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Structural Modifications of Mononuclear Ruthenium Complexes: A Combined Experimental and Theoretical Study on the Kinetics of Ruthenium-Catalyzed Water Oxidation
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
2011 (Engelska)Ingår i: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 50, nr 2, s. 445-449Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Small change, big difference: A minor structural modification of water-oxidation catalysts changes the kinetics of O2 evolution from second- to first-order (see scheme). According to DFT calculations, the torsional flexibility of the chelating ligands and their reorganization through the catalytic cycle are implicated in pathway selectivity, and the auxiliary carboxylate group becomes involved in proton-coupled nucleophilic attack.

Ort, förlag, år, upplaga, sidor
2011. Vol. 50, nr 2, s. 445-449
Nyckelord [en]
density functional calculations, homogeneous catalysis, N, O ligands, ruthenium, water splitting
Nationell ämneskategori
Kemi
Identifikatorer
URN: urn:nbn:se:kth:diva-31388DOI: 10.1002/anie.201005141ISI: 000286729300017Scopus ID: 2-s2.0-78650882640OAI: oai:DiVA.org:kth-31388DiVA, id: diva2:403705
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning
QC 20110314Tillgänglig från: 2011-03-14 Skapad: 2011-03-14 Senast uppdaterad: 2017-12-11Bibliografiskt granskad
Ingår i avhandling
1. 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: 2019-12-20Bibliografiskt granskad

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Duan, LeleSun, Licheng

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Tong, LianpengDuan, LeleXu, YunhuaSun, Licheng
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