A Dinuclear Ruthenium-Based Water Oxidation Catalyst: Use of Non-Innocent Ligand Frameworks for Promoting Multi-Electron Reactions.
Insight into how H2 O is oxidized to O2 is envisioned to facilitate the rational design of artificial water oxidation catalysts, which is a vital component in solar-to-fuel conversion schemes. Herein, we report on the mechanistic features associated with a dinuclear Ru-based water oxidation catalyst. The catalytic action of the designed Ru complex was studied by the combined use of high-resolution mass spectrometry, electrochemistry, and quantum chemical calculations. Based on the obtained results, it is suggested that the designed ligand scaffold in Ru complex 1 has a non-innocent behavior, in which metal-ligand cooperation is an important part during the four-electron oxidation of H2 O. This feature is vital for the observed catalytic efficiency and highlights that the preparation of catalysts housing non-innocent molecular frameworks could be a general strategy for accessing efficient catalysts for activation of H2 O.
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden).
Tanja M
TM
Laine
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden). markusk@organ.su.se.
Markus D
MD
Kärkäs
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden). rongzhen@hust.edu.cn.|Key Laboratory for Large-Format Battery Materials and System, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (P.R. China). rongzhen@hust.edu.cn.
Rong-Zhen
RZ
Liao
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden).
Per E M
PE
Siegbahn
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden). bjorn.akermark@organ.su.se.
Björn
B
Åkermark
density functional calculations; electrochemistry; ligands; ruthenium; water splitting