Hydrobromic acid (HBr) has significant potential as an inexpensive feedstock for hydrogen gas (H) solar fuel production through HBr splitting. Mesoporous thin films of anatase TiO or SnO/TiO core-shell nanoparticles were sensitized to visible light with a new Ru polypyridyl complex that served as a photocatalyst for bromide oxidation. These thin films were tested as photoelectrodes in dye-sensitized photoelectrosynthesis cells. In 1 N HBr (aq), the photocatalyst undergoes excited-state electron injection and light-driven Br oxidation. The injected electrons induce proton reduction at a Pt electrode. Under 100 mW cm white-light illumination, sustained photocurrents of 1.5 mA cm were measured under an applied bias. Faradaic efficiencies of 71 ± 5% for Br oxidation and 94 ± 2% for H production were measured. A 12 μmol h sustained rate of H production was maintained during illumination. The results demonstrate a molecular approach to HBr splitting with a visible light absorbing complex capable of aqueous Br oxidation and excited-state electron injection.

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http://dx.doi.org/10.1021/jacs.7b09367DOI Listing

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