One- or Two-Electron Water Oxidation, Hydroxyl Radical, or H₂O₂ Evolution

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H₂O₂) or hydroxyl radicals (^•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O₂ evolution. We develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to ^•OH, H₂O₂, and O₂.