Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation

Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol−1), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.