Electrochemical copolymerization of aniline with m-aminophenol and novel electrical properties of the copolymer in the wide pH range

A copolymer, poly(aniline-co-m-aminophenol), has been synthesized using repeated potential cycling. The monomer concentration ratio, acid concentration and applied potential strongly affect the copolymerization rate and the properties of the copolymer. The optimum conditions for the copolymerization are that the scan potential range is controlled between −0.10 and 0.95 V (vs.SCE), and a solution consists of 0.34 M aniline, 0.012 M m-aminophenol and 2 M H₂SO₄. The IR spectra of the copolymers demonstrate that the m-aminophenol units are included in the copolymer chains. The cyclic voltammograms of the copolymers in 0.3 M Na₂SO₄ solution with various pH values were performed at the potential ranges from −0.20 to 0.80 V and at a scan rate of 60 mV s⁻¹. The results indicate that the copolymer still hold 41.7% of the electrochemical activity when the copolymer electrode was transferred from a solution of pH 5.0 to a solution of pH 11.0 in the potential range of −0.20 to 0.80 V. An impedance plot of the copolymer in a solution with pH 12.0 and at 0.40 V is constructed of a semicircle and a Warburg line with a slope of 1. This means that the electrode reaction of the copolymer at pH 12.0 is also under mass transfer control. The conductivity of the copolymer prepared under the optimum conditions is 1.42 S cm⁻¹, and slightly depends on the pH value. Thus, the pH dependence of the electrical properties of the copolymer is improved compared with poly(aniline-co-o-aminophenol), and is much better than that of the parent polyaniline.     

A promising copolymer of aniline and m-aminophenol: Chemical preparation, novel electric properties and characterization

A copolymer, poly(aniline-co-m-aminophenol), was synthesized chemically. The monomer concentration ratio strongly affects the copolymerization rate and the properties of the copolymer. A solution consisting 0.34 M aniline, 0.012 M m-aminophenol, 0.47 M ammonium peroxydisulfate and 2 M H₂SO₄ was found to be an optimum mixture for the chemical copolymerization. The visible spectra show that a high concentration ratio of m-aminophenol/aniline in the mixture inhibits the chain growth of the copolymer. The spectra of IR and ¹H NMR demonstrate that m-aminophenol units are included in the copolymer chain, which play a key role in extending usable pH region of the copolymer. The result of cyclic voltammograms in a wide potential region of −0.20-0.80 V (vs. SCE) indicates that the copolymer prepared under the optimum condition still held 52.7% of the electrochemical activity when the copolymer electrode was transferred from a solution of pH 4.0 to a solution of pH 11.0, which is much better than that of polyaniline. The X-ray diffraction spectra and images of the copolymers reveal a fact that the changes in the crystal structure and morphology of the copolymers are as a function of the monomer ratio in the mixture. The conductivity of the copolymer prepared under the optimum condition is 2.3 S cm⁻¹ and slightly depends on the pH value.     

Poly(aniline-co-o-aminophenol) nanostructured network: Electrochemical controllable synthesis and electrocatalysis

Poly(aniline-co-o-aminophenol) (copolymer) with nanostructured network has been synthesized in the presence of ferrocenesulfonic acid, using repeated potential cycling between −0.10 and 0.86 V (versus SCE). The sizes of the fibers in the nanostructures can be controlled by the number of the cycles during copolymerization. The presence of ferrocenesulfonic acid possessing a larger molecular size with positive charges is favorable for the formation of nanostructures. The SEM images reveal a fact that the copolymer films synthesized under different cycles are constructed of interwoven fibers with average diameters in a range of 70-107 nm. The copolymer with the nanostructured network deposited on a platinum foil offers a convenient way to study directly the electrochemical property of nanostructures and can effectively catalyze the electrochemical oxidation of catechol in the Na₂SO₄ solution with pH 5.0. It was found that the electrochemical oxidation of catechol was affected by the sizes of the copolymer fibers. Evidence is that its anodic peak potential increases with increasing the diameter of the fibers in the nanostructures. The copolymer synthesized in the presence of ferrocenesulfonic acid has a good electrochemical activity at pH ≤ 9.0, a larger usable potential window and faster electron transfer ability compared with the copolymer synthesized in the absence of ferrocenesulfonic acid.     

A new method for characterizing the growth and properties of polyaniline and poly(aniline-co-o-aminophenol) films with the combination of EQCM and in situ FTIR spectroelectrochemisty

A new method of in situ piezoelectric Fourier transform infrared (FTIR) spectroelectrochemisty, i.e., the combination of in situ FTIR and electrochemical quartz crystal microbalance (EQCM), was developed to study the electropolymerization of aniline and aniline-co-o-aminophenol, to investigate the properties of the polymers in 0.2 M HClO₄. The piezoelectric electrochemical studies showed that the copolymerization process was changed in the presence of o-aminophenol and the copolymer exhibited different electrochemical behaviors from polyaniline and poly-o-aminophenol. The effects of the molar ratio of o-aminophenol on the copolymerization speed and the scan rate or pH values on the electroactivity of the copolymer were also investigated. The results suggested that the copolymer formed in the case of F = 0.1 had good stability and electroactivity than polyaniline at different pH values. The results obtained by the way of in situ piezoelectric FTIR spectroelectrochemisty indicated that the copolymerization process and the properties of the copolymer were different from that of polyaniline. The polymerization mechanisms and the structure of the two polymers were also different from each other. The copolymer formed through head-to-tail coupling of the two monomers via NH groups was a new polymer rather than a mixture of polyaniline and poly-o-aminophenol.     

The electrochemical copolymerization of aniline with 2,4-diaminophenol and the electric properties of the resulting copolymer

The copolymerization of aniline and 2,4-diaminophenol (DAP) was first carried out in an acidic solution under a constant potential of 0.75 V. The copolymerization rate was found to increase with an increasing ratio of monomer DAP to aniline in the mixture. The opposite is true of the electrochemical copolymerization of aniline and o-aminophenol or m-aminophenol. The difference is due to the two kinds of electron-donating groups in DPA. Poly(aniline-co-2,4-diaminophenol) (PADAP), when synthesized under optimal conditions, has a good redox activity from pH < 1 to 11.0 in a wide potential region. Its conductivity is 0.26 S cm⁻¹, which is very close to that of polyaniline synthesized under the same conditions in the absence of DAP. The pH dependence of PADAP conductivity was found to be better than that of polyaniline. PADAP that is synthesized under optimal conditions has unique magnetic resonance properties in NMR and ESR; molecules that are synthesized in the presence of other DAP to aniline concentration ratios have different properties. The monomer concentration ratio in the mixture and the applied potential strongly affect the properties of PADAP.     

Synthesis and high electrochemical activity of poly(aniline-co-2-amino-4-hydroxybenzenesulfonic acid)

Poly(aniline-co-2-amino-4-hydroxybenzenesulfonic acid) (PAAHB) was synthesized using chemical oxidative copolymerization of aniline and 2-amino-4-hydroxybenzenesulfonic acid (AHB) in the presence of an ionic liquid at 50 °C. The conductivity of the PAAHB copolymer synthesized at the optimum conditions is 0.47 S cm⁻¹ that is lower than that of polyaniline, but is slightly affected by water. The cyclic voltammograms demonstrate that the PAAHB copolymer has excellent redox activity from highly acidic solution to pH 12.0 in a wider potential range. This is attributed to the synergistic effect of the SO₃⁻ and OH functional groups in the copolymer chain and the ionic liquid incorporated into the PAAHB film. It is evident that the pH dependence of the redox activity and conductivity of the PAAHB copolymer prepared chemically is much better than that of polyaniline, and is further improved, compared to the PAAHB copolymer prepared electrochemically. The proton NMR spectrum of the PAAHB copolymer demonstrates that the SO₃⁻ group exists in the copolymer chain instead of the SO₃H group. The ESR spectra show that the ESR signal intensity is a function of the monomer concentration ratio of AHB to aniline in the mixture. The morphology of the PAAHB copolymer is also dependent on the monomer concentration ratio in the mixture.     

Potentiodynamic deposition of poly (o-anisidine-co-metanilic acid) on mild steel and its application as corrosion inhibitor

For the first time, poly (o-anisidine-co-metanilic acid) (PASM) was deposited on mild steel substrate by electrochemical polymerization of o-anisidine and metanilic acid monomers in aqueous solution of 0.1 M H₂SO₄. The electrochemical polymerization of o-anisidine takes place in the presence of metanilic acid monomer and uniform, strongly adherent coating was obtained on the substrate. The electroactivity of copolymer was studied by cyclic voltammetry and AC impedance techniques. There is an increasing anodic current due to oxidation of metanilic acid monomer at the surface of the electrode when the applied potential is cycled from −0.2 V to 0.8 V. These deposits were characterized by Fourier transform infrared (FTIR) spectroscopy, UV-vis and TG/DTA techniques. The effect of various concentrations of PASM copolymer solution in acid rain corrosive media has been studied through potentiodynamic polarization, AC impedance and I-E curve methods. The soluble form of polymeric solution provided better anti-corrosive behavior in artificial acid rain solution.     

Scale-up of a fixed bed electrochemical reactor consisting of parallel screen electrode used for p-aminophenol production

The behavior of a fixed bed consisting of amalgamated copper screens has been investigated for the electrolytic reduction of nitrobenzene to p-aminophenol under potentiostatic condition (controlled potential). The preparative electrolysis of nitrobenzene was carried out using supporting electrolytes consisting of 2 M H₂SO₄ in a solution of 50% 2-propanol/50% water (v/v). The criterion for scale-up (?_n) was determined through application of one-dimensional model. The polarization curves that describe the reduction of nitrobenzene to p-aminophenol were obtained experimentally by using a pilot scale for different nitrobenzene concentrations and flow rates of catholyte.It was found that the effectiveness factor (?_n) increases with increasing flow rate, and decreasing nitrobenzene concentration. An optimum thickness of bed equal to 0.6 cm was obtained, in which the effectiveness factor not less than 0.588, to ensure a well distribution of current and potential.     

In situ UV-vis spectroelectrochemistry of poly(o-phenylenediamine-co-m-toluidine)

Results of in situ UV-vis spectroelectrochemical studies of the electropolymerization of o-phenylenediamine (OPD), m-toluidine (MT) and the copolymerization of OPD with MT are reported. Electropolymerization was performed in aqueous acidic medium at a constant potential of E_SCE = 1.0 V at an indium doped tin oxide (ITO) coated glass electrode. The course of homopolymerization was followed for MT and OPD solutions with various monomer concentrations. The spectral characteristics of the mixed solutions were studied at a constant concentration of MT and various concentrations of OPD in the comonomer feed. An absorption band at λ = 497 nm was assigned to the head-to-tail mixed dimer/oligomer resulting from the cross reaction between OPD and MT cation radicals. UV-vis spectra recorded during copolymerization show dependence of the growth of the band at λ = 497 nm on OPD concentration in the feed. At lower OPD feed concentration it appears as the major band in the corresponding spectra. The UV-vis spectra recorded for the copolymer films suggest the incorporation of both monomer units in the copolymer. The FT-IR spectra of the copolymers show the presence of phenazine type structures in the copolymer backbone.     

Oxygen reduction mechanism on copper in a 0.5 M H2SO4

The mechanism of the oxygen reduction reaction (ORR) in a naturally aerated stagnant 0.5 M H₂SO₄ was studied using electrochemical methods. The cathodic polarization curve showed three different regions; electrochemical impedance spectroscopy (EIS) measurement was used accordingly. The EIS data were analyzed, and the mechanism for the ORR was proposed consequently. The three regions include a limiting current density region with the main transfer of 4e⁻ controlled by diffusion (−0.50 V < E < −0.40 V), a combined kinetic-diffusion region (−0.40 V < E < −0.20 V) with an additional 2e⁻ transfer due to the adsorption of the anions, and a hump phenomenon region (−0.20 V < E < −0.05 V), in which the chemical redox between the anodic intermediate and the cathodic intermediate , together with the electrochemical reaction, synergistically results in the acceleration of the ORR. Therefore, a coupled electrochemical/chemical process (the EC mechanism) in the hump phenomenon region was proposed, and a good agreement was found between the experimental and fitted results. The EC mechanism was confirmed by the deaerated experiments.     

Hydrogen evolution on conducting polymer electrodes in acidic media

Hydrogen evolution reaction (HER) was studied on polyaniline (PAn), polypyrrole (PPy) and on aniline/pyrrole (PAn–PPy) copolymer in acidic solutions. The cathodic Tafel slopes (b_c) and exchange current densities (j₀) were calculated from Tafel curves obtained in solutions of X M H₂SO₄ (X = 0.1, 0.2, 0.3, 0.4 and 0.5 M). Activation energies (E_a) were determined. The E_a-values were found to be ca. 26 for PAn, 36.5 for PPy, 40.6 for PAn–PPy and 20.6 kJ mol⁻¹for Pt.     

Electrochemical behavior of LiCoO2 in a saturated aqueous Li2SO4 solution

The electrochemical behavior of a commercial LiCoO₂ with spherical shape in a saturated Li₂SO₄ aqueous solution was investigated with cyclic voltammetry and electrochemical impedance spectroscopy. Three redox couples at E_SCE = 0.87/0.71, 0.95/0.90 and 1.06/1.01 V corresponding to those found at ELi/Li⁺=4.08/3.83, 4.13/4.03 and 4.21/4.14 V in organic electrolyte solutions were observed. The diffusion coefficient of lithium ions is 1.649 × 10⁻¹⁰ cm² s⁻¹, close to the value in organic electrolyte solutions. The results indicate that the intercalation and deintercalation behavior of lithium ions in the Li₂SO₄ solution is similar to that in the organic electrolyte solutions. However, due to the higher ionic conductivity of the aqueous solution, current response and reversibility of redox behavior in the aqueous solution are better than in the organic electrolyte solutions, suggesting that the aqueous solution is favorable for high rate capability. The charge transfer resistance, the exchange current and the capacitance of the double layer vary with the charge voltage during the deintercalation process. At the peak of the oxidation (0.87 V), the charge transfer resistance is the lowest. These fundamental results provide a good base for exploring new safe power sources for large scale energy storage.     

Electrosyntheses of poly(neutral red), a polyaniline derivative

The electrochemical oxidation of neutral red in 0.5 mol dm⁻³ H₂SO₄ solution was carried out by using repeated potential cycling between −0.20 and 1.20 V (versus SCE). The polymer film was electrochemically deposited on a platinum anode and had an electrochemical activity in the solution of 0.5 mol dm⁻³ Na₂SO₄ with pH ≤ 4.0. The result from the X-ray photoelectron spectroscopy (XPS) experiment shows that the anions can be doped into the polymer film during the electropolymerization reaction of neutral red. The scanning electron microscopy (SEM) micrograph shows the surface of poly(neutral red) film deposited on the platinum foil is covered with a micro-structured network of mass interwoven fibers with a diameter of 2-4 μm. A straight fiber of the unsystematic micro-fibers is longer than 0.4 mm. The UV-vis spectrum and infrared spectrum (IR) of the polymer are different from those of the monomer.     

Development and application of a poly(2,2′-dithiodianiline) (PDTDA)-coated screen-printed carbon electrode in inorganic mercury determination

In this work, monomer solutions of aniline (ANI) and 2,2′-dithiodianiline (DTDA), an aniline derivative containing -S-S- links, were prepared and used in the electrochemical copolymerisation of ANI and DTDA by cyclic voltammetry on a screen-printed electrode (SPE) in 1 M HCl. Electropolymerisation of aniline on the surface of the screen-printed working electrode was performed by sweeping the potential between −500 and + 1100 mV (vs. Ag/AgCl) at a sweep rate of 100 mV/s. Electrocopolymerisation was performed with a mixture of ANI and DTDA by sweeping the potential between −200 and + 1100 mV (vs. Ag/AgCl) at a sweep rate of 100 mV/s [J.L. Hobman, J.R. Wilson, N.L. Brown, in: D.R. Lovley (Ed.), Environmental Microbe Metal Interactions, ASM Press, Herndon, Va, 2000, p. 177]. The cyclic voltammogram (CV) for each of the electrochemically deposited polyaniline (PANI) and the mixture of ANI and DTDA for the co-polymer polymerisation on SPCE were recorded for electrochemical analysis of the peak potential data for the mono and copolymer. Anodic stripping voltammetry (ASV) was used to evaluate a solution composed of (1 × 10⁻⁶ M HgCl₂, 0.1 M H₂SO₄, 0.5 M HCl), in the presence of the co-polymer sensor electrode. The Hg²⁺ ions were determined as follows: (i) pre-concentration and reduction on the modified electrode surface and (ii) subsequent stripping from the electrode surface during the positive potential sweep. The experimental conditions optimised for Hg²⁺ determination included the supporting electrolyte concentration and the accumulation time. The results of the study have shown the use of a conducting polymer modified SPCE as an alternative transducer for the voltammetric stripping and analysis of inorganic Hg²⁺ ions.     

Electrochemical behavior of p-tert-butyl calix[8]arene in CH2Cl2

The electrochemical behavior of p-tert-butyl calix[8]arene has been investigated by cyclic voltammetry. The result shows that there is an irreversible electrochemical oxidative wave when the potential ranges from −0.3 to 1.6 V versus Ag/0.1 M AgNO₃ in acetonitrile (Ag/Ag⁺). At 25 °C, the peak potential is ca. 1.43 V (versus Ag/Ag⁺) at scan rate of 0.05 V s⁻¹. The number of the electrons transferred in the electrochemical reaction is four. The diffusion coefficient of p-tert-butyl calix[8]arene is 2.8 × 10⁻⁵ cm² s⁻¹. The diffusion activation energy is 12.3 kJ mol⁻¹.     

Electrochemical behaviour of passive films on molybdenum-containing austenitic stainless steels in aqueous solutions

Passivation and its breakdown reactions have been studied on Mo-containing stainless steel specimens using different electrochemical techniques. Mo-containing stainless steel specimens were polarized in both naturally aerated NaCl and Na₂SO₄ solutions of different concentrations at 25 ± 0.2 °C between −1000 and 1500 mV versus saturated calomel electrode (SCE). The results of potentiodynamic polarization showed that i_corr and i_c increases with increasing either Cl⁻ or SO₄²⁻ concentration indicating the decrease in passivity of the formed film. EIS measurements under open circuit conditions confirmed that the passivity of the film decrease with increase in either Cl⁻ or SO₄²⁻ concentration.     

Inactivation of Escherichia coli in Na2SO4 electrolyte using boron-doped diamond anode

Electrochemical disinfection in chloride-free electrolyte has attracted more and more attention due to advantages of no production of disinfection byproducts (DBPs), and boron-doped diamond (BDD) anode with several unique properties has shown great potential in this field. In this study, inactivation of Escherichia coli (E. coli) was investigated in Na₂SO₄ electrolyte using BDD anode. Firstly, disinfection tests were carried on at different current density. The inactivation rate of E. coli and also the concentration of hydroxyl radical (OH) increased with the current density, which indicated the major role of OH in the disinfection process. At 20 mA cm⁻² the energy consumption was the lowest to reach an equal inactivation. Moreover, it was found that inactivation rate of E. coli rose with the increasing Na₂SO₄ concentration and they were inactivated more faster in Na₂SO₄ than in NaH₂PO₄ or NaNO₃ electrolyte even in the presence of OH scavenger, which could be attributed to the oxidants produced in the electrolysis of SO₄²⁻, such as peroxodisulfate (S₂O₈²⁻). And the role of S₂O₈²⁻ was proved in the disinfection experiments. These results demonstrated that, besides hydroxyl radical and its consecutive products, oxidants produced in SO₄²⁻ electrolysis at BDD anode played a role in electrochemical disinfection in Na₂SO₄ electrolyte.     

Raman spectroelectrochemical study of self-doped copolymers of aniline and selected aminonaphthalenesulfonates

Novel self-doped polyaniline-like copolymers have been prepared by electrochemical copolymerization of aniline with four aminonaphthalenesulfonates. All copolymer films prepared show their electrochemical redox activity even in pH-neutral solutions at a midpoint potential around 0.0 V versus Ag/AgCl. Raman spectroelectrochemical study of the copolymers prepared has been done with a red laser excitation (632.8 nm) within a broad electrochemical potential window of 0.0-1.0 V, and specific Raman features have been identified. Raman bands within the range of 1300-1400 cm⁻¹ have been discussed regarding localized or delocalized polaronic ν_s(CN⁺) vibrations. The influence of sulfonate group position in aminonaphthalenesulfonates on the parameters of polaronic bands has been demonstrated.     

Influence of electrochemically prepared poly(pyrrole-co-N-methyl pyrrole) and poly(pyrrole)/poly(N-methyl pyrrole) composites on corrosion behavior of copper in acidic medium

Poly(pyrrole-co-N-methyl pyrrole) copolymer and poly(pyrrole)/poly(N-methyl pyrrole) bilayer composites were electrochemically synthesized on copper by cyclic voltammetry from aqueous solution of 0.3 M oxalic acid and 0.1 M monomer. Synthesis of copolymers were performed with different monomer feed ratios (pyrrole:N-methyl pyrrole, 8:2, 6:4, 5:5, 4:6 and 2:8) and in order to determine the copolymer, which has the best corrosion performance, anodic polarization was applied to copolymer coated samples. It was found that the performance of coatings was strongly dependent to the monomer feed ratio and the copolymer synthesized with 8:2 concentration ratio showed the most protective property compared to others. Bilayer of poly(pyrrole)/poly(N-methyl pyrrole) was also synthesized to compare the anticorrosive properties. Polymer films were characterized by ATR-FTIR spectroscopy and SEM techniques. Corrosion behavior of polymer composites was investigated in 0.1 M H₂SO₄ solution by anodic polarization and electrochemical impedance spectroscopy. Different approaches such as phase angle at high frequency and areas under Bode plots were used to evaluate corrosion performances of the coatings. Copolymer and bilayer coatings were found to have higher protection effect than single polypyrrole coatings. Moreover, bilayer coating exhibited better protection efficiency than copolymer coating against corrosion of copper when the obtained results were compared.