Ion-Selective Electrodes with Three-Dimensionally Ordered Macroporous Carbon as the Solid Contact

Lai, Chaohua; Fierke, Melissa A.; Stein, and Andreas; Bühlmann, Philippe

doi:10.1021/ac070132b

Cited by 272 publications

(253 citation statements)

References 45 publications

(74 reference statements)

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“…These membranes are frequently interrogated by the simplest electrochemistry technique, potentiometry, and are typically sensitive to ion activity changes in the sample solution [4]. While traditional membrane electrodes are backside contacted with an aqueous electrolyte [5,6], recent efforts aimed at replacing the inner solution by a solid contact ion-to-electron transducer [7,8], which includes conducting polymers [6,9,10] and nanostructured materials [8,[11][12][13] as potential candidates to replace the inner filling solution and the Ag/AgCl element.…”

Section: Introductionmentioning

confidence: 99%

All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Jarolímová

Crespo

Afshar

et al. 2013

Journal of Electroanalytical Chemistry

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a b s t r a c tAn all solid contact ion-selective electrode based on poly(vinyl chloride) covalently modified with ferrocene moieties allows one to operate the membrane in a chronopotentiometric sensing mode. The membrane is considered as initially non-perm-selective towards anions, and an applied anodic current provokes a defined anion flux in direction of the membrane. With this protocol, a variety of anions can be depleted at the membrane surface. Since this model system does not yet contain an ionophore, their order of preference follows the expected Hofmeister selectivity sequence. The all solid-state configuration tolerates an imposed current density of 1.4 lA mm À2 , which translates into an upper detection limit of ca. 1.2 mM. Higher current densities of up to 31.2 lA mm À2 are possible with addition of freely dissolved alkyl ferrocene derivative for an expected upper detection limit of 17.0 mM. Numerical simulations are performed in order to establish the fundamental basis of the mechanism that takes place in this all solid-state membrane electrode. The oxidation of bound Fc and the ion-transfer process are considered in the simulation. In view of developing an analytical sensor, different anions are tested. A linear range of two orders of magnitude from 0.01 to 1 mM is found. The membranes are evaluated over several days, displaying practically the same slopes and intercepts, with a RSD of less than 2%. Electrochemical limitations of free Fc and bound Fc are critical evaluated. This approach should allow one to develop a new family of solid-state chronopotentiometric ion sensors that require relatively high current densities.

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Section: Introductionmentioning

confidence: 99%

All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Jarolímová

Crespo

Afshar

et al. 2013

Journal of Electroanalytical Chemistry

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“…The mainstream of the SCISE research is based on electrically conducting polymers (ECPs) [34][35][36] , large surface area carbon materials 32,[37][38][39][40] and their (nano)composites [41][42][43] , but also many other important types of SC materials have been reported such as redox polymers 44 , electronion exchange resins 45 , redox-active self-assembled monolayers 32 , tetrakis(4-chlorophenyl)borate anion doped nanocluster films 46 , nanoporous Au films 47 , and threedimensional molybdenum sulfide nanoflowers. 48 SCISEs with adequate potential stability were reported for both the ECP and carbon materials, but the use of large surface area inert carbon materials apparently results in better potential stabilities and less susceptibility to environmental conditions.…”

mentioning

confidence: 99%

“…48 SCISEs with adequate potential stability were reported for both the ECP and carbon materials, but the use of large surface area inert carbon materials apparently results in better potential stabilities and less susceptibility to environmental conditions. 37,39 In turn, ECPs have an essential advantage in terms of controlled local deposition by electropolymerization aiding the miniaturization and mass fabrication of SCISEs. [49][50][51] However, they show a larger degree of complexity both due to the diversity of the ECPs and doping ions as well as due to the mechanism of the stabilization of the inner phase boundary potential.…”

mentioning

confidence: 99%

Pre-Polarized Hydrophobic Conducting Polymer Solid-Contact Ion-Selective Electrodes with Improved Potential Reproducibility

Papp

Lindfors

et al. 2017

Anal. Chem.

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Electrically conducting polymers (ECPs) are one of the most popular types of materials to interface ion-selective membranes (ISMs) with electron conducting substrates to construct solid contact ion-selective electrodes (SCISEs). For optimal ion-to-electron transduction and potential stability, the p-doped ECPs with low oxidation potentials such as PPy need to be generally in their conducting form along with providing a sufficiently hydrophobic interface to counteract the aqueous layer formation. The first criterion requires that the ECPs are in their oxidized state, but the high charge density of this state is detrimental for the prevention of the aqueous layer formation. We offer here a solution to this paradox by implementing a highly hydrophobic perfluorinated anion (perfluorooctane sulfonate, PFOS -) as doping ion by 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 which the oxidized form of the ECP becomes hydrophobic. The proof of concept is shown by using polypyrrole (PPy) films doped with PFOS -(PPy-PFOS) as the solid contact in K + -selective SCISEs (K + -SCISE). Prior to applying the plasticized poly(vinyl chloride) ISM, the oxidation state of the electrodeposited PPy-PFOS was adjusted by polarization to the known open circuit potential of the solid contact in 0.1 M KCl. We show that the pre-polarization results in a hydrophobic PPy-PFOS film with a water contact angle of 97±5º, which effectively prevents the aqueous layer formation under the ISM. Under optimal conditions the K + -SCISEs had a very low standard deviation of E 0 of only 501.0±0.7 mV that is the best E 0 reproducibility reported for ECP-based SCISEs.

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“…4 Additionally, an undesired water layer with about 100 Å thickness under the ion-selective membrane is another resource of potential drift, 5 which unintentionally acts as an inner filling solution with extremely small volume that reequilibrates on each and every change in sample composition and subsequently influences the boundary potential. 6 Both sources of potential instability can be eliminated by applying a variety of materials as solid contacts, such as lipophilic redox-active self-assembled monolayers, 7 conducting polymers, 8 fullerene, 9 three-dimensionally ordered macroporous (3DOM) carbon, 10 carbon nanotubes, 11 graphene, 12,13 gold nanoparticles, 14 and nanoclusters. 15 However, some of those materials may be not suitable for developing robust miniaturized ISEs.…”

mentioning

confidence: 99%

All-Solid-State Polymeric Membrane Ion-Selective Miniaturized Electrodes Based on a Nanoporous Gold Film as Solid Contact

2014

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ABSTRACT:A new type of all-solid-state polymeric membrane ion-selective electrodes (ISEs) is developed by using a nanoporous gold (NPG) film as solid contact. The NPG film is in situ formed on the surface of a gold wire electrode by the multicyclic electrochemical alloying/dealloying method. The characteristics of the NPG film, such as the large surface area, high double layer capacitance, and good conductivity, have been demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy. The NPG film offers a well-defined interface between the electronic conductor and the ion-selective membrane. The NPG filmbased all-solid-state K + ISE shows a stable Nernstian response within the concentration range from 10 −6 to 10 −2 M, and the detection limit is 4.0 × 10 −7 M. The proposed electrode exhibits an improved potential stability with a reduced water layer in comparison with the coated-wire K + -ISE, which is due to the bicontinuous electron-and ion-conducting properties of the ionophore-doped polymeric membrane/NPG film interlayer. Unlike the additionally coated intermediate layers as single-use solid contacts, the in situ formed NPG film as solid contact is reusable. This work provides a versatile method for fabricating the robust, reliable, and low-maintenance miniaturized ISEs.

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Ion-Selective Electrodes with Three-Dimensionally Ordered Macroporous Carbon as the Solid Contact

Cited by 272 publications

References 45 publications

All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Pre-Polarized Hydrophobic Conducting Polymer Solid-Contact Ion-Selective Electrodes with Improved Potential Reproducibility

All-Solid-State Polymeric Membrane Ion-Selective Miniaturized Electrodes Based on a Nanoporous Gold Film as Solid Contact

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