The methane dry reforming (DRM) reaction mechanism was explored via mechanochemically prepared Pd/CeO2 catalysts (PdAcCeO2M), which yield unique Pd-Ce interfaces, where PdAcCeO2M has a distinct reaction mechanism and higher reactivity for DRM relative to traditionally synthesized impregnated Pd/CeO2 (PdCeO2IW). In situ characterization and density functional theory calculations revealed that the enhanced chemistry of PdAcCeO2M can be attributed to the presence of a carbon-modified Pd0 and Ce4+/3+ surface arrangement, where distinct Pd-CO intermediate species and strong Pd-CeO2 interactions are activated and sustained exclusively under reaction conditions. This unique arrangement leads to highly selective and distinct surface reaction pathways that prefer the direct oxidation of CHx to CO, identified on PdAcCeO2M using isotope labeled diffuse reflectance infrared Fourier transform spectroscopy and highlighting linear Pd-CO species bound on metallic and C-modified Pd, leading to adsorbed HCOO [1595 cm-1] species as key DRM intermediates, stemming from associative CO2 reduction. The milled materials contrast strikingly with surface processes observed on IW samples (PdCeO2IW) where the competing reverse water gas shift reaction predominates.
