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, cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(H(2)O)(bpy)(2)](4+), the first well-defined molecular catalyst for water oxidation, stepwise 4e(-)/4H(+) oxidation occurs to give the reactive precursor [(O)Ru(V)ORu(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 (In(2)O(3):Sn) electrodes toward catalytic water oxidation by the blue dimer at electrodes derivatized by surface phosphonate binding of [Ru(4,4'-((HO)(2)P(O)CH(2))(2)bpy)(2)(bpy)](2+). Surface binding dramatically improves the rate of surface oxidation of the blue dimer and induces water oxidation catalysis.
Jurss
Jonah W
JW
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
Concepcion
Javier C
JC
Norris
Michael R
MR
Templeton
Joseph L
JL
Meyer
Thomas J
TJ
D002384:Catalysis; D019281:Dimerization; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry*; D013499:Surface Properties; D014867:Water / Q000737:chemistry*
D009942:Organometallic Compounds; D014867:Water; D012428:Ruthenium