Structure design and mechanism study of Sc@P10C12M2 catalysts for methanol dehydrogenation to methyl formate

The Sc@P10C12M2 catalysts were first constructed and utilized for methanol conversion reaction. In this work, DFT-D3 calculations were employed to investigate the conversion of CH3OH to CHOOCH3 on four different types of the Sc@P10C12M2 catalysts (M = Fe, Co, Ni, and Cu). The results indicate that the selectivity and formation activity of CHOOCH3 are influenced by the choice of metals. Specifically, the Sc@P10C12Ni2 catalyst demonstrates superior catalytic activity with an activation free energy and activity of 0.64 eV and 1.97 lgk/s−1 for the rate-limiting step at 298 K. This research reveals a structure–activity relationship for Sc@P10C12M2 catalysts, highlighting that catalytic performance is correlated with metal types, spin states, and charges. These insights provide theoretical guidance for the rational design of efficient methanol conversion catalysts.