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Ce-IV- and Light-Driven Water Oxidation by [Ru(terpy)(pic)(3)](2+) Analogues: Catalytic and Mechanistic Studies
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0003-1662-5817
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0002-4521-2870
2011 (English)In: CHEMSUSCHEM, ISSN 1864-5631, Vol. 4, no 2, 238-244 p.Article in journal (Refereed) Published
Abstract [en]

A series of mononuclear ruthenium polypyridyl complexes [Ru(Mebimpy)(pic)(3)](PF6)(2) (2; Mebimpy=2,6-bis(1-methylbenzimidazol-2-yl)pyridine; pic=4-picoline), Ru(bimpy)(pic)(3) (3; H(2)bimpy=2,6-bis(benzimidazol-2-yl)pyridine), trans-[Ru(terpy)-(pic)(2)Cl](PF6) (4; terpy=2,2';6',2 ''-terpyridine), and trans-[Ru(terpy)(pic)(2)(OH2)](ClO4)(2) (5) are synthesized and characterized as analogues of the known Ru complex, [Ru(terpy)(pic)(3)](PF6)(2) (1). The effect of the ligands on electronic and catalytic properties is studied and discussed. The negatively charged ligand, bimpy(2-), has a remarkable influence on the electrochemical events due to its strong electron-donating ability. The performance in light- and Ce-IV-driven (Ce-IV=Ce(NH4)(2)(NO3)(6)) water oxidation is successfully demonstrated. We propose that ligand exchange between pic and H2O occurs to form the real catalyst, a Ru-aqua complex. The synthesis and testing of trans[Ru(terpy)(pic)(2)(OH2)](ClO4)(2) (5) confirmed our proposal. In addition, complex 5 possesses the best catalytic activity among these five complexes.

Place, publisher, year, edition, pages
2011. Vol. 4, no 2, 238-244 p.
Keyword [en]
electrochemistry, homogeneous catalysis, photochemistry, ruthenium, water chemistry
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-31641DOI: 10.1002/cssc.201000313ISI: 000288043400016Scopus ID: 2-s2.0-79951807046OAI: oai:DiVA.org:kth-31641DiVA: diva2:405204
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note
QC 20110321Available from: 2011-03-21 Created: 2011-03-21 Last updated: 2011-09-22Bibliographically approved
In thesis
1. Artificial Water Splitting: Ruthenium Complexes for Water Oxidation
Open this publication in new window or tab >>Artificial Water Splitting: Ruthenium Complexes for Water Oxidation
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns the development and study of Ru-based water oxidation catalysts (WOCs) which are the essential components for solar energy conversion to fuels. The first chapter gives a general introduction about the field of homogenous water oxidation catalysis, including the catalytic mechanisms and the catalytic activities of some selected WOCs as well as the concerns of catalyst design. The second chapter describes a family of mononuclear Ru complexes [Ru(pdc)L3] (H2pdc = 2,6-pyridinedicarboxylic acid; L = pyridyl ligands) towards water oxidation. The negatively charged pdc2 dramatically lowers the oxidation potentials of Ru complexes, accelerates the ligand exchange process and enhances the catalytic activity towards water oxidation. A Ru aqua species [Ru(pdc)L2(OH2)] was proposed as the real catalyst. The third chapter describes the analogues of [Ru(terpy)L3]2+ (terpy = 2,2′:6′,2′′-terpyridine). Through the structural tailor, the ligand effect on the electrochemical and catalytic properties of these Ru complexes was studied. Mechanistic studies suggested that these Ru-N6 complexes were pre-catalysts and the Ru-aqua species were the real WOCs. The forth chapter describes a family of fast WOCs [Ru(bda)L2] (H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid). Catalytic mechanisms were thoroughly investigated by electrochemical, kinetic and theoretical studies. The main contributions of this work to the field of water oxidation are (i) the recorded high reaction rate of 469 s−1; (ii) the involvement of seven-coordinate Ru species in the catalytic cycles; (iii) the O-O bond formation pathway via direct coupling of two Ru=O units and (iv) non-covalent effects boosting up the reaction rate. The fifth chapter is about visible light-driven water oxidation using a three component system including a WOC, a photosensitizer and a sacrificial electron acceptor. Light-driven water oxidation was successfully demonstrated using our Ru-based catalysts.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. 80 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:48
Keyword
water oxidation, ruthenium, electrochemistry, DFT calculation, photoelectrochemistry, negatively charged ligand, catalyst
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-40848 (URN)978-91-7501-083-0 (ISBN)
Public defence
2011-10-07, E3, Osquars backe 14, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20110922Available from: 2011-09-22 Created: 2011-09-21 Last updated: 2011-09-22Bibliographically approved

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Duan, LeleSun, Licheng

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