Electrochemical impedance spectroscopy of poly(N-methyl pyrrole) on carbon fiber microelectrodes and morphology

This work reports the supercapacitive properties of electrochemically grown homopolymer films on carbon fiber microelectrode (CFME) via poly(N-methyl pyrrole) (P(NMPy)) which is characterized by cyclic voltammetry (CV), Fourier transform infrared reflectance (attenuated total reflection) spectroscopy (FTIR-ATR), scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). Microporosity of P(NMPy) electrocoated carbon fiber microelectrodes facilitated improved capacitance and redox behaviours by applying different DC potentials in electrochemical impedance spectroscopic measurements. The capacitance values of P(NMPy)/CFME is obtained (0.059 F) which is in the range of manufactured values.     

Electrochemical impedance spectroscopy of poly[carbazole-co-N-p-tolylsulfonyl pyrrole] on carbon fiber microelectrodes,equivalent circuits for modelling

Polycarbazole (PCz) and copolymerization of carbazole (Cz) and N-p-tolylsulfonyl pyrrole (pTsp), P(Cz-co-pTsp), thin films have been cyclovoltammetrically coated onto carbon fiber electrodes as an active functionalized microelectrode in sodium perchlorate (NaClO₄)/acetonitrile (ACN) medium. The resulting thin films of homopolymer and copolymer were characterised by using Fourier transform infrared reflectance spectroscopy (ATR-FTIR), energy dispersive X-ray (EDX) point analysis, scanning electron microscopy (SEM) and atomic force microscopy (AFM). An electrical impedance study on the prepared electrodes is reported in the present paper under different feed ratios of [pTsp]₀/[Cz]₀ during electrochemical impedance spectroscopic (EIS) measurements. Specific capacitance (C_sp) were calculated, P(Cz-co-pTsp) in feed ratio of [pTsp]₀/[Cz]₀ = 200 has preserved more capacitive behavior especially at lower frequency (C_sp = ∼156 mF g⁻¹) than polycarbazole (C_sp = ∼2.1 mF g⁻¹. The electrochemical impedance data fitted to three different equivalent models were used to find out numerical values of the proposed components.     

Morphological and impedance studies on electropolymerized 3,4-(2,2-dibenzylpropylenedioxy)thiophene nanostructures on micron sized single carbon fiber

Micron sized single carbon fibers were cyclovoltammetrically coated with poly[3,4-(2,2-dibenzylpropylenedioxy)thiophene] resulting in a nanofiber network at the surface. The method provides conjugated polymer nanostructures covalently and uniformly bound to micron sized substrates. When the electropolymerization is carried out with different electrolytes in acetonitrile the dopant influences the structure of the coating layer what is proved by electrochemical impedance spectroscopy and electron microscopy. Electrodes based on poly[3,4-(2,2-dibenzylpropylenedioxy)thiophene] on single carbon fiber microelectrodes (SCFMEs) prepared in Bu₄NPF₆/ACN show the best capacitance performance due to their higher surface area. The improvement is attributed to the formed nanofiber network structure which results in a more efficient charge transport and collection.     

Morphological and impedance studies on electropolymerized 3,4-(2,2-dibenzylpropylenedioxy)thiophene nanostructures on micron sized single carbon fiber

Micron sized single carbon fibers were cyclovoltammetrically coated with poly[3,4-(2,2-dibenzylpropylenedioxy)thiophene] resulting in a nanofiber network at the surface. The method provides conjugated polymer nanostructures covalently and uniformly bound to micron sized substrates. When the electropolymerization is carried out with different electrolytes in acetonitrile the dopant influences the structure of the coating layer what is proved by electrochemical impedance spectroscopy and electron microscopy. Electrodes based on poly[3,4-(2,2-dibenzylpropylenedioxy)thiophene] on single carbon fiber microelectrodes (SCFMEs) prepared in Bu₄NPF₆/ACN show the best capacitance performance due to their higher surface area. The improvement is attributed to the formed nanofiber network structure which results in a more efficient charge transport and collection.Impedance spectra show the typical form of Z_IM vs. Z_RE curves for transmission-line at a frequency of 10 Hz, with transition to almost pure capacitive behavior up to 10 MHz. Equivalent circuit modeling was simulated for the electrolyte/polymer film/SCFME system. A good agreement was achieved for the calculated capacitances in comparison with the experimental EIS measurement results.     

Poly(N-methylpyrrole) electrodeposited on copper: Corrosion protection properties

Electrochemical synthesis of poly(N-methylpyrrole) films on copper electrodes from an aqueous oxalic acid has been achieved. A potential higher than 2 V (SCE) was needed to generate the polymer, for this reason, the polymer was in the overoxidized state. The inhibiting corrosion properties of this coating on copper were investigated for the first time in aqueous 0.1 M sodium chloride solution using potentiodynamic polarization, Tafel analyses, open-circuit potential and electrochemical impedance spectroscopy. Corrosion protection properties comparable to those of polypyrrole (PPy) films were observed for these films. A physical barrier effect is the most likely protection mechanism.     

Electrophoretic deposition of nanocomposites formed from polythiophene and metal oxides

An electrophoretic deposition (EPD) procedure was adopted for the cathodic preparation of thin films of conducting polymer/metal oxide nanocomposites with a core-shell structure. The deposition process was investigated at different potentials and in various solvents. The mechanism and kinetics of the electrophoretic deposition were studied via quartz crystal microbalance (QCM) and zeta-potential measurements.The properties of the composite layers were studied by electrochemical methods (cyclic voltammetry, impedance spectroscopy) and photocurrent measurements. The reversible redox potential of polythiophene films was about 0.75 V_SCE. The p-type semiconducting behaviour of the reduced polythiophene was studied by photocurrent measurements. In the case of using TiO₂ (n-type semiconductor) as a core material, an n/p heterojunction was observed. In the photocurrent spectra the maximum of the cathodic peak of polythiophene was found around λ = 500 nm (2.5 eV), depending on the applied potential. It is in agreement with the results of UV-vis optical spectra of deposited layers and of pressed pellets. The flatband potential of polythiophene in the heterojunction with TiO₂, obtained from photocurrent measurements, was 0.53 V_SCE.     

Physical and electrochemical characterization of nanocomposites formed from polythiophene and titaniumdioxide

A simple method for covering titanium dioxide particles with a polythiophene film by chemical preparation was developed. The resulting nanocomposites consisted of a titanium dioxide core with a grain size of 25-250 nm and a polythiophene shell between 1 and 2 nm thickness. The composites were characterized by scanning electron microscopy, thermogravimetry, X-ray photoelectron spectroscopy, cyclovoltammetry, impedance spectroscopy and photocurrent spectroscopy. The content of polythiophene in the composite (determined by thermogravimetry), was between 2% and 5%. Disk-like electrodes were prepared by pressing and then characterized by various electrochemical methods. A reversible redox potential of the polythiophene of +1.0 V (NHE) was determined by cyclic voltammetry. The reduced form of polythiophene behaved as a p-type semiconductor so that the composite with n-type TiO₂ contained the properties of a p/n-junction. In the photocurrent spectra (depending on the applied potential), the characteristic anodic peaks of the TiO₂ at λ=320 nm and cathodic peaks of the polythiophene around λ=500 nm were found. A new cathodic peak observed at 370 nm was explained as a new feature of the pn interface.     

A carbon nanotube/polyvanillin composite film as an electrocatalyst for the electrochemical oxidation of nitrite and its application as a nitrite sensor

We report a simple method for the stable dispersion of multi-walled carbon nanotubes (MWNTs) in water by vanillin and controllable surface addition onto carbon fiber microelectrodes (CFE) via electropolymerization. We have characterized these polyvanillin-carbon nanotube (PVN-MWNT) composite films with techniques including scanning electron microscopy (SEM), infrared spectroscopy (IR) and voltammetry. These investigations showed that the films have a uniform porous nanostructure with a large surface area. This PVN-MWNT composite-modified CFE (PVN-MWNT/CFE) exhibited a sensitive response to the electrochemical oxidation of nitrite. Under optimal working conditions, the oxidation peak current of nitrite linearly increased with its concentration in the range of 0.2 μM-3.1 mM, with the system exhibiting a lower detection limit of 50 nM (S/N = 3). We successfully applied the PVN-MWNT/CFE system to the determination of nitrite from lake water. The efficient recovery of nitrite indicated that this electrode was able to detect nitrite in real samples.     

Self-assembled monolayers-based immunosensor for detection of Escherichia coli using electrochemical impedance spectroscopy

An electrochemical impedance immunosensor for the detection of Escherichia coli was developed by immobilizing anti-E. coli antibodies at an Au electrode. The immobilization of antibodies at the Au electrode was carried out through a stable acyl amino ester intermediate generated by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydrosuccinimide (NHS), which could condense antibodies reproducibly and densely on the self-assembled monolayer (SAM). The surface characteristics of the immunosensor before and after the binding reaction of antibodies with E. coli were characterized by atomic force microscopy (AFM). The immobilization of antibodies and the binding of E. coli cells to the electrode could increase the electro-transfer resistance, which was directly detected by electrochemical impedance spectroscopy (EIS) in the presence of Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ as a redox probe. A linear relationship between the electron-transfer resistance and the logarithmic value of E. coli concentration was found in the range of E. coli cells from 3.0 × 10³ to 3.0 × 10⁷ cfu mL⁻¹ with the detection limit of 1.0 × 10³ cfu mL⁻¹. With preconcentration and pre-enrichment steps, it was possible to detect E. coli concentration as low as 50 cfu/mL in river water samples.     

Synthesis and characterization of carbon-coated Li0.5Ni0.25TiOPO4 anode material

Li_0.5Ni_0.25TiOPO₄/C composite was synthesized by the co-precipitation method using polyethylene glycol as carbon source. X-ray diffraction study showed that the as-prepared material crystallizes in the monoclinic system (S.G. P2₁/c). This 3D structure exhibits an open framework favourable to intercalation reactions. The morphology and the microstructure characterisation was performed by scanning electron microscopy (SEM). Small particles (∼1 μm) coated by carbon were observed. Raman study confirms the presence of carbon graphite in the Li_0.5Ni_0.25TiOPO₄/C composite. Cyclic voltammetry (CV) and charge-discharge galvanostatic cycling were used to characterize its electrochemical properties. The Li_0.5Ni_0.25TiOPO₄/C composite exhibits excellent electrochemical performances with good capacity retention for 50 cycles. Approximately 200 mAh/g could be reached at C, C/2, C/5 and C/20 rates in the 0.5-3 V potential range. These results clearly evidenced the positive effect of the carbon coating on the electrochemical properties of the studied phosphate.     

Synthesis and charge carrier mobility of a solution-processable conjugated copolymer based on cyclopenta[c]thiophene

A new polymer comprising alternate thiophene and didodecyloxymethyl substituted cyclopenta[c]thiophene unit, PDCPTT, was synthesized by the Stille coupling reaction and characterized by ¹H NMR, GPC, TGA, DSC, XRD, UV-vis absorption spectroscopy, photoluminescence spectroscopy and cyclic voltammetry. The copolymer is readily soluble in tetrahydrofuran, chloroform and toluene at ambient conditions and exhibits good thermal stability as it does not exhibit noteworthy weight loss until ∼300 °C under nitrogen. This polymer possesses a broad absorption band ranging at 400-650 nm (with an optical band gap of 1.90 eV). The DFT calculation predicts the polymer to be planar and the calculated band gap is only 0.17 eV higher than the experimentally determined band gap. Didodecyloxymethyl-3,4-cyclopentane substitution on alternate thiophene in a polythiophene, hitherto unexplored, showed an effective polymer based field effect transport characteristics; exhibiting hole mobility ≈1.4 × 10⁻² cm² V⁻¹ s⁻¹.     

Preparation, crystallization, electrical conductivity and thermal stability of syndiotactic polystyrene/carbon nanotube composites

A homogeneous dispersion of multi-walled carbon nanotubes (MWCNTs) in syndiotactic polystyrene (sPS) is obtained by a simple solution dispersion procedure. MWCNTs were dispersed in N-methyl-2-pyrrolidinone (NMP), and sPS/MWCNT composites are prepared by mixing sPS/NMP solution with MWCNT/NMP dispersion. The composite structure is characterized by scanning electron microscopy and transmission electron microscopy. The effect of MWCNTs on sPS crystallization and the composite properties are studied. The presence of MWCNTs increases the sPS crystallization temperature, broadens the crystallite size distribution and favors the formation of the thermodynamically stable β phase, whereas it has little effect on the sPS γ to α phase transition during heating. By adding only 1.0 wt.% pristine MWCNTs, the increase in the onset degradation temperature of the composite can reach 20 °C. The electrical conductivity is increased from 10^{−10∼−16} (neat sPS) to 0.135 S m⁻¹ (sPS/MWCNT composite with 3.0 wt.% MWCNT content). Our findings provide a simple and effective method for carbon nanotube dispersion in polymer matrix with dramatically increased electrical conductivity and thermal stability.     

Electrochemical Polymerization of Thiophene and Poly(3-hexyl)thiophene,Nanocomposites with TiO2, and Corrosion Protection Behaviors

Thiophene, 3-hexylthiophene, and their nanocomposites with TiO₂ were electropolymerized on Al1050 electrode by chronoamperometric technique. Different concentrations of thiophene and 3-hexylthiophene homopolymers and their nanocomposites with TiO₂ (2% in total content) were characterized by attenuated total reflection Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersion X-ray analysis, and electrochemical impedance spectroscopy. The anticorrosion tests for homopolymers and nanocomposite films were examined on Al1050 in 3.5% NaCl solution. Poly(3-hexylthiophene)/TiO₂ nanocomposite films gave the highest protection efficiency of 98% because the amount of defects was much lower than that for the poly(3-hexylthiophene), polythiophene, and polythiophene/TiO₂ films.     

Characterization of the anisotropy of pyrolytic carbon by Raman spectroscopy

The anisotropy of pyrolytic carbon is one of the most important properties for the development of TRISO (tristructural isotropic) coated fuel particles. Polarized Raman spectroscopy has been used to measure the anisotropy of pyrolytic carbon coatings ranging from high (highly oriented pyrolytic graphite) to low texture samples. Values obtained were correlated to the texture measured from the orientation angle (OA) of selected area electron diffraction patterns. The nodal behavior of the Raman intensity signals in graphite has been used to observe changes in the first order bands when the laser and scattered signal were polarized parallel or perpendicular to the graphene layers. Texture observed by Raman spectroscopy was largely affected by the orientation of the graphene layers inside growth features. Discrepancies in the values of texture measured between Raman spectroscopy and the OA was due to the difference of spatial resolution of each technique, 0.2 μm for OA and 2 μm for Raman spectroscopy. Both polarized Raman spectroscopy and nano-indentation were used to characterize the inner pyrolytic carbon in coated fuel particles before and after SiC deposition at 1500 °C.     

Electrochemical impedance spectroscopy and corrosion behaviour of Al2O3-Ni nano composite coatings

In this paper, the results on the electrochemical impedance spectroscopy and corrosion properties of electrodeposited nanostructured Al₂O₃-Ni composite coatings are presented. The nanocomposite coatings were obtained by codeposition of alumina nanoparticles (13 nm) with nickel during plating process. The coating thickness was 50 μm on steel support and an average of nano Al₂O₃ particles inside of coatings at 15 vol.% was present. The structure of the coatings was investigated by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure. The electrochemical behavior of the coatings in the corrosive solutions was investigated by polarization potentiodynamic and electrochemical impedance spectroscopy methods. As electrochemical test solutions 0.5 M sodium chloride and 0.5 M potassium sulphate were used in a three electrode open cell. The corrosion potential is shifted to more negative values for nanostructured coatings in 0.5 M sodium chloride. The polarization resistance in 0.5 M sodium chloride decreases in 24 h, but after that increases slowly. In 0.5 M potassium sulphate solution the polarization resistance decreases after 2 h and after 30 h of immersion the polarization resistance is higher than that of the beginning value. The corrosion rate calculated by polarization potentiodynamic curves obtained after 30 min from immersion in solution is smaller for nanostructured coatings in 0.5 M potassium sulphate (4.74 μm/year) and a little bit bigger in 0.5 M sodium chloride (5.03 μm/year).     

Carbothermal synthesis of boron nitride coating on PAN carbon fiber

Boron nitride (BN) thin coating has been formed on the surface of chemically activated polyacrylonitrile (PAN) carbon fiber by dip coating method. Dip coating was carried out in saturated boric acid solution followed by nitridation at a temperature of 1200 °C in nitrogen at atmospheric pressure to produce BN coating. Chemical activation improved surface area of PAN fiber which favours in situ carbothermal reduction of boric acid. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) have shown the formation of boron nitride. The X-ray photoelectron spectroscopy reveals that the coating forms a composite layer of carbon, BN/BO_xN_y and some graphite like BCN with local structure of B–N–C and B(N–C)₃. The oxidation resistance of the coated fiber was significantly higher than uncoated carbon fiber. Tensile strength measurement reveals that the BN coated fiber maintained 90% of its original strength. As compared to chemical vapor deposition (CVD), this process is simple, non-hazardous and is expected to be cost effective.     

Electropolymerization of N‐hydroxyethylcarbazole on carbon fiber microelectrodes

N‐Hydroxyethylcarbazole (EtOHCz) was electropolymerized on carbon fiber microelectrodes (CFMEs). The polyEtOHCz‐modified CFME was characterized with FTIR‐ATR, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The polymer/CFME electrode exhibited the capacitive behavior and also good stability up to 2.0 V. The presence of hydoxylic group of the monomer seems to be an advantage on polymerization because of the unpaired electrons of oxygen, which would make ease at first stage for the adsorbtion on carbon fiber. The estimated value of the low‐frequency redox capacitance (C_LF) was found to increase with increasing dc potential. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cathodoluminescence and electron field emission of boron-doped a-C:N films

The optical and electrical properties of so-called carbon nitride films (a-C:N) and boron doped so-called carbon nitride films (a-C:N:B) are studied with cathodoluminescence (CL) spectroscopy and electron field emission measurement. The a-C:N films were first deposited on Si by a filtered cathodic arc plasma system, and then boron ions (∼1 × 10¹⁶ cm⁻²) were implanted into the a-C:N films to form a-C:N:B films by a medium current implanter. The structural and morphological properties of a-C:N and a-C:N:B films were then analyzed using secondary ion mass spectrometer, X-ray photoelectron spectroscopy, FT-IR spectra, Raman spectroscopy and atomic force microscopy. The a-C:N film exhibits luminescence of blue light (∼2.67 eV) and red light (∼1.91 eV), and the a-C:N:B film displays luminescence of blue light (∼2.67 eV) in CL spectra measured at 300 K. Furthermore, the incorporated boron atoms change the electron field emission property, which shows a higher turn on field for the a-C:N:B film (3.6 V/μm) than that for the a-C:N film (2.8 V/μm).     

Electrochemical tolazoline sensor based on gold nanoparticles and imprinted poly-o-aminothiophenol film

Amperometric detection of tolazoline (TL) was carried out on a gold nanoparticles (AuNPs)/poly-o-aminothiophenol (PoAT)-modified electrode by a molecular imprinting technique and electropolymerization method. The modification procedure was characterized via electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The recognition between the imprinted sensor and target molecule was observed by measuring the variation of amperometric response of the oxidation-reduction probe, K₃Fe(CN)₆ on electrode. Under the optimal experimental conditions, the peak currents were proportional to the concentrations of tolazoline in two ranges of 0.05-5.0 μg mL⁻¹ and 5.0-240 μg mL⁻¹ with the detection limit of 0.016 μg mL⁻¹. Meanwhile the prepared sensor showed sensitive and selective binding sites for tolazoline. The enhancement of sensitivity was attributed to the presence of AuNPs which decreased the electron-transfer impedance.     

A comparative study on protective properties of electrosynthesized poly(pyrrole)/poly(N-methylpyrrole), poly(pyrrole)/poly(N-phenylpyrrole), poly(pyrrole)/poly(N-methoxyphenylpyrrole) composite coatings

In this study, three sets of different bilayered composite coatings of pyrrole and N-substituted pyrroles were synthesized by a layer-by-layer approach on copper surface and corrosion performances of the synthesized materials were compared. Electrodepositions of poly(N-methylpyrrole), poly(N-phenylpyrrole), and poly(N-methoxyphenylpyrrole) were performed in nonaqueous medium on a poly(pryrrole)-coated copper surface using cyclic voltammetry. The morphologies of the resulting bilayered composite coatings of poly(pyrrole)/poly(N-methylpyrrole), poly(pyrrole)/poly(N-phenylpyrrole), and poly(pyrrole)/poly(N-methoxyphenylpyrrole) were investigated by scanning electron microscopy. Stabilities of a doping-dedoping process of the composites were determined from the cyclic voltammetric study of the bilayer-coated electrodes in a monomer-free solution. Corrosion performances of the bilayer composite-coated and uncoated copper electrodes were investigated in 0.1 M H₂SO₄ solution using open circuit potential–time (E _ocp–t) curves, anodic polarization, and electrochemical impedance spectroscopy. All the investigated bilayered coatings gave significant enhancement in the corrosion resistance of copper, compared to the single poly(pyrrole) coating. Stability and corrosion tests revealed that the composite material poly(pyrrole)/poly(N-methoxyphenylpyrrole) exhibited higher electrochemical stability and corrosion resistant behavior than the other bilayered composite coatings.