Electrogenerated chemi luminescence from Ru(BPY)(3)(2+) ion-exchanged in carbon nanotube/perfluorosulfonated ionomer composite films

The electrochemistry and electrogenerated chemiluminescence (ECL) of ruthenium(II) tris(bipyridine) (Ru(bpy)(3)(2+)) ion-exchanged in carbon nanotube (CNT)/Nafion composite films were investigated with tripropylamine (TPA) as a coreactant at a glassy carbon (GC) electrode. The major goal of this work was to investigate and develop new materials and immobilization approaches for the fabrication of ECL-based sensors with improved sensitivity, reactivity, and long-term stability. Ru(bpy)(3)(2+) could be strongly incorporated into Nafion film, but the rate of charge transfer was relative slow and its stability was also problematic. The interfusion of CNT in Nafion resulted in a high peak current of Ru(bpy)(3)(2+) and high ECL intensity. The results indicated that the composite film had more open structures and a larger surface area allowing faster diffusion of Ru(bpy)(3)(2+) and that the CNT could adsorb Ru(bpy)(3)(2+) and also acted as conducting pathways to connect Ru(bpy)(3)(2+) sites to the electrode. In the present work, the sensitivity of the ECL system at the CNT/Nafion film-modified electrodes was more than 2 orders of magnitude higher than that observed at a silica/Nafion composite film-modified electrode and 3 orders of magnitude higher than that at pure Nafion films.

A study of the electrochemical characteristics of the Co(salen)-Nafion modified electrode

A Co(salen)-Nafion modified electrode was prepared by immersing a glassy carbon electrode coated with the Nafion film into the aqueous solution with saturated Co(salen), The modified electrode showed a stable electrochemical reaction of Co(salen) at about 0 V(vs, SCE), The result of XPS indicated the valence of cobalt in Co(salen) changes from +2 before to +3 after Co(salen) enters the Nafion film, It is due to forming axis coordination of cobalt with sulfonic group in Nafion film, It was found that the mode of electron transfer in Co(salen)-Nafion modified electrode was controlled by physical diffusion and electron hopping, It was also found that the modified electrode could catalyze the reduction of O-2 to H2O2. The real catalyst may be the adduct of Co-I(salen) and O-2.

Electrochemical characteristics of glucose oxidase adsorbed at carbon nanotubes modified electrode with ionic liquid as binder

Multiwall carbon nanotubes (CNTs)-modified electrode has been prepared by using ionic liquid (IL) as the binder. The as-prepared CNTs-IL composite modified electrode has good biocompatibility and is a suitable matrix to immobilize biomolecules. Glucose oxidase (GOx), containing flavin adenine dinucleotide as active site, stably adsorbed on modified electrode surface has resulted in the direct electron transfer. The electron transfer rate of 9.08 s(-1) obtained is much higher than that of GOx adsorbed on the CNTs papers (1.7 s(-1)), and the process is more reversible with small redox peak separation of 23 mV This may be due to the synergetic promotion of CNTs and IL to electron transfer of the protein, especially the IL as the binder, showing better electrochemical properties than that of chitosan and Nafion. Furthermore, GOx adsorbed at the modified electrode exhibits good stability and keeps good electrocatalytic activity to glucose with broad linear range up to 20 mM. Besides, the simple preparation procedure and easy renewability make the system a basis to investigate the electron transfer kinetics and biocatalytic performance of GOx and provide a promising platform for the development of biosensors.

STUDY ON MASS-TRANSPORT IN EASTMAN-AQ POLYMER FILM BY USING NON-STEADY-STATE CHRONOAMPEROMETRY AT AN ULTRAMICRODISK ELECTRODE

Non-steady-state chronoamperometry of ultramicroelectrodes is a powerful method for the study of mass transport in polymer films. This method has many advantages over the conventional methods at a macroelectrode and the steady state method at an ultramicroelectrode, which yield the most information. The apparent diffusion coefficient, D(app), and the concentration of reactant in the film, c(f), can be determined from a single experiment without knowing the thickness of the film. We studied the transport of several species such as Ru(NH3)63+, Ru(bpy)3(2+), NR and MV2+ in Eastman-AQ polymer film coated ultramicroelectrodes by using this method.

Embracing ligands. Synthesis, characterisation and the correlation between 59Co NMR and ligand field parameters of Co(III) complexes with a new class of nitrogen-thioether multidentate ligand

The syntheses of the hexadentate ligands 2,2,10,10-tetra(methyleneamine)-4,8-dithiaundecane (PrN(4)S(2)amp), 2,2,11,11-tetra(methyleneamine)-4,9-dithiadodecane (BuN(4)S(2)amp), and 1,2-bis(4,4-methyleneamine)-2-thiapentyl)benzene (XyN(4)S(2)amp) are reported and the complexes [Co(RN(4)S(2)amp)](3+) (R = Pr, Bu, Xy) characterised by single crystal X-ray study. The low-temperature (11 K) absorption spectra have been measured in Nafion films. From the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(1g) and (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10D(q), B and C) have been determined. DFT calculations suggest that significant interaction between the d-d and CT excitations occurs for the complexes. The calculations offer an explanation for the observed deviations from linearity of the relationship between Co-59 magnetogyric ratio and beta(DeltaE)(-1) (beta = the nephelauxetic ratio; DeltaE the energy of the (1)A(1g) --> T-1(1g) transition) for a series of amine and mixed amine/thioether donor complexes.

Synthesis and characterization of cobalt(III) complexes with sinambic amplector ligands

The synthesis of the hexadentate ligand 5,6-dimethyl-2,2,9,9-tetra(methyleneamine)-4,7-dithiadecane (1,2-Me(2)EtN(4)S(2)amp) is reported. The diastereiosomers were separated as cobalt(III) complexes using cation exchange chromatography. The rac and mesa isomers were characterized by NMR (C-13, H-1, Co-59), ESI-MS, UV-Vis spectroscopy and cyclic voltammetry. Single crystals of [Co(rac-1,2-Me(2)EtN(4)S(2)amp)] Cl-2(ClO4) (.) 2H(2)O were characterized by X-ray diffraction. The low-temperature (11 K) absorption spectra of the complexes have been measured in Nafion films and from the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10Dq, B and C) were determined. These results, in conjunction with the Co-59 NMR data, are used to further explore the relationship between the Co-59 magnetogyric ratio (gamma(Co)) and the product of the nephelauxetic ratio and the wavelength of the (1)A(1g) --> T-1(1g) transition (beta(DeltaE)(-1)) for complexes of mixed donor nitrogen-thioether ligands. (C) 2004 Elsevier Ltd. All rights reserved.

PEDOT:PSS self-assembled films to methanol crossover reduction in Nafion (R) membranes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Self-assembled films from chitosan and poly(vinyl sulfonic acid) on Nafion® for direct methanol fuel cell

Chitosan/poly(vinyl sulfonic acid) (PVS) films have been prepared on Nafion® membranes by the layer-by-layer (LbL) method for use in direct methanol fuel cell (DMFC). Computational methods and Fourier transform infrared (FTIR) spectra suggest that an ionic pair is formed between the sulfonic group of PVS and the protonated amine group of chitosan, thereby promoting the growth of LbL films on the Nafion® membrane as well as partial blocking of methanol. Chronopotentiometry and potential linear scanning experiments have been carried out for investigation of methanol crossover through the Nafion® and chitosan/PVS/Nafion® membranes in a diaphragm diffusion cell. On the basis of electrical impedance measurements, the values of proton resistance of the Nafion® and chitosan/PVS/Nafion® membranes are close due to the small thickness of the LbL film. Thus, it is expected an improved DMFC performance once the additional resistance of the self-assembled film is negligible compared to the result associated with the decrease in the crossover effect.

Probing second harmonic components of pH-sensitive Redox processes in a mesoporous TiO2-Nafion film electrode with Fourier-transformed large-amplitude sinusoidally modulated voltammetry

Electrochemical processes in mesoporous TiO2-Nafion thin films deposited on indium tin oxide (ITO) electrodes are inherently complex and affected by capacitance, Ohmic iR-drop, RC-time constant phenomena, and by potential and pH-dependent conductivity. In this study, large-amplitude sinusoidally modulated voltammetry (LASMV) is employed to provide access to almost purely Faradaic-based current data from second harmonic components, as well as capacitance and potential domain information from the fundamental harmonic for mesoporous TiO2-Nafion film electrodes. The LASMV response has been investigated with and without an immobilized one-electron redox system, ferrocenylmethyltrimethylammonium+. Results clearly demonstrate that the electron transfer associated with the immobilized ferrocene derivative follows two independent pathways i) electron hopping within the Nafion network and ii) conduction through the TiO2 backbone. The pH effect on the voltammetric response for the TiO2 reduction pathway (ii) can be clearly identified in the 2nd harmonic LASMV response with the diffusion controlled ferrocene response (i) acting as a pH independent reference. Application of second harmonic data derived from LASMV measurement, because of the minimal contribution from capacitance currents, may lead to reference-free pH sensing with systems like that found for ferrocene derivatives.

Energy harvesting using ionic electro-active polymer thin films with Ag-based electrodes

In this paper we employ the phenomenon of bending deformation induced transport of cations via the polymer chains in the thickness direction of an electro-active polymer (EAP)-metal composite thin film for mechanical energy harvesting. While EAPs have been applied in the past in actuators and artificial muscles, promising applications of such materials in hydrodynamic and vibratory energy harvesting are reported in this paper. For this, functionalization of EAPs with metal electrodes is the key factor in improving the energy harvesting efficiency. Unlike Pt-based electrodes, Ag-based electrodes have been deposited on an EAP membrane made of Nafion. The developed ionic metal polymer composite (IPMC) membrane is subjected to a dynamic bending load, hydrodynamically, and evaluated for the voltage generated against an external electrical load. An increase of a few orders of magnitude has been observed in the harvested energy density and power density in air, deionized water and in electrolyte solutions with varying concentrations of sodium chloride (NaCl) as compared to Pt-based IPMC performances reported in the published literature. This will have potential applications in hydrodynamic and residual environmental energy harvesting to power sensors and actuators based on micro-andn nano-electro-mechanical systems (MEMS and NEMS) for biomedical,maerospace and oceanic applications.

Layer-by-Layer Assembly of Nafion on Surlyn with Ultrahigh Water Vapor Barrier

A layer-by-layer approach was used for the fabrication of multilayer films for ultra high gas barrier applications. The ultra high gas barrier material was designed by incorporating Nafion layer in between bilayers of poly(ethylene imine) and poly(acrylic acid) on a Surlyn substrate. When the barrier film with self-assembled Nafion is exposed to the moist environment, Nafion absorbs and desorbs water molecules simultaneously, thereby reducing the ingress of moisture in to the film. In order to study the effect of Nafion, the fabricated barrier materials with and without the presence of Nafion were tested for water vapor barrier properties. The barrier films were further used for encapsulating organic photovoltaic devices and were evaluated for their potential use in barrier applications. The devices encapsulated with the films containing Nafion exhibited better performance when subjected to accelerated aging conditions. Therefore, this study demonstrates the effectiveness of self-assembled Nafion in reducing the water vapor permeability by nearly five orders of magnitude and in increasing the lifetimes of organic devices by similar to 22 times under accelerated weathering conditions.

Nafion/PTFE composite membranes for fuel cell applications

Porous polytetrafluoroethylene (PTFE) membranes were used as support material for Nafion((R))/PTFE composite membranes. The composite membranes were synthesized by impregnating porous PTFE membranes with a self-made Nafion solution. The resulting composite membranes were mechanically durable and quite thin relative to traditional perfluorosulfonated ionomer membranes (PFSI); we expect the composite membranes to be of low resistance and cost. In this study, we used three kinds of porous PTFE films to prepare Nafion/PTFE composite membranes of different thickness. Scanning electron micrographs and oxygen permeabilities showed that Nafion resin is distributed uniformly in the composite membrane and completely plug the micropores, there is a continuous thin Nation film present on the PTFE surface. The variation in water content of the composite and Nafion 115 membranes with temperature was determined. At the same temperature, water content of the composite membranes was smaller than that of the Nafion 115. In both dry and wet conditions, maximum strength and break strength of C-325(#) and C-345(#) were larger than those of Nafion 112 due to the reinforcing effect of the porous PTFE films. And the PEMFC performances and the lifetime of the composite membranes were also tested on the self-made apparatus. Results showed that the bigger the porosity of the substrate PTFE films, the better the fuel cell performance; the fuel cell performances of the thin composite membranes were superior to that of Nation 115 membrane; and after 180 h stability test at 500 mA/cm(2), the cell voltage showed no obvious drop. (C) 2002 Published by Elsevier Science B.V.

Electrochemiluminescence from tris(2,2 '-bipyridyl)ruthenium(II)-graphene-Nafion modified electrode

An electrochemiluminescence (ECL) sensor based on Ru(bpy)(3)(2+)-graphene-Nafion composite film was developed. The graphene sheet was produced by chemical conversion of graphite, and was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and Raman spectroscopy. The introduction of conductive graphene into Nafion not only greatly facilitates the electron transfer of Ru(bpy)(3)(2+), but also dramatically improves the long-term stability of the sensor by inhibiting the migration of Ru(bpy)(3)(2+) into the electrochemically inactive hydrophobic region of Nafion. The ECL sensor gives a good linear range over 1 x 10(-7) to 1 x 10(-4) M with a detection limit of 50 nM towards the determination of tripropylamine (TPA), comparable to that obtained by Nafion-CNT.

Direct electron transfer and electrocatalysis of glucose oxidase immobilized on glassy carbon electrode modified with Nafion and mesoporous carbon FDU-15

In this paper, it was found that glucose oxidase (GOD) has been stably immobilized on glassy carbon electrode modified with mesoporous carbon FDU-15 (MC-FDU-15) and Nafion by simple technique. The sorption behavior of GOD immobilized on MC-FDU-15 matrix was characterized by transmission electron microscopy (TEM), ultraviolet-visible (UV-vis), FTIR, respectively, which demonstrated that MC-FDU-15 could facilitate the electron exchange between the active center of GOD and electrode. The direct electrochemistry and electrocatalysis behavior of GOD on the modified electrode were characterized by cyclic voltammogram (CV) which indicated that GOD immobilized on Nafion and MC-FDU-15 matrices display direct, reversible and surface-controlled redox reaction with an enhanced electron transfer rate constant of 4.095 s(-1) in 0.1 M phosphate buffer solution (PBS) (pH 7.12).

Solid-state electrochemiluminescence sensor based on the Nafion/poly(sodium 4-styrene sulfonate) composite film

An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)(3)(2+) immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.