Ion Selectivity Research Articles

Molecular architecture of a novel indoline-fused chromenylium-cyanine probe carrying methionine biomolecule for ultrasensitive analyzing Hg2+ ion in real samples

In this study, by decorating the chromenylium-cyanine structure with an indoline ring, a new sensor platform CSI with a highly rigid structure and improved photophysical properties was developed for the first time. The CSI platform was modified with glyoxal and L-methionine methyl ester to produce a new NIR, ratiometric, and switch-on probe (CIME). This probe is biocompatible, water soluble, and has a specific binding mode for Hg2+ ion selectivity. The crystal structure of CSI was determined by x-ray crystallography, and its electronic characteristics, including HOMO-LUMO energy levels were determined by quantum mechanical calculations. CIME is the first instance of an indoline-fused chromenylium-cyanine used for quantification of trace level of Hg2+ in both the living cells and the environment. The new probe has a high level of selectivity and sensitivity for Hg2+ in aqueous media, with broad linear ranges (0–300 μM for UV-Vis and 0–225 μM for fluorescence). It has a rapid response time of 30 seconds, and UV-Vis and fluorescence detection limits of 7.4 ng/mL and 0.13 ng/mL, respectively. Probe quantitatively detected Hg2+ in real samples using UV-Vis, fluorescence spectrophotometry and a smartphone. The interaction between CIME and Hg2+ was verified by FTIR, HRMS and DFT calculations. Furthermore, the ability of CIME to sense Hg2+ in living cells was confirmed in both MCF-7 cells and 3T3 cells.

Anti‐Swelling 3D Nanohydrogel for Efficient Osmotic Energy Conversion

AbstractOsmotic energy conversion based on reverse electrodialysis (RED) technology has attracted intense attention. As the key component, the ion‐selective membranes should meet the basic requirements of high power density, high mechanical strength, and easy preparation. Polyelectrolyte hydrogel materials are good candidates, due to their high charge density. However, the severe swelling effect decreases the ion selectivity and mechanical strength. To solve this problem, an anti‐swelling 3D nanohydrogel is demonstrated, which is in situ polymerized in the nanoporous polyimide (PI) membrane, exhibiting ultrahigh power density in osmotic energy conversion. Because of the nano‐confinement of the PI matrix, the swelling ratio of the nanohydrogel decreases to 37.5% from 593.2% of the bulk hydrogel. Meanwhile, the hybrid membrane exhibits excellent mechanical strength (≈89.5 MPa). Under a 500‐fold concentration gradient, the nanohydrogel generates a power density of up to 48.5 W m−2, one order of magnitude higher than that of the bulk hydrogel. The anti‐swelling 3D nanohydrogel introduces a new concept in designing separation membranes for osmotic energy conversion.

An Optical Au3+ Sensor Based on layer-by-layer PEI/PAA-Rho thin Films on ITO.

This study presents the development of a sensitive and selective gold ion (Au3+) sensor utilizing layer-by-layer (LbL) assembled thin films composed of polyethylenimine (PEI) and poly (acrylic acid) (PAA) conjugated with rhodamine (Rho). The first study revealed that the polymeric sensors (PAA-Rho) demonstrated significant selectivity and sensitivity in their colorimetric and fluorescence responses to Au3+ compared to other metal ions. In their spirolactam form, the polymeric sensors were non-fluorescent but could selectively transform into the fluorescent ring-opened amide form upon interaction with Au3+ ions, resulting in fluorescence enhancement and observable color changes. Common co-existing metal ions showed negligible interference in the detection of Au3+. The LbL sensor exhibited a linear increase in absorbance with the addition of bilayers, confirming successful film deposition. Surface morphology analysis using SEM, along with structural confirmation via ATR-FTIR and XRD, further validated the sensor's capability to detect cation. Results demonstrated that the LbL sensor exhibited selectivity for Au3+ ions within the range 1 × 10-6 to 1 × 10-3 M. This approach offers an easily understandable and intrinsically sensitive means for detecting Au3+ ions in both environmental and biological applications.

Cationic Covalent Organic Framework-Modified Polypropylene Separator for High-Performance Lithium Metal Batteries.

As an important component of lithium batteries, the wettability and thermal stability of the separator play a significant role in cell performance. Despite the availability of numerous commercial separators, issues such as low ion selectivity and poor thermal stability continue to limit the efficiency and reliability of the batteries. Herein, two cationic covalent organic frameworks (Br-COF and TFSI-COF) with abundant imidazole cationic groups were designed to modify commercial polypropylene (PP) separators. The strong lithium-ion affinity of the cationic COF enables the effective dissociation of lithium salt ion clusters, simplifying the solvent structure of lithium ions to promote lithium ions transport. Additionally, solvent anions can be anchored to the cationic COF by electrostatic interactions, reducing side reactions on the lithium metal anode surface to form a favorable SEI layer, which can effectively inhibit the growth of lithium dendrites. The rapid dissociation of anions in lithium salts with some organic solvents and cationic COFs was revealed by a molecular dynamics simulation. A LiF-rich SEI layer on the lithium metal anode surface was formed, which can speed up Li+ transport at interfaces, leading to consistent lithium deposition and outstanding battery performance. The ordered porous structure of the cationic COF provides interconnected and continuous channels, improving the wettability between the liquid electrolyte and separators, which is conducive to ion transport. When paired with a LiFePO4 cathode and electrolyte (1.0 M LiTFSI in DEC: EC: DMC = 1:1:1), the LiFePO4/TFSI-COF@PP/Li cell demonstrates a prominent cycling capacity of 148.0 mAh g-1 at 0.5 C with a Coulombic efficiency of 98.0% in the first cycle, and the capacity retention is 82.0% after 100 cycles, showing good cycling stability. Thus, this investigation provides inspiration for the expansion of cationic COF-modified separators for next-generation lithium metal batteries.

Crown ether-functionalized nanofiltration membranes with high ions selectivity for Li+/Mg2+ separation

Extraction of lithium resources from salt lake brines is an effective method to solve the shortage of lithium resources nowadays. However, magnesium-lithium separation has become a critical issue for lithium extraction from salt lakes with high Mg2+/Li+ ratio, due to the similar ionic characteristics of Li+ (0.38 nm), and Mg2+ (0.43 nm). Herein, an amine monomer containing crown ether group (4′-aminobenzo-15-crown-5-ether (NH2–B15C5)) was introduced into the interfacial polymerization (IP) process of piperazine (PIP) and homotrimethylene tricarbonyl chloride (TMC) to prepare polyamide (PA) nanofiltration (NF) membranes with Li+ selective transport channels. NH2–B15C5 shows good compatibility and selective complexation to Li+, which acts as Li+ selective transport channels effectively retaining Mg2+ and allowing Li+ to cross the membrane smoothly, therefore solving the problem of poor lithium-magnesium separation performance of most of the NF membranes currently. Molecular dynamics simulations (MD) also confirmed that NH2–B15C5 has a stronger affinity for Li+ than for Mg2+. The NH2–B15C5/PIP-TMC membrane exhibited excellent separation performance and water permeance in simulated salt lake brine (2000 ppm, WMg/Li = 100), where the SLi, Mg and water permeance were 32.2 and 8.22 L·m−2·h−1·bar−1. Importantly, the crown ether is introduced into the PA separator layer in the form of covalent bonds, hence showing excellent stability. Overall, an NF membrane with high lithium-magnesium separation performance was designed for the extraction of lithium resources from high Mg2+/Li+ ratio salt lake brine.

Cell membrane-inspired COF/AAO hybrid nanofluidic membrane with ion current rectification properties for ultrasensitive detection of E. coli

Nanofluidic membranes hold great prospects in sensitive and rapid detection of bioanalysts, while remaining lacking robust and general approaches for specificity. In this work, we introduce a cell membrane-inspired nanofluidic membrane with excellent ion current rectification properties as a simple and robust platform for label-free and ultrasensitive biosensing. The asymmetric nanofluidic membrane is prepared by coupling a two-dimensional covalent organic framework (COF) membrane to an anodic aluminum oxide (AAO) nanochannel via hydrogen bonding. The prepared COF/AAO membrane presents selective ion transport due to the asymmetric structure and anion selectivity of COF. With the large surface area and abundant functional modification sites of COF, further grafting of the recognition unit can be easily achieved to mimic the recognition process of receptors and ligands on cell membranes. As a proof of concept, the application in bacterial detection is demonstrated by covalently bonded Concanavalin A as recognition units. The highly amplified ionic current based on ion current rectification properties of the COF/AAO membrane allows sensitive and selective bioanalysis. Specifically, the proposed asymmetric nanofluidic membrane presents a linear detection range from 10 to 106 CFU/mL with an ultralow detection limit of 7 CFU/mL for E. coli. This work reveals the great potential of COF/AAO hybrid nanofluidic membrane as a sensor for rapid and precise bioanalysis.

Effectively Sieving Alkali Metal Ions Using Functionalized Graphene Oxide Membranes by Exploiting Water-Repellent Interactions.

Sieving membranes capable of discerning different alkali metal ions are important for many technologies, such as energy, environment, and life science. Recently, two-dimensional (2D) materials have been extensively explored for the creation of sieving membranes with angstrom-scale channels. However, because of the same charge and similar hydrated sizes, mostly laminated membranes typically show low selectivity (<10). Herein, we report a facile and scalable method for functionalizing graphene oxide (GO) laminates by dually grafting cations and water-repellent dimethylsiloxane (DMDMS) molecules to achieve high selectivities of ∼50 and ∼20 toward the transport of Cs+/Li+ and K+/Li+ ion pairs, surpassing many of the state-of-the-art laminated membranes. The enhanced selectivity for alkali metal ions can be credited to a dual impact: (i) strong hydrophobic interactions between the incident cations' hydration shells and the water-repellent DMDMS; (ii) the efficient screening of electrostatic interactions that hamper selectivity.

Ionic selectivity of nanopores: Comparison among cases under the hydrostatic pressure, electric field, and concentration gradient

The ionic selectivity of nanopores is crucial for the energy conversion based on nanoporous membranes. It can be significantly affected by various parameters of nanopores and the applied fields driving ions through porous membranes. Here, with finite element simulations, the selective transport of ions through nanopores is systematically investigated under three common fields, i.e. the electric field (V), hydrostatic pressure (p), and concentration gradient (c). For negatively charged nanopores, through the quantitative comparison of the cation selectivity (t+) under the three fields, the cation selectivity of nanopores follows the order of t+V > t+c > t+p. This is due to the transport characteristics of cations and anions through the nanopores. Because of the strong transport of counterions in electric double layers under electric fields and concentration gradients, the nanopore exhibits a relatively higher selectivity to counterions. We also explored the modulation of t+ on the properties of nanopores and solutions. Under all three fields, t+ is directly proportional to the pore length and surface charge density, and inversely correlated to the pore diameter and salt concentration. Under both the electric field and hydrostatic pressure, t+ has almost no dependence on the applied field strength or ion species, which can affect t+ in the case of the concentration gradient. Our results provide detailed insights into the comparison and regulation of ionic selectivity of nanopores under three fields which can be useful for the design of high-performance devices for energy conversion based on nanoporous membranes.

Supramolecular-Coordinated Nanofiltration Membranes with Quaternary-Ammonium Cyclen for Efficient Lithium Extraction from High Magnesium/Lithium Ratio Brine

Ion-selective membranes (ISM) with sub-nanosized pore channels hold significant potential for applications in saline wastewater treatment and resource recovery. Herein, novel synergistic ion channels featuring bi-periodic structures were constructed through the coordination of functional Cyclen (quaternary_1,4,7,10-tetraazacyclododecane, Q_Cyclen) and Cu2+-m-Phenylenediamine (Cu2+-MPD) to develop supramolecular membranes for lithium extraction. The exterior quaternary ammonium-rich sites exhibit a significant Donnan exclusion effect, resulting in tremendous mono/divalent (Li+/Mg2+) ion selectivity; while the interior regular-confined channels of Cyclen yield a fast vehicular pathway, facilitating water molecules and Li+ ion-selective transport. The optimized membrane exhibited an increased water permeance of 19.2 L·m-2·h-1·bar-1 and simultaneously promoted Li+/Mg2+ selectivity (achieving a selectivity of 18.5 under a Mg2+/Li+ mass ratio of 30), surpassing the trade-off limit of conventional nanofiltration membranes. Due to the acquired excellent Li+/Mg2+ selectivity, lithium extraction from simulated salt-lake brines was successfully achieved through a two-stage nanofiltration process, reducing the Mg2+/Li+ mass ratio from 40 to 1.1. This work validates the applicability of macrocyclic with intrinsic sub-nanosized channels and desired multifunctionality for developing high-performance ISM for efficient lithium separation and beyond.

Building block design of thermally regenerable metal–organic framework composites for highly selective lithium adsorption

Crown ether-based organic lithium adsorbent has good stability for diverse lithium extraction scenarios, but hindering by its relatively low selectivity. Here, we report a building block design strategy for fabricating highly selective and thermally regenerable 12-crown-4 (12CE4) based lithium adsorbent. The synergistic coordination and ion-sieving blocks can sufficiently improve the ion selectivity and adsorption capacity of pNCE@MOF fabricated by copolymerizing thermosensitive segment and 12CE4 inside MOF. With the aid of synergistic coordination component of sulfonate group (SS), its Li+/Mg2+ selectivity increased from 12.9 to 21.8 (pNCE-SS@UiO-66) tested in 10,000 ppm salt solutions. Moreover, the 6.0 Å window of UiO-66 could successfully sieve hydrated Li+ (7.64 Å) and Mg2+ (8.56 Å), enhancing the selectivity 3.3 times from 5.1 for pNCE-SS@MOF-808 (10.0 Å) to 21.8. The adsorption capacity of pNCE-SS@UiO-66 was also optimized from 1.00 to 1.47 mmol·g−1. Furthermore, this material demonstrated a lithium selectivity of 11.5–19.8 in synthetic brines with a Mg/Li ratio of 1 to 0.1. Importantly, it could be fully regenerated in warm water at ≥ 40 °C. This work opens the door to constructing highly ion-selective functional materials via a modular method.

Surface functionalized porous MXene (Ti3C2Tx)/Polyethyleneimine membrane for efficient osmotic energy conversion

The development of ion-selective membranes is crucial for achieving efficient osmotic power conversion in reverse electrodialysis system. However, balancing ion selectivity and ion permeability in membranes remains a challenge, limiting improvements in energy conversion efficiency for practical applications. In this study, we develop efficient cation exchange membranes by integrating versatile aromatic hydroxyl groups with MXene nanosheets and polyethyleneimine (PEI) into their lamellar structure. This approach holds promise for achieving non-swelling, high selectivity, and enhanced power density for osmotic energy conversion. The abundance positive surface charge within PEI molecules, combined with the 2D sub-nanochannels of MXene nanosheets, facilitates the biomimetic replication of channel size, chemical groups, and adjustable charge density in the resulting membranes. The fabrication of these membranes is easily achieved through simple hydrothermal, functionalization, and surface-charged techniques, suggesting promising scalability. These membranes exhibit remarkable stability against swelling in aqueous solutions for up to 25 days and demonstrate a high selectivity of 0.95 and a superior output power density of 18.3 W/m2 in artificial river water and seawater.

Thermally-switchable adsorbent for selective uranium extraction from wastewater

Uranium extraction from uranium-containing wastewater is a promising solution to the uranium resource shortage, but the extraction process faces significant challenges such as poor selectivity, low elution efficiency, and recovery difficulties. In this study, we developed thermally responsive uranium ion-imprinted magnetic mesoporous microspheres (Fe3O4@mSiO2@FIIP) using polymer F-127 as a thermosensitive switch and sodium phytate as a crosslinking monomer, enabling effective uranium recovery from uranium-containing wastewater. By adjusting the adsorption and elution temperatures, Fe3O4@mSiO2@FIIP achieved higher adsorption selectivity and elution efficiency compared to ion-imprinted magnetic mesoporous microspheres without F-127 (Fe3O4@mSiO2@IIP). Additionally, Fe3O4@mSiO2@FIIP demonstrated superior selectivity for uranium ions over other cations compared to non-imprinted magnetic mesoporous microspheres (Fe3O4@mSiO2@NIP). It exhibited excellent salt resistance, reaching adsorption equilibrium within 60 min with a maximum adsorption capacity of 529.5 mg/g. Life cycle assessment (LCA) and techno-economic assessment (TEA) indicated that Fe3O4@mSiO2@FIIP is more environmentally friendly and economically feasible for treating uranium-containing wastewater. This study provides a new paradigm for synthesizing thermosensitive imprinting materials, holding significant potential for uranium recovery applications.

Microwave-assisted supramolecular double crosslinked chitosan-based molecularly imprinted polymer for synergistic recognition and selective recovery of Cd(II) and As(V) from water: Performance and mechanistic insights

A novel model of the sustainable double crosslinked molecularly imprinted polymer (D-Crosslinked MIP) represented as a supramolecular imprinted polymer was synthesized via the bulk polymerization method. The primary crosslinking was fabricated using biomacromolecule chitosan as a functional monomer and glutaraldehyde as a crosslinker. The primary crosslinked was subjected to dynamic interactions in a secondary crosslinking by binding Al2O3-NPs and TiO2-NPs, forming the supramolecular D-Crosslinked-MIP. The dually crosslinked formed from combining three distinct crosslinkers in one system for the interaction with As(V) and Cd(II). A microwave was employed to evaluate the performance of the designed material in selectivity and extraction of metal ions from water. The FT-IR, XRD, TG/DTA, SEM-EDX, TEM, and XPS were used to verify the characteristics of (D-nano-Al2O3@Crosslinked Chitosan@D-nano-TiO2). The type of solvents, selectivity, interferences, microwave-contact time, pH, temperatures, concentrations, and regeneration were investigated. By using the D-Crosslinked-MIP, at 15 s, Cd(II) revealed a recovery capacity of 99.03 %, Qmax 862.07 mg/g, while As(V) demonstrated a recovery capacity of 99.06 %, Qmax 850.75 mg/g. The D-Crosslinked-MIP exhibited BETs of 69.01 m2/g with a pore volume of 0.2340 cm3/g owing to polymeric crosslinking by metal oxide NPs. The kinetics, isotherm models, and mechanisms of dually crosslinking and extraction of toxic metals were discussed.

Highly Anion-Conductive Viologen-Based Two-Dimensional Polymer Membranes as Nanopower Generators.

Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3 nm), much smaller than the duple Debye length in the diluted electrolyte (6-20 nm), as well as low charge density (<4.5 mC m-2). Here, we introduce a π-conjugated viologen-based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m-2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m-2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl-, contributing to an outstanding power density of ~55 W m-2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N-containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl- ion transport pathway. This work demonstrates the great promise of large-area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

A Highly Sensitive and Selective Iron Ion Fluorescent Probe for Water‐Soluble Pillar[5]Arene

AbstractA novel d‐gluconamide‐functionalized water‐soluble pillar[5]arene (GWP5) was synthesized through a simple synthetic route. GWP5 showed a remarkable aggregation‐induced emission (AIE) with increasing concentration. This feature served as the basis for the construction of an AIE‐based sensor for fluorescence detection of Fe3+ with high sensitivity and selectivity, with a linear relationship between luminescence quenching and Fe3+ concentration observed from 0 to 20 µM, and a limit of detection of 7.84 × 10−9 M. This fluorescent probe could be applied to the detection of Fe3+ ions in real environmental water samples and in serum samples.

Selective ion channel adsorbents facilitate efficient and low environmental impact extraction of liquid lithium resources

As lithium is the cornerstone of green energy development, it is crucial to realize a low environmental impact and efficient lithium extraction process. Ion-sieve adsorption is the most widely used method to extract liquid lithium resources, but this method is only efficient under alkaline conditions for H+ and Mg2+ competing adsorption. Conventional methods are often accompanied by the consumption of quantities of alkali, the generation of solid waste, and the acidification of liquid lithium resources. To address these issues, a selective ion-channel adsorbent was constructed. The composition comprises an ion sieve adsorbent and an organic carrier with a zwitterionic quaternary ammonium base group. This group storages OH-in situ, hinders H+ diffusion, slows down Mg2+ diffusion, and accelerates Li+ diffusion by relying on the difference in binding energies, which reduces the competing adsorption and avoids acidification and solid waste generation. The saturated adsorption capacity (21.38mg/g) and selectivity of the adsorbent are 4.7 and 24 times higher than that of conventional ion-sieve adsorbent under neutral conditions respectively. The dosage of alkali is 1/256 of the traditional method, the effluent remains neutral and no solid waste is generated. This study presents an environmental and effective adsorbent for lithium extraction.

Selective Single-Atom Adsorption for Precision Separation of Lead Ions in Tap Water via Capacitive Deionization

Capacitive deionization (CDI) offers a cost-effective and low-energy method for selective removal of Pb2+ from drinking water. Modifying CDI electrode surfaces with functional groups presents a versatile approach to enhancing selective ion adsorption capacity. However, a comprehensive understanding of the selectivity and removal efficiency of Pb2+ among diverse functional groups remains unexplored. Here, we investigated the effects of different functional groups (-SH, -COOH, and -NH2) attached to the graphene oxide (GO) electrode surfaces on Pb2+ selectivity and removal efficiency. Surprisingly, GO-COOH demonstrated single-atom adsorption of Pb2+, displaying superior removal efficiency and selectivity compared with -SH and -NH2, although -SH possesses significant chelation capability for Pb2+. Both density functional theory (DFT) calculations and X-ray pair distribution function (PDF) analyses confirmed that Pb2+ exhibits a theoretically higher affinity to -COOH. This research deepens our understanding of the interactions between functional groups and heavy metal ions, enabling selective and rapid separation of target cations for water purification.

Assessment of salt-free electrodialysis metathesis: A novel process for brine management in brackish water desalination using monovalent selective ion exchange membranes

Since reverse osmosis (RO) is often limited to a water recovery of 70–85 %, implementing a secondary process like electrodialysis metathesis (EDM) to treat concentrate can increase system water recovery. This study explores salt-free electrodialysis metathesis (SF-EDM) as an alternative to conventional EDM to investigate its performance in the zero discharge desalination (ZDD) process. SF-EDM utilizes monovalent-selective ion exchange membranes, eliminating the need for sodium chloride (NaCl) as a substitution solution. This approach generates one diluate stream and two highly soluble concentrate streams enriched in calcium and sulfate, respectively. In this article, a series of lab-scale tests based on synthetic and real RO concentrate were performed to investigate how SF-EDM performs operating at high water recovery with a feedwater with high scaling potential. We critically analyze the performance in terms of salinity reduction, selectivity, and energy consumption. Results of the study show that without the addition of NaCl, the process was able to selectively separate sulfate and calcium into two concentrate streams achieve a salinity reduction of 93 % and a total system water recovery (RO and SF-EDM) of 90 %. A technoeconomic analysis found SF-EDM to be 80 % of the cost of conventional EDM making it a competitive technology for brackish water RO concentrate management.

Cation selectivity during flow electrode capacitive deionization

Efficient separation of specific ions from aqueous media is crucial for advanced water treatment and resource recovery. Flow electrode capacitive deionization (FCDI) offers potential for selective ion removal through continuous operation. This study evaluates the performance of selective cation separation using a commercial activated carbon slurry in a multi-ion solution of monovalent (Li+, Na+, K+) and bivalent (Ca2+, Mg2+) cations. We assess ion removal and cation selectivity under different operational parameters, such as applied potential, slurry flow rate, and feed water flow rate. Our data show that bivalent cations, namely Ca2+ and Mg2+, are preferentially removal due to their higher charge-to-size ratio, aligning with hydrated ion sizes. The highest separation rate was observed for Ca2+ (5.7 μg cm−2 min−1), and the lowest for Li+ (0.2 μg cm−2 min−1). At the highest applied voltage (1.2 V), charge efficiencies reached 70 %, with an energy consumption of 41 Wh mol−1 for nearly complete cation removal. Optimal conditions were identified with a slurry flow rate of 6 mL min−1, feed water flow rate of 2 mL min−1, activated carbon content of 10 mass%, 1 mass% carbon black, and a cell voltage of 1.2 V. These findings highlight the importance of optimizing operational parameters to enhance ion removal.

Pilot-scale capacitive deionization for water softening: Performance, energy consumption, and ion selectivity

Capacitive deionization (CDI) has emerged as an efficient process for hardness control than traditional water-softening technologies. However, few systematic studies have been conducted on water softening using pilot-scale CDI systems. For industrial applications, it is essential to investigate deionization performance, energy consumption, and selectivity for divalent cations through pilot-scale studies. In this study, we examined the deionization performance and energy consumption of a pilot-scale CDI process for effective water softening. The key operational variables analyzed were the applied voltage (200–300 V (i.e., 1.0–1.5 V per pair)), feed concentration (550–1250 mg/L), recovery ratio (50–80 %), flow rate (3–5 L/min), and adsorption/desorption time (80–180 s). Within this range, a high voltage, low feed concentration, low recovery ratio, high flow rate, and long adsorption/desorption times are advantageous for the total dissolved solids (TDS) removal ratio. In terms of energy efficiency, expressed as TDS removal per unit energy consumption, a low voltage, low feed concentration, low recovery ratio, fast flow rate, and long adsorption/desorption time are beneficial. Additionally, we investigated the selective removal of Ca2+ over Na+ under various operating conditions, as well as its impact on enhancing energy efficiency. The pilot CDI system achieved a Ca/Na selectivity coefficient of approximately 2.4 and it was analyzed to achieve up to 45 % energy-saving efficiency compared to nonselective systems (i.e., selectivity coefficient = 1). The results of this study are expected to provide valuable data for the application of CDI to water softening and hardness control processes.