Ceria has been widely used as support in electrocatalysis for its high degree of oxygen storage, fast oxygen mobility, and reduction and oxidation properties at mild conditions. However, it is unclear what are the underlying principles and the nature of surface involved. By controlling the growth of various morphologies of ceria nanoparticles, it is demonstrated that the cubic-form of ceria, predominantly covered with higher energy polar surface (100), as support for Pd gives much higher activity in the electrocatalytic oxidation of formic acid than ceria of other morphologies (rods and spheres) with low-indexed facets ((110) and (111)). High-resolution transmission electron spectroscopy confirms the alternating layer-to-layer of cations and anions in (100) surface, and the electrostatic repulsion of oxygen anions within the same layers gives intrinsically higher oxygen vacancies on this redox active surface in order to reduce surface polarity. Density functional theory calculations suggest that the properties of fast oxygen mobility to reoxidize the CO-poisoned Pd may arise from the overdosed oxygens on these ceria surface layers during electro-oxidation hence sustaining higher activity.

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