Density-functional calculations of the conversion of methane to methanol on platinum-decorated sheets of graphene oxide

Abstract

By means of calculations based on density-functional theory (DFT), we have investigated the conversion of methane on two platinum atoms supported with a graphene-oxide sheet (Pt₂/GO). In our calculations, a CH₄ molecule can be adsorbed around the Pt atoms of the Pt₂/GO sheet with adsorption energies within −0.11 to −0.53 eV; an elongated C–H bond indicates that Pt atoms on that sheet can activate the C–H bond of a CH₄ molecule. The role of the GO sheet in the activation of CH₄ was identified according to an analysis of the electronic density: the GO sheet induces the d-band of Pt atoms to generate several specific d_z² state features above the Fermi level, which enabled the activation of the C–H bond of CH₄ in generating an evident area of overlap with the hydrogen s orbital of the C–H bond. Upon a dioxygen molecule being added onto the Pt₂/GO sheet, this molecule can react with activated CH₄ according to mechanisms of form , and restore the original Pt₂/GO sheet.