English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
Add to Basket
  Local TagsRelease HistoryDetailsSummary

Released
Journal Article

Reactive oxygen species in iridium-based OER catalysts

MPS-Authors
/persons/resource/persons104550

Pfeifer,  Verena
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
Catalysis for Energy, Group EM-GKAT, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Elektronenspeicherring BESSY II;

/persons/resource/persons135780

Jones,  Travis
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons22257

Wrabetz,  Sabine
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons85190

Massué,  Cyriac
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
MPI for Chemical Energy Conversion;

/persons/resource/persons104341

Velasco Vélez,  Juan
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
MPI for Chemical Energy Conversion;

/persons/resource/persons80761

Scherzer,  Michael
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
MPI for Chemical Energy Conversion;

/persons/resource/persons21590

Hävecker,  Michael
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
MPI for Chemical Energy Conversion;

/persons/resource/persons21743

Knop-Gericke,  Axel
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons22071

Schlögl,  Robert
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
MPI for Chemical Energy Conversion;

External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)

c6sc01860b.pdf
(Publisher version), 701KB

Supplementary Material (public)
There is no public supplementary material available
Citation

Pfeifer, V., Jones, T., Wrabetz, S., Massué, C., Velasco Vélez, J., Arrigo, R., et al. (2016). Reactive oxygen species in iridium-based OER catalysts. Chemical Science, 7(11), 6791-6795. doi:10.1039/C6SC01860B.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002B-0EA6-C
Abstract
Tremendous effort has been devoted towards elucidating the fundamental reasons for the higher activity of hydrated amorphous IrIII/IV oxyhydroxides (IrOx) in the oxygen evolution reaction (OER) in comparison with their crystalline counterpart, rutile-type IrO2, by focusing on the metal oxidation state. Here we demonstrate that, through an analogy to photosystem II, the nature of this reactive species is not solely a property of the metal but is intimately tied to the electronic structure of oxygen. We use a combination of synchrotron-based X-ray photoemission and absorption spectroscopies, ab initio calculations, and microcalorimetry to show that holes in the O2p states in amorphous IrOx give rise to a weakly bound oxygen that is extremely susceptible to nucleophilic attack, reacting stoichiometrically with CO already at room temperature. As such, we expect this species to play the critical role of the electrophilic oxygen involved in O-O bond formation in the electrocatalytic OER on IrOx. We propose that the dynamic nature of the Ir framework in amorphous IrOx imparts the flexibility in Ir oxidation state required for the formation of this active electrophilic oxygen.