Electrocatalytic oxidation of ascorbic acid at polypyrrole nanowire modified electrode

Polypyrrole (PPy) nanowire modified electrodes were prepared electrochemically by template-free method based on graphite electrodes. The freshly prepared electrodes were dipped in 10% HClO₄ solution at least 24 h for removal of carbonate ions. The modified electrodes toward ascorbic acid were characterized by potentiostatic method. The experiment's results show that the PPy modified electrodes have obvious electrocatalytic effect toward ascorbic acid oxidation. The oxidation current density has a good linearity in the concentration range of 5.0 × 10⁻⁴ and 2.0 × 10⁻² mol L⁻¹ of ascorbic acid. The determination sensitivity may be significantly affected by the thickness of PPy film and pH of the test solution. The method has promising application in determination of ascorbic acid in the real samples.     

A comparative study on polyaniline degradation by an electrochemical quartz crystal impedance system: electrode and solution effects

By combining the piezoelectric quartz crystal impedance (PQCI) and electrochemical impedance spectroscopy (EIS) measurements, we conducted a comparative study on polyaniline (PANI) degradation in different media, HClO₄ and H₂SO₄, and on different piezoelectric quartz crystal (PQC) electrodes, Pt and Au. It is concluded that (1) the PANI film grown on an Au electrode is more stable than that on a Pt electrode; (2) the PANI degradation reaction abides by the zero-order kinetic law in HClO₄ with rate constants from 0.17 to 2.25 Hz s⁻¹ on Pt and 0.16 to 0.83 Hz s⁻¹ on Au, but the first-order kinetic law in H₂SO₄ with rate constants from 2.61×10⁻³ to 7.00×10⁻³ s⁻¹ on Pt and 1.00×10⁻³ to 5.00×10⁻³ s⁻¹ on Au at different ion concentrations. The contrary effects of ClO₄⁻ and SO₄²⁻ on PANI degradation may be understood from the Hofmeister series of anions; (3) the dissolution of the PANI film bulk, the increase of film porosity and the film attenuation occurred simultaneously during degradation via systematic analyses of the motional resistance (R₁)and electrochemical impedance spectra responses, etc.     

Mechanism of polypyrrole and silver nanorod formation in lauric acid–cetyl trimethyl ammonium bromide coacervate gel template: Physical and conductivity properties

Polypyrrole (PPy) and silver (Ag) nanorods are synthesized in cetyl trimethylammonium bromide–lauric acid (CTAB–LA) complex coacervate gel template. When PPy–CTAB–LA system is polymerized with AgNO₃, Ag nanorods are produced while use of ammonium persulphate (APS) as initiator yields PPy nanorods. Ag-nanorods are produced from the initial stage while PPy nanorods take a longer time. The average diameter of Ag nanorods varies from 60 to 145 nm by increasing AgNO₃ concentration from 0.27 M to 1.08 M and that of PPy varies from 145 nm to 345 nm by changing pyrrole concentration from 1 × 10^?4 to 2 × 10^?4 M, respectively. Fourier transformed infrared (FTIR) spectra indicate stabilization of Ag nanorods through complexation of PPy with adsorbed Ag⁺ ions. PPy nanoparticles are stabilized by adsorbed sulphate ions and lauric acid, both are acting as dopant to it. FFT pattern and EDX spectra clearly indicate the presence of Ag nanocrystals and PPy on the surface of Ag nanorods, respectively. The mechanism of nanorod formation is attributed from UV–Vis spectra showing a red shift of surface plasmon band of Ag and π–π* transition band of PPy with time. The highest dc conductivity of PPy–Ag composite is found to be 414.2 S/cm, 7 orders higher than that of PPy nanorods (9.3 × 10^?4 S/cm). PPy–Ag systems show Ohmic behavior while PPy nanorods exhibit semi-conducting behavior. The preferential formation of Ag nanorod in AgNO₃ initiated polymerization is attributed to the higher cohesive force of Ag than that of PPy. With two times higher LA and CTAB concentration in the gel the Ag nanorod diameter decreases only 12% while that of PPy nanorod decreases by 50%. Possible reasons are discussed from the hard and soft nature of the two nanorods and from the elasticity of the gel template.     

Theoretical and experimental study of photocurrent action spectrum of ITO/sexithiophene/Al structure

We have studied photovoltaic cells using sexithiophene in (ITO/6T/Al) structure, and we have measured the action spectrum obtained by illumination through the aluminum side which is compared to the measured absorption spectrum. Two models were used to interpret this experiment: the Ghosh model using the carriers diffusion property in the bulk, and the kinetic model describing the dynamic behavior of the charge carriers in the device. The confrontation of these models with the experimental spectra allows us to reach the diffusion length of electron–hole pair L=2×10⁻⁶ cm. We also give the mobility of carriers (μ_n≈1.5×10⁻⁴ cm²/V s, and μ_p≈1.5×10⁻⁵ cm²/V s) and their diffusion coefficients (D_n≈4×10⁻⁶ cm²/s, and D_p≈4×10⁻⁷ cm²/s).     

Effect of various parameters on the conductivity of free standing electrosynthesized polypyrrole films

Electrical characteristics of polypyrrole films electrodeposited in different aqueous electrolyte solutions including p-toluenesulfonate, naphtalenesulfonate, nitrate, tetrafluoroborate, and perchlorate anions were investigated using the Van der Pauw procedure. The polymer films were synthesized by electrochemical oxidation at a fixed potential. Experimental parameters including the pyrrole concentration, electrolyte, applied potential and substrate were shown to affect the electrical conductivity σ of polypyrrole films. Since the substrate contributes significantly to the overall conductivity of polypyrrole-coated electrodes, the results obtained with free standing polymer films appeared more reliable. The results indicated that the p-toluenesulfonate doped PPy film showed the highest average conductivity (σ_293 K = 4.5 × 10⁵ S m^?1) whereas the perchlorate doped one produced the lowest of all the films prepared (σ_293 K = 2 × 10⁴ S m^?1).     

Preparation,crystal structures and electrical conducting properties of new charge-transfer salts: (ET)2·SO3CF3 and (ET)·ClO4

Two new charge-transfer (CT) salts: (ET)₂·SO₃CF₃ and (ET)·ClO₄ were prepared by chemical oxidation of ET with AgSO₃CF₃ and AgClO₄, respectively. Their crystal structures were determined: monoclinic system, Cc, a=35.239(7) Å, b=6.5440(13) Å, c=14.646(3) Å, β=110.26(3)°, V=3168.5(11) Å³ for (ET)₂·SO₃CF₃; monoclinic system, C2/c, a=15.981(3) Å, b=10.627(2) Å, c=11.495(2) Å, β=120.61(3)°, V=1680.2(6) Å³ for (ET)·ClO₄. Electrical conductivity measurements indicate that (ET)₂·SO₃CF₃ shows semi-conducting behaviour with room temperature conductivity of 0.29 S cm⁻¹, while (ET)·ClO₄ is an insulator.     

Tris(trifluoromethylsulfonyl)methide-doped polypyrrole as a conducting polymer actuator with large electrochemical strain

A free-standing polypyrrole (PPy) film actuator, prepared electrochemically from a methyl benzoate solution of 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide (DMPIMe), exhibited up to 36.7% electrochemical strain in a propylene carbonate (PC)/water solution of lithium bis(nonafluorobutylsulfonyl)imide, Li(C₄F₉SO₂)₂N (LiNFSI). The maximum electrochemical strain of Me-doped PPy film depended on the electrolyte used for driving the Me-doped PPy actuator. When a PC/water mixed solution of lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) was used as the driving electrolyte, the maximum electrochemical strain, measured by cycling between −0.9 and +0.7 V versus Ag/Ag⁺ at 2 mV s⁻¹, was 24.2%, smaller than that (30.0%) driven with LiNFSI. When a PC/water suspension of DMPIMe was used as the driving electrolyte, the maximum electrochemical strain was 31.9%. However, the response speed of Me-doped PPy actuator driven with DMPIMe was slower than those driven with Li(C_nF_2n+1SO₂)₂N, due presumably to the size and shape of the anions. The addition of CF₃COOH in electrolytic solutions for electropolymerization increased the maximum electrochemical strains (36.7% and 36.6%) of Me-doped PPy actuator driven by using a PC/water solution of LiNFSI and a PC solution of DMPIMe, respectively.     

Alkyl chain length dependence of the field-effect carrier mobility in regioregular poly(3-alkylthiophene)s

The field-effect mobility of holes in regioregular poly(3-alkylthiophene)s was determined for a series of 5 alkyl chain lengths from C₄ (n-butyl) to C₁₂ (n-dodecyl). Contrary to a previous report, a non-monotonic dependence of field-effect mobility on alkyl chain length was found. The average hole mobility varied from 1.2 × 10⁻³ cm²/Vs in poly(3-butylthiophene) and 1 × 10⁻² cm²/Vs in poly(3-hexylthiophene) to 2.4 × 10⁻⁵ cm²/Vs for poly(3-dodecylthiophene). We believe that the hexyl side chain is optimum for charge transport because of better self-organization in poly(3-hexylthiophene) compared to other polymers in the series. The present results provide an important structure–carrier mobility relationship for the regioregular poly(3-alkylthiophene)s which are of wide interest for thin film transistors and photovoltaic cells.     

Protonation-induced rearrangements in Langmuir films and redox properties of Langmuir–Blodgett films of 2-(n-alkyl)fulleropyrrolidines

The effect of protonation of the pyrrolidine ring nitrogen of 2-(n-alkyl)fulleropyrrolidines, C₆₀pyr–C_m (m=4, 6, 8, 10 and 12), on the properties of the Langmuir and Langmuir–Blodgett (LB) films was investigated. The isotherms of both surface pressure (π) and surface potential change (ΔV) versus area per molecule (A) for the Langmuir films of C₆₀pyr–C_m were determined simultaneously. It was found that the longer the alkyl chain of the fulleropyrrolidine the larger is the film compressibility, κ, i.e., κ(C₆₀pyr–C₄)=(2.1±0.4)×10⁻² m mN⁻¹, κ(C₆₀pyr–C₈)=(3.5±0.4)×10⁻² m mN⁻¹ and κ(C₆₀pyr–C₁₂)=(4.1±0.5)×10⁻² m mN⁻¹, as expected for the liquid surface films. The values of surface area at zero surface pressure (A₁) differ in the range 0.6 nm² molecule⁻¹ (for m=4–8) to 1.4 nm² molecule⁻¹ (for m=10–12), indicating that all 2-(n-alkyl)fulleropyrrolidines form multilayer or aggregated films on neutral water subphase. However, acidification of the water subphase increases the A₁ values for all investigated fulleropyrrolidines up to ca. 1.9 nm² molecule⁻¹, i.e., the value corresponding to maximum area occupied by a fulleropyrrolidine at horizontal orientation in a monolayer film. Apparently, 2-(n-alkyl)fulleropyrrolidinium cations formed at low pH are markedly de-aggregated in the films and their orientation is changed due to protonation of the pyrrolidine nitrogen. Similarly, however, less pronounced effects are observed if ionic strength of the subphase solution, I, is increased in the range 0≤I≤1.0 mol dm⁻³ NaCl. The Langmuir films formed on a water subphase were the most stable with respect to the LB transfer onto 5 MHz Au–quartz crystal vibrators. Simultaneous cyclic voltammetry and piezoelectric microgravimetry at an electrochemical quartz crystal microbalance of these films showed at least two electroreductions where the fulleropyrrolidine mono anions were stable with respect to dissolution.     

High-temperature oxidation and hot corrosion of Cr2AlC

High-temperature oxidation and hot corrosion behaviors of Cr₂AlC were investigated at 800–1300 °C in air. Thermogravimetric–differential scanning calorimetric test revealed that the starting oxidation temperature for Cr₂AlC is about 800 °C, which is 400 °C higher than other ternary transition metal aluminum carbides. Thermogravimetric analyses demonstrated that Cr₂AlC displayed excellent high-temperature oxidation resistance with parabolic rate constants of 1.08 × 10⁻¹² and 2.96 × 10⁻⁹ kg² m⁻⁴ s⁻¹ at 800 and 1300 °C, respectively. Moreover, Cr₂AlC exhibited exceptionally good hot corrosion resistance against molten Na₂SO₄ salt. The mechanism of the excellent high-temperature corrosion resistance for Cr₂AlC can be attributed to the formation of a protective Al₂O₃-rich scale during both the high-temperature oxidation and hot corrosion processes.     

Studies on electrochemical copolymerization of aniline with o-phenylenediamine and degradation of the resultant copolymers via electrochemical quartz crystal microbalance and scanning electrochemical microscope

Electropolymerization of aniline in sulfuric acid solution in the presence of o-phenylenediamine (oPD) of various concentrations was investigated via the electrochemical quartz crystal microbalance (EQCM) technique. It was found that the polymerization occurred more favorably at high aniline-to-oPD molar ratios (F₁, 20 or above). The stabilities of the resultant copolymers against degradation were efficiently improved compared with that of polyaniline (PANI). The first-order kinetic constants for polymer degradation were estimated to be 2.07 × 10⁻³ s⁻¹ for polyaniline, and 3.91 × 10⁻⁴ and 1.28 × 10⁻⁴ s⁻¹ for copolymers with F₁ values of 50 and 20, respectively. The degradation product, benzoquinone, was also detected at the tip electrode of a scanning electrochemical microscope (SECM).     

Thermal expansion of the W5Si3 and T2 phases of the W–Si–B system investigated by high-temperature X-ray diffraction

The coefficients of thermal expansion (CTE) of the W₅Si₃ and T₂ phases of the W–Si–B system were determined using high-temperature X-ray diffraction in the 298–1273 K temperature interval. Alloys with nominal compositions 62.5W37.5Si (at%) and 58W21Si21B (at%) were prepared from high-purity materials through arc melting followed by heat treatment at 2073 K for 12 h under argon atmosphere. The highly different thermal expansion coefficients of W₅Si₃ along the a (5.0 × 10⁻⁶ K⁻¹) and c (16.3 × 10⁻⁶ K⁻¹) axes lead to a high thermal expansion anisotropy (α_c/α_a ≅ 3.3). On the other hand, the T₂-phase exhibits similar thermal expansion coefficients along the a (6.9 × 10⁻⁶ K⁻¹) and c (7.6 × 10⁻⁶ K⁻¹) axes, indicating a behavior close to isotropic (α_c/α_a ≅ 1.1).     

Structure–conductivity relationships in chemical polypyrroles of low,medium and high conductivity

Chemically synthesized polypyrroles of low (σ < 75 S/cm), medium (75 < σ < 200 S/cm) and high (σ > 200 S/cm) electrical conductivity (σ) with the same dopant and degree of doping have been investigated by means of Wide Angle X-ray Scattering (WAXS), ¹³C Cross Polarized Magic Angle Spinning Nuclear Magnetic Resonance (¹³C CP/MAS NMR) spectroscopy and Fourier Transform Infrared (FTIR) Spectroscopy to establish structure–conductivity relationships useful for industrial applications. A similar amorphous structure was found by WAXS even for the higher conducting PPy (σ = 288 S/cm). WAXS spectra for polypyrroles of medium and high conductivity showed a weak peak at 2θ = 10–11° due to improved order of the counterions in these materials. The effect of the counterion size in the asymmetry of the PPy main WAXS peak was elucidated by performing ion exchange of the Cl⁻ dopant with counterions of larger size such as BF₄⁻ and ClO₄⁻. From ¹³C CP/MAS NMR measurements predominantly α–α′ bonding was found in these materials. The main ¹³C CP/MAS NMR resonance peak of PPy located at 126–128 ppm was broadened upon increasing conductivity. Interestingly, a linear relationship was observed between the half-width at half-height (HWHH) of the ¹³C CP/MAS NMR peak and conductivity where a doubling of the polypyrrole conductivity leads to an increase of HWHH by 6–7 ppm. FTIR data of these materials were analysed in the framework of the Baughman–Shacklette theory describing the dependence of conductivity on conjugation length. By comparison of model predictions and experimental results, the PPy samples were found to be in the regime of long conjugation lengths, L ≫ K₂/k_BT, where K₂ is a parameter related to the energy change on going from j − 1 to j charges on a conjugated segment of conjugation length L, k_B the Boltzman constant and T is the absolute temperature.     

Laser doping of chromium as a double acceptor in silicon carbide with reduced crystalline damage and nearly all dopants in activated state

Chromium, a p-type dopant, has been incorporated into silicon carbide by laser doping. Secondary ion mass spectrometric data revealed enhanced solid solubility (2.29 × 10¹⁹ cm⁻³ in 6H–SiC and 1.42 × 19¹⁹ cm⁻³ in 4H–SiC), exceeding the equilibrium limit (3 × 10¹⁷ cm⁻³ in 6H–SiC above 2500 °C). The roughness, surface chemistry and crystalline integrity of the doped sample were examined by optical interferometry, energy dispersive X-ray spectrometry and transmission electron microscopy, respectively, and showed no crystalline disorder due to laser heating. Deep-level transient spectroscopy confirmed Cr as a deep-level acceptor with activation energies E_v + 0.80 eV in 4H–SiC and E_v + 0.45 eV in 6H–SiC. The Hall effect measurements showed that the hole concentration (1.942 × 10¹⁹ cm⁻³) is almost twice the average Cr concentration (1 × 10¹⁹ cm⁻³), confirming that almost all of the Cr atoms were completely activated to the double acceptor state by the laser-doping process without requiring any additional annealing step.     

The role of anthraquinone sulfonate dopants in promoting performance of polypyrrole composites as pseudo-capacitive electrode materials

We report the role of anthraquinone sulfonate dopants in promoting performance of electro-synthesized polypyrrole (PPy) composites for use in electrochemical supercapacitors. The incorporation of anthraquinone sulfonate species into the polymer matrix can significantly improve the surface area of PPy composites that are composed of submicron-/nano-sized particles, as evidenced from scanning electron microscopy (SEM) results. Cyclic voltammetry and galvanostatic charge–discharge measurements in 1 M KCl solution reveal that these dopants result in an improved specific capacitance, a wide working potential range and enhanced long-cycle stability as compared to ClO₄^? dopant. Among the samples investigated, the resulting PPy/AQS (9,10-anthraquinone-2-sulfonic acid sodium salt) composite exhibits the highest specific capacitance of 608 F g^?1 at a scan rate of 5 mV s^?1 within a potential range between ?0.9 and 0.5 V (vs. saturated calomel electrode, SCE).     

Effect of growth rate on microstructure and mechanical properties of directionally solidified multiphase intermetallic Ni–Al–Cr–Ta–Mo–Zr alloy

The effect of growth rate on microstructure and mechanical properties of directionally solidified (DS) multiphase intermetallic alloy with the chemical composition Ni–21.9Al–8.1Cr–4.2Ta–0.9Mo–0.3Zr (at.%) was studied. The DS ingots were prepared at constant growth rates V ranging from 5.56 × 10⁻⁶ to 1.18 × 10⁻⁴ ms⁻¹ and at a constant temperature gradient at the solid–liquid interface of G_L = 12 × 10³ K m⁻¹. Increasing growth rate increases volume fraction of dendrites and decreases primary dendritic arm spacing, mean diameter of α-Cr (Cr-based solid solution) and γ′(Ni₃Al) precipitates within the dendrites. Room-temperature compressive yield strength, ultimate compressive strength, hardness and microhardness of dendrites increase with increasing growth rate. All room-temperature tensile specimens show brittle fracture without yielding. The brittle-to-ductile transition temperature for tensile specimens is determined to be about 1148 K. Minimum creep rate is found to depend strongly on the applied stress and temperature according to the power law with a stress exponent of n = 7 and apparent activation energy for creep of Q_a = 401 kJ/mol.     

Synthesis and characterization of triphenylamine derivatives by oxidative polymerization

Hole transport polymers consisting of 4-methoxytriphenylamine (P-MOTPA) and 4-n-butyltriphenylamine (P-BTPA) were synthesized by oxidative coupling reaction using FeCl₃ as an oxidant. These polymers had good solubility and their thin films showed sufficient morphological stability. ¹H NMR and ¹³C NMR revealed that the monomers were exclusively connected at the p-positions of unsubstituted phenyl groups. Polymers had UV absorption maximum around 370 nm. Cyclic voltammograms of polymers showed well-defined pairs of reduction and oxidation peaks at 1.1 V versus Ag/AgCl, indicating that the polymers are electrochemically active. P-MOTPA and P-BTPA had hole drift mobility of being 4.04 × 10⁻⁵ and 2.98 × 10⁻⁵ cm²/V s at the electric field of 50 V/μm, respectively.     

Preparation and characterization of a polypyrrole hybrid film with [Ni(dmit)2]2−, bis(1,3-dithiole-2-thione-4,5-dithiolate)nickellate(II)

The synthesis of a hybrid material obtained by electropolymerization of a solution of pyrrole and [NEt₄]₂[Ni(dmit)₂] (dmit = 1,3-dithiole-2-thione-4,5-dithiolato) in acetonitrile solution is reported. The material was characterized by cyclic voltammetry, UV–vis and infrared spectroscopies, scanning electron microscopy (SEM), atomic force microscopy (AFM) and thermal gravimetric analysis (TGA). The FTIR spectroscopy showed that the [Ni(dmit)₂]²⁻ anion has been inserted in the polypyrrole framework and was not destroyed or modified during the polymerization process. The voltammetric analysis indicated that the material has electroactivity and undergoes redox processes associated with the conducting polymer and the counteranion. The cyclic voltammetry results also suggest that the counteranion is not trapped in the PPy matrix undergoing anion exchange during the redox cycle of PPy. The PPy/[Ni(dmit)₂]²⁻ exhibits good thermal stability and a intrinsic conductivity value in the range of semiconductors (10⁻³ S cm⁻¹).     

Z-scan measurements of third-order optical non-linearities in poly(phenylacetylenes)

Poly(phenylacetylene) (PPA) and poly(p-methoxyphenylacetylene) (PMOPPA) were synthesized by catalytic polymerization of monosubstituted alkynes and were fully characterized by conventional techniques. Linear and third-order non-linear optical properties of polymers solutions were investigated at λ=780 nm using a Z-scan set-up equipped with a femtosecond laser source at different operating regimes. A high repetition rate (76 MHz) regime was used to measure the linear and non-linear absorption coefficients by means of thermo-optical effects. Values of the linear and non-linear absorption coefficients were α=4.9×10⁻³ cm⁻¹ and β=1.1×10⁻¹¹ cm W⁻¹ for PPA and α=2×10⁻² cm⁻¹ and β=2.1×10⁻¹⁰ cm W⁻¹ for PMOPPA. Very low repetition rate (14 Hz) excitation was used to evidence the purely-optical non-linear refractive indexes, that were γ=6×10⁻¹⁸ cm² W⁻¹ and γ=11×10⁻¹⁸ cm² W⁻¹, respectively, for PPA and PMOPPA.     

Ions transport and self-doping in layer-by-layer conducting polymer films

The self-doping mechanism for charge transport is investigated in layer-by-layer (LBL) films from two conducting polymers, namely poly(o-methoxyaniline) (POMA) and poly(3-thiophene acetic acid) (PTAA). The efficiency of charge intercalation, defined as the ratio between the charge and the mass change, is twice for the POMA/PTAA LBL film in comparison with a cast POMA film. This is attributed to differences in the diffusion-controlled charge and mass transport, where distinct ionic species participate in the LBL films, as demonstrated with experiments using a quartz crystal microbalance. The doping efficiency for LBL film is the same, i.e., 3.93 × 10⁻⁴ and 3.56 × 10⁻⁴ g/C for the Li⁺ and (C₂H₅)₄N⁺ doped films, and is different for the cast POMA film, i.e., 11.3 × 10⁻⁴ for Li⁺ and 6.45 × 10⁻⁴ g/C for (C₂H₅)₄N⁺. Therefore, once no significant differences in the intercalation mechanism are observed when different cations, Li⁺ or (C₂H₅)₄N⁺, are used with the LBL films, this indicates that the self-doping mechanism is controlled by the exchange of anions.