Bulk and surface analysis of Hägg Fe carbide(Fe5C2): a density functional theory study

Abstract

A comprehensive density functional theory (DFT) study analysingthe bulk and various low Miller index surfaces of Hägg Fe carbide(Fe5C2), considered to be the active phase in Fe-catalysed Fischer–Tropsch synthesis (FTS),has been carried out. The DFT determined bulk structure of Hägg Fe carbide(Fe5C2) is found to be in good agreement with reported monoclinic(C 2/c) XRD data, independently of whether a monoclinic(C 2/c) or triclinic () bulk structure is used as input for calculations. Attention is focused on the constructionof a surface energy stability trend with subsequent correlation with particular surfaceproperties. It is found that a (010) Miller index plane results in the most stable surface(2.468 J m−2), while a (101) surface is the least stable(3.281 J m−2). The systematic comparison of calculated surface energies with surface properties such asthe number of dangling bonds and surface atom density (within a broken bond model), aswell as unrelaxed surface energies, relative ruggedness of surfaces, degree of surfacerelaxation upon optimization, total spin density changes of surfaces compared to the bulk,etc, result in only an approximate correlation with the surface stability trend in selectedcases. From the results it is concluded that the relative surface energies fall in a narrowrange and that a large number of additional surfaces may be defined, e.g. fromhigher Miller index planes, sharing similar surface energy values. The results serveto demonstrate the rich complexity and diverse nature of the Fe carbide phaseresponsible for FTS, effectively laying the foundation for further fundamental studies.