Competition between dopants on redox reaction of polypyrrole

The surface of PPy prepared in a multiple electrolyte solution such as NaDS-NaClO₄ in H₂O shows a coarser structure than that of the polymer prepared in a single electrolyte system. DS⁻ with a large aliphatic chain is used as a dopant in preparation of PPy. The dopant is trapped in PPy when the polymer is reduced in an aqueous system. A cation Na⁺ or K⁺ is inserted into the polymer to balance the free DS⁻ liberated form and remained in it on reduction. PPy doped with DS⁻ shows a high degree of redox reactivity in the system of TBADS-AN but a poor stability in repeated redox process. The degree and rate of redox reactivity enhance when an aqueous solution of NaClO₄ is used as an electrolyte system. Both Na⁺ and ClO₄⁻take part in the redox reaction and the reduction process is intense at only one current potential.     

A Self‐Binding,Melt‐Castable,Crystalline Organic Electrolyte for Sodium Ion Conduction

The preparation and characterization of the cocrystalline solid–organic sodium ion electrolyte NaClO₄(DMF)₃ (DMF=dimethylformamide) is described. The crystal structure of NaClO₄(DMF)₃ reveals parallel channels of Na⁺ and ClO₄⁻ ions. Pressed pellets of microcrystalline NaClO₄(DMF)₃ exhibit a conductivity of 3×10⁻⁴ S cm⁻¹ at room temperature with a low activation barrier to conduction of 25 kJ mol⁻¹. SEM revealed thin liquid interfacial contacts between crystalline grains, which promote conductivity. The material melts gradually between 55–65 °C, but does not decompose, and upon cooling, it resolidifies as solid NaClO₄(DMF)₃, permitting melt casting of the electrolyte into thin films and the fabrication of cells in the liquid state and ensuring penetration of the electrolyte between the electrode active particles.     

Metallic and non-metallic redox response of conducting polymers

The potentiometric response of electrodes coated with polypyrrole or poly(N-methylpyrrole) films with different doping anions was studied in solutions containing the redox couples: Fe(CN)₆^3−/4−, Ru(NH₃)₆^3+/2+ and Fe(Ill)/Fe(II). The stable potential measured with the electrodes was the potential of the redox couple. The response time was instant for polypyrrole doped with dodecylsulphate ions, PPy(DS) and slow for the polymers doped with mobile anions. On the basis of electrochemical measurements and chemical analysis by EDAX spectroscopy it was found that with the PPy(DS) electrode the potentiometric response was of the ‘metallic’ type, with no change in the oxidation state of the bulk polymer. With the other polymer systems studied reduction or oxidation of the polymer bulk took place when it was in contact with a redox couple in the solution.     

Die kinetische polarographische Stufe des Urans in Gegenwart von Chlorat-Ionen

An increase of the 2nd polarographic uranium(VI) wave has been observed in the presence of chlorate ions in HClO₄–NaClO₄, or HClO₄–NaClO₄–NaCl supporting electrolyte, resp. The polarographic measurements at different temperatures and at various perchloric acid concentrations show that this increase is due to a kinetic U(III)-U(IV) current. The activation parameters of the U(III)-U(IV) oxidation reaction with ClO₃ ^– have been calculated usingKautecky's method.The approximately 5fold increase of the 2nd polarographic wave allows the determination of small amounts of uranium (10^–5–10^–6 mole/l).

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A Self‐Binding,Melt‐Castable,Crystalline Organic Electrolyte for Sodium Ion Conduction

The preparation and characterization of the cocrystalline solid–organic sodium ion electrolyte NaClO₄(DMF)₃ (DMF=dimethylformamide) is described. The crystal structure of NaClO₄(DMF)₃ reveals parallel channels of Na⁺ and ClO₄^? ions. Pressed pellets of microcrystalline NaClO₄(DMF)₃ exhibit a conductivity of 3×10^?4 S cm^?1 at room temperature with a low activation barrier to conduction of 25 kJ mol^?1. SEM revealed thin liquid interfacial contacts between crystalline grains, which promote conductivity. The material melts gradually between 55–65 °C, but does not decompose, and upon cooling, it resolidifies as solid NaClO₄(DMF)₃, permitting melt casting of the electrolyte into thin films and the fabrication of cells in the liquid state and ensuring penetration of the electrolyte between the electrode active particles.     

NH_4~+对甲酸在炭载Pd催化剂上氧化性能的影响

为了解HClO4、NH4ClO4和NaClO4电解液对炭载Pd(Pd/C)催化剂电极对甲酸氧化的电催化性能的影响,在用X射线衍射(XRD)谱、能量色散谱(EDS)和透射电子显微镜(TEM)对Pd/C催化剂进行表征的基础上,采用电化学方法测量了Pd/C催化剂在不同电解液中对甲酸氧化的电催化性能.发现在不同电解液中,Pd/C催化剂对甲酸氧化的电催化活性和稳定性按NH4ClO4NaClO4HClO4的次序降低.由于甲酸的存在,不同电解液的pH相差较小,因此,电解液的pH影响较小,而阳离子的影响较大.在NaClO4电解液中的性能优于在HClO4电解液中的性能是pH的影响.在NH4ClO4电解液中的性能优于在NaClO4电解液中是由于NH4+能降低CO在Pd/C催化剂电极上的吸附强度和吸附量,这一发现对提高直接甲酸燃料电池(DFAFC)的性能很有意义.     

Role and effect of dopant ion on sorption-induced motion of polypyrrole films

The sorption-induced bending and recovery motion of PPy films containing different dopant ions have been investigated, and the interaction between water vapor and PPy was studied from sorption isotherms and kinetics. It was found that the PPy/BF₄ film exhibited the most rapid motion, and the initial speeds of bending and recovery motion were 7.9 and 5.9 mm s⁻¹, respectively. The linear expansion coefficient of the film increased in order of PPy/DBS, PPy/TsO, PPy/ClO₄, and PPy/BF₄, which is consistent with the packing density of the PPy chains (ϕ_PPy). The dual-mode sorption model applied to the isothermal sorption of water vapor to the PPy demonstrated that the Langmuir's capacity constant increased in the same order with the ϕ_PPy, while the Henry's law constant was nearly constant. The sorption kinetics obeyed Fickian despite the dimensional change of the films, and the PPy/BF₄ film had the largest diffusion coefficient of 3.13 × 10⁻⁸ cm² s⁻¹. The experimental results indicated that the kind of dopant ion was crucial to the thermodynamics and kinetics of sorption, and the quick and intensive bending motion of PPy/BF₄ films was attributed to the fast diffusion of water vapor, which caused the large dimensional change of the film.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2635–2642, 1998     

Influence of Anions on Electrochemical Properties of Polypyrrole-Modified Electrodes

The influence of anions ClO₄ ^–, NO₃ ^–, Cl^–, SO₄ ^2–, and DDS^– (dodecyl sulfate) on the cyclic voltammetric response of polypyrrole-modified electrodes is studied. The change in the film composition is examined by electron probe microanalysis. It is established that essential changes in the shape of voltammograms take place during cycling if the anions are not sufficiently freely mobile in the polymer film and insertion of cations from the solution is necessary to guarantee electroneutrality of the system. Some differences between the mobility of Cl^– ions and ClO₄ ^– or NO₃ ^– ions are in good agreement with the results of semi-empirical quantum chemical calculations showing that the interaction of Cl^– and Br^– ions with pyrrole oligomers is stronger than that of NO₃ ^– or ClO₄ ^– ions. Nevertheless, it is established that the peak current determined from voltammograms increases linearly with the increase of the scan rate with very high correlation coefficient. It means that it is possible to describe the behavior of ClO₄ ^–, NO₃ ^– and Cl^– ions in the framework of the model of free ions. The redox behavior of the PPy films doped with anions of low mobility such as SO₄ ^2– and DDS^– depends essentially on the nature of cations in the test solution. It is found that the mobility of cations increases in the row Li⁺ < Na⁺ < K⁺ < Cs⁺. The mobility of DDS^– ions in the PPy in ethanolic solution is significantly higher and their electrochemical properties are quite similar to PPy|Cl or NO₃ ^– film in aqueous solution.     

Facile cation electro-insertion into layer-by-layer assembled iron phytate films

Molecular layer-by-layer assembly from pre-saturated aqueous solutions of Fe³⁺ and phytate is employed to build up iron phytate deposits on tin-doped indium oxide (ITO) electrodes. Globular films with approximately 1 nm growth per layer are observed by AFM imaging and sectioning. In electrochemical experiments the iron phytate films show well-defined voltammetric responses consistent with an immobilised Fe(III/II) redox system in aqueous (LiClO₄, NaClO₄, KClO₄, phosphate buffer) and in ethanolic (LiClO₄, NaClO₄, NBu₄ClO₄) electrolyte solutions. The Fe(III/II) redox system is reversible and cation insertion/expulsion occurs fast on the timescale of voltammetric experiments even for more bulky NBu₄⁺ cations and in ethanolic solution. Peak shape analysis and scan rate dependent midpoint potentials suggest structural changes accompanying the redox process and limiting propagation. Iron phytate is proposed as a versatile and essentially colourless cation electro-insertion material and as a potential energy storage material.     

Cylic Voltammetric Studies on the Electrode Reaction of Polyacetylene Secondary Cell

Cells of lithium / Polyacetylene containing 0.5 · 1.5 M LiClO₄ in propylene carbonate as supporting electrolyte are constructed. The mechanism for electrochemical redox process of polyacetylene is studied using cyclic voltammetry in the potential range from ?0.8 to 0.2 volt vs. S.C.E. The electrode reactions are identified to be diffusion controlled. The difference of the peak potentials between the oxidation and reduction, ΔEp, is found to be a function of the scan time per cycle (τ sec/cycle) and is influenced by concentration of supporting electrolyte and isomeric structures of polyacetylene. However, there is a better reversible redox process of polyacetylene when the ClO₄^? - ions diffuse successfully in and out of the Polymer film, which has the cis-form structure, in concentrated supporting electrolyte solution and having a long scan time per cycle (τ). When the scan potential is extended to a more positive region, another peak is found, which may correspond to the irreversible chemical reaction caused by over-doping. The over-doping process is found to be controlled by the electrical field strength, concentration of the supporting electrolyte and isomerism of polyacetylene.     

Semi-micro ion chromatography of iodide in seawater

Large sample volume injections including both on-column analyte focusing and on-column matrix elimination techniques were examined for semi-micro ion chromatography of trace iodide (I⁻) in seawater. A semi-microcolumn (35×1 mm I.D.) packed with styrene–divinylbenzene copolymer with high anion-exchange capacity and a mobile phase of 0.03 M NaClO₄+0.5 M NaCl+5 mM sodium phosphate buffer, pH 6.0, was used. Iodide in seawater was effectively concentrated on the column by both electrostatic and hydrophobic interactions and was eluted without peak broadening. ClO₄⁻ (NaClO₄) in the mobile phase was effective for the elution of iodide and Cl⁻ (NaCl) for both the concentration of iodide (I⁻) with hydrophobicity and the removal of interference by the major anions. An excess of major anions in seawater did not disturb the detection of iodide at UV 226 nm. The relative standard deviations for successive injections of 5 and 1 μg/l I⁻ (2 ml of 35‰ artificial seawater) were 1.5 and 5.8% (n=5, each), respectively. The slope of calibration curve (by peak area) using the semi-microcolumn was ∼2.8-times higher than that for a conventional column with the same resin (150×4.6 mm I.D.) The present method had a detection limit of 0.2 μg/l I⁻ for 2 ml of 35‰ artificial seawater and was successfully applied to seawater samples.     

Polypyrrole Bilayers: Charge Trapping and Application for Amperometric Ions Sensing

Bilayers composed of polypyrrole: doped by perchlorate ions (PPy(ClO₄) – anion exchanging inner layer) and by dodecyl sulfate ions (PPy(DS) – cation exchanging outer layer) are very effective charge trapping systems that are usually not observed for other bilayers comprised of polypyrrole. Chronopotentiometric experiments carried out for oxidation and reduction showed that the trapping effect in the inner layer resulted from different ion exchange properties of the component polymers, leading to a low permeability of the reduced outer layer towards anions. Estimated diffusion coefficients of Cl^? anions in the oxidized and reduced PPy(DS) are in the range of 10^?9 and lower than 10^?10 cm² s^?1, respectively. The presence of the outer layer limiting the ion transfer was found to be beneficial to improve the signal resolution in amperometric mode of ion sensing within wide KCl concentration range, from 10^?5 M up to 3 M. The influence of experimental conditions (film thickness, response time) on optimization of this novel kind of polymeric bilayer ion sensors was studied.     

Electrochemistry and electrochromic properties of phenanthroline-iron(II/III) complex films

New films of the iron complexes with bis((2-hydroxyphenyl)methylaminosulfonyl)bathophenanthroline(HPBP) and bis((2-aminophenyl)methylaminosulfonyl)bathophenanthroline(APBP) ligands are prepared on the electrode surfaces by electrochemical polymerization. The resulting film-coated electrode shows a well-defined reversible voltammogram corresponding to the redox reaction of the Fe(II/III) complexes and an electrochromic change from red(absorption maximum: 540 nm) to colorless. The response rate of the color change to a potential step was found to be correlated to the apparent diffusion coefficient(Dapp) for the homogeneous charge-transport process within the film. The Dapp values estimated are (3-4) × 10⁻⁹cm²s⁻¹ for the [Fe(APBP)₃] film and(1-2) × 10⁻⁸cm²s⁻² for the [Fe(HPBP)₃] film, respectively, by potential-step chronoamperometric and chronocoulometric methods. The result of electrochemical quartz crystal microbalance(EQCM) measurements⁴) and dependence of the formal potential of the metal complex of the Fe(II/III) redox couple with activity of the supporting electrolyte anion in NaClO₄ aqueous solution showed that anion, cation, and solvent move simultaneously across the polymer film/solution interface during the redox reaction. A piezoelectric admittance measurement⁴⁾ of the poly[Fe(APBP)₃] coated quartz crystal electrode showed that the viscosity of the film is affected by the oxidation state of iron.     

Counter-Ion Influence on Polypyrrole Potentiometric pH Sensitivity

The pH sensitivity of conducting polymer films is an important issue from the sensor design point of view. The doping and supporting electrolyte anions effect on the potentiometric sensitivity and response time of polypyrrole (PPy) electrodes towards changes of solution pH were studied. It was found that (i) the response of PPy doped by easily exchangeable common anions (Cl^–, NO₃ ^–, ClO₄ ^–) in their solutions (KCl, KNO₃, NaClO₄) is slow. In contrast, (ii) polypyrrole films deposited in the presence of weak acid anions (phthalates, oxalates, salicylates) were characterised by instantaneous responses in the above mentioned solutions. On the basis of electrochemical experiments (open circuit potential vs. time dependencies, cyclic voltammetry, EQCM), the observed differences were attributed to different mechanisms of pH sensitivity of tested films. The long response times are related to the incorporation of the solution ions into the film in order to compensate charges created due to protonation. On the other hand, if the ion-exchange is hindered as in the case of (ii), instantaneous open circuit responses are observed due to polarisation of the oxidised polymer layer, analogously to the metal electrode. Moreover, for these films the internal pH buffering within the polymer membrane will weaken the pH change effect.The mechanisms were confirmed in the course of studying the pH effect in solutions containing anions easily (KCl, NaClO₄, KNO₃) or hardly exchangeable with polypyrrole (K₂SO₄, sodium poly(4-styrenesulphonate) solutions) acidified with H₂SO₄.     

Reconstruction of Solid Electrolyte Interphase with SrI2 Reactivates Dead Li for Durable Anode-Free Li-Metal Batteries

Without excess Li, anode-free Li-metal batteries (AFLMBs) have been proposed as the most likely solution to realizing highly-safe and cost-effective Li-metal batteries. Nevertheless, short cyclic life puzzles conventional AFLMBs due to anodic dead Li accumulation with a local current concentration induced by irreversible electrolyte depletion, insufficient active Li reservoir and slow Li⁺ transfer at the solid electrolyte interphase (SEI). Herein, SrI₂ is introduced into carbon paper (CP) current collector to effectively suppress dead Li through synergistic mechanisms including reversible I⁻/I₃⁻ redox reaction to reactivate dead Li, dielectric SEI surface with SrF₂ and LiF to prevent electrolyte decomposition and highly ionic conductive (3.488 mS cm⁻¹) inner layer of SEI with abundant LiI to enable efficient Li⁺ transfer inside. With the SrI₂-modified current collector, the NCM532/CP cell delivers unprecedented cyclic performances with a capacity of 129.2 mAh g⁻¹ after 200 cycles.     

Proton-Reservoir Hydrogel Electrolyte for Long-Term Cycling Zn/PANI Batteries in Wide Temperature Range

Advanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO₄)₂ was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at −35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm⁻², and the Zn/PANI battery can provide ultra-high stable specific capacity of 79.6 mAh g⁻¹ for more than 70 000 cycles at 15 A g⁻¹. This can be mainly ascribed to the −SO₃⁻H⁺ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton-supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.     

Gas phase reactions of Cl2O with X−(D2O)n=0–4 (X = O,OD, O2, DO2, and O3)

The reactions of Cl₂O with the cluster ions X⁻(D₂O)_n=0–4 (X = O, OD, O₂, DO₂, and O₃) were studied in a He buffer gas at temperatures within the range 171–298 K and pressures of 0.27–0.51 Torr, using a flow-tube apparatus. All ions were found to react with Cl₂O at rates slower than predicted by the collision rate and the charge center was transferred from X⁻ to Cl⁻ or ClO⁻. The primary product ions Cl⁻(DOCl) and ClO⁻(DOCl) were observed to react further to produce the ions Cl₃O⁻ and Cl₃O₂⁻. The rate constants for the observed reactions are reported and the role that thermodynamics plays in determining possible reaction channels is discussed.     

Electrochemical Examination of Copper(II) Complexes with Octaazamacrocyclic Ligand and Heterocyclic Dithiocarbamate

Mixed ligand dinuclear copper(II) complexes of the general formula [Cu₂(Rdtc)tpmc)](ClO₄)₃ with octaazamacrocyclic ligand tpmc and four different heterocyclic dithiocarbamate ligands Rdtc^?, as well as the complexes [Cu₂(tpmc)](ClO₄)₄ and [Cu(tpmc)](ClO₄)₂?2H₂O were studied in aqueous NaClO₄ and HClO₄ solutions by cyclic voltammetry on glassy carbon electrode. The electrochemical properties of the ligands and Cu(II) complexes were correlated with their electronic structure. Conductometric experiments showed different stoichiometry in complexation of tpmc with Cu²⁺ ions and transport of ions in acetonitrile and in aqueous media. These studies clarified the application of this macrocyclic ligand as ionophore in a PVC membrane copper(II) selective electrode and contributed elucidation of its sensor properties.     

Raman intensities of liquids: absolute scattering activities and ClO bond EOPs of ClO−, ClO−2, ClO−3 and ClO−4 ions in aqueous solution

Absolute Raman scattering activities of aqueous solutions of the following ions have been measured: ClO⁻, ClO⁻₂, ClO⁻₃, ClO⁻₄. Electro-optical parameters (EOPs) for the ClO bonds in these compounds were calculated. Equilibrium bond polarizabilities and their derivatives with respect to bond length can be correlated with the number of valence electrons in non-bonding and antibonding orbitals. High equilibrium bond polarizability goes with small polarizability derivatives, and vice versa, for the compounds studied here.     

Study of the bromide oxidation by bromate in zwitterionic micellar solutions

The redox reaction Br⁻ + BrO₃⁻ has been studied in aqueous zwitterionic micellar solutions of N‐tetradecyl‐N, N‐dimethyl‐3‐ammonio‐1‐propanesulfonate, SB3‐14, and N‐hexadecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propanesulfonate, SB3‐16. A simple expression for the observed rate constant, k_obs, based on the pseudophase model, could explain the influences of changes in the surfactant concentration on k_obs. The kinetic effect of added NaClO₄ on the reaction rate in SB3‐14 micellar solutions has also been studied. They were rationalized by considering the binding of the perchlorate anions to the sulfobetaine micelles and their competition with the reactive bromide ions for the micellar surface. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 388–394, 2000