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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Heterogeneous Multilayer Nanopores via Chemically Tuned Dielectric Breakdown for Single‐Molecule Sensing

Solid-state nanopores are powerful platforms for single-molecule sensing, yet their performance is often constrained by fabrication complexity, noise, and limited control over surface properties. Here we report a direct method to fabricate heterogeneous multilayer nanopores using chemically tuned controlled dielectric breakdown (CT-CDB). We integrate hBN, MoS 2 , or graphene atop a silicon nitride membrane to form five distinct bilayer and tri-layer architectures, with bare SiN x nanopore as a control. CT-CDB achieves pore formation reproducibly through material-stacks with high efficiency, good pore size control, and strong yield, validated by various characterizations. Transferrin protein translocation experiments, supported by simulations, reveal that multilayer configurations modulate protein conformations, ionic current blockade and dwell time distributions, reflecting combined effects of membrane type, interfacial chemistry, and local electric field gradients. A supervised machine learning framework is implemented to assist identifying multilayer structure effects embedded in signal signatures, with over 96% accuracy. This work presents a modular and scalable framework for functional nanopore engineering with complex structural integration, thereby expanding the potential of 2D materials in single-molecule sensing applications.

2D materials↗
DOE OSTI2025

Composite Behavior of Nanopore Array Large Memristors

Synthetic nanopores were recently demonstrated with memristive and nonlinear voltage-current behaviors, akin to ion channels in a cell membrane. Such ionic devices are considered a promising candidate for the development of brain-inspired neuromorphic computing techniques. In this work, we show the composite behavior of nanopore-array large memristors, formed with different membrane materials, pore sizes, electrolytes, and device arrangements. Anodic aluminum oxide (AAO) membranes with 5 nm and 20 nm diameter pores and track-etched polycarbonate (PCTE) membranes with 10 nm diameter pores are tested and shown to demonstrate memristive and nonlinear behaviors with approximately 107–1010 pores in parallel when electrolyte concentration across the membranes is asymmetric. Ion diffusion through the large number of channels induces time-dependent electrolyte asymmetry that drives the system through different memristive states. The behaviors of series composite memristors with different configurations are also presented. In addition to helping understand fluidic devices and circuits for neuromorphic computing, the results also shed light on the development of field-assisted ion-selection-membrane filtration techniques as well as the investigations of large neurons and giant synapses. Further work is needed to de-embed parasitic components of the measurement setup to obtain intrinsic large memristor properties.

Chemistry↗
DOE OSTI2021

Understanding Electrical Conduction and Nanopore Formation During Controlled Breakdown

Controlled breakdown has recently emerged as a highly appealing technique to fabricate solid-state nanopores for a wide range of biosensing applications. This technique relies on applying an electric field of approximately 0.4–1 V nm –1 across the membrane to induce a current, and eventually, breakdown of the dielectric. Although previous studies have performed controlled breakdown under a range of different conditions, the mechanism of conduction and breakdown has not been fully explored. Here, electrical conduction and nanopore formation in SiN x membranes during controlled breakdown is studied. It is demonstrated that for Si-rich SiN x , oxidation reactions that occur at the membrane-electrolyte interface limit conduction across the dielectric. However, for stoichiometric Si 3 N 4 the effect of oxidation reactions becomes relatively small and conduction is predominately limited by charge transport across the dielectric. Several important implications resulting from understanding this process are provided which will aid in further developing controlled breakdown in the coming years, particularly for extending this technique to integrate nanopores with on-chip nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enzymatically active high-flux selectively gas-permeable membranes for enhanced oil recovery and carbon capture

A membrane structure for moving a gaseous object species from a first region having an object species first concentration, through the membrane structure, to a second region having an object species second concentration different from the first concentration is described. The membrane includes a supporting substrate having a plurality of pores therethrough, each of the plurality of pores defined by a first end, a second end and a surface of the supporting substrate extending between the first end and the second end as well as a nanoporous layer within the plurality of pores, wherein the nanoporous layer comprises a hydrophilic layer and a hydrophobic layer. The membrane also includes a liquid transport medium within the hydrophilic layer. The liquid transport medium includes a liquideous permeation medium and at least one enzyme within the liquideous permeation medium. The at least one enzyme is reinforced by at least one stabilizing component.

Rempe, Susan Lynne↗
DOE OSTI2025

Neutral but Impactful: Gallium Cluster-Induced Nanopores from Beam-Blanked Gallium Ion Sources

Neutral atoms originating from liquid metal ion sources are an often-overlooked source of contamination and damage in focused ion beam microscopy. Beyond ions and single atoms, these sources also generate atom clusters. While most studies have investigated charged clusters, here we demonstrate that neutral clusters are also formed. These neutral clusters bypass the electrostatic beam blanking system, allowing them to impinge on samples even when the ion beam is blanked. We investigate this phenomenon using thin (≤20 nm) freestanding membranes of hexagonal boron nitride, silicon, and silicon nitride as targets. Randomly dispersed nanopores that form upon neutral cluster exposure are revealed. The average nanopore diameter is ∼2 nm with a narrow size distribution, suggesting that the atom clusters have a preferred size. Various electron microscopy techniques are used to characterize the nanopores, including high-resolution transmission electron microscopy, multislice ptychography, and electron energy-loss spectroscopy. Finally, we show how electron irradiation in the transmission electron microscope can be used to both remove any amorphous material that may clog the pores and to controllably grow the pores to specific sizes. Tunable nanopores such as these are interesting for nanofluidic applications requiring size-selective membranes.

Byrne, Dana O↗
DOE OSTI2020

Bottom-up Assembly of Nanoporous Graphene with Emergent Electronic States

The incorporation of nanoscale pores into a sheet of graphene allows it to switch from an impermeable semimetal to a semiconducting nanosieve. Nanoporous graphenes are desirable for applications ranging from high-performance semiconductor device channels to atomically thin molecular sieve membranes, and their performance is highly dependent on the periodicity and reproducibility of pores at the atomic level. Achieving precise nanopore topologies in graphene using top-down lithographic approaches has proven to be challenging due to poor structural control at the atomic level. Alternatively, atomically precise nanometer-sized pores can be fabricated via lateral fusion of bottom-up synthesized graphene nanoribbons. This technique, however, typically requires an additional high temperature cross-coupling step following the nanoribbon formation that inherently yields poor lateral conjugation, resulting in 2D materials that are weakly connected both mechanically and electronically. Here, we demonstrate a novel bottom-up approach for forming fully conjugated nanoporous graphene through a single, mild annealing step following the initial polymer formation. We find emergent interface-localized electronic states within the bulk band gap of the graphene nanoribbon that hybridize to yield a dispersive two-dimensional low-energy band of states. We show that this low-energy band can be rationalized in terms of edge states of the constituent single-strand nanoribbons. The localization of these 2D states around pores makes this material particularly attractive for applications requiring electronically sensitive molecular sieves.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi‐Purpose Polyamine Functionalization

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10–30 nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm 2 and GO layer thicknesses of ≈500 nm are fabricated, and they exhibited a stable dye water permeance of 75 L m −2 h −1 bar −1 , rejection of >99.5% for Direct red and Congo red, and Na 2 SO 4 /dye separation factor of 300–500, superior to state-of-the-art commercial membranes. Furthermore, the versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

amine functionalization↗
DOE OSTI2023

Self-assembly of co-continuous nanostructured copolymer templates with compositional and architectural dispersity

In our previous DOE-supported project (DE-SC0016208), we demonstrated that a particular architecture dubbed ‘randomly end-linked copolymer networks’ (RECNs) led to especially robust self-assembly of disordered cocontinuous nanostructures. Such structures, wherein both microphases are fully percolating in three dimensions, are attractive for a wide-variety of energy-relevant applications including purification membranes, separators in batteries and fuel cells, catalyst supports, and high surface area electrodes. In the current project we sought to substantially extend our fundamental understanding of how different types of randomness in blocky copolymer architecture contribute to the robust formation of disordered cocontinuous nanostructures. To do so, we filled in the sizable gap between the previously studied cases of randomly linked linear multiblock copolymers and RECNs by studying two intermediate cases: (i) random miktoarm star polymers, which contain dispersity in the number of the two chemically-incompatible strands located at each junction and therefore the preferred interfacial curvature of each polymer, and (ii) randomly branched copolymers, which also possess bridging strands that stretch across domains and apply local ‘elastic’ forces to the interfaces. In addition, we studied a different network architecture, statistically crosslinked copolymer networks, that is more straightforward to prepare using chain growth polymerization methods, enabling more facile formation of cocontinuous nanostructures. Finally, we extended our approaches from model systems based on polystyrene and poly(lactic acid) to copolymer architectures containing either (i) polysulfone, an engineering polymer that provides excellent mechanical properties for membrane applications, or (ii) polyacrylonitrile, providing a convenient route to nanoporous carbon materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Simultaneously Blocking Chemical Crosstalk and Internal Short Circuit via Gel-Stretching Derived Nanoporous Non-Shrinkage Separator for Safe Lithium-Ion Batteries

The separator, an ionic permeable and electronic insulating membrane between cathode and anode, plays a crucial role in the electrochemical and safety performance of batteries. However, the commercial polyolefin separators not only suffer from inevitable thermal shrinkage at elevated temperature, but also fail to inhibit the hidden chemical crosstalk of reactive gases such as O 2 , leading to often reported thermal runaway (TR) and hence preventing large-scale implementation of high-energy-density lithium-ion batteries. Herein, a nanoporous non-shrinkage separator (GS-PI) was fabricated via a novel gel-stretching orientation approach to eliminate TR. In situ synchrotron small angle X-ray scattering during heating clearly showed that the as-prepared thin GS-PI separator exhibits superior mechanical tolerance at high temperature, thus effectively preventing internal short circuit. Meanwhile, the unique nanoporous structure design further blocks chemical crosstalk and the associated exothermic reactions. Accelerating Rate Calorimetry test revealed that the practical 1 Ah LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)/graphite pouch cell using GS-PI nanoporous separator show a maximum temperature rise (dT/dt max ) of only 3.7 °C s -1 compared to 131.6 °C s -1 in the case of Al 2 O 3 @PE macroporous separator. Furthermore, despite the reduced pore size, the GS-PI separator demonstrates better cycling stability than conventional Al 2 O 3 @PE separator at high temperature without sacrificing specific capacity and rate capability.

25 ENERGY STORAGE↗
DOE OSTI2023

Ionomer-free nanoporous iridium nanosheet electrodes with boosted performance and catalyst utilization for high-efficiency water electrolyzers

Increasing the catalyst utilization efficiency and simplifying electrode fabrication processes are crucial to accelerate development of low-cost proton exchange membrane electrolyzer cells (PEMECs). Here, we develop a facile route to fabricate ionomer-free iridium nanosheet integrated electrodes, in which nanoporous iridium nanosheets (IrNS) with abundant exposed edges and nanopores are deposited on thin titanium liquid/gas diffusion layers (TT-LGDLs) via a low-temperature chemical synthesis strategy. Further, benefiting from high catalytic activity, good electrode conductivity and excellent liquid/gas transport properties, such nanoporous IrNS electrodes with low catalyst loadings require low cell voltages of 1.65 V and 1.78 V at 3000 and 6000 mA/cm 2 , respectively. More impressively, a stable performance can be well maintained under extremely high current density tests of 5000 mA/cm 2 , demonstrating the potential of low-loading nanoporous IrNS electrodes in solid-electrolyte based electrochemical conversion cells that require high current density operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ceramic cation exchange materials

Cation exchange membranes and materials including silica-based ceramics, and associated methods, are provided. In some aspects, cation exchange membranes that include a silica-based ceramic that forms a coating on and/or within a porous support membrane are described. The cation exchange membranes and materials may have certain structural or chemical attributes (e.g., pore size/distribution, chemical functionalization) that, alone or in combination, can result in advantageous performance characteristics in any of a variety of applications for which selective transport of positively charged ions through membranes/materials is desired. In some embodiments, the silica-based ceramic contains relatively small pores (e.g., substantially spherical nanopores) that may contribute to some such advantageous properties. In some embodiments, the cation exchange membrane or material includes sulfonate and/or sulfonic acid groups covalently bound to the silica-based ceramic.

Newbloom, Gregory Matthew↗
DOE OSTI2024

Catalyst

Nanoporous oxygen reduction catalyst material comprising at least 90 collectively Pt, Ni, and Ta. The nanoporous oxygen reduction catalyst material is useful, for example, in fuel cell membrane electrode assemblies.

Steinbach, Andrew J. L.↗
DOE OSTI2020

Gating of Hydrophobic Nanopores with Large Anions

In this report, understanding ion transport in nanoporous materials is critical to a wide variety of energy and environmental technologies, ranging from ion-selective membranes, drug delivery, and biosensing, to ion batteries and supercapacitors. While nanoscale transport is often described by continuum models that rely on a point charge description for ions and a homogeneous dielectric medium for the solvent, here, we show that transport of aqueous solutions at a hydrophobic interface can be highly dependent on the size and hydration strength of the solvated ions. Specifically, measurements of ion current through single silicon nitride nanopores that contain a hydrophobic-hydrophilic junction show that transport properties are dependent not only on applied voltage but also the type of anion. We find that in Cl - -contained solutions the nanopores only conducted ionic current above a negative voltage threshold. On the other hand, introduction of large polarizable anions, such as Br - and I - , facilitated the pore wetting, making the pore conductive at all examined voltages. Molecular dynamics simulations revealed that the large anions, Br - and I - , have a weaker solvation shell compared to that of Cl - , and consequently were prone to migrate from the aqueous solution to the hydrophobic surface, leading to the anion accumulation responsible for pore wetting. The results are essential for designing nanoporous systems that are selective to ions of the same charge, for realization of ion-induced wetting in hydrophobic pores, as well as for fundamental understanding on the role of ion hydration shell on the properties of solid/liquid interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electrochemical Probing of Steric, Electrostatic and Hydrophobic Interactions of Large Cations in Polymers of Intrinsic Microporosity

Porous membranes have been used for many applications, including separations in biotechnology, the food industry, water purification, and even energy storage devices. The benefit of polymers of intrinsic microporosity (PIMs) is their consistently sized nanopore channels. Inherent functionalities of the PIM structure not only create these channels but are also available for further modifications that can change the interactions of ions and molecules inside of the pore. Here we design solid state nanopores on which are drop-casted two different PIMs, functionalized with either a cyano group or a carboxylic acid. Ionic transport through the membranes is investigated based on pore size and charge-charge interactions, as well as steric and hydrophobic interactions. Achieving specific ion selectivity with easily processable porous membranes opens new avenues for water purification strategies and energy storage.

25 ENERGY STORAGE↗
DOE OSTI2022

Matrimid substrates with bicontinuous surface and macrovoids in the bulk: A nearly ideal substrate for composite membranes in CO 2 capture

Scalable fabrication of thin-film composite (TFC) membrane for post-combustion carbon capture is often limited by the availability of high-performance nanoporous substrate. Ideally, the substrate should allow for fast gas transport at the selective layer/substrate interface as well as in the bulk of the substrate. In this study, highly permeable Matrimid substrates were prepared via vapor- and nonsolvent-induced phase separations. The phase separation mechanism of the Matrimid®/N-methyl-2-pyrrolidone casting solution was modulated by the addition of LiCl to control the solution thermodynamic stability, and nanoporous Matrimid substrates were formed with a bicontinuous surface and macrovoids in the bulk. This hierarchically optimized structure resulted in a CO 2 permeance of 2.60 × 10 5 GPU (1 GPU = 1 × 10 –6 cm 3 (STP) cm –2 s –1 cmHg –1 = 3.349 × 10 –10 mol m –2 s –1 Pa –1 ), which was ca. 11 times more permeable than a benchmark polyethersulfone substrate with cellular pores. The benefit of using this new substrate was demonstrated by coating a 170-nm amine-containing polymer to form a TFC facilitated transport membrane. The membrane exhibited a CO 2 permeance of 932 GPU at 57°C, which was 72 GPU higher than the counterpart coated on the benchmark substrate. Meanwhile, the CO 2 /N 2 selectivity was remained at 158. This permeance improvement could be well explained by the resistance-in-series model, where the improved permeance was attributed to the reductions in substrate and lateral diffusion mass transfer resistances. The upper bound (UB) analysis indicates that the Matrimid substrate is nearly ideal for the state-of-the-art polymers for CO 2 /N 2 separation. Here, the substrate improvement could also reduce the parasitic energy associated with the membrane process due to the reduced membrane cost and flue gas compression requirement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nanotube-Supported Phospholipid Bilayers (Final Technical Report)

The overarching goal of this project was to attain fundamental understanding of structural organization, self-assembly, and function of redox-active enzymes and biological energy transduction systems localized at biological (cellular membranes) as well as manmade bio-nano interfaces. During this project we developed (1) nanopore surfaces suitable to stabilization of functional redox active enzymes and (2) experimental protocols for loading for loading of redox active enzymes into nanopores and taking advantage of self-assembly for forming layer(s) of redox active enzymes inside the nanochannels formed in anodic aluminum oxide (AAO) substrates.

14 SOLAR ENERGY↗
DOE OSTI2025

Cation selectivities in zwitterion grafted nanopores: effect of zwitterion architecture

Selective separation of monovalent cations is a critical challenge in applications such as water purification and lithium recovery from salt brines. Cross-linked zwitterionic amphiphilic copolymer (ZAC-X) membranes have gained attention for their exceptional anion permselectivity, attributed to self-assembled zwitterion-lined nanodomains that interact preferentially with anions according to their hydrated radii r hyd . However, these membranes show minimal selectivity among monovalent cations, despite significant differences in their hydration structures, motivating studies on the underlying mechanisms of cation transport and selectivity in this family of materials. In this study, we conducted molecular dynamics simulations of aqueous salt solutions within zwitterion-functionalized nanopores to elucidate the influence of dipole orientation of the zwitterionic (ZI) ligands on cation diffusivities, partitioning, and permeabilities. To this end, we examined two contrasting ZI ligand architectures: Motif A (surface–cation–anion, S–ZI + –ZI − ) and Motif B (surface–anion–cation, S–ZI − –ZI + ). Our results show that in Motif A, the sulfonate groups of the ZI ligands are localized near the pore center radially, leading to strong electrostatic interactions with small bare cations (Mg 2+ and Li + ). This configuration results in high cation partitioning but low cation diffusion, maintaining solution-diffusion tradeoff typical of functionalized membranes. In contrast, Motif B show that sulfonate groups shift radially toward the mid-region of the pore. This shift, especially for small bare cations, introduces steric constraints that weaken their interactions with the sulfonate groups, thereby enhancing hydration and lowering partitioning, while still maintaining their low self-diffusivity. These findings establish zwitterion dipole orientation as a powerful design lever for tuning cation selectivity in membrane systems and offer molecular-level insights for engineering next-generation ion separation materials.

Morishita, Kazuya [Univ. of Texas, Austin, TX (Uni↗
DOE OSTI2023

Controlling Nanoscale Pore Size and Wall Composition in Polycarbonate Membranes via Atomic Layer Deposition and Sequential Infiltration Synthesis: Implications for High Water Permeance

Polymer membranes have a wide variety of applications, ranging from water treatment to energy storage. Many of these applications require precise control over the membrane porosity and surface chemistry. In this study, we explore the modification of isoporous polycarbonate (PC) track-etched membranes (PCTEs) by atomic layer deposition (ALD) and sequential infiltration synthesis (SIS) to tune the pore size and the pore wall surface chemistry. We first performed a detailed study of Al 2 O 3 ALD and SIS in PCTE using a variety of in situ and ex situ measurements. We discovered that short precursor exposure times are critical to achieve conformal Al 2 O 3 ALD in the PCTE nanopores, while longer precursor exposure times resulted in Al 2 O 3 SIS within the bulk of the PC leaving the membranes brittle. Next, we tuned the PCTE pore size via Al 2 O 3 ALD and studied its effect on the water contact angle and the water permeance. Here, we found that the membranes became more hydrophilic, and the permeance decreased with increasing ALD Al 2 O 3 cycles. Finally, we studied the effect of hydrophilic (SnO 2 )/hydrophobic (In 2 O 3 ) ALD metal oxide coatings on membrane properties. We found that the most hydrophilic SnO 2 showed the highest water flux and the least hydrophilic In 2 O 3 showed the lowest water flux through the PCTE membranes. Our results demonstrate that ALD is an effective method to tune the surface and transport properties of PCTE membranes, but care must be exercised to avoid SIS and bulk modification of the polymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗