Mechanistic Insight into the Formation of Acetic Acid from the Direct Conversion of Methane and Carbon Dioxide on Zinc-Modified H–ZSM-5 Zeolite

Abstract

Methane and carbon dioxide are known greenhouse gases, and the conversion of these two C₁-building blocks into useful fuels and chemicals is a subject of great importance. By solid-state NMR spectroscopy, we found that methane and carbon dioxide can be co-converted on a zinc-modified H–ZSM-5 zeolite (denoted as Zn/H–ZSM-5) to form acetic acid at a low temperature range of 523–773 K. Solid-state ¹³C and ¹H MAS NMR investigation indicates that the unique nature of the bifunctional Zn/H–ZSM-5 catalyst is responsible for this highly selective transformation. The zinc sites efficiently activate CH₄ to form zinc methyl species (−Zn–CH₃), the Zn–C bond of which is further subject to the CO₂ insertion to produce surface acetate species (−Zn–OOCCH₃). Moreover, the Brønsted acid sites play an important role for the final formation of acetic acid by the proton transfer to the surface acetate species. The results disclosed herein may offer the new possibility for the efficient activation and selective transformation of methane at low temperatures through the co-conversion strategy. Also, the mechanistic understanding of this process will help to the rational design of robust catalytic systems for the practical conversion of greenhouse gases into useful chemicals.