Hydrogenated Molybdenum Oxide Overlayers Formed on Mo Nitride Nanosheets in Ambient-Pressure CO₂/H₂ Gases

Transition metal nitrides (TMN) often exhibit high catalytic activity in many important reactions. Due to their low stability in a reaction environment, it remains as a crucial issue to reveal surface active structures in catalytic reactions, particularly for the cases containing both oxidative and reductive gases. Herein, MoN and Mo₂N nanosheets have been constructed on Al₂O₃(0001) and Au foil surfaces, and in situ surface characterizations are performed on the model catalysts in ambient-pressure CO₂, H₂, and CO₂ + H₂ gases. In situ Raman spectroscopy and quasi in situ X-ray photoelectron spectroscopy (XPS) analysis indicate that MoO₃ and defective MoO_3- overlayers form on both MoN and Mo₂N surfaces in CO₂, and the surface oxidation occurs under a milder condition on Mo₂N than on MoN. Further, a hydrogenated Mo oxide (HMoO_3-) overlayer forms in a CO₂ + H₂ atmosphere, as confirmed using quasi in situ XPS and time-of-flight secondary ion mass spectroscopy. The surface analysis over the model nitride catalysts suggests that O and/or H atoms may be incorporated into surface layers to form the active structure in many O and H-containing reactions.