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

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

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Author(s)
Regier, Tom Z.
•
Peak, Derek
•
Sayed, Sayed Youssef
•
Risch, Marcel
•
Stoerzinger, Kelsey Ann
•
Shao-Horn, Yang
Date Issued
July 2015
Journal
The Journal of Physical Chemistry C
Publisher
American Chemical Society (ACS)
Citation
Risch, Marcel, Kelsey A. Stoerzinger, Tom Z. Regier, Derek Peak, Sayed Youssef Sayed, and Yang Shao-Horn. “Reversibility of Ferri-/Ferrocyanide Redox During Operando Soft X-Ray Spectroscopy.” The Journal of Physical Chemistry C 119, no. 33 (August 20, 2015): 18903–18910.
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Author's final manuscript
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.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Department of Mechanical Engineering
Massachusetts Institute of Technology. Research Laboratory of Electronics
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
http://hdl.handle.net/1721.1/109590
DOI of Published Version
https://doi.org/10.1021/acs.jpcc.5b04609
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