Surfactant-mediated morphology evolution and self-assembly of cerium oxide nanocrystals for catalytic and supercapacitor applications

Surfactant plays a remarkable role in determining the growth process (facet exposition) of colloidal nanocrystals (NCs) and the formation of self-assembled NC superstructures, the underlying mechanism of which, however, still requires elucidation. In this work, the mechanism of surfactant-mediated morphology evolution and self-assembly of CeO2 nanocrystals is elucidated by exploring the effect that surfactant modification has on the shape, size, exposed facets, and arrangement of the CeO2 NCs. It is directly proved that surfactant molecules determine the morphologies of the CeO2 NCs by preferentially bonding onto Ce-terminated {100} facets, changing from large truncated octahedra (mostly {111} and {100} exposed), to cubes (mostly {100} exposed) and small cuboctahedra (mostly {100} and {111} exposed) by increasing the amount of surfactant. The exposure degree of the {100} facets largely affects the concentration of Ce3+ in the CeO2 NCs, thus the cubic CeO2 NCs exhibit superior oxygen storage capacity and excellent supercapacitor performance due to a high fraction of exposed active {100} facets with great superstructure stability.