Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy

Marcel Risch, Kelsey A. Stoerzinger, Tom Z. Regier, Derek Peak, Sayed Youssef Sayed, Yang Shao-Horn

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

The ferri-/ferrocyanide redox couple is ubiquitous in many fields of physical chemistry. We studied its photochemical response to intense synchrotron radiation by in situ X-ray absorption spectroscopy (XAS). For photon flux densities equal to and above 2 × 1011 s-1 mm-2, precipitation of ferric (hydr)oxide from both ferricyanide and ferrocyanide solutions was clearly detectable, despite flowing fast enough to replace the solution in the flow cell every 0.4 s (flow rate 1.5 mL/min). During cyclic voltammetry, precipitation of ferric (hydr)oxide was promoted at reducing voltages and observed below 1011 s-1 mm-2. This was accompanied by inhibition of the ferri-/ferrocyanide redox, which we probed by time-resolved operando XAS. Our study highlights the importance of considering both electrochemical and spectroscopic conditions when designing in situ experiments.

Original languageEnglish (US)
Pages (from-to)18903-18910
Number of pages8
JournalJournal of Physical Chemistry C
Volume119
Issue number33
DOIs
StatePublished - Aug 20 2015
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

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