Nanoporous Membranes Research Articles

Covalent Organic Framework Packed Nanoporous Membrane for Continuous Removal of Bisphenol A from Agricultural Irrigation Wastewater.

BPA, a typical endocrine disruptor, poses a significant threat to the growth of crops and thereby jeopardizes sustainable agriculture products and human health. In this work, a water-stabilized imine covalent organic framework (TpBD-COF) packed nanochannel membrane was constructed. The TpBD-COF membrane achieves high selective removal of BPA attributed to the subdivision of the pores by the filled COF, which further reduces the porous size and effectively eliminates the distance barrier between the selective sites of TpBD-COF membranes and BPA. The selective removal ratio of BPA was 5.79 times higher than that of the bare membrane, while the removal capacity reached 6.78 nM cm-2 min-1. It can eliminate BPA from irrigation wastewater and ensure crop growth. The application of COF-filled nanoporous membrane provides not only a size-matching strategy for the development of specific continuous removal of BPA but also a theoretical reference for membrane removal of other organic pollutants in agricultural irrigation water environment.

Performance of Single Nanopore and Multi-Pore Membranes for Blue Energy.

The salinity gradient power extracted from the mixing of electrolyte solutions at different concentrations through selective nanoporous membranes is a promising route to renewable energy. However, several challenges need to be addressed to make this technology profitable, one of the most relevant being the increase of the extractable power per membrane area. Here, the performance of asymmetric conical and bullet-shaped nanopores in a 50 nm thick membrane are studied via electrohydrodynamic simulations, varying the pore radius, curvature, and surface charge. The output power reaches ~60 pW per pore for positively charged membranes (surface charge σw=160 mC/m2) and ~30 pW for negatively charges ones, σw=-160 mC/m2 and it is robust to minor variations of nanopore shape and radius. A theoretical argument that takes into account the interaction among neighbour pores allows to extrapolate the single-pore performance to multi-pore membranes showing that power densities from tens to hundreds of W/m2 can be reached by proper tuning of the nanopore number density and the boundary layer thickness. Our model for scaling single-pore performance to multi-pore membrane can be applied also to experimental data providing a simple tool to effectively compare different nanopore membranes in blue energy applications.

Enhancing electrocatalytic oxidation via spatial confinement in Ti4O7 Nanopore Membranes: Synthesis, Characterization, and Mechanistic insights

Enhancing electrocatalytic oxidation via spatial confinement in Ti4O7 Nanopore Membranes: Synthesis, Characterization, and Mechanistic insights

Nanoporous Membranes from Bacterial Cellulose Derivatives for Water Treatment

Nanoporous Membranes from Bacterial Cellulose Derivatives for Water Treatment

Driving DNA Nanopore Membrane Insertion through Dipolar Coupling.

DNA nanopores appear to be a plausible alternative to the use of transmembrane proteins. The specificity and programmability of DNA interactions allow the design of synthetic channels that insert into lipid bilayers and can regulate the ionic transport across them. In this Communication, we investigate the dependence of insertion capabilities on the electrostatic properties of the nanopore and show that the presence of a permanent electric dipole is an important factor for the nanopore to insert into the membrane. On the contrary, in the absence of such a dipole, most DNA nanopores bind to the bilayer without channel formation. We also show that this modification does not hinder the possibility of triggering a measurable conformational change with a single short oligonucleotide.

Resolving the Size and Charge of Small Particles: A Predictive Model of Nanopore Mechanics.

The movement of small particles and molecules through nanopore membranes is widespread and has far-reaching implications. Consequently, the development of mathematical models is essential for understanding these processes on a micro level, leading to deeper insights. In this endeavor, we suggested a model based on a set of empirical equations to predict the transport of substances through a solid-state nanopore and the associated signals generated during their translocation. This model establishes analytical relationships between the ionic current and electrical double-layer potential observed during analyte translocation and their size, charge, and mobility in an electrolyte solution. This framework allows for rapid interpretation and prediction of the nanopore system's behavior and provides a means for quantitatively determining the physical properties of molecular analytes. To illustrate the analytical capability of this model, ceria nanoparticles were investigated while undergoing oxidation or reduction within an original nanopore device. The results obtained were found to be in good agreement with predictions from physicochemical methods. This developed approach and model possess transferable utility to various porous materials, thereby expediting research efforts in membrane characterization and the advancement of nano- and ultrafiltration or electrodialysis technologies.

An easily fabricated nanoporous Au membrane in drug detection with reusable functionality and high SERS performance.

Amethod for detecting methamphetamine (MET), ketamine (KET), and morphine (MOP) molecules is presentedusing a reusable substrate based on SERS. The SERS substrate was prepared by etching the Au/Ag alloy film to synthesize a nanoporous Au membrane (AuNPM). By optimizing the preparation conditions and using rhodamine 6G (R6G) as an analyte, the AuNPM exhibited good SERS performance with a limit of detection (LOD) of 10-9mol L-1. A competitive immunoassay category has been applied to the detection of MET, KET, and MOP. The MET, KET, and MOP antigens were functionalized on the surface of theAuNPM to specifically bind to the related drug antibodies. The Au nanoparticles (AuNPs) modified with 4-mercaptobenzoic acid (4-MBA) and antibodies against MET, KET, and MOP were used as nanotags. The 4-MBA served as the reporting molecule and drug antibodies were used to bind to free drug molecules in the target solution. The mixture of nanotags and target solution was dropped onto the antigen-modified AuNPM (antigen/AuNPM), and the free nanotags bind to the antigen/AuNPM. By comparing the SERS intensity of 4-MBA with the presence or absence of drug molecules, the drugs were qualitatively and quantitatively identified. Through this category, the LODs for detecting MET, KET, and MOP were 0.1, 1, and 1ngmL-1, respectively. This study proposes an effective method for constructing SERS-based detection of drug molecules with good potential for practical applications.

Self-Assembly of Hierarchical Silicon-Containing Block Copolymers with Cross-Linkable 3 nm Smectic Motifs for Nanopatterning and Osmotic Energy Conversion Membranes.

Highly-dense small-feature-size nanopatterns and nanoporous membranes are important in advanced microelectronics, nanofiltration, and biomimic device manufacturing. Here, we report the synthesis and self-assembly of a series of high-interaction-parameter (high-χ) silicon-containing hierarchical block copolymers (BCPs) with cross-linkable subordering chalcone motifs, which possess both an intrinsic native etching contrast for nanofabrication and cross-linkability under ultraviolet light for generating free-standing membranes. BCPs with a volume fraction of chalcone block of 55-74% form ordered primary nanostructures with period 15-22 nm including lamellae, double gyroid, hexagonally packed cylinders, and body-centered cubic spheres of the minority Si-containing block. The majority PChMA block self-assembles into a highly ordered 3 nm smectic sublattice, and cross-linking after self-assembly enables the formation of free-standing isoporous membranes. Both silicon oxide nanopatterns and free-standing nanoporous osmotic energy conversion membranes are generated by etching films of these BCPs. This work demonstrates that the combination of hierarchical ordering and cross-linkable motifs in a high-interaction parameter BCP enables applications in both nanofabrication and free-standing functional porous membranes.

The morphology and thermo-regulating properties of electrospun PVA/PEG/Ag nanofibers of water and formic acid solvents

The solvent utilized in the electrospinning solution significantly impacts the morphology and thermal properties of PVA/PEG/Ag nanofibers. To prevent leakage of PEG, solid-liquid phase change, a suitable encapsulation method involves utilizing a combined single-phase electrospinning that incorporates PEG and supporting polymer of PVA. This study aims to investigate the production of thermal-regulating nanofibers from a solution containing PEG 6000, PVA, and AgNO3 precursor using electrospinning method. The influence of water and formic acid as a solvent on the morphology of the nanofibers was examined using SEM. The selected nanofiber characteristics and thermal performance were evaluated through FE-SEM, FT-IR, XRD, DSC, PCM leakage, and DTG tests. SEM images revealed that the formic acid-based nanofibers, consisting of two polymers and two polymer/Ag NPs, exhibited a nanoporous membrane, possibly due to enhanced cross-linking compared to water-based nanofibers. The results of the DSC indicated that fusion and solidification enthalpies of the selected water-based nanofibers were measured as 70.09 and −85.43 J/g, respectively. Unexpectedly, the DSC results indicated higher enthalpies compared to unheated samples. SEM image after thermal cycles, leakage results, and DTG of water-based nanofibers demonstrated their production with thermal stability, reliability, and the potential for creating shape-stable, thermally regulating fabricated nanofibers for various applications.

Analysis of graphene as a potential filtration membrane for desalination at varying operating conditions using molecular dynamics simulation and response surface methodology

ABSTRACT Water scarcity is a critical global issue exacerbated by pollution and overuse, necessitating sustainable water management solutions. Desalination using membrane technology presents a promising approach for freshwater production. This study investigated the performance of nanoporous (NPG) membranes for desalination, focusing on the influence of pressure and temperature on water flux and ion rejection. Utilizing molecular dynamics (MD) simulations with the LAMMPS package, this study evaluates NPG membranes under various conditions of pressures and temperatures. The simulations demonstrate that increasing both the pressure and temperature enhances the water flux without compromising ion rejection. The results indicate that at 300 K and 50 MPa, the water flux exceeds 2000 L/m2 h bar, significantly outperforming traditional reverse osmosis membranes, which typically achieve a capacity of approximately 1 L/m2 h bar. These findings were validated experimentally, aligning with previous research and confirming the superior performance of NPG membranes. A statistical model derived from response surface methodology revealed a linear relationship between pressure, temperature, and water flux. The study concludes that NPG membranes offer a high efficiency and scalable solution for desalination, with significant potential for energy savings and cost reduction. This study underscores the viability of NPG membranes in addressing global freshwater shortages and provides a pathway for sustainable water production.

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.

Energy and exergy analysis of a novel solar-powered passive multi-stage osmosis desalination system for sustainable water production

Climate change and population growth constantly exacerbate global water scarcity, and seawater desalination technology is crucial to addressing this crisis. Conventional fossil-fuel desalination poses environmental and economic challenges, especially in remote, water-scarce regions. Renewable energy offers sustainable options for seawater desalination; however, most related technologies face challenges in flexible deployment. Among passive technologies, interfacial evaporation still confronts issues of salt accumulation impacting desalination efficiency. Therefore, this study investigates a novel solar-powered passive multi-stage osmosis device that emulates mangroves’ transpiration and natural osmosis processes. Harnessing solar energy, it employs hydrophilic nanoporous membranes for water movement and evaporation and an osmosis membrane for solute retention, aiming for efficient seawater desalination without external power and pressure. Energy and exergy analyses reveal key efficiency factors. Results reveal significant pressure gradients across the osmosis membrane as a challenge. Optimizing salinity and adjusting the area ratio of the nanoporous membrane to the osmosis membrane is vital for stability and performance. Moreover, potential increases in water production from 0.97 kg/m2/h to 3.53 kg/m2/h with a five-stage setup, though benefits diminish with additional stages due to heat/exergy losses. The exergy efficiency increases from 0.14 % for a five-stage device to 0.18 % for a ten-stage system. This study demonstrates the solar-powered passive multi-stage osmosis device’s dependence on solar flux and highlights the importance of optimizing the air gap thickness and insulation to boost efficiency.

Molecular Dynamics Simulation of Membrane Distillation for Different Salt Solutions in Nanopores.

Nanoporous membranes offer significant advantages in direct contact membrane distillation applications due to their high flux and strong resistance to wetting. This study employs molecular dynamics simulations to explore the performance of membrane distillation in a single nanopore, mainly focusing on wetting behavior, liquid entry pressure, and membrane flux variations across different concentrations and types of salt solutions. The findings indicate that increasing the NaCl concentration enhances the wetting of membrane pores, thereby decreasing the entry pressure of the solution. However, at the same salt concentration, the differences in wetting and liquid entry pressure among various salts, including CaCl2, KCl, NaCl, and LiCl, are minimal. The presence of hydrated ions significantly reduces membrane flux. As the concentration of NaCl solutions increases, the number of hydrated ions rises, thereby lowering the membrane flux of the salt solution. Furthermore, the type of salt has a pronounced effect on the structure of hydrated ions. Solutions with Ca2+ and Li+ exhibit the smallest first-layer radius of hydrated ions. Under the same salt concentration, KCl solutions demonstrate the highest membrane distillation flux, while CaCl2 solutions show the lowest flux.

Creative synthesis of pH-dependent nanoporous pectic acid grafted with acrylamide and acrylic acid copolymer as an ultrasensitive and selective riboflavin electrochemical sensor in real samples

In current research, an innovative pectic acid was grafted with poly (acrylamide-co-acrylic acid) [PA-g-poly (AAm-co-AA)] nanoporous membrane using a free radical-mediated grafting copolymerization process. The optimized parameters for the grafting copolymerization reaction such as initiator concentration, monomer concentrations, polymerization reaction time, and temperature were studied. Additionally, the solid content, graft percentage, and conversion were calculated. The unique polymeric membrane was characterized using Fourier-transform infrared spectroscopy (FT-IR), thermal gravimetry (TG), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) supported by energy dispersive X-ray spectroscopy (EDX). The formulated novel PA-g-poly (AAm-co-AA) had a nanoporous structure with a diameter of 113 nm. pH-dependent swelling and biodegradation measurements were also studied. The electrochemical characterizations of PA-g-poly (AAm-co-AA) were conducted through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Furthermore, the screen-printed electrode (SPE) was modified with pure PA and the new generation of its grafted polymeric nanoparticles to detect and quantify the concentration of riboflavin (RF) in real samples using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The modified electrode showed two linear concentration ranges from 0.01 - 2 nM and 2 – 90 nM with low detection limits (LODs) of 0.004 and 0.97 nM, respectively, demonstrating high sensitivity. Besides, the fabricated sensor exhibited more selectivity, simplicity, great reproducibility, repeatability, and good stability. Finally, the PA-g-poly (AAm-co-AA)-modified SPE based sensor was effectively used in real sample analysis of egg yolk, milk, and vitamin B2 drugs with good recovery rates.

Microstructural design of crown nanopores in graphene membrane for efficient desalination process

Designing a membrane with simultaneous high water permeability and desalination rate to overcome the trade-off presents a persistent and substantial challenge. In this paper, we employed molecular dynamics simulations to design the structure of the graphene crown ether reverse osmosis membrane and elucidate the relationship between the membrane's microscopic separation mechanism and its structure-activity.The results show that the water permeability through crown graphene nanopores exceeded that of the original graphene nanopores by an order of magnitude, and hundreds of times greater than that of the traditional reverse osmosis membrane. Additionally, the water permeation in multilayer crown graphene nanopores also surpassed that in monolayer original graphene nanopores. The water permeability exceeds 46.73 L/cm2/day/Mpa with 100 % salt rejection. Furthermore, the various sizes and shapes of graphene nanopores significantly influence water permeation. Within crown graphene nanopores, a narrow pore enables superior water permeation and salt rejection compared to a circular shape, unlike original graphene nanopores. Observed from MD simulation trajectories,this highly water permeation is caused by the hydrogen bonding between crown ether graphene and water molecules. First-principle calculations further confirm that water transport in graphene crown ether is energetically more favorable than in original graphene nanopores. Our findings support crown graphene membranes as promising candidates for seawater desalination.

Scan-Rate-Dependent Ion Current Rectification in Bipolar Interfacial Nanopores.

This study presents a theoretical investigation into the voltammetric behavior of bipolar interfacial nanopores due to the effect of potential scan rate (1-1000 V/s). Finite element method (FEM) is utilized to explore the current-voltage (I-V) properties of bipolar interfacial nanopores at different bulk salt concentrations. The results demonstrate a strong impact of the scan rate on the I-V response of bipolar interfacial nanopores, particularly at relatively low concentrations. Hysteresis loops are observed in bipolar interfacial nanopores under specific scan rates and potential ranges and divided by a cross-point potential that remains unaffected by the scan rate employed. This indicates that the current in bipolar interfacial nanopores is not just reliant on the bias potential that is imposed but also on the previous conditions within the nanopore, exhibiting history-dependent or memory effects. This scan-rate-dependent current-voltage response is found to be significantly influenced by the length of the nanopore (membrane thickness). Thicker membranes exhibit a more pronounced scan-rate-dependent phenomenon, as the mass transfer of ionic species is slower relative to the potential scan rate. Additionally, unlike conventional bipolar nanopores, the ion current passing through bipolar interfacial nanopores is minimally affected by the membrane thickness, making it easier to detect.

Permeability of gas molecules through sub-nanometer nitrogen-terminated porous graphene membranes: A DFT study

We present a systematic theoretical investigation of gas permeability through single-layer nanoporous graphene membranes with N-terminated (pyridinic and mixed pyridinic/pyrrolic) pores for He, H2, N2, O2, CO, CO2, H2O, and CH4. Our study is based on density functional theory transition-state calculations and the kinetic theory of gasses. We systematically evaluate pores of varying sizes and shapes up to 5.7 Å in diameter. According to our findings, membranes with pores in the size regime (4.5 Å - 5.0 Å) may exhibit industrially acceptable permeance to several gas molecules and advanced selectivity. Notably, we found that, among a few others, a pore with the same topological features at the pore boundary as those of the characteristic pore of g-C3N4 carbon nitride, is particularly promising. In addition, membranes with larger pores, ∼5.5 Å - 5.7 Å, can effectively separate CH4 from the other molecules. Our findings support the advanced potential of single-layer graphene membranes with nitrogen-terminated sub-nanometer pores, for gas separation applications.

In situ generation of (sub) nanometer pores in MoS2 membranes for ion-selective transport

Ion selective membranes are fundamental components of biological, energy, and computing systems. The fabrication of solid-state ultrathin membranes that can separate ions of similar size and the same charge with both high selectivity and permeance remains a challenge, however. Here, we present a method, utilizing the application of a remote electric field, to fabricate a high-density of (sub)nm pores in situ. This method takes advantage of the grain boundaries in few-layer polycrystalline MoS2 to enable the synthesis of nanoporous membranes with average pore size tunable from <1 to ~4 nm in diameter (with in situ pore expansion resolution of ~0.2 nm2 s−1). These membranes demonstrate selective transport of monovalent ions (K+, Na+ and Li+) as well as divalent ions (Mg2+ and Ca2+), outperforming existing two-dimensional material nanoporous membranes that display similar total permeance. We investigate the mechanism of selectivity using molecular dynamics simulations and unveil that the interactions between cations and the sluggish water confined to the pore, as well as cation-anion interactions, result in the different transport behaviors observed between ions.

Molecular kinetic modelling of non-equilibrium evaporative flows

Recent years have seen the emergence of new technologies that exploit nanoscale evaporation, ranging from nanoporous membranes for distillation to evaporative cooling in electronics. Despite the increasing depth of fundamental knowledge, there is still a lack of simulation tools capable of capturing the underlying non-equilibrium liquid–vapour phase changes that are critical to these and other such technologies. This work presents a molecular kinetic theory model capable of describing the entire flow field, i.e. the liquid and vapour phases and their interface, while striking a balance between accuracy and computational efficiency. In particular, unlike previous kinetic models based on the isothermal assumption, the proposed model can capture the temperature variations that occur during the evaporation process, yet does not require the computational resources of more complicated mean-field kinetic approaches. We assess the present kinetic model in three test cases: liquid–vapour equilibrium, evaporation into near-vacuum condition, and evaporation into vapour. The results agree well with benchmark solutions, while reducing the simulation time by almost two orders of magnitude on average in the cases studied. The results therefore suggest that this work is a stepping stone towards the development of an accurate and efficient computational approach to optimising the next generation of nanotechnologies based on nanoscale evaporation.

Investigation of High Frequency Irreversible Electroporation for Canine Spontaneous Primary Lung Tumor Ablation.

In this study, the feasibility of treating canine primary lung tumors with high-frequency irreversible electroporation (H-FIRE) was investigated as a novel lung cancer treatment option. H-FIRE is a minimally invasive tissue ablation modality that delivers bipolar pulsed electric fields to targeted cells, generating nanopores in cell membranes and rendering targeted cells nonviable. In the current study, canine patients (n = 5) with primary lung tumors underwent H-FIRE treatment with an applied voltage of 2250 V using a 2-5-2 µs H-FIRE waveform to achieve partial tumor ablation prior to the surgical resection of the primary tumor. Surgically resected tumor samples were evaluated histologically for tumor ablation, and with immunohistochemical (IHC) staining to identify cell death (activated caspase-3) and macrophages (IBA-1, CD206, and iNOS). Changes in immunity and inflammatory gene signatures were also evaluated in tumor samples. H-FIRE ablation was evident by the microscopic observation of discrete foci of acute hemorrhage and necrosis, and in a subset of tumors (n = 2), we observed a greater intensity of cleaved caspase-3 staining in tumor cells within treated tumor regions compared to adjacent untreated tumor tissue. At the study evaluation timepoint of 2 h post H-FIRE, we observed differential gene expression changes in the genes IDO1, IL6, TNF, CD209, and FOXP3 in treated tumor regions relative to paired untreated tumor regions. Additionally, we preliminarily evaluated the technical feasibility of delivering H-FIRE percutaneously under CT guidance to canine lung tumor patients (n = 2). Overall, H-FIRE treatment was well tolerated with no adverse clinical events, and our results suggest H-FIRE potentially altered the tumor immune microenvironment.