Boosting Direct Oxidation of Methane with Molecular Oxygen at Low Temperature over Rh/ZSM‐5 Catalyst

Abstract As a clean fossil energy and chemical feedstock, development of breakthrough strategies for direct conversion of methane (CH4) into various chemicals under mild reaction conditions is highly desired. Herein, Rh/ZSM‐5 catalyst was reported to convert CH4 to oxygenates with molecular oxygen (O2) in the presence of CO at low temperature with promising catalytic performance. The oxygenates productivity reached as high as 5638.0 μmol gcat.−1 h−1. Structure characterization confirmed the existence of highly dispersed Rh2O3 nanoparticles with an average diameter of 2.4 nm in the Rh/ZSM‐5 catalyst. Based on control experiments and mechanism study, it was suggested that CO plays a pivotal role over the Rh/ZSM‐5 catalyst to boost direct oxidation of methane. CO participates in water‐gas‐shift reaction to produce in‐situ H species, which enables to form *OH, *OOH and H2O2 active species by reacting with O2. The as‐obtained *OH, *OOH and H2O2 species will thus render high activity for methane oxidation.