MoS 2 Catalysts Selectively Achieve High Yield of Liquid Oxygenate from Direct Conversion of Methane via Hydroxyl Radicals
Steven L. Farrell, Juan D. Jiménez, Dominik Wierzbicki, Jie Zhang, Anna X. Chen, Jordi Llorca, AM Milinda Abeykoon, Uddhav Kanbur, Yuting Li, Long Qi, Shannon M. Mahurin, Michelle K. Kidder, Emanuele Telari, Albert Bruix, Arephin Islam, Akhil Tayal, Jorge Moncada, Ayaskanta Sahu, Eli Stavitski, Sanjaya D. SenanayakeABSTRACT
Directly converting methane (CH 4 ) into liquid oxygenates (e.g., methanol) can circumvent the cost and engineering limits of natural gas transportation and storage. However, oxygenate yields from CH 4 remain low, and sulfur present in natural gas hinders activity in most catalysts. To overcome these barriers, we employ bulk molybdenum disulfide (MoS 2 ), a low‐cost, robust catalyst which selectively produces large quantities of liquid oxygenates (>900 µmol/g cat ∙hr) from methane in the presence of hydroxyl (OH • ) radicals produced from dilute hydrogen peroxide (H 2 O 2 ) at 75°C. Under realistic reaction conditions, MoS 2 partially and reversibly adopts a metastable, more electrically conductive phase (1T’) that can only be observed through in situ structural probes. Herein, we elucidate that redox synergy between H 2 O 2 and MoS 2 produces active OH • radical species that selectively transform CH 4 to surface methoxy species at the gas‐solid liquid interface, leading to the unitary production of liquid oxygenate at a rate competitive with more costly precious metal catalysts, without additional catalyst preparation steps.