Pt metal-CeO2 interaction: direct observation of redox coupling between Pt0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce(0.98)Pt(0.02)O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study.

Pt ions-CeO(2) interaction in Ce(1-x)Pt(x)O(2-delta) (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO(2) and Ce(0.98)Pt(0.02)O(2-delta) mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt(0) to Pt(2+) and Pt(4+) state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) reduces to CeO(2-y) (y=0.35) after applying 1.2 V, which is not reversible; Ce(0.98)Pt(0.02)O(2-delta) reaches a steady state with Pt(2+):Pt(4+) in the ratio of 0.60:0.40 and Ce(4+):Ce(3+) in the ratio of 0.55:0.45 giving a composition Ce(0.98)Pt(0.02)O(1.74) at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce(0.98)Pt(0.02)O(1.95) to Ce(0.98)Pt(0.02)O(1.74) within the potential range of 0.0-1.2 V. Thus, Ce(0.98)Pt(0.02)O(2-delta) forms a stable electrode for oxidation of H(2)O to O(2) unlike CeO(2). A linear relation between oxidation of Pt(2+) to Pt(4+) with simultaneous reduction in Ce(4+) to Ce(3+) is observed demonstrating Pt-CeO(2) metal support interaction is due to reversible Pt(0)/Pt(2+)/Pt(4+) interaction with Ce(4+)/Ce(3+) redox couple.