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/SiO2 via 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.

Exploiting two-dimensional morphology of molybdenum oxycarbide to enable efficient catalytic dry reforming of methane.

The two-dimensional morphology of molybdenum oxycarbide (2D-Mo2COx) nanosheets dispersed on silica is found vital for imparting high stability and catalytic activity in the dry reforming of methane. Here we report that owing to the maximized metal utilization, the specific activity of 2D-Mo2COx/SiO2 exceeds that of other Mo2C catalysts by ca. 3 orders of magnitude. 2D-Mo2COx is activated by CO2, yielding a surface oxygen coverage that is optimal for its catalytic performance and a Mo oxidation state of ca. +4. According to ab initio calculations, the DRM proceeds on Mo sites of the oxycarbide nanosheet with an oxygen coverage of 0.67 monolayer. Methane activation is the rate-limiting step, while the activation of CO2 and the C-O coupling to form CO are low energy steps. The deactivation of 2D-Mo2COx/SiO2 under DRM conditions can be avoided by tuning the contact time, thereby preventing unfavourable oxygen surface coverages.

Molybdenum carbide and oxycarbide from carbon-supported MoO3 nanosheets: phase evolution and DRM catalytic activity assessed by TEM and in situ XANES/XRD methods.

Molybdenum carbide (ß-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 Mo2CxOy as an intermediate phase during the transformation of d-MoO3/C to ß-Mo2C/C. It was found that Mo2CxOy could not be completely carburized to ß-Mo2C under a He atmosphere at 750 °C, instead a reduction in H2 is required. The ß-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 ß-Mo2C/C to Mo2CxOy/C. Notably, the gradual oxidation of ß-Mo2C/C to Mo2CxOy/C correlates directly with the increased activity of the competing reverse water gas shift reaction.