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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Molecular Simulations of CH 4 and CO 2 Diffusion in Rigid Nanoporous Amorphous Materials

Molecular diffusion in nanoporous materials is important in determining the rate of equilibration of various adsorption processes and plays a pivotal role in kinetic separations and membrane-based separations. Because generating realistic structures of amorphous nanoporous materials is difficult, far less is known about diffusion in amorphous nanoporous materials than in their crystalline counterparts. Here, we present molecular dynamics simulations assessing the room-temperature self-diffusion of CH 4 and CO 2 in a wide range of rigid amorphous nanoporous materials, including porous carbons, kerogens, polymers of intrinsic microporosity, and hyper-cross-linked polymers. Our results are the largest collection of molecular diffusivities in amorphous nanoporous materials to date. In each material, the diffusivity increases with the adsorbate concentration at low and moderate adsorbate concentrations, reaching a maximum before decreasing due to steric effects at higher concentrations. The observed diffusivities are much slower than that would be expected based on standard descriptions of Knudsen diffusivity. Here we show that the observed diffusivities are not correlated in a simple way with scalar descriptors of the pore structures such as the pore limiting diameter.

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

Interconnected Nanoporous Polysulfone by the Self-Assembly of Randomly Linked Copolymer Networks and Linear Multiblocks

Porous materials have attracted considerable attention due to their versatile applications, especially in water purification. Interconnected nanoporous structures are distinguished by their high degree of porosity and resistance to clogging, as well as their insensitivity to nanostructural orientation. Previous works on randomly linked copolymer systems have shown that they can effectively produce disordered cocontinuous nanostructures, which upon removal of one component yield interconnected nanoporous materials. However, the cocontinuous nanomaterials previously developed using polystyrene (PS) and poly(d,l-lactic acid) (PLA) strands, and the resulting interconnected nanoporous PS monoliths, were far too brittle to enable practical use as membranes. Here, we study the self-assembly of randomly linked copolymer networks prepared using blocks of the engineering polymer polysulfone (PSU). A wide cocontinuous regime (spanning 40 wt %) was found for randomly end-linked copolymer networks (RECNs) constructed from PSU and PLA strands, via a combination of mechanical testing, gravimetry, small-angle X-ray scattering, and scanning electron microscopy. The PSU/PLA cocontinuous nanomaterial with symmetric composition showed 2.4 times higher Young’s modulus and ~100 times greater toughness than the corresponding PS/PLA sample. The interconnected nanoporous PSU fabricated after etching of PLA even exhibited 1.6 times greater toughness than PS/PLA prior to PLA removal. To facilitate the production of thin films of cocontinuous nanomaterials, we applied solution-processable randomly linked linear PSU/PLA multiblock polymers onto ultrafiltration membranes. Here, the interconnected nanoporous PSU thin film generated by etching PLA was found to effectively reject 50 nm diameter particles without significantly compromising permeability. This discovery presents a valuable addition to the existing techniques used to fabricate PSU membranes. In contrast to traditional methods, which are sensitive to processing conditions, produce a wide range of pore sizes, and offer limited adjustability of pore size, the current technique is anticipated to enable interconnected PSU membranes with more uniform and tailorable porosity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Diffusion-to-Imbibition Transition in Water Sorption in Nanoporous Media: Theoretical Studies

The ability to predict multiphase fluid transport in nanoporous rocks such as shales is critical for many geoscience applications, for example unconventional hydrocarbon production, geologic carbon sequestration, and nuclear waste disposal. When the pore sizes approach nanoscales, the impact of the molecular interaction forces between fluids and solids becomes increasingly important. These forces can alter macroscopic fluid phase behavior and control transport. Recent experimental studies have shown that capillary condensation and subsequent imbibition of liquid water can occur in hydrophilic nanoporous media even if the vapor phase is at a critical relative humidity (rhcrit) well below vapor saturation. This study presents a theoretical investigation of the processes controlling adsorption, capillary condensation and imbibition in nanoporous media, using the square-gradient classical density functional theory. The proposed theoretical model explicitly includes the relevant interaction forces among fluids and solids in macroscopic porous media. Application of the model to a relative-humidity-controlled water adsorption experiment is presented to demonstrate the impact of water-pore wall attractive forces on multiphase water behavior in a hydrophilic silicon nanoporous medium. Here, the model represents well the measured time-dependent evolution of the water imbibition front inside the nanoporous medium and also explains the diffusion-like water transport regimes observed at rh < rh crit and the imbibition-like flow regimes observed at rh > rh crit . The study furthermore gives an insight on hysteresis phenomenon in adsorption and desorption isotherms.

58 GEOSCIENCES↗
DOE OSTI2021

Selective filling of n-hexane in a tight nanopore

Abstract Molecular sieving may occur when two molecules compete for a nanopore. In nearly all known examples, the nanopore is larger than the molecule that selectively enters the pore. Here, we experimentally demonstrate the ability of single-wall carbon nanotubes with a van der Waals pore size of 0.42 nm to separate n-hexane from cyclohexane—despite the fact that both molecules have kinetic diameters larger than the rigid nanopore. This unexpected finding challenges our current understanding of nanopore selectivity and how molecules may enter a tight channel. Ab initio molecular dynamics simulations reveal that n-hexane molecules stretch by nearly 11.2% inside the nanotube pore. Although at a relatively low probability (28.5% overall), the stretched state of n-hexane does exist in the bulk solution, allowing the molecule to enter the tight pore even at room temperature. These insights open up opportunities to engineer nanopore selectivity based on the molecular degrees of freedom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Evolution of nanopores in hexagonal boron nitride

Abstract The engineering of atomically-precise nanopores in two-dimensional materials presents exciting opportunities for both fundamental science studies as well as applications in energy, DNA sequencing, and quantum information technologies. The exceptional chemical and thermal stability of hexagonal boron nitride (h-BN) suggest that exposed h-BN nanopores will retain their atomic structure even when subjected to extended periods of time in gas or liquid environments. Here we employ transmission electron microscopy to examine the time evolution of h-BN nanopores in vacuum and in air and find, even at room temperature, dramatic geometry changes due to atom motion and edge contamination adsorption, for timescales ranging from one hour to one week. The discovery of nanopore evolution contrasts with general expectations and has profound implications for nanopore applications of two-dimensional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH 4 -CO 2 - H 2 O) Interactions in Shale Nanopores under Reservoir Conditions (Quarterly Report)

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement. CO 2 and H 2 O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4 ) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested as an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4 -CO 2 -H 2 O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4 -CO 2 -H 2 O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.

04 OIL SHALES AND TAR SANDS↗
NASA NTRS2008

Fabricating Nanodots using Lift-Off of a Nanopore Template

A process for fabricating a planar array of dots having characteristic dimensions of the order of several nanometers to several hundred nanometers involves the formation and use of a thin alumina nanopore template on a semiconductor substrate. The dot material is deposited in the nanopores, then the template is lifted off the substrate after the dots have been formed. This process is expected to be a basis for development of other, similar nanofabrication processes for relatively inexpensive mass production of nanometerscale optical, optoelectronic, electronic, and magnetic devices. Alumina nanopore templates are self-organized structures that result from anodization of aluminum under appropriate conditions. Alumina nanopore templates have been regarded as attractive for use in fabricating the devices mentioned above, but prior efforts to use alumina nanopore templates for this purpose have not been successful. One reason for the lack of success is that the aspect ratios (ratios between depth and diameter) of the pores have been too large: large aspect ratios can result in blockage of deposition and/or can prevent successful lift-off. The development of the present process was motivated partly by a requirement to reduce aspect ratios to values (of the order of 10) for which there is little or no blockage of deposition and attempts at lift-off are more likely to be successful. The fabrication process is outlined.

Yang, Eui-Hyeok↗
NASA NTRS2017

Novel Approach to Quantification of Telomere Length with Direct Nanopore Sequencing and PCR Amplification

The ends of human chromosomes contain telomeres, or tandem arrays of repeating DNA sequences capped by multiple associated proteins that protect chromosomal ends from degradation. Telomeres function to preserve genomic stability by preventing natural chromosomal ends from being recognized as broken DNA double-strand breaks and triggering inappropriate DNA damage responses. Mounting evidence shows telomere length is an inherited trait that decreases with cellular division and normal aging. In addition, telomere length also appears to be influenced by other factors such as cellular oxidative stress, radiation and mechanical unloading of tissues as in microgravity. To measure these potential effects of the space environment on telomere lengths and cellular aging and regenerative potential we developed a novel telomere measurement approach based on nanopore sequencing of PCR amplified bar-coded chromosome termini. Specifically, telomeres can be directly enriched using barcode sequences ligated to the end of a free end- repaired telomere using the WetLab-2 facility SmartCycler on ISS. Prior to the ligation and amplification protocol a proteinase K digestion of capping proteins followed by a single 95-degree C heat denaturation of the protease is included. After digestion and bar-code ligation, PCR amplification will initiate with the ligated barcoded sequence, suppressing amplification of intra-genomic fragments and resulting in long read barcoded telomere amplicons including the nanopore motor protein sequences. Purified PCR amplicons are then used for nanopore sequencing library generation by simple addition of motor proteins and sequencing library is loaded into the MinION nanopore DNA-sequencer. Amplicon sequence reads from the nanopore device can be base-called quickly on ISS due to barcoding ligation and subsequent PCR amplification enhancing the telomere sequence resolution. If successfully implemented on ISS this technique will provide a novel means of measuring regenerative ability of somatic stem cells in astronauts, and of determining whether spaceflight in microgravity alters their telomere lengths and causes premature cellular aging.

Ma, Kristin R.↗
DOE OSTI2022

Boosting the H 2 –D 2 Exchange Activity of Dilute Nanoporous Ti–Cu Catalysts through Oxidation–Reduction Cycle–Induced Restructuring

The use of nanoporous metals as catalysts has attracted significant interest in recent years. Their high-curvature, nanoscale ligaments provide not only high surface area but also a high density of undercoordinated step edge and kink sites. However, their long-term stability, especially at higher temperatures, is often limited by thermal coarsening and the associated loss of surface area. Herein, it is demonstrated that the nanoscale morphology of nanoporous Cu can be regenerated by applying oxidation/reduction cycles at 250 °C. Specifically, the morphological evolution and H 2 dissociation activity of hierarchical nanoporous Cu catalysts doped with Ti during structural rearrangement triggered by oxidative and reductive atmospheres at elevated temperatures are studied. In addition to coarsening of the structure at elevated temperatures, oxidation at 400 °C causes an expansion of the ligaments. Further, subsequent reduction at 400 °C leads to the formation of particles and a drop in the H 2 dissociation activity compared the fresh catalyst. However, performing the redox cycle at 250 °C reverses coarsening and boosts the H 2 dissociation activity for the hydrogen–deuterium (H 2 –D 2 ) reaction. Herein, the possibility to reverse coarsening is demonstrated, thereby mitigating the loss of activity frequently observed in nanoporous catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ionically Active MXene Nanopore Actuators

Reversible electrochemical intercalation of cations into the interlayer space of 2D materials induces tunable physical and chemical properties in them. In MXenes, a large class of recently developed 2D carbides and nitrides, low intercalation energy, high storage capacitance, and reversible intercalation of various cations have led to their improved performance in sensing and energy storage applications. In this work, a coupled nanopore-actuator system where an ultrathin free-standing MXene film serves as a nanopore support membrane and ionically active actuator is reported. In this system, the contactless MXene membrane in the electric field affects the cation movement in the field through their (de)intercalation between individual MXene flakes. This results in reversible swelling and contraction of the membrane monitored by ionic conductance through the nanopore. This unique nanopore coupled to a mechanical actuation system could provide new insights into designing single-molecule biosensing platforms at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 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

Experiments on the Capillary Condensation/Evaporation Hysteresis of Pure Fluids and Binary Mixtures in Cylindrical Nanopores

Here, a new experimental method, i.e., isochoric cooling/heating cycle measurement using differential scanning calorimeter (DSC), is applied to investigate the hysteretic phenomenon of pure components and mixtures confined in two different types of cylindrical nanopores (SBA-15 and KIT-6). The capillary condensation/evaporation hysteresis end point (T he ) for a specific system is determined by performing a series of measurements with different densities by increasing initial temperature and pressure. We confirm that for a pure component, T he is lower when confined in smaller nanopores, whereas T he for CH 4 /CO 2 and CH 4 /C 2 H 6 mixtures at the specific composition investigated are higher than that of pure CO 2 and C 2 H 6 , respectively, when confined in the same nanopores. To the best of our knowledge, this is the first time that T he of fluid mixture is experimentally studied, which further demonstrates that binary mixtures behave similarly to pure fluids when confined in nanoporous media. At low temperatures where hysteresis is observed, the shape as well as the duration of the exothermic peak (due to capillary condensation) and endothermic peak (due to capillary evaporation) indicate that capillary condensation, rather than capillary evaporation, takes place at/near a thermodynamic equilibrium. Within the accuracy of the measurements, we find that the total heat of capillary condensation is identical to that of capillary evaporation for all systems examined, regardless of the presence of hysteresis. By comparing the heat per unit volume among different systems, we also find that the heat per unit volume of the phase transition of confined pure fluid is lower than that of bulk, which further demonstrates that the molar density of confined pure liquid is less than that of bulk pure liquid at saturation.

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

Grain boundary formation through particle detachment during coarsening of nanoporous metals

Significance Nanoporous metals are prototypical bicontinuous structures that have a large surface area and many applications. We demonstrate that an in-grain orientation spread develops during coarsening in nanoporous metals, leading to the formation of a nanocrystalline–nanoporous structure. The process of particles detaching and reattaching as the structure coarsens is identified as a mechanism of grain boundary formation. Coarsening the structure results in significant particle detachment with detachment rates that vary drastically with changes in the volume fraction and volume fraction inhomogeneities in the nanostructure. These results demonstrate that particle detachment must be understood to have full control of the nanocrystalline–nanoporous structure and improve material properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Three-Dimensional Imaging and Quantification of Gas Storativity in Nanoporous Media via X-rays Computed Tomography

This study provides the engineering science underpinnings for improved characterization and quantification of the interplay of gases with kerogen and minerals in shale. Natural nanoporous media such as shale (i.e., mudstone) often present with low permeability and dual porosity, making them difficult to characterize given the complex structural and chemical features across multiple scales. These structures give nanoporous solids a large surface area for gas to sorb. In oil and gas applications, full understanding of these media and their sorption characteristics are critical for evaluating gas reserves, flow, and storage for enhanced recovery and CO 2 sequestration potential. Other applications include CO 2 capture from industrial plants, hydrogen storage on sorbent surfaces, and heterogeneous catalysis in ammonia synthesis. Therefore, high-resolution experimental procedures are demanded to better understand the gas–solid behavior. In this study, CT imaging was applied on the sub-millimeter scale to shale samples (Eagle Ford and Wolfcamp) to improve quantitative agreement between CT-derived and pulse decay (mass balance) derived results. Improved CT imaging formulations are presented that better match mass balance results, highlighting the significance of gas sorption in complex nanoporous media. The proposed CT routine implemented on the Eagle Ford sample demonstrated a 17% error reduction (22% to 5%) when compared to the conventional CT procedure. These observations are consistent in the Wolfcamp sample, emphasizing the reliability of this technique for broader implementation of digital adsorption studies in nanoporous geomaterials.

42 ENGINEERING↗
DOE OSTI2021

A Micrometer‐Sized Silicon/Carbon Composite Anode Synthesized by Impregnation of Petroleum Pitch in Nanoporous Silicon

Porous silicon (Si)/carbon nanocomposites have been extensively explored as a promising anode material for high-energy lithium (Li)-ion batteries (LIBs). However, shrinking of the pores and sintering of Si in the nanoporous structure during fabrication often diminishes the full benefits of nanoporous Si. Herein, a scalable method is reported to preserve the porous Si nanostructure by impregnating petroleum pitch inside of porous Si before high-temperature treatment. The resulting micrometer-sized Si/C composite maintains a desired porosity to accommodate large volume change and high conductivity to facilitate charge transfer. It also forms a stable surface coating that limits the penetration of electrolyte into nanoporous Si and minimizes the side reaction between electrolyte and Si during cycling and storage. A Si-based anode with 80% of pitch-derived carbon/nanoporous Si enables very stable cycling of a Si||Li(Ni0.5Co0.2Mn0.3)O 2 (NMC532) battery (80% capacity retention after 450 cycles). It also leads to low swelling in both particle and electrode levels required for the next generation of high-energy LIBs. In conclusion, the process also can be used to preserve the porous structure of other nanoporous materials that need to be treated at high temperatures.

anode materials↗
DOE OSTI2020

Electrowetting‐Mediated Transport to Produce Electrochemical Transistor Action in Nanopore Electrode Arrays

Abstract Understanding water behavior in confined volumes is important in applications ranging from water purification to healthcare devices. Especially relevant are wetting and dewetting phenomena which can be switched by external stimuli, such as light and electric fields. Here, these behaviors are exploited for electrochemical processing by voltage‐directed ion transport in nanochannels contained within nanopore arrays in which each nanopore presents three electrodes. The top and middle electrodes (TE and ME) are in direct contact with the nanopore volume, but the bottom electrode (BE) is buried beneath a 70 nm silicon nitride (SiN x ) insulating layer. Electrochemical transistor operation is realized when small, defect‐mediated channels are opened in the SiN x . These defect channels exhibit voltage‐driven wetting that mediates the mass transport of redox species to/from the BE. When BE is held at a potential maintaining the defect channels in the wetted state, setting the potential of ME at either positive or negative overpotential results in strong electrochemical rectification with rectification factors up to 440. By directing the voltage‐induced electrowetting of defect channels, these three‐electrode nanopore structures can achieve precise gating and ion/molecule separation, and, as such, may be useful for applications such as water purification and drug delivery.

Kwon, Seung‐Ryong↗
DOE OSTI2025

Characterization of kerogen nanopores using 2D NMR relaxation and MD simulations

The characterization of kerogen nanopores is crucial for predicting the geostorage capacity and recoverability of natural gas in unconventional gas shale reservoirs. Towards this end, a powerful technique is presented which integrates 2D NMR T 1 -T 2 relaxation measurements with molecular dynamics (MD) simulations of hydrocarbons confined in the nanopores of kerogen. The integrated NMR-MD technique is demonstrated using T 1 -T 2 measurements of kerogen isolates and organic-rich chalks saturated with heptane, together with MD simulations of heptane completely dissolved in a realistic kerogen model. The NMR-MD results are used to extract the swelling ratio and nanopore size distribution of kerogen as a function of depth in the reservoir. The effects of organic nanoconfinement on the T 1 relaxation dispersion and T 2 residual dipolar coupling of heptane are investigated, as well as the effect of downhole effective stress on the kerogen nanopore size as a function of depth and compaction. Potential applications in partially depleted gas shale reservoirs are discussed, including CO 2 utilization/geostorage, geostorage of green H 2 , and integration of the NMR-MD technique with thermodynamic models for predicting the competitive sorption of gas mixtures in kerogen.

Compaction↗