The use of solid‐contact ion‐selective electrodes (ISEs) is of interest to many clinical, environmental, and industrial applications. However, upon extended exposure to samples and under thermal and mechanical stress, adhesion between these membranes and underlying substrates often weakens gradually. Eventually, this results in the formation of a water layer at the interface to the underlying electron conductor and in delamination of the membrane from the electrode body, both major limitations to long‐term monitoring. To prevent these problems without increasing the complexity of design with a mechanical attachment, we use photo‐induced graft polymerization to simultaneously attach ionophore‐doped crosslinked poly(decyl methacrylate) sensing membranes covalently both to a high surface area carbon as ion‐to‐electron transducer and to inert polymeric electrode body materials (i.e., polypropylene and poly(ethylene‐co‐tetrafluoroethylene)). The sensors provide high reproducibility (standard deviation of E0 of 0.2 mV), long‐term stability (potential drift 7 μV h−1 over 260 h), and resistance to sterilization in an autoclave (121 °C, 2.0 atm for 30 min). For this work, a covalently attached H+ selective ionophore was used to prepare pH sensors with advantages over conventional pH glass electrodes, but similar use of other ionophores makes this approach suitable to the fabrication of ISEs for a variety of analytes.

As solid-contact potentiometric sensors based on novel materials have reached exceptional stabilities with drifts in the low μV/h range and long-term and calibration-free potentiometric measurements gain more and more attention, reference electrode designs that used to be satisfactory for most users do not satisfy the needs of new challenging applications. It is important that the interface between a reference electrode and the sample, often provided by a salt bridge, remains constant in ion composition over time. Excessive restriction of the flow of the bridge electrolyte, e.g., by using nanoporous frits or gelled reference electrolyte solutions, can result in contamination of the salt bridge with sample components and depletion of the reference electrolyte by diffusion into samples. This can be avoided by using salt bridges that flow freely into the sample. However, commonly used reference electrodes with free-flowing junctions often suffer either from experimental difficulties in assuring a minimum flow rate or from excessive flow rates that require frequent replenishing of the bridge electrolyte. To this end, we developed a reference electrode that contains a concentrated electrolyte contacting samples through a 10.2 μm capillary. By applying a minimal pressure of 10.0 kPa, a flow rate of 100 nL/h is achieved. This maintains a constant liquid junction potential at the interface with the sample and avoids contamination of the reference electrode, as evidenced by a potential stability of 6 ± 3 μV/h over 21 days. With such a minimal flow rate, there is no need to refill the reference electrode electrolyte for years.

Porous glass frits are frequently used to contain the salt bridges through which reference electrodes interface samples. Prior work with widely used glass frits with 4-10 nm diameter pores showed that, when samples have a low electrolyte strength, electrostatic screening of sample ions by charged sites on the glass surface occurs. This creates an ion-specific phase-boundary potential at the interface between the sample and frit, and it biases the potential of the reference half-cell. Use of frits with much larger pores eliminates this problem but results in the need for frequent replenishing of the bridge electrolyte. A methodical study to determine the optimum pore size has been missing. We show here that charge screening of sample ions occurs when the pore size of nanoporous glass frits is on the order of 1-50 nm and samples have a low electrolyte strength. An increase in pores size to 100 nm eliminates charge screening in samples with ionic strengths in the 1.0 M to 3.3 × 10-4 M range. However, the rates of electrolyte solution flow through frits with 1, 5, 20, 50, and 100 nm pores are still low, which makes diffusion the dominant mode of ion transport into and out of these frits. Consequently, the flow of bridge electrolyte into samples is not fast enough to prevent diffusion of ions and electrically neutral components from the sample diffusing into the salt bridge, which can result in cross contamination among samples.

A vital part of almost every experimental electrochemical set up is the reference electrode. As the development of working and indicator electrodes progresses to sensors with greater long-term stability and efficiency, it is important for reference electrodes to keep up with that progress. In this review, the deficiencies of commonly used reference electrodes are discussed, and recent work in the development of new reference electrode designs for more stable and reliable electrochemical experiments is highlighted. This encompasses work with salt-bridge reference electrodes comprising nanoporous and capillary junctions, solid-contact reference electrodes, and ionic liquid-based reference electrodes.

While paper is an excellent material for use in many other portable sensors, potentiometric paper-based sensors have been reported to perform worse than conventional rod-shaped electrodes, in particular in view of limits of detection (LODs). Reported here is an in-depth study of the lower LOD for Cl– measurements with paper-based devices comprising AgCl/Ag transducers. Contamination by Cl– from two commonly used device materialsa AgCl/Ag ink and so-called ashless filter paperwas found to increase the concentration of Cl– in paper-contained samples far above what is expected for the spontaneous dissolution of the transducer’s AgCl, thereby worsening lower LODs. In addition, for the case of Ag+, the commonly hypothesized adsorption of metal cations onto filter paper was found not to significantly affect the performance of AgCl/Ag transducers. We note that in the context of chemical analysis, metal impurities of paper are often mentioned in the literature, but Cl– contamination of paper has been overlooked.