Reversibility of Ferri-Ferrocyanide Redox during in-Situ Soft X-Ray Spectroscopy
Bibliographic record
Abstract
Ferri-ferrocyanide is a common facile redox couple in electrochemistry and related fields; select applications include charge storage in flow batteries, prevention of electrolyte decomposition in batteries, redox shuttling in dye-sensitized solar cells and photoanodes, as well as measuring charge transfer on catalytic surfaces. Ferri-ferrocyanide is also frequently employed as a standard to establish new steady-state and time-resolved in-situ spectroscopy methods. Despite the ubiquity of the ferri-ferrocyanide redox couple in diverse fields, discussion exists as to whether its kinetics may depend on the composition of both the electrode and electrolyte. Furthermore, ferri-ferrocyanide decomposes when exposed to ionizing radiation such as soft X-rays at a synchrotron, which may lead to electrodeposition on the electrode. We studied the photochemical response of ferri-ferrocyanide to intense synchrotron radiation by in-situ X-ray absorption spectroscopy at the iron L edge. For photon flux densities above a defined threshold, precipitation of ferric (hydr)oxide from both ferricyanide and ferrocyanide solutions was clearly detectable. The formation of the precipitate was accelerated during cyclic voltammetry, which we probed by time-resolved in-operando X-ray absorption spectroscopy. The iron redox was completely inhibited in the probed volume after only two electrochemical cycles (70 min). Our study highlights the importance of considering both electrochemical and spectroscopic conditions when designing in-situ experiments that can shed light on charge transfer and chemistry of active sites in energy and health research.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".