Enhancing the performance of a novel CoRu/CeO2 bimetallic catalyst for the dry reforming of methane via a mechanochemical process

A mechanochemical synthesis method has been used to synthesize CoRu nanoparticles supported on CeO2 for methane dry reforming. In this work, we study the effect of Ru addition to Co/CeO2-based catalysts and of the synthesis method by screening their catalytic activity, using synchrotron X-ray diffraction (XRD), and operando near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). Ruthenium addition directly impacts the reducibility of cobalt species and results in smaller particle sizes, as demonstrated by H2-temperature programmed reduction and XRD. NAP-XPS shows that Ru modifies the metal-support interaction, as evidenced by the higher Ce3+/Ce ratios for the bimetallic samples and tuning the oxidation state of Ru. The synthesis method also influences the dispersion of Co and Ru on the surface. Mechanochemically-prepared samples (mono- and bimetallic) outperformed the conventionally-synthesized counterparts by reaching higher CH4 and CO2 conversions, resulting in a stable CoRu/CeO2 catalyst for 24 h at 700 °C and yielding an H2/CO ratio close to 1.