A Molecular Z‐Scheme Artificial Photosynthetic System Under the Bias‐Free Condition for CO2 Reduction Coupled with Two‐electron Water Oxidation: Photocatalytic Production of CO/HCOOH and H2O2.

Bio‐inspired molecular‐engineered systems have been extensively investigated for the half‐reactions of H2O oxidation or CO2 reduction with sacrificial electron donors/acceptors. However, there has yet to be reported a device for dye‐sensitized molecular photoanodes coupled with molecular photocathodes in an aqueous solution without the use of sacrificial reagents. Herein, we will report the integration of SnIV‐ or AlIII‐tetrapyridylporphyrin (SnTPyP or AlTPyP) decorated tin oxide particles (SnTPyP/SnO2 or AlTPyP/SnO2) photoanode with the dye‐sensitized molecular photocathode on nickel oxide particles containing [Ru(diimine)3]2+ as the light‐harvesting unit and [Ru(diimine)(CO)2Cl2] as the catalyst unit covalently connected and fixed within poly‐pyrrole layer (RuCAT‐RuC2‐PolyPyr‐PRu/NiO). The simultaneous irradiation of the two photoelectrodes with visible light resulted in H2O2 on the anode and CO, HCOOH, and H2 on the cathode with high Faradaic efficiencies in purely aqueous conditions without any applied bias is the first example of artificial photosynthesis with only two‐electron redox reactions. [ABSTRACT FROM AUTHOR]