RESUMEN

Strontium-substituted lanthanum cobaltite (La0.8 Sr0.2 CoO3 ) matrix-stabilized Co0 /CoII catalytic sites were prepared, which present tunable C-O and C-C hydrogenolysis activity for the vapor-phase upgrading of oxygenated arenes. CoII sites associated with oxygen vacancies were favored at low temperatures and performed selective C-O hydrogenolysis, in which Sr-substitution facilitated oxygen vacancy formation, leading to approximately 10 times higher reactivity compared to undoped LaCoO3 . Co0 sites were favored at high temperatures and performed extensive C-C bond hydrogenolysis, generating a wide range of alkanes. The lower reaction order with P H 2 (1.1±0.1) for C-C hydrogenolysis than for C-O hydrogenolysis (2.0±0.1) led to a high selectivity towards C-C hydrogenolysis at low P H 2 . The Co3 O4 surfaces featured a narrower temperature window for obtaining the respective optimal CoII and Co0 pairs compared to analogous perovskite surfaces; whereas, the perovskite matrix stabilizes these pairs for selective C-O and C-C hydrogenolysis. This stabilization effect offers an additional handle to control reactivity in oxide catalysts.

RESUMEN

Bimetallic nanoparticle encapsulation in microporous zeolite crystals is a promising route for producing catalysts with unprecedented reaction selectivities. Herein, a novel synthetic approach was developed to produce PtZnx nanoclusters encapsulated inside zeolite micropores by introducing Pt2+ cations into a zincosilicate framework via ion exchange, and subsequent controlled demetallation and alloying with framework Zn. The resulting zeolites featured nanoclusters with sizes of approximately 1 nm, having an interatomic structure corresponding to a PtZnx alloy as confirmed by pair distribution function (PDF) analysis. These materials featured simultaneous shape and substrate specificity demonstrated by the selective production of p-chloroaniline from the competitive hydrogenation of p-chloronitrobenzene and 1,3-dimethyl-5-nitrobenzene.

RESUMEN

We synthesized Pt supported catalysts by the glucose assisted hydrothermal method, in which a carbon template was used to form a porous CeO2 structure upon calcination. Special emphasis was given to evaluate the influence of calcination parameters in the structural and textural properties of the catalysts and the final impact in the catalytic activity of CO oxidation reaction under hydrogen rich atmosphere (PROX-CO). We show that at 350 °C the carbon matrix was already mostly burnt and that higher temperatures and holding times mostly increase the CeO2 crystallite sizes. The sample prepared at 350 °C presented the highest surface area, 106 m2 ·g-1, in comparison to 60-70 m2 ·g-1 obtained for all other conditions. Transmission electron microscopy images of the catalyst calcined at 600 °C for 6 h showed 200 nm spheres formed by aggregation of ceria crystallites with crystalline domains of about 20 nm. All samples showed similar catalytic activity in PROX-CO indicating that the creation of the catalytic sites were mostly determined during the synthesis conditions and the catalytic performance were not deeply affected by the differences on CeOx matrix.

RESUMEN

Core-shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core-shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. The ability to control shell coverage and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.

RESUMEN

We report the colloidal synthesis of dumbbell-like Au0.5Cu0.5@Fe3O4 nanocrystals (AuCu@FeOx NCs) and the study of their properties in the CO oxidation reaction. To this aim, the as-prepared NCs were deposited on γ-alumina and pretreated in an oxidizing environment to remove the organic ligands. A comparison of these NCs with bulk Fe3O4-supported AuCu NCs showed that the nanosized support was far more effective in preventing the sintering of the metal domains, leading thus to a superior catalytic activity. Nanosizing of the support could be thus an effective, general strategy to improve the thermal stability of metallic NCs. On the other hand, the support size did not affect the chemical transformations experienced by the AuCu NCs during the activation step. Independently from the support size, we observed indeed the segregation of Cu from the alloy phase under oxidative conditions as well as the possible incorporation of the Cu atoms in the iron oxide domain.

RESUMEN

The immobilization of gold nanoparticles (Au NPs) on silica is made possible by the functionalization of the silica surfaces with organosilanes. Au NPs could only be stabilized and firmly attached to silica-support surfaces that were previously modified with amino groups. Au NPs could not be stabilized on bare silica surfaces and most of the NPs were then found in the solution. The metal-support interactions before and after the Au NP formation, observed by X-ray absorption fine structure spectroscopy (XAFS), indicate a stronger interaction of gold(III) ions with amino-modified silica surfaces than with the silanol groups in bare silica. An amino-modified, silica-based, magnetic support was used to prepare an active Au NP catalyst for the chemoselective oxidation of alcohols, a reaction of great interest for the fine chemical industry.

RESUMEN

We synthesized magnetic spinel ferrites from trimetallic single-source precursors. Fe(II), Co(II), and Ni(II) ferrite nanoparticles in the range of 9-25 nm were synthesized by solvothermal decomposition of trimetallic acetate complex precursors in benzyl ether in the presence of oleic acid and oleylamine, using 1,2-dodecanediol as the reducing agent. For comparison, spinel ferrite nanoparticles were synthesized by stoichiometric mixtures of metal acetate or acetylacetonate salts. The nanoparticles (NP) were characterized by TEM, DLS, powder XRD, and Raman spectroscopy; and their magnetic properties were characterized by ZFC-FC and M(H) measurements. The ferrite-NP were more homogeneous and had a narrower size distribution when trimetallic complexes were used as precursors. As a consequence, the magnetic properties of these ferrite-NP are closer to the aimed room temperature superparamagnetic behavior, than are those of other ferrites obtained by a mixture of salts.

RESUMEN

Hydrogen reduction of cationic or neutral Ir(i) compounds, namely [Ir(COD)(2)]BF(4) and [Ir(COD)Cl](2)respectively. in the ionic liquid (IL) 1-alkyl-3-methylimidazolium tetrafluoroborate affords either irregularly sized spherical (from 1.9 +/- 0.4 to 3.6 +/- 0.9 nm) or worm-like metal nanoparticles, depending on the nature of the imidazolium alkyl group and the type of iridium precursor. The ionic Ir(i) precursor tends to be dissolved and concentrated on the IL polar domains (populated by the imidazolium nucleus and tetrafluoroborate anions) while the neutral precursor dissolves preferentially in the non-polar region of the IL (populated mainly by N-alkyl side chains). The size, or volume, of the nano-region where the Ir(i) precursor is dissolved and reduced, determines the size and, probably, the shape of the formed nanoparticles. The HR-TEM image shows that the Ir(0) with worm-like shape are polycrystalline and formed from aggregation individual "spherical" nanoparticles of around 1.9 nm. The catalytic activity of Ir(0) NPs on the hydrogenation of cyclohexene (0.01 mol L(-1) of Ir atoms in IL, 75 degrees C, 8 bar of H(2), 500 rpm stirring, 1/1000 Ir(0)/cyclohexene ratio) is always greater in C(1)C(10)I.BF(4) than C(1)C(4)I.BF(4), regardless of the nature of Ir(i) precursor. Moreover, the cyclohexene hydrogenations performed with Ir(0) nanocatalysts made from ionic Ir(i) precursor are approximately twice faster than those NPs obtained from the neutral Ir(i) precursor, in the same IL.

RESUMEN

The relationship between crystallization and growth of colloidal iron oxide nanoparticles during isothermal annealing was addressed in this work. The structural, morphological and chemical modifications of the nanoparticles during thermal treatments were followed by combination of electron microscopy, X-ray diffraction and spectroscopic methods. The initially monodisperse spherical nanoparticles with amorphous and partially oxidized structure evolved during the treatments, depending on the temperature and treatment time. Core-void-shell nanoparticles or single crystal nanoparticles and hollow polycrystalline nanoparticles, both with well defined Fe(3)O(4) oxide phase, are formed depending on the conditions. This evolution was interpreted as a result of the Kirkendall effect associated to mass redistribution and fragmentation of the nanoparticles, bringing new information about the effect of post-synthesis treatments on the crystallinity and morphology of colloidal nanoparticles.

RESUMEN

This work focuses on synthetic methods to produce monodisperse Ni colloidal nanoparticles (NPs), in the 4-16 nm size range, and their structural characterization. Narrow size distribution nanoparticles were obtained by high-temperature reduction of a nickel salt and the production of tunable sizes of the Ni NPs was improved compared to other methods previously described. The as-synthesized nanoparticles exhibited spherical shape and highly disordered structure, as it could be assigned by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Annealing at high temperature in organic solvent resulted in an increase of nanoparticle atomic ordering; in this case, the XRD pattern showed an fcc-like structure. Complementary data obtained by X-ray absorption spectroscopy confirmed the complex structure of these nanoparticles. Temperature dependence of the magnetic susceptibility of these highly disordered Ni NPs showed the magnetic behavior cannot be described by the conventional superparamagnetic theory, claiming the importance of the internal structure in the magnetic behavior of such nanomaterials.

Asunto(s)

Coloides/química , Cristalización/métodos , Modelos Químicos , Modelos Moleculares , Nanoestructuras/química , Nanoestructuras/ultraestructura , Níquel/química , Simulación por Computador , Sustancias Macromoleculares/química , Magnetismo , Ensayo de Materiales , Conformación Molecular , Nanotecnología/métodos , Tamaño de la Partícula , Propiedades de Superficie

RESUMEN

Aspects of the growth mechanism of silver triangular nanoplates by photochemical synthesis were addressed by detailed characterization using ultraviolet-visible spectroscopy, electron microscopies, and atomic force microscopy. The quantitative characterization of their size and thickness during the reaction showed that both increase with time as well as the aspect ratio. Samples irradiated by different wavelengths showed that the size of the nanoplates can be controlled by the incident wavelength and it is responsible for the increase of the aspect ratio, but the thickness seems to be determined by the conditions of the initial seeds. It was also found that irradiation with wavelength out of resonance with the surface plasmon of the initial seeds leads to a slower kinetics. The results suggested that rational exploration of the synthesis parameter such as the type of the initial seeds in combination with the wavelength irradiation may lead to a broader type of particles already obtained by this method.

Asunto(s)

Nanopartículas/química , Nanoestructuras/química , Nanotecnología/métodos , Fármacos Fotosensibilizantes , Plata/química , Argón/química , Borohidruros/química , Borohidruros/efectos de la radiación , Citratos/química , Citratos/efectos de la radiación , Frío , Luz , Microscopía de Fuerza Atómica , Microscopía Electrónica de Transmisión , Nanopartículas/efectos de la radiación , Nanopartículas/ultraestructura , Nanoestructuras/efectos de la radiación , Nanoestructuras/ultraestructura , Tamaño de la Partícula , Fármacos Fotosensibilizantes/síntesis química , Fármacos Fotosensibilizantes/química , Plata/efectos de la radiación , Nitrato de Plata/química , Nitrato de Plata/efectos de la radiación , Citrato de Sodio , Espectrofotometría Ultravioleta , Resonancia por Plasmón de Superficie , Factores de Tiempo , Agua/química

RESUMEN

Novel silver nanoparticles/polyaniline composites were obtained through a two-phase water/toluene interfacial reaction. We show that by rigorously controlling the reaction time, different structures of the nanocomposites can be obtained, such as a thin sheet of polyaniline around the silver nanoparticles or a polymer mass with nanoparticles homogeneously embedded within it. Samples were characterized by FT-IR, UV-vis-NIR and Raman spectroscopy, X-ray diffraction, cyclic voltammetry, TEM, and HRTEM. Conductivity and current-voltage characteristics of the nanocomposites were measured, and the results indicate that different properties result from the different structures in which the nanocomposites were formed.

RESUMEN

Metal nanoparticles (NP) are very attractive because of their size- and shape-dependent properties. A widely used preparation of ligand-stabilized metal NP is the two-phase liquid-liquid method using dodecanethiol (DT) as ligand. This work presents various procedures to synthesize dodecanethiol-capped silver NPs, all of them based on a two-phase liquid-liquid method. Small alterations in the synthetic parameters lead to dramatic modifications in the nanoparticles' average size, size distribution width, stability, and structure, as well as in their ability to self-assemble.

Asunto(s)

Nanopartículas/química , Plata/química , Compuestos de Sulfhidrilo/química , Fenómenos Químicos , Química Física , Concentración de Iones de Hidrógeno , Cinética , Tamaño de la Partícula

RESUMEN

hcp Co disk-shaped nanocrystals were obtained by rapid decomposition of cobalt carbonyl in the presence of linear amines. Other surfactants, in addition to the amines, like phosphine oxides and oleic acid were used to improve size dispersion, shape control, and nanocrystal stability. Co disks are ferromagnetic in character and they spontaneously self-assemble into long ribbons. X-ray and electron diffraction, electron microscopy, and SQUID magnetometry have been employed to characterize this material.

Asunto(s)

Cobalto/química , Nanotecnología/métodos , Aminas/química , Monóxido de Carbono/química , Microscopía Electrónica , Tensoactivos/química , Difracción de Rayos X

RESUMEN

Semiconductor nanocrystals with narrow and tunable fluorescence are covalently linked to oligonucleotides. These biocompounds retain the properties of both nanocrystals and DNA. Therefore, different sequences of DNA can be coded with nanocrystals and still preserve their ability to hybridize to their complements. We report the case where four different sequences of DNA are linked to four nanocrystal samples having different colors of emission in the range of 530-640 nm. When the DNA-nanocrystal conjugates are mixed together, it is possible to sort each type of nanoparticle by using hybridization on a defined micrometer-size surface containing the complementary oligonucleotide. Detection of sorting requires only a single excitation source and an epifluorescence microscope. The possibility of directing fluorescent nanocrystals toward specific biological targets and detecting them, combined with their superior photostability compared to organic dyes, opens the way to improved biolabeling experiments, such as gene mapping on a nanometer scale or multicolor microarray analysis.

Asunto(s)

ADN/química , Colorantes Fluorescentes/química , Semiconductores , ADN/genética , Oro/química , Nanotecnología/métodos , Análisis de Secuencia por Matrices de Oligonucleótidos/métodos , Dióxido de Silicio/química