Surface chemistry of supported Ru nanoparticles investigated during CO2 hydrogenation by NAP-XPS

• Al 2 O 3 supported Ru model catalyst is investigated by NAP-XPS under O 2 , CO 2 , CO 2 /H 2. • Stable and reproducible synthesis of size-selected Ru nanoparticles is accomplished. • Overlapping C and Ru region is resolved, including RuO x transient surface oxide. • Ru is reduced under vacuum and reaction conditions as the temperature increases. • C=C species are observed at 350 °C on the catalyst under CO 2 , but not CO 2 + 4 H 2 . In situ investigation of the surface composition of catalyst particles improves the understanding of the active species in heterogeneous catalysis. This study analyzed the surface chemistry of ruthenium nanoparticles supported on alumina during CO 2 methanation. A model ruthenium catalyst was synthesized via DC magnetron sputtering and depositing the size selected 3.3 nm Ru-particles on an Al 2 O 3 sample. The sample was transferred into the analyzing chamber under UHV conditions and analyzed using NAP-XPS. The emitted photoelectrons show that the main oxidation state of Ru after the deposition is RuO x , transient surface oxide. In vacuum, increasing temperature resulted in the reduction of Ru to its metallic state. The hydrogen presence in the methanation feed lowered the temperature required for the reduction from 200 °C to 100 °C. In contrast, the temperature of reduction of RuO x under CO 2 atmosphere increased from 200 °C to 300 °C as CO 2 is a mild oxidant. The reaction intermediates of the CO 2 reduction at 350 °C consist of C–C and C–H bonds, whereas the absence of H 2 leads to the formation of C=C bonds on the surface. The Ru particle size on alumina was investigated by TEM and size stability under reactive conditions was observed over the in-situ experimental timescale of hours.