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Insights into Ru-Based Molecular Water Oxidation Catalysts: Electronic and Noncovalent-Interaction Effects on Their Catalytic Activities
KTH, School of Chemical Science and Engineering (CHE), Chemistry.ORCID iD: 0000-0003-1662-5817
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.
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2013 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 52, no 14, 7844-7852 p.Article in journal (Refereed) Published
Abstract [en]

A series of Ru-bda water oxidation catalysts [Ru(bda)L-2] (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; L = [HNEt3][3-SO3-pyridine], 1; 4-(EtOOC)-pyridine, 2; 4-bromopyridine, 3; pyridine, 4; 4-methoxypyridine, 5; 4-(Me2N)-pyridine, 6; 4-[Ph(CH2)(3)]-pyridine, 7) were synthesized with election-donating/-withdrawing groups and hydro-philic/hydrophobic groups in the axial ligands. These complexes were characterized by H-1 NMR spectroscopy, high-resolution mass spectrometry, elemental analysis, and electrochemistry. In addition, complexes 1 and 6 were further identified by single crystal X-ray crystallography, revealing a highly distorted octahedral configuration of the Ru coordination sphere. All of these complexes are highly active toward Ce-IV-driven (Ce-IV = Ce(NH4)(2)(NO3)(6)) water oxidation with oxygen evolution rates up to 119 mols of O-2 per mole of catalyst per second. Their structure-activity relationship was investigated. Electron-withdrawing and noncovalent interactions (attraction) exhibit positive effect on the catalytic activity of Ru-bda catalysts.

Place, publisher, year, edition, pages
2013. Vol. 52, no 14, 7844-7852 p.
Keyword [en]
Mononuclear Ruthenium Complexes; O-O Bond; Iridium Complexes; Redox Properties; Functional-Model; Photosystem-Ii; O-2 Evolution; Efficient; Ligands; Site
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-129127DOI: 10.1021/ic302687dISI: 000322087100007ScopusID: 2-s2.0-84880260882OAI: diva2:650142

QC 20130920

Available from: 2013-09-20 Created: 2013-09-19 Last updated: 2015-09-16Bibliographically 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.
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:40
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
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)
Swedish Energy Agency

QC 20150916

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

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