The development of systems for photocatalytic CO2reduction with water as a reductant and solar light as an energy source is one of the most important milestones on the way to artificial photosynthesis. Although such reduction can be performed using dye-sensitized molecular photocathodes comprising metal complexes as redox photosensitizers and catalyst units fixed on a p-type semiconductor electrode, the performance of the corresponding photoelectrochemical cells remains low,e.g., their highest incident photon-to-current conversion efficiency (IPCE) equals 1.2%. Herein, we report a novel dye-sensitized molecular photocathode for photocatalytic CO2reduction in water featuring a polypyrrole layer, [Ru(diimine)3]2+as a redox photosensitizer unit, and Ru(diimine)(CO)2Cl2as the catalyst unit and reveal that the incorporation of the polypyrrole network significantly improves reactivity and durability relative to those of previously reported dye-sensitized molecular photocathodes. The irradiation of the novel photocathode with visible light under low applied bias stably induces the photocatalytic reduction of CO2to CO and HCOOH with high faradaic efficiency and selectivity (even in aqueous solution), and the highest IPCE is determined as 4.7%. The novel photocathode is coupled with n-type semiconductor photoanodes (CoOx/BiVO4and RhOx/TaON) to construct full cells that photocatalytically reduce CO2using water as the reductant upon visible light irradiation as the only energy input at zero bias. The artificial Z-scheme photoelectrochemical cell with the dye-sensitized molecular photocathode achieves the highest energy conversion efficiency of 8.3 × 10−2% under the irradiation of both electrodes with visible light, while a solar to chemical conversion efficiency of 4.2 × 10−2% is achieved for a tandem-type cell using a solar light simulator (AM 1.5, 100 mW cm−2).
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