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Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand
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.
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2010 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, no 15, 4659-4668 p.Article in journal (Refereed) Published
Abstract [en]

Two mononuclear ruthenium complexes [RuL(pic)(3)] (1) and [RuL(bpy)(pic)] (2) (H2L = 2,6-pyridinedicarboxylic acid, pic=4-picoline, bpy = 2,2'-bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium-based water oxidation catalysts using [Ce(NH4)(2)(NO3)(6)] (Ce-IV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnovers(-1). Under acidic conditions, the equatorial 4-picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the Rum state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using Ce-IV as oxidant, [RuL(pic)(2)(H2O)](+) is proposed as the real water oxidation catalyst.

Place, publisher, year, edition, pages
2010. Vol. 16, no 15, 4659-4668 p.
Keyword [en]
electrochemistry, homogeneous catalysis, oxidation, ruthenium, water splitting
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-27911DOI: 10.1002/chem.200902603ISI: 000277331000027Scopus ID: 2-s2.0-77950824222OAI: oai:DiVA.org:kth-27911DiVA: diva2:383045
Note
QC 20110104Available from: 2011-01-04 Created: 2011-01-03 Last updated: 2017-12-11Bibliographically 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)
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Supervisors
Note
QC 20110922Available from: 2011-09-22 Created: 2011-09-21 Last updated: 2011-09-22Bibliographically approved

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