Surface Catalysis of Water Oxidation by the Blue Ruthenium Dimer

Single-electron activation of multielectron catalysis has been shown to be viable in catalytic water oxidation with stepwise proton-coupled electron transfer, leading to high-energy catalytic precursors. For the blue dimer, crs,cis-[(bpy)(2)(H2O)(RuORuIII)-O-III(H2O)(bpy)(2)](4+), the first well-defined molecular catalyst for water oxidation, stepwise 4e(-)/4H(+) oxidation occurs to give the reactive precursor [(O)(RuORuV)-O-V(O)](4+). This key intermediate is kinetically inaccessible at an unmodified metal oxide surface, where the only available redox pathway is electron transfer We report here a remarkable surface activation of indium-tin oxide (In2O3:Sn) electrodes toward catalytic water oxidation by the blue dimer at electrodes denvatized by surface phosphonate binding of [Ru(4,4'-((HO)(2)P(O)CH2)(2)bpy)(2)(bpy)](2+) Surface binding dramatically improves the rate of surface oxidation of the blue dimer and induces water oxidation catalysis