Effect of electrolyte nature on the electrochemical synthesis and doping of polyaniline and poly-3-phenylthiopene

Pokhodenko, V. D.; Krylov, V. A.

doi:10.1016/0379-6779(91)91125-t

Cited by 19 publications

(7 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[22][23][24][25][26] However, experiments using other CPs revealed that the role of the electrolytic agent and the solvent in the n-doping is even higher than in the pdoping. [28][29][30] According to these observations, in a recent study, Suárez-Herrera and coworkers 27 showed that the negative charge of the n-doped PEDOT stabilizes when imidazolium-containing ionic liquids are used as dopant cations, resulting in a high ndoping concentration with respect to than obtained with tetra-alkylammonium cations. [22][23][24][25][26] On the other hand, ionenes are high charged polymers (polyelectrolytes) in which the ionic groups form part of the macromolecular backbone.…”

Section: Introductionmentioning

confidence: 99%

Cationic ionene as an n-dopant agent of poly(3,4-ethylenedioxythiophene)

Saborío

Bertrán

Lanzalaco

et al. 2018

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We report the reduction of poly(3,4-ethylenedioxythiophene) (PEDOT) films with a cationic 1,4-diazabicyclo[2.2.2]octane-based ionene bearing N,N'-(meta-phenylene)dibenzamide linkages (mPI). Our main goal is to obtain n-doped PEDOT using a polymeric dopant agent rather than small conventional tetramethylammonium (TMA), as is usual. This has been achieved using a three-step process, which has been individually optimized: (1) preparation of p-doped (oxidized) PEDOT at a constant potential of +1.40 V in acetonitrile with LiClO4 as the electrolyte; (2) dedoping of oxidized PEDOT using a fixed potential of -1.30 V in water; and (3) redoping of dedoped PEDOT applying a reduction potential of -1.10 V in water with mPI. The resulting films display the globular appearance typically observed for PEDOT, with mPI being structured in separated phases forming nanospheres or ultrathin sheets. This organization, which has been supported by atomistic molecular dynamics simulations, resembles the nanosegregated phase distribution observed for PEDOT p-doped with poly(styrenesulfonate). Furthermore, the doping level achieved using mPI as the doping agent is comparable to that achieved using TMA, even though ionene provides distinctive properties to the conducting polymer. For example, films redoped with mPI exhibit much more hydrophilicity than the oxidized ones, whereas films redoped with TMA are hydrophobic. Similarly, films redoped with mPI exhibit the highest thermal stability, while those redoped with TMA show thermal stability that is intermediate between those of the latter and the dedoped PEDOT. Overall, the incorporation of an mPI polycation as the n-dopant into PEDOT has important advantages for modulating the properties of this emblematic conducting polymer.

show abstract

Section: Introductionmentioning

confidence: 99%

Cationic ionene as an n-dopant agent of poly(3,4-ethylenedioxythiophene)

Saborío

Bertrán

Lanzalaco

et al. 2018

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…penetrate into the film due to its smaller size [65]. Alkali metal salts are not suitable electrolyte materials for our purpose because n-doping of polythiophene appears to be inhibited by the large solvation shell which accompanies them in acetonitrile solution, [119,120] although n-doping of poly-3-phenyl benzene in LiClO 4 electrolyte in acetonitrile has been reported [121]. Even trace amounts of alkali metal cations present in the electrolyte have been shown to impede severely the ability to n-dope polythiophene [119].…”

Section: Theoretical Calculation Methodsmentioning

confidence: 99%

“…The probability of this step should be closely related to the spin density of the unpaired electron and the steric effect between the two cations. 120.968 C 8 -C 9 1.400 < C 7 C 6 C 11 117.617 C 9 -C 10 1.402 < C 6 C 7 C 8 121.061 C 9 -C 12 1.511 < C 7 C 8 C 9 121.322 C 10 -C 11 1.391 < C 8 C 9 C 10 117.639 < C 8 C 9 C 12 121.476 < C 10 C 9 C 12 120.885 < C 9 C 10 C 11 121.281 < C 6 C 11 C 10 121.077 Since the oxidation of a dimer is easier than that of a monomer, the radical cation of the dimer also formed undergoes further coupling reactions with other radical cations. [191][192][193].…”

Section: Uv-visible and Electrochemical Bandgaps Of 3-phenylthiophenementioning

confidence: 99%

Electrochemical materials science: calculation vs. experiment as predictive tools in tailoring intrinsically conducting polythiophenes

Alhalasah

Holze

2006

Microchim Acta

View full text Add to dashboard Cite

) wurde elektrochemisch polymerisiert, um Filme zu erhalten, die umkehrbar reduziert und oxidiert werden konnten (nund p-dotiert wurden). Die Oxidationspotentiale der Monomere und die formalen Potentiale der n und pDotierprozesse der Polymere wurden mit Resonanz-und induktiven Effekten der Substituenten (Hammett konstanten) am Phenylring sowie semiempirisch errechneten Bildungswärmen der Monomereradikalkationen korreliert. Außerdem wurden die Oxidationspotentiale mit den Ionisierungspotentialen der Monomere verglichen, die über die Dichtefunktionialtheorie (DFT) errechnet wurden, die der Energie für das Erzeugen der Radikalkationen entsprechen.Um theoretische Grundlagen für die Einstufen-Bildung regioregulär α-konjungierter Oligo-und Polythiophene zu erhalten, wurden die elektronischen Zustände von 3-Phenylthiophen-Derivaten anhand von Molekülorbitalberechnungen auf Grundlage der Dichtefunktionaltheorie mit Becke's Drei-Parameter-Funktion (B3LYP), sowie mit den Basissätzen 6-31G(d) und 3-21G(d) erklärt. Die Reaktivität der Verknüpfung von monound oligo-3-Phenylthiophenen wurde von den berechneten ungepaarten Elektronenspindichten der entsprechenden Radikal-Anionen abgeleitet. Die Ionisierungspotentiale, die den Energien zur Erzeugung der Radikal-Anionen während der Oxidation entsprechen, wurden abgeschätzt. Die aus den 3-Phenylthiophenen entstandenen regioselektiven Hauptprodukte können gut durch die Größe der Spindichten erklärt werden. Da die Verknüpfungsreaktion an der zwei-Position des Thiophnrings (C-2) sterisch durch die Phenylgruppe und den Thiophenring gehindert ist, startet die Initiierung der 3-Phenylthiophene über die Bildung eines Kopf-SchwanzDimers. Folglich spielt das Kopf-Schwanz-Dimer eine wichtige Rolle bei den Wachstumsreaktionen der 3-Phenylthiophene. Die Ursache dafür liegt darin, dass das Kopf-Schwanz-Dimer in 5′-Position die höchste SpinDichte besitzt und die Wahrscheinlichkeit einer Kopf-Kopf-Verknüpfung aufgrund der sterischen Hinderung zwischen dem Thiophenring und der Phenylgruppe gering ist.Polymerfilme von 3-Phenylthiophenderivaten, die durch elektrochemische Polymerisation synthetisiert wurden, sind in situ und ex situ durch Resonanz-Raman-Spektroskopie bei verschiedenen Anregungswellenlängen, sowie durch in situ und ex situ UV-Vis Spektroskopie analysiert wurden.Die Entwicklung der in situ UV-Vis-Spektren der Polymer von 3-Phenylthiophene nach der Dotierung wird durch ähnliche Eigenschaften gekennzeichnet, wie für viele Polythiophene mit einem hohen Grad der Konjugation beobachtet. Während der schrittweisen Oxidation der Poly-3-phenylthiophen Filme verringert sich die Intensität der Absorption wegen des Überganges * → π π Experiment as Predictive Tools inTailoring Intrinsically Conducting PolythiophenesA series of 3-(p-X-phenyl) thiophene monomers (X= -H, -CH 3 , -OCH 3 , -COCH 3 , -COOC 2 H 5 , -NO 2 ) was electrochemically polymerized to furnish polymer films that could be reversibly reduced and oxidized (n-and p-doped). The oxidation potentials of the monomers and formal potenti...

show abstract

“…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].…”

mentioning

confidence: 98%

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

Сидоров

Pud

2010

Theor Exp Chem

View full text Add to dashboard Cite

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

show abstract

Effect of electrolyte nature on the electrochemical synthesis and doping of polyaniline and poly-3-phenylthiopene

Cited by 19 publications

References 3 publications

Cationic ionene as an n-dopant agent of poly(3,4-ethylenedioxythiophene)

Cationic ionene as an n-dopant agent of poly(3,4-ethylenedioxythiophene)

Electrochemical materials science: calculation vs. experiment as predictive tools in tailoring intrinsically conducting polythiophenes

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

Contact Info

Product

Resources

About