The role of ion and solvent transport during the redox process of conducting polymers

The understanding of the redox behavior of conducting polymers is essential for a successful application of these so-called synthetic metals as functional coatings. The redox process involves the exchange of ions and solvent molecules. This so called doping/dedoping process involves changes of the mechanical and the electronic structure of the polymer. This paper discusses investigations at poly(3,4-ethylenedioxythiophene (PEDOT) and poly(pyrrole) (Ppy) by the electrochemical quartz crystal microbalance (EQCM) technique and electrochemical impedance spectroscopy (EIS). In the case of PEDOT a determination of the anion and the solvent fluxes was possible, and it was found that most anions replace solvent molecules upon their incorporation. The doping/dedoping mechanism of Ppy is more complicated. Here, the first redox cycles are characterized by a complex interplay of cation, anion and solvent fluxes with irreversible changes of the polymer structure. However, in combination with EIS new insights of the ion and solvent exchange and its influence on the electronic properties can be achieved.     

Ion exchange properties of polypyrrole studied by electrochemical quartz crystal microbalance (EQCM)

The electrochemical polymerization of pyrrole in aqueous solution was studied as a function of a variety of parameters, such as magnitude of current density and monomer concentration. The possibility of quantitative replacement of counterions by solution anions was studied in detail using the electrochemical quartz crystal microbalance (EQCM) technique. It was found that the polymer structure can be manipulated, even after synthesis. The manipulation was revealed to be dependent on various factors, including the nature of the counterion and of the electrolyte concentration. On the basis of these observations, a two-layer structure is suggested for polypyrrole-based polymers. © 1999 Society of Chemical Industry     

In-situ QCM-D analysis reveals four distinct stages during vapour phase polymerisation of PEDOT thin films

Gaining a deeper understanding of the growth of poly(3,4-ethylenedioxythiophene) (PEDOT) films by vapour phase polymerisation (VPP) is essential for the rational design and optimization of such films. The VPP process was used to synthesise films of PEDOT on oxidant-coated substrates. Atomic force microscopy images showed that the morphology of the films changed considerably with time. Utilising a quartz crystal microbalance with dissipation measurement (QCM-D), we found that the kinetics of polymerisation and the viscoelastic properties of the films varied. The data reveal four distinct stages in film growth. Each stage produces a layer having different conductivity values, from a low of 276 S cm⁻¹ to a high of 1196 S cm⁻¹. Conductivity and electrochromic optical contrast, Δ%Tx, can thus be maximized by appropriate termination of the polymerisation reaction. Factors determining the polymerisation rate and changes in conductivity and optical performance are discussed.     

Room temperature ionic liquids in electrosynthesis and spectroelectrochemical characterization of poly(para-phenylene)

Room temperature ionic liquids (RTILs) were used in electrochemical polymerization and in doping studies (oxidation and reduction) of poly(para-phenylene) (PPP). Cyclic voltammetry was used simultaneously with Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy. Electropolymerization and doping of PPP were done by potential scanning in acetonitrile (ACN + 0.1 M TBAPF₆), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) and butylmethylpyrrolidinium bis (trifluoromethylsulfonyl) imide ([BMP][Tf₂N]). The cyclic voltammograms recorded during polymerization of the PPP film indicate that the best film growth was achieved in [BMIM][PF₆]. The films made in [BMP][Tf₂N] were more stable than films made in ACN (0.1 M TBAPF₆). Results from p-doping studies show that doping can be made at higher potentials in RTILs than in ACN (0.1 M TBAPF₆). It was also found that n-doping can be performed in RTILs at higher negative potentials (−2.2 V) than in ACN (0.1 M TBAPF₆) (−1.8 V). The best n-doping response was achieved in [BMP][Tf₂N]. Also, n-doping in [BMIM][PF₆] was better than in ACN (0.1 M TBAPF₆). The in situ ATR-FTIR spectroscopy was used to study p- and n-doping of PPP films. During both p- and n-doping the spectra indicated formation of infrared active vibration bands (IRAV) in the wavenumber region 1600-800 cm⁻¹. The obtained IRAV bands correlate to the theoretical modes calculated by Zerbi and co-workers according to the effective conjugation coordinate theory (ECC). All these results indicate that RTILs are good solvents in spectroscopic and electrochemical studies of conducting polymers.     

Fluorinated functionalized EDOT-based conducting films

Three ethylenedioxithiophene (EDOT) derivatives bearing either perfluoro- or ether perfluoro-alkyl chains were synthesized with the objective to prepare films with dry and chemically immobilized lubrication properties. The corresponding fluorinated PEDOT films were deposited on platinum surface by electropolymerization. Cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) analyses (both quartz resonant frequency and resonant admittance) of the growing steps are described. The electroactive behavior of the films versus their doping level was followed by electrochemical impedance spectroscopy (EIS) through equivalent circuit fitting procedure and compared to their CV responses. Hysteresis in fit parameters corresponding to capacity and film resistance between the forward and the backward scans are observed and discussed. Control of the chemical structures and charge effects on PEDOT chains are followed by an XPS analysis. From these analyses, it appears that the fluorinated side-arm does not alter both the growing and the electrical properties of the films in respect to the pristine PEDOT taken as reference.     

Interaction of BSA protein with copper evaluated by electrochemical impedance spectroscopy and quartz crystal microbalance

The interaction of bovine serum albumin (BSA) protein with copper in phosphate buffer solution has been studied by a combination of electrochemical impedance spectroscopy (EIS) close to the open circuit potential, with simultaneous monitoring by the electrochemical quartz crystal microbalance (EQCM), in order to throw light on BSA adsorption. Copper films were electroplated onto gold quartz crystals and mounted in the EQCM. Experiments were conducted in the presence and absence of dissolved oxygen and of BSA and the results show the influence of O₂ on the protein/metal interaction and also show specific interactions between BSA and copper. The good reproducibility obtained in these experiments suggests future application to other systems and which should lead to a better understanding of the use of such types of protein as corrosion inhibitors.     

Water sorption and diffusional properties of a cured epoxy resin measured using alternating ionic liquids/aqueous electrolytes in electrochemical impedance spectroscopy

The protective quality of a coating is often measured by how long it delays the arrival of water to the substrate. The transport of water in, redistribution within, and eventually through a coating to the substrate has long been investigated through electrochemical impedance spectroscopy (EIS). EIS measurements employing alternating nonaqueous (room temperature ionic liquids, RTIL) and aqueous electrolytes elucidated the behavior of water within the coating. Diffusion coefficients could be measured and the redistribution of water into percolating paths identified. The use of RTIL alternating with aqueous electrolytes allows determination of intrinsic properties (water volume fraction at saturation and relative dielectric) and kinetic properties predicted by the Brasher Kingsbury formulation. This article focuses on the sensitivity of these intrinsic and kinetic properties to test duration in an unique experimental method.     

Electrochemical behavior of thin polycrystalline rhodium layers studied by cyclic voltammetry and quartz crystal microbalance

Electrochemical behavior of thin polycrystalline Rh layers has been studied in 0.5 M H₂SO₄ solution by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). The properties of surface oxide formed on freshly electrodeposited Rh are different than on electrochemically aged Rh. The analysis of frequency changes in both hydrogen and oxygen regions is presented. It is suggested that hydrogen desorption occurs simultaneously with the adsorption of HSO₄⁻ ions, whose maximum surface coverage reaches ca. 8%. The EQCM results indicate that RhO is the main species formed during Rh surface oxidation. Metal dissolution proceeds during electrode cycling to sufficiently high potentials. The amount of dissolved metal increases with an increase in potential and a decrease in scan rate.     

Redox behavior and optical response of nanostructured poly(3,4-ethylenedioxythiophene) films grown in a camphorsulfonic acid based micellar solution

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been electropolymerized from an aqueous micellar solution comprising camphorsulfonic acid (CSA), lithium trifluoromethanesulfonate (LiCF₃SO₃) and EDOT. The inclusion of the dopants CS⁻ and CF₃SO₃⁻ in the polymer structure and an unusually high doping level of 0.54 have been ascertained by the X-ray photoelectron spectroscopy. Transmission electron microscopy and atomic force microscopy studies show that the micellar effect of CSA leads to a morphology wherein polymer particles link together to form elongated shapes and also endows the film with a surface roughness of 25-30 nm. These nanostructures permit a facile intercalation-deintercalation of anions in the film during redox cycling. Electrochemical impedance spectroscopy show that the charge transfer phenomenon at the PEDOT-electrolyte interface is dominant in the high frequency region and diffusion controlled ionic movement prevails in the low frequency regime. The use of these films as potential cathodes in electrochromic windows is rationalized not only on the basis of their high scalability and ease of processing but also due to their large coloration efficiency (123 cm² C⁻¹) and transmission modulation (50%) at a photopic wavelength of 550 nm. But further improvement in color-bleach kinetics and reproducibility of redox behavior is desirable to broaden their spectrum of utility.     

Adsorption of bovine serum albumin and fibrinogen on hydrophilicity-controllable surfaces of polypyrrole doped with dodecyl benzene sulfonate—A combined piezoelectric quartz crystal impedance and electrochemical impedance study

Combined measurements of piezoelectric quartz crystal impedance (PQCI) and electrochemical impedance (EI) were utilized to monitor in situ adsorption of two proteins (bovine serum albumin and fibrinogen) onto the hydrophilicity-controllable surfaces of polypyrrole (PPY) doped with dodecyl benzene sulfonate (DBS). Three of these polymer films, PPY/DBS-I, PPY/DBS-II and PPY/DBS-III, were obtained by galvanostatic electropolymerization of pyrrole in aqueous solutions containing 0.6, 1.2 and 2.0 mmol L⁻¹ sodium dodecyl benzene sulfonate (SDBS), respectively. The PPY/DBS-II obtained from electropolymerization of pyrrole in the presence of 1.2 mmol L⁻¹ SDBS (the critical micelle concentration of SDBS in aqueous solution, CMC) exhibited the greatest hydrophobicity, as suggested by contact angle measurement. And the saturation-adsorption amounts for both proteins were found to be greatest on the surface. The kinetics and adsorption mechanisms of both proteins adsorbed on these three surfaces were discussed. Langmuir and Freundlich models were used for explaining the adsorption behavior of proteins, giving that Langmuir model is better for bovine serum albumin (BSA) and both model are not so available for fibrinogen.     

Electropolymerization of ethylene dioxythiophene (EDOT) in micellar aqueous solutions studied by electrochemical quartz crystal microbalance and surface plasmon resonance

Electropolymerization of 3,4-ethylene dioxythiophene (EDOT) on gold electrodes was studied in situ by means of an electrochemical quartz crystal microbalance (EQCM) and by surface plasmon resonance spectroscopy (SPR) using aqueous micellar monomer solutions. Electrodeposition from micellar solutions performed by cyclic voltammetry (CV) displayed an enhanced rate as compared to surfactant concentrations lower than the critical micelle concentration (cmc) or in surfactant-free monomer solutions. EQCM data indicate the occurrence of additional film growth during the reductive scan to large negative potentials which does not occur in electropolymerization experiments using potentiostatic pulses or cyclovoltammetric cycles with less negative potential scans. Our results further suggest that in the case of the anionic surfactant the oxidation potential of the monomer is lowered even at surfactant concentrations below the cmc. AFM investigations show a slightly enhanced roughness of the films obtained from micellar monomer solutions.     

Solubility of neutral and charged polymers in ionic liquids studied by laser light scattering

The solubility and chain conformation of different types of homopolymers in low viscosity ionic liquids (ILs), 1-allyl-3-methylimidazolium chloride ([AMIM][Cl]) at 50 °C and 1-butyl-3-methylimidazolium formate ([BMIM][COOH]) at 25 °C, were studied by laser light scattering (LLS). For neutral polymers, such as polyvinyl alcohol and polysulfonamide, aggregation occurred in all the cases except for polyvinyl alcohol in [BMIM][COOH]. For negative polyelectrolytes, such as DNA and polystyrene sulfonate, single chain conformation was observed. However, the hydrodynamic radius of both polymers was much smaller than that in good solvents, suggesting that the chains were condensed. Cellulose was soluble in [AMIM][Cl], and non-diffusive mode was observed by dynamic light scattering. Zeta potential analysis indicated that cellulose exhibited the feature of polyelectrolyte. The solubility of homopolymers could be qualitatively explained by treating polymer/IL as a ternary system: polymer, cation, and anion. It was the mutual interactions determined the solubility and conformation of polymers in ILs.     

Solvent effects on electrochemical behavior of poly(ferrocenylsilane) films

The electrochemical behaviors of poly(ferrocenylsilane) (PFS) films in organic solutions were investigated by means of cyclic voltammetry (CV) and electrochemical quartz crystals microbalance (EQCM). The influences of solvent on the electrochemical behavior of the films were discussed. In “good” solvents, the supporting electrolytes dissociated completely, the films were solvent-swollen moderately which provided a favorable condition for the electrolyte ions penetrating through, and the CV behavior of the films exhibited reversible or nearly reversible features. With increasing the carbon chain length of solvent molecule, however, the polarity of solvent reduced, which conduced to decrease the dissociation of electrolyte and the swelling of the polymer film. The efficiency of electrochemical reaction in the film was depressed, and the CV behavior of the film exhibited low reversibility. The solvent effects on the oxidation process of films exhibited more noticeable than the reduction process. The results supported the viewpoint that penetration of the electrolyte anions played an important role on the charge balance and transfer in the films during the CV process. The different electrochemical behaviors of the two PFS films in various organic solutions indicated that molecular structure of polymer had important influence on the electrochemical properties of the PFS.     

Electropolymerization of poly(3-methylthiophene) in pyrrolidinium-based ionic liquids for hybrid supercapacitors

The ionic liquids (ILs) N-butyl-N-methyl-pyrrolidinium trifluoromethanesulfonate (PYR₁₄Tf) and N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide (PYR₁₃FSI) are investigated as electropolymerization media for poly(3-methylthiophene) (pMeT) in view of their use in carbon/IL/pMeT hybrid supercapacitors. Data on the viscosity, solvent polarity, conductivity and electrochemical stability of PYR₁₄Tf and PYR₁₃FSI as well as the effect of their properties on the electropolymerization and electrochemical performance of pMeT, which features >200 Fg⁻¹ at 60 °C when prepared and tested in such ILs, are reported and discussed; the results of the electrochemical characterization in N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide of the so-obtained pMeT are also given, for comparison.     

EQCM study of the ECL quenching of the tris(2,2′-bipyridyl)ruthenium(II)/tris-n-propylamine system at a Au electrode in the presence of chloride ions

Significant effect of chloride ions on the electrogenerated chemiluminescence (ECL) behavior of the ruthenium(II)tris(2,2′-bipyridine) (Ru(bpy)₃²⁺)/tri-n-propylamine (TPrA) system at a Au electrode was reported. At low concentrations (e.g., [Cl⁻] < 5 mM), the ECL was enhanced; at relatively high concentrations, however, the ECL intensity decreased with the increase of the [Cl⁻]. At [Cl⁻] = 90 mM, ∼50% and 100% ECL inhibition was observed for the first and the second ECL wave, respectively. The electrogenerated gold-chloride complexes (AuCl₂⁻ and AuCl₄⁻) which were verified using an electrochemical quartz-crystal microbalance (EQCM) method were found to be responsible for the ECL inhibition. This study suggests that care must be taken when a Au working electrode is used for ECL studies in chloride-containing buffer solutions (widely used in DNA probes) and/or with the commonly used chloride-containing reference electrodes since in these cases the ECL behavior may significantly disagree with that obtained using other electrodes and reaction media.     

A study on the electrochromic properties of polyaniline/silica composite films with an enhanced optical contrast

A polyaniline (PANI)/silica (SiO₂) composite film was prepared by a simple in situ electrodeposition method, and its electrochromic (EC) properties were studied. When PANI was electrodeposited in the presence of SiO₂ particles, the resulting PANI/SiO₂ composite films possessed higher surface areas, larger redox charge capacities, and higher doping levels, thus enhanced optical contrasts. By incorporating SiO₂ particles into the PANI film, the transmittance change at 700 nm from 10.7% to 16.4%, or an enhancement of ca. 50%, was achieved when operating between −0.5 V and 0 V. In addition, x-ray photoelectron spectroscopy (XPS) indicated that the formation of the highly oxidized PANI might have been retarded through the addition of SiO₂ particles. Furthermore, the growth mechanism of the PANI/SiO₂ composite film was proposed.     

Prediction of viscosity of imidazolium-based ionic liquids using MLR and SVM algorithms

In this work, two models, one integrating the fragment contribution-corresponding states (FC-CS) method with multiple linear regression (MLR) algorithm and another. With support vector machine (SVM) algorithm, are proposed to predict the viscosity of imidazolium-based ionic liquids (ILs). The FC-CS method is applied to calculate the pseudo-critical volume and compressibility factor (V_c and Z_c) as well as the boiling point temperature (T_b) which are employed to predict the viscosity with the MLR and SVM algorithms. A large data set of 1079 experimental data points of 45 imidazolium-based ILs covering a wide range of pressure and temperature is applied to validate the two models. The average absolute relative deviation (AARD) of the entire data set of the MLR and SVM is 24.2% and 3.95%, respectively. The nonlinear model developed by the SVM algorithm is much better than the linear model built by the MLR, which indicates the SVM algorithm is more reliable in the prediction of the viscosity of imidazolium-based ILs.     

Multiple time constant modelling of a printed conducting polymer electrode

Constant phase elements (CPE) are routinely used to describe the frequency response of electrochemical systems. However, this approach is often scientifically unsatisfactory because the physical origin of the phase is unclear. Here we observe CPE-like behaviour in a conducting polymer poly(3,4-ethylenedioxythiophene)/poly(styrene-4-sulfonate) (PEDOT:PSS) film that was inkjet printed onto paper to form a flexible electrochemical double layer capacitor electrode. We show that the response of the electrochemically active film can also be described using a physical model with multiple parallel finite RC (resistor–capacitor) transmission lines whose lengths and time constants are determined by the distribution of the measured film thickness. The modeled volumetric capacitance and ionic conductivity match those determined experimentally, suggesting that the physical origin of the constant phase response is a distribution of mass transport limited time constants.     

Preparation of the molecularly imprinted polymers-based capacitive sensor specific for tegafur and its characterization by electrochemical impedance and piezoelectric quartz crystal microbalance

Molecularly imprinted polymers (MIPs)-based capacitive sensor specific for tegafur was constructed by electropolymerization of m-aminophenol onto the surface of gold electrode and the Au-coated quartz crystal electrodes. Electrochemical impedance (EI) and quartz crystal microbalance (QCM) were employed to characterize the modified gold electrodes and the modified Au-coated quartz crystals, respectively. Unlike the capacitive sensors reported in the previous literatures, the present sensors were not treated with alkanethiol after electropolymerization and show even more satisfactory performance. QCM measurements also confirmed the imprinting effect of the polymer layers.     

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks.