Advantages and limitations of hydrogen peroxide for direct oxidation of methane to methanol at mono-copper active sites in Cu-exchanged zeolites

Abstract

The efficiency of direct catalytic oxidation of methane to methanol (DMTM) is significantly influenced by oxidants. However, realizing a one-pot DMTM using dioxygen remains challenging. Hydrogen peroxide is still the most frequently reported green oxidant for DMTM, with high selectivity for methanol. To gain insight into the influence of oxidants on DMTM performance, we computationally investigated the reaction mechanisms involved in DMTM using H2O2 at mono-copper sites in three types of Cu-exchanged zeolites with different micropore sizes. We identified the advantages and limitations of H2O2 as an oxidant. In contrast to the O–O bond in O2, the O–O bond in H2O2 can be easily broken to produce reactive surface oxygen species, which enable the facile C–H bond activation of methane at a low temperature. However, because of the radical-like process of C–H bond activation at mono-copper sites, actualizing the preferential C–H bond activation of methane is kinetically challenging compared to that of methanol. Moreover, the lower O–H bonding energy of H2O2 would result in self-decomposition of H2O2. Despite these bottlenecks, kinetic analysis shows that improving catalysts to boost the DMTM performance using H2O2 is a promising approach.