The conversion of CO2 and CH4 to acetic acid over the Au-exchanged ZSM-5 catalyst: a density functional theory study

Abstract

The direct conversion of methane and carbon dioxide to acetic acid is one of the most challenging research topics. Using the density functional theory (M06-L) the study reveals the catalytic activity of the Au(I)-ZSM-5 zeolite in this reaction. The Au(I)-ZSM-5 is represented by a 34T quantum cluster model. The activation of the C–H bond over the Au-ZSM-5 zeolite would readily take place via the homolytic σ-bond activation with an energy barrier of 10.5 kcal mol⁻¹, and subsequent proton transfer from the Au cation to the zeolitic oxygen, yielding the stable methyl–gold complex adsorbed on the zeolite Brønsted acid. The conversion of CO₂ on this bi-functional catalyst involves the Brønsted acid site playing a role in the protonation of CO₂ and the methyl–gold complex acting as a methylating agent. The activation energy of 52.9 kcal mol⁻¹ is predicted.