EQCM and XPS investigations on the redox switching of conducting poly(o-aminophenol) films electrosynthesized onto Pt substrates

Carbone, Maria Elvira Egidia; Ciriello, Rosanna; Granafei, Sara; Guerrieri, Antonio; Salvi, Anna Maria

doi:10.1016/j.electacta.2015.07.047

Cited by 21 publications

(25 citation statements)

References 37 publications

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“…Given the neutral ambient required to form insulating PoAP, their presence could only be justified by strong intra-chain or inter-chain interactions between neighboring groups of PoAP chains or be just the result of misinterpretation given the overlapping of shake up satellites found at higher BEs associated to carbon, oxygen, and nitrogen in oAP [6] clearly less identifiable after polymerization, being masked by the Pt extrinsic background, as already remarked. [6,17,18] In summary, by judging the overall and partial mass balance of carbon, oxygen, nitrogen, and platinum surface components, the results obtained show strong consistencies in term of composition of PoAP chains as a function of the number of CV cycles. This consistency supports our assumption on the complete formation of PoAP chains soon after the end of monomer oxidation in the course of the first cycle.…”

Section: Xps Analysismentioning

confidence: 86%

“…Water molecules within polymer chains are testified by the binding energies of nitrogen peaks, indicative of H-bond interactions. We have registered in the course of our investigation on PoAP, [6,7,17,18] chemical shifts of both ammine and immine components from their neutral state, respectively, found at 399.9 eV [6] (oAP) and 398.8 eV [17] (conducting PoAP vacuum dehydrated), depending on their partial charging, [7,17] to a full ionization when rinsing with HClO 4. [17] Given the low intensity of nitrogen, particularly at lower number of cycles in this work, our curve-fitting choice is the only plausible approach, grouping all the closely spaced chemical states of immine and ammine in the two peaks given in Table 1, which then show variable BEs of their maximum, in dependence of δ + shifts resultant of each functionality and even number of cycling ( Table 1).…”

Section: Xps Analysismentioning

confidence: 99%

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XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

Carbone

Ciriello

Guerrieri

et al. 2015

Surface & Interface Analysis

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The finite electrosynthesis, requiring 20 voltammetric cycles at neutral pH, of insulating poly(o-aminophenol) (PoAP)and its polymerization mechanism and chemical structure up to the outermost surface were reported in previous work. By reducing the number of voltammetric cycles, XPS, atomic force microscopy, and electrochemical experiments were here confined to partially grown PoAP to better understand the role of the platinum surface on the initial adhesion mechanism and polymer growth. XPS results from reduced number and conventional 20 cycles show that PoAP composition is the same at any cycle. The main differences imaged by atomic force microscopy between 1, 5, and 20 cycles are on the amount of 'small-sized particles' adsorbed on platinum prone to 'fill' the empty sites. The progressive filling of the platinum sites with cycles was also proved by electrochemical test with potassium-ferricyanide. These new results add valuable information, which sustain previous hypotheses on the growth process of PoAP chains, their composition, and lateral alignment. Some questions, concerning the identification of PoAP anchoring bonds on platinum, lateral H-bonds with water, and inter-chains interactions, still remain unanswered and will be further addressed by the employment of new advanced means of investigation already in progress.

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Section: Xps Analysismentioning

confidence: 86%

Section: Xps Analysismentioning

confidence: 99%

XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

Carbone

Ciriello

Guerrieri

et al. 2015

Surface & Interface Analysis

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“…In addition, the identification of the ions at mass 424 allowed the confirmation of the presence of carbonyl terminal groups, already observed by XPS, not only for the insulating PoAP but also for the conductive form of the same polymer obtained from monomer acidic solutions …”

Section: Discussionmentioning

confidence: 99%

ToF‐SIMS study of stages in the electrochemical growth of insulating poly(o‐aminophenol) films

Carbone

Ciriello

Salvi

et al. 2016

Surface & Interface Analysis

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Previous XPS investigations of insulating poly(o‐aminophenol) (PoAP), electrosynthesized by cyclic voltammetry on Pt substrates, revealed the formation of a thin film of about 7 nm of thickness, firmly adherent onto the electrode surface and stable even under Ultra High Vacuum (UHV) conditions. A constant repeat formula made of alternating quinoneimine and monomer units was derived with polymer chains terminating as carbonyl‐type groups. Based on these findings, we have continued our investigation on insulating PoAP by employing time‐of‐flight SIMS whose superior surface sensitivity is well‐known. The aim was to corroborate the polymer structure with particular reference to the top surface layers in view of possible bio‐applications and to understand the possible way of interaction with the underlying platinum electrode surface. In order to do this, we analyzed PoAP films grown at different levels of the electrochemical synthesis (1, 5, and 20 scan cycles) and the platinum substrate itself. The individuation of the main characteristic fragments and the behavior of their intensity by varying the stage of the electropolymerization allowed to confirm the polymer structure and the presence of terminating carbonyl groups. Remarkably, from the analysis of the PoAP/Pt interface at the early stage of the polymer formation, it was possible to discern that polymer chains tend to interact with the electrode surface preferentially by the nitrogen atom of the oxidized monomers. Copyright © 2016 John Wiley & Sons, Ltd.

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“…The voltammograms are ill-defined for pH higher than 3 and for pH close to 5 the cathodic peak practically disappears. 53,63 Furthermore, it has been proposed that the redox mechanism in acidic media is complex involves both the addition and elimination of protons. 63 The oxidation of POAP (red) is a two-electron process coupled to the release of two protons.…”

Section: Nanoscale Accepted Manuscriptmentioning

confidence: 99%

How to control the ionic transport through a nanochannel using a redox polymer

Cayón¹,

Laucirica²,

Terrones³

2020

Preprint

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EQCM and XPS investigations on the redox switching of conducting poly(o-aminophenol) films electrosynthesized onto Pt substrates

Cited by 21 publications

References 37 publications

XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

XPS, AFM, and electrochemical investigation on the inner composition of insulating poly(o‐aminophenol), PoAP, deposited on platinum by CV, as a function of the number of cycles

ToF‐SIMS study of stages in the electrochemical growth of insulating poly(o‐aminophenol) films

How to control the ionic transport through a nanochannel using a redox polymer

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