The shape-controlled synthesis of cuprous oxide (Cu2O) photocatalysts with both low or high index crystal planes has received increasing attention due to their unique facet-dependent properties. Since they are cheap and earth abundant, these well-defined Cu2O nanostructures are extensively used for different photocatalytic reactions, also because of their strong visible light absorption capability. However, further development will still be needed to enhance the efficiency and photostability of Cu2O to expand its industrial application. We start this review by summarizing the synthetic advancement in the facet engineering of Cu2O and other associated hybrid Cu2O-based heterostructures with a special emphasis put on their growth mechanism. We then discuss different facet-dependent properties, which are relevant to photocatalysis. In the subsequent section, we present a critical discussion on the photocatalytic performance of faceted Cu2O nanostructures during organic synthesis, hydrogen production, and carbon dioxide photoreduction. The relation between photocatalytic efficiency and product selectivity with exposed crystal facets or with different compositions of hybrid nanostructures is also discussed. Finally, important strategies are proposed to overcome the photostability issue, while outlining the course of future development to further boost the technological readiness of well-defined Cu2O-based photocatalysts.
