Density-functional theory study of the reaction pathway for methanol demethanation on (n = 3,4)

Minimum-energy pathways for the demethanation reaction CH3OH + Ni n + (n = 3,4)→NinO+ + CH4 have been computed to examine why this reaction occurs preferentially on Ni 4 + . Stationary points of paths for the demethanation of CH3OH on Ni n + (n = 3,4), which provide possible reaction pathways, were characterized and the associated activation barriers were evaluated on both Ni 3 + and Ni 4 + via density-functional theory calculations. On Ni 4 + , all the transition states along the minimum-energy path are energetically below the reactant asymptote, whereas on Ni 3 + , the transition states are above it.