Theoretically Predicted CO Adsorption and Activation on the Co-Doped hcp-Fe7C3 Catalyst

The Hcp-Fe7C3 phase has attracted more attention due to the high catalytic activity in Fischer-Tropsch synthesis (FTS) reactions. In this work, the adsorption and activation of CO on a Co-doped hcp-Fe7C3 catalyst were investigated by density functional theory (DFT) in order to understand the effect of Co doping on the initial step of FTS reactions on iron-based catalysts. Different Co-doped hcp-Fe7C3 001 and 11 over bar 0 surfaces were constructed, and the CO adsorption configurations were studied. The calculated results show that the structure of the 001 surface remains basically unchanged after doping with Co atoms, while the replacement of Fe or C atoms on 11 over bar 0 surfaces with Co atoms has a significant impact on the surface structure. The top sites on the doped Co atoms of hcp-Fe7C3 are disadvantages for the CO adsorption, whereas the T, 2F, or 3F sites around the doped Co atoms are beneficial for promoting the adsorption of CO. The CO direct dissociation pathways on the four types of Co-doped hcp-Fe7C3 001 surfaces are exothermic, while the H-assisted dissociation pathways of CO are endothermic. The H-assisted activation via HCO on the 3F1 site of the 2Co2-doped hcp-Fe7C3 001 surface shows the lowest energy barrier of 1.96 eV. For the Co-doped hcp-Fe7C3 11 over bar 0 surfaces, the H-assisted activation via HCO is the preferred activation pathway for CO on the Co-doped surfaces with the energy barrier of approximately 1.30 eV.