Electrochemical Synthesis of Cu₂O Concave Octahedrons with High-Index Facets and Enhanced Photoelectrochemical Activity

High-index-faceted nano-/microcrystals exhibit enhanced catalytic activity and can thus serve as new-generation catalysts owing to their high density of low-coordinated atoms, leading to significantly enhanced catalytic activity. In this study, an effective electrochemical approach termed cyclic scanning electrodeposition (CSE) was developed to convert a thin Cu film into Cu₂O concave octahedrons enclosed by 24 {344} high-index facets at room temperature with high yield and high throughput. The formation mechanism and the role of each ion in the electrolyte were systematically studied, which facilitated the design of a high-index-faceted metal/metal oxide through CSE. We also presented a general formula to identify the structure of an individual crystal enclosed by {khh} high-index facets based on the crystals oriented along three low-index zone axes and imaged by transmission electron microscopy. Experimental results demonstrated the Cu₂O concave octahedrons to be highly efficient, cost-effective catalysts for photoelectrochemical hydrogen production. This new technology is a promising route for the synthesis of metal or metal oxide crystals with high activity and has a great potential for several advanced applications, such as clean energy conversion.