This study developed a new type of all-solid-state ion-selective electrode based on a transducing layer of a network of single-walled carbon nanotubes. The extraordinary capacity of carbon nanotubes to promote electron transfer between heterogeneous phases made the presence of electroactive polymers or any other ion-to-electron-transfer promoter unnecessary. The new transducer layer was characterized by environmental scanning electron microscopy and electrochemical impedance spectroscopy. The stability of the electrical potential of the new solid-contact electrode was examined by performing current-reversal chronopotentiometry, and the influence of the interfacial water film was assessed by the potentiometric water layer test. The performance of the new electrode was evaluated by determining K+ with an ion-selective membrane that contained the well-known valinomycin ion carrier. The new electrode had a Nernstian slope (58.4 mV/decade), dynamic ranges of four logarithmic units, and selectivities and limits of detection comparable to other solid-contact electrodes. The short response time (less than 10 s for activities higher than 10(-5.5) M) and the stability of the signal over several days makes these new electrodes very promising candidates for attaining true miniaturization.

Porous carbon materials and carbon nanotubes were recently used as solid contacts in ion-selective electrodes (ISE), and the signal transduction mechanism of these carbon-based materials is therefore of great interest. In this work the ion-to-electron transduction mechanism of carbon nanotubes is studied by using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Single-walled carbon nanotubes (SWCNT) are deposited on glassy carbon (GC) disk electrodes by repetitive spraying, resulting in SWCNT layers with thicknesses of 10, 35, and 50 mum. The impedance spectra of these GC/SWCNT electrodes in contact with aqueous electrolyte solution show a very small resistance and a large bulk capacitance that is related to a large effective double layer at the SWCNT/electrolyte interface. Interestingly, the impedance response of GC/SWCNT is very similar to that of poly(3,4-ethylenedioxythiophene) (PEDOT) film electrodes studied earlier under the same experimental conditions. The same equivalent circuit is valid for both types of materials. The reason is that both materials can be described schematically as an asymmetric capacitor where one side is formed by electronic charge (electrons/holes) in the SWCNT wall or along the conjugated polymer chain of PEDOT and the other side is formed by ions (anions/cations) in the solution (or in the ion-selective membrane when used as a solid contact in ISE).

Multi-walled carbon nanotubes (MWCNT) are shown to be efficient transducers of the ionic-to-electronic current. This enables the development of a new solid-contact pH-selective electrode that is based on the deposition of a 35-microm thick layer of MWCNT between the acrylic ion-selective membrane and the glassy carbon rod used as the electrical conductor. The ion-selective membrane was prepared by incorporating tridodecylamine as the ionophore, potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as the lipophilic additive in a polymerized methylmethacrylate and an n-butyl acrylate matrix. The potentiometric response shows Nernstian behaviour and a linear dynamic range between 2.89 and 9.90 pH values. The response time for this electrode was less than 10 s throughout the whole working range. The electrode shows a high selectivity towards interfering ions. Electrochemical impedance spectroscopy and chronopotentiometry techniques were used to characterise the electrochemical behaviour and the stability of the carbon-nanotube-based ion-selective electrodes.

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