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Artificial Water Splitting: Ruthenium Complexes for Water Oxidation
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi. (Licheng Sun's group)ORCID-id: 0000-0003-1662-5817
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 [en]
water oxidation, ruthenium, electrochemistry, DFT calculation, photoelectrochemistry, negatively charged ligand, catalyst
Nationell ämneskategori
Organisk kemi
Identifikatorer
URN: urn:nbn:se:kth:diva-40848ISBN: 978-91-7501-083-0 (tryckt)OAI: oai:DiVA.org:kth-40848DiVA, id: diva2:442476
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
Delarbeten
1. Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand
Öppna denna publikation i ny flik eller fönster >>Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand
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2010 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, nr 15, s. 4659-4668Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Two mononuclear ruthenium complexes [RuL(pic)(3)] (1) and [RuL(bpy)(pic)] (2) (H2L = 2,6-pyridinedicarboxylic acid, pic=4-picoline, bpy = 2,2'-bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium-based water oxidation catalysts using [Ce(NH4)(2)(NO3)(6)] (Ce-IV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnovers(-1). Under acidic conditions, the equatorial 4-picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the Rum state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using Ce-IV as oxidant, [RuL(pic)(2)(H2O)](+) is proposed as the real water oxidation catalyst.

Nyckelord
electrochemistry, homogeneous catalysis, oxidation, ruthenium, water splitting
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:kth:diva-27911 (URN)10.1002/chem.200902603 (DOI)000277331000027 ()2-s2.0-77950824222 (Scopus ID)
Anmärkning
QC 20110104Tillgänglig från: 2011-01-04 Skapad: 2011-01-03 Senast uppdaterad: 2017-12-11Bibliografiskt granskad
2. The Ru complexes containing pyridine-dicarboxylate ligand: electronic effect on their catalytic activity toward water oxidation
Öppna denna publikation i ny flik eller fönster >>The Ru complexes containing pyridine-dicarboxylate ligand: electronic effect on their catalytic activity toward water oxidation
2011 (Engelska)Ingår i: Faraday discussions (Online), ISSN 1359-6640, E-ISSN 1364-5498, Vol. 155, s. 267-275Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Two series of mononuclear ruthenium complexes [Ru(pdc)L-3] (H(2)pdc = 2,6-pyridinedicarboxylic acid; L = 4-methoxypyridine, 1; pyridine, 2; pyrazine, 3) and [Ru(pdc)L-2(dmso)] (dmso = dimethyl sulfoxide; L = 4-methoxypyridine, 4; pyridine, 5) were synthesized and spectroscopically characterized. Their catalytic activity toward water oxidation has been examined using Ce-IV (Ce(NH4)(2)(NO3)(6)) as the chemical oxidant under acidic conditions. Complexes 1, 2 and 3 are capable of catalyzing Ce-IV-driven water oxidation while 4 and 5 are not active. Electronic effects on their catalytic activity were illustrated: electron donating groups increase the catalytic activity.

Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:kth:diva-40905 (URN)10.1039/c1fd00101a (DOI)000299793100018 ()2-s2.0-84857067133 (Scopus ID)
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning
Original title: The Ru-pdc Complexes: Electronic Effect on Their Catalytic Activity toward CeIV-Driven Water Oxidation QC 20120227Tillgänglig från: 2011-09-22 Skapad: 2011-09-22 Senast uppdaterad: 2017-12-08Bibliografiskt granskad
3. Ce-IV- and Light-Driven Water Oxidation by [Ru(terpy)(pic)(3)](2+) Analogues: Catalytic and Mechanistic Studies
Öppna denna publikation i ny flik eller fönster >>Ce-IV- and Light-Driven Water Oxidation by [Ru(terpy)(pic)(3)](2+) Analogues: Catalytic and Mechanistic Studies
2011 (Engelska)Ingår i: CHEMSUSCHEM, ISSN 1864-5631, Vol. 4, nr 2, s. 238-244Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

A series of mononuclear ruthenium polypyridyl complexes [Ru(Mebimpy)(pic)(3)](PF6)(2) (2; Mebimpy=2,6-bis(1-methylbenzimidazol-2-yl)pyridine; pic=4-picoline), Ru(bimpy)(pic)(3) (3; H(2)bimpy=2,6-bis(benzimidazol-2-yl)pyridine), trans-[Ru(terpy)-(pic)(2)Cl](PF6) (4; terpy=2,2';6',2 ''-terpyridine), and trans-[Ru(terpy)(pic)(2)(OH2)](ClO4)(2) (5) are synthesized and characterized as analogues of the known Ru complex, [Ru(terpy)(pic)(3)](PF6)(2) (1). The effect of the ligands on electronic and catalytic properties is studied and discussed. The negatively charged ligand, bimpy(2-), has a remarkable influence on the electrochemical events due to its strong electron-donating ability. The performance in light- and Ce-IV-driven (Ce-IV=Ce(NH4)(2)(NO3)(6)) water oxidation is successfully demonstrated. We propose that ligand exchange between pic and H2O occurs to form the real catalyst, a Ru-aqua complex. The synthesis and testing of trans[Ru(terpy)(pic)(2)(OH2)](ClO4)(2) (5) confirmed our proposal. In addition, complex 5 possesses the best catalytic activity among these five complexes.

Nyckelord
electrochemistry, homogeneous catalysis, photochemistry, ruthenium, water chemistry
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:kth:diva-31641 (URN)10.1002/cssc.201000313 (DOI)000288043400016 ()2-s2.0-79951807046 (Scopus ID)
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning
QC 20110321Tillgänglig från: 2011-03-21 Skapad: 2011-03-21 Senast uppdaterad: 2011-09-22Bibliografiskt granskad
4. Isolated Seven-Coordinate Ru(IV) Dimer Complex with HOHOH (-) Bridging Ligand as an Intermediate for Catalytic Water Oxidation
Öppna denna publikation i ny flik eller fönster >>Isolated Seven-Coordinate Ru(IV) Dimer Complex with HOHOH (-) Bridging Ligand as an Intermediate for Catalytic Water Oxidation
2009 (Engelska)Ingår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 131, nr 30, s. 10397-+Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

With the inspiration from an oxygen evolving complex (OEC) in Photosystern II (PSII), a mononuclear Ru(II) complex with a tetradentate ligand containing two carboxylate groups has been synthesized and structurally characterized. This Ru(II) complex showed efficient catalytic properties toward water oxidation by the chemical oxidant cerium(IV) ammonium nitrate. During the process of catalytic water oxidation, Ru(III) and Ru(IV) species have been successfully isolated as intermediates. To our surprise, X-ray crystallography together with HR-MS revealed that the Ru(IV) species is a seven-coordinate Ru(IV) dimer complex containing a [HOHOH](-) bridging ligand. This bridging ligand has a short O center dot center dot center dot O distance and is hydrogen bonded to two water molecules. The discovery of this very uncommon seven-coordinate Ru(IV) dimer together with a hydrogen bonding network may contribute to a deeper understanding of the mechanism for catalytic water oxidation. It will also provide new possibilities for the design of more efficient catalysts for water oxidation, which is the key step for solar energy conversion into hydrogen by tight-driven water splitting, the ultimate challenge in artificial photosynthesis.

Identifikatorer
urn:nbn:se:kth:diva-18657 (URN)10.1021/ja9034686 (DOI)000268644400031 ()2-s2.0-68049108505 (Scopus ID)
Anmärkning
QC 20100525Tillgänglig från: 2010-08-05 Skapad: 2010-08-05 Senast uppdaterad: 2017-12-12Bibliografiskt granskad
5. The First Replication of the Water Oxidation Activity of Photosystem-II by a Molecular Ruthenium Catalyst
Öppna denna publikation i ny flik eller fönster >>The First Replication of the Water Oxidation Activity of Photosystem-II by a Molecular Ruthenium Catalyst
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(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:kth:diva-40901 (URN)
Anmärkning
QS 2011Tillgänglig från: 2011-09-22 Skapad: 2011-09-22 Senast uppdaterad: 2011-09-22Bibliografiskt granskad
6. Visible Light-Driven Water Oxidation by a Molecular Ruthenium Catalyst in Homogeneous System
Öppna denna publikation i ny flik eller fönster >>Visible Light-Driven Water Oxidation by a Molecular Ruthenium Catalyst in Homogeneous System
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2010 (Engelska)Ingår i: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 49, nr 1, s. 209-215Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Discovery of an efficient catalyst bearing low overpotential toward water oxidation is a key step for light-driven water splitting into dioxygen and dihydrogen. A mononuclear ruthenium complex, Ru(II)L(pic)(2) (1) (H2L = 2,2'-bipyridine-6,6'-dicarboxylic acids pic = 4-picoline), was found capable of oxidizing water eletrochemically at a relatively low potential and promoting light-driven water oxidation using a three-component system composed of a photosensitizer, sacrificial electron acceptor, and complex 1. The detailed electrochemical properties of 1 were studied, and the onset potentials of the electrochemically catalytic curves in pH 7.0 and pH 1.0 solutions are 1.0 and 1.5 V, respectively. The low catalytic potential of 1 under neutral conditions allows the use of [Ru(bpy)(3)](2+) and even [Ru(dmbpy)(3)](2+) as a photosensitizer for photochemical water oxidation. Two different sacrificial electron acceptors, [Co(NH3)(5)Cl]Cl-2 and Na2S2O8, were used to generate the oxidized state of ruthenium tris(2,2'-bipyridyl) photosensitizers. In addition, a two-hour photolysis of I in a pH TO phosphate buffer did not lead to obvious degradation, indicating the good photostability of our catalyst. However, under conditions of light-driven water oxidation, the catalyst deactivates quickly. In both solution and the solid state under aerobic conditions, complex 1 gradually decomposed via oxidative degradation of its ligands, and two of the decomposed products, sp(3) C-H bond oxidized Ru complexes, were identified. The capability of oxidizing the sp(3) C-H bond implies the presence of a highly oxidizing Ru species, which might also cause the final degradation of the catalyst.

Nyckelord
O-O BOND, ARTIFICIAL PHOTOSYNTHESIS, FUNCTIONAL-MODEL, EXCITED-STATE, RU(II) COMPLEXES, REDOX PROPERTIES, PHOTOSYSTEM-II, O-2 EVOLUTION, OXYGEN, LIGAND
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:kth:diva-19065 (URN)10.1021/ic9017486 (DOI)000272935800023 ()2-s2.0-73349134347 (Scopus ID)
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning

QC 20100525

Tillgänglig från: 2010-08-05 Skapad: 2010-08-05 Senast uppdaterad: 2017-12-12Bibliografiskt granskad
7. Visible light-driven water oxidation catalyzed by a highly efficient dinuclear ruthenium complex
Öppna denna publikation i ny flik eller fönster >>Visible light-driven water oxidation catalyzed by a highly efficient dinuclear ruthenium complex
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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.

Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:kth:diva-26833 (URN)10.1039/c0cc01250e (DOI)000281237600022 ()2-s2.0-77956042575 (Scopus ID)
Anmärkning
QC 20101206Tillgänglig från: 2010-12-06 Skapad: 2010-11-29 Senast uppdaterad: 2017-12-11Bibliografiskt granskad

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