CO2 Activation on Ni(111) and Ni(110) Surfaces in the Presence of Hydrogen

The structure sensitivity of CO₂ activation in the presence of H₂ has been identified by ambient-pressure X-ray photoelectron spectroscopy (APXPS) on Ni(111) and Ni(110) surfaces under identical reaction conditions. Based on the APXPS results and computer simulations, we propose that, around room temperature, the hydrogen-assisted activation of CO₂ is the major reaction path on Ni(111), while the redox pathway of CO₂ prevails on Ni(110). With increasing temperature, the two activation pathways are activated in parallel. While the Ni(111) surface is fully reduced to the metallic state at elevated temperatures, two stable Ni oxide species can be observed on Ni(110). Turnover frequency measurements indicate that the low-coordinated sites on Ni(110) promote the activity and selectivity of CO₂ hydrogenation to methane. Our findings provide insights into the role of low-coordinated Ni sites in nanoparticle catalysts for CO₂ methanation.