Diminished photoisomerization of active ruthenium water oxidation catalyst by anchoring to metal oxide electrodes

Diane K. Zhong, Shengliang Zhao, Dmitry Polyansky, Etsuko Fujita

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Surface-binding of molecular water oxidation catalysts through phosphonated ligands offers a promising strategy for attaching homogeneous catalysts onto conductive or semiconductive oxide surfaces for heterogeneous catalysis. In this work, the highly active [Ru(tpy)(pynap)OH2]2+ (tpy = 2,2′:6′,2″-terpyridine; pynap = 2-(pyrid-2′-yl)-1,8- naphthyridine) water oxidation catalyst is attached onto metal oxide electrodes through a phosphate group. Electrochemical and photoelectrochemical results confirm that ruthenium oxidation chemistries and water oxidation proficiency remain largely unaffected by phosphonation. Surface-binding reveals minimal photoisomerization of the active d-form and allows us to evaluate photoelectrochemical and mechanistic properties of the catalyst. Spectroelectrochemical experiments support the evolution of multiple ruthenium oxidation states in agreement with Pourbaix diagrams. Although photoisomerization of d-[Ru(H2PO3-tpy)(pynap)OH 2]2+ is considerably hindered when the catalyst is attached onto a rigid oxide electrode, surface desorption remains a major challenge.

Original languageEnglish
Pages (from-to)140-147
Number of pages8
JournalJournal of Catalysis
Volume307
DOIs
Publication statusPublished - 2013

Fingerprint

Photoisomerization
Ruthenium
Oxides
ruthenium
metal oxides
Metals
catalysts
Oxidation
oxidation
Electrodes
Catalysts
electrodes
Water
water
Naphthyridines
oxides
Catalyst supports
Catalysis
catalysis
Desorption

Keywords

  • Photoisomerization
  • Ruthenium catalyst
  • Surface-binding
  • Water oxidation

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Diminished photoisomerization of active ruthenium water oxidation catalyst by anchoring to metal oxide electrodes. / Zhong, Diane K.; Zhao, Shengliang; Polyansky, Dmitry; Fujita, Etsuko.

In: Journal of Catalysis, Vol. 307, 2013, p. 140-147.

Research output: Contribution to journalArticle

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AB - Surface-binding of molecular water oxidation catalysts through phosphonated ligands offers a promising strategy for attaching homogeneous catalysts onto conductive or semiconductive oxide surfaces for heterogeneous catalysis. In this work, the highly active [Ru(tpy)(pynap)OH2]2+ (tpy = 2,2′:6′,2″-terpyridine; pynap = 2-(pyrid-2′-yl)-1,8- naphthyridine) water oxidation catalyst is attached onto metal oxide electrodes through a phosphate group. Electrochemical and photoelectrochemical results confirm that ruthenium oxidation chemistries and water oxidation proficiency remain largely unaffected by phosphonation. Surface-binding reveals minimal photoisomerization of the active d-form and allows us to evaluate photoelectrochemical and mechanistic properties of the catalyst. Spectroelectrochemical experiments support the evolution of multiple ruthenium oxidation states in agreement with Pourbaix diagrams. Although photoisomerization of d-[Ru(H2PO3-tpy)(pynap)OH 2]2+ is considerably hindered when the catalyst is attached onto a rigid oxide electrode, surface desorption remains a major challenge.

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