TY - JOUR
T1 - Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy
AU - Risch, Marcel
AU - Stoerzinger, Kelsey A.
AU - Regier, Tom Z.
AU - Peak, Derek
AU - Sayed, Sayed Youssef
AU - Shao-Horn, Yang
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/8/20
Y1 - 2015/8/20
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84939792999&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84939792999&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.5b04609
DO - 10.1021/acs.jpcc.5b04609
M3 - Article
AN - SCOPUS:84939792999
SN - 1932-7447
VL - 119
SP - 18903
EP - 18910
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 33
ER -