Unraveling CO adsorption on model single-atom catalysts

J. Hulva, M. Meier, R. Bliem, Z. Jakub, F. Kraushofer, M. Schmid, U. Diebold, C. Franchini, G. S. Parkinson

Institut für Angewandte Physik, TU Wien, 1040 Wien, Austria
Computational Materials Physics, University of Vienna, 1090 Wien, Austria
Università di Bologna, Bologna, Italy
Advanced Research Center for Nanolithography, 1098XG Amsterdam, Netherlands

Science 371 (2021) 375-379

Understanding how the local environment of a "single-atom" catalyst affects stability and reactivity remains a challenge. We present an in-depth study of copper1, silver1, gold1, nickel1, palladium1, platinum1, rhodium1, and iridium1 species on Fe3O4(001), a model support in which all metals occupy the same twofold-coordinated adsorption site upon deposition at room temperature. Surface science techniques revealed that CO adsorption strength at single metal sites differs from the respective metal surfaces and supported clusters. Charge transfer into the support modifies the d-states of the metal atom and the strength of the metal-CO bond. These effects could strengthen the bond (as for Ag1-CO) or weaken it (as for Ni1-CO), but CO-induced structural distortions reduce adsorption energies from those expected on the basis of electronic structure alone. The extent of the relaxations depends on the local geometry and could be predicted by analogy to coordination chemistry.

Corresponding author: Gareth S. Parkinson (parkinson at iap_tuwien_ac_at).

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