The world of sensors is diverse and is advancing at a rapid pace due to the fact of its high demand and constant technological improvements. Electrochemical sensors provide a low-cost and convenient solution for the detection of variable analytes and are widely utilized in agriculture, food, and oil industries as well as in environmental and biomedical applications. The popularity of electrochemical sensing stems from two main advantages: the variability of the reporting signals, such as the voltage, current, overall power output, or electrochemical impedance, and the low theoretical detection limits that originate from the differences in the Faradaic and nonFaradaic currents. This review article attempts to cover the latest advances and applications of electrochemical sensors in different industries. The role of nanomaterials in electrochemical sensor research and advancements is also examined. We believe the information presented here will encourage further efforts on the understanding and progress of electrochemical sensors.

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Electrochemical Sensors and Their Applications: A Review

From environmental monitoring to point-of-care biofluid analysis, rapid ion determination requires robust analytical tools. In recent years, driven by the development of materials science and processing technology, solid-contact ion-selective electrodes (SC-ISEs) with high-performance functional materials and creative structures have shown great potential for routine and portable ion detection. In particular, the introduction of nanomaterials as ion-to-electron transducers and the adoption of different performance enhancement strategies have significantly promoted the development of SC-ISEs. Besides, with the increasing miniaturization, flexibility, and dependability of SC-ISEs, this field has gradually begun to evolve from conventional potentiometric ion sensing to integrated sensing systems with broader application scenarios. This comprehensive review covers pioneering research on functional materials and state-of-the-art technologies for the construction of SC-ISEs, with an emphasis on new development trends and applications.

Recent advances in solid-contact ion-selective electrodes: functional materials, transduction mechanisms, and development trends.

After a long history and conflicting views, solid-contact (SC) solvent polymeric membrane ion-selective electrodes (ISEs) emerged as reliable potentometric-sensing devices with unique advantages. From the large variety of proposed SCs inherently conductive polymers emerged as the materials of choice. In our view, the most attractive feature of SC ISEs is their compatibility with thin- and thick-film microfabrication technologies that can provide cheap, mass-produced sensors and sensor arrays that can be integrated with the measuring, data acquisition, and control electronics in a straightforward way. However, despite the impressive properties of certain SC electrodes and their potential advantages, they remained primarily in the research laboratories. To make the jump from the research laboratories into commercial devices, it would be essential to prove that miniaturized SC ISEs can indeed match or surpass the performance characteristics of the conventional, liquid-contact macroelectrodes. In addition, it would be important to settle on the quality control criteria and testing protocols for assessing the performance characteristics of SC electrodes. It could help in interpreting the sometimes-inconsistent experimental data. Once cheap, miniaturized, SC ISEs will mach the performance characteristics of macroscopic-size electrodes, it is expected to have an important impact in a variety of applications requiring robust, maintenance-free, or single-use ISEs, e.g., in homecare or bedside diagnostics, environmental analysis, and quality control assessment. In addition, reliable SC ISEs are expected to revitalize the field of ion-selective field effect transistors and open new possibilities in combination with nanowire-based devices.

Quality control criteria for solid-contact, solvent polymeric membrane ion-selective electrodes

For certain ionophores of extremely high lipophilicity, kinetic limitations of the carrier-induced ion transfer between aqueous and membrane phase may heavily disturb the electromotive behaviour of the ion-selective membrane electrode. These limitations may be overcome by adding tetraphenylborates to the membrane phase. Membranes prepared with different 3,6-dioxaoctanediamide homologues and potassium tetrakis (p-chlorophenyl) borate as phase-transfer catalyst all exhibit the same ion selectivity as well as theoretical electrode response. This behaviour is corroborated by a theoretical description of the ion-transfer process

Catalysis of Ion Transfer by Tetraphenylborates in Neutral Carrier-Based Ion-Selective Electrodes

Ion selective electrodes

On the basis of model calculations, a series of electrically neutral lipophilic molecules was designed and synthesized. These carrier ligands may be tailored to ion selectivities suitable for practical application as components in liquid-membrane electrodes selective for Ca2+, Ba2+, Li+ and Na+ respectively. Some of the selectivities observed are far superior to systems known to date. By incorporating these ligands in PVC membranes, lifetimes of more than one year may be obtained. Through a special treatment with lipophilic anions (e.g. tetraphenylborate), silver surfaces may be coated with thin layers of ligand-impregnated PVC to obtain metal contacted membrane electrodes of high e.m.f. stability. They are perfectly suited for use as components in flow-through and in miniaturized electrode systems.

Recent developments in the field of ion selective electrodes

The requirements for neutral complexing agents behaving as ion carriers (ionophores) in membranes of ion-selective electrodes are discussed. Emphasis is placed on the lipophilicity of such compounds, on the kinetics (free energy of activation) of the ligand exchange reaction, and on the parameters inducing selectivity, e.g., molecular structures and aspects of membrane technology.

Design and application of neutral carrier-based ion-selective electrodes. Plenary lecture

Lipophilic salts consisting of either lipophilic cations and hydrophilic anions or hydrophilic cations and lipophilic anions act in liquid membranes as anion exchangers and cation exchangers, respectively. A large number of corresponding membrane electrodes have been described in the literature (for reviews see [2, 4, 6]). A comparison of the ion selectivities obtained with a variety of different anion exchangers corroborates the theoretical prediction that the structure of the ion exchanger molecules involved should have only minor influences on the observable ion selectivities [2,4–7]. The selectivity sequences correlate nicely with the sequence of the free energies of hydration of the ions (cf. [4–5]).

Effects of Lipophilic Charged Sites on the Electromotive Behavior of Liquid Membrane Electrodes

Effect of the lipophilicity of 3,6-dioxaoctanedioic diamides on their behavior as ionophores

Ion transport induced by electrically charged ionophores in model membranes with magnesium and calcium selectivity

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