In
precious metal catalysts, the interaction between the precious
metal and oxide support, denoted the strong metal–support interaction
(SMSI), is closely related to catalytic activity. However, there are
few studies of the effects of the SMSI on catalytic activity and the
properties of catalytic active sites. Therefore, the valence band
spectra of Rh catalysts on various supports were measured using X-ray
photoelectron spectroscopy and a more surface-sensitive experimental
technique, extreme ultraviolet-excited photoelectron spectroscopy.
There is a good correlation between the catalytic activities of these
Rh catalysts in the CO–NO reaction and the energy difference
between the peaks of the Rh metal and Rh2O3 components
in the valence band spectra. The cause of the difference in the activities
of the Rh catalysts on various supports is analyzed based on density
functional theory calculations using two models: Rh metal/support
and Rh2O3/support. Rh metal and Rh2O3 contribute to the activity of the CO–NO reaction.
NO dissociation is promoted on the Rh metal surface, where the SMSI
induces enhanced oxygen adsorption. Conversely, CO oxidation is promoted
on the Rh2O3 surface, where the oxygen bonding
is weakened by the SMSI. This study reveals the critical mechanisms
whereby SMSIs contribute to oxygen-mediated reactions on catalyst
surfaces.