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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Molecular insights into CO 2 -to-bicarbonate transformation in functionalized anion exchange ionomers for electrochemical separations

Bipolar membrane (BPM) electrochemical processes are a promising platform for carbon dioxide (CO 2 ) separations, but the molecular level thermodynamic and kinetic understanding of CO 2 -to-bicarbonate (HCO 3 − ) transformation remain poorly understood. This study employs a multiscale computational approach to systematically explore the adsorption and reactive transformation of CO 2 in five anion exchange ionomer systems. Classical molecular dynamics (MD) simulation results demonstrate that polymers with imidazolium groups significantly reduce CO 2 diffusion and enhance (OH − )–CO 2 interactions due to stronger electrostatic and π-interactions. Compared to the commonly used quaternary ammonium ionomers, imidazolium-functionalized ionomers show improved CO 2 proximity and interaction strength. Ab initio MD and density functional theory (DFT) calculations reveal that the benzyl-substituted imidazolium (IM-Ben) substantially reduces the energy barrier for HCO 3 − formation (∼72 meV lower) compared to the alkyl-substituted IM-nBu, while also mitigating imidazolium deprotonation under moderate hydration conditions. Transition state analysis shows IM-Ben forms more extensive hydrogen-bonding networks, which stabilize the transition state structure and contribute to a lower energy barrier for bicarbonate formation. These findings highlight the advantage of the adjacent benzyl moiety in enabling efficient CO 2 -to-bicarbonate transformation via hydrated hydroxide ion counterions, offering mechanistic insights and clear molecular design principles for optimizing anion exchange ionomers at bipolar membrane interfaces for electrochemical CO 2 separation applications.

Bipolar membranes, Reactive transformation of CO2,↗
DOE OSTI2020

Imaging how thermal capillary waves and anisotropic interfacial stiffness shape nanoparticle supracrystals

Abstract Development of the surface morphology and shape of crystalline nanostructures governs the functionality of various materials, ranging from phonon transport to biocompatibility. However, the kinetic pathways, following which such development occurs, have been largely unexplored due to the lack of real-space imaging at single particle resolution. Here, we use colloidal nanoparticles assembling into supracrystals as a model system, and pinpoint the key role of surface fluctuation in shaping supracrystals. Utilizing liquid-phase transmission electron microscopy, we map the spatiotemporal surface profiles of supracrystals, which follow a capillary wave theory. Based on this theory, we measure otherwise elusive interfacial properties such as interfacial stiffness and mobility, the former of which demonstrates a remarkable dependence on the exposed facet of the supracrystal. The facet of lower surface energy is favored, consistent with the Wulff construction rule. Our imaging–analysis framework can be applicable to other phenomena, such as electrodeposition, nucleation, and membrane deformation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Electrosynthesis of ethylene glycol from C 1 feedstocks in a flow electrolyzer

Ethylene glycol is a widely utilized commodity chemical, the production of which accounts for over 46 million tons of CO 2 emission annually. Here we report a paired electrocatalytic approach for ethylene glycol production from methanol. Carbon catalysts are effective in reducing formaldehyde into ethylene glycol with a 92% Faradaic efficiency, whereas Pt catalysts at the anode enable formaldehyde production through methanol partial oxidation with a 75% Faradaic efficiency. With a membrane-electrode assembly configuration, we show the feasibility of ethylene glycol electrosynthesis from methanol in a single electrolyzer. The electrolyzer operates a full cell voltage of 3.2 V at a current density of 100 mA cm -2 , with a 60% reduction in energy consumption. Further investigations, using operando flow electrolyzer mass spectroscopy, isotopic labeling, and density functional theory (DFT) calculations, indicate that the desorption of a *CH 2 OH intermediate is the crucial step in determining the selectively towards ethylene glycol over methanol.

09 BIOMASS FUELS↗
DOE OSTI2026

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↗
DOE OSTI2021

Framework for predicting the fractionation of complex liquid feeds via polymer membranes

The separation of complex liquid hydrocarbon mixtures was recently demonstrated using the glassy polymer SBAD-1, showing that small molecule fractionation is possible by such organic membrane materials. Here, in this work, we develop a framework that will enable workable predictions of permeate flux and composition in complex hydrocarbon liquids through intrinsically porous glassy polymers. The predictions are made by incorporating experimentally-derived unary sorption and diffusion parameters in a Maxwell-Stefan framework coupled with multicomponent sorption models and various distinct diffusion phenomena. Across the range of sorption and diffusion phenomena considered, both the conventional Flory-Huggins model and the proposed Langmuir + Flory-Huggins sorption model combined with a simple average guest diffusivity or a more complex free-volume theory-based transport resulted in the lowest prediction error for three chosen multicomponent separations. The proposed Maxwell-Stefan framework simply requires pure component transport parameters to allow a fast approximation of the separation of multicomponent liquid hydrocarbon feeds that can potentially be extended to more complex feeds such as crude oil fractions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. In this work, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen‐modified TiN (oxi‐TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi‐TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi‐TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X‐ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi‐TiN originates from highly oxidized Ir δ+ under OER conditions. Density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

58 GEOSCIENCES↗
DOE OSTI2022

Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here, in this work, we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

Choi, Chungseok↗
DOE OSTI2025

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. Herein, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen-modified TiN (oxi-TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi-TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi-TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X-ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi-TiN originates from highly oxidized Ir δ+ under OER conditions. Further, density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

In situ measurements↗
DOE OSTI2020

Proton-conducting oxides for energy conversion and storage

Proton-conducting oxides are a class of solid-state ion-conducting ceramic materials that demonstrate significant hydrogen ion (proton) conductivity at intermediate temperatures (e.g., 300–700 °C). They are garnering significant attention due to several unique characteristics that distinguish them from both higher temperature oxygen ion conducting oxides and lower temperature proton-conducting polymers. By enabling proton-mediated electrochemistry under both dry and wet environments at moderate temperatures, protonic ceramics provide unique opportunities to enhance or synergize a diverse range of complementary electrochemical and thermochemical processes. Because of this potential, significant efforts have been devoted to advancing numerous energy-related applications using these materials. This review aims to comprehensively summarize these applications and analyze the most up-to-date and future developments of proton-conducting oxides. We aim to bring together this diverse subject matter by integrating the fundamentals of proton-conducting oxides with application-oriented insights. We begin with a historical roadmap, followed by a basic overview of the materials, theories and fundamentals, and fabrication and processing technologies underlying the field. The central section of our review summarizes major applications and developments of proton-conducting ceramics, ranging from maturing applications approaching commercialization to embryonic technologies just now emerging from the lab. These include protonic ceramic fuel cells, protonic ceramic electrolysis cells, reversible protonic ceramic electrochemical cells, protonic ceramic membrane reactors, and protonic ceramic electrochemical reactors. For each application, we analyze both the prospects and challenges and offer recommendations for future research directions so that tomorrow's researchers can continue to advance the development and commercialization of these fascinating materials.

Duan, Chuancheng (ORCID:0000000218261415)↗
NASA NTRS1988

Surface and through crack problems in orthotropic plates

The present treatment of the general mode I crack problem in bending- and membrane-loaded orthotropic plates proceeds by formulating the bending problem for a series of planar and through-cracks; by independently varying the six independent constants, the effect of material orthotropy on the stress intensity factor is determined. The surface-crack problem is then formulated by means of the line-spring model, using a transverse-shear theory of plate bending. Attention is given to composite laminates with through-cracks or semielliptic surface cracks. A significant effect is noted for material orthotropy.

Erdogan, F.↗
DOE OSTI2022

Bioinspired Macrocyclic Molecule Supported Two‐Dimensional Lamellar Membrane with Robust Interlayer Structure for High‐Efficiency Nanofiltration

Abstract 2D lamellar membranes (2DLMs) are used for efficient desalination and nanofiltration. However, weak interactions between adjacent stacked nanosheets result in susceptibility to swelling that limits practical applicability. Inspired by the super adhesion of multi‐point suction cups on octopus tentacles, a 2DLM is constructed from Ti 3 C 2 T x MXene supported by the macrocyclic “multi‐point” molecule cucurbit[5]uril (CB5) and demonstrated for nanofiltration of methyl blue (MB) and enrichment of uranyl carbonate. Experimental results and density functional theory calculations indicate that CB5 rivets to the surface of the nanoflakes through strong stable interactions between its multiple binding sites and surface hydroxyl functional groups on MXene nanosheets. This novel 2DLM exhibits excellent nanofiltration performance (69 L m −2 h −1 bar −1 permeance with 93.6% rejection for MB) and can be recycled at least 30 times without significant degradation. The 2DLM exhibits excellent swelling resistance at high salinity, with a demonstration of selective enrichment of uranyl carbonate from artificial water and natural seawater. The results provide a new strategy for constructing highly stable 2DLMs with interlayer spacing controllable from sub‐nano to nanometer scales, for size‐selective sieving of molecules and ions, high‐efficiency nanofiltration, and other applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Silica-copper catalyst interfaces enable carbon-carbon coupling towards ethylene electrosynthesis

Membrane electrode assembly (MEA) electrolyzers offer a means to scale up CO 2 -to-ethylene electroconversion using renewable electricity and close the anthropogenic carbon cycle. To date, excessive CO 2 coverage at the catalyst surface with limited active sites in MEA systems interferes with the carbon-carbon coupling reaction, diminishing ethylene production. With the aid of density functional theory calculations and spectroscopic analysis, here we report an oxide modulation strategy in which we introduce silica on Cu to create active Cu-SiO x interface sites, decreasing the formation energies of OCOH* and OCCOH*—key intermediates along the pathway to ethylene formation. We then synthesize the Cu-SiO x catalysts using one-pot coprecipitation and integrate the catalyst in a MEA electrolyzer. By tuning the CO 2 concentration, the Cu-SiO x catalyst based MEA electrolyzer shows high ethylene Faradaic efficiencies of up to 65% at high ethylene current densities of up to 215 mA cm -2 ; and features sustained operation over 50 h.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Determination of monomer concentrations in crystallizing lysozyme solutions

We have developed a non-optical technique for the study of aggregation in lysozyme and other protein solutions. By monitoring the rate at which lysozyme traverses a semipermeable membrane it was possible to quantitate the degree of aggregation in supersaturated solutions. Using this technique, we have measured the concentration of monomers and larger aggregates in under- and oversaturated lysozyme solutions, and in the presence of crystals, at pH 4.0 and 3 percent NaCl (0.1M NaAc). Comparison of these concentration profiles with (110) face growth rate data supports the theory that tetragonal lysozyme crystals grow by addition of preformed aggregates and not by monomer addition. The data suggest that a considerable population of aggregates larger than dimers are present at lysozyme concentrations above 22 mg/ml. Determination of dimer concentrations, and equilibrium constants for subsequent aggregation levels, are currently underway.

Wilson, L. J.↗
DOE OSTI2024

Optimizing Nonaqueous Sodium–Polysulfide Redox-Flow Batteries: The Role of Solvation Effects with Glyme Solvents

Nonaqueous redox-flow batteries (NARFBs) that use economical alkali metals and the corresponding metal polysulfides are highly attractive for grid-scale energy storage. Although sodium–sulfur systems have been recognized as promising candidates and have been the focus of many studies due to their high earth abundance and energy density, an understanding of the role of the solvation chemistry of commonly used glyme solvents is missing. Herein, we report a systematic investigation into the solvation effects of glyme-based Na-S electrolytes through comprehensive physiochemical experiments and Density Functional Theory (DFT) simulations. Our findings revealed, on one hand, that an optimal coordination strength between glymes and Na + could maintain a relatively smooth Na + diffusion. On the other hand, glyme solvents with extended chain lengths shift the reduction potential of S 8 2– negatively to elevate the formation barrier of undesirable short-chain polysulfides (S n 2– , n ≤ 4) that have high membrane permeability. This solvation phenomenon not only mitigates capacity fading but also extends the operational longevity of the Na-S NARFBs. In conclusion, the results underscore the critical roles of balanced solvent–cation interactions and controlled redox potentials in improving the stability and efficiency of Na-S NARFB systems, marking a significant advancement in the development of sustainable energy storage solutions.

25 ENERGY STORAGE↗
DOE OSTI2022

Stability Analysis of Substituted Cobaltocenium [Bis(cyclopentadienyl)cobalt(III)] Employing Chemistry-Informed Neural Networks

Cobaltocenium derivatives are promising components of the anion exchange membranes due to their excellent thermal and alkaline stability under the operating conditions of a fuel cell. Here we present an efficient modeling approach of assessing the chemical stability of substituted cobaltocenium CoCp 2 + based on the computed electronic structure enhanced by machine learning techniques. Within the aqueous environment, the positive charge of the metal cation is balanced by the hydroxide anion through formation of the CoCp 2 + OH¯ complexes, whose dissociation is studied within the implicit solvent employing density functional theory. The data set of about 118 species based on 42 substituent groups characterized by a range of electron- donating (ED) and electron-withdrawing (EW) properties is constructed and analyzed. Given 12 carefully chosen chemistry-informed descriptors of the complexes and relevant fragments, the stability of the complexes is found to strongly correlate with the energies of the highest occupied and lowest unoccupied molecular orbitals, modulated by a switching function of the Hirshfeld charge. The latter is used as a measure of the electron withdrawing-donating character of the substituents. Based on this observation from the conventional regression analysis, two fully connected, feed-forward neural network (FNN) models with different unit structures, called the chemistry-informed (CINN) and the quadratic (QNN) neural networks, are developed. Both models predict the bond dissociation energies of the cobaltocenium complexes with mean relative errors less than 5.40% and average absolute errors less than 0.94 kcal/mol. The results show the potential of QNN to efficiently capture more complex relationships. Here, the concept of incorporating the domain (chemical) knowledge/insight into the neural network structure paves the way to applications of machine learning techniques with small data sets, ultimately leading to better predictive models compared to the conventional regression analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The Roles of Oil–Water Interfaces in Forming Ultrasmall CaSO 4 Nanoparticles

In natural and engineered environmental systems, calcium sulfate (CaSO 4 ) nucleation commonly occurs at dynamic liquid–liquid interfaces. Although CaSO 4 is one of the most common minerals in oil spills and oil–water separation, the mechanisms driving its nucleation at these liquid–liquid interfaces remain poorly understood. Here, in this study, using in situ small-angle X-ray scattering (SAXS), we examined CaSO 4 nucleation at oil–water interfaces and found that within 60 minutes of reaction, short rod-shaped nanoparticles (with a radius of gyration (R g ) of 17.2 ± 2.7 nm and a length of 38.2 ± 5.8 nm) had formed preferentially at the interfaces. Wide-angle X-ray scattering (WAXS) analysis identified these nanoparticles as gypsum (CaSO 4 ·2H 2 O). In addition, spherial nanoparticles measuring 4.1 nm in diameter were observed at oil–water interfaces, where surface-enhanced Raman spectroscopy (SERS) revealed an elevated pH compared to the bulk solution. The negatively charged oil–water interfaces preferentially adsorb calcium ions, collectively promoting CaSO 4 formation there. CaSO 4 particle formation at the oil–water interface follows a nonclassical nucleation (N-CNT) pathway by forming ultrasmall amorphous spherical particles which then aggregate to form intermediate nanoparticles, subsequently growing into nanorod-shaped gypsum. These findings of this study provide insights into mineral scaling during membrane separation and can inform more efficient oil transport in energy recovery systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Theory of idealized two-dimensional ballute in Newtonian hypersonic flow

A differential equation governing the geometry of a two-dimensional ballute in hypersonic flow and its constraining boundary conditions are derived under idealized assumptions. By solving these equations, the shape of the ballute is determined over a range of conditions. Lift, drag, pitching moment, and the allowed limit of center-of-gravity location for stability (meta-center) are then calculated using Newtonian hypersonic approximation. It is shown that the meta-center occurs near the forward end because of compliance of the ballute membrane to the shock layer pressures, especially at low free-stream densities. In order for the vehicle employing the ballute to be stable at all densities, the center of gravity must be within approximately the forward 20 percent of overall length of the vehicle. However, typical flight trajectories of an aeroassisted orbital transfer vehicle employing the ballute for aerobraking show that the vehicle may be able to complete its atmospheric flight without tumbling provided that the center of gravity is located within the forward 43 percent of the vehicle length because of the relatively short duration of flight through the destabilizing low-density regime.

Park, C.↗