Daniela Zanchet

Chemical Synthesis and Structural Characterization of Highly Disordered Ni Colloidal Nanoparticles

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.

Inter-atomic distance contraction in thiol-passivated gold nanoparticles

Abstract Size-dependent inter-atomic distance contraction was investigated by Extended X-ray Absorption Fine Structure in thiol-capped gold nanoparticles. A slight nearest-neighbor distance reduction was observed as a function of particle diameter (2–4 nm range) but, for all samples, it was less than 1%. This value contrasts with the larger effect expected and found in other systems, especially for the smallest particles (2 nm) where it is twice as small. Our analysis also points out a short metal–ligand bond, suggesting a rather strong surface interaction. We interpreted these results as a passivant effect where the metal–ligand interaction partially compensates the expected lattice contraction.

Magnetic and structural properties of fcc/hcp bi-crystalline multilayer Co nanowire arrays prepared by controlled electroplating

We report on the structural and magnetic properties of crystalline bi-phase Co nanowires, electrodeposited into the pores of anodized alumina membranes, as a function of their length. Co nanowires present two different coexistent crystalline structures (fcc and hcp) that can be controlled by the time of pulsed electrodeposition. The fcc crystalline phase grows at the early stage and is present at the bottom of all the nanowires, strongly influencing their magnetic behavior. Both structural and magnetic characterizations indicate that the length of the fcc phase is constant at around 260–270 nm. X-ray diffraction measurements revealed a strong preferential orientation (texture) in the (1 0–1 0) direction for the hcp phase, which increases the nanowire length as well as crystalline grain size, degree of orientation, and volume fraction of oriented material. The first-order reversal curve (FORC) method was used to infer both qualitatively and quantitatively the complex magnetization reversal of the nanowires...

Structure and morphology of spinel MFe2O4 (M=Fe, Co, Ni) nanoparticles chemically synthesized from heterometallic complexes.

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.

On the Stabilization of Gold Nanoparticles over Silica‐Based Magnetic Supports Modified with Organosilanes

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.

Effects of dipolar interactions on the magnetic properties of γ-Fe2O3 nanoparticles in the blocked state

The role played by dipolar interactions in the coercive field and remanence of nanoparticle systems is studied using different concentrations of nearly monodisperse nanoparticles of γ-Fe2O3. The 9.0nm particles are isolated by organic encapsulation and diluted in paraffin. Magnetic properties were investigated by means of hysteresis obtained at different temperatures, zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves, and the so-called ΔM technique. The analysis of the experimental data points to the existence of a demagnetizing role played by the dipolar interaction in the coercive field.

Dipolar interaction and size effects in powder samples of colloidal iron oxide nanoparticles

Dipole–dipole interactions in nanostructured materials deeply affect their magnetic properties, and detailed studies are still required to fully understand them. In this work, the dependence of magnetic properties on particle size has been evaluated in powder samples of Fe oxide nanoparticles produced by colloidal methods. Zero-field-cooled and field-cooled magnetization curves and magnetization versus applied field data have been analysed by taking into account dipolar interactions through a correction to the classical superparamagnetic model. Morphological and magnetic data were in very good agreement, which has allowed us to quantify relevant physical parameters, such as the anisotropy constant, magnetic moment, and interacting volume for our system.

Interplay between crystallization and particle growth during the isothermal annealing of colloidal iron oxide nanoparticles

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.

Magnetic behavior of Ni nanoparticles with high disordered atomic structure

This report concerns the magnetic properties of colloidal Ni nanoparticles (NPs) obtained by chemical reduction of Ni(II) salt in an organic solvent. The NPs present a complex and disordered atomic structure, where small clusters of a few Ni atoms appear to coexist within each NP. These NPs exhibit interesting magnetic properties, with a low temperature ferromagnetic order followed by a transition from ferromagnetic to a “spin-glass-like” state as the temperature decreases. The results are discussed considering the role of the atomic ordering of the NPs on the corresponding magnetic behavior.

Transition Metal Nitride Core-Noble Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

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.