Tulio C. R. Rocha

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.

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.

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.

Preparation of Ag/HOPG model catalysts with a variable particle size and an in situ xps study of their catalytic properties in ethylene oxidation

The preparation of model silver catalysts supported on highly oriented pyrolytic graphite is described, and the effect of the Ag particle size on the catalytic ethylene oxidation into ethylene oxide, studied by in situ XPS and mass spectrometry, is considered. For a mean particle diameter of 8 nm, the adsorbed oxygen species characterized by an O 1s binding energy of 530.8 ± 0.2 eV (electrophilic oxygen) forms on the silver surface exposed to the ethylene-oxygen reaction mixture. Larger silver particles with a mean diameter of 40 nm additionally contain the adsorbed oxygen species characterized by an O 1s binding energy of 529.2 ± 0.2 eV (nucleophilic oxygen). The presence of both oxygen species on the surface of the larger particles ensures the formation of ethylene oxide, while the sample with the smaller silver particles is inactive in the epoxidation reaction. The O 1s signal at 530.8 eV is partly due to oxygen dissolved in the subsurface layers of silver.

High Resolution PDF Measurements on Ag Nanoparticles

The quantitative analysis of structural defects in Ag nanoparticles was addressed in this work. We performed atomic scale structural characterization by a combination of x‐ray diffraction (XRD) using the Pair Distribution Function analysis (PDF) and High Resolution Transmission Electron Microscopy (HRTEM). The XRD measurements were performed using an innovative instrumentation setup to provide high resolution PDF patterns