Ändra sökning
RefereraExporteraLänk till posten
Permanent länk

Direktlänk
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annat format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annat språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
Ce-IV- and Light-Driven Water Oxidation by [Ru(terpy)(pic)(3)](2+) Analogues: Catalytic and Mechanistic Studies
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.ORCID-id: 0000-0003-1662-5817
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.ORCID-id: 0000-0002-4521-2870
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.

Ort, förlag, år, upplaga, sidor
2011. Vol. 4, nr 2, s. 238-244
Nyckelord [en]
electrochemistry, homogeneous catalysis, photochemistry, ruthenium, water chemistry
Nationell ämneskategori
Kemi
Identifikatorer
URN: urn:nbn:se:kth:diva-31641DOI: 10.1002/cssc.201000313ISI: 000288043400016PubMedID: 21328553Scopus ID: 2-s2.0-79951807046OAI: oai:DiVA.org:kth-31641DiVA, id: diva2:405204
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning
QC 20110321Tillgänglig från: 2011-03-21 Skapad: 2011-03-21 Senast uppdaterad: 2020-03-09Bibliografiskt 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

Open Access i DiVA

Fulltext saknas i DiVA

Övriga länkar

Förlagets fulltextPubMedScopus

Personposter BETA

Duan, LeleSun, Licheng

Sök vidare i DiVA

Av författaren/redaktören
Duan, LeleXu, YunhuaTong, LianpengSun, Licheng
Av organisationen
Organisk kemi
Kemi

Sök vidare utanför DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetricpoäng

doi
pubmed
urn-nbn
Totalt: 154 träffar
RefereraExporteraLänk till posten
Permanent länk

Direktlänk
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annat format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annat språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf