Mononuclear Ruthenium Complexes that Catalyze Water to Dioxgen Oxidation
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
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.
Trita-CHE-Report, ISSN 1654-1081 ; 2012:55
Ruthenium complex, Homogeneous catalysis, Water oxidation, O2 evolution, anionic ligand, Molecular catalyst, Electrocatalysis, Kinetics, Artificial photosynthesis, Light-driven, Immobilization of catalyst
Organic Chemistry Inorganic Chemistry Energy Systems
IdentifiersURN: urn:nbn:se:kth:diva-104765ISBN: 978-91-7501-517-0OAI: oai:DiVA.org:kth-104765DiVA: diva2:567277
2012-11-30, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Thummel, Randolph, Professor
Sun, Licheng, Professor
QC 201211122012-11-122012-11-122012-11-13Bibliographically approved
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