Effects of deposited Pt particles on the reducibility of CeO2(111)

Abstract

The interaction of Pt particles with the regular CeO₂(111) surface has been studied using Pt₈ clusters as representative examples. The atomic and electronic structure of the resulting model systems have been obtained through periodic spin-polarized density functional calculations using the PW91 exchange-correlation potential corrected with the inclusion of a Hubbard U parameter. The focus is on the effect of the metal–support interaction on the surface reducibility of ceria. Several initial geometries and orientations of Pt₈ with respect to the ceria substrate have been explored. It has been found that deposition of Pt₈ over the ceria surface results in spontaneous oxidation of the supported particle with a concomitant reduction of up to two Ce⁴⁺ cations to Ce³⁺. Oxygen vacancy formation on the CeO₂(111) surface and oxygen spillover to the adsorbed particle have also been considered. The presence of the supported Pt₈ particles has a rather small effect (∼0.2 eV) on the O vacancy formation energy. However, it is predicted that the spillover of atomic oxygen from the substrate to the metal particle greatly facilitates the formation of oxygen vacancies: the calculated energy required to transfer an oxygen atom from the CeO₂(111) surface to the supported Pt₈ particle is only 1.00 eV, i.e. considerably smaller than 2.25 eV necessary to form an oxygen vacancy on the bare regular ceria surface. This strongly suggests that the propensity of ceria systems to store and release oxygen is directly affected by the presence of supported Pt particles.