Methylamine decomposition on nickel surfaces: A density functional theory study

The adsorption and decomposition of methylamine on Ni(1 1 1), Ni(1 0 0), stepped Ni(1 1 1), and nitrogen atom modified Ni(1 0 0) (denoted N–Ni(1 0 0)) have been studied with the DFT–GGA method using the periodic slab models. The initial scissions of C–H, N–H and C–N bond are considered. The adsorption energies under the most stable configurations for the possible species and the activation energies for the possible initial elementary reactions involved are obtained in the present work. Through systematic exploring of the kinetics mechanism of methylamine decomposition on these four surfaces, it is found that the reactivity of these surfaces decreased with the order of stepped Ni(1 1 1) > Ni(1 0 0) > Ni(1 1 1) > N–Ni(1 0 0). This indicates that the reactivity is related to the openness of the surface, and the presence of nitrogen atom reduces the reactivity of the Ni(1 0 0). For the three reactions, the barriers decreased with the order of C–N > N–H > C–H on Ni(1 1 1) and Ni(1 0 0), whereas they decreased with the order of C–N > C–H > N–H on stepped Ni(1 1 1) and N–Ni(1 0 0).