Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media

Biaobiao Zhang; Fei Li; Rong Zhang; Chengbing Ma; Lin Chen; Licheng Sun

doi:10.1039/c6cc04003a

Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media

Chem Commun (Camb). 2016 Jun 30;52(55):8619-22. doi: 10.1039/c6cc04003a.

Authors

Biaobiao Zhang¹, Fei Li¹, Rong Zhang¹, Chengbing Ma², Lin Chen¹, Licheng Sun³

Affiliations

¹ State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), 116024 Dalian, China. lifei@dlut.edu.cn.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, China.
³ State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), 116024 Dalian, China. lifei@dlut.edu.cn and Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, 10044 Stockholm, Sweden.

PMID: 27332794
DOI: 10.1039/c6cc04003a

Abstract

A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.