Simple mechanisms of CH4 reforming with CO2 and H2O on a supported Ni/ZrO2 catalyst

Abstract

To understand the metal–support interaction of oxide supported transition metal catalysts, we computed the reaction mechanisms of dry and steam reforming of methane on a tetragonal ZrO₂(101) supported Ni catalyst. Based on the limited number of active sites on the surface, an irregular and non-ideal Ni₁₃ cluster on ZrO₂(101) is identified as a catalyst. A simple reaction mechanism is proposed, and the first direct dissociation step of CO₂, CH₄ and H₂O is the most difficult based on the computed Gibbs free energies and no surface CH_XO and CH_XOH intermediates are involved, different from that on the flat Ni(111) surface. Analysis of other supported nickel catalysts shows that not only the support but also the size and shape of the metal clusters play an important role in the reaction mechanisms and kinetics.