Crystal facet engineering of semiconductors has been proven to be an effective strategy to increase photocatalytic performances. However, the mechanism involved in the photocatalysis is not yet known. Herein, we report our success in that photocatalytic performances of the Cl(-) ion capped CoO octahedrons with exposed {111} facets were activated by a treatment using AgNO3 and NH3·H2O solutions. The clean CoO {111} facets were found to be highly reactivity faces. On the basis of the polar structure of the exposed {111} surfaces, a charge separation model between polar {111} surfaces is proposed. There is an internal electric field between polar {111} surfaces due to the spontaneous polarization. The internal electric field provides a driving force for charge separation. The reduction and oxidation reactions selectively take place on the positive and negative polar {111} surfaces. The charge separation model provides a clear insight into charge transfer in the semiconductor nanocrystals with high photocatalytic activities and offer guidance to design more effective photocatalysts, solar cells, photoelectrodes, and other photoelectronic devices.

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