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 (CH 4 ) into various chemicals under mild reaction conditions is highly desired. Herein, Rh/ZSM‐5 catalyst was reported to convert CH 4 to oxygenates with molecular oxygen (O 2 ) in the presence of CO at low temperature with promising catalytic performance. The oxygenates productivity reached as high as 5638.0 μmol g cat. −1 h −1 . Structure characterization confirmed the existence of highly dispersed Rh 2 O 3 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 H 2 O 2 active species by reacting with O 2 . The as‐obtained *OH, *OOH and H 2 O 2 species will thus render high activity for methane oxidation.