CO Activation over Nanoshaped CeO Decorated with Nickel for Low-Temperature Methane Dry Reforming.

Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into H and CO (syngas). CeO nanorods, nanocubes, and nanospheres were decorated with 1-4 wt % Ni. The materials were structurally characterized using TEM and XANES/EXAFS. The CO activation was analyzed by DFT and temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO morphologies expose {111} and {100} terminating facets, varying the strength of the CO interaction and redox properties, which influence the CO activation. Temperature-programmed CO DRIFTS analysis revealed that under hydrogen-lean conditions mono- and bidentate carbonates are hydrogenated to formate intermediates, which decompose to HO and CO. In excess hydrogen, methane is the preferred reaction product. The CeO cubes favor the formation of a polydentate carbonate species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria's surface, resulting in less-abundant surface sites for CO dissociation.