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• W2149774022 abstract "Ion-selective electrode is one of electrochemical devices for the determination of specific ion concentration in analyte. In general, the ion-selective electrodes consist of an ion-selective membrane, internal solution, and internal reference electrode. To miniaturize the ionselective electrodes, a coated wire electrode; so-called CWE, which is a metallic wire electrode covered with ion-selective membrane, has been developed. CWEs show, however, insufficient potential stability and reproducibility because of the absence of the charge transfer process at the membrane/electrode interface and the omission of an inner reference electrode. To stabilize the electrodes by introduction of proper charge transfer process, our group have been utilized cation insertion materials, such as manganese oxides, as an internal mediating layer. Manganese oxides, which is a mixed ion/electron conductor, are selected as internal layers to stabilize the electrode potential. In addition, polycationdoped manganese oxides can reversibly insert/extract anions into/from manganese dioxide interlayers by the electrochemical process. In this study, we examine poly(allylamine) (PAAm)doped manganese oxides (PAAm-MnOx) as the internal mediation layers for the Cl ion sensing electrode. PAAmMnOx layers were deposited on Pt substrates by electrodeposition method. The electrodeposition bath used consisted of 2 mmol dm MnSO4 aqueous solutions and 0.2 mol dm PAAm (in monomer unit). The pH of bath was adjusted to 5.0 by addition of a diluted HCl solution. Electrodeposition was carried out by applying 1.0 V vs. Ag/AgCl under a constant charge condition (330 mC/cm). Chloride ion selective membranes were casted on the top of Pt or Pt/PAAm-MnOx electrodes using the THF solution; Bisthiourea-1 as Cl ion ionophore, o-NPOE as a plasticizer, PVC as a membrane matrix, and TDDMACl as an anion exchanger were used. Figure 1 compares the potential response of the Pt/PAAm-MnOx electrode with or without the ionselective membrane to Cl ion activity. The Pt/PAAmMnOx electrodes show stable response to Cl ion in KCl solution, but the response to the Cl activity is somewhat deviated from an ideal Nernstian behavior. The Pt/PAAmMnOx/PVC electrode exhibits quick and nearly ideal Nernstian response. Long-term potential stability of Pt/PVC (as CWE) and Pt/PAAm-MnOx/PVC electrodes in 0.01 mol dm KCl is compared in Fig. 2. The potential of the Pt/PVC electrode changes beyond ± 200 mV for 10 days, whereas the Pt/PAAm-MnOx/PVC electrode has good potential stability (less than ± 20 mV for 10 days). Figure 3 reveals chronopotentiometry response for cathodic and then anodic polarization at ±1 nA. The potential of the Pt/PVC electrode drastically changes as a function of time. In contrast, the Pt/PAAm-MnOx/PVC electrode shows excellent potential stability, which changes less than ± 1 mV in the same condition. The results suggest that PAAm-MnOx as the internal mediating layer effectively reduces the resistance of the all-solid-state electrode, and thus improves the potential stability as ion-sensing electrode. References [1] C. Suzuki et al., Proceedings of the 51st Chemical Sensor Symposium in Japan, Abs. #22 (2010). [2] M. Nakayama et al., Langmuir, 22, 3864 (2006). Fig. 1 Potentiometric response of a Pt/PAAm-MnOx electrode (squares) and Pt/PAAm-MnOx/PVC electrode (circles) to different Cl activity." @default.
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• W2149774022 date "2012-01-01" @default.
• W2149774022 modified "2023-09-26" @default.
• W2149774022 title "All-Solid-State Chloride Ion-Selective Electrodes Using Polycation-Doped Manganese Oxides" @default.
• W2149774022 doi "https://doi.org/10.1149/ma2012-02/2/140" @default.
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