Accumulation of multiple oxidative equivalents at a single site by cross-surface electron transfer on TiO2

The photodriven accumulation of two oxidative equivalents at a single site was investigated on TiO2 coloaded with a ruthenium polypyridyl chromophore [Ru(bpy)2((4,4'-(OH)2PO)2bpy)](2+) (Ru(II)P(2+), bpy = 2,2'-bipyridine, ((OH)2PO)2-bpy = 2,2'-bipyridine-4,4'-diyldiphosphonic acid) and a water oxidation catalyst [Ru(Mebimpy) ((4,4'-(OH)2PO-CH2)2bpy)(OH2)](2+) (Ru(II)OH2(2+), Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine, (4,4'-(OH)2PO-CH2)2bpy) = 4,4'-bis-methlylenephosphonato-2,2'-bipyridine). Electron injection from the metal-to-ligand charge transfer (MLCT) excited state of -Ru(II)P(2+) (-Ru(II)P(2+)*) to give -Ru(III)P(3+) and TiO2(e(-)) was followed by rapid (<20 ns) nearest-neighbor -Ru(II)OH2(2+) to -Ru(III)P(3+) electron transfer. On surfaces containing both -Ru(II)P(2+) and -Ru(III)OH2(3+) (or -Ru(III)OH(2+)), -Ru(II)OH2(2+) was formed by random migration of the injected electron inside the TiO2 nanoparticle and recombination with the preoxidized catalyst, followed by relatively slow (μs-ms) non-nearest neighbor cross-surface electron transfer from -Ru(II)OH2(2+) to -Ru(III)P(3+). Steady state illumination of coloaded TiO2 photoanodes in a dye sensitized photoelectrosynthesis cell (DSPEC) configuration resulted in the buildup of -Ru(III)P(3+), -Ru(III)OH(2+), and -Ru(IV)═O(2+), with -Ru(IV)═O(2+) formation favored at high chromophore to catalyst ratios.