Mechanisms of Transforming CH _x to CO on Ni(111) Surface by Density Functional Theory

Abstract

To elucidate feasible routes of producing CO from CH₃ and unravel the effect of adsorbed O on CH _x transformation, the reactivity of CH _x (x = 1–3) with and without the assistance of adsorbed atomic O on Ni(111) was explored using density functional theory calculations. The adsorption energies of CH _x (x = 0–3) were found to be significantly reduced on an O-preadsorbed Ni(111) surface compared to a pure surface. Furthermore, O-assisted one-step dehydrogenation of CH _x (x = 1–3) features energy barriers and thus is difficult to proceed. In terms of energy, the direct dissociation of CH₃ is favorable, except for the last CH dehydrogenation, which is energy intensive. Interestingly, in O-assisted two-step CH transformation to CO via CHO intermediate, the barrier is dramatically lowered. The successive dehydrogenations of CH _xO (x = 1–3) were also found to be a route for CO formation. Finally, two possible pathways from CH₃ to CO are proposed: (a) CH₃ → CH₂ → CH → CHO → CO; (b) CH₃ → CH₃O → CH₂O → CHO → CO.

Keywords

Density functional theory / CH _x transformation / CO / Ni(111)

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