Breaking Simple Scaling Relations through Metal-Oxide Interactions: Understanding Room-Temperature Activation of Methane on M/CeO2 (M = Pt, Ni, or Co) Interfaces.

The clean activation of methane at low temperatures remains an eminent challenge and a field of competitive research. In particular, on late transition metal surfaces such as Pt(111) or Ni(111), higher temperatures are necessary to activate the hydrocarbon molecule, but a massive deposition of carbon makes the metal surface useless for catalytic activity. However, on very low-loaded M/CeO2 (M = Pt, Ni, or Co) surfaces, the dissociation of methane occurs at room temperature, which is unexpected considering simple linear scaling relationships. This intriguing phenomenon has been studied using a combination of experimental techniques (ambient-pressure X-ray photoelectron spectroscopy, time-resolved X-ray diffraction, and X-ray absorption spectroscopy) and density functional theory-based calculations. The experimental and theoretical studies show that the size and morphology of the supported nanoparticles together with strong metal-support interactions are behind the deviations from the scaling relations. These findings point toward a possible strategy for circumventing scaling relations, producing active and stable catalysts that can be employed for methane activation and conversion.