Redox-Active Ligand Assisted Catalytic Water Oxidation by a Ru IV =O Intermediate

Water splitting is one of the most promising solutions for storing solar energy in a chemical bond. Water oxidation is still the bottleneck step because of its inherent difficulty and the limited understanding of the O-O bond formation mechanism. Molecular catalysts provide a platform for understand...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-03, Vol.59 (10), p.4000-4008
Main Authors: Shi, Jing, Guo, Yu-Hua, Xie, Fei, Chen, Qi-Fa, Zhang, Ming-Tian
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Water splitting is one of the most promising solutions for storing solar energy in a chemical bond. Water oxidation is still the bottleneck step because of its inherent difficulty and the limited understanding of the O-O bond formation mechanism. Molecular catalysts provide a platform for understanding this process in depth and have received wide attention since the first Ru-based catalyst was reported in 1982. Ru =O is considered a key intermediate to initiate the O-O bond formation through either a water nucleophilic attack (WNA) pathway or a bimolecular coupling (I2M) pathway. Herein, we report a Ru-based catalyst that displays water oxidation reactivity with Ru =(O) with the help of a redox-active ligand at pH 7.0. The results of electrochemical studies and DFT calculations disclose that ligand oxidation could significantly improve the reactivity of Ru =O toward water oxidation. Under these conditions, sustained water oxidation catalysis occurs at reasonable rates with low overpotential (ca. 183 mV).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201910614