Amperometric detection studies of Nafion/indium hexacyanoferrate film for the determination of electroinactive cations in ion chromatography

An amperometric detector based on the chemical modification of Nafion and indium (III) hexacyanoferrate (II, III) thin film (Nafion/In-CN-Fe) onto a glassy carbon (GC) electrode, was first successfully used for the determination of electroinactive cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺) in single column ion chromatography (IC). A set of well-defined peaks of electroinactive cations was obtained. The detection limits of the cations are 8.9 × 10^–6 mol/L for Li⁺, 2.3 × 10^–6 mol/L for Na⁺, 5.2 × 10^–6 mol/L for K⁺, 4.8 × 10^–6 mol/L for Rb⁺, 4.0 ׶10^–6 mol/L for Cs⁺ and 5.3 × 10^–6 mol/L for NH₄ ⁺ at a single-to-noise ratio of 3. The proposed method was quick, sensitive and simple. The cations in rainwater and mineral water were successfully analyzed by this method.     

A novel photoelectrochemical hydrogen peroxide sensor based on nickel(II)-potassium hexacyanoferrate-graphene hybrid materials modified n-silicon electrode

A platinum (Pt) film coated n-silicon (Pt/n-n⁺-Si) was modified with nickel(II)-potassium hexacyanoferrate (NiHCF)-graphene sheets (GS) hybrid and used as a photo-electrochemical (PEC) sensor for non-enzyme hydrogen peroxide (H₂O₂) detection. A NiHCF film was deposited on the surface of GS/Pt/n-n⁺-Si electrode by chemical method. The structure and composition of the NiHCF film was characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). PEC behavior of the NiHCF-GS/Pt/n-n⁺-Si electrode was investigated using cyclic voltammetry (CV) under illumination. The modified electrode has been used as PEC sensor for H₂O₂ detection with a linear range of 2.0 × 10^?6–2.9 × 10^?3 M and a detection limit of 1.0 × 10^?6 M at a signal-to-noise ratio of 3 in a two-electrode cell with a Pt plate as counter electrode. The characteristics of GS layer have been discussed in both the improvement of sensibility and selectivity.     

Development of a new all solid contact Cs<Superscript>+</Superscript> ion selective electrode

Studies were carried out to develop all solid contact cesium ion selective electrode with 25,27-bis(1-octyloxy)calix[4]arene-crown-6 as an ionophore. Polyaniline (PANI), deposited on Pt electrode by electrochemical method, was used as a transducer. Three different types of electrodes were made with variation in thickness of PANI film and gold nanoparticles doped PANI as transducers. The best response was observed with ISE having Au nanoparticles doped PANI as a transducer. The optimised ISE gave Nernstian response in the range 10^?7 to 10^?2 M with the slope of 55.0 ± 0.6 mV/decade of Cs⁺. The response of ISE for Cs⁺ is fairly constant above the pH 4. The developed ISE was successfully employed to determine Cs⁺ in simulated high level nuclear waste solutions and CsCl spiked tap water samples.     

Polymeric membrane coated graphite cesium selective electrode based on 4′,4″(5′) di–tert-butyl di-benzo-18-crown-6

A new PVC membrane coated graphite electrode for cesium ion based on 4′,4″(5′)di–tert-butyl di-benzo-18-crown-6 (DTBDB18C6) as ionophore was prepared. The electrode shows a near Nernstian response of 57.0 ± 1.8 mV decade^?1 over a wide activity range of 6.0 × 10^?6–1.0 × 10^?1 mol L^?1 with a limit of detection 4.0 × 10^?6 mol L^?1. The proposed electrode is suitable for use in aqueous solution in the pH range of 3.0–9.5. It has a fast response time of 10 s and can be used for at least 1 month without any considerable divergence in potential. The selectivity coefficients for Cs⁺ ion with respect to ammonium, alkali, alkaline earth and some selected transition metal ions were determined and showed a superior selectivity over Li⁺, Na⁺ and alkaline earth metal ions. The new electrode was applied for determination of Cs⁺ in spiked tap water. The electrode was also used as indicator electrode in potentiometric titration of Cs⁺ with sodium tetraphenyl borate.     

Application of Nafion／Cobalt Hexacyanoferrate Chemically Modified Electrodes for the Determination of Electroinactive Cations by Ion Chromatography

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｉｏｎｃｈｒｏｍａｔｏｇｒａｐｈｙ (ＩＣ)ｈａｓｂｅｅｎｒｅｃｏｇｎｉｚｅｄａｓａｕｓｅｆｕｌｍｅｔｈｏｄｆｏｒｔｈｅｓｅｐａｒａｔｉｏｎｏｆｉｎｏｒｇａｎｉｃａｎｉｏｎｓａｎｄｃａｔｉｏｎｓｓｉｎｃｅｉｔｓｉｎｔｒｏｄｕｃｔｉｏｎｂｙＳｍａｌｌｅｔａｌ .ｉｎ 1975 .1ＡｓｉｇｎｉｆｉｃａｎｔｔｒｅｎｄｉｎｔｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆＩＣｍｅｔｈｏｄｉｓｓｅａｒｃｈｆｏｒｓｅｎｓｉｔｉｖｅａｎｄｕｎｉｖｅｒｓａｌｄｅｔｅｃｔｉｏｎｍｅｔｈｏｄｓ .Ｔｈｅｍａｉｎｄｅｔ…     

Preparation of Thallium Hexacyanoferrate Film and Mixed‐Film Modified Electrodes with Cobalt(II) Hexacyanoferrate

Thallium hexacyanoferrate films have been prepared from various aqueous electrolyte solutions using consecutive cyclic voltammetry. The cyclic voltammograms recorded the direct deposition of thallium hexacyanoferrate films from the mixing of Tl³⁺ and [Fe(CN)₆]^3? ions from solutions of seven cations: Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, H⁺, and Tl⁺. An electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry were used to study the in situ growth of the thallium hexacyanoferrate films. The thallium hexacyanoferrate film shows a single redox couple with a formal potential between +0.6 V and +1.2 V, and shows a cation effect (H⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, and Tl⁺). A mixed film and a two‐layered modified electrodes composed of a thallium hexacyanoferrate film with cobalt(II) hexacyanoferrate film were prepared.     

Synthesis and electrochemical properties of a novel calix[4]arene derivative for facilitated transfer of alkali metal ions across water/1,2-dichloroethane micro-interface

The alkali metal ion transfers facilitated by a novel calix[4]arene derivative (OPEC) across the water/1,2-dichloroethane (1,2-DCE) micro-interface supported at the tip of a micropipette were presented. The well-defined voltammetric behaviours except Cs⁺ was obtained by cyclic voltammetry and differential pulse voltammetry. The bulk concentration of metal ions was much higher than that of OPEC in the performed measurements. The diffusion coefficient of OPEC in the 1,2-DCE phase was calculated as 5.18 ± 0.70 × 10^? 6 cm² s^? 1. On the basis of the changes of the half-wave transfer potentials, the logarithms of the association constants having 1:1 ionophore–ion complex stoichiometry for Li⁺, Na⁺, K⁺ and Rb⁺ in 1,2-DCE were determined as 4.80, 4.62, 4.98 and 5.32, respectively. The facilitated ion transfers were also evaluated by the Randles equivalent circuit used for ac-impedance data analysis.     

Tungsten oxide bronzes with alkali metals

Single-phase samples of tungsten bronzes M _x WO₃ (M = K⁺, Rb⁺, Cs⁺) are prepared by solid-state synthesis. The reversibility of the M_0.33WO₃/M⁺-solid electrolyte interface is studied subject to the alkali metal nature and humidity over a wide temperature interval. The exchange current density at 24°C and 58%-relative humidity is 3.6 × 10^?4 A/cm² for the Rb_0.33WO₃/Rb⁺-solid electrolyte interface; 2.2 × 10^?4 A/cm² for the Cs_0.33WO₃/Cs⁺-solid electrolyte interface; and 1.3 × 10^?4 A/cm² for the K_0.33WO₃/K⁺-solid electrolyte interface. A correlation between the reversibility of the bronze|solid electrolyte interface, which is characterized by the exchange current density, and the rate of potential equilibration in sensor systems, where the bronze is a reference electrode, is revealed. Ionic component of the conductivity of the synthesized tungsten oxide bronzes is measured at a background of the predominant electronic conductivity. The ionic conductivity is three orders of magnitude lower than the electronic conductivity; it decreases in the series Rb_0.33WO₃ > Cs_0.33WO₃ > K_0.33WO₃, amounting to 2.3 × 10^?2, 2.1 × 10^?3, and 2 × 10^?4 S cm^?1, respectively. The working capacity of the M_0.3WO₃ bronzes as reference electrodes in sensor systems for carbon dioxide detection is evaluated. The plots of the cell potential vs. the CO₂ concentration in the electrochemical cells are linear, their slopes (59 ± 1 mV/decade) are characteristic for one-electron process. The fastest response to changes in the CO₂ concentration was obtained with the sensor system that used Rb_0.33WO₃ as reference electrode.     

Investigation of O7+ swift heavy ion irradiation on molybdenum doped indium oxide thin films

Molybdenum (0.5 at%) doped indium oxide thin films deposited by spray pyrolysis technique were irradiated by 100 MeV O⁷⁺ ions with different fluences of 5×10¹¹, 1×10¹² and 1×10¹³ ions/cm². Intensity of (222) peak of the pristine film was decreased with increase in the ion fluence. Films irradiated with the maximum ion fluence of 1×10¹³ ions/cm² showed a fraction of amorphous nature. The surface microstructures on the surface of the film showed that increase in ion fluence decreases the grain size. Mobility of the pristine molybdenum doped indium oxide films was decreased from ～122 to 48 cm²/V s with increasing ion fluence. Among the irradiated films the film irradiated with the ion fluence of 5×10¹¹ ions/cm² showed relatively low resistivity of 6.7×10^?4 Ω cm with the mobility of 75 cm²/V s. The average transmittance of the as-deposited IMO film is decreased from 89% to 81% due to irradiation with the fluence of 5×10¹¹ ions/cm².     

Electrochemical deposition and characterization of polyppyrrole coatings doped with nickel cobalt oxide for environmental applications

Electrochemical depositions of hybrid polypyrrole/nickel cobalt oxide (PPy/NiCoO) coatings onto ferritic stainless steel surface were carried out with different electrochemical techniques from 0.1 M pyrrole (Py) in 0.2-M oxalic acid (OA) solution and less than 150-nanometer-sized NiCoO particles. The structural properties of the composite were investigated by using different methods such as transmission electron microscopy (TEM), scanning electron microscopy (SEM) with energy-dispersive X-ray spectrometer (EDS) and Raman spectroscopy. The embedded NiCoO particles, uniformly distributed onto the surface of the PPy film, have similar oxide ratios corresponding to a mixed oxide structure. The electrochemical characterization was done using polarization curves and linear sweep voltammetry (LSV) related to oxygen reduction reaction (ORR) in alkaline solution and hydrogen peroxide as an oxygen source. Concerning the exchange current densities for ORR, the obtained values (between 1.06 and 1.45?×?10^?3 mA cm^?2 for a total amount of NiCoO of 0.1 mg cm^?2) are comparable with other polymer films with Pt.     

Evaluation of electrodes coated with metal hexacyanoferrate as amperometric sensors for nonelectroactive cations in flow systems

Two electrodes modified with either nickel or cupric hexacyanoferrate films were evaluated and compared as sensors for nonelectroactive cations in a flow-injection system. Both gave responses for group 1A and ammonium ions, but only the electrode modified with cupric hexacyanoferrate was sufficiently stable for use in flowing solutions. This electrode responded to K⁺, NH, Rb⁺, and Cs⁺ ions rather selectively. Within this group, the selectivity could be controlled from general to almost specific toward Cs⁺ by the potential at which the electrode was poised. The electrode was compatible with a mobile phase of dilute nitric acid commonly used in ion chromatography, and chromatographic detection limits of 2 × 10⁻⁷ M and linear responses over two decades were obtained. The electrode was applied to the ion chromatographic analysis of K⁺ and NH in urine and K⁺ in blood serum samples.     

Dielectric properties and surface morphology of swift heavy ion beam irradiated polycarbonate films

Swift heavy ion beam irradiation induces modification in the dielectric properties and surface morphologies of polycarbonate (PC) films. The PC films were irradiated by 55 MeV energy of C⁵⁺ beam at various ions fluences ranging from 1 × 10¹¹ to 1 × 10¹³ ions cm^?2. The dielectric properties (i.e., dielectric constant, dielectric loss, and AC conductivity) and surface morphologies of pristine and SHI beam irradiated PC films were investigated by dielectric measurements, atomic force microscopy (AFM), and optical microscopy. The dielectric measurements show that the dielectric constant, dielectric loss, and AC conductivity increase with ion fluences and temperature, however, the dielectric constant and AC conductivity decrease while dielectric loss increases with frequency. AFM shows the increase in average roughness values with ion fluences. The change of color in PC films has been observed from colorless to yellowish and then dark brown with increases of ion fluence by using optical microscopy.     

Three-body ion—ion recombination in mercury-halide lasers

The role of ion—ion recombination in the formation of excited states in mercury-halide lasers is outlined. A generalization of Natanson's treatment to unequal-mass constituents and general mean free paths is proposed. Rates as high as (2.6–1.5) × 10^?6 cm³ s^?1 are hence determined for the recombination of Hg⁺ with F^?, Cl^?, Br^? and I^? respectively, in Ar at (1.7–3.5) atm and 300 K. Somewhat higher rates (3.4?1.9) × 10^?6 cm³ s^?1 at slightly lower densities are obtained for the corresponding cases involving Ar⁺.     

Focused ion beam implantation of Ga in Si and Ge: fluence‐dependent retention and surface morphology

Focused ion beam implantation of 30‐keV Ga⁺ ions in single‐crystalline Si and Ge was investigated by SIMS, using Cs⁺ primary ions for sputtering. Nine different implantation fluences ranging from 1 × 10¹³ to 1 × 10¹⁷ Ga⁺‐ions/cm² were used, with implanted areas of 40 × 40 µm². The Ga concentration distributions of these implants were determined by SIMS depth profiling. Such 30‐keV Ga implantations were also simulated by a dynamic Monte‐Carlo code that takes into account the gradual change of the near‐surface composition due to the Ga incorporation. In both approaches, an essentially linear increase of the Ga peak concentrations with fluence is found up to ～1 × 10¹⁶cm^?2; for higher fluences, the Ga content approaches a saturation level which is reached at about (1–2) × 10¹⁷cm^?2. The measured and simulated peak concentrations of the Ga distributions are in good agreement. The most probable ranges obtained from the experiments correspond closely with the respective values from the simulations. The surface morphology caused by Ga⁺ implantation was investigated by atomic force microscopy (AFM). The AFM data indicate that for low fluences (<3 × 10¹⁵cm^?2) the surface within the implanted areas is growing outward (i.e. is swelling). For increasingly higher fluences, sputter‐induced erosion of the surface becomes dominant and distinct craters are formed for fluences above ～1 × 10¹⁶cm^?2. At the boundary of the implanted region a wall‐like structure is found to form upon Ga implantation; its height is growing with increasing fluence, reaching a value of ～15 nm at 1 × 10¹⁷ Ga⁺‐ions/cm². Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,metal ion complexation and first use of a thia-aza substituted macrocyclic diamide as a novel sensing material for preparation of selective and sensitive poly(vinyl chloride)-membrane potentiometric sensors for Ag+ ion

A novel thia-aza substituted macrocyclic diamide 7,10,13-triaza-1-thia-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione (L) was synthesized and stability of its complexes with several alkaline earth, transition and heavy metal ions were studied conductometrically in methanol solution. The resulting 1:1 Ag⁺–L complex found to be the most stable one among all cation complexes studied. The optimized structures of the ligand and its Ag⁺ complex were also investigated. Based on the preliminary results thus obtained, L was used as an excellent sensing material to prepare polymeric membrane (PME) and coated graphite (CGE) silver-selective electrodes. The electrodes revealed a Nernstian behavior over wide Ag⁺ ion concentration ranges (i.e., 2.0 × 10^?6–1.0 × 10^?2 M for PME and 5.0 × 10^?7–1.0 × 10^?2 M for CGE). The potentiometric responses were independent of pH of the test solution in the range 2.9–6.8. The electrodes possessed advantages of low resistance, relatively fast response time, long lifetimes and, especially, good selectivity relative to a wide variety of other cations. The electrodes were used, as indicator electrodes, in the potentiometric titration of silver ion and in the determination of Ag⁺ ion in waste water, photographic emulsion, radiographic and photographic films and dental amalgams.     

Conductive and optical properties of PPV modified by N+ ion implantation

In this article, a soluble poly[2‐methoxy‐5‐(3′‐methyl)butoxy]‐p‐phenylene vinylene (MMB‐PPV) was synthesized by dehydrochlorination reaction and the MMB‐PPV film was implanted by nitrogen ions (N⁺) with the ion dose and energy in the range of 3.8 × 10¹⁵ to 9.6 × 10¹⁶ ions/cm² and 15–35 keV, respectively. The surface conductivity, optical absorption, optical band gap (E_g) of modified MMB‐PPV film were studied, and the third‐order nonlinear optical susceptibility (χ⁽³⁾) as well as its environmental stability of modified MMB‐PPV film were also measured by degenerate four‐wave mixing system. The results showed that the surface conductivity of MMB‐PPV film was up to 3.2 × 10^?2 S when ion implantation was performed with the energy of 35 keV at an ion dose of 9.6 × 10¹⁶ ions/cm², which was seven order of magnitude higher than that of the pristine film. UV‐Vis absorption spectra demonstrated that the optical absorption of MMB‐PPV film was enhanced gradually in the visible region followed by a red shift of optical absorption threshold and the E_g value was reduced from 2.12 eV to 1.59 eV with the increase of ion dose and energy. The maximum χ⁽³⁾ value of 2.45 × 10^?8 esu for modified MMB‐PPV film was obtained with the ion energy of 20 keV at an ion dose of 3.8 × 10¹⁶ ions/cm², which was almost 33 times larger than that for pristine film. In comparison to the reduction of 17% in the χ⁽³⁾ value of pristine MMB‐PPV film, the maximum χ⁽³⁾ value of 2.45 × 10^?8 esu for modified MMB‐PPV film decreased by over 5.3% when they had been exposed under the same ambient conditions for 90 days. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2072–2077, 2010     

Amperometric Determination of Inositol Based on Electrocatalytic Oxidation on a Glass Carbon Electrode Modified by Nickel Hexacyanoferrate Films

Abstract

A novel method to determinate inositol based on the electrocatalytic oxidation of inositol on the surface of a nickel hexacyanoferrate (NiHCF)–modified electrode was reported. The determination of inositol can be performed in the range of 1.0×10^?4 to 5.8×10^?3 mol/L with a detection limit of 5.0×10^?5 mol/L.     

Mechanism of ion transport in hybrid materials based on MF-4SC perfluorinated sulfonation-exchange membranes and acid zirconium phosphate nanoparticles

The relationship between the transport properties of various salt forms (H⁺, Li⁺, Na⁺, Cs⁺) of MF-4SC hybrid membranes containing nanoparticles of crystalline acid zirconium phosphate Zr(HPO₄)₂ at various relative humidities are investigated with the use of impedance studies and NMR spectroscopy. Modification of the membranes leads to a marked increase in ion mobility, and the maximum effect is observed under reduced humidity conditions. The conductivity of a modified membrane at a relative humidity of 10% is 1.6 × 10^?4 Ω^?1 cm^?1, that is, almost 1.5 orders of magnitude greater than the conductivity of an initial membrane under the same conditions.     

Enhanced lithium-ion intercalation and conduction of transparent tantalum oxide films by lithium addition with an atmospheric pressure plasma jet

An investigation is conducted on enhancing lithium-ion intercalation and conduction performance of transparent organo tantalum oxide (TaO _y C _z ) films, by addition of lithium via a fast co-synthesis onto 40 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates at the short exposed durations of 33–34 s, using an atmospheric pressure plasma jet (APPJ) at various mixed concentrations of tantalum ethoxide [Ta(OC₂H₅)₅] and lithium tert-butoxide [(CH₃)₃COLi] precursors. Transparent organo-lithiated tantalum oxide (Li _x TaO _y C _z ) films expose noteworthy Li⁺ ion intercalation and conduction performance for 200 cycles of reversible Li⁺ ion intercalation and deintercalation in a 1 M LiClO₄-propylene carbonate electrolyte, by switching measurements with a potential sweep from ?1.25 to 1.25 V at a scan rate of 50 mV/s and a potential step at ?1.25 and 1.25 V, even after being bent 360° around a 2.5-cm diameter rod for 1000 cycles. The Li⁺ ionic diffusion coefficient and conductivity of 6.2?×?10^?10 cm²/s and 6.0?×?10^?11 S/cm for TaO _y C _z films are greatly progressed of up to 9.6?×?10^?10 cm²/s and 7.8?×?10^?9 S/cm for Li _x TaO _y C _z films by co-synthesis with an APPJ.     

Protic ionic liquid-based gel polymer electrolyte: structural and ion transport studies and its application in proton battery

Proton-conducting free standing gel polymer electrolyte (GPE) films containing protic ionic liquid, 1-butyl-3-methylimidazolium hydrogen sulphate, immobilized in blend of poly(vinylidenefluoride-co-hexafluoropropylene) and poly(vinylpyrrolidone) have been prepared by solution-cast technique. Films have been characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), differential scanning calorimetry (DSC), complex impedance spectroscopy, and cyclic voltammetry. Ionic conductivity of the semicrystalline and porous GPE films has been obtained as ~3.9?×?10^?3 S cm^?1 at room temperature. Protonic nature of conduction in the films has been established by performing cyclic voltammetry and complex impedance spectroscopy on the cells having both blocking (stainless steel) and both reversible electrodes (Zn + ZnSO₄.7H₂O). The electrochemical stability window of the films has been found as ~3.8 V. The highest conducting film has been used as a separator and proton conductor to fabricate a proton battery of configuration Zn + ZnSO₄.7H₂O |GPE film| PbO₂ + V₂O₅. The battery shows an open circuit voltage of ~1.62 V. Energy density of the cell has been obtained as 35.2 W h kg^?1 for low current drain. Rechargeability of the cell has been tested for ten cycles. The maximum discharge capacity of the cell has been obtained as ~2.50 mA h g^?1 during the first discharge cycle.