dynamic-electrochemical-measurement-of-chloride-ions

Dynamic Electrochemical Measurement of Chloride Ions

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver ...

University of Twente

Ion selective electrodes (ISE) are used extensively for the potentiometric determination of ion concentrations in electrolytes. However, the inherent drift in these measurements and the requirement of a stable reference electrode restrict the feasibility of this method for long-term in-situ applications. This work presents a chronopotentiometric approach to minimize drift and avoid the use of a conventional reference electrode for measuring chloride ion concentration. An anodic current pulse is applied to a Ag/AgCl working electrode which initiates a faradaic reaction that depletes the chloride ions near the electrode surface. The rate of change in potential at the Ag/AgCl electrode, due to chloride ion depletion, reaches an inflection point once the chloride ions deplete completely near the electrode surface. The moment of the inflection point, also known as the transition time, is a function of the chloride ion concentration and is described by the Sand equation. It is shown that the square root of the transition time is linearly proportional to the chloride ion concentration. Drift in the response over two weeks is negligible: 59 μM/day when measuring 1 mM of Cl(-) ions using a 10 A m(-2) current pulse. The transition time at a specific ion concentration can be tuned by the applied current pulse, e.g., in a solution containing 5 mM chloride ions, the transition times with current pulses of 10 and 20 A m(-2) are 1.56 and 0.25s, respectively. The moment of inflection determines the response, and thus is independent of the absolute potential of reference electrode. Therefore, any metal wire can act as a pseudo-reference electrode, enabling this approach for long-term and integrated-sensor applications such as measurement inside concrete structures.

No more conventional reference electrode: transition time for determining chloride ion concentration.

The fabrication of 3 x 3 crossbar arrays measuring 20 μm in width was demonstrated. The bipolar resistive switching characteristics in manganese oxide nanoparticles were investigated in the crossbar structure of top electrode (Au)/nanoparticle assembly/bottom electrode (Ti) on SiO2/Si substrate. The monodisperse manganese oxide nanoparticles measuring 13 nm in diameter were chemically synthesized by thermal decomposition of manganese acetate in the presence of oleic acid at high temperature. The nanoparticles were assembled as a layer measuring 30 nm thick by repeated dip-coating and annealing steps. The Au/nanoparticle assembly/Ti devices performed the bipolar behavior associated with the formation and sequential rupture of multiple conducting filaments in applying bias on Au electrode. When the voltage was swept from to +5 V to the Au top electrode, the reset voltage was observed at - 4.4 V. As the applied voltage swept from 0 to -5 V, the set voltage occurred at (-) -1.8 V.

Resistive switching characteristics of manganese oxide nanoparticle assembly with crossbar arrays.

Chloride is a crucial anion for various analytical applications from biological to environmental applications. In order to measure the chloride ion concentration, a measurement system is needed which can detect this concentration for prolonged times reliably. Chronopotentiometry is a technique which does not need a long term stable reference electrode and is therefore very suitable for prolonged ion concentration measurements. As the used electrode might be fouled by reaction products, this work focuses on a chronopotentiometric approach with a separated sensing electrode (sensor) and actuating electrode (actuator). Both actuation and sensor electrode are made of Ag/AgCl. A constant current is applied to the actuator and will start the reaction between Ag and Cl-, while the resulting Cl- ion concentration change is observed through the sensor, which is placed close to the actuator. The time it takes to locally deplete the Cl- ions is called transition time. Experiments were performed to verify the feasibility of this approach. The performed experiments show that the sensor detects the local concentration changes resulting from the current applied to the actuator. A linear relation between the Cl- ion concentration and the square root of the transition time was observed, just as was predicted by theory. The calibration curves for different chips showed that both a larger sensor and a larger distance between sensor and actuator resulted in a larger time delay between the transition time detected at the actuator and the sensor.

Sensor-actuator system for dynamic chloride ion determination.

To investigate the nature of the switching phenomenon at the metal-tantalum oxide interface, we fabricated a memory device in which a tantalum oxide amorphous layer acted as a switching medium. Different metals were deposited on top of the tantalum oxide layer to ensure that they will react with some of the oxygen contents already present in the amorphous layer of the tantalum oxide. This will cause the formation of metal oxide (MOx) at the interface. Two devices with Ti and Cu as the top electrodes were fabricated for this purpose. Both devices showed bipolar switching characteristics. The SET and RESET voltages for the Ti top electrode device were ~+1.7 V and ~-2 V, respectively, whereas the SET and RESET voltages for the Cu top electrode device were ~+0.9 V and ~-0.9 V, respectively. In the high-resistance state (HRS) conduction, the mechanisms involved in the devices with Ti and Cu top electrodes were space-charge limited conduction (SCLC) and ohmic, respectively. On the other hand, in the low-resistance state (LRS), the Ti top electrode device undergoes SCLC at a high voltage and ohmic conduction at a low voltage, and the Cu top electrode again undergoes ohmic conduction. From the consecutive sweep cycles, it was observed that the SET voltage gradually decreased with the sweeps for the Cu top electrode device, whereas for the Ti top electrode device, the set voltage did not vary with the sweeps.

Investigation of Switching Phenomenon in Metal-Tantalum Oxide Interface.

The fabrication of hybrid structure with TiO2 nanoparticle assembly and Ta2O5 thin film layer was demonstrated. The close-packed nanoparticles could influence the resistive switching behaviors due to the huge numbers of interface states and vacancies in the nanoparticle assembly. The device with hybrid structure presented the typical bipolar resistive switching characteristics in the structure of Ti/TiO2/Ta2O5/Au on SiO2/Si substrate. The set voltage was observed at -0.7 V, and the reset voltage occurred at (-)-0.7 V, which was smaller than that of Ta2O5 layer only. The electrical conduction mechanisms were the ohmic conduction at low resistance state (LRS) and the space charge limited conduction at high resistance state (HRS), respectively. The devices showed stable current ratio of LRS to HRS. The temperature dependent properties of the devices were also investigated. The device with nanoparticle assembly showed better electrical characteristics with low HRS current level and stable LRS current level with respect to the temperature.

Article	Year
No more conventional reference electrode: transition time for determining chloride ion concentration. Analytica chimica acta\| PubMed ID: 24703217	2014
Resistive switching characteristics of manganese oxide nanoparticle assembly with crossbar arrays. Journal of nanoscience and nanotechnology\| PubMed ID: 25958496	2014
Sensor-actuator system for dynamic chloride ion determination. Analytica chimica acta\| PubMed ID: 26320957	2015
Investigation of Switching Phenomenon in Metal-Tantalum Oxide Interface. Journal of nanoscience and nanotechnology\| PubMed ID: 26726372	2015
Resistive Switching Characteristics of Tantalum Oxide Thin Film and Titanium Oxide Nanoparticles Hybrid Structure. Journal of nanoscience and nanotechnology\| PubMed ID: 26726561	2015

Yawar Abbas

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