The remarkable performance of a single iridium atom supported on hematite for methane activation: a density functional theory study

Abstract

Methane is the major component of natural gas, and it significantly contributes to global warming. In this study, we investigated methane activation on the α-Fe₂O₃(110) surface and M/α-Fe₂O₃(110) surfaces (M = Ag, Ir, Cu, or Co) using the density-functional theory (DFT) + U method. Our study shows that the Ir/α-Fe₂O₃(110) surface is a more effective catalyst for C–H bond activation than other catalyst surfaces. We have applied electron density difference (EDD), density of states (DOS), and Bader charge calculations to confirm the cooperative CH⋯O and agostic interactions between CH₄ and the Ir/α-Fe₂O₃(110) surface. To further modify the reactivity of the Ir/α-Fe₂O₃(110) surface towards methane activation, we conducted a study of the effect of oxygen vacancy (O_V) on C–H activation and CH₄ dehydrogenation. In the comparison of pristine α-Fe₂O₃(110), Ir/α-Fe₂O₃(110), and Ir/α-Fe₂O₃(110)–O_V surfaces, the Ir/α-Fe₂O₃(110)–O_V surface is the best in terms of CH₄ adsorption energy and C–H bond elongation, whereas the Ir/α-Fe₂O₃(110) surface catalyst has the lowest C–H bond activation barrier for the CH₄ molecule. The calculations indicate that the Ir/α-Fe₂O₃(110)–O_V surface could be a candidate catalyst for CH₄ dehydrogenation reactions.