Electropolymerization of 3-methylthiophene studied by multiflux convolution

Correia, J. Pinto; Vieil, E.; Abrantes, L.M.

doi:10.1016/j.jelechem.2004.06.036

Cited by 19 publications

(17 citation statements)

References 28 publications

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“…On the whole, these results indicate the specific transfer of charged oligomers into the solution, which is in accord with the findings of Haier [8]. On the other hand, the subsequent transformations of these products indeed lead to the appearance of oligomers in solution, which, as shown by Correia [12], diffuse toward the anode and participate in the polymerization reaction, reducing its overvoltage. This scheme, in particular, is confirmed by the cyclic voltammogram after the synthesis (Fig.…”

Section: Resultssupporting

confidence: 89%

“…Another mechanism has also been proposed for annihilation of the oligomer radical-cations through nucleophilic addition of 3MT to these radical-cations with subsequent elimination of a proton [11]. Furthermore, we should note that, according to Correia et al [12], 3MT trimers mainly enter the solution and then undergo polymerization on the electrode.…”

Section: Resultsmentioning

confidence: 73%

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In situ spectroelectrochemical study of dissolved oligomer products formed in the electrochemical polymerization of 3-methylthiophene

Сидоров

Pud

2010

Theor Exp Chem

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An in situ spectroelectrochemical study was carried out on the formation of 3-methylthiophene oligomer radical-cations (monomer, dimer, and trimer) and the 3-methylthiophene dihydrocation in the solution bulk during the electrochemical synthesis of a poly-3-methylthiophene coating on a conducting glass electrode. A dependence of the concentration of products formed on the cation radius (Li + and Na + ) and nature of the anion (ClO 4 -and BF 4 -) of the base electrolyte was established. The conversion of charged components into neutral dimers and tetramers of 3-methylthiophene after termination of the anodic polymerization was shown in accord with reported results on the electrochemical polymerization of thiophenes.The rather good results obtained in the use of poly(3-alkylthiophene), including poly-(3-methylthiophene) (P3MT) in photovoltaic, sensor, and electrochemical devices [1] is a function not only of the current level of understanding of the physical and chemical aspects of the nature of the polymer but also of the high quality of the polymers obtained. The mechanisms of the chemical and electrochemical polymerization of their polymers have been described in rather considerable detail in the literature [2][3][4]. In particular, the electrochemical polymerization of 3-alkylthiophenes is known to proceed through a radical-cation mechanism with formation of long polyconjugated chains [3]. The polymer is obtained in an oxidized state, in which the positive charge is compensated by the base electrolyte anions. Thus, the structure and properties of the resultant poly(3-alkylthiophenes) should depend on the nature of these anions [5]. We should note that while the effect of these anions on the electrochemical polymerization and properties of the resultant polymer is rather clear and has been extensively studied, the functions of the electrolyte cations in such systems have not received adequate attention as a consequence of their apparent insignificance. However, in the case of the galvanostatic electrochemical polymerization of 3-phenylthiophene (3PT), Pokhodenko and Krylov [6] found that overvoltage of this process drops in the cation series Bu 4 N + > Et 4 N + > Na + > Li + . The oxidation potential of 3PT decreases in virtually the same series (without Et 4 N + ) [7]. According to Pokhodenko et al. [6,7], such an effect of the base electrolyte cations on the electrochemical stage of the process is related to the interaction of these cations with the sulfur atom of the uncharged aromatic thiophene ring. Furthermore, the electrochemical polymerization of 3MT is accompanied by a transition of the intermediate 3MT oligomer radical-cations to the solution bulk from the anode surface (where oxidation of the monomer occurs). These charged intermediates subsequently undergo chemical reaction with 158 0040-5760/10/4603-0158

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 73%

In situ spectroelectrochemical study of dissolved oligomer products formed in the electrochemical polymerization of 3-methylthiophene

Сидоров

Pud

2010

Theor Exp Chem

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“…The changes on the concentration of SE species are developed at the same time and position; however, the magnitude of these changes depends on the ratio of their respective diffusion coefficients. This outcome would become particularly important when the influence of H + or OH À is being considered to hypothesize about some complex systems [29,33,34,44]. On the other hand, for the case of SE ions with similar diffusion coefficients and equivalent charge, the product z K D K (z A D A ) À1 will be equal or close to À1.…”

Section: Discussionmentioning

confidence: 98%

“…Under these conditions, the sign of oc K /ox (or oc A /ox) will depend on the position where its derivation is evaluated with regard to the maximum (or minimum) of concentration rather than on the difference C Ã j À C jð0;tÞ that is commonly assumed. Usually, the concentration gradients of SE are analyzed to describe the ion exchange of these ions at the electrode [11,31,33,34,44]. According to the last outcomes, however, this description could not always be accurate, and further in-depth analysis of the movement of charges of electroactive species could be required.…”

Section: General Aspects: Reversible Casementioning

confidence: 99%

Charge neutralization process of mobile species developed during potentiodynamic conditions. Part 1: Theory

Garay

Barbero

2008

Journal of Electroanalytical Chemistry

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“…The coupling of electrochemical and optical techniques has been often used to gather a deeper knowledge of the electrosynthesis process [18][19][20]. In particular, in situ ellipsometry has already been successfully employed for the study of the electropolymerization of thiophene and its derivatives [18,21,22], as well as in the analysis of the redox properties of the deposited films [23].…”

Section: Introductionmentioning

confidence: 99%

An ellipsometric study of poly(3,4-ethylenedioxythiophene) electrosynthesis – from the initial stages to thick layers formation

Abrantes

Correia

Melato

2010

Journal of Electroanalytical Chemistry

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Electropolymerization of 3-methylthiophene studied by multiflux convolution

Cited by 19 publications

References 28 publications

In situ spectroelectrochemical study of dissolved oligomer products formed in the electrochemical polymerization of 3-methylthiophene

In situ spectroelectrochemical study of dissolved oligomer products formed in the electrochemical polymerization of 3-methylthiophene

Charge neutralization process of mobile species developed during potentiodynamic conditions. Part 1: Theory

An ellipsometric study of poly(3,4-ethylenedioxythiophene) electrosynthesis – from the initial stages to thick layers formation

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