Surface Reduction State Determines Stabilization and Incorporation of Rh on α‐Fe2O3(11¯02)

• DOI: 10.1002/admi.202001908
• Publication Date: 2021-02-07T22:03:35Z
• Authors: Florian Kraushofer; Nikolaus Resch; Moritz Eder; Ali Rafsanjani‐Ab...; Sarah Tobisch; Zdenek Jakub; Giada Franceschi; Michele Riva; Matthias Meier; Michael Schmid; Ulrike Diebold; Gareth S. Parkinson
• Keywords: Condensed Matter - Materials Science; Materials Science (cond-mat.mtrl-sci); FOS: Physical sciences; 01 natural sciences; ddc:; 0104 chemical sciences

AbstractIron oxides (FeOx) are among the most common support materials utilized in single atom catalysis. The support is nominally Fe2O3, but strongly reductive treatments are usually applied to activate the as‐synthesized catalyst prior to use. Here, Rh adsorption and incorporation on the () surface of hematite (α‐Fe2O3) are studied, which switches from a stoichiometric (1 × 1) termination to a reduced (2 × 1) reconstruction in reducing conditions. Rh atoms form clusters at room temperature on both surface terminations, but Rh atoms incorporate into the support lattice as isolated atoms upon annealing above 400 °C. Under mildly oxidizing conditions, the incorporation process is so strongly favored that even large Rh clusters containing hundreds of atoms dissolve into the surface. Based on a combination of low‐energy ion scattering (LEIS), X‐ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) data, as well as density functional theory (DFT), it is concluded that the Rh atoms are stabilized in the immediate subsurface, rather than the surface layer.