Effects of Interfacial Electron Transfer in Metal Complex–Semiconductor Hybrid Photocatalysts on Z-Scheme CO2 Reduction under Visible Light

The Z-scheme CO2 reduction activity of metal complex–semiconductor hybrid photocatalysts was investigated in detail with a focus on the interfacial electron transfer process. Semiconductors of GaN:ZnO solid solutions, TaON, and Ta/N-codoped TiO2 were examined as components of the hybrid photocatalyst in combination with a binuclear Ru(II) complex. The (photo)physical properties of the semiconductor part were found to strongly affect the efficiency of interfacial electron transfer from/to the Ru complex photosensitizer unit, which was attached to the semiconductor surface. The photocatalytic activity of the hybrids showed a reasonable relationship with the efficiencies of forward and backward electron transfer. Among the three semiconductors, the highest activity was obtained with GaN:ZnO, which had the most negative conduction band potential among the semiconductors examined. The experimental results clearly demonstrated that analyses of the emission quenching process of the excited photosensitizer moiety of the binuclear Ru(II) complex allowed visualization of the interfacial electron transfer between the semiconductor and the Ru complex, giving us a rational guideline to improve the efficiency of the hybrid photocatalyst for Z-scheme CO2 reduction