Water Reduction Photocathodes Based on Ru Complex Dyes Covered with a Conjugated Polymer Nanosheet

Water-splitting dye-sensitized photoelectrochemical cells are promising devices for resolving energy and environmental problems by producing H₂, a clean energy source, from water and sunlight. However, their performance is still limited because of dye desorption from the electrode and their weak light-absorption efficiency. In this study, we fabricated two water-reducing photocathodes, NiO|RuCP/BQPy and NiO|RuCP-Zr-RuP/BQPy, by combining the layer-by-layer formation of mono- (RuCP) and bi- (RuCP and RuP with Zr⁴⁺cations) layer molecular films of Ru(II) dyes, respectively, on a p-type NiO substrate with the chemical vapor deposition of the nanosheet catalyst based on the BQPy organic polymer comprising benzoquinone and pyrrole moieties. These photocathodes produced H₂under visible light irradiation and a small electrical bias in a 0.1 M Na₂SO₄aqueous solution (λ > 420 nm, 65 mW cm^-2, E = -0.254 V versus normal hydrogen electrode, and pH 3). Both the photocurrent value and amount of H₂produced by double-dye-layered NiO|RuCP-Zr-RuP/BQPy were smaller than those of NiO|RuCP/BQPy, probably because of the energy transfer inactivation between the Ru(II) dyes, which competes with the reductive quenching (i.e., electron injection) by NiO. Ru(II) dye desorption from the NiO|RuCP/BQPy photocathode was significantly reduced to approximately a third of that of NiO|RuCP, indicating that the deposited BQPy polymer improved the durability of the photocathode. The deposition of the BQPy polymer can be easily performed under mild conditions (60 °C in air); therefore, this technique shows great potential application for the construction of various types of dye-sensitized water-reducing photocathodes.