A study of cyanide oxidation using electrochemical/electrospray mass spectrometry

Guo, Tao; Illies, Andreas J.; Cammarata, Vince; Arndt, Michael; Sonzogni, William C.

doi:10.1016/j.jelechem.2007.07.002

Cited by 9 publications

(5 citation statements)

References 15 publications

(23 reference statements)

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“…Guo et al . studied the electrochemical oxidation of cyanide in acetonitrile by electrospray‐mass spectrometry (ES‐MS) and similarly reported nucleophilic addition of cyanide to cyanogen, observing various (CN) n oligomers, but no (CN) 2 [123] …”

Section: Resultsmentioning

confidence: 99%

“…[121,122] Guo et al studied the electrochemical oxidation of cyanide in acetonitrile by electrospray-mass spectrometry (ES-MS) and similarly reported nucleophilic addition of cyanide to cyanogen, observing various (CN) n oligomers, but no (CN) 2 . [123] An attempt was made by us to conduct DEMS measurements on NaCN/carbon composite electrodes similar to those of Pan et al, [121] with the further intent, similar to the Li 2 CO 3 decomposition study of Freiberg et al, [85] to also quantify the consumed NaCN and thereby (CN) 2 amounts. However, this proved unsuccessful, as with the only available PVDF binder, slurry gelation was observed upon the presence of NaCN.…”

Section: Mechanistic Considerations and Discussionmentioning

confidence: 99%

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Elucidating Gas Evolution of Prussian White Cathodes for Sodium‐ion Battery Application: The Effect of Electrolyte and Moisture

Dreyer,

Maddar,

Kondrakov

et al. 2024

Batteries & Supercaps

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As global energy storage demand increases, sodium‐ion batteries are often considered as an alternative to lithium‐ion batteries. Hexacyanoferrate cathodes, commonly referred to as Prussian blue analogues (PBAs), are of particular interest due their low‐cost synthesis and promising electrochemical response. However, because they consist of ~50 wt% cyanide anions, a possible release of highly toxic cyanide gases poses a significant safety risk. Previously, we observed the evolution of (CN)2 during cycling via differential electrochemical mass spectrometry (DEMS), but were unable to determine a root cause or mechanism. In this work, we present a systematical investigation of the gas evolution of Prussian white (PW) with different water content via DEMS. While H2 is the main gas detected, especially in hydrated PW and during overcharge (4.6 V vs. Na+/Na), the evolution of CO2 and (CN)2 depends on the electrolyte conductive salt. The use of oxidative NaClO4 instead of NaPF6 is the leading cause for the formation of (CN)2. Mass spectrometric evidence of trace amounts of HCN is also found, but to a much lower extent than (CN)2, which is the dominant safety risk when using NaClO4‐containing electrolyte. Despite being a good model salt, it is not a viable option for commercial applications.

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Section: Resultsmentioning

confidence: 99%

Section: Mechanistic Considerations and Discussionmentioning

confidence: 99%

Elucidating Gas Evolution of Prussian White Cathodes for Sodium‐ion Battery Application: The Effect of Electrolyte and Moisture

Dreyer,

Maddar,

Kondrakov

et al. 2024

Batteries & Supercaps

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“…4, is believed to be due to the surface chemical reaction process where both CN − and O 2 need to be absorbed on the surface of metal. However if the concentration of CN − is too high, many of active sites on the metal surface will be occupied by CN − , which will not favour the absorption of O 2 .Therefor the existence of an optimum ratio between the concentration of cyanide and oxygen was also observed in the cyanide leaching of gold [13][14][15][16] .…”

Section: Effect Of Cyanide Concentrationmentioning

confidence: 99%

Study on Dissolution Different of Metal Palladium Powder and Place

Zhao

Zhang

Dai

2014

AMR

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The chemistry of the dissolution of Palladium in pressure-cyanide has not received considerable attention. At room temperature and pressures, the reaction between sodium cyanide and Palladium does not occur because of poor kinetics. However, at elevated temperatures between 100-160 °C, Palladium can be leached by sodium cyanide like the reaction of gold. A research study has been undertaken to develop the fundamentals of a method for the direct dissolution of Palladium In this work, the dissolution of Palladium powder and place were measured in pressure clear cyanide solution. The cyanide leaching reaction mechanism is also discussed. The data of Palladium powder and place at different cyanide concentrations, different temperature and different oxygen pressure are obtained. The dissolution rate of metal Palladium powder and place were found to be relate to the cyanide and oxygen level.

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“…At these high temperatures, free cyanide is readily hydrolysed and oxidized and is decomposed more quickly than the complexed cyanide. Electrochemical oxidation of cyanide at platinum electrodes has been studied by various electrochemical methods in aqueous solution [19] . The results suggest that the cyanide oxidation is an irreversible one-electron transfer process which is characterized by diffusion control.…”

Section: Effect Of P O2mentioning

confidence: 99%

Study on Pressure-Cyanide Dissolution of Metal Platinum Powder

Zhao

2012

AMR

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A research study has been undertaken to develop the fundamentals of a method for the direct dissolution of Metal Platinum. At room temperature and pressures, the reaction between sodium cyanide and platinum group metals (PGMs) does not occur because of poor kinetics. However, at elevated temperatures between 20°C and 180°C, PGMs can be dissolved by sodium cyanide like the reaction of gold. In this work, the dissolution of Platinum was measured in pressure clear cyanide solution. The data at different cyanide concentrations, different temperature and different oxygen pressure are obtained. With increasing cyanide concentration and oxygen pressure, the dissolution first increased to a maximum value and then decreased. With increasing temperature the dissolution is increased. The dissolution was found to have a relation of the cyanide and oxygen level. The dissolution was independent of rotation speed for oxygen-saturated solutions and cyanide concentrations above 5 mol.m-3 and was well below chemical reaction-limited for cyanide and oxygen.

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A study of cyanide oxidation using electrochemical/electrospray mass spectrometry

Cited by 9 publications

References 15 publications

Elucidating Gas Evolution of Prussian White Cathodes for Sodium‐ion Battery Application: The Effect of Electrolyte and Moisture

Elucidating Gas Evolution of Prussian White Cathodes for Sodium‐ion Battery Application: The Effect of Electrolyte and Moisture

Study on Dissolution Different of Metal Palladium Powder and Place

Study on Pressure-Cyanide Dissolution of Metal Platinum Powder

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