This chapter reviews the classification and synthesis of the yolk–shell structure, as well as an overview of the current application of the structure in the field of photoelectrocatalysis, aiming to use the yolk–shell structure to be effectively utilized in heterogeneous photoelectrocatalytic reactions. It enhances the scattering of light in the empty shell and efficiently utilizes light while providing a large enough surface to create more active sites, both of them also can significantly improve charge utilization efficiency, and then to improve photoelectrocatalysis performance. The yolk–shell structure provides an ideal platform for more efficient use of carriers. All photocatalytic reactions are driven by carriers, and the charge utilization efficiency of each step determines the overall performance of photocatalysis. Photoelectrocatalysis is a promising method to directly convert solar energy into chemical energy. It is an important research direction in which morphology determines properties in recent years. Due to its unique structural characteristics, the yolk–shell structure integrates the properties of the internal and external materials and complements each other’s deficiencies. The yolk–shell (core–shell) is an orderly assembled structure formed by one nanomaterial encapsulating another nanomaterial through chemical bonds or other forces.
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