Ion transport in two-dimensional flexible nanoporous membranes
Ion transport through 2D nanoporous membrane and the vibrational coupling between ions and membrane.
42 ENGINEERING↗
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Water content modulation enables selective ion transport in 2D MXene membranes
Separation membranes are critical for a range of processes, including but not limited to water desalination, chemical and fuel production, and recycling and recovery applications. Fundamentally, there are intrinsic trade-offs between permeability and selectivity. Local water organization and content can impact membrane structure (short- and long-range) in laminar transition metal carbide (MXene) membranes and impact selective ion permeation. Intercalation of chaotropic cesium (Cs + ) ions within the layers reduces the water content in the membrane and at the surface which cannot be found in the intercalation of other ions. Additionally, 3D imaging using focused ion beam scanning electron microscopy showed fewer defects in the Cs-MXene membrane, due to reduced local water content, leading to more efficient ion sieving. X-ray diffraction and density functional theory calculations on the nanochannel structure demonstrated that the chaotropic ion results in the smallest nanochannel size and induces a stronger resistance to water-induced nanochannel swelling. With a narrower nanochannel, the Cs-MXene membrane limits ion transport pathways, resulting in more selective transport of lithium over other metal cations, as evidenced in both experiment and molecular dynamics simulations. In conclusion, our findings highlight the potential for controlling the structural organization of 2D MXene membranes to enable on-demand transport of ions for diverse applications.
36 MATERIALS SCIENCE↗
Ion Transport in Self-Assembled Peptoid Membranes with Carbon Nanotube Porin Channels
Artificial membranes that combine high ionic selectivity with mechanical robustness remain a key challenge for next-generation separation technologies. Here, we report ion transport measurements in biomimetic membranes composed of crystalline peptoid nanosheets co-assembled with carbon nanotube porins (CNTPs). Pure peptoid sheets formed defect-free, ion-impermeable membranes, which were then suspended over small SiN x nanopore apertures for ion transport measurements. Incorporation of CNTPs into the peptoid sheet matrix made these membranes ion permeable, with ion conductance values consistent with ion transport through individual and multiple carbon nanotube channels. In conclusion, the modularity and molecular order of peptoid membranes, combined with the exceptional conductance properties of CNTPs, position this platform as a versatile framework for assembling programmable, selective, and robust nanofluidic membranes that can bridge the performance gap between biological and synthetic membrane materials.
Biotechnology↗
Influence of Rigidity–Hydration Coupling on Size-Dependent Diffusion in Hydrated Polymer Membranes
Selective ion transport in polymer membranes depends critically on how penetrant motion couples to polymer dynamics and hydration. Yet, the mechanistic interplay between polymer rigidity, water content, and penetrant size remains poorly understood, especially in the regime where the penetrant diameter, polymer Kuhn length, and correlation length are comparable. Here, we employ coarse-grained molecular dynamics simulations to systematically investigate penetrant diffusion in hydrated polymer networks across a broad range of water volume fractions, chain rigidities, and penetrant sizes. The results reveal a transition from a decoupled regime, where small penetrants diffuse nearly independently of polymer relaxation, to a coupled regime in which large penetrants require cooperative polymer motion for transport. Increasing polymer rigidity amplifies the sensitivity of diffusivity to hydration, particularly at low water content, leading to pronounced deviations from Stokes−Einstein scaling. Comparison with scaling theories and free-volume models shows that classical nanoparticle-based frameworks fail to capture this intermediate regime. To address this gap, we extend the Yasuda model to incorporate polymer rigidity through a single parameter that quantifies the dynamic contribution of chain stiffness to free-volume fluctuations. The resulting model collapses diffusivity data across all sizes, water contents, and rigidities, providing a unified description of penetrant transport in hydrated polymer matrices. Furthermore, these findings establish polymer rigidity as a key, tunable determinant of diffusion and offer a framework for interpreting size-dependent transport in ion-selective membranes.
diffusion↗
Unraveling Ion Transport in Trifluoromethanesulfonimide Pentablock Copolymer Membranes in Nonaqueous Electrolytes
Cation exchange membranes provide a key function in various nonaqueous energy storage technologies. As such, understanding the role of a nonaqueous liquid electrolyte on ion transport through a membrane is imperative. This study unravels relationships between membrane ion transport and electrolyte salt concentration utilizing a trifluoromethanesulfonimide-based pentablock copolymer membrane with polar and nonpolar nonaqueous electrolyte solutions. Here, the membrane plasticized with propylene carbonate (PC) exhibits a single-ion conductivity of 9.3 × 10 –6 S/cm at 25 °C. Tailoring the nonaqueous electrolyte and electrolyte salt concentration enables the single-ion conducting membrane to maintain a high cation transport number, >0.75, and boost ion conductivity more than 10 times to 1.3 × 10 –4 S/cm at 25 °C for the PC-based electrolyte solution. The findings provide critically important design parameters for energy storage systems utilizing nonaqueous electrolytes, such as Li- and Na-ion batteries and nonaqueous flow battery technologies.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Polyamide-Based Ion Exchange Membranes: Cation-Selective Transport through Water Purification Membranes
Ion-selective membranes are necessary components of many electrochemical systems including fuel cells, electrolyzers, redox flow batteries, and electrodialyzers. Perfluorinated sulfonated membranes (PFSMs) dominate these applications due to their excellent combination of fast ion transport, stability, and processability. However, perfluorinated cation exchange membranes (CEMs) are expensive, and their production process involves chemistry that generates toxic perfluorinated chemicals. The development of affordable, nonfluorinated membranes with a competitive combination of high ion selectivity, transport, and stability could help enable the widespread use of the technologies listed above while hastening the development of emerging electrochemical systems, including aqueous alkaline CO 2 sorbent regeneration. To this end, we pursue the use of thin-film composite polyamide (PA-TFCs) membranes–those that typically find application in reverse osmosis and nanofiltration desalination–as cation-selective exchange membranes. Given their negative surface charge under neutral-to-alkaline conditions, PA-TFCs can serve as effective CEMs in these pH regimes. We prepared a series of PA-TFCs from traditional monomers (trimesoyl chloride and piperazine) and compared their thicknesses, charge densities, water transport properties, ion transport properties, and long-term stability in a high pH environment to traditional CEMs (Nafion and FKE) and commercial nanofiltration and reverse osmosis membranes. We find that some of the best-performing PA-TFC membranes have similar resistances and Na + transference numbers compared to Nafion 117 in Na 2 SO 4 and NaHCO 3 -containing solutions. This proof-of-principle study suggests that further optimization of PA-TFCs could enable cost-effective ion exchange membrane alternatives to PFSMs.
36 MATERIALS SCIENCE↗
Hydration size-dependent transport of ions across nanoporous graphene membranes
Nanoporous atomically-thin membranes are promising candidates for metal ion separations due to their chemical stability and high permeance and selectivity, but experimental evidence of the mechanisms responsible for ion-ion selectivity is sparse. Here, in this work, we measured the simultaneous diffusion of a dilute mixture of ten different Group I, Group II, and rare earth cations in a salt background across nanoporous graphene (NPG) membranes with sub-nanometer pores. The membranes exhibited ion-ion selectivity, including between similarly-charged ions. Cation transport was governed primarily by the hydrated ion size that was consistent with continuum models of ion diffusion, with additional influence of the ionic charge. Selectivity enhancement was achieved by modifying ion sizes using an ion-selective complexing agent. Our study provides evidence of the importance of size-sieving and electrostatic mechanisms governing ion transport across NPG, and allows for quantitative prediction of transport rates to guide future development of ion-selective atomically-thin membranes.
36 MATERIALS SCIENCE↗
Specific ion effects on ion transport in charged polymer membranes
Selective separation of like-charged ions is a central challenge in applications such as critical mineral recovery. Electrochemical membrane–based separations offer promising pathways to address this need, but a limited fundamental understanding of ion transport in charged polymer membranes hampers the development of highly selective materials. This study elucidates the role of specific ion effects (SIEs) in ion transport through charged polymer membranes by integrating experimental measurements of ion mobility and in situ ion/ion and ion/water interactions in model charged polymer membranes with results from molecular dynamics simulations on analogous systems. We demonstrate that solvent-mediated ion interactions drive pronounced SIEs within the studied membranes, with the ion softness, i.e., the malleability of ion hydration shells, from hard/soft acid/base (HSAB) theory emerging as a key predictor of transport properties. HSAB theory also explains the observed mechanism of solvent-mediated ion interactions. Our findings offer a mechanistic framework for designing membranes with tailored ion selectivity, potentially enabling efficient separations of chemically similar ions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Versatile Synthetic Platform for Polymer Membrane Libraries Using Functional Networks
Poly(ethylene glycol) (PEG) diacrylate copolymer networks containing pentafluorophenyl active esters can be quantitatively substituted with a wide variety of primary amines, enabling the development of a versatile synthetic platform for the preparation of polymer hydrogel and membrane libraries. Here, by tuning the starting network, a high degree of control over cross-linking density, water uptake, and functional group incorporation can be reproducibly achieved, which is vital for elucidating structure–property relationships in ion transporting membranes. From the same cross-linked scaffold, a diversity of basic, acidic, and solute-chelating moieties were obtained through functionalization, which allows for tailored uptake of basic and acidic organic dyes and metal chloride salts. Ion permeation and sorption measurements for a series of polymer networks with controlled cross-linking density and varied imidazole grafting densities illustrate the ability of this platform to isolate the effect of chemical functionality on ion transport from the effects of cross-linking density and water content.
36 MATERIALS SCIENCE↗
The effect of ion pairing on speciation and transport in ion exchange membranes at varying hydration levels: A four-state model
Understanding ion pairing in ion exchange membranes (IEMs) is essential for advancing IEM applications in energy and environmental technologies. Here, this study introduces a four-state molecular dynamics model to quantify speciation and transport within Nafion-117, specifically examining the role of ion pairing in monovalent and divalent counterions (NaCl, Na 2 SO 4 , and MgSO 4 ). By analyzing radial distribution functions (RDFs) and molecular snapshots, we distinguish ion pairing modes and classify counterions into four states: condensed counterion, condensed ion pair, free ion pair, and free counterion. A key finding is that while divalent counterions (e. g., Mg 2+ ) maintain stable speciation across hydration levels, monovalent counterions (e.g., Na + ) show notable speciation shifts with hydration. Both monovalent and divalent counterions are not diffusive when condensed onto the polymer (sorbed to membrane functional groups). In contrast, free counterions are diffusive across all hydration levels. To evaluate the overall diffusivity of counterions, four-state fractions and diffusivities are computed, each contributing to counterion transport. The condensed/free ion speciation for multivalent sulfate salts aligns with previous revisions to the Donnan-Manning framework that include ion pairing, thereby validating its relevance to established membrane theories. The four-state model's diffusivity results support several current ion exchange assumptions, including that the condensed counterions are immobile, while uncondensed counterions are mobile. The four-state model offers insights into contact ion pairing within IEMs, highlighting its potential even when undetected in aqueous solution experiments. This work advances the theoretical understanding of counterion speciation in IEMs while identifying model limitations that suggest avenues for refinement, such as distinguishing water-mediated ion pairs between fully hydrated ions.
Ion exchange membranes↗
Impact of Ion–Ion Correlated Motion on Salt Transport in Solvated Ion Exchange Membranes
The influence of dynamical ion-ion correlations and ion pairing on salt transport in ion exchange membranes remain poorly understood. In this study, we use the framework of Onsager transport coefficients within atomistic molecular dynamics sim- ulations to study the impact of ion-ion correlated motion on salt transport in hydrated polystyrene sulfonate membranes and compare with the results from aqueous salt so- lutions. At sufficiently high salt concentrations, cation-anion dynamical correlations exert a significant influence on both salt diffusivities and conductivities. Anion-anion distinct correlations, arising from the imbalance between the concentration of free (mo- bile) cations and anions, and the retarding effect of the fixed charge groups on cations, proves to be an additional important feature for polymer membranes. Furthermore, our results demonstrate that dynamical correlations should become an important consideration in experimental measurements of salt diffusivities and conductivities for non-dilute salt solutions in polymer membranes.
36 MATERIALS SCIENCE↗
Measurement of ion transport properties in ion exchange membranes for photoelectrochemical water splitting
Photoelectrochemical (PEC) water-splitting systems have the unique ability to produce renewable hydrogen directly from sunlight, independent of the electrical grid. These systems are therefore appealing technological options for resilient long-term energy storage. Ion selective membranes, such as monopolar and bipolar membranes, are a vital component of PEC water-splitting systems. These membranes allow for ionic conduction between the cathode and anode chambers, separation of products, and improved catalyst environments for reactions. In order to measure key properties and to study the performance of these ion exchange membranes, it is imperative to develop a robust testing protocol that can be used across the field. This paper introduces two standard electrochemical cells designed to directly measure ion transport properties in monopolar and bipolar membranes. The first electrochemical cell uses commercially available Pt disk electrodes to preform electrochemical impedance spectroscopy (EIS) and reliably measure through-plane conductivity of monopolar membranes. The second electrochemical cell uses four-point measurements with Luggin capillaries and a series of membrane configurations to perform current density-voltage and Faradaic efficiency (FE) measurements for water dissociation (WD) reactions on bipolar membranes. The cell designs and techniques laid out below allow for accurate measurement of ion transport parameters in ion exchange membranes, direct comparison of membranes being developed across the field, and in turn, greater advancements in ion exchange membranes and PEC water-splitting systems.
cation exchange membrane↗
Ion Transport in Charged Membranes: Linking Electric-Field-Driven Mechanisms to Pore Size via Perturbation Analysis
Ion-exchange membranes are a critical component in electrochemical systems. Nevertheless, the understanding and modeling of ion transport within these porous structures have been limited by particular complexity reductions, either ignoring the dimensionality of their porous network architecture or imposing geometric assumptions (i.e., overlapping double layers). Before addressing this morphology-transport gap, a framework that relates the driving forces of transport to the geometry of a single pore is required. In this work, our modeling domain consists of a two-dimensional single pore with charged walls, connecting two identical electrolyte reservoirs. Using the Poisson-Nernst-Planck equations and regular perturbation theory, we decouple the electric fields and analyze the driving forces of ion transport, specifically electromigration and induced electroosmosis within the pore. These processes are described as analytical functions of the interaction aspect ratio, ?, defined as the ratio of the pore radius to the Debye length. Using this parameter, our study (i) describes the interplay between electromigrative and electroosmotic mechanisms that set ionic conductivity, (ii) identifies a dimensionless group of intrinsic electrolyte properties that indicates the predominant driving force, and (iii) provides a qualitative, confinement-dependent perspective on selectivity in ion-conducting membranes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Oxy-Combustion System Process Optimization
The overall objective of this work is to develop a new chemical absorbent-based, high pressure, CO 2 purification system to remove the residual oxygen that currently contaminates the recovered CO 2 , and to optimize the Pressurized Oxy-Combustion (POxC) process to minimize the Cost of Electricity (COE) generated in this advanced combustion process. TDA developed and validated the performance of the oxygen removal system for CO 2 purification. In collaboration with the Advanced Power & Energy Program (APEP) of University of California, Irvine (UCI), we optimized the POxC process, including thermal management, heat integration, and power cycle optimization using process design and modeling supported with Aspen Plus® process simulations. The techno-economic analysis results indicate that the pressurized oxycombustion coal power plant with Ion-transport membrane (ITM) air separation unit (ASU) (Case 2 – 30.55%) does not show an advantage over a cryogenic ASU (Case 1 – 31.24%) while TDA’s sorption-based ASU (Case 4 - 32.61%) shows a significant advantage over the cryogenic ASU (Case 1 – 331.24%). The specific plant costs show a wide range with a low of $2544/kW for Case 11C (TDA ASU, co-sequestering the SO x , and ultra-supercritical steam cycle) to a high of $2975/kW for Case 12A (cryogenic ASU and sCO 2 cycle). In general, the ITM ASU based cases have lower specific plant costs than the corresponding cryogenic ASU based cases while the TDA ASU based cases show the lowest specific plant costs. The main reason for lowering these costs is the higher overall plant thermal efficiency which decreases the plant cost on a $ per kW basis. Next comparing the cases with different power cycle working fluid conditions in terms of temperature and pressure while all utilizing steam, similar trends as the plant costs may be observed. However, with the supercritical CO 2 (sCO 2 ) cycle, the increase in thermal efficiency of the sCO 2 cycle was not able to offset its increase in plant cost making the plant costs higher than those of the corresponding steam cycle cases. The Cost of Electricity (COE) again shows similar trends as the specific plant costs. The COE for Case 11C at $110.1/MWh is also the lowest, but among all cases that do not co-sequester the SO x , Case 12C (TDA ASU and sCO 2 cycle) has the lowest COE at $\$$117.5/MWh while the highest is for Case 8A (cryogenic ASU and supercritical steam cycle) at $130.4/MWh.
20 FOSSIL-FUELED POWER PLANTS↗
Multi-Constituent Airborne Contaminants Capture with Low Cost Oxide Getters and Mitigation of Cathode Poisoning in Solid Oxide Fuel Cell
The technical effort and scientific findings, discussed in this report, documents operational barriers and associated long term performance stability challenges posed by the presence of trace airborne multi-constituent contaminants present in high-temperature electrochemical systems, including Solid Oxide Fuel Cells (SOFCs), Solid Oxide Electrolysis Cells (SOECs), Ion Transport Membranes, and Gas Separation systems. Above systems, offering promises for cleanliness and energy efficiency, face challenges with electrode poisoning stemming from the presence of trace contaminants including gaseous Cr/B/Si vapors in the presence of intrinsic contaminants SO 2 /CO 2 /H 2 O gases. The study indicates that the long-term electrical performance degradation in SOFC systems can be traced to electrochemical, structural, and mechanical changes across cell, stack, and balance of plant components resulting from interactions with trace contaminants leading to increase in both ohmic and non-ohmic polarizations. The degradation primarily results from solid-state and gas-phase materials migration, electrode poisoning, and interactions at the cell and stack levels. Cathode degradation emerges as a significant factor impacting overall SOFC performance, especially related to the presence of intrinsic and extrinsic airborne impurities such as SOx, CrOx(OH)y, SOx, Si(OH)x, and HBOx. Although at trace levels, prolong systems operation at higher airflow (3-10X stoichiometric) allow the accumulation of contaminants within the cell components leading to electrical performance degradation through poisoning and electrode deactivation.
20 FOSSIL-FUELED POWER PLANTS↗
Tunable Ion Transport with Freestanding Vermiculite Membranes
Membranes integrating two-dimensional (2D) materials have emerged as a category with unusual ion transport and potentially useful separation applications in both aqueous and nonaqueous systems. The interlayer galleries in these membranes drive separation and selectivity, with specific transport properties determined by the chemical and structural modifications within the inherently different interlayers. Here, in this work, we report an approach to tuning interlayer spacing with a single source material–exfoliated and restacked vermiculite with alkanediamine cross-linkers–to both control the gallery height and enhance the membrane stability. The as-prepared cross-linked 2D vermiculite membranes exhibit ion diffusivities tuned by the length of the selected diamine molecule. The 2D nanochannels in these stabilized vermiculite membranes enable a systematic study of confined ionic transport.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Intrapore energy barriers govern ion transport and selectivity of desalination membranes
A fundamental study elucidates the mechanisms underlying selective ion transport through desalination membranes.
36 MATERIALS SCIENCE↗
Interfacial interactions between polymers and selective adsorbents influence ion transport properties of boron scavenging ion-exchange membranes
The recent emergence of adsorptive ion-exchange membranes (IEMs), designed by the synergistic integration of highly selective porous aromatic frameworks (PAFs) with ion-exchange polymers, has enabled simultaneous desalination and targeted removal of specific solutes (e.g., mercury, iron, boron, etc.). While the addition of highly selective PAFs to IEMs yields membranes with entirely new functions, PAF-polymer interactions, and the effects of such interactions on ion transport properties of the membranes, are not well understood. In this study, we developed cross-linked adsorptive cation- and anion-exchange membranes (CEMs and AEMs) for simultaneous desalination and boron removal via in-situ formation of the cross-linked polymer network around the boron selective PAF particles. Here we systematically investigated the influence of PAF loading level on PAF-polymer interactions as well as the equilibrium and transport properties of the adsorptive IEMs. The interactions between the PAF and the ion-exchange polymer matrix differed for the CEMs and AEMs due to differences in the fixed charge group chemistry. Notably, the sulfonate groups of the CEMs can form hydrogen bonds with the hydroxyl groups of the PAF, while the quaternary ammonium groups in the AEMs cannot. These differences in interfacial interactions did not significantly impact counter-ion transport across the adsorptive IEMs but had a significant influence on co-ion transport, which affected the counter-ion/co-ion selectivity of the membranes. The selectivity of the adsorptive CEMs decreased while that of the adsorptive AEMs increased with PAF loading level. The results of this study underscore the importance of controlling interfacial interactions when designing adsorptive IEMs for simultaneous water desalination and solute capture and recovery.
36 MATERIALS SCIENCE↗