Search

Nanomaterials based on Pd nanoparticles supported on Vulcan carbon (XC-72R) were prepared by the organometallic approach in one-pot and mild conditions (3 bar hydrogen and room temperature) using Pd(dba)2 (bis (dibenzylideneacetone) palladium (0)) as metal source and hexadecylamine (HDA) as stabilizer. High-resolution transmission electron microscopy (HR-TEM) evidenced the presence of well-dispersed Pd nanoparticles of ca. 4.5 nm mean size onto the carbon support (Pd/HDA/C). Scanning and transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) allowed to determine the chemical composition of the nanomaterials. When the Pd/HDA/C nanomaterial was submitted to heating treatment (ht) at 400 °C under air (referred as Pd/HDA/C@air-ht), X-ray photoelectron spectroscopy (XPS) and HR-TEM/STEM-EELS analyses suggested the presence of interactions between PdO and Pd(0) as a result of the formation of Pd@PdO core–shell nanoparticles. The highest oxidation current magnitude during methanol oxidation reaction is ascribed to the heat-treated material, linked with a better electron and mass transfer processes at the electrode interface. This can be attributed to electronic interactions at the core–shell formed, which might promote different redox processes at the electrode interface during CH3OH deprotonation in the alkaline electrolyte. [ABSTRACT FROM AUTHOR]

The synthesis of Rh nanoparticles has been performed through an organometallic approach starting from the tris(allyl) rhodium complex, Rh(η3-C3H5)3, as precursor and using an alcohol as both a solvent and a stabilizer, under mild reaction conditions (room temperature; 3 bar H2). The influence of the alcohol used, among methanol, propanol or heptanol, on the morphological and structural characteristics as well as on the magnetic and electrocatalytic properties of the obtained Rh nanoparticles has been investigated. Assemblies of Rh nanoparticles of various sizes have been observed depending on the alkyl chain length of the alcohol used. A noticeable effect of the nanostructured character of these Rh nanoparticles is the appearance of a ferromagnetic ordering at room temperature due to a modified electronic structure. Magnetic moments per atom were determined as follows: 0.099, 0.073 and 0.036 µB for methanol, heptanol and propanol, respectively. The electrochemical evaluation of these Rh nanoparticles on the oxygen reduction reaction (ORR) showed that the electroactivity depends on the chain length of the alcohol; thus, Rh-heptanol system displayed the highest electroactivity for ORR. [ABSTRACT FROM AUTHOR]

Structural and spectroscopic properties of tetranuclear ruthenium hydrido clusters, and to a less extent, of hexanuclear ruthenium hydrido clusters, are investigated theoretically. Some of these (H)nRuk(L)m (k = 4, 6) clusters were experimentally synthesized and characterized. Non-existing structures are also considered in order to examine the role of ligands on their structure, vibrational spectra and 1HNMR chemical shifts. The calculated properties are found in very good agreement with experimental data, when available. Beyond the intrinsic interest elicited by transition metal clusters, these compounds are also considered in this paper as relevant to diamagnetic ruthenium nanoparticles as well as building blocks of hcp surfaces, which is the ruthenium nanoparticle lattice. On the basis of the very good agreement between experiments and theory, the structural and spectroscopic properties of several model clusters are also predicted in order to bring additional data which may help to analyze the spectral signature of ruthenium nanoparticles. A particular emphasis is put on 1H NMR, which is of high practical importance for characterizing the presence of hydrides in ruthenium clusters and nanoparticles. Several topics are discussed: the structural preference of surface hydrides for terminal-, edge-bridging or face-capping coordination modes, hydrides adsorption energies, the possible presence of interstitial hydrogen atoms, the dependence of 1H chemical shifts on ligands and on electron counting. [ABSTRACT FROM AUTHOR]

Review: 74 refs. [ABSTRACT FROM AUTHOR]

Here we report on the organometallic synthesis of polyvinylpyrrolidone (PVP)-stabilized palladium-rhodium nanostructures that display high electrochemical properties when used as carbon-supported electrodes (Pd x Rh 1-x -PVP/C) for methanol oxidation reaction (MOR). These nanostructures were synthesized by hydrogenation of the tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba) 3) and tris(allyl) rhodium (Rh(η3-C 3 H 5) 3) complexes, in tetrahydrofuran (THF) under mild reaction conditions (room temperature and 3 bar H 2) and in the presence of PVP as stabilizer. The influence of methanol concentration (0.5, 1.0 and 2.0 M) as well as different scan rates (5–100 mV s−1) was evaluated to determine changes in the stability and catalytic activity. The organometallic approach and the use of PVP for the preparation of PdRh electrode materials promoted the formation of highly dispersed nanostructures, that led to a remarkably enhanced methanol electro-oxidation in alkaline medium. This high catalytic behavior can reasonably arise from a synergistic effect between Pd and Rh metals as, under the applied conditions, Rh is expected to enhance the Pd ability to oxidize methanol to CO 2 (oxophilic character) as well as the catalyst stability. From all the evaluated electrode materials, Pd 8 Rh 2 -PVP/C electrode showed the highest mass activity at high methanol concentration (2.0 M) and low scan rate (10 mV s−1). This catalyst showed a performance up to 26 times higher than that of Pd-PVP/C and interestingly an electroactivity superior to that of previously reported PdRh catalysts. [Display omitted] • This synthesis led to the formation of well-dispersed nanostructures of size <5 nm. • Pd 8 Rh 2 -PVP/C showed an enhanced performance, up to 26 times higher than Pd-PVP/C. • CVs shifts in the oxidation peak potential towards (-) values as Rh amount increases. • Oxophilic character in the PdRh alloys is favored at low Rh quantities. [ABSTRACT FROM AUTHOR]

The synthesis of metal nanoparticles dispersed inside the grains of a porous inorganic support was carried out by "dry impregnation" in a fluidized bed. The principle of this technique consists in the spraying of a solution containing a metal source into a hot fluidized bed of porous particles. The metal source can be of different nature such as metal salts, organometallic precursors or colloidal solutions. The experimental results obtained from iron oxide deposition on a porous silica gel as support, constitute the core of this article but others results concerning the deposition of rhodium from a colloidal suspension containing preformed rhodium nanoparticles are also described. More precisely, this study aims to understand the effect of the bed temperature during the impregnation step, the initial particle porosity and the calcination operating protocol on the metallic nanoparticles dispersion and location in the silica porous particles. The so-obtained products were characterized by various techniques in order to determine their morphology, their surface properties and the dispersion of the nanoparticles inside the support. The results showed that, under the chosen operating conditions, the deposit efficiency is close to 100% and the competition between the drying rate, depending on the process-related variables, and the capillary penetration rate, depending on the physicochemical related variables, controls the deposit location. A quasi uniform deposit inside the support particles is observed for soft drying. The metal nanoparticles size is controlled by the pore mean diameter of the support as well as the calcination operating protocol. [ABSTRACT FROM AUTHOR]

The synthesis of catalytic or not composite materials by dry impregnation in fluidized bed is described. This process can be carried out under mild conditions from solutions of organometallic precursors or colloidal solutions of preformed nanoparticles giving rise to reproducible metallic nanoparticles containing composite materials with a high reproducibility. The adequate choice of the reaction conditions makes possible to deposit uniformly the metal precursor within the porous matrix or on the support surface. When the ratio between the drying time and the capillary penetration time ( tsec/ tcap) is higher than 10, the impregnation under soft drying conditions leads to a homogeneous deposit inside the pores of the particles of support. The efficiency of the metal deposition is close to 100%, and the size of the formed metal nanoparticles is controlled by the pores diameter. Finally, some of the presented composite materials have been tested as catalysts: iron-based materials were used in carbon-nanotubes synthesis, while Pd and Rh composite materials have been investigated in hydrogenation reactions. [ABSTRACT FROM AUTHOR]

Abstract: The organometallic synthesis of ruthenium nanoparticles stabilized by water-soluble alkyl sulfonated diphosphines as ligands is described for the first time. After isolation, the so-obtained nanoparticles could be easily dispersed into water giving rise to stable aqueous colloidal solutions without precipitation over the course of several months. The catalytic behaviour of these aqueous colloidal solutions has been investigated in the hydrogenation of unsaturated substrates (tetradecene, styrene and acetophenone) in biphasic liquid–liquid conditions, showing interesting results in terms of reactivity. Interestingly, small structural differences in the backbone of the diphosphine ligands influence the catalytic activity of these nanocatalysts. In addition, preliminary tests of recycling showed promising results with neither loss of activity or significant precipitation. [Copyright &y& Elsevier]

Abstract: Both (Ni, Pt) and bimetallic (Ni x Pt; x =1, 2, 3) nanoparticles have been synthesized by hydrogenation of Ni(cod)2 ad Pt2(dba)3 in the presence of a weak coordinating ligand, hexadecylamine (CH3(CH2)15NH2, HDA). These nanostructures were characterized by different techniques (Fourier Transform-Infrared Spectroscopy (FT-IR), High-Resolution Transmission Electron Microscopy (HRTEM)), and were evaluated as Hydrogen Evolution Reaction electrocatalysts in 0.5M sulfuric acid. The effects of varying the platinum amount during the synthesis were systematically studied by Cyclic Voltammetry (CV), polarization measurements and electrochemical impedance spectroscopy (EIS) techniques. HRTEM shows that the bimetallic nanostructures display a different morphology compared to that observed for pure Ni and Pt ones. The process of hydrogen adsorption–desorption in the as-prepared electrodes seems to occur in (110) and (100) facets. It was found that the increase in the activity for the HER is due to an increased electrochemical active surface area (ECSA) and/or stabilization in the case of elemental electrode materials; and to the effect of Pt amount in the case of the Ni–Pt nanostructures (synergistic effect leads to lower overpotential). It has been established that the main pathway for the HER is Volmer–Heyrovsky. [Copyright &y& Elsevier]

Abstract: The production of supported catalysts by impregnation method of porous supports can be carried out in a fluidized bed. This technique allows to obtain, in only one apparatus, catalysts which by the traditional way must successively undergo the stages of impregnation, filtration, drying and calcination/activation. This paper deals with the results of experiments related to the manufacture of traditional catalysts and new generation catalysts containing various metals (nickel, manganese, copper, palladium) deposited on a porous support such as alumina or silica gel. Moreover, it was shown that the reproducible synthesis of metallic nanoparticles of size, composition and controlled surface quality could be carried out under mild conditions with organometallic precursors. The principle of this technique consists in the spraying of a solution containing a metallic precursor into a hot fluidised bed of porous fine particles as chosen support. The adequate choice of operating conditions makes possible a uniform deposit of the metal precursor inside the porous matrix. After the impregnation step, the decomposition of the metallic precursor and metal activation can be operated in the same reactor. For organometallic complexes the decomposition/activation is achieved at low temperature (T <80 °C) under a reactive atmosphere (H2/N2 mixture) giving then rise to the synthesis of metal nanoparticles with controlled size and composition. Feasibility studies and optimisation of the operating conditions have been carried out, solid characterization and catalytic tests have been conducted to validate the process. In the case of asymmetric catalysts, Pd nanoparticles associated to cinchonidine as an asymmetric ligand inside silica particles have been prepared by this process for the ethyl pyruvate hydrogenation. [Copyright &y& Elsevier]

Abstract: This study reports an efficient method for the preparation of well-dispersed ruthenium nanoparticles of controlled size loaded into micelle-templated silica (MTS). This method is based on an organometallic approach consisting in mild decomposition of Ru(COD)(COT) (COD=η4-cycloocta-1,5-diene; COT=η6-cycloocta-1,3,5-triene) embedded inside mesostructured porous silica. The role assigned to the regular channels of MTS is to host and stabilize the metal nanoparticles. Different procedures of precursor decomposition, variation of metal loadings and of MTS pore sizes were examined in order to identify the crucial parameters governing the location, size and dispersion of the nanoparticles. The composite materials were characterized using elemental analysis, thermal gravimetric analysis, X-ray diffraction, nitrogen sorption at 77K and TEM. The advantage of this new procedure lies in the absence of particles sintering due to the Ru reduction at room temperature and the stabilization of the nanoparticles by suitable pore size of the host. [Copyright &y& Elsevier]