Stacking disorder in silicon carbide supported cobalt crystallites: an X-ray diffraction, electron diffraction and high resolution electron microscopy study

Supported cobalt Fischer–Tropsch catalysts are characteristically nanoparticulate and the reduced SiC supported catalyst was found to contain both HCP and FCC polymorphs. This is reflected in the powder XRD patterns and generally there is a poor fit between the experimental and calculated diffractograms. This was ascribed to small crystallite sizes and the occurrence of disorder, manifested as peak broadening and peak shifts. Selected area electron diffraction data of suitably oriented cobalt catalyst grains on silicon carbide supports show non-periodic disorder in the zone axis orientations that contain the common (001) (HCP) and (111) (FCC) reciprocal lattice planes. Both FCC and HCP polymorphs are present in the same grains and these show disorder mainly in the HCP component. The disorder is further examined using high angle annular dark field (HAADF) scanning transmission electron microscopy at atomic resolution and the stacking sequences elucidated. Random sequences of mainly FCC are interrupted by HCP sequences and twin surfaces with reverse stacking sequences are also present. This study highlights the presence of significant disorder in cobalt catalyst grains confirmed by HAADF microscopy.