Inverse single-site Fe1(OH)X/Pt(111) model catalyst for preferential oxidation of CO in H2

Inverse oxide/metal model systems are frequently used to investigate catalytic structure-function relationships at an atomic level. By means of a novel atomic layer deposition process, growth of single-site Fe1Ox on a Pt(111) single crystal surface was achieved, as confirmed by scanning tunneling microscopy (STM). The redox properties of the catalyst were characterized by synchrotron radiation based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). After calcination treatment at 373 K in 1 mbar O-2 the chemical state of the catalyst was determined as Fe3+. Reduction in 1 mbar H-2 at 373 K demonstrates a facile reduction to Fe2+ and complete hydroxylation at significantly lower temperatures than what has been reported for iron oxide nanoparticles. At reaction conditions relevant for preferential oxidation of CO in H-2 (PROX), the catalyst exhibits a Fe3+ state (ferric hydroxide) at 298 K while re-oxidation of iron oxide clusters does not occur under the same condition. CO oxidation proceeds on the single-site Fe-1(OH)(3) through a mechanism including the loss of hydroxyl groups in the temperature range of 373 to 473 K, but no reaction is observed on iron oxide clusters. The results highlight the high flexibility of the single iron atom catalyst in switching oxidation states, not observed for iron oxide nanoparticles under similar reaction conditions, which may indicate a higher intrinsic activity of such single interfacial sites than the conventional metal-oxide interfaces. In summary, our findings of the redox properties on inverse single-site iron oxide model catalyst may provide new insights into applied Fe-Pt catalysis.

Automated summary

Inverse oxide/metal model systems were used to study catalytic structure-function relationships at an atomic level. Single-site Fe1Ox was grown on a Pt(111) single crystal surface using atomic layer deposition, showing high flexibility in oxidation states and higher intrinsic activity compared to iron oxide nanoparticles. The redox properties of the catalyst were characterized by AP-XPS and the catalyst exhibited efficient CO oxidation at lower temperatures than traditional iron oxide clusters.