A New Planar Potentiometric Sensor for In Situ Measurements.

A new construction of a potentiometric sensor was introduced for the first time. It relies on the use of two membranes instead of one, as in the well-known coated-disc electrode. For this purpose, a new electrode body was constructed, including not one, but two glassy carbon discs covered with an ion-selective membrane. This solution allows for the sensor properties to be enhanced without using additional materials (layers or additives) on the membrane. The new construction is particularly useful for in situ measurements in environmental samples. Two ion-selective polymeric membranes were used, namely H+ and K+-selective membranes, to confirm the universality of the idea. The tests conducted included chronopotentiometric tests, electrochemical impedance spectroscopy, and potentiometric measurements. The electrical and analytical parameters of the sensors were evaluated and compared for all tested electrodes to evaluate the properties of the planar electrode versus previously known constructions. Research has shown that the application of two membranes instead of one allows for the resistance of an electrode to be lowered and for the electrical capacitance to be elevated. Improving the electrical properties of an electrode resulted in the enhancement of its analytical properties. The pH measurement range of the planar electrode is 2-11, which is much wider in contrast to that of the single-membrane electrode. The linear range of the K+-selective planar electrode is wider than that of the coated-disc electrode and equals 10-6 to 10-1 M. The response time turned out to be a few seconds shorter, and the potential drift was smaller due to the application of an additional membrane in the electrode construction. This research creates a new opportunity to design robust potentiometric sensors, as the presented construction is universal and can be used to obtain electrodes selective to various ions.

Application of Metal Oxide Nanoparticles in the Field of Potentiometric Sensors: A Review.

Recently, there has been rapid development of electrochemical sensors, and there have been numerous reports in the literature that describe new constructions with improved performance parameters. Undoubtedly, this is due to the fact that those sensors are characterized by very good analytical parameters, and at the same time, they are cheap and easy to use, which distinguishes them from other analytical tools. One of the trends observed in their development is the search for new functional materials. This review focuses on potentiometric sensors designed with the use of various metal oxides. Metal oxides, because of their remarkable properties including high electrical capacity and mixed ion-electron conductivity, have found applications as both sensing layers (e.g., of screen-printing pH sensors) or solid-contact layers and paste components in solid-contact and paste-ion-selective electrodes. All the mentioned applications of metal oxides are described in the scope of the paper. This paper presents a survey on the use of metal oxides in the field of the potentiometry method as both single-component layers and as a component of hybrid materials. Metal oxides are allowed to obtain potentiometric sensors of all-solid-state construction characterized by remarkable analytical parameters. These new types of sensors exhibit properties that are competitive with those of the commonly used conventional electrodes. Different construction solutions and various metal oxides were compared in the scope of this review based on their analytical parameters.

Hydrous Cerium Dioxide-Based Materials as Solid-Contact Layers in Potassium-Selective Electrodes.

This paper introduces hydrous cerium dioxide applied for the first time as a solid-contact layer in ion-selective electrodes. Cerium dioxide belongs to the group of metal oxides that exhibit both redox activity and a large surface area and therefore was considered to be an appropriate material for the solid-contact layer in potentiometric sensors. The material was examined both standalone and as a component of composite materials (with the addition of carbon nanomaterial or conducting polymer). Three cerium dioxide-based materials were tested as solid-contact layers in potentiometric sensors in the context of their microstructure, wettability, and electrical properties. The addition of hydrous cerium dioxide was shown to enhance the properties of carbon nanotubes and poly(3-octylthiophene-2,5-diyl) by increasing the value of electrical capacitance (798 µF and 112 µF for hCeO2-NTs and hCeO2-POT material, respectively) and the value of contact angle (100° and 120° for hCeO2-NTs and hCeO2-POT material, respectively). The proposed sensor preparation method is easy, without the need to use an advanced apparatus or specific conditions, and fast; sensors can be prepared within an hour. Designed hCeO2-based electrodes exhibit competitive linear range and potential stability within the wide range of pH values (2.0-11.5). Designed electrodes are dedicated to potassium determination in environmental and clinical samples.

The New Reliable pH Sensor Based on Hydrous Iridium Dioxide and Its Composites.

The new reliable sensor for pH determination was designed with the use of hydrous iridium dioxide and its composites. Three different hIrO2-based materials were prepared and applied as solid-contact layers in pH-selective electrodes with polymeric membrane. The material choice included standalone hydrous iridium oxide; composite material of hydrous iridium oxide, carbon nanotubes, and triple composite material composed of hydrous iridium oxide; carbon nanotubes; and poly(3-octylthiophene-2,5-diyl). The paper depicts that the addition of functional material to standalone metal oxide is beneficial for the performance of solid-state ion-selective electrodes and presents the universal approach to designing this type of sensors. Each component contributed differently to the sensors' performance-the addition of carbon nanotubes increased the electrical capacitance of sensor (up to 400 µF) while the addition of conducting polymer allowed it to increase the contact angle of material changing its wetting properties and enhancing the stability of potentiometric response. Hydrous iridium oxide contacted electrodes exhibit linear response in wide linear range of pH (2-11) and stable potentiometric response (the lowest potential drift of 0.036 mV/h is attributed to the electrode with triple composite material).

Graphene Flakes Decorated with Dispersed Gold Nanoparticles as Nanomaterial Layer for ISEs.

This paper proposes a new type of solid-contact layer based on graphene/gold nanoparticles for ion-selective electrodes. A novel approach to preparing the material for intermediate layer by modifying the graphene flakes by gold nanoparticles is presented. With this approach, we observed a large surface area of material and in consequence high electrical capacitance of electrodes. We have obtained satisfactory results demonstrating that the modification of graphene with gold allows for enhancing electrical and wetting properties of carbon nanomaterial. Electrical capacitance of designed nanocomposite-contacted electrode equals to approximately 280 µF, which in consequence ensures great long-term potential stability defined by the potential drift of 36 µV/h. The modification of graphene with nanoparticles completely changed its wetting properties, as the designed material turned out to be hydrophobic with a water contact angle of 115°. Graphene/gold nanoparticles-contacted electrodes are insensitive to the changing light conditions, exhibiting near-Nernstian response in the potassium concentration range between 10-5.9 M and 10-1 M of K+ ions and may be applied in the pH range between 2 and 10.5.

High Capacity Nanocomposite Layers Based on Nanoparticles of Carbon Materials and Ruthenium Dioxide for Potassium Sensitive Electrode.

This work presents the new concept of designing ion-selective electrodes based on the use of new composite materials consisting of carbon nanomaterials and ruthenium dioxide. Using two different materials varying in microstructure and properties, we could obtain one material for the mediation layer that adopted features coming of both components. Ruthenium dioxide characterized by high electrical capacity and mixed electronic-ionic transduction and nano-metric carbon materials were reportedly proved to improve the properties of ion-selective electrodes. Initially, only the materials and then the final electrodes were tested in the scope of the presented work, using scanning and transmission electron microscope, contact angle microscope, and various electrochemical techniques, including electrochemical impedance spectroscopy and chronopotentiometry. The obtained results confirmed beneficial influence of the designed nanocomposites on the ion-selective electrodes' properties. Nanosized structure, high capacity (characterized by the electrical capacitance value from approximately 5.5 mF for GR + RuO2 and CB + RuO2, up to 14 mF for NT + RuO2) and low hydrophilicity (represented by the contact angle from 60° for GR+RuO2, 80° for CB+RuO2, and up to 100° for NT + RuO2) of the mediation layer materials, allowed us to obtain water layer-free potassium-selective electrodes, characterized by rapid and stable potentiometric response in a wide range of concentrations-from 10-1 to 10-6 M K+.

Potassium-Selective Solid-Contact Electrode with High-Capacitance Hydrous Iridium Dioxide in the Transduction Layer.

This work presents new material for solid-contact layers-hydrous iridium dioxide IrO2·2H2O, characterized by high electrical capacitance value, evaluated using chronopotentiometry (1.22 mF) and electrochemical impedance spectroscopy (1.57 mF). The remarkable electrical parameters of layers resulted in great analytical parameters of IrO2·2H2O-contacted potassium-selective electrodes. Various parameters of ion-selective electrodes were examined in the scope of this work using a potentiometry method including: linear range, repeatability, stability of potentiometric response and sensitivity to varying measurement conditions. The analytical parameters obtained for solid-contact electrodes were compared with the ones obtained for coated disc electrodes to evaluate the influence of the iridium dioxide layer. The linear range of the IrO2·2H2O-contacted K+-selective electrodes covered concentrations of K+ ions from 10-6 to 10-1 M and the potential stability was estimated at 0.097 mV/h. The IrO2·2H2O-contacted electrodes turned out to be insensitive to varying light exposure and changes in the pH values of measured solutions (in the pH range of 2 to 10.5). A water layer test proved that, contrary to the coated disc electrode, the substantial water film is not formed between the ion-selective membrane and iridium dioxide layer.

Potentiometric Sensor with High Capacity Composite Composed of Ruthenium Dioxide and Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate.

This work presents the first-time application of the ruthenium dioxide-poly(3,4-ethylenedioxythiophene) polystyrene sulfonate high-capacity composite material as a mediation layer in potassium selective electrodes, which turned out to significantly enhance the electrical and analytical parameters of the electrodes. The idea was to combine the properties of two different types of materials: a conducting polymer, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, and a metal oxide, ruthenium dioxide, in order to obtain the material for a solid-contact layer of great electrical and physicochemical parameters. The preparation method for composite material proposed in this work is fast and easy. The mediation layer material was examined using a scanning electron microscope and chronopotentiometry in order to confirm that all requirements for mediation layers materials were fulfilled. Ruthenium dioxide-poly(3,4-ethylenedioxythiophene) polystyrene sulfonate nancomposite material turned out to exhibit remarkably high electrical capacitance (of approximately 17.5 mF), which ensured great performance of designed K+-selective sensors. Electrodes of electrical capacity equal to 7.2 mF turned out to exhibit fast and stable (with only 0.077 mV potential change per hour) potentiometric responses in the wide range of potassium ion concentrations (10-6 M to 10-1 M). The electrical capacity of ruthenium dioxide-poly(3,4-ethylenedioxythiophene) polystyrene sulfonate-contacted electrodes characterized by electrical capacitance parameters was the highest reported so far for this type of sensor.

Optimization of Ruthenium Dioxide Solid Contact in Ion-Selective Electrodes.

Ruthenium dioxide occurs in two morphologically varied structures: anhydrous and hydrous form; both of them were studied in the scope of this work and applied as mediation layers in ion-selective electrodes. The differences between the electrochemical properties of those two materials underlie their diverse structure and hydration properties, which was demonstrated in the paper. One of the main differences is the occurrence of structural water in RuO2•xH2O, which creates a large inner surface available for ion transport and was shown to be a favorable feature in the context of designing potentiometric sensors. Both materials were examined with SEM microscope, X-ray diffractometer, and contact angle microscope, and the results revealed that the hydrous form can be characterized as a porous structure with a smaller crystallite size and more hydrophobic properties contrary to the anhydrous form. Potentiometric and electrochemical tests carried out on designed GCD/RuO2/K+-ISM and GCD/RuO2•xH2O/K+-ISM electrodes proved that the loose porous microstructure with chemically bounded water, which is characteristic for the hydrous form, ensures the high electrical capacitance of electrodes (up to 1.2 mF) with consequently more stable potential (with the potential drift of 0.0015 mV/h) and a faster response (of a few seconds).

Ruthenium dioxide nanoparticles as a high-capacity transducer in solid-contact polymer membrane-based pH-selective electrodes.

A new approach is presented for the design of ion selective electrodes. Ruthenium dioxide nanoparticles were incorporated into solid-contact electrodes, and their properties were studied for the case of pH-selective electrodes. The use of the RuO2 is shown to significantly improve the potentiometric response, while no redox response is observed. The use of RuO2 results in a Nernstian slope (59 mV/decade) towards hydrogen ions over a wide linear range (pH 2 to 12). The results obtained by chronopotentiometry reveal small resistance, and the capacitance is as high as 1.12 mF. This results in a good stability of the response and in a low potential drift (0.89 µV∙s-1). The electrodes exhibit properties nearly as excellent as those of a glass electrode, but they are much smaller, less fragile, and easy to use. Graphical abstractSchematic representation of the construction of the new kind of electrodes along with calibration and chronopotentiometric plots compared to non-modified GCD/H+-ISM and modified GCD/RuO2/H+-ISM electrodes, respectively. The use of ruthenium dioxide results in a wide analytical pH range (2-12) and in high electrical capacitance (1.12 mF).