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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 487 records · Page 27

Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution Reaction

The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addition to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodynamics equilibria, which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-density xenon pulsed light, mixed transition metal salt precursors undergo rapid chemical transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to commercial IrO 2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addition influences surface activity the most by promoting higher oxidation states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addition to renewable energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Capacity Adsorption—Dominated Potassium and Sodium Ion Storage in Activated Crumpled Graphene

In this study, structurally and chemically defective activated-crumbled graphene (A-CG) is employed to achieve unique synergy of large reversible potassium (K) and sodium (Na) ion storage capacity with fast charging and extended cyclability. A-CG synthesis consists of low temperature spraying of graphene oxide slurry, followed by partial reduction annealing and air activation. For K storage, the reversible capacities are 340 mAh g -1 at 0.04 A g -1 , 261 mAh g -1 at 0.5 A g -1 , and 210 mAh g -1 at 2 A g -1 . For Na storage, the reversible capacities are 280 mAh g -1 at 0.04 A g -1 , 191 mAh g -1 at 0.5 A g -1 , and 151 mAh g -1 at 2 A g -1 . A-CG shows a stable intermediate rate (0.5 Ag -1 ) cycling with both K and Na, with minimal fade after 2800 and 8000 cycles. These are among the most favorable capacity—rate capability—cyclability combinations recorded for potassium-ion battery and sodium-ion battery carbons. Electroanalytical studies (cyclic voltammetry, galvanostatic intermittent titration technique, b -value) and density functional theory (DFT) reveal that enhanced electrochemical performance originates from ion adsorption at various defects, such as Stone–Wales defects. Moreover, DFT highlights enhanced thermodynamic stability of A-CG with adsorbed K versus with adsorbed Na, explaining the unexpected higher reversible capacity with the former.

25 ENERGY STORAGE↗

Platinum/Tantalum Carbide Core–Shell Nanoparticles with Sub‐Monolayer Shells for Methanol and Oxygen Electrocatalysis

Abstract Core–shell architectures provide great opportunities to improve catalytic activity, but achieving nanoparticle stability under electrochemical cycling remains challenging. Herein, core–shell nanoparticles comprising atomically thin Pt shells over earth‐abundant TaC cores are synthesized and used as highly durable electrocatalysts for the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) needed to drive direct methanol fuel cells (DMFCs). Characterization data show that a thin oxidic passivation layer protects the TaC core from undergoing dissolution in the fuel cell‐relevant potential range, enabling the use of partially covered Pt/TaC core–shell nanoparticles for MOR and ORR with high stability and enhanced catalytic performance. Specifically, at the anode the surface‐oxidized TaC further enhances MOR activity compared to conventional Pt nanoparticles. At the cathode, the Pt/TaC catalyst feature increases tolerance to methanol crossover. These results show unique synergistic advantages of the core–shell particles and open opportunities to tailor catalytic properties for electrocatalytic reactions.

Chemistry↗

Electrolyte Design and Optimization for Alkali Metal‐Sulfur Batteries

Alkali metal-sulfur batteries, including lithium-sulfur (Li-S), sodium-sulfur (Na-S), and potassium-sulfur (K-S) systems, have garnered significant attention as promising electrochemical energy storage (EES) technologies. Among them, Li-S batteries stand out as strong contenders for next-generation energy storage, owing to their high energy density and the cost-effectiveness of sulfur-based cathodes. However, with the rapid technological advances and the escalating energy demand, lithium resources are becoming increasingly scarce, making it imperative to explore alternative metal anodes to replace lithium. Therefore, Na-S and K-S batteries, serving as counterparts to Li-S systems, are emerging as formidable contenders for next-generation energy storage technologies due to the abundant and cost-effective nature of sodium and potassium. Although Na-S and K-S batteries possess considerable potential in the energy sector, their development is still in its infancy, with performance constrained by the nascent state of electrolyte design and optimization. This review article provides a comprehensive overview of recent advancements and developments in liquid electrolytes for alkali metal-sulfur batteries. Additionally, it identifies key challenges and proposes future research directions aimed at enhancing electrolyte stability, optimizing interfacial compatibility, and improving the overall performance of alkali metal-sulfur batteries.

25 ENERGY STORAGE↗

Designing Magnetic Properties in CrSBr through Hydrostatic Pressure and Ligand Substitution

Abstract Magnetic van der Waals (vdW) materials are a promising platform for producing atomically thin spintronic and optoelectronic devices. The A‐type antiferromagnet CrSBr has emerged as a particularly exciting material due to its high magnetic ordering temperature, semiconducting electrical properties, and enhanced chemical stability compared to other vdW magnets. Exploring mechanisms to tune its magnetic properties will facilitate the development of nanoscale devices based on vdW materials with designer magnetic properties. Here it is investigated how the magnetic properties of CrSBr change under pressure and ligand substitution. Pressure compresses the unit cell, increasing the interlayer exchange energy while lowering the Néel temperature. Ligand substitution, realized synthetically through Cl alloying, anisotropically compresses the unit cell and suppresses the Cr‐halogen covalency, reducing the magnetocrystalline anisotropy energy and decreasing the Néel temperature. A detailed structural analysis combined with first‐principles calculations reveals that alterations in the magnetic properties are intricately related to changes in direct Cr–Cr exchange interactions and the Cr–anion superexchange pathways. Further, it is demonstrated that Cl alloying enables chemical tuning of the interlayer coupling from antiferromagnetic to ferromagnetic, which is unique among known two‐dimensional magnets.

Telford, Evan J.↗

Incorporating Lanthanum into Mesoporous Silica Foam Enhances Enzyme Immobilization and the Activity of Penicillin G Acylase Due to Lewis Acid-Base Interactions

Penicillin G acylase (PGA) has been immobilized on a lanthanum-incorporated mesostructured cellular foam (La-MCF) support by using the interaction between the strong Lewis acid sites on the surface of La-MCF and the free amino groups of lysine residues of PGA. The La-MCF support was successfully synthesized in situ through the addition of a citric acid (CA) complexant. The results of pyridine-IR spectroscopy show the presence of strong Lewis acid sites on the surface of the prepared La-MCF (with CA), attributed to the incorporation of lanthanum species into the framework of MCF. Through interaction with the strong Lewis acid sites, the enzymes can be firmly immobilized on the surface of the support. The results indicate that PGA/La-MCF (with CA) exhibits a high specific activity and greatly enhanced operational stability. For the hydrolysis of penicillin G potassium salt, the initial specific activity of PGA/La-MCF (with CA) reaches 10023 U/g. Finally, even after being recycled 10 times, PGA/La-MCF (with CA) retains 89 % of its initial specific activity, much higher than the 77 % of PGA/Si-MCF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Characterization of Methacrylamide-Based Block Random Copolymers via Amine Functionalization of Polystyrene- Block -Poly(Pentafluorophenyl Methacrylate) Toward Enhanced Amenability to Manufacturing Criteria in Nanolithography

Recent interest in manipulating the chemistry of block copolymers (BCPs) to manage the covarying properties necessary to meet manufacturing criteria in nanolithography has resulted in the development and expansion of the A-block-(B-random-C) BCP architecture, where the random block allows for the decoupling of thermodynamic and wetting properties. Previous reports of such BCPs have used click chemistry to create the desired random block, but all such instances possess additional functional groups that are susceptible to undesirable side reactions upon annealing, such as cross-linking and surface grafting. This study reports the substitution reaction of polystyrene-block-poly(pentafluorophenyl methacrylate) (PS-b-PPFMA) with primary amines. The resulting methacrylamide structure of the functionalized random block has only an amide linkage between the attached functional group and the polymer backbone, thereby omitting any sources of side reactions within the BCP. The outcomes of this report also demonstrate the enhanced thermal stability of these materials by virtue of their stable amide bonds. A range of random copolymer compositions is assessed to develop BCPs in which the random block has approximately the same surface energy as the PS block. These BCPs can self-assemble into perpendicular lamellae and are therefore promising candidates for directed self-assembly.

block copolymers↗

Characterization of promoter elements of isoprene‐responsive genes and the ability of isoprene to bind START domain transcription factors

Abstract Isoprene has recently been proposed to be a signaling molecule that can enhance tolerance of both biotic and abiotic stress. Not all plants make isoprene, but all plants tested to date respond to isoprene. We hypothesized that isoprene interacts with existing signaling pathways rather than requiring novel mechanisms for its effect on plants. We analyzed the cis‐regulatory elements (CREs) in promoters of isoprene‐responsive genes and the corresponding transcription factors binding these promoter elements to obtain clues about the transcription factors and other proteins involved in isoprene signaling. Promoter regions of isoprene‐responsive genes were characterized using the Arabidopsis cis‐regulatory element database. CREs bind ARR1, Dof, DPBF, bHLH112, GATA factors, GT‐1, MYB, and WRKY transcription factors, and light‐responsive elements were overrepresented in promoters of isoprene‐responsive genes; CBF‐, HSF‐, WUS‐binding motifs were underrepresented. Transcription factors corresponding to CREs overrepresented in promoters of isoprene‐responsive genes were mainly those important for stress responses: drought‐, salt/osmotic‐, oxidative‐, herbivory/wounding and pathogen‐stress. More than half of the isoprene‐responsive genes contained at least one binding site for TFs of the class IV (homeodomain leucine zipper) HD‐ZIP family, such as GL2, ATML1, PDF2, HDG11, ATHB17. While the HD‐zipper‐loop‐zipper (ZLZ) domain binds to the L1 box of the promoter region, a special domain called the steroidogenic acute regulatory protein‐related lipid transfer, or START domain, can bind ligands such as fatty acids (e.g., linolenic and linoleic acid). We tested whether isoprene might bind in such a START domain. Molecular simulations and modeling to test interactions between isoprene and a class IV HD‐ZIP family START‐domain‐containing protein were carried out. Without membrane penetration by the HDG11 START domain, isoprene within the lipid bilayer was inaccessible to this domain, preventing protein interactions with membrane bound isoprene. The cross‐talk between isoprene‐mediated signaling and other growth regulator and stress signaling pathways, in terms of common CREs and transcription factors could enhance the stability of the isoprene emission trait when it evolves in a plant but so far it has not been possible to say what how isoprene is sensed to initiate signaling responses.

60 APPLIED LIFE SCIENCES↗

Designing Advanced Electrolytes for High-Voltage High-Capacity Disordered Rocksalt Cathodes

Lithium (Li)-excess transition metal oxide materials which crystallize in the cation-disordered rock salt (DRX) structure are promising cathodes for realizing low-cost, high-energy-density Li batteries. However, the state-of-the-art electrolytes for Li-ion batteries cannot meet the high-voltage stability requirement for high-voltage DRX cathodes, thus new electrolytes are urgently demanded. It has been reported that the solvation structures and properties of the electrolytes critically influence the performance and stability of the batteries. In this study, the structure–property relationships of various electrolytes with different solvent-to-diluent ratios are systematically investigated through a combination of theoretical calculations and experimental tests and analyses. This approach guides the development of electrolytes with unique solvation structures and characteristics, exhibiting high voltage stability, and enhancing the formation of stable electrode/electrolyte interphases. These electrolytes enable the realization of Li||Li 1.094 Mn 0.676 Ti 0.228 O 2 (LMTO) DRX cells with improved performance compared to the conventional electrolyte. Specifically, Li||LMTO cells with the optimized advanced controlled-solvation electrolyte deliver higher specific capacity and longer cycle life compared to cells with the conventional electrolyte. Additionally, the investigation into the structure–property relationship provides a foundational basis for designing advanced electrolytes, which are crucial for the stable cycling of emerging high-voltage cathodes.

25 ENERGY STORAGE↗

Microstructural evolution in Cu-Nb processed via friction consolidation

Immiscible alloys, whether in well-mixed or layered forms, are of increasing interest based on their novel structural and functional properties, such as enhanced thermal stability against grain growth or radiation-induced defect trapping at the interfaces. To address the need for new approaches to tailor microstructures, the microstructural development of an immiscible Cu-Nb alloy processed via friction consolidation of elemental powders is investigated. Friction consolidation is a solid-phase processing technique that imparts severe plastic strain into a deforming volume resulting in elevated temperatures below the melting temperature of the alloy. Two distinct processing pathways were chosen to understand the effect of thermomechanical conditions on the final microstructure. The microstructure was characterized using scanning electron microscopy, scanning transmission electron microscopy, and X-ray diffraction techniques. Path 1 exhibited larger strain, strain rate, and temperature as compared with path 2. In path 1, agglomerated Nb particles were present in the recrystallized ultrafine-grained Cu matrix, while in path 2 extremely fine and dispersed Nb particles were present in a highly deformed Cu matrix. In both pathways, supersaturation of Cu in Nb lattices was noted, but not vice-versa. The asymmetry in mixing is explained based on deformation-based, thermodynamic and kinetic factors. These findings provide a pathway for creation of novel tailored microstructures and improved properties in any number of binary immiscible alloy systems.

Cu-Nb alloys, Microstructural refinement, Friction↗

Impact of lowering potassium contamination in liquid scintillation cocktails for ultra-sensitive radiation detection

Intrinsic 40 K radioactive backgrounds from impurities of natural K in liquid scintillation cocktails have previously been demonstrated to limit their use in ultra-sensitive applications. Here, this work explores two methodologies in parallel for the reduction of 40 K backgrounds in the cocktails, and lays the groundwork for use in ultra-sensitive applications. In one method, alternative low-K liquid scintillation matrix constituents were identified and in the other, a simple purification method for single components and finished cocktails was developed. Both methods were verified via ICP-MS analysis. Liquid scintillation counting of selected purified cocktails demonstrated background reduction, improved stability, and enhanced performance. The best performing purified cocktail was also counted on a custom-built ultra-low background liquid scintillation counter, with results below the detector background.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Nonlinear viscoelastic response of silicone additively manufactured direct ink write (DIW) foams under repetitive compression

To investigate dynamic fatigue behavior of foam in military protective applications, such as helmets, additively manufactured (AM) foams were compressively strained into the plateau region using a reduced design of experiments. A simple power law was found to govern the decline in dynamic stiffness (complex modulus) as the foams underwent the purchase order requirement of 10,000 cycles of small deformation in the plateau region. This rate of decline was newly found to correlate with the degree of nonlinearity in the material’s deformation, quantified using total harmonic distortion. Materials with low nonlinearity exhibited relatively stable stiffness across cycles, while those with high nonlinearity experienced greater losses. The observed nonlinearity depended on both applied stress and strain rate. A strong linear correlation (R 2 = 0.78) was identified between second-order nonlinearity and the time-dependent stiffness response. Two lattice structures were examined: face-centered tetragonal (FCT) and simple cubic (SC). The SC material exhibited higher total harmonic distortion (5%) and lower stiffness retention than the FCT (2%). In conclusion, these results suggest that for cyclic compression applications in a wide variety of industries such as packaging, personal protective equipment, or aerospace, selecting materials with lower stress and greater structural uniformity can enhance the stability of dynamic performance.

42 ENGINEERING↗

Impacts of Lanthanum Impurities on Nickel-Rich Cathode Materials

The widespread use of lithium-ion batteries (LIBs) has led to environmental concerns and exacerbated the scarcity of essential minerals, underscoring the urgent need for effective recycling strategies. Among various recycling methods, the hydrometallurgical process is distinguished by its energy efficiency and minimal environmental impact. Nickel-metal hydride (Ni-MH) batteries are a significant source of nickel sulfate (NiSO 4 ) for hydrometallurgical recycling due to their substantial nickel content. A significant challenge arises from the effective separation of lanthanum (La), which results in at least 20 ppm of La being present in the recycled NiSO 4 . This study explores a critical aspect of the recycling process: the impact of La 3+ impurities, introduced through recycled NiSO 4 , on the performance of the synthesized nickel-rich cathode materials. We conducted a thorough investigation into how La 3+ influences morphology and structural integrity during both the synthesis of precursors and the production of cathode materials. Our findings indicate that La 3+ impurities do not adversely affect the morphology or structural integrity of the cathode precursors relative to virgin materials. However, higher concentrations of La 3+ reduce the discharge capacity with enhanced cycle stability by minimizing cation mixing between lithium (Li + ) and nickel (Ni 2+ ) ions within the cathode. Furthermore, this stability is crucial for extending battery life. Therefore, controlling the concentration of La 3+ impurities is essential for optimizing the electrochemical performance of recycled cathode materials.

Corrosion↗

Nanotwinned alloys under high pressure

Nanotwinned alloys are of interest due to their high strength and ductility, but twin boundaries may not be stable under shear. Computational studies indicate that high hydrostatic pressure may suppress detwinning mechanisms. Here, in this study, we investigate the microstructural changes of nanotwinned-nanocrystalline copper-nickel and Inconel 725 alloys under quasi-hydrostatic pressures up to 50 gigapascals (GPa). The alloys are compressed in a diamond anvil cell. In-situ x-ray diffraction (XRD) and ex-situ transmission electron microscopy (TEM) were employed to monitor microstructural changes. Twin boundary deformation and grain growth occur at 11.4 GPa quasi-hydrostatic pressure in the copper-nickel alloy. Molecular dynamics (MD) simulations reveal that hydrostatic pressure causes elevated local shear stress at grain boundaries, which leads to atomic rearrangements. A superposition of hydrostatic and deviatoric pressures lead to partial dislocation mediated twin boundary migration. In contrast, the Inconel 725 alloy showed stable twin and grain boundaries up to a quasi-hydrostatic pressure of 12.7 GPa. Texture, high solid solution strengthening, and low stacking fault energy are hypothesized to the enhanced microstructural stability in Inconel 725.

36 MATERIALS SCIENCE↗

The role of catalyst acidity and microstructure on light olefin selectivity in polyethylene deconstruction in short contact time pulse Joule-heated reactors

The growing volume of plastics waste, compounded with a low recycling rate, has led to an alarming amount of plastics ending up in landfills or being incinerated. While pyrolysis offers a route for plastic waste deconstruction, its product distribution is often broad and poorly controlled due to unselective radical chemistry at high temperatures. We recently demonstrated that rapid pulse Joule-heated catalytic cracking over HZSM-5, combined with small fractions of steam, can achieve high selectivity (>80 %) toward C 2 -C 4 olefins, while significantly reducing coking compared to continuous Joule heating. Here, we investigate how acid catalyst properties, such as silica/alumina ratio, zeolite topology, and catalyst porosity, influence light olefin selectivity during polyethylene deconstruction via rapid pulse Joule heating. We demonstrate that silica-to-alumina ratios of ∼30 yield high light olefin selectivity, and small-pore zeolites favor light olefins at the expense of increased coke formation. To mitigate coking, we synthesize HZSM-5 nanosheets and hierarchical zeolites (MFI, FAU, and CHA). Furthermore, these catalysts achieve an ethylene selectivity of approximately 35 %, a twofold increase over prior catalytic pyrolysis. Additionally, co-feeding steam and incorporating hierarchical porosity reduce coke formation and enhance catalyst stability.

Catalytic cracking↗

Enhanced flexibility and thermal conductivity of HfC decorated carbon nanofiber mats

Future-generation spacecraft components allude discovery of novel materials that can withstand extreme environments (>2000 °C). The combined effect of ultra-high temperature ceramics (UHTCs) and carbon fibers (C f ) can satisfy the demanding requirements of aerospace applications. A novel, hybrid, and flexible hafnium carbide (HfC)-decorated carbon nanofiber (C nf ) mat was fabricated via electrospinning. Enhanced thermal stability of the flexible HfC decorated C nf over C nf can be elucidated from the 20-fold increment in thermal conductivity and the onset of degradation at higher temperatures (840 °C). Successful integration of multi-layered sandwich lattice using in-housed fabricated HfC decorated C nf showed retention of the fibrous structure even after extreme spark plasma sintering (SPS) process at 1850 °C. Fabricating a similar multi-layered structure using procured C f was unsuccessful due to bundled agglomeration and micron-sized fibers. High-load indentation suggests that HfC decorated C nf interlayer is stronger (~2.3 times) than the parent UHTC with no cracking at the interface. Compared with the HfC matrix, the indentation-damaged area at the interface reduced up to ~56% due to toughening mechanisms such as C nf , fiber pull-out and bridging. The synthesized HfC decorated Cnf mat is proposed as an ultra-thin filler material for joining similar or dissimilar UHTCs while maintaining similar chemistry and better mechanical integrity at the interface. Furthermore, the findings insinuate a new paradigm in designing hybrid and flexible ceramic-containing materials for thermal protection systems (TPS) of future-generation spacecraft components that can mitigate failure in extreme environments (>2000 °C).

36 MATERIALS SCIENCE↗