Embedding Metal in the Interface of a p-n Heterojunction with a Stack Design for Superior Z-Scheme Photocatalytic Hydrogen Evolution.

The construction of a p-n heterojunction is an efficient strategy to resolve the limited light absorption and serious charge-carrier recombination in semiconductors and enhance the photocatalytic activity. However, the promotion effect is greatly limited by poor interfacial charge transfer efficiency as well as reduced redox ability of charge carriers. In this work, we demonstrate that the embedding of metal Pd into the interface between n-type C3N4 and p-type Cu2O can further enhance the interfacial charge transfer and increase the redox ability of charge carriers through the design of the C3N4-Pd-Cu2O stack nanostructure. The embedded Pd nanocubes in the stack structure not only trap the charge carriers from the semiconductors in promoting the electron-hole separation but also act as a Z-scheme "bridge" in keeping the strong reduction/oxidation ability of the electrons/holes for surface reactions. Furthermore, Pd nanocubes also increase the bonding strength between the two semiconductors. Enabled by this unique design, the hydrogen evolution achieved is dramatically higher than that of its counterpart C3N4-Cu2O structure without Pd embedding. The apparent quantum efficiency (AQE) is 0.9% at 420 nm for the designed C3N4-Pd-Cu2O. This work highlights the rational interfacial design of heterojunctions for enhanced photocatalytic performance.