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Highly Active Ruthenium-Based Water Oxidation Catalyst with an Easy Access to the Catalytically Active Species
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-7249-7437
(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Abstract [en]

Herein is described a highly active ruthenium-based water oxidation catalyst [RuIV(mcbp)(O)(py)2] (5, mcbp2− = 2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine), which can be generated from either [RuII(mcbp)(py)2] (4II) or [RuIII(Hmcbp)(py)2]2+ (4III). Complexes 4II and 4III were isolated and characterized by single crystal X-ray analysis, NMR, UV-vis, FT-IR, ESI-HRMS, EPR, and elemental analysis, and their redox properties were studied in detail by electrochemical and spectroscopic methods. Unlike for the parent catalyst [Ru(tda)(py)2] (1, tda2− = [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylate), for which full transformation to the catalytically active species [RuIV(tda)(O)(py)2] (2) could not be carried out — stoichiometric generation of the catalytically active Ru-aqua complex 5 from 4II was achieved under mild conditions (pH 7.0) and short reaction times. The redox properties of the catalyst were studied and its activity for electrocatalytic water oxidation was evaluated, reaching TOFmax ≈ 40 000 s−1 at pH 9.0 (from the foot-of-the-wave analysis, FOWA), which is comparable to the activity of the state-of-the-art catalyst 2.

Nyckelord [en]
artificial photosynthesis, water oxidation catalyst, oxygen evolution, ruthenium, molecular catalysis
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-161300OAI: oai:DiVA.org:su-161300DiVA, id: diva2:1257366
Tillgänglig från: 2018-10-19 Skapad: 2018-10-19 Senast uppdaterad: 2018-10-22Bibliografiskt granskad
Ingår i avhandling
1. Ru-Based Water Oxidation Catalysts: Development and Mechanistic Studies
Öppna denna publikation i ny flik eller fönster >>Ru-Based Water Oxidation Catalysts: Development and Mechanistic Studies
2018 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm University, 2018. s. 73
Nyckelord
ruthenium, catalysis, water oxidation, artificial photosynthesis
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-160718 (URN)978-91-7797-466-6 (ISBN)978-91-7797-467-3 (ISBN)
Disputation
2018-12-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Anmärkning

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

Tillgänglig från: 2018-11-12 Skapad: 2018-10-18 Senast uppdaterad: 2018-11-02Bibliografiskt granskad

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