Potassium-selective Membrane Research Articles

Toward circular greenhouse wastewater reuse: advancements in cation exchange membranes for selective Na+/K+ separation using electrodialysis systems

ABSTRACT Driven by the growing need for alternative water sources and forthcoming stringent nutrient discharge regulations, there is growing interest in developing selective membrane solutions to facilitate circular greenhouse wastewater reuse (as emphasized in the European Union's Horizon 2020 ULTIMATE project). For electrodialysis systems, sodium (Na+) over potassium (K+) selective membranes are essential to achieve minimal liquid discharge. This study addresses the challenge of developing selective, efficient, and scalable Na+/K+ cation exchange membranes. State-of-the-art cation exchange membrane developments were reviewed and the functionalization of commercial membranes with crown ethers was identified as a promising approach. Two crown ether–modified membranes (15-crown-5 (15C5) and 18-crown-6 (18C6)) were developed, characterized, and tested in equimolar and greenhouse wastewater binary feed ratios. While the results demonstrated low overall selectivity, the 15C5-modified membrane showed a marginal enhancement in K+ selectivity, suggesting the need for further optimization. The study concludes with recommendations for the future development of Na+/K+ selective membranes, highlighting the potential of machine learning approaches to expedite progress. This research provides a foundational step toward practical and scalable Na+/K+ ion separation solutions, for achieving minimal liquid discharge in greenhouse horticulture.

Insights into solid-contact ion-selective electrodes based on laser-induced graphene: Key performance parameters for long-term and continuous measurements.

This work aims to serve as a comprehensive guide to properly characterize solid-contact ion-selective electrodes (SC-ISEs) for long-term use as they advance toward calibration-free sensors. The lack of well-defined SC-ISE performance criteria limits the ability to compare results and track progress in the field. Laser-induced graphene (LIG) is a rapid and scalable method that, by adjusting the CO2 laser parameters, can create LIG substrates with tunable surface properties, including wettability, surface chemistry, and morphology. Herein, we fabricate laser-induced graphene (LIG) solid-contact electrodes using different laser settings and subsequently convert them into ion-selective sensors using a potassium-selective membrane. We measure the aforementioned tunable surface properties and correlate them with resultant low-frequency capacitance and water layer formation in an effort to pinpoint their effects on the sensitivity (Nernstian response), reproducibility (E°' variation), and potential stability of the LIG-based SC-ISEs. More specifically, we demonstrate that the surface wettability of the LIG substrate, which can be tuned by controlling the lasing parameters, can be modified to exhibit hydrophobic (contact angle > 90°) and even highly hydrophobic surfaces (contact angle ≈ 130°) to help reduce sensor drift. Recommendations are also provided to ensure proper and robust characterization of SC-ISEs for long-term and continuous measurements. Ultimately, we believe that a comprehensive understanding of the correlation between LIG tunable surface properties and SC-ISE performance can be used to improve the electrochemical behavior and stability of SC-ISEs designed with a wide range of materials beyond LIG.

High-Performance Potassium-Selective Biosensor Platform Based on Resistive Coupling of a-IGZO Coplanar-Gate Thin-Film Transistor.

The potassium (K+) ion is an essential mineral for balancing body fluids and electrolytes in biological systems and regulating bodily function. It is associated with various disorders. Given that it exists at a low concentration in the human body and should be maintained at a precisely stable level, the development of highly efficient potassium-selective sensors is attracting considerable interest in the healthcare field. Herein, we developed a high-performance, potassium-selective field-effect transistor-type biosensor platform based on an amorphous indium gallium zinc oxide coplanar-gate thin-film transistor using a resistive coupling effect with an extended gate containing a potassium-selective membrane. The proposed sensor can detect potassium in KCl solutions with a high sensitivity of 51.9 mV/dec while showing a low sensitivity of <6.6 mV/dec for NaCl, CaCl2, and pH buffer solutions, indicating its high selectivity to potassium. Self-amplification through the resistive-coupling effect enabled an even greater potassium sensitivity of 597.1 mV/dec. Additionally, we ensured the stability and reliability of short- and long-term detection through the assessment of non-ideal behaviors, including hysteresis and drift effects. Therefore, the proposed potassium-sensitive biosensor platform is applicable to high-performance detection in a living body, with high sensitivity and selectivity for potassium.

Spectroelectrochemistry with Ultrathin Ion-Selective Membranes: Three Distinct Ranges for Analytical Sensing.

We present spectroelectrochemical sensing of the potassium ion (K+) at three very distinct analytical ranges—nanomolar, micromolar, and millimolar—when using the same ion-selective electrode (ISE) but interrogated under various regimes. The ISE is conceived in the all-solid-state format: an ITO glass modified with the conducting polymer poly(3-octylethiophene) (POT) and an ultrathin potassium-selective membrane. The experimental setup is designed to apply a potential in a three-electrode electrochemical cell with the ISE as the working electrode, while dynamic spectral changes in the POT film are simultaneously registered. The POT film is gradually oxidized to POT+, and this process is ultimately linked to K+ transfer at the membrane-sample interface, attending to electroneutrality requirements. The spectroelectrochemistry experiment provides two signals: a voltammetric peak and a transient absorbance response, with the latter of special interest because of its correspondence with the generated charge in the POT and thus with the ionic charge expelled from the membrane. By modifying how the ion analyte (K+ but also others) is initially accumulated into the membrane, we found three ranges of response for the absorbance: 10–950 nM for an accumulation-stripping protocol, 0.5–10 μM in diffusion-controlled cyclic voltammetry, and 0.5–32 mM with thin-layer cyclic voltammetry. This wide response range is a unique feature, one that is rare to find for a sensor and indeed for any analytical technique. Accordingly, the developed sensor is highly appealing for many analytical applications, especially considering the versatility of samples and ion analytes that may be spotted.

Selective Ion Capturing via Carbon Nanotubes Charging.

We present a phenomenon consisting of the synergistic effects of a capacitive material, such as carbon nanotubes (CNTs), and an ion-selective, thin-layer membrane. CNTs can trigger a charge disbalance and propagate this effect into a thin-layer membrane domain under mildly polarization conditions. With the exceptional selectivity and the fast establishment of new concentration profiles provided by the thin-layer membrane, a selective ion capture from the solution is expected, which is necessarily linked to the charge generation on the CNTs lattice. As a proof-of-concept, we investigated an arrangement based on a layer of CNTs modified with a nanometer-sized, potassium-selective membrane to conform an actuator that is in contact with a thin-layer aqueous solution (thickness of 50 μm). The potassium ion content was fixed in the solution (0.1–10 mM range), and the system was operated for 120 s at −400 mV (with respect to the open circuit potential). A 10-fold decrease from the initial potassium concentration in the thin-layer solution was detected through either a potentiometric potassium-selective sensor or an optode confronted to the actuator system. This work is significant, because it provides empirical evidence for interconnected charge transfer processes in CNT–membrane systems (actuators) that result in controlled ion uptake from the solution, which is monitored by a sensor. One potential application of this concept is the removal of ionic interferences in a sample by means of the actuator to enhance precision of analytical assessments of a charged or neutral target in the sample with the sensor.

Tuned ionophore-based bi-membranes for selective transport of target ions

Bi-membranes were developed and studied as selective barrier in the transport of calcium and potassium. The bi-membranes consisted of an ion-selective membrane and a conducting polymer (polypyrrole) membrane. The ion-selective membrane acted as a selective barrier for ions while the conducting polymer acted as an electrochemically controlled barrier. The thickness of the membrane was tuned in order to obtain the best membrane transport properties. Owning to the presence of the ion-selective membrane the bi-membranes demonstrated permselectivity and selectivity towards the studied target ions. In this particular investigation NO3− was also transported with the cations across the bi-membranes. The calcium-selective membrane showed higher transport of nitrate than potassium-selective membrane. The potentiometric investigation of both membranes revealed that at high ion concentrations using this type of electrochemical system, as in bi-membranes, the co-extraction of anion together with cation into the ion-selective membrane took place. The ion couple was transported across the membrane into the receiving solution.

Instrument-free control of the standard potential of potentiometric solid-contact ion-selective electrodes by short-circuiting with a conventional reference electrode.

A simple, instrument-free method to control the standard potential (E°) of potentiometric solid-contact ion-selective electrodes (SC-ISE) is described. In this method, the electrode potential of a SC-ISE is reset by short-circuiting the electrode with a metallic wire to a conventional Ag/AgCl/3 M KCl reference electrode (RE) in a solution containing primary ions. The method is studied experimentally for SC-ISEs where the conducting polymer poly(3,4-ethylenedioxythiophene) doped with the bulky anion poly(sodium 4-styrenesulfonate), PEDOT(PSS), is used as the solid contact. Three different types of ion-selective membranes (ISMs) are studied: two potassium-selective membranes, with and without the lipohilic additive tetradodecylammonium tetrakis(4-chlorophenyl)borate (ETH-500) and a cation-sensitive membrane without an ionophore. When the SC-ISE is short-circuited with the RE, the PEDOT(PSS) layer is oxidized or reduced, thereby shifting the potential of the SC-ISE to the proximity of the potential of the RE so that the potential difference between these two electrodes becomes zero or close to zero. The slope of the calibration curve is preserved after the short-circuit treatment of the SC-ISEs. The short-circuiting method is an important step toward calibration-free potentiometric analysis.

Electrochemical control of the standard potential of solid-contact ion-selective electrodes having a conducting polymer as ion-to-electron transducer

This work addresses the well-known problem of variations in the standard potential (E°) of solid-contact ion-selective electrodes (SC-ISEs) that have a conducting polymer (CP) as ion-to-electron transducer covered by a polymeric ion-selective membrane. Poly(3,4-ethylene dioxythiophene) doped with poly(sodium 4-styrenesulfonate), i.e. PEDOT(PSS), was electrodeposited on glassy carbon (GC) disk electrodes and used as the solid contact for three different types of PVC-based membranes in order to elucidate the possibility to electrochemically control E° for this type of SC-ISE. The GC/PEDOT(PSS) electrode was thus coated with potassium-selective membranes with and without the lipophilic salt tetradocedylammonium tetrakis(4-clorophenyl)borate (ETH-500) and by a cation-sensitive membrane without ionophore. The results show that the standard potential of the studied types of SC-ISEs can be shifted by applying a potential that deviates from the open-circuit potential of the electrode in the chosen electrolyte solution or by applying current pulses in the nA range.

Detection Limits of Thin Layer Coulometry with Ionophore Based Ion-Selective Membranes

We report here on a significant improvement in lowering the low detection limit of thin layer coulometric sensors based on liquid ion-selective membranes, using a potassium-selective system as a model example. Various possible processes that may result in an elevated residual current reading after electrolysis were eliminated. Self-dissolution of AgCl on the Ag/AgCl inner element may result in a residual ion flux that could adversely affect the lower detection limit. It was here replaced with an Ag/AgI inner pseudoreference electrode where the self-dissolution equilibrium is largely suppressed. Possible residual currents originating from a direct contact between inner element and ion-selective membranes were eliminated by introducing an inert PVDF separator of 50 μm diameter that was coiled around the inner element by a custom-made instrument. Finally, the influence of electrolyte fluxes from the outer solution across the membrane into the sample was evaluated by altering its lipophilic nature and reducing its concentration. It was found that this last effect is most likely responsible for the observed residual current for the potassium-selective membranes studied here. For the optimized conditions, the calibration curves demonstrated a near zero intercept, thereby paving the way to the coulometric calibration-free sensing of ionic species. A linear calibration curve for the coulometric cell with valinomycin potassium-selective membrane was obtained in the range of 100 nM to 10 μM potassium in the presence of a 10 μM sodium background. In the presence of a higher (100 μM) concentration of sodium, a reliable detection of 1-100 μM of potassium was achieved.

Development and application of a fluorescent sensor for potassium ions based on a calix[6]arene ionophore and a novel cationic dye

A plasticised poly(vinyl chloride) optode membrane incorporated with a calix[6]arene hexaester, a H+-selective chromoionophore (3,3′,5,5′-tetramethyl-N,N-dibenzylbenzidine, a novel synthetic cationic dye) and a lipophilic potassium tetrakis(4-chlorophenyl)borate was used as a sensing device for the indirect optical determination of potassium ions. It exhibited a reversible response to the potassium ion in 0.05 mol/l HCl buffer media in the concentration range from 1 × 10− 6 to 1 × 10− 2 mol/l. The linear range was from 1.53 × 10− 5 to 3.20 × 10− 3 mol/l. The proposed optode sensor exhibited a fast response of less than 1 min, good repeatability (n = 7, RSD = 3.62%) at 5 × 10− 5 mol/l, and long-term stability with 92% of its initial sensitivity after 1 month of storage. The selectivity of the potassium-selective membrane allows its application for the detection of the potassium concentration in real sample analysis. The result was satisfactory compared with atomic absorption spectrometry.

Microelectrode array fabricated in low temperature cofired ceramic (LTCC) technology

This work presents the development of a novel construction of an integrated microelectrode array. The device was fabricated on a ceramic support, with the use of low temperature cofired ceramics technology. Model potassium-selective membranes were applied on the surface of PdAg/AgCl electrodes formed on the ceramic substrate. The obtained microsensors exhibited very good repeatability, reproducibility, and sensitivity. The array of microelectrodes covered with polymeric layers of various selectivities was applied as an electronic tongue to differentiate between various diet supplements.

Thermodynamic investigation of KCl in the ternary KCl/LiCl/ H 2 O mixed electrolyte system based on potentiometric method

The results of a thermodynamic investigation of KCl salt in the ternary KCl+LiCl+H 2O electrolyte system by potentiometric method are reported in this work. The experimental potentiometric data were obtained from a galvanic cell by combining a solvent polymeric (PVC) potassium-selective membrane electrode (K + ISE), containing Valinomycin as ionophore, and an Ag/AgCl electrode. The measurements were performed, at similar constant ionic strengths, in different series of mixed salt solutions, each characterized by a fixed salt molal ratio r (where r = m 1 / m 2 = 0.1 , 0.2 , 1 , 5 , 10 , and m 1 , m 2 are the molalities of KCl and LiCl, respectively). The non-ideal behaviour of the system was described on the base of the Pitzer ion-interaction model for mixed salts, over the ionic strength ranging from 0.01 up to about 5 mol/kg, at 298.15 K. Based on the obtained Pitzer ion-interaction parameters, the osmotic coefficients, solvent activities, and excess Gibbs free energies were determined for these investigated ternary electrolyte systems.

Planar potentiometric sensors based on Au and Ag microelectrodes and conducting polymers for flow-cell analysis

Back-side contact Au and Ag microelectrodes were used as transducers to construct planar all-solid-state electrodes suitable for flow-through analysis. The microsensors were based on plasticized PVC potassium-selective membranes containing ion-electron conducting polymer—polypyrrole doped with di(2-ethylhexyl) sulfosuccinate. The proposed technique allowed simple construction of microsensors in one step, by membrane solution casting directly on the surface of the planar metallic transducers. The performance of the microsensors based on Au and Ag transducers were determined and compared with planar sensors based on internal electrolyte immobilized in polyHEMA. The addition of the polypyrrole to the membrane composition did not influence on the selectivity, reproducibility and long-term stability of the microsensors but improved their standard potential stability in time in comparison with coated-wire type sensors. Moreover, all-solid-state microsensors based on Au transducers exhibited better signal stability than Ag based sensors.

Protein adsorption to planar electrochemical sensors and sensor materials

Abstract In electrochemical sensing devices, aimed for acute and chronic in vivo application, the active surface of the sensor is often negligible compared to the overall surface area of the device in contact with the biological host. Consequently, to minimize the perturbation of an implanted sensor on the in vivo environment the chemical composition and surface texturing of the complete device (the active sensor, sensor substrate, and “accessories”) have to be considered. In our work, the adsorption of three abundant proteins (albumin, IgG, and fibrinogen) was determined quantitatively on untreated and modified sensor substrates and sensing membrane surfaces. In this study, a flexible polyimide-based material (Kapton ®) was used as sensor substrate with or without an amorphous diamond-like carbon (DLC) or an amorphous oxygen-containing DLC (o-DLC) coating. The ion-sensitive membranes were cast from high-molecular-weight (HMW) or carboxylated poly(vinyl chloride) (PVC) and were doped with increasing concentrations of highly hydrophilic poly(ethylene oxide) (PEO). The potentiometric characteristics of the potassium-selective membranes cast with up to 6 % PEO were the same as those without PEO. However, the PEO-modified PVC membranes elicited a large amount of protein adsorption, especially in terms of albumin.

Miniaturized back-side contact transducer for potentiometric sensors

A novel type of a miniature transducer for potentiometric sensors was designed and tested. The transducer is made from an ordinary printed circuit board using a typical technology. As a result, a back-side contact structure was obtained, which can be mounted in flow systems. The advantage of the fabrication process is its cheapness and flexibility in designing modified structures. The measurement properties of the transducer were tested as a chloride sensor. Then the structure was covered with polyHEMA and a potassium-selective membrane and tested as a potassium sensor. The performance and the long-term stability of the sensors with plasticized PVC and Siloprene based potassium-selective membranes were compared.

Towards reversibility of ion transfer across the interface between valinomycin membranes and aqueous electrolyte solutions

Valinomycin-based potassium-selective membranes doped with potassium tetrakis(4-chlorophenyl)borate (KClTPB) or sodium tetrakis(4-fluorophenyl)borate (NaFTPB) are studied in KCl, NaCl, and CaCl2 solutions by potentiometric and electrochemical impedance methods. Before contact with KCl, membranes doped with NaFTPB provide Nernstian potentiometric response to Na+ ions, which is lost after conditioning the membranes in KCl. The membranes doped with KClTPB even before contact with KCl give no Nernstian response to Na+ ions. In CaCl2 solutions, none of the membranes provide a regular potentiometric response. Despite the difference in potentiometric behavior, the impedance spectra of the membranes are very similar in all solutions regardless of prior conditioning of the membranes. No evidence for a hindrance towards charge transfer processes is observed. The results suggest that the membrane/solution interface is reversible for interfering ions as well as for potassium, and the contamination of solutions with the latter is the sole reason for the lack of Nernstian response in the interfering electrolytes.

Potassium-Selective Membrane Sensors Based on Two Recently Synthesized Poly( oxyethylene) Derivatives *

Two poly(oxyethylene) derivatives 1,1O-bis(2'-benzoic acid)-1,4,7,1O-tetradecane (Ll) and 1,7-bis(2'-benzoic acid)-1,4,7-trioxaheptane(L2) were used as suitable ionophoresfor the preparation ofpotassium-selective PVC-membraneelectrodes. The resulting electrodes based on L1 and L2 exhibit linear responses to the activity of K ions within the concentration ranges of 3.1 x 10'5-2.7 x 10'2 M and 2.0 x 10'5-7.3X 10'2M with the slopes of 61.8 and 62.6 mV per decade, respectively. The electrodes show relativelyfast response times of 25-30 s and can be usedfor at least 3 months without any considerable divergence in potential. The working pH range of the electrodes is 3-11. The selectivity coefficients of the electrodes for potential interfering cations including alkali, alkaline earth and transition metal ions are reported.

Improved potassium-selective membrane using valinomycin as ionophore for ion-selective microdevices

Ion-selective field effect transistors (ISFETs) were tested for their suitability for clinical work. They were intended for use in the analysis of blood and serum, where the concentration of specific ions, e.g. sodium and potassium, is of critical importance. The optical sensitivity of ISFETs and a new membrane composition for use in the clinical chemistry were evaluated. ISFETs with a polyimide/valinomycin membrane were shown to operate satisfactorily in the presence of proteins, encouraging the further development of these ISFETs as clinical sensors. ETH 2041 (tetra- n-undecyl 3,3′, 4,4′–benzophenone tetracarboxylate) and DGD (diethylene dibenzoate) were the plasticizers used and their performances were compared. Valinomycin was used as ionophore. The membranes were calibrated using the dip (solutions in the 10 −1–10 −5 mol dm −3 KCl range) and the constant volume dilution methods. Both membrane compositions gave good Nernstian responses. The ETH 2041 plasticizer was found to yield devices more selective to potassium ion than the more easily usable DGD.

A chronoamperometric method to estimate changes in the membrane composition of ion-selective membranes.

A new chronoamperometric method is used to estimate changes in the membrane composition of mobile-site, ionophore-based membranes. The characteristic features of the chronoamperometric curves (initial current, slope, break time) of valinomycin-based, potassium-selective membranes loaded with potassium tetrakis(4-chlorophenyl)borate are correlated with the mobile-site and free ionophore concentration in the membrane. limiting cases for strong and negligible ion pair formation are distinguished. Replicate measurements indicate a relative standard deviation in the calculated values less than 10%. The practical applicability of the method was tested with membranes incorporated into conventional ion-selective electrode bodies or cast onto microfabricated planar sensor structures.

Potassium-selective conductometric sensor

Potassium-selective membranes known as sensing modules for potentiometric ion-selective electrodes are studied in ac-impedance mode. It is shown that the bulk resistance of thin (20–250 μm) membranes depends on the composition of aqueous bathing solution. The results are explained in terms of surface conductivity in space-charge region, in the vicinity of water microdroplets in membranes. A planar potassium-selective sensor with a conductometric signal is proposed.