Investigation of Ni/Ni₃C Nanoparticle Synthesis for Application as a Catalyst in Carbon Nanostructure Growth

Author(s)

Silva, Crystian W. C. ; Cabrera-Pasca, Gabriel A. ; Souza, Katiusse S. ; Costa, Cleidilane S. ; Costa, Messias S. ; Correa, Bruno S. ; Ferreira, Wanderson L. ; Freitas, Rafael S. ; Carbonari, Artur W. ; Otubo, Larissa

• Document type: Journal article
• Source: ACS APPLIED NANO MATERIALS; v. 6, n. 22, p. 16-pg., 2023-11-08.

Abstract

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 degrees 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 In-111(Cd-111) 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 (nu(Q)) of 23 MHz and a hyperfine field (B-hf) 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. (AU)

• FAPESP's process: 17/50332-0 - Scientific, technological and infrastructure qualification in radiopharmaceuticals, radiation and entrepreneurship for health purposes (PDIp)
• Grantee: Marcelo Linardi
• Support Opportunities: Research Grants - State Research Institutes Modernization Program
• FAPESP's process: 14/14001-1 - Project and construction of a digital spectrometer:A more eficient equipment to investigate materials using PAC technique
• Grantee: Rajendra Narain Saxena
• Support Opportunities: Regular Research Grants
• FAPESP's process: 14/50279-4 - Brasil Research Centre for Gas Innovation
• Grantee: Julio Romano Meneghini
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 20/15230-5 - Research Centre for Greenhouse Gas Innovation - RCG2I
• Grantee: Julio Romano Meneghini
• Support Opportunities: Research Grants - Research Centers in Engineering Program