1992
DOI: 10.1149/1.2069204
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Solvation Phenomena in Polyvinylferrocene Films: Effect of History and Redox State

Abstract: The water content of electrochemically deposited polyvinylferrocene films was studied using the electrochemical quartz crystal microbalance. Unhydrated films were introduced into aqueous sodium perchlorate solution. Using cyclic voltammetry, the mass and charge change accompanying electrochemical cycling between oxidized and reduced states was determined. During the first oxidation cycle, water uptake into the unhydrated film is triggered after ca. 40% conversion. Of the water taken up during the first cycle, … Show more

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Cited by 46 publications
(26 citation statements)
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“…We have shown previously [45] how such processes can -presumably through the associated free volume changes -result in slow equilibration of net neutral (non-field-driven) species, namely salt and/or solvent. As a consequence of this, we have previously noted the difference between the initial and subsequent voltammetric EQCM responses of a PPy film redox cycled in a 1:1 aqueous electrolyte [46,47]; here we extend the investigation to 1:2 electrolytes. Fig.…”
Section: Effect Of Multiple Potential Cycles (Prior Redox History)supporting
confidence: 51%
See 1 more Smart Citation
“…We have shown previously [45] how such processes can -presumably through the associated free volume changes -result in slow equilibration of net neutral (non-field-driven) species, namely salt and/or solvent. As a consequence of this, we have previously noted the difference between the initial and subsequent voltammetric EQCM responses of a PPy film redox cycled in a 1:1 aqueous electrolyte [46,47]; here we extend the investigation to 1:2 electrolytes. Fig.…”
Section: Effect Of Multiple Potential Cycles (Prior Redox History)supporting
confidence: 51%
“…These figures show that the unusual feature of sulfate, namely the lesser accessible charge, is retained upon extended cycling. We attribute this feature to charge (and associated ion) trapping on the experimental timescale [46]. This effect is specific to the sulfate ion since, as the data of Fig.…”
Section: Steady-state Redox Cyclementioning
confidence: 79%
“…The first cycle shows lower peak current and a more anodic peak potential than the following ones. This phenomenon has been called the secondary ''break-in'' effect 56 or history effect. 57 The effect was tested using PBD.…”
Section: Poly(vinylferrocene) (Pvf)mentioning
confidence: 99%
“…[18][19][20] Studies into the electrochemical behaviour of pVFc films have shown how the voltammetric response is dependant on the anion present within the solution. 8,10,[21][22][23][24][25][26][27][28] The stability of the oxidation wave upon repetitive scanning was found to be dependant on the size of the anion, with larger anions producing less stable signals. This anion sensitivity was minimized by controlling both the scan rate and potential range.…”
Section: Introductionmentioning
confidence: 99%