Selective ion removal has been a point of focus in capacitive deionization because of its industrial applications such as water purification, water softening, heavy metal separation and resource recovery. Conventionally, carbon is used as electrode material for selectivity. However, recent developments focus on intercalation materials such as Prussian Blue Analogues, due to their size-based preference towards cations. Selectivity of nickel hexacyanoferrate electrodes from a mixture of Na⁺, Mg²⁺, and Ca²⁺ ions was studied in this work. Here, a CDI cell with two identical NiHCF electrodes was operated in two desalination modes: (a) cyclic, in which ions are removed from and released into the same water reservoir and thus, the ion concentration remains the same after one cycle, and (b) continuous, in which ions are removed from one water reservoir and released back in a different reservoir. An average separation factor of ≈15 and 25, reflecting the selectivity of the electrodes, was obtained for Na⁺ over Ca²⁺ and Mg²⁺ from an equimolar solution of Na⁺, Ca²⁺ and Mg²⁺ in both, cyclic and continuous desalination. It was concluded that NiHCF, used in a symmetric CDI cell, is a promising material for highly selective removal of Na⁺ from a multivalent ion mixture.

This study demonstrates the effective separation of alkali metal cations using a Supported Liquid Membrane (SLM) containing lipophilic, negatively charged borate moieties, operating under electro dialysis conditions. The selectivity of the membrane is essentially based on differences in dehydration energy and mobility between ion species. The system favors the ion species with the largest crystal radius, despite its lower mobility. In mixtures of K⁺ and Na⁺, the SLM separates K⁺ from Na⁺ with a separation efficiency ranging from ~20% to 90%, depending on the feed solution composition. With solutions containing either K⁺ or Na⁺ and Li⁺, the K⁺/Na⁺ over Li⁺ separation efficiency is nearly 100%. Addition of 15-crown-5 derivative does not improve SLM behavior, but slows down the K⁺ current by approximately 30% whereas the Na⁺ current remains unaffected. As supported by simulations, the free K⁺ and Na⁺ ratio in the membrane (and with that the current ratio) is entirely defined by partitioning and the feed concentration ratio, regardless the presence of 15-crown-5. As a result, the current ratio of two ion species can be described exclusively in terms of their feed concentrations and crystal radii because the latter parameter defines both partitioning and mobility.

A novel ion separation methodology using a cation-exchange membrane modified with iron oxide nanoparticles (Fe3O4 NPs) coated with polyhexamethylene guanidine (PHMG) is proposed. The separation is performed in an electrodialysis cell, where firstly phosphate is electro-adsorbed to the PHMG@Fe3O4 NP coating, followed by a desorption step by applying an electric current.

To the best of our knowledge, for the first time MIL-53(Al) and NH ₂ -MIL-53(Al) modified α-alumina membranes are investigated for the adsorption of organic dyes from organic solvents. These new, modified membranes show excellent adsorption of high concentrations of Rose Bengal dye in methanol and isopropanol solutions.

Here, we report the covalent coupling of poly (styrene-co-maleic anhydride) onto γ-alumina to develop high-performance organic solvent nanofiltration (OSN) membranes. A high molecular weight (M _w ) alternating copolymer of maleic anhydride (MA) and styrene (St) was synthesized and directly grafted to the γ-alumina membrane, while commercially available low M _w random copolymers of St and MA were also investigated. We show that solute rejection and membrane permeability strongly depend on the nature of the applied copolymer. In particular, the M _w of the copolymer applied is potentially the key for improving the membrane performance. When a high M _w copolymer was applied, the grafted layer covered the surface of the membrane. This results in membranes with significantly improved rejection, while maintaining a high permeability. In contrast, we observed pore grafting by applying low M _w copolymers, which resulted in membranes with slightly higher rejection and dramatically lower permeability compared to unmodified membrane. The best results were obtained by grafting γ-alumina with a high M _w alternating copolymer. These membranes showed a solute rejection of 98% for Sudan Black B (457 g mol ⁻¹ ) in toluene, while the permeability remained high at 2.9 L m ⁻² h ⁻¹ bar ⁻¹ .

The development of controlled polymerization techniques in the last decade has enabled polymer brushes to be grown from inorganic substrates with precision. Less studied are brushes grown from concave geometries of high curvature, such as mesopores, despite their application potential in the separation sciences. The method used here, surface-initiated, activators-regenerated-by-electron-transfer, atom-transfer radical polymerization (SI-ARGET-ATRP), is used to grow a polystyrene brush grown from aluminum oxide pores of 5 nm diameter, to-date the most confined geometry in which ATRP has been conducted. The brush is characterized by TGA, AFM, and FTIR, the latter two methods applied specifically to the external brush. Additionally, permporometry as well as permeability and retention measurements are used to characterize the graft within the mesopores. We show that the brush length is tunable, that the brush length is solvent-dependent, and we also demonstrate the application potential of this hybrid material as an organic solvent nanofiltration membrane. This new class of membranes shows excellent performance: a toluene permeability of 2.0 L m⁻² h⁻¹ bar⁻¹ accompanied by a 90% rejection of diphenylanthracene (MW 330 g mol⁻¹).

Capacitors made of interdigitated electrodes (IDEs) as a transducer platform for the sensing of volatile organic compounds (VOCs) have advantages due to their lower power operation and fabrication using standard micro-fabrication techniques. Integrating a micro-electromechanical system (MEMS), such as a microhotplate with IDE capacitor, further allows study of the temperature- dependent sensing response of VOCs. In this paper, the design, fabrication, and characterization of a low-power MEMS microhotplate with IDE capacitor to study the temperature-dependent sensing response to methanol using Zeolitic imidazolate framework (ZIF-8), a class of metal-organic framework (MOF), is presented. A Titanium nitride (TiN) microhotplate with aluminum IDEs suspended on a silicon nitride membrane is fabricated and characterized. The power consumption of the ZIF-8 MOF-coated device at an operating temperature of 50 ∘ C is 4.5 mW and at 200 ∘ C it is 26 mW. A calibration methodology for the effects of temperature of the isolation layer between the microhotplate electrodes and the capacitor IDEs is developed. The device coated with ZIF-8 MOF shows a response to methanol in the concentration range of 500 ppm to 7000 ppm. The detection limit of the sensor for methanol vapor at 20 ∘ C is 100 ppm. In situ study of sensing properties of ZIF-8 MOF to methanol in the temperature range from 20 ∘ C to 50 ∘ C using the integrated microhotplate and IDE capacitor is presented. The kinetics of temperature-dependent adsorption and desorption of methanol by ZIF-8 MOF are fitted with double-exponential models. With the increase in temperature from 20 ∘ C to 50 ∘ C, the response time for sensing of methanol vapor concentration of 5000 ppm decreases by 28%, whereas the recovery time decreases by 70%.

We report an advanced treatment method for phosphoric acid recovery from leached sewage sludge ash. Layer-by-layer (LbL) polyelectrolyte deposition has been used as a tool to modify and convert a hollow ultrafiltration membrane into a nanofiltration (NF) LbL membrane for H₃PO₄ recovery. To build the LbL membrane, poly(styrenesulfonate) PSS was chosen as polyanion, while three different polycations were used: a permanently charged polyelectrolyte, poly(diallyldimethylammonium chloride), PDADMAC; a pH-dependent charged polyelectrolyte poly(allylamine hydrochloride), PAH; and a PAH modified with guanidinium groups (PAH-Gu). Based on detailed surface characterizations (AFM, XPS and Zeta-potential) it was concluded that both charge density and pH-responsiveness of the polycations are key parameters to control the final membrane surface structure and transport properties. The surface properties of LbL-coated membranes were correlated with the membrane filtration performance, when exposed to the real leached sewage sludge ash solution. The highest permeability was recorded for (PDADMAC/PSS)₆, a result that was rationalized on its loose, and possibly less interpenetrated, structure, followed by (PAH-Gu/PSS)₆ characterized by a more dense, compact layer. H₃PO₄ recovery was the highest in the case of (PDADMAC/PSS)₆, but the retention of multivalent metals (Fe³⁺ and Mg²⁺) was low, leading to a more contaminated permeate. The opposite trend was observed for (PAH-Gu/PSS)_6, resulting in a less metal-contaminated, but also a less H₃PO₄-concentrated permeate. Our LbL-modified membranes were found to improve the permeability and H₃PO₄ recovery compared to a commercially available acid-resistant NF membrane.

Microporous polymer frameworks have attracted considerable attention to make novel separation layers owing to their highly porous structure, high permeability, and excellent molecular separation. This study concerns the fabrication and properties of thin melamine-based microporous polymer networks with a layer thickness of around 400 nm, supported on an α-alumina support and their potential use in organic solvent nanofiltration. The modified membranes show excellent solvent purification performances, such as n-heptane permeability as high as 9.2 L m⁻² h⁻¹ bar ⁻¹ in combination with a very high rejection of approximately 99 % for organic dyes with molecular weight of ≥457 Da. These values are higher than for the majority of the state-of-the-art membranes. The membranes further exhibit outstanding long-term operation stability. This work significantly expands the possibilities of using ceramic membranes in organic solvent nanofiltration.

A model is presented for the Na⁺ and K⁺ levels in the irrigation water of greenhouses, specifically those for the cultivation of tomato. The model, essentially based on mass balances, not only describes the accumulation of Na⁺ but includes a membrane unit for the selective removal of Na⁺ as well. As determined by the membrane properties, some of the K⁺ is removed as well. Based on real-life process parameters, the model calculates the Na⁺ and K⁺ concentration at three reference points. These process parameters include the evapotranspiration rate, the K⁺ uptake by the plants, the Na⁺ and K⁺ content of the fertilizer, the Na⁺ leaching out from the hydroponic substrate material, and the Na⁺ and K⁺ removal efficiency of the membrane unit. Using these parameters and given a constant K⁺ concentration of the irrigation water entering the greenhouse of 6.6 mM (resulting in the optimal K⁺ concentration for tomato cultivation), the composition of the solution is completely defined at all three reference points per irrigation cycle. Prime aim of this investigation is to explore the requirements for the selective membrane that currently is developed in our lab. It is found that even for a limited Na⁺ over K⁺ selectivity of 6, after a number of cycles the Na⁺ level reaches steady state at a level below the upper (toxic) threshold for tomato cultivation (20 mM). Economic aspects and ways of implementation of such a system are briefly discussed.

Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

In this study we describe a novel and simple method to couple covalently poly (maleic anhydride-alt-1-alkenes) to γ-alumina nanofiltration membranes for the first time. The 1-alkenes varied from 1-hexene, 1-decene, 1-hexadecane to 1-octadecene. The grafting reaction was between the reactive anhydride moieties of the polymer and surface hydroxyl groups, resulting in highly stable bonds. The modified membranes were investigated for their permeation and rejection performance of Sudan Black (SB, M_w 457 Da) in either toluene or ethyl acetate (EA) solution, and very high rejections (> 90%) and high permeation flux were observed compared to unmodified membranes. Initially, the SB in toluene solution was found to bind strongly to the surface hydroxyl groups of the unmodified membranes, an effect not observed in EA solution.

Silicon semiconductors with a thin surface layer of silica were first modified with polyelectrolytes (polyethyleneimine, polystyrene sulfonate and poly(allylamine)) via a facile layer-by-layer deposition approach. Subsequently, lipid vesicles were added to the preformed polymeric cushion, resulting in the adsorption of intact vesicles or fusion and lipid bilayer formation. To study involved interactions we employed optical reflectometry, electrochemical impedance spectroscopy and fluorescent recovery after photobleaching. Three phospholipids with different charge of polar head groups, i.e. 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1,2-dioleoyl-sn-glycero-3-phospho-L-serine (DOPS) and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) were used to prepare vesicles with varying surface charge. We observed that only lipid vesicles composed from 1:1 (mole:mole) mixture of DOPC/DOPS have the ability to fuse onto an oppositely charged terminal layer of polyelectrolyte giving a lipid bilayer with a resistance of >100 kΩ. With optical reflectometry we found that the vesicle surface charge is directly related to the amount of mass adsorbed onto the surface. An interesting observation was that zwitterionic polar head groups of DOPC allow the adsorption on both positively and negatively charged surfaces. As found with fluorescent recovery after photobleaching, positively charged surface governed by the presence of poly(allylamine) as the terminal layer resulted in intact DOPC lipid vesicles adsorption whereas in the case of a negatively charged silica surface formation of lipid bilayers was observed, as expected from literature.

During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant-assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al-containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.

Fingermarks are trace evidence of great forensic importance, and their omnipresence makes them pivotal in crime investigation. Police and law enforcement authorities have exploited fingermarks primarily for personal identification, but crucial knowledge on when fingermarks were deposited is often lacking, thereby hindering crime reconstruction. Biomolecular constituents of fingermark residue, such as amino acids, lipids and proteins, may provide excellent means for fingermark age determination, however robust methodologies or detailed knowledge on molecular mechanisms in time are currently not available. Here, we address fingermark age assessment by: (i) drafting a first protein map of fingermark residue, (ii) differential studies of fresh and aged fingermarks and (iii), to mimic real-world scenarios, estimating the effects of donor contact with bodily fluids on the identification of potential age biomarkers. Using a high-resolution mass spectrometry-based proteomics approach, we drafted a characteristic fingermark proteome, of which five proteins were identified as promising candidates for fingermark age estimation. This study additionally demonstrates successful identification of both endogenous and contaminant proteins from donors that have been in contact with various bodily fluids. In summary, we introduce state-of-the-art proteomics as a sensitive tool to monitor fingermark aging on the protein level with sufficient selectivity to differentiate potential age markers from body fluid contaminants.

In this study, the preparation of a new, functional anion-exchange membrane (AEM), containing guanidinium groups as the anion-exchanging sites (Gu-100), is described as well as the membrane characterization by XPS, water uptake, permselectivities, and electrical resistances. The functional membrane was also employed in pH-dependent electrodialysis experiments using model dairy wastewater streams. The properties of the new membrane are compared to those of a commercially available anion-exchange membrane bearing conventional quaternary ammonium groups (Gu-0). Guanidinium was chosen for its specific binding properties toward oxyanions: e.g., phosphate. This functional moiety was covalently coupled to an acrylate monomer via a facile two-step synthesis to yield bulk-modified membranes upon polymerization. Significant differences were observed in the electrodialysis experiments for Gu-0 and Gu-100 at pH 7, showing an enhanced phosphate and citrate transport for Gu-100 in comparison to Gu-0. At pH 10 the difference is much more pronounced: for Gu-0 membranes almost no phosphate and citrate transport could be detected, while the Gu-100 membranes transported both ions significantly. We conclude that having guanidinium groups as anion-exchange sites improves the selectivity of AEMs. As the presented monomer synthesis strategy is modular, we consider the implementation of functional groups into a polymer-based membrane via the synthesis of tailor-made monomers as an important step toward selective ion transport, which is relevant for various fields, including water treatment processes and fuel cells.

We have investigated in detail properties of hybrid polyelectrolyte-anion exchange membranes (AEMs) having different amounts of a guanidinium-modified poly(allylamine hydrochloride) (PAH-Gu) derivative (2, 5, and 8 wt%). The presence of guanidinium groups at the membrane surface was confirmed by XPS. For 2 and 5 wt% the blended membranes are homogeneous, while at 8 wt% segregation is observed by AFM. The membrane permselectivity and ionic electrical resistance for phosphate reduce upon incorporation of the PAH-Gu in the membrane, reflecting an increased co-ion (H⁺ and Na⁺) permeation. We conclude that PAH-Gu loaded in the AEM favors an interaction with phosphate. In electrodialysis, using sodium sulfate and sodium dihydrogen phosphate at equal concentrations in the source phase a slight preference for phosphate was observed. Our work shows that this facile membrane fabrication procedure shows great potential in terms of tuning the membrane properties. One way to boost selective ion transport could be by increasing the number of functional groups in the membrane.

Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH₂-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0-100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH₂-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ_0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH₂-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing the promise of this type of chemical sensors.

The electrochemical behavior of three differently charged drug molecules (zwitter-ionic acetylcarnitine, bi-cationic succinylcholine and tri-cationic gallamine) was studied at the interface between two immiscible electrolyte solutions. Tetramethylammonium was used as a model mono cationic molecule and internal reference. The charge and molecular structure were found to play an important role in the drug lipophilicity. The studied drugs gave a linear correlation between the water – octanol (logP_octanol) partition coefficients and the electrochemically measured water – 1,2-dichloroethane (logP_DCE) partition coefficients. Comparison with tetraalkylammonium cations indicating that the correlation between logP_octanol and logP_DCE is molecular structure dependent. The highest measured sensitivity and lowest limit of detection were found to be 0.543 mA·dm³·mol^{− 1} and 6.25 μM, respectively, for the tri-cationic gallamine. The sensitivity for all studied ions was found to be a linear function of molecular charge. The dissociation constant of the carboxylic group of zwiter-ionic acetylcarnitine was calculated based on voltammetric parameters and was found to be 4.3. This study demonstrates that electrochemistry at the liquid – liquid interface is powerful technique when it comes to electroanalytical or pharmacokinetic drug assessment.