Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy
Author(s)Regier, Tom Z.; Peak, Derek; Sayed, Sayed Youssef; Risch, Marcel; Stoerzinger, Kelsey Ann; Shao-Horn, Yang; ... Show more Show less
MetadataShow full item record
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.
DepartmentMassachusetts 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
The Journal of Physical Chemistry C
American Chemical Society (ACS)
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.
Author's final manuscript