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Sensitizer-Catalyst Assemblies for Water Oxidation
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0003-1662-5817
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2015 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 54, no 6, 2742-2751 p.Article in journal (Refereed) Published
Abstract [en]

Two molecular assemblies with one Ru(II)-polypyridine photosensitizer covalently linked to one Ru(II)(bda)L2 catalyst (1) (bda = 2,2'-bipyridine-6,6'-dicarboxylate) and two photosensitizers covalently linked to one catalyst (2) have been prepared using a simple C-C bond as the linkage. In the presence of sodium persulfate as a sacrificial electron acceptor, both of them show high activity for catalytic water oxidation driven by visible light, with a turnover number up to 200 for 2. The linked photocatalysts show a lower initial yield for light driven oxygen evolution but a much better photostability compared to the three component system with separate sensitizer, catalyst and acceptor, leading to a much greater turnover number. Photocatalytic experiments and time-resolved spectroscopy were carried out to probe the mechanism of this catalysis. The linked catalyst in its Ru(II) state rapidly quenches the sensitizer, predominantly by energy transfer. However, a higher stability under photocatalytic condition is shown for the linked sensitizer compared to the three component system, which is attributed to kinetic stabilization by rapid photosensitizer regeneration. Strategies for employment of the sensitizer-catalyst molecules in more efficient photocatalytic systems are discussed.

Place, publisher, year, edition, pages
2015. Vol. 54, no 6, 2742-2751 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-164446DOI: 10.1021/ic502915rISI: 000351325200028PubMedID: 25700086Scopus ID: 2-s2.0-84925014467OAI: oai:DiVA.org:kth-164446DiVA: diva2:807462
Funder
Swedish Research CouncilKnut and Alice Wallenberg FoundationSwedish Energy Agency
Note

QC 20150423

Available from: 2015-04-23 Created: 2015-04-17 Last updated: 2017-12-04Bibliographically approved
In thesis
1. Artificial Photosynthesis: Molecular Catalysts for Water Oxidation
Open this publication in new window or tab >>Artificial Photosynthesis: Molecular Catalysts for Water Oxidation
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Artificial photosynthesis provides a promising solution to the future sustainable energy system. Water is the only suitably sufficient protons and electrons supplier by the reaction of water oxidation. However, this reaction is both kinetically and thermodynamically demanding, leading to a sluggish kinetics unless the introduction of a catalyst.The theme of this thesis is to design, synthesize and evaluate molecular catalysts for water oxidation. This thesis consists of seven parts:The first chapter presents a general introduction to the field of homogenous catalysis of water oxidation, including catalysts design, examination and mechanistic investigation.The second chapter investigates the electronic and noncovalent-interaction effects of the ligands on the activities of the catalysts.In the third chapter, halogen substitutes are introduced into the axial ligands of the ruthenium catalysts. It is proved that the hydrophobic effect of the halogen atom dramatically enhanced the reactivity of the catalysts.Chapter four explores a novel group of ruthenium catalysts with imidazole-DMSO pair of axial ligands, in which the DMSO is proved to be crucial for the high efficiency of the catalysts.Chapter five describes the light-driven water oxidation including the three-component system and the sensitizer-catalyst assembled system. It is found that the common Ru(bpy)32+ dye can act as an electron relay and further benefit the electron transfer as well as the photo-stability of the system.In chapter six, aiming to the future application, selected ruthenium catalysts have been successfully immobilized on electrodes surfaces, and the electrochemical water oxidation is achieved with high efficiency.Finally, in the last chapter, a novel molecular catalyst based on the earth abundant metal ―nickel has been designed and synthesized. The activities as well as the mechanism have been explored.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. 82 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:40
Keyword
artificial photosynthesis, water oxidation, ruthenium complexes, nickel complexes, cerium, photo-catalysts, photosensitizer, electrochemistry, immobilization.
National Category
Organic Chemistry Physical Chemistry
Research subject
Chemistry; Energy Technology
Identifiers
urn:nbn:se:kth:diva-173622 (URN)978-91-7595-659-6 (ISBN)
Public defence
2015-10-13, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Energy Agency
Note

QC 20150916

Available from: 2015-09-16 Created: 2015-09-15 Last updated: 2015-09-16Bibliographically approved

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Duan, LeleLi, FushengSun, Licheng

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