Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 119, Issue 33, Pages 18903-18910Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.5b04609
Keywords
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Funding
- Skoltech-MIT Center for Electrochemical Energy Storage
- Singapore-MIT Alliance for Research and Technology (SMART)
- National Science Foundation [DMR-1419807]
- Canadian Foundation for Innovation
- Natural Sciences and Engineering Research Council of Canada
- University of Saskatchewan
- Government of Saskatchewan
- Western Economic Diversification Canada
- National Research Council Canada
- Canadian Institutes of Health Research
- National Science Foundation Graduate Research Fellowship [DGE-1122374]
- Natural Sciences and Engineering Research Council (NSERC) of Canada
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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 x 10(11) s(-1) mm(-2), precipitation of ferric (hydr)oxide from both ferricyanide and ferro cyanide 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 10(11) 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.
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