Molybdenum carbide and oxycarbide from carbon-supported MoO₃ nanosheets: phase evolution and DRM catalytic activity...

Molybdenum carbide (β-Mo₂C) supported on carbon spheres was prepared via a carbothermal hydrogen reduction (CHR) method from delaminated nanosheets of molybdenum(vi) oxide (d-MoO₃/C). The carburization process was followed by combined in situ XANES/XRD analysis revealing the formation of molybdenum oxycarbide Mo₂C_xO_y as an intermediate phase during the transformation of d-MoO₃/C to β-Mo₂C/C. It was found that Mo₂C_xO_y could not be completely carburized to β-Mo₂C under a He atmosphere at 750 °C, instead a reduction in H₂ is required. The β-Mo₂C/C obtained showed activity and stability for the dry reforming of methane at 800 °C and 8 bar. In situ XANES/XRD evaluation of the catalyst under DRM reaction conditions combined with high resolution TEM analysis revealed the evolution of β-Mo₂C/C to Mo₂C_xO_y/C. Notably, the gradual oxidation of β-Mo₂C/C to Mo₂C_xO_y/C correlates directly with the increased activity of the competing reverse water gas shift reaction.