CO on a Rh/Fe₃O₄ single-atom catalyst: high-resolution infrared spectroscopy and near-ambient-pressure scanning...

Infrared reflection absorption spectroscopy (IRAS) offers a powerful route to bridging the materials and pressure gaps between surface science and powder catalysis. Using a newly developed IRAS setup optimised for dielectric single crystals, we investigate CO adsorption on the model single-atom catalyst Rh/Fe₃O₄(001). IRAS resolves three species: monocarbonyls at isolated, twofold-coordinated Rh adatoms, monocarbonyls at fivefold-coordinated Rh atoms embedded in the surface, and gem-dicarbonyls at isolated, twofold-coordinated Rh adatoms. Under ultra-high vacuum (UHV) conditions, RhCO monocarbonyl species at adatom sites dominate. Rh(CO)₂gem-dicarbonyl formation is kinetically hindered and occurs predominantly through CO-induced dissociation of Rh dimers rather than sequential adsorption of two CO molecules at an isolated, twofold Rh adatom. The sequential-adsorption pathway to Rh(CO)₂ becomes accessible at millibar CO pressures as evidenced by near-ambient-pressure scanning tunnelling microscopy (NAP-STM). These findings link the UHV behaviour to that expected under realistic reaction conditions. Assignments of the vibrational frequencies to individual species rely on isotopic labelling, thermal treatments, and a review of previous SPM, XPS, and TPD data, supported by density functional theory (DFT)-based calculations. While theory provides qualitative insight, such as the instability of dicarbonyls on fivefold-coordinated Rh atoms, it does not yet reproduce experimental frequencies quantitatively and is sensitive to the computational parameters, highlighting the need for robust experimental benchmarks. The spectroscopic fingerprints established here provide a reliable foundation for identifying Rh coordination environments in oxide-supported single-atom catalysts.