Fundamental Science on Oxygen Storage Capacity of Cerium Complex Oxides for Advanced On-Board Diagnostics (1) Kinetic Observation of Cerium Valence Change Using Synchrotron Radiation

<div class="section abstract"><div class="htmlview paragraph">On-board diagnosis (OBD) of gasoline vehicle emissions is detected by measuring the fluctuations of the rear oxygen sensor due to the time-dependent deterioration of the oxygen storage capacity (OSC) contained in the automotive catalyst materials. To detect OBD in various driving modes of automobiles with an order of magnitude higher accuracy than before, it is essential to understand the OSC mechanism based on fundamental science.</div><div class="htmlview paragraph">In this study, time-resolved dispersive X-ray absorption fine structure (DXAFS) using synchrotron radiation was used to carry out a detailed analysis not only of the OSC of ceria-based complex oxides, which had previously been roughly understood, but also of how differences in design parameters such as the type of precious metals, reducing gases (CO and H<sub>2</sub>), detection temperatures, and mileages (degree of deteriorations) affect the OSC rate in a fluctuating redox atmosphere.</div><div class="htmlview paragraph">A fundamental characteristic was clearly demonstrated in ceria-based complex oxides: the oxygen release rate accompanying the generation of oxygen vacancies is overwhelmingly slower than the oxygen storage rate that restores the crystal structure. Another interesting result was revealed: when precious metals are supported, a competitive reaction occurs between the precious metal and the ceria-based complex oxide in the release/storage of oxygen, and the change in cerium valence from tetravalent to trivalent actually slows down. Furthermore, it was proven that CZY is more durable than CZ in terms of both OSC rate and amount. In this way, the basic scientific properties of ceria-based complex oxides, which are necessary for designing OBD logic, have been clarified.</div></div>