title: A self-improved water-oxidation catalyst: is one site really enough?
abstract: The homogeneous catalysis of water oxidation by transition-metal complexes has experienced spectacular development over the last five years. Practical energy-conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water-oxidation catalyst that is generated by self-assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water-oxidation catalyst that does not decompose over extended periods of time.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain).
authors.forename: Isidoro
authors.initials: I
authors.lastname: López
authors.forename: Mehmed Z
authors.initials: MZ
authors.lastname: Ertem
authors.forename: Somnath
authors.initials: S
authors.lastname: Maji
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
authors.forename: Anke
authors.initials: A
authors.lastname: Keidel
authors.forename: Uwe
authors.initials: U
authors.lastname: Kuhlmann
authors.forename: Peter
authors.initials: P
authors.lastname: Hildebrandt
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer
authors.forename: Victor S
authors.initials: VS
authors.lastname: Batista
authors.forename: Antoni
authors.initials: A
authors.lastname: Llobet
keywords: density functional calculations; reaction mechanisms; resonance Raman spectroscopy; ruthenium electrochemistry; water-oxidation catalysis