Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Evidence for Oxidative Decay of a Ru-Bound Ligand during Catalyzed Water Oxidation
Show others and affiliations
2017 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 7, no 4, 2607-2615 p.Article in journal (Refereed) Published
Abstract [en]

In the evaluation of systems designed for 800 catalytic water oxidation, ceric ammonium nitrate (CAN) is often used as a sacrificial electron acceptor. One of the sources of failure for such systems is oxidative decay of the catalyst in the presence of the strong oxidant CAN (E-ox = +1.71 V). Little progress has been made in understanding the circumstances behind this decay. In this study we show that a 2-(2'-hydroxphenyl) derivative (LH) of 1,10-phenanthroline (phen) in the complex [Ru(L)(tpy)](+) (tpy = 2,2';6',2 ''-terpyridine) can be oxidized by CAN to a 2-carboxy-phen while still bound to the metal. This complex is, in fact, a very active water oxidation catalyst. The incorporation of a methyl substituent on the phenol ring of LH slows down the oxidative decay and consequently slows down the catalytic oxidation. An analogous system based on bpy (2,2'-bipyridine) instead of phen shows much lower activity under the same conditions. Water molecule association to the Ru center of [Ru(L)(tpy)](+) and carboxylate donor dissociation were proposed to occur at the trivalent state. The resulting [Ru-III-OH2] was further oxidized to [Ru-IV=O] via a PCET process.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2017. Vol. 7, no 4, 2607-2615 p.
Keyword [en]
mononuclear Ru catalysts, water oxidation, anionic ligands, 2-carboxyphenanthroline, ligand decay
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-206687DOI: 10.1021/acscatal.6b03278ISI: 000398986700045OAI: oai:DiVA.org:kth-206687DiVA: diva2:1094147
Note

QC 20170509

Available from: 2017-05-09 Created: 2017-05-09 Last updated: 2017-05-09Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Ahlquist, Mårten S. G.Fan, Ting
By organisation
Theoretical Chemistry and Biology
In the same journal
ACS Catalysis
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

Altmetric score

Total: 29 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf