Ni3X-type alloy catalysts for dry reforming of methane with high catalytic activity and stability: A density functional theory study

Ni-based catalysts are considered as one of the most promising Methane dry reforming (DRM) reaction catalysts for large-scale industrial applications due to their low cost and high efficiency. However, the inactivation problem caused by carbon deposition limits their application. In this study, we calculated the catalytic activity and carbon deposition resistance of 14 Ni3X-type (X = V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Nb, Mo, Rh, Sn, Sb) alloy catalysts by density functional theory (DFT). Ni-based catalysts with high catalytic activity were predicted based on the reactants activation ability of the catalysts. Carbon deposition resistance of the catalysts is predicted from three aspects: the difficulty of C species generation, the difficulty of C species removal and the difference of C* and O* generation ability. We also explored the measurement of catalyst activity and stability through descriptors. Finally, Ni3X alloys with high activity and stability, such as Ni3V, Ni3Cr, Ni3Mn, Ni3Nb, and Ni3Mo, were selected and considered to have high potential application value. Among them, the superiority of Ni3Mo catalytic performance was further verified through reaction mechanism and microkinetic modeling. Our work can explain some existing studies and provide new insights for the research of new Ni-based catalysts.