Polyoxometallates as inorganic templates for electrocatalytic network films of ultra-thin conducting polymers and platinum nanoparticles

Karnicka, Katarzyna; Chojak, Małgorzata; Miecznikowski, Krzysztof; Skunik, Magdalena; Baranowska, Beata; Kolary, Aneta; Piranska, Aleksandra; Pałys, Barbara; Adamczyk, L.; Kulesza, Paweł J.

doi:10.1016/j.bioelechem.2004.06.005

Cited by 69 publications

(48 citation statements)

References 68 publications

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“…POMs have been studied as monolayers or organic-inorganic hybrids in contact with different supporting electrolytes [34,35], and as single crystals in the absence of external liquid phase [21][22][23][24][25][26]. The electrochemical analysis of the most popular Keggin-type POMs (phosphotungstate and tungstosilicate) in the presence of acidic solution revealed three reversible reduction peaks originating from two one-electron processes followed by one two-electron process [17,21,22,36].…”

Section: Introductionmentioning

confidence: 99%

Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Adamczyk

Miecznikowski

2013

J Solid State Electrochem

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We demonstrate the electrochemical characteristics of the, poorly described in the literature, mixed-valence proton conducting solid borotungstic acid single crystal, H 5 BW 12 O 40 xH 2 O, in the absence of liquid electrolyte phase. We performed electrochemical measurements in an all-solid cell with a gold fiber ultramicrodisk (diameter 10, 25, and 40 μm) working electrode, a silver semi-reference disk electrode, and a glassy carbon ring counter electrode. Diagnostic experiments at different scan rates aimed at probing the model of mass transport and potential kinetic limitations. Such bulk parameters as the effective diffusion coefficient of charge propagation and the concentration of mixed-valence redox centers were determined by two methods. The first method is based on the analysis of both Cottrellian and steady-state currents (the mixed-regimes method), and the second method provides the true diffusion coefficient (transport coefficient free of the migration influence) for both the substrate and the product of the electrode reaction. Together, these methods constitute a double potential step chronoamperometry experiment. The data obtained with these electrochemical experiments (effective diffusion coefficients, concentration of mixed-valence redox centers, etc.) can support the results obtained with other techniques (XRD, FTIR, and TGA).

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Section: Introductionmentioning

confidence: 99%

Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Adamczyk

Miecznikowski

2013

J Solid State Electrochem

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“…Recently, various hybrid systems with POMs have been proposed and studied for solid-state applications [14][15][16]. Common representative examples include the systems containing POMs immobilized within conducting polymers [17], gel matrices [18], Langmuir-Blodgett layers [19], or as adsorbates existing on nanoparticles' surfaces [20][21][22]. A high anionic charge of POM layers or adsorbates permits their application as linking agents during fabrication of three-dimensional network films consisted of anionic and cationic species interconnected via simple electrostatic interactions.…”

Section: Introductionmentioning

confidence: 99%

“…A high anionic charge of POM layers or adsorbates permits their application as linking agents during fabrication of three-dimensional network films consisted of anionic and cationic species interconnected via simple electrostatic interactions. This layer-by-layer concept was applied to the formation of POM-based hybrid films containing conducting polymers [20][21][22][23], positively charged organics like poly(vinylpyridine) or poly(ethylenimine) [24] and transition metal (Fe, Ru, Os, Cu) complexes [2,[25][26][27].…”

Section: Introductionmentioning

confidence: 99%

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Hybrid materials utilizing polyelectrolyte-derivatized carbon nanotubes and vanadium-mixed addenda heteropolytungstate for efficient electrochemical charging and electrocatalysis

Sosnowska

Góral-Kurbiel

Skunik-Nuckowska

et al. 2013

J Solid State Electrochem

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Preparation and electrochemical behavior of new hybrid materials composed of multi-walled carbon nanotubes (CNTs) that were derivatized with poly(diallyldimethylammonium) chloride and modified with vanadium-mixed addenda Dawson-type heteropolytungstate, [P 2 W 17 VO 62 ] 8− , is described here. These nanostructured composite systems exhibited fast dynamics of charge propagation. They were characterized by the transport (effectively diffusional) kinetic parameter of approximately 8×10 −8 cm −2 s −1/2 and the specific capacitance parameter of 82 F g −1 (at the charging/discharging current of 200 mA g −1 ). The latter parameter for bare CNTs was found to be only 50 F g −1 under analogous conditions. These observations were based on the results of galvanostatic charging-discharging, cyclic voltammetric, and AC impedance spectroscopic measurements. The improved capacitance properties were attributed to the systems' pseudocapacitive features originating from the fast redox transitions of the [P 2 W 17 VO 62 ] 8− polyanions. In addition to the fast redox conduction, the proposed organicinorganic hybrid materials exhibited interesting electrocatalytic activity toward reduction of bromate in the broad concentration range (sensitivity, 0.24 mA cm −2 mmol −1 dm 3 ).

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“…Owing to their inherent 5 characteristics, POMs are presented as excellent candidates for electrocatalytic reduction of hydrogen peroxide. [43][44][45] In order to prepare chemically modified electrodes for electrocatalytic reduction of H 2 O 2 , POMs have been immobilized onto modified silica gel, 46 multilayer assemblies 47,48 or ordered mesoporous 10 carbon. 49 In this work, transition metal-substituted Dawson-type POMs were immobilized via doping ion insertion during the electropolymerization of polypyrrole.…”

Section: Introductionmentioning

confidence: 99%

Transition metal ion-substituted polyoxometalates entrapped in polypyrrole as an electrochemical sensor for hydrogen peroxide

Anwar

Vagin

Laffir

et al. 2012

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A conducting polymer was used for the immobilization of various transition metal ion-substituted Dawson-type polyoxometalates (POMs) onto glassy carbon electrodes. Voltammetric responses of films of different thicknesses were stable within the pH domain 2-7 and reveal redox processes associated with the conducting polymer, the entrapped POMs and incorporated metal ions. The resulting POM doped 10 polypyrrole films were found to be extremely stable towards redox switching between the various redox states associated with the incorporated POM. An amperometric sensor for hydrogen peroxide detection based upon the POM doped polymer films was investigated. The detection limits were 0.3 and 0.6 uM, for the Cu 2+ -and Fe 3+ -substituted POM-doped polypyrrole films respectively, with a linear region from 0.1 up to 2mM H 2 O 2 . Surface characterization of the polymer films was carried out using atomic force 15 microscopy, x-ray photoelectron spectroscopy and scanning electron microscopy. IntroductionPolyoxometalates (POMs) are a widely increasing class of inorganic early transition metal-oxide clusters. The structural and compositional diversity among this class of compounds have 20 enabled them to be promising candidates for a wide range of applications across material science, medicine, biotechnology, nanotechnology and catalysis. [1][2][3][4][5][6][7][8][9][10][11][12] The general structure of POMs consists of MO 6 units joined together by edge or corner sharing and connected tetrahedrally to a centrally bonded heteroatom 25 (usually phosphorus or silicon). One of the MO 6 units can be removed from the structure at higher pH and substituted with different metal ions allowing for controllable molecular design.Various strategies have been used for immobilization of POMs onto different surfaces, safeguarding their inherent properties. 30 These include: sol-gel technique, 13 polyoxometalates. 38,39 Despite the high selectivity and sensitivity of enzyme-modified electrodes, 40, 41 the limitation of usage of these systems is related to the difficulty in obtaining the optimal conditions and the lack of the enzymatic activity over a period of time, 42 POMs inside the polymer matrix were accessible for voltammetric studies in acidic medium. The films exhibited stable redox responses in the pH range of 2-7. Surface characterization was carried out using the AFM, XPS and SEM. Electrocatalytic activity of the films containing iron and copper-20 substituted POMs towards the reduction of hydrogen peroxide was studied by amperometry at physiological conditions (pH 6.5) and compared with the performance of the same POMs in solution 50 and immobilized onto an electrode surface via multilayer assemblies. 19 Conducting polymer-based POM-doped 25 polypyrrole films reveal the best analytical characteristics for hydrogen peroxide reduction in comparison with some other approaches. Experimental 30 MaterialsThe potassium salts of all the substituted Dawson type polyoxometalates investigated were synthesized and characterised by both ele...

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Polyoxometallates as inorganic templates for electrocatalytic network films of ultra-thin conducting polymers and platinum nanoparticles

Cited by 69 publications

References 68 publications

Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Hybrid materials utilizing polyelectrolyte-derivatized carbon nanotubes and vanadium-mixed addenda heteropolytungstate for efficient electrochemical charging and electrocatalysis

Transition metal ion-substituted polyoxometalates entrapped in polypyrrole as an electrochemical sensor for hydrogen peroxide

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