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Visible light-driven water oxidation catalyzed by a highly efficient dinuclear ruthenium complex
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0003-1662-5817
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
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2010 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 46, no 35, 6506-6508 p.Article in journal (Refereed) Published
Abstract [en]

Visible light-driven water oxidation has been achieved by the dinuclear ruthenium complex 1 with a high turnover number of 1270 in a homogeneous system in the presence of a Ru polypyridine complex photosensitizer.

Place, publisher, year, edition, pages
2010. Vol. 46, no 35, 6506-6508 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-26833DOI: 10.1039/c0cc01250eISI: 000281237600022Scopus ID: 2-s2.0-77956042575OAI: oai:DiVA.org:kth-26833DiVA: diva2:374827
Note
QC 20101206Available from: 2010-12-06 Created: 2010-11-29 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)
Opponent
Supervisors
Note
QC 20110922Available from: 2011-09-22 Created: 2011-09-21 Last updated: 2011-09-22Bibliographically approved
2. Mononuclear Ruthenium Complexes that Catalyze Water to Dioxgen Oxidation
Open this publication in new window or tab >>Mononuclear Ruthenium Complexes that Catalyze Water to Dioxgen Oxidation
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The theme of this thesis is the development of mononuclear Ru-based complexes that are capable of catalyzing the water oxidation (or O2-evolving) reaction, e.g. 2 H2O → O2 + 4 H+ + 4 e. Several families of mononuclear Ru water oxidation catalysts were designed and prepared. They feature with anionic ancillary ligands that contain carboxylate or phenolate donors. The properties of the catalysts were investigated in various aspects including coordination geometry, electrochemical behavior, and ligand exchange. All catalysts showed outstanding catalytic activity towards water oxidation in the presence of cerium(IV) ammonium nitrate as a sacrificial oxidant. High-valent Ru intermediates involved in the reactions were characterized both experimentally and theoretically. The kinetics of catalytic water oxidation was examined based on one catalyst and a prevailing catalytic pathway was proposed. The catalytic cycle involved a sequence of oxidation steps from RuII−OH2 to RuV=O species and O−O bond formation via water-nucleophilic-attack to the RuV=O intermediate. By comparing properties and catalytic performance of Ru catalysts herein with that of previously reported examples, the effect of anionic ancillary ligands was clearly elucidated in the context of catalytic water oxidation. Aiming to further application in an envisaged artificial photosynthesis device, visible light-driven water oxidation was conducted and achieved primarily in a homogeneous three-component system containing catalyst, photosensitizer, and sacrificial electron acceptor. Moreover, one model Ru catalyst was successfully immobilized on ordinary glass carbon surface through a facile and widely applicable method.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 101 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:55
Keyword
Ruthenium complex, Homogeneous catalysis, Water oxidation, O2 evolution, anionic ligand, Molecular catalyst, Electrocatalysis, Kinetics, Artificial photosynthesis, Light-driven, Immobilization of catalyst
National Category
Organic Chemistry Inorganic Chemistry Energy Systems
Identifiers
urn:nbn:se:kth:diva-104765 (URN)978-91-7501-517-0 (ISBN)
Public defence
2012-11-30, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20121112

Available from: 2012-11-12 Created: 2012-11-12 Last updated: 2012-11-13Bibliographically approved

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