Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • 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
The Impact of Ligand Carboxylates on Electrocatalyzed Water Oxidation
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0003-1256-501X
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Show others and affiliations
Number of Authors: 62021 (English)In: Accounts of Chemical Research, ISSN 0001-4842, E-ISSN 1520-4898, Vol. 54, no 17, p. 3326-3337Article, review/survey (Refereed) Published
Abstract [en]

Fossil fuel shortage and severe climate changes due to global warming have prompted extensive research on carbon-neutral and renewable energy resources. Hydrogen gas (H-2), a clean and high energy density fuel, has emerged as a potential solution for both fulfilling energy demands and diminishing the emission of greenhouse gases. Currently, water oxidation (WO) constitutes the bottleneck in the overall process of producing H-2 from water. As a result, the design of efficient catalysts for WO has become an intensively pursued area of research in recent years. Among all the molecular catalysts reported to date, ruthenium-based catalysts have attracted particular attention due to their robust nature and higher activity compared to catalysts based on other transition metals. Over the past two decades, we and others have studied a wide range of ruthenium complexes displaying impressive catalytic performance for WO in terms of turnover number (TON) and turnover frequency (TOF). However, to produce practically applicable electrochemical, photochemical, or photo-electrochemical WO reactors, further improvement of the catalysts' structure to decrease the overpotential and increase the WO rate is of utmost importance. WO reaction, that is, the production of molecular oxygen and protons from water, requires the formation of an O-O bond through the orchestration of multiple proton and electron transfers. Promotion of these processes using redox noninnocent ligand frameworks that can accept and transfer electrons has therefore attracted substantial attention. The strategic modifications of the ligand structure in ruthenium complexes to enable proton-coupled electron transfer (PCET) and atom proton transfer (APT; in the context of WO, it is the oxygen atom (metal oxo) transfer to the oxygen atom of a water molecule in concert with proton transfer to another water molecule) to facilitate the O-O bond formation have played a central role in these efforts. In particular, promising results have been obtained with ligand frameworks containing carboxylic acid groups that either are directly bonded to the metal center or reside in the close vicinity. The improvement of redox and chemical properties of the catalysts by introduction of carboxylate groups in the ligands has proven to be quite general as demonstrated for a range of mono- and dinudear ruthenium complexes featuring ligand scaffolds based on pyridine, imidazole, and pyridazine cores. In the first coordination sphere, the carboxylate groups are firmly coordinated to the metal center as negatively charged ligands, improving the stability of the complexes and preventing metal leaching during catalysis. Another important phenomenon is the reduction of the potentials required for the formation of higher valent intermediates, especially metal-oxo species, which take active part in the key O-O bond formation step. Furthermore, the free carboxylic acid/carboxylate units in the proximity to the active center have shown exciting proton donor/acceptor properties (through PCET or APT, chemically noninnocent) that can dramatically improve the rate as well as the overpotential of the WO reaction.

Place, publisher, year, edition, pages
2021. Vol. 54, no 17, p. 3326-3337
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-197954DOI: 10.1021/acs.accounts.1c00298ISI: 000695520400005PubMedID: 34488345OAI: oai:DiVA.org:su-197954DiVA, id: diva2:1606446
Available from: 2021-10-27 Created: 2021-10-27 Last updated: 2022-02-25Bibliographically approved

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textPubMed

Authority records

Das, BiswanathRahaman, AhiburÅkermark, Björn

Search in DiVA

By author/editor
Das, BiswanathRahaman, AhiburÅkermark, Björn
By organisation
Department of Organic Chemistry
In the same journal
Accounts of Chemical Research
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 23 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • 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