Nanostructured composites with precipitated silica – Ni crystallites coated by char with carbonized starch

Abstract

Hybrid carbons/metals/metal (metalloid) oxides composites could be effective adsorbents for low– and high–molecular weight compounds, polar and nonpolar, gaseous and liquid. The presence of metal nanocrystallites and carbon nanostructures could provide catalytic properties in redox reactions. For more effective use of hybrid composites, their morphological, structural, textural, and adsorption characteristics should be appropriate for target applications and, therefore, well controlled. Therefore, the aim of this study was to synthesize carbon/metal/silica nanostructured composites with varied content of metal (Ni) to control the mentioned characteristics. Precipitated silica Sipernat 50 was selected as a substrate. Potato starch was used as a carbon precursor. Nickel nitrate (Ni(NO₃)₂·6H₂O) of varied amounts was used as a precursor of Ni nanoparticles reduced upon the starch carbonization. After the starch carbonization and Ni reduction, a set of C/Ni/silica samples was studied using atomic force microscopy, X–ray diffraction, X–ray fluorescence spectroscopy, nitrogen and p-nitrophenol adsorption, thermogravimetry, and Raman spectroscopy. The presence of nickel phase results in the formation of smaller but denser packed char nanoparticles. Estimation of possible contribution of pores accessible for nitrogen molecules in silica globules and outer surface of carbon/Ni particles suggests that the carbon phase is porous that provides a significant part of the specific surface area of the composites. Amorphous silica and char phases are characterized by the presence of certain nuclei of radius (R) < 1 nm and 2 nm < R < 10 nm estimated from the XRD patterns using full peak profile analysis with a self–consistent regularization procedure. Ni crystallites are of several sizes, since particle size distributions include two–three peaks in the range of 3–13 nm in radius. The Raman spectra show that the main changes with increasing Ni content are characteristic to sp³ carbon structures (D line) in contrast to the sp² structures (G line). The pore size distributions (both differential and incremental) demonstrate complex changes in a broad size range due to increasing Ni content in composites. As a whole, changes in the Ni content in nanostructured C/Ni/silica composites allow one to control the morphological, structural, and textural characteristics of the whole materials.