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  • Artigo IPEN-doc 30219
    Investigation of Ni/Ni3C nanoparticle synthesis for application as a catalyst in carbon nanostructure growth
    2023 - SILVA, CRYSTIAN W.C.; CABRERA-PASCA, GABRIEL A.; SOUZA, KATIUSSE S.; COSTA, CLEIDILANE S.; COSTA, MESSIAS S.; CORREA, BRUNA S.; FERREIRA, WANDERSON L.; FREITAS, RAFAEL S.; CARBONARI, ARTUR W.; OTUBO, LARISSA
    The synthesis of functional Ni/Ni3C nanoparticles has attracted significant interest, especially in the field of electrocatalysis, where these promising nanoparticles are employed to develop sophisticated electrocatalysts, particularly for hydrogen production through the hydrogen evolution reaction. However, the significant reactivity of these systems makes them susceptible to degradation, compromising their catalyst performance. One solution explored to mitigate this problem involves the catalytic growth of carbon nanostructures to encapsulate and protect these nanoparticles. The mechanisms for the formation of carbon nanostructures from nanoparticles remain the subject of this study. Among the reported processes, the annealing of nanocatalysts has been described as a highly effective method for producing such systems. This process is influenced by parameters, such as the temperature, atmosphere, and structural and morphological characteristics of the nanocatalysts. In the work reported here, we evaluated the influence of different ligand pairs (oleylamine/oleic acid and oleylamine/palm kernel oil) on the structural, morphological, and magnetic properties of Ni/Ni3C nanoparticles obtained through thermal decomposition at 240 °C for 3 h. Additionally, we investigated the impact of annealing in a nitrogen atmosphere on the structural properties of these nanoparticles and the growth of carbon nanostructures as a protective mechanism. The analyses include conventional techniques such as X-ray diffraction, transmission electron microscopy (TEM), magnetization measurements, and thermogravimetric analysis with differential scanning calorimetry. Additionally, local analysis was conducted using perturbed angular correlation spectroscopy (PAC) across a broad temperature range (30–693 K), utilizing the radioactive tracer 111In(111Cd) for these measurements. The characterizations revealed that palm kernel oil contributes to the formation of nanoparticles with a higher Ni3C content, a broader size distribution, and a lower saturation magnetization. The PAC measurements in the range of 30–50 K, along with density functional theory calculations, indicated the absence of the Ni-hcp phase in the nanoparticles, a topic frequently discussed in the literature. Moreover, the presence of Ni3C regions with carbon deficiency was identified, characterized by a quadrupole frequency (νQ) of 23 MHz and a hyperfine field (Bhf) of 1 T. The temperature-dependent local analysis, combined with thermal analysis and TEM measurements, confirmed the development of carbon nano-onions around the nanoparticles during thermal treatment above 695 K in a nitrogen atmosphere. This observation demonstrates that nanoparticles obtained with palm kernel oil, which has the highest Ni3C content, offer superior encapsulation of Ni nuclei through these graphitic nanostructures.
  • Artigo IPEN-doc 29041
    Local crystalline structure of doped semiconductor oxides characterized by perturbed angular correlations
    2022 - BURIMOVA, ANASTASIA; CARBONARI, ARTUR W.; LIMA, NICOLE P. de; MIRANDA FILHO, ARNALDO A.; SOUZA, ALEXANDRE P. dos S.; SALES, TATIANE da S.N.; FERREIRA, WANDERSON L.; PEREIRA, LUCIANO F.D.; CORREA, BRUNO S.; SAXENA, RAJENDRA N.
    Doping semiconductor oxides with trace amounts of non-native elements can improve their properties such as bandgap and conductivity. The lack of local techniques makes the precise characterization of these materials difficult. Among the few techniques capable of providing local characterization, those based on hyperfine interactions at probe nuclei have the advantage of being well established, probing the material homogeneously and completely, thus investigating different regions of material. Some of these techniques are also quite sensitive even at extremely low dopant concentrations. The perturbed angular correlation technique, combined with first-principles calculations, has recently been shown to be a powerful method for characterizing doped semiconductor oxides. In this paper, we present a brief review of the unique information extracted from the semiconductor investigation with such a complex approach, including semiconductor oxides doped with cadmium and other elements. A strong relationship between the local environment, including electronic structure, and the nature of the dopant and the native element of the doped oxides is also shown.