title: What factors control O2 binding and release thermodynamics in mononuclear ruthenium water oxidation catalysts? A theoretical exploration.
abstract: Mononuclear Ru-based water oxidation catalysts (WOCs) constitute an important class of WOCs for water splitting. This work constitutes a systematic study of Ru-O2 complexes of mononuclear ruthenium WOCs, with a focus on the thermodynamics of water-assisted O2 release in various electronic states and conformations. Our extensive DFT study reveals several factors that affect the O2 release thermodynamics: (1) steric effect from the ligand sphere of Ru; (2) trans effect of ligands trans to O2; (3) oxygen cis coordinating effect; (4) carbon coordinating effect; and (5) Ru coordination strength. Some of these effects could selectively stabilize/destabilize some states/conformations of the Ru-O2 complexes relative to Ru-OH2 complexes, and affect thereby the O2 release thermodynamics. The identification and rationalization of factors for O2 release thermodynamics, as in this work, could be helpful toward a better understanding of this final step of the ruthenium-catalyzed water oxidation.
authors.affiliation: Key Laboratory of Green Chemical Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, China.
authors.forename: Guiling
authors.initials: G
authors.lastname: Zhang
authors.forename: Kejuan
authors.initials: K
authors.lastname: Chen
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.forename: Jiannian
authors.initials: J
authors.lastname: Yao
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik