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Visible light-driven water oxidation catalyzed by a highly efficient dinuclear ruthenium complex
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.ORCID-id: 0000-0003-1662-5817
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
Visa övriga samt affilieringar
2010 (Engelska)Ingår i: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 46, nr 35, s. 6506-6508Artikel i tidskrift (Refereegranskat) 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.

Ort, förlag, år, upplaga, sidor
2010. Vol. 46, nr 35, s. 6506-6508
Nationell ämneskategori
Kemi
Identifikatorer
URN: urn:nbn:se:kth:diva-26833DOI: 10.1039/c0cc01250eISI: 000281237600022Scopus ID: 2-s2.0-77956042575OAI: oai:DiVA.org:kth-26833DiVA, id: diva2:374827
Anmärkning
QC 20101206Tillgänglig från: 2010-12-06 Skapad: 2010-11-29 Senast uppdaterad: 2017-12-11Bibliografiskt granskad
Ingår i avhandling
1. Artificial Water Splitting: Ruthenium Complexes for Water Oxidation
Öppna denna publikation i ny flik eller fönster >>Artificial Water Splitting: Ruthenium Complexes for Water Oxidation
2011 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: KTH Royal Institute of Technology, 2011. s. 80
Serie
Trita-CHE-Report, ISSN 1654-1081 ; 2011:48
Nyckelord
water oxidation, ruthenium, electrochemistry, DFT calculation, photoelectrochemistry, negatively charged ligand, catalyst
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:kth:diva-40848 (URN)978-91-7501-083-0 (ISBN)
Disputation
2011-10-07, E3, Osquars backe 14, KTH, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Anmärkning
QC 20110922Tillgänglig från: 2011-09-22 Skapad: 2011-09-21 Senast uppdaterad: 2011-09-22Bibliografiskt granskad
2. Mononuclear Ruthenium Complexes that Catalyze Water to Dioxgen Oxidation
Öppna denna publikation i ny flik eller fönster >>Mononuclear Ruthenium Complexes that Catalyze Water to Dioxgen Oxidation
2012 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: KTH Royal Institute of Technology, 2012. s. 101
Serie
Trita-CHE-Report, ISSN 1654-1081 ; 2012:55
Nyckelord
Ruthenium complex, Homogeneous catalysis, Water oxidation, O2 evolution, anionic ligand, Molecular catalyst, Electrocatalysis, Kinetics, Artificial photosynthesis, Light-driven, Immobilization of catalyst
Nationell ämneskategori
Organisk kemi Oorganisk kemi Energisystem
Identifikatorer
urn:nbn:se:kth:diva-104765 (URN)978-91-7501-517-0 (ISBN)
Disputation
2012-11-30, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Anmärkning

QC 20121112

Tillgänglig från: 2012-11-12 Skapad: 2012-11-12 Senast uppdaterad: 2012-11-13Bibliografiskt granskad

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