The structural evolution of Mo₂C and Mo₂C/SiO₂ under dry reforming of methane conditions: morphology and support effects

The thermal carburization of MoO₃ nanobelts (nb) and SiO₂-supported MoO₃ nanosheets under a 1 : 4 mixture of CH₄ : H₂ yields Mo₂C-nb and Mo₂C/SiO₂. Following this process by in situ Mo K-edge X-ray absorption spectroscopy (XAS) reveals different carburization pathways for unsupported and supported MoO₃. In particular, the carburization of α-MoO₃-nb proceeds via MoO₂, and that of MoO₃/SiO₂via the formation of highly dispersed MoO_x species. Both Mo₂C-nb and Mo₂C/SiO₂ catalyze the dry reforming of methane (DRM, 800 °C, 8 bar) but their catalytic stability differs. Mo₂C-nb shows a stable performance when using a CH₄-rich feed (CH₄ : CO₂ = 4 : 2), however deactivation due to the formation of MoO₂ occurs for higher CO₂ concentrations (CH₄ : CO₂ = 4 : 3). In contrast, Mo₂C/SiO₂ is notably more stable than Mo₂C-nb under the CH₄ : CO₂ = 4 : 3 feed. The influence of the morphology of Mo₂C and its dispersion on silica on the structural evolution of the catalysts under DRM is further studied by in situ Mo K-edge XAS. It is found that Mo₂C/SiO₂ features a higher resistance to oxidation under DRM than the highly crystalline unsupported Mo₂C-nb and this correlates with an improved catalytic stability. Lastly, the oxidation of Mo in both Mo₂C-nb and Mo₂C/SiO₂ under DRM conditions in the in situ XAS experiments leads to an increased activity of the competing reverse water gas shift reaction.