface Ru-D species in comparison to surfactant-stabilized colloidal Ru nanoparticles of similar sizes. Surprisingly, hydrogenolysis of the [Ru(cod)(cot)]3.5@MOF-5 inclusion compound at the milder condition of 25 degrees C does not lead to the quantitative formation of Ru nanoparticles. Instead, formation of a ruthenium-cyclooctadiene complex with the arene moiety of the bdc linkers of the framework takes place, as revealed by (13)C MAS NMR, PXRD, and TEM.

On-chip and freestanding elastic carbon films for micro-supercapacitors

Flexible power for flexible electronics A challenge for flexible electronics is to couple devices with power sources that are also flexible. Ideally, they could also be processed in a way that is compatible with current microfabrication technologies. Huang et al. deposited a relatively thick layer of TiC on top of an oxide-coated Si film. After chlorination, most, but importantly not all, of the TiC was converted into a porous carbon film that could be turned into an electrochemical capacitor. The carbon films were highly flexible, and the residual TiC acted as a stress buffer with the underlying Si film. The films could be separated from the Si to form free-floating films, with the TiC providing a support layer. Science, this issue p. 691 Porous carbon-based supercapacitors are directly fabricated onto silicon substrates. Integration of electrochemical capacitors with silicon-based electronics is a major challenge, limiting energy storage on a chip. We describe a wafer-scale process for manufacturing strongly adhering carbide-derived carbon films and interdigitated micro-supercapacitors with embedded titanium carbide current collectors, fully compatible with current microfabrication and silicon-based device technology. Capacitance of those films reaches 410 farads per cubic centimeter/200 millifarads per square centimeter in aqueous electrolyte and 170 farads per cubic centimeter/85 millifarads per square centimeter in organic electrolyte. We also demonstrate preparation of self-supported, mechanically stable, micrometer-thick porous carbon films with a Young’s modulus of 14.5 gigapascals, with the possibility of further transfer onto flexible substrates. These materials are interesting for applications in structural energy storage, tribology, and gas separation.

An Efficient Strategy to Drive Nanoparticles into Carbon Nanotubes and the Remarkable Effect of Confinement on Their Catalytic Performance

Are you in? Bimetallic PtRu nanoparticles have been selectively confined inside or deposited outside carbon nanotubes (see picture). The confined nanoparticles display significantly higher selectivity and catalytic activity in hydrogenation reactions.

Catalytic Formation of Carbon–Carbon Bonds by Activation of Carbon–Hydrogen Bonds

The direct functionalization of C–H bonds by formation of a C–C bond is an interesting and important alternative to coupling reactions involving halide derivatives. These reactions are complex but during the past few years a number of new systems have been developed which display promising scope. This microreview will briefly mention the different mechanisms leading to C–H activation and describe the new systems leading to the catalytic formation of carbon–carbon bonds.

Ruthenium Nanoparticles Stabilized by N-Heterocyclic Carbenes: Ligand Location and Influence on Reactivity

We thank V. Colliere and L. Datas (UPS-TEMSCAN) and P. Lecante (CNRS-CEMES) for TEM/HR-TEM and WAXS facilities, respectively. CNRS and ANR (Siderus project ANR-08-BLAN-0010-03) are also thanked for financial support. P.L. is grateful to the Spanish Ministerio de Educacion for a research contract. Financial support from the Junta de Andalucia (project no. FQM-3151) and the Spanish Ministerio de Ciencia e Innovacion (projects CTQ2010-17476 and CONSOLIDER-INGENIO 2010 CSD2007-00006, FEDER support) is acknowledged. O.R.-W. thanks the Spanish Ministerio de Ciencia e Innovacion for a research grant.

A Simple Chemical Route toward Monodisperse Iron Carbide Nanoparticles Displaying Tunable Magnetic and Unprecedented Hyperthermia Properties

We report a tunable organometallic synthesis of monodisperse iron carbide and core/shell iron/iron carbide nanoparticles displaying a high magnetization and good air-stability. This process based on the decomposition of Fe(CO)(5) on Fe(0) seeds allows the control of the amount of carbon diffused and therefore the tuning of nanoparticles magnetic anisotropy. This results in unprecedented hyperthermia properties at moderate magnetic fields, in the range of medical treatments.

Surface Chemistry of InP Quantum Dots: A Comprehensive Study

Advanced (1)H, (13)C, and (31)P solution and solid-state NMR studies combined with IR spectroscopy were used to probe, at the molecular scale, the composition and the surface chemistry of indium phosphide (InP) quantum dots (QDs) prepared via a non-coordinating solvent strategy. This nanomaterial can be described as a core-multishell object: an InP core, with a zinc blende bulk structure, is surrounded first by a partially oxidized surface shell, which is itself surrounded by an organic coating. This organic passivating layer is composed, in the first coordination sphere, of tightly bound palmitate ligands which display two different bonding modes. A second coordination sphere includes an unexpected dialkyl ketone and residual long-chain non-coordinating solvents (ODE and its isomers) which interact through weak intermolecular bonds with the alkyl chains of the carboxylate ligands. We show that this ketone is formed during the synthesis process via a decarboxylative coupling route and provides oxidative conditions which are responsible for the oxidation of the InP core surface. This phenomenon has a significant impact on the photoluminescence properties of the as-synthesized QDs and probably accounts for the failure of further growth of the InP core.

Influence of the self-organization of ionic liquids on the size of ruthenium nanoparticles: effect of the temperature and stirring

The size of ruthenium nanoparticles is governed by the degree of self-organization of the imidazolium based ionic liquid in which they are generated from (η4-1,5-cyclooctadiene)(η6-1,3,5-cyclooctatriene)ruthenium: the more structured the ionic liquid, the smaller the size.

Synthesis of tin and tin oxide nanoparticles of low size dispersity for application in gas sensing.

Nanocomposite core-shell particles that consist of a Sn0 core surrounded by a thin layer of tin oxides have been prepared by thermolysis of [(Sn(NMe2)2)2] in anisole that contains small, controlled amounts of water. The particles were characterized by means of electronic microscopies (TEM, HRTEM, SEM), X-ray diffraction (XRD) studies, photoelectron spectroscopy (XPS), and Mossbauer spectroscopy. The TEM micrographs show spherical nanoparticles, the size and size distribution of which depends on the initial experimental conditions of temperature, time, water concentration, and tin precursor concentration. Nanoparticles of 19 nm median size and displaying a narrow size distribution have been obtained with excellent yield in the optimized conditions. HRTEM, XPS, XRD and Mossbauer studies indicate the composite nature of the particles that consist of a well-crystallized tin beta core of approximately equals 11 nm covered with a layer of approximately equals 4 nm of amorphous tin dioxide and which also contain quadratic tin monoxide crystallites. The thermal oxidation of this nanocomposite yields well-crystallized nanoparticles of SnO2* without coalescence or size change. XRD patterns show that the powder consists of a mixture of two phases: the tetragonal cassiterite phase, which is the most abundant, and an orthorhombic phase. In agreement with the small SnO2 particle size, the relative intensity of the adsorbed dioxygen peak observed on the XPS spectrum is remarkable, when compared with that observed in the case of larger SnO2 particles. This is consistent with electrical conductivity measurements, which demonstrate that this material is highly sensitive to the presence of a reducing gas such as carbon monoxide.

Organized 3D-alkyl imidazolium ionic liquids could be used to control the size of in situ generated ruthenium nanoparticles?

The synthesis of ruthenium nanoparticles, RuNPs from the organometallic complex (η4-1,5-cyclooctadiene)(η6-1,3,5-cyclooctatriene)ruthenium(0), Ru(COD)(COT) in various imidazolium derived ionic liquids, ILs: [RMIm][NTf2] (R = CnH2n + 1 with n = 2; 4; 6; 8; 10), and [R2Im][NTf2] (RBu) and [BMMIm][NTf2] has been performed, under 0.4 MPa of H2, at 25 °C or at 0 °C with or without stirring. A relationship between the size of IL non-polar domains calculated by molecular dynamics simulation and the RuNP size measured by TEM has been found, suggesting that the phenomenon of crystal growth is probably controlled by the local concentration of Ru(COD)(COT) and consequently is limited to the size of the non-polar domains. Moreover, the rigid 3D organization based on C2–H⋯anion bonding and chosen experimental conditions, could explain the non-aggregation of RuNPs.