Probing Catalytic Sites and Adsorbate Spillover on Ultrathin FeO<sub>2-<i>x</i></sub> Film on Ir(111) during CO Oxidation.

Yin, Hao; Yan, Yu-Wei; Fang, Wei; Brune, Harald · ACS Nano · 2024

basic_science · Level V

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Abstract

The spatially resolved identification of active sites on the heterogeneous catalyst surface is an essential step toward directly visualizing a catalytic reaction with atomic scale. To date, ferrous centers on platinum group metals have shown promising potential for low-temperature CO catalytic oxidation, but the temporal and spatial distribution of active sites during the reaction and how molecular-scale structures develop at the interface are not fully understood. Here, we studied the catalytic CO oxidation and the effect of co-adsorbed hydrogen on the FeO<sub>2-<i>x</i></sub>/Ir(111) surface. Combining scanning tunneling microscopy (STM), isotope-labeled pulse reaction measurements, and DFT calculations, we identified both FeO<sub>2</sub>/Ir and FeO<sub>2</sub>/FeO sites as active sites with different reactivity. The trilayer O-Fe-O structure with its Moiré pattern can be fully recovered after O<sub>2</sub> exposure, where molecular O<sub>2</sub> dissociates at the FeO/Ir interface. Additionally, as a competitor, dissociated hydrogen migrates onto the oxide film with the formation of surface hydroxyl and water clusters down to 150 K.