Polypyrrole electropolymerized on aluminum alloy 1100 doped with oxalate and tungstate anions

Polypyrrole films doped with oxalic acid and tungstate were potentiostatically electropolymerized on aluminum alloy 1100. Two statistical factorial designs (fractional and complete) were used to study the influence of the synthesis variables on the film performance against corrosion. Corrosion protection of the polypyrrole films doped with oxalate and tungstate anions (PPy/OXA/W) on the aluminum alloy was evaluated by potentiometric and electrochemical impedance spectroscopy (EIS) measurements in a 0.05 mol L⁻¹ NaCl solution. The results obtained showed that the best performance against corrosion was detected with the PPy/OXA/W film synthesized at 1.0 V, 1.5 C in 0.2 mol L⁻¹ pyrrole, 0.1 mol L⁻¹ oxalic acid and 0.05 mol L⁻¹ sodium tungstate solutions provide a protective effect against corrosion.     

Alumoxo-heteropoly compounds as weakly coordinating anions for metallocenes in the oligomerization of alkenes

The in situ synthesis of methylalumoxane (MAO) on the crystalline structure of heteropoly acids generates a highly active and weakly coordinating compound for the metallocene catalyst. The MAO-phase formed by the controlled hydrolysis of trimethylaluminum covers the Keggin unit of the heteropoly compound, as is verified with several spectroscopic techniques. The primary Keggin structure of the heteropoly compound is preserved and MAO-formation induces an intensive charge transfer in the VIS-region. ²⁷Al-NMR of alumoxo-phosphotungstate illustrates the reversible interaction of the Lewis acid Al of the anchored alumoxane with the bridging oxygen atoms of the phosphotungstate Keggin structure.

The interaction of the alumoxo-heteropoly compound with an ansa-metallocene produces a highly active catalyst for the co-oligomerization of ethene and propene. The softness of the heteropoly compound combined with the pseudo-liquid phase formation of the alumoxo-heteropoly compounds exceeds the activity of the homogeneous system and the stability of the heterogeneous MAO-anchored materials. The composition of the Keggin structure determines the catalytic potential of the metallocene which is transformed in a temperature dependent oligomerization and a fluctuating alternation of monomer and comonomer. The molecular weight and the methyl branching of the oligomer molecules are designing tools for the physicochemical features of a synthetic lubricant. A comparable charge delocalization over each heteropoly compound results in a single-sited catalytic system inducing a small dispersity of oligomer products.     

Ion transport investigations of polypyrroles doped with different anions by EQCM and CER techniques

The ion transfer in redox processes of conducting polypyrrole doped with various anions, such as 1-naphthalenesulfonate, 10-camphorsulfonate, p-toluenesulfonate, dodecylbenzenesulfonate was investigated by electrochemical quartz crystal microbalance (EQCM), contact electric resistance (CER), and cyclic voltamperometry in situ techniques. By using this setup, the doping levels of the synthesized PPy films and mobility of charge carries in these materials in KCl aqueous solution under linear potential scan were determined.     

Oxygen reduction on oxide/polypyrrole composite electrodes: effect of doping anions

Multilayered composite electrodes on glassy carbon, GC, having the structure GC/PPy/PPy(Ox)/PPy, with PPy the polypyrrole and Ox a mixed valence oxide of transition metals, exhibit high reactivity and stability towards the oxygen reduction reaction (orr), when the orr proceeds electrocatalytically on the oxide particles dispersed throughout the inner layer, PPy(Ox). However the nature and concentration of the doping anions, A, of PPy have a profound effect on the resulting orr currents, due to their effects on the conductivity and morphology of the PPy layers. The paper shows and discusses these effects in the case of the composite electrode with Ox = Cu_1.4Mn_1.6O₄ and A = Cl⁻, ClO₄⁻, NO₃⁻, PF₆⁻ and SO₄²⁻, in acid solution (pH 2.2). Optimal conditions were encountered with Cl⁻.     

Study of the factors determining the mobility of ions in the polypyrrole films doped with aromatic sulfonate anions

The electrochemical redox behavior of the polypyrrole (PPy) films doped with benzenesulfonate (BS), p-toluenesulfonate (pTS) and naphtalene-1,5-disulfonate (NDS) was investigated by cyclic voltammetry, the chemical composition of the films was determined by XDS, the surface morphology was characterized by AFM, and the interactions between pyrrole oligomers and the anions were modeled with quantum chemical methods. It is the first detailed comparative study of the properties of these interesting systems with two complementing interactions (electrostatic and aromatic stacking). It was shown than these relatively similar aromatic sulfonate anions have rather different behavior in PPy films. The results showed that the redoxactivity of polypyrrole films doped with sulfonate ions increases in the sequence pTS < BS < NDS. The comparison of voltammograms measured in the presence of different anions with PPy films synthesized in the same solution show that the PPy/pTS films have the most densely packed and the PPy/NDS films the least densely packed structure of the three. The mobility of ions in these films is mainly determined by the packing of the films, which in turn partly depends on the interactions between the dopant-anion and polymer chains.     

Synthesis, characterization, and catalytic application of copper(I) nitrile cations with perfluorinated weakly coordinating anions

Complexes of the type [Cu(CH₃CN)₄]⁺[A]^– ([A]^– = [B(C₆F₅)₄]^– (1), [B{C₆H₃(CF₃)₂}]^– (2), [(C₆F₅)₃B–C₃H₄N₂–B(C₆F₅)₃]^– (3)) are synthesized and characterized. Their utilization as catalysts in cyclopropanation and aziridination reactions of olefins, forming three membered rings is explored. The compounds are found to catalyze both reactions in moderate to good yields being the best results obtained with compound 1. The more weakly the nitrile ligands are coordinated to the metal center, the better is the catalytic performance of the catalyst.     

The corrosion-inhibiting effect of polypyrrole films doped with p-toluene-sulfonate,benzene-sulfonate or dodecyl-sulfate anions,as coating on stainless steel in NaCl aqueous solutions

This article presents a study of the conditions for electro-synthesis of polypyrrole (PPy) films on stainless steel, in the presence of the anions p-toluene-sulfonate (pTS), benzene-sulfonate (BS) or dodecyl-sulfate (DS). Cyclic voltammetry (CV) was used in the synthesis of the polypyrrole films on the stainless steel (SS). These polymeric films were characterized by IR and UV–vis spectroscopy and their morphology and thickness were analyzed by scanning electron microscopy (SEM). Their performance as protective films against corrosive processes presented by the SS/PPy-pTS, SS/PPy-BS or SS/PPy-DS systems was evaluated in 0.1 M NaCl aqueous solution. The study of the corrosion processes of the stainless steel/polymer systems was conducted through measurements of open circuit potential (E_OCP), polarization curves (PC) and electrochemical impedance spectroscopy (EIS). The results showed that the protective capacity of these polymeric systems on stainless steel, mainly with regard to pitting, depends on the nature of the anion dopant used during electro-synthesis of the PPy film. The best performance was seen with the dopants pTS and BS.     

Polypyrrole micro- and nanowires synthesized by electrochemical polymerization of pyrrole in the aqueous solutions of pyrenesulfonic acid

Polypyrrole (PPy) micro- and nanowires were synthesized through electrochemical polymerization of pyrrole in the aqueous solutions of 1-pyrenesulfonic acid (PSA), in which PSA acted as both surfactant and dopant. Macroscopic studies (SEM and TEM) indicated that the PPy wires have diameters of 120-500 nm and length of several micrometers. Electrochemical investigation demonstrated that the PPy wires have much stronger electrochemical activity than the conventional flat PPy film because of their higher specific surface area. Furthermore, the PSA doped PPy wires showed strong emission in an aqueous dispersion. A possible micelle guided formation mechanism has been proposed and investigated.     

Photoelectronic and transport properties of polypyrrole doped with a dianionic dye

Polypyrrole (PPy) doped with dodecylsulfate (DS) and an organic dye (indigo carmine, IC) was electrochemically prepared and characterized by Raman spectroscopy and X-ray diffraction (XRD). The photoelectrochemical properties of PPy-DS and PPy-DS-IC in contact with an electrolytic solution containing a redox couple were studied using the theories for the semiconductor ∣ electrolyte interface. Results indicate that the system containing IC presents a higher photocurrent density under polychromatic illumination and faster response time when compared with PPy-DS. This fact was assigned to the formation of molecular-scale paths in PPy-DS-IC. The IC molecules lying perpendicularly between PPy chains, as confirmed by the X-ray analysis, could facilitate the mass transport at the interface and increase the ordering degree to provide better electronic charge transfer in the bulk. Although the photoelectrochemical devices presented here do not present all the properties of inorganic-based devices, we discuss some strategies to enhance the photoelectrochemical properties and response time of conducting polymers used in these type of systems.     

Simultaneous monitoring of the transport of anions and cations across polypyrrole based composite membranes

A mechanism for the macroscopic charge balance during the transport of anions and cations across polypyrrole based composite membranes is proposed. For the mechanism to be studied, anions and cations were monitored simultaneously across PPy based composite membranes, which are known to have cation exchange (PPy(PSS)), anion exchange (PPy(ClO₄)) and mixed ion exchange properties (PPy(pTS)). Even though none of the membranes were found to be completely permselective, the flux of cations was higher than that of anions across the PPy(PSS) composite membrane, while the flux of anions was higher than that of cations across the PPy(ClO₄) composite membrane. Distinct changes in pH of the receiving solution were also observed. These were a decrease in pH when a predominantly anion exchanging polypyrrole composite membrane was used, and an increase in pH when a membrane that maintains charge balance principally by cation exchange was used. When membranes which display approximately equal permeability towards anions and cations were used the pH of the receiving solution was ca. 6–8. There was only a negligible flux of Ca²⁺ across the PPy(PSS) membrane in the transport experiments carried out with the source solution consisting of either Ca(NO₃)₂ or an equimolar mixture of KNO₃ and Ca(NO₃)₂. The PPy(PSS) composite membrane was impermeable towards NO₃⁻ ions when the source solution was Ca(NO₃)₂ but permeability towards NO₃⁻ was observed when the source solution was either KNO₃ or an equimolar mixture of KNO₃ and Ca(NO₃)₂.     

Influence of anion and pH on the electrochemical behaviour of polypyrrole synthesised in alkaline media

The electrochemical behaviour of conducting polypyrrole films electrosynthesised on vitreous carbon electrodes in alkaline solutions has been investigated by means of cyclic voltammetry and open circuit potentiometric measurements. The shape and evolution of the voltammograms during cycling depend strongly on the kind of anion and solution pH used. From these results, anion and cation participation in the redox process of the polymer has been analysed. The transport of anions like NO₃⁻ or Cl⁻ is dominant, while the transport of OH⁻ is the most important contribution when the polymer is cycled in the presence of anions that cannot be incorporated into the polymer matrix. The incorporation of Na⁺ also takes place and its contribution is more significant as deposition charge increases. The characteristics of the films are compared with those obtained in acid media. The polymerisation efficiency is similar in both cases. Films electrodeposited in alkaline solution can be doped and undoped in acid solution without loosing its redox behaviour.     

Glassy carbon electrode modified with a bilayer of multi-walled carbon nanotube and polypyrrole doped with new coccine: Application to the sensitive electrochemical determination of Sumatriptan

A promising electrochemical sensor was developed based on a layer by layer process by electro-polymerization of pyrrole in the presence of new coccine (NC) as dopant anion on the surface of the multi-walled carbon nanotubes (MWCNTs) pre-coated glassy carbon electrode (GCE). The modified electrode was used as a new and sensitive electrochemical sensor for voltammetric determination of sumatriptan (SUM). The electrochemical behavior of SUM was investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results showed a remarkable increase (∼12 times) in the anodic peak current of SUM in comparison to the bare GCE. The effect of experimental variables such as, drop size of the casted MWCNTs suspension, pH of the supporting electrolyte, accumulation conditions and the number of cycles in the electro-polymerization process on the electrode response was investigated. Under the optimum conditions, the modified electrode showed a wide linear dynamic range of 0.02–10.0 μmol L⁻¹ with a detection limit of 6 nmol L⁻¹ for the voltammetric determination of SUM. The prepared electrode showed high sensitivity, stability and good reproducibility in response to SUM. This sensor was successfully applied for the accurate determination of trace amounts of SUM in pharmaceutical and clinical preparations.     

Polypyrrole films functionalized with pendant titanocene dichloride complexes: Ellipsometric study of the electropolymerization process

Electrochemical and ellipsometric methods have been used to study the electropolymerization process of a functionalized monomer, Tc3Py (in which pyrrole is covalently bonded with titanocene dichloride complex) on platinum electrode from a dilute monomer solution in acetonitrile. The deposition has been performed in the potentiodynamic regime. A new method for the acquisition and treatment of ellipsometric data has been proposed which allowed us to analyze the evolution of the film properties at each potential. The model of a single uniform layer was unable to describe the ellipsometric experimental observations with the necessary precision. A proper fitting of the data has been achieved considering a model of two layers having identical values of the refractive index but different values of the extinction coefficient (higher absorption for the outer layer). The analysis of the calculated values of the optical parameters of these layers has led to the assumption that both layers represent morphologically the same medium (i.e. that the whole polymer film is uniform) while the higher extinction coefficient of the external layer was due to a penetration into it of solute oligomers possessing an intensive absorption at the wavelength of the observation, 633 nm. The dependences of the thicknesses of each layer and of the whole film on the cycle number have been established, the increment of the growth (5.5 nm per cycle) being constant within the whole deposition procedure. The variation of the optical constants of the layers during the potential cycling was determined and interpreted. The calculated values for the extinction coefficients and the layer thicknesses have been used to estimate how the film absorbance changes during the potential cycling. Its comparison with the same characteristic measured directly in a spectroelectrochemical cell for a film deposited at the ITO electrode surface has provided an extra evidence in favor of the above hypothesis on the film being a morphologically uniform material, with incorporated solute oligomers in its outer layer.     

ac-Electrogravimetry study of ionic and solvent motion in polypyrrole films doped with an heteropolyanion, SiMo12O40

One way to immobilize heteropolyanions on an electrode is to entrap them into a film of conducting polymer. In the present work, a polypyrrole film doped with a Keggin-type heteropolyanion, SiMo₁₂O₄₀⁴⁻, obtained by electrochemical way was studied.We focus on the charge compensation process, which occurs when the heteropolyanions entrapped into the polymer are reduced or re-oxidized. First, electrochemical quartz crystal microbalance analyses were performed, then, to determine if solvent motion takes place, ac-electrogravimetry measurements were carried out. In fact, in concentrated acidic solution, only protons are involved in the charge compensation. In low acidic solution (pH 3) having a high potassium concentration (0.5 M) both proton and potassium ions are involved whereas at pH 5.2 only potassium motion takes place. These findings are in good agreement with the acido-basic properties of SiMo₁₂O₄₀⁶⁻. In all cases, no solvent motion was pointed out.     

Effects of anion and cation doping on the thermoelectric properties of n-type PbS

The PbCl_xS_1-x and Pb_1-xBi_xS (x? =?0–0.05) bulks were fabricated with a facile method of hydrothermal synthesis and microwave sintering, and the effect of anionic and cationic donors on the thermoelectric performance of PbS was investigated. Although Cl^? and Bi³⁺ both effectively improved the thermoelectric properties of n-type PbS, more excellent thermoelectric performance was obtained from Cl^? doped samples because of higher electrical property and lower thermal conductivity at higher temperature (T? >?600?K). The thermoelectric figure of merit (ZT) reaches 1.04 for PbCl_0.015S_0.985 at 800?K and increases with temperature increasing without sign of saturation, which is probably the highest value ever reported for single-phase polycrystalline n-type PbS. The results also indicate that the hydrothermal synthesis and microwave sintering can realize anion doping as well as cation doping for n-type PbS at low cost, and PbS should be a robust alternative for PbTe thermoelectric materials.     

Investigation of the Thermal Behavior of Polypyrrole/Carbon Nanotube Composites and Utilization as Capacitive Material or Support for Catalysts

In this study, polypyrrole (PPy)/carbon nanotube (CNT) composites were synthesized by in situ chemical oxidative polymerization of a pyrrole monomer on CNT. Two different types of CNT having different structural properties were used. The composites were characterized using BET surface area analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA) techniques. Thermal decomposition kinetics of PPy/CNT composites was studied by thermal gravimetric analysis techniques (TG/DTG (differential thermal gravimetric)) at different heating rates (2.5, 5, 7.5, and 10?K min^?1). Kinetic parameters of the composites were obtained from the TG and DTG curves using the Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) models. The electrochemical capacitive properties of the composites were investigated by the cyclic voltammetry (CV) technique. Pt nanoparticles were decorated on the plain CNTs and composite materials via the microwave irradiation method.     

掺杂离子及掺杂工艺对钛酸钡性能的影响

钛酸钡基陶瓷是一种新兴的多功能电子陶瓷材料，由于其优异的电学性能而在很多领域有着广泛的应用，掺杂离子以及掺杂工艺对钛酸钡的性能有显著的影响。对常用的几种掺杂离子，如钙、镁、铅、锶、锆、锡和稀土元素，以及各种掺杂工艺对钛酸钡性能的影响进行了简单评述，并预测了未来的研究方向。     

trans-5-Palladatricyclo[4.1.0.02,4]heptanes: Complexes with monodentate,weakly coordinating ligands,formation of new derivatives and synthetic limitations

The bis(acetone) complex of tetramethyl rac-3,3,7,7-tetramethyl-trans-5-palladatricyclo[4.1.0.0^2,4]heptane-1,2,4,6-tetracarboxylate rac- 1a was crystallized and investigated by X-ray structure analysis. Unlike in complexes with bidendate ligands in rac- 1a · 2(acetone), only a small deviation from the square planar coordination of palladium was observed. Efforts to crystallize the analogous pyridine, acetonitrile and benzonitrile complexes failed; but the labile complexes rac- 1a · 2([D₅]pyridine) and rac- 1a · 2([D₃] acetonitrile) as well as rac- 1a · 2([D₆]acetone) could be characterized by ¹H and ¹³C NMR spectra and a fast ligand exchange was proven by nmr. Then the ability of different 1,2-disubstituted cyclopropenes to form trans-5-pallada-tricyclo[4.1.0.0^2,4] heptanes 1 was investigated. Only the diesters 5c–e lead to PTHs, with a diester possessing sterically demanding substituents in 3-position of the cyclopropene and with other substituents in 1- respectively 2-position of the cyclopropene either the cyclopropene-formation or the PTH-formation failed.     

Structural changes of cerium doped copper ferrites during sintering process and magneto-electrical properties assessment

Crystalline CuCe_xFe_2-xO₄ nanoparticles with different rare earth metal content (x = 0.00, 0.03, 0.05, 0.08 and 0.10) were synthesized using a co-precipitation technique that involves a 600 °C calcination treatment. The newly obtained powders were pressed into pellets and heated up to 950 °C in order to form a compact and less porous material, ideal for dielectric measurements. X-ray investigations revealed a structural modification from typical cubic system to a tetrahedral spinel form, accompanied by Ce³⁺ cations exclusion and formation of secondary phases. The amount of phases and cations distribution were determined by Rietveld refinement method. A degradation process of cerium doped copper ferrite was proposed based on X-ray analysis and Rietveld refinement. Furthermore, the magnetic behavior of both 600 °C and 950 °C samples was investigated from the hysteresis loops recorded from a vibrating sample magnetometer (VSM) in a ±10 kOe range. Room temperature dielectric values for the 950 °C samples were determined using the parallel-plate capacitor configuration in a frequency range of 10 Hz – 1 MHz.     

Electrochemical preparation and properties of polypyrrole and its blend with poly(vinyl sulfonate) doped with perchlorate anions

In this article, we report polypyrrole (PPy)/poly(vinyl sulfonate) (PVS) and PPy/perchlorate (ClO) composite films generated by the electrochemical oxidation of pyrrole on a glassy carbon electrode (GCE) in an aqueous solution. The response of the produced films to an applied potential at 0.7 V was obtained by a cyclic voltammetry study in acetonitrile media. The films were significantly similar in their electrochemical behavior when ClO ions doped during the redox process. We concluded that with an increasing number of cycles, the anodic current increased because the number of the electroactive participants transported in the copolymer matrix was increased. Theoretical studies based on the Nernst and Butler–Volmer equations indicated that the ClO ion was transported during the oxidation/reduction process of the PPY/PVS and PPY/ClO films. The produced films were characterized further by means of IR spectroscopy, electrochemical impedance spectroscopy, and scanning electron microscopy to verify that the anion of ClO was doped into the copolymer matrix as well. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010