Electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with sulfonated thiophenes

Sulfonated thiophenes, sodium 2-(3-thienyloxy)ethanesulfonate (C₆H₇S₂O₄Na) and sodium 6-(3-thienyloxy)hexanesulfonate (C₁₀H₁₅S₂O₄Na), were synthesized and used in the fabrication of ion-selective electrodes (ISEs) sensitive and selective to Ag⁺. The Ag⁺-ISEs were prepared by galvanostatic electropolymerization of 3,4-ethylenedioxythiophene (EDOT) on glassy carbon (GC) electrodes, with either C₆H₇S₂O₄⁻ or C₁₀H₁₅S₂O₄⁻ as the charge compensator (doping ion) for p-doped poly(3,4-ethylenedioxythiophene) (PEDOT). Potentiometric measurements were carried out with these sensors, GC/PEDOT(C₆H₇S₂O₄⁻) and GC/PEDOT(C₁₀H₁₅S₂O₄⁻), to study and compare their sensitivity and selectivity to silver ions. PEDOT(C₆H₇S₂O₄⁻) and PEDOT(C₁₀H₁₅S₂O₄⁻) films were also studied by using other techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance (EQCM) and Fourier transform infrared spectroscopy (FTIR).Results from the potentiometric measurements showed that the difference in length of the alkyl chain of the doping ions C₆H₇S₂O₄⁻ and C₁₀H₁₅S₂O₄⁻ has no significant effect on the sensitivity or selectivity of GC/PEDOT(C₆H₇S₂O₄⁻) and GC/PEDOT(C₁₀H₁₅S₂O₄⁻) sensors to Ag⁺. More differences can be seen in the cyclic voltammograms and EIS spectra of the sensors. FTIR spectra confirmed that both C₆H₇S₂O₄⁻ and C₁₀H₁₅S₂O₄⁻ act as doping ions in the electrosynthesis of PEDOT-based films and they are not irreversibly immobilized in the polymer backbone.     

Achieving efficient poly(3,4-ethylenedioxythiophene)-based supercapacitors by controlling the polymerization kinetics

In this study, we have prepared a series of poly(3,4-ethylenedioxythiophene) (PEDOT) with various molecular weight by using an inhibitor, imidazole (Im). The X-ray diffraction (XRD) results show that the PEDOT with larger molecular weight enhances the polymer chain ordering and stacking which leads to higher conductivity. With increasing the amount of Im, the conductivity of PEDOT can be increased from 4.01 S cm⁻¹ (Im = 0.0 M) to 153.6 S cm⁻¹ (Im = 1.8 M). Comparisons of the cyclic voltammetry (CV), it enables correlation between the conductivity and specific capacitance, which is important for understanding the electrochemical capacitive behavior of conjugated polymer for pseudo-capacitor application. The PEDOT prepared with 1.8 M Im shows a specific capacitance of 124 F g⁻¹, which is 2.2 times larger than the one without Im (57 F g⁻¹).     

Chemical cross-linking of conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using poly(ethylene oxide) (PEO)

Hybrid films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) were prepared with different molecular weights of poly(ethylene oxide) (PEO). The cross-linking reaction between PEO and PEDOT:PSS was performed at high temperature and confirmed by using differential scanning calorimeter (DSC), contact angle measurement, and solid-state ¹H NMR. The effect of chemical reaction on the conductivity and morphology of these hybrid films was studied by using 4-point probe and atomic force microscope (AFM), respectively. As-spun PEO/PEDOT:PSS films have lower electric conductivity due to the addition of nonconductive PEO, and exhibits no molecular weight dependence on conductivity. After chemical cross-linking reaction at high temperature, only PEDOT:PSS films with lowest molecular weight PEO additives show enhanced conductivity with increasing reaction time. AFM result indicates that the heat-treated PEO/PEDOT:PSS hybrid films show grain-like morphology compared to ethylene glycol treated PEDOT:PSS films which shows continuous PEDOT domain. In the present work we demonstrate that the cross-linking reaction can be used to improve the wet stability of PEDOT:PSS nanofiber, showing good water resistance and excellent dimensional stability.     

Different steps in the electrosynthesis of poly(3,4-ethylenedioxythiophene) on platinum

The initial stages of poly(3,4-ethylenedioxythiophene) (PEDOTh) film growth on platinum electrodes from TBAClO₄/acetonitrile solution are investigated by means of current-time transient measurements and tapping mode atomic force microscopy. It is shown that, for growth potentials in the range 1.17-1.29 V vs. SCE, the deposition process involves the formation of oligomers in the solution, progressive nucleation of centres of the new phase and three-dimensional growth of a first compact layer followed by a non-uniform distribution of granular-like clusters, whose number and size increase with the synthesis potential and charge. The obtained results reveal that PEDOTh films prepared at distinct potentials but with the same growth charge (Q_g) display similar electroactivities. They also depict that the electrochemical behaviour of the films is a function of the charge used for the synthesis, namely the reduction of tick PEDOTh layers (Q_g > 20 mC cm⁻²) includes more that one step, as a consequence of the formation of a two-layered polymer film.     

A comprehensive study of the interactions between DNA and poly(3,4-ethylenedioxythiophene)

The interaction between poly(3,4-ethylenedioxythiophene), a conducting polymer with excellent electrical and electrochemical properties, and plasmid DNA has been investigated using electrophoresis, UV-visible and CD spectroscopy, and quantum mechanical calculations. Analyses of mixtures with different DNA:polymer mass ratios indicate that, in all cases, interactions form immediately and induce structural alterations in DNA. Furthermore, the existence of interactions between poly(3,4-ethylenedioxythiophene) and specific nucleotides sequences has been evidenced by adding restriction enzymes to the mixtures. In contrast, interactions between DNA and poly(3-methylthiophene), a similar polyheterocyclic conducting polymer but without hydrogen bonding acceptors, are weak or do not exist. These results suggest that, in addition to non-specific electrostatic interactions between the charged phosphate groups of DNA and the positively charged fragments of the conducing polymers, specific hydrogen bonding interactions play a crucial role. The ability of 3,4-ethylenedioxythiophene units to form hydrogen bonds with the methylated analogues of DNA bases has been examined in different environments using MP2/6-31G(d) and MP2/6-311++G(d,p) calculations. Results indicate that, in environments with low polarity, the formed interactions are significantly stronger than those reached by unsubstituted thiophene and similar to those established by pyrrole. However, in polar environments (aqueous solution) 3,4-ethylenedioxythiophene provides stronger interactions with nucleic acids than both thiophene and pyrrole. These theoretical results are fully consistent with experimental observations.     

Poly(Δ-dicyclopenta[2,1-b:3,4-b′]dithiophene-co-3,4-ethylenedioxythiophene): Electrochemically generated low band gap conducting copolymers

A low HOMO-LUMO gap, alkene bridged bis-bithiophene (Δ^4,4′-dicyclopenta [2,1-b:3,4-b′]dithiophene) has been copolymerized with electron rich 3,4-ethylenedioxythiophene, to produce copolymers with reduced band gaps and enhanced conductivities. Electrochemical band gaps as low as 0.1 eV have been observed, but maximum conductivities were only ca. 0.3 mS cm⁻¹. Poor matching of the HOMO energies of the two components, together with cross-conjugation at the alkene bridge appear to limit charge carrier mobilities. These results provide further evidence that the use of donor and acceptor moieties to decrease band gaps leads to materials with decreased charge carrier mobilities due to charge localization.     

Structural, chemical and electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) prepared with various counter-ions and heat treatments

Electrochemical deposition of the conjugated polymer poly(3,4-ethylenedioxythiophene) (PEDOT) forms thin, conductive films that are especially suitable for charge transfer at the tissue-electrode interface of neural implants. For this study, the effects of counter-ion choice and annealing parameters on the electrical and structural properties of PEDOT were investigated. Films were polymerized with various organic and inorganic counter-ions. Studies of crystalline order were conducted via X-ray diffraction (XRD). Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to investigate the electrical properties of these films. X-ray photoelectron spectroscopy (XPS) was used to investigate surface chemistry of PEDOT films. The results of XRD experiments showed that films polymerized with certain small counter-ions have a regular structure with strong (100) edge-to-edge correlations of PEDOT chains at ∼1.3 nm. After annealing at 170 °C for 1 h, the XRD peaks attributed to PEDOT disappeared. PEDOT polymerized with LiClO₄ as a counter-ion showed improved impedance and charge storage capacity after annealing at 160 °C.     

Accumulation of Cu(II) cations in poly(3,4-ethylenedioxythiophene) films doped by hexacyanoferrate anions and its application in Cu-selective electrodes with PVC based membranes

Electrochemical properties of poly(3,4-ethylenedioxythiophene) doped with hexacyanoferrate(II,III) ions (PEDOT(HCF)) were studied in the presence of Cu²⁺ ions. Voltammetric and EDAX studies revealed retention of hexacyanoferrate anions in the polymer film and accumulation of Cu(II) cations, as well as formation of solid copper hexacyanoferrate near the polymer surface.Accumulation of Cu²⁺ ions was found to be advantageous from the point of view of PEDOT(HCF) applications as a solid contact (ion-to-electron transducer) in all-solid-state Cu²⁺-selective electrodes with solvent polymeric polyvinyl chloride (PVC) based membrane, containing Cu²⁺-selective ionophore. Binding of Cu²⁺ ions in the conducting polymer layer results in analyte ions flux into the transducer phase. Thus, pronounced enhancement of selectivity of the all-solid-state Cu²⁺-selective electrode or lower detection limit of the potentiometric response range was achieved, reaching under optimised conditions 10⁻⁷ M CuSO₄.     

Electrosyntheses and characterizations of a new soluble conducting copolymer of 5-cyanoindole and 3,4-ethylenedioxythiophene

The copolymerization of 5-cyanoindole (CNIn) and 3,4-ethylenedioxythiophene (EDOT) was successfully performed electrochemically in acetonitrile containing tetrabutylammonium tetrafluoroborate by direct oxidation of monomer mixtures. The electrochemical properties of the copolymers were studied by cyclic voltammetry. The influence of applied polymerization potential on the synthesis of copolymer was investigated. This novel copolymer owns the advantages of poly(5-cyanoindole) (PCNIn) and poly(3,4-ethylenedioxythiophene) (PEDOT), i.e., good redox activity, good thermal stability and high conductivity. The copolymer was soluble in dimethyl sulfoxide. The fluorescence spectra indicate that the copolymer is a good blue-light emitter. The structure and morphology of the copolymers were investigated by UV–vis, infrared spectroscopy, ¹H NMR spectra and scanning electron microscopy (SEM), respectively.     

Simultaneous novel synthesis of conducting and non-conducting halogenated polymers by electroinitiation of (2,4,6-trichloro- or 2,6-dichlorophenolato)Ni(II) complexes

NiL₂(Ph)₂·xH₂O [L=3,5-dimethylpyrazole or N-methyl imidazole; Ph=DCP or TCP; x=0, 1 or 3] complexes were synthesised and characterised by analytical and spectroscopic methods using elemental analysis and FTIR. The electrochemical behavior of the complexes was studied by cyclic voltammetry in tetrabutylammoniumtetrafluoroborate-N,N-dimethylformamide electrolyte-solvent couple. Cyclic voltammogram of the complexes displayed two-step oxidation processes under the nitrogen gas atmosphere. The polymerization of the complexes was accomplished in the same solvent-electrolyte couple by the constant potential electrolysis of NiL₂(Ph)₂·xH₂O, synthesizing the poly(di- or monochlorophenylene oxide)s via free radical mechanism. The simultaneous polymerization of non-conducting polymer and conducting polymer (the conductivity of 0.7 S cm⁻²) were achieved by electroinitiated polymerization of Ni(DMPz)₂(TCP)₂. The structural analysis of the polymers were performed using FTIR, ¹H NMR and ¹³C NMR spectroscopic techniques and DSC for the thermal analysis. The kinetics of the polymerization was followed by in situ UV-vis spectrophotometer during the electrolysis. The low temperature ESR spectrum of the electrolysis solution also confirmed the formation of phenol radical (g=2.0028). One electron oxidation process of NiL₂(DCP)₂·xH₂O produces a new Ni(II) complex, Ni(L-L)(DCP)₂(S) by the rapid decomposition of Ni^IIIL₂(DCP)₂ into a ligand radical producing a singlet with the g value of 2.0015. Second electron oxidation process generates oligemers, which could not be isolated from the electrolyte solution.     

Solvent effect on the nucleation and growth mechanisms of poly(thiophene)

Applying the step potential method, the effect of parameters such as solvent, potential, electrolyte and monomer concentration on the nucleation and growth processes of poly(thiophene) on Pt electrode in tetrabuthylammonium hexafluorophosphate-acetonitrile or dichloromethane has been studied. The j/t transients were generally fitted by means of a mathematical equation that considers different contributions. In acetonitrile the j/t transient (0<t<30 s) present three contributions corresponding to the following mechanisms: two-dimensional instantaneous nucleation (IN2D), three-dimensional progressive nucleation (PN3D_CT) under charge transfer control and three-dimensional progressive nucleation (PN3D_dif) under diffusion control. Similar results were obtained in dichloromethane, but in this case the 3D_CT nucleus presented an instantaneous nucleation mechanism (IN3D_ct). A second wave has been observed in the j/t transients obtained in CH₃CN at t>30 s, which was fitted by a mathematical equation that included two contributions corresponding to a PN3D_CT and PN3D_dif mechanisms. In general, the charge associated to each contribution depended on the solvent, the monomer and electrolyte concentration and the applied potential. However, the PN3D_CT (CH₃CN) or IN3D_CT (CH₂Cl₂) mechanisms were always the more important contributions. The scanning electron microscopy (SEM) analysis of the deposits morphology are in agreement with the nucleation and growth models that are proposed by this method.     

Synthesis and characterization of conducting and non-conducting polymers of sodium 2,4,6-trichlorophenolate by microwave initiation

A novel synthesis of poly(dichlorophenylene oxide) and a conducting polymer were achieved simultaneously from 2,4,6-trichlorophenol in a very short time, using microwave energy. The characterizations of poly(dichlorophenylene oxide) and the conducting polymer were performed by DSC, TGA, elemental analysis, FTIR, ¹H and ¹³C NMR, SEM, MS and X-ray diffraction spectrometer analyses. The combined molecular weight of the polymer, 1.8×10⁴, was determined by using viscometry measurement. Poly(dichlorophenylene oxide) displaces selectivity in the favor of mainly 1,2-addition structure. The optimum conditions for the polymer and the conducting polymer synthesis were 70 W for 5 min and 100 W for 1 min, respectively. The direct synthesis of highly conducting polymer, with the conductivity of 0.3 S cm⁻² were achieved in the absence of applied doping process in a very short time sequence. Conductivity-temperature relation was examined for the conducting polymer.     

Comparison of the thermally stable conducting polymers PEDOT, PANi, and PPy using sulfonated poly(imide) templates

We showed that it is possible to use sulfonated poly(amic acid)s (SPAA) to template polymerize 3,4-ethylenedioxythiophene (EDOT) to PEDOT, resulting in an aqueous dispersion of conducting polymer. This study compares PEDOT with poly(aniline) (PANi) and poly(pyrrole) PPy using the same and another, more rigid, poly(amic acid) template. A variety of system parameters, including reaction time, conductivity, and overall thermal stability, were noted to change systematically depending on the systems chosen. PANi-SPAA takes less than one tenth of the reaction time of PEDOT-SPAA (12 h versus 7 days), and results in higher conductivities at room temperature (ca. 10 S/cm). However, it is not as thermally stable as the PEDOT-SPAA system; conductivity is not measureable after annealing at 300 °C. PPy-SPAA was found to be more thermally stable than PANi-SPAA (less mass lost at 300 °C), but it was still more conductive than un-doped PEDOT-SPAA by a factor of 1000 (ca. 1.0 S/cm).     

Electrochemical and spectroelectrochemical study on bilayer films composed of C60 and poly(3,4-ethylenedioxythiophene) PEDOT

Bilayers of drop casted C₆₀ fullerene films and electrochemically synthesized poly(3,4-ethylenedioxythiophene) (PEDOT) films have been studied. The PEDOT film was polymerised by cyclic voltammetry on top of the drop casted C₆₀ fullerene film. The bilayer films were produced and characterized in three different electrolytes; tetrabutylammoniumhexafluorophosphate (TBAPF₆) and lithium hexafluorophosphate (LiPF₆) in acetonitrile (ACN) and in the ionic liquid 1-butyl-3-methyl-imidazolium tetrafluoroborate (BMIMBF₄). The bilayers were studied by cyclic voltammetry and in situ Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy. Both p- and n-doping of the bilayer films were studied and compared with PEDOT films prepared in organic media.     

导电聚合物PEDOT/PSS-MPEG的制备及性能

引言导电高分子既有导体材料的光电学特性,又有良好的力学性能和可加工性[1],这使得导电高分子材料具有广泛的应用前景。聚噻吩类有机导电材料[2]就是这类材料中的一种。聚噻吩的室温电导率     

Preparation and characterisation of poly(3,4-ethylenedioxythiophene) and poly(3,4-ethylenedioxythiophene)/poly(neutral red) modified carbon film electrodes, and application as sensors for hydrogen peroxide

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been prepared for the first time on carbon-film electrodes (CFE) in aqueous solution using electropolymerisation by potential cycling, potentiostatically and galavanostatically. Characterisation of the modified electrodes was done by cyclic voltammetry and electrochemical impedance spectroscopy and the stability of the polymer films was probed. The coated electrodes were tested for application as hydrogen peroxide sensors, by oxidation and reduction. A novel polymer film was also formed by modification of CFE by co-electropolymerisation of EDOT and the phenazine dye neutral red (NR) – (PEDOT/PNR) with a view to enhancing the properties for sensor applications. It was found that hydrogen peroxide reduction at the PEDOT/PNR coated electrodes could be carried out at a less negative potential, the sensor performance comparing very favourably with that of other polymer-modified electrodes reported in the literature.     

Electrochemical synthesis and characterization of poly[3-(ω-bromoalkyl)thiophene]s

A novel series of functionalized polythiophenes incorporating 3-(ω-bromoalkyl) pendants are synthesized by electrochemical polymerization. The effect of the solvent on the electrosynthesis is investigated. The polymeric films are characterized using cyclic voltammetry, FT-IR, AFM and SEM microscopy. The poly[3-(6-bromohexyl)thiophene] film cast on GC or ITO electrode surface is compared with a sample obtained by a chemical method.     

Preparation of the thermally stable conducting polymer PEDOT - Sulfonated poly(imide)

We describe the template polymerization of EDOT with sulfonated poly(amic acid) (SPAA), resulting in a stable conducting polymer aqueous dispersion, PEDOT-SPAA, with particle size ca. 63 nm. In films of PEDOT-SPAA, the sulfonated poly(amic acid) template undergoes imidization within 10 min at temperatures greater than 150 °C, resulting in PEDOT-sulfonated poly(imide) (PEDOT-SPI) with 10-fold conductivity enhancement. This material is highly thermally stable as compared to PEDOT-PSS. Thermal stability is necessary for many processing applications of conducting polymers, including annealing for OPVs and melt-processing of polycarbonate for device encasement. Isothermal TGA experiments were run at 300 °C for PEDOT-PSS and PEDOT-SPAA and we found that PEDOT-SPAA had a smaller slope for degradation. Annealing of films at 300 °C for 10 min caused the conductivity of PEDOT-PSS films to be unmeasurable (<1 × 10⁻⁵ S/cm), while those of PEDOT-SPAA increased 6-fold. Secondary doping of the PEDOT-SPAA system with additives commonly used for PEDOT-PSS was also investigated.     

Cocrystallization mechanism of poly(3-alkyl thiophenes) with different alkyl chain length

The crystallization rates of poly(3-alkyl thiophene) (P3AT) cocrystals having different alkyl chain length (e.g. hexyl and octyl) of the components are measured using differential scanning calorimetry (DSC) technique. Two pairs of cocrystals with varying compositions of the components viz. poly(3-octyl thiophene) (P3OT(R), regioregularity 89 mol%) and poly(3-hexyl thiophene) [P3HT(R), regioregularity 92 mol% and P3HT-2 regioregularity 82 mol%] are used. In both the systems the isothermal temperature range (TR) in the same time scale of crystallization is found to decrease with increasing alkyl chain length in the blends. The crystallization rate at the same T_c decreases with increasing alkyl chain length P3AT concentration and the Avrami exponent values of cocrystals are same with those of the component values. The low Avrami exponent values (0.23-1.16) in all the samples suggest the presence of rigid amorphous portion which can not diffuse out quickly from the crystal growth front (soft impingement). Analysis of crystallization rate using Laurintzen-Hoffman (L-H) growth rate theory indicates that there is regime-I to regime-II transition in all the samples. The product of lateral (σ) and end surface energy (σ_e) values are found to decrease with increasing the concentration of longer alkyl chain P3AT in the blend. Analysis of σ values according to a theory of Hoffman et al. [Hoffman JD, Miller RL, Marand H, Rotiman DR. Macromolecules 1992;25:2221. [14]] indicates that there is chain extension of the components in the melt of the blends, however, the entropy of cocrystallization has different sign to the two systems. Cocrystallization in P3HT(R)/P3OT(R) system is an entropy driven process but that in P3HT(2)/P3OT(R) system is entropy forbidden process. A possible explanation of cocrystallization in the later system has been attributed from small interaction between the components.     

A theoretical study on the interaction between N-methylpyrrole and 3,4-ethylenedioxythiophene units in copolymer molecules

Quantum mechanical calculations at the density functional theory level have been used to examine the interaction between 3,4-ethylenedioxythiophene and N-methylpyrrole units when they are directly linked in copolymer chains. Specifically, in this study, which was motivated by experimental observations of electrochemically synthesized copolymers, the conformation and electronic properties of co-oligomers formed by two, three and four units have been examined in both neutral and radical cation states. Results reveal significant differences, especially in the radical cation state, between the co-oligomers and the corresponding individual homo-oligomers, which have also been explored considering the same theoretical method. Furthermore, electronic properties of oligomers have been used to estimate those of poly(3,4-ethylenedioxythiophene), poly(N-methylpyrrole) and the copolymer with alternated structure, which have been compared among them. The overall results allowed to understand the anomalous features detected in copolymers prepared by electrochemical techniques from 3,4-ethylenedioxythiophene and N-methylpyrrole mixtures, which were initially attributed to some type of unfavourable interaction between the two types of monomeric units.