Surface Structure Dependence of SO2 Interaction with Ceria Nanocrystals with Well-Defined Surface Facets

Abstract

The effects of the surface structure of ceria (CeO2) on the nature, strength, and amount of species resulting from SO2 adsorption were studied using in situ IR and Raman spectroscopies coupled with mass spectrometry, along with first-principles calculations based on density functional theory (DFT). CeO2 nanocrystals with different morphologies, namely, rods (representing a defective structure), cubes (100 facet), and octahedra (111 facet), were used to represent different CeO2 surface structures. IR and Raman spectroscopic studies showed that the structure and binding strength of adsorbed species from SO2 depend on the shape of the CeO2 nanocrystals. SO2 adsorbs mainly as surface sulfites and sulfates at room temperature on CeO2 rods, cubes, and octahedra that were either oxidatively or reductively pretreated. The formation of sulfites is more evident on CeO2 octahedra, whereas surface sulfates are more prominent on CeO2 rods and cubes. This is explained by the increasing reducibility of the surface oxygen in the order octahedra < cubes < rods. Bulk sulfites are also formed during SO2 adsorption on reduced CeO2 rods. The formation of surface sulfites and sulfates on CeO2 cubes is in good agreement with our DFT results of SO2 interactions with the CeO2(100) surface. CeO2 rods desorb SO2 at higher temperatures than cubes and octahedra nanocrystals, but bulk sulfates are formed on CeO2 rods and cubes after high-temperature desorption whereas only some surface sulfates/sulfites are left on octahedra. This difference is rationalized by the fact that CeO2 rods have the highest surface basicity and largest amount of defects among the three nanocrystals, so they bind and react with SO2 strongly and are the most degraded after SO2 adsorption cycles. The fundamental understanding obtained in this work on the effects of the surface structure and defects on the interaction of SO2 with CeO2 provides insights for the design of more sulfur-resistant CeO2-based catalysts.