The enhanced reducibility of the surface of ceria relative to the bulk has long been established. Several studies also show that ceria nanoparticles with different facets exhibit different catalytic activities. Despite consensus that the activity is correlated with the surface Ce3+ concentration, experimental measurements of this concentration as a function of termination are lacking. Here, X-ray absorption near-edge spectroscopy (XANES) is used to quantify the Ce3+ concentration in films with (001), (110), and (111) surface terminations under reaction relevant conditions. While an enhanced Ce3+ concentration is found at the surfaces, it is surprisingly insensitive to film orientation.
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This work was supported primarily by NSF DMR-1505103. The XANES experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Part of this work made use of the Pulsed Laser Deposition Shared Facility and the X-ray Diffraction Facility at the Materials Research Center at Northwestern University, supported by the National Science Foundation MRSEC program (DMR-1720139) and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205).
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Yuan, W., Haile, S.M. Insensitivity of the extent of surface reduction of ceria on termination: comparison of (001), (110), and (111) faces. MRS Communications 10, 636–641 (2020). https://doi.org/10.1557/mrc.2020.73