Passivating Surface States on Water Splitting Cuprous Oxide Photocatalyst with Bismuth Decoration.

To enhance the visible light photocatalystic activity of Cu 2 O(100) surface, we performed first-principles calculations on the structural, electronic and optical properties of a bismuth (Bi)-decorated Cu 2 O(100) surface (Bi@Cu 2 O(100)). It is shown that the Bi prefer to be loaded to the hollow sites among four surface oxygen atoms and tend to individual dispersion instead of aggregating on the surface due to the lowest formation energy and larger distance between two Bi atoms at the surface than the Bi clusters; the coverage of around 0.25 monolayer Bi atoms can effectively eliminate the surface states and modify the band edges to satisfy the angular momentum selection rules for light excited transition of electrons, and the loaded Bi atoms contribute to the separation of photogenerated electron-holes. The relative positions between the band edges and the redox potentials are suitable for photocatalytic hydrogen production from the redox water, and moreover, the optical absorption spectrum indicates a positive response of the Bi 0 . 25 @Cu 2 O(100) to visible light, implying that the Bi 0 . 25 @Cu 2 O(100) is a promising visible light photocatalyst.