Solid Contact Ion-Selective Electrodes for in Situ Measurements at High Pressure.

Solid contact polymeric ion-selective electrodes (SC-ISEs) have been fabricated using microporous carbon (µPC) as the ion-to-electron transducer, loaded with a liquid membrane cocktail containing both ionophore and additive dissolved in plasticizer. These SC-ISEs were characterized and shown to be suitable for analysis in aqueous environments at pressures of 100 bar. Potassium ISEs, prepared in this manner, showed excellent performance at both atmospheric and elevated pressures, as evaluated by their response slopes and potential stability. These novel SC-ISEs were shown to be capable of measuring K+ at pressures under which traditional liquid-filled ISEs fail. Furthermore, the effect of pressure on the response of these sensors had little or no effect on potential, sensitivity, or limit of detection. High pressure sensor calibrations were performed in standard solutions as well as simulated seawater samples to demonstrate their usefulness as sensors in a deep-sea environment. These novel SC-ISE sensors show promise of providing the ability to make in situ real-time measurements of ion-fluxes near deep-ocean geothermal vents.

Electrochemistry of aqueous colloidal graphene oxide on Pt electrodes.

The electrochemical behavior of colloidal solutions of graphene oxide (GO) is described here in detail. The GO reduction is shown to exhibit near-reversible electron transfer on Pt electrodes, based on E1/2 and ΔEp values. The observed peak current is found to depend linearly on the concentration of the GO and the square root of the scan rate, suggesting that the response is diffusion-limited. The difference between the experimental and diffusion-only limited theoretical current values suggests that migration may be hindering mass transport to the electrode surface. Varying the type and concentration of the supporting electrolyte showed that mass transport is weakly influenced by the presence of negative charges on the graphene particles. The effect of pH on GO was also investigated, and it was found that the reduction peak heights were directly related to proton concentration in acidic solutions. On the basis of the results presented here, we propose that the observed response of GO on Pt electrodes is a result of the reduction of protons from the colloidal double layer. This difference is observed only because the Pt electrode surface can efficiently catalyze proton reduction.