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.

Rietveld and pair distribution function study of Hägg carbide using synchrotron X-ray diffraction.

Fischer-Tropsch (FT) synthesis is an important process in the manufacturing of hydrocarbons and oxygenated hydrocarbons from mixtures of carbon monoxide and hydrogen (syngas). The reduced iron catalyst reacts with carbon monoxide and hydrogen to form bulk Fe(5)C(2) Hägg carbide (χ-HC) during FT synthesis. Arguably, χ-HC is the predominant catalyst phase present in the working iron catalyst. Deactivation of the working catalyst can be due to oxidation of χ-HC to iron oxide, a step-wise decarburization to cementite (θ-Fe(3)C), carbon formation or sintering with accompanying loss of catalytic performance. It is therefore critical to determine the precise crystal structure of χ-HC for the understanding of the synthesis process and for comparison with the first-principles ab initio modelling. Here the results of high-resolution synchrotron X-ray powder diffraction data are reported. The atomic arrangement of χ-HC was confirmed by Rietveld refinement and subsequent real-space modelling of the pair distribution function (PDF) obtained from direct Fourier transformation. The Rietveld and PDF results of χ-HC correspond well with that of a pseudo-monoclinic phase of space group Pi [a = 11.5661 (6) Å, b = 4.5709 (1) Å, c = 5.0611 (2) Å, α = 89.990 (5)°, ß = 97.753 (4)°, γ = 90.195 (4)°], where the Fe atoms are located in three distorted prismatic trigonal and one octahedral arrangement around the central C atoms. The Fe atoms are distorted from the prismatic trigonal arrangement in the monoclinic structure by the change in C atom location in the structure.