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Chemical and Photochemical Water Oxidation Mediated by an Efficient Single-Site Ruthenium Catalyst
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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2016 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 9, no 24, p. 3448-3456Article in journal (Refereed) Published
Abstract [en]

Water oxidation is a fundamental step in artificial photosynthesis for solar fuels production. In this study, we report a single-site Ru-based water oxidation catalyst, housing a dicarboxylate-benzimidazole ligand, that mediates both chemical and light-driven oxidation of water efficiently under neutral conditions. The importance of the incorporation of the negatively charged ligand framework is manifested in the low redox potentials of the developed complex, which allows water oxidation to be driven by the mild one-electron oxidant [Ru(bpy)(3)](3+) (bpy = 2,2'-bipyridine). Furthermore, combined experimental and DFT studies provide insight into the mechanistic details of the catalytic cycle.

Place, publisher, year, edition, pages
2016. Vol. 9, no 24, p. 3448-3456
Keywords [en]
electrochemistry, homogeneous catalysis, photochemistry, ruthenium, water oxidation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-141313DOI: 10.1002/cssc.201601171ISI: 000394571500013PubMedID: 27966290OAI: oai:DiVA.org:su-141313DiVA, id: diva2:1086634
Funder
Swedish Research CouncilKnut and Alice Wallenberg FoundationCarl Tryggers foundation Available from: 2017-04-03 Created: 2017-04-03 Last updated: 2018-10-19Bibliographically approved
In thesis
1. Ru-Based Water Oxidation Catalysts: Development and Mechanistic Studies
Open this publication in new window or tab >>Ru-Based Water Oxidation Catalysts: Development and Mechanistic Studies
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Oxidation of water constitutes one of the most challenging processes in artificial photosynthesis, which aims at storing solar energy in the form of chemical bonds of high-energy fuels. To facilitate this process, efficient and durable water oxidation catalysts have to be developed and integrated into the complete photosynthetic cells. Importantly, the intricate complexity of such devices requires the catalyst not only to be highly efficient and robust, but also operate through a well-defined mechanism.

This thesis describes the development and mechanistic studies of new water oxidation catalysts based on ruthenium. The first part of the thesis describes the synthesis of a dinuclear ruthenium-based catalyst active for both chemical and light-driven water oxidation. This catalyst displayed a pronounced influence of the acetonitrile co-solvent on the redox properties, which was studied in detail by electrochemical methods. In the second part, a new benzimidazole-based mononuclear catalyst was evaluated. The activity of the catalyst was studied for chemical and light-driven water oxidation, and insight into the operating mechanism was provided with the help of density functional theory calculations. In the third part of the thesis, a new mononuclear ruthenium-based catalyst was prepared and evaluated for electrochemically-driven water oxidation. This catalyst displayed activity similar to that of the current state-of-the-art water oxidation catalyst, while eliminating its main drawback, that is incomplete activation. The redox properties of the new catalyst were studied in detail by electrochemical and spectroscopic techniques, providing insight into the origins of its improved performance. Finally, in the fourth part of the thesis, a heterogeneous nanoparticulate catalyst immobilized on a solid support is described. The catalyst displayed high activity and stability during chemical and light-driven water oxidation, which was attributed to the small average particle size and efficient anchoring of the catalyst to the heterogeneous support via an oxidatively-stable linker.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2018. p. 73
Keywords
ruthenium, catalysis, water oxidation, artificial photosynthesis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-160718 (URN)978-91-7797-466-6 (ISBN)978-91-7797-467-3 (ISBN)
Public defence
2018-12-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Available from: 2018-11-12 Created: 2018-10-18 Last updated: 2018-11-02Bibliographically approved

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Abdel-Magied, Ahmed F.Shatskiy, AndreyLiao, Rong-ZhenLaine, Tanja M.Siegbahn, Per E. M.Kärkäs, Markus D.Åkermark, BjornJohnston, Eric V.
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