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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex

We have determined the identity of the complexes extracted into the ALSEP process solvent from solutions of nitric acid. The ALSEP process is a new solvent extraction separation designed to separate americium and curium from trivalent lanthanides in irradiated nuclear fuel. ALSEP employs a mixture of two extractants, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and N,N,N',N'-tetra(2-ethylhexyl)diglycolamide (TEHDGA) in n-dodecane, which makes it difficult to ascertain the nature of the extracted metal complexes. It is often asserted that the weak acid extractant HEH[EHP] does not participate in the extracted complex under ALSEP extraction conditions (2–4 M HNO 3 ). However, the analysis of the Am extraction equilibria, Nd absorption spectra, and Eu fluorescence emission spectra of metal-loaded organic phases argues for the participation of HEH[EHP] in the extracted complex despite the high acidity of the aqueous phases. The extracted complex was determined to contain fully protonated molecules of HEH[EHP] with an overall stoichiometry of M(TEHDGA) 2 (HEH[EHP]) 2 ·3NO 3 . Computations also demonstrate that replacing one TEHDGA molecule with one (HEH[EHP]) 2 dimer is likely energetically favorable compared to Eu(TEHDGA) 3 ·3NO 3 , whether the HEH[EHP] dimer is monodentate or bidentate.

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

Synthesis and Characterization of Copolymers and Nanocomposites from Limonene, Styrene and Organomodified-Clay Using Ultrasonic Assisted Method

In the present work, we report a simple synthesis method for preparation of copolymers and nanocomposites from limonene and styrene using clay as a catalyst. The copolymerization reaction is carried out by using a proton exchanged clay as a catalyst called Mag-H+. The effect of temperature, reaction time and amount of catalyst were studied, and the obtained copolymer structure (lim-co-sty) is characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H-NMR) and differential scanning calorimetry (DSC). The molecular weight of the obtained copolymer is determined by gel permeation chromatography (GPC) and is about 4500 g·mol−1. The (lim-co-sty/Mag 1%, 3%, 7% and 10% by weight of clay) nanocomposites were prepared through polymer/clay mixture in solution method using ultrasonic irradiation, in the presence of Mag-CTA+ as green nano-reinforcing filler. The Mag-CTA+ is organophilic silicate clay prepared through a direct exchange process, using cetyltrimethylammonuim bromide (CTAB). The prepared lim-co-sty/Mag nanocomposites have been extensively characterized by FT-IR spectroscopy, X-ray diffraction (XRD), scanning electronic microscopy (SEM) and transmission electronic microscopy (TEM). TEM analysis confirms the results obtained by XRD and clearly show that the obtained nanocomposites are partially exfoliated for the lower amount of clay (1% and 3% wt) and intercalated for higher amounts of clay (7% and 10% wt). Moreover, thermogravimetric analysis (TGA) indicated an enhancement of thermal stability of nanocomposites compared with the pure copolymer.

Derdar, Hodhaifa↗
DOE OSTI2021

Dynamic infrared gas analysis from longleaf pine fuel beds burned in a wind tunnel: observation of phenol in pyrolysis and combustion phases

Pyrolysis is the first step in a series of chemical and physical processes that produce flammable organic gases from wildland fuels that can result in a wildland fire. We report results using a new time-resolved Fourier transform infrared (FTIR) method that correlates the measured FTIR spectrum with an infrared thermal image sequence, enabling the identification and quantification of gases within different phases of the fire process. The flame from burning fuel beds composed of pine needles (Pinus palustris) and mixtures of sparkleberry, fetterbush, and inkberry plants was the natural heat source for pyrolysis. Extractive gas samples were analyzed and identified in both static and dynamic modes synchronized to thermal infrared imaging: a total of 29 gases were identified including small alkanes, alkenes, aldehydes, nitrogen compounds, and aromatics, most previously measured by FTIR in wildland fires. This study presents one of the first identifications of phenol associated with both pre-combustion and combustion phases using ca. 1 Hz temporal resolution. Preliminary results indicate ~2.5× greater phenol emissions from sparkleberry and inkberry compared to fetterbush, with differing temporal profiles.

09 BIOMASS FUELS↗
DOE OSTI2026

High hardness and oxidation-resistant Cr-containing medium entropy ZrTaW diboride

This study reports the successful synthesis of a Cr-containing (Zr 0.30 Ta 0.34 Cr 0.06 W 0.30 )B 2 medium-entropy boride (MEB) via an in-situ reactive borothermal reduction route from oxide precursors. High-energy ball milling was employed to homogenize the precursor mixture prior to reactive densification. X-ray diffraction confirmed the formation of a predominantly AlB₂-type hexagonal diboride structure together with a secondary (W X , M 1-X )B monoboride phase. Microstructural characterization revealed compositional heterogeneity and localized W-rich regions associated with the secondary phase. The synthesized medium-entropy boride exhibited enhanced mechanical properties, which are attributed to lattice distortion and solid-solution strengthening effects. Thermogravimetric analysis revealed complex multistage oxidation behavior, and the oxidation resistance was compared with conventional ultra-high-temperature diborides. The results demonstrate the strong relationship between oxide-derived processing, compositional complexity, phase evolution, and oxidation behavior, highlighting the potential of medium-entropy borides for high-temperature structural applications

36 MATERIALS SCIENCE↗
DOE OSTI2025

End-to-End Automated Segmentation Framework for Four-Dimensional Scanning Transmission Electron Microscopy Data

Four-dimensional scanning transmission electron microscopy (4D-STEM) is powerful for rapidly characterizing arrays of nanoparticles produced via high-throughput synthesis. However, such 4D-STEM datasets typically contain thousands of nanoparticles, each characterized by thousands of diffraction patterns spatially distributed across the nanoparticle, necessitating efficient and comprehensive analysis. We propose an end-to-end segmentation framework to automatically segment each nanoparticle into regions with distinct composition/orientation of crystal grains, using only the 4D-STEM data. Bragg disk information is extracted in a physics-informed manner from the diffraction patterns at each spatial location and combined with the real space coordinates to form feature vectors. These feature vectors are then used as inputs to a Gaussian mixture model (GMM) to segment the nanoparticle into distinct regions. We also develop two visualization tools based on the GMM outputs to infer the interface transition and the degree of superposition. Our framework comprehensively integrates machine learning tools and physics knowledge, and provides a basis for substantially compressing enormous 4D-STEM datasets, e.g., by replacing the full 4D-STEM dataset for each nanoparticle with only a single set of Bragg disk features for each distinct crystal grain identified in the nanoparticle. In this article, we demonstrate the power of our framework by presenting results for real, complex datasets.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Concrete Compositions Used in Neutronics Analyses for Design of the Second Target Station Project

The purpose of this letter is to document the concrete compositions used by the Second Target Station (STS) Project Neutronics Group. Members of the Neutronics Group all have access to these compositions in our MCNP Master Model, which is stored on the ORNL GitLab server. It is expected that all STS Neutronics staff members will use these compositions in their analyses, unless all stakeholders agree to an exception. It is impossible to know the detailed composition of concrete before its constituents have been purchased, mixed, and a chemical analysis performed. Therefore, the STS Neutronics Group decided to use the same concrete compositions used by the Neutronics Group at the First Target Station (FTS). Furthermore, this leads to consistency between the analyses performed by the FTS and STS Neutronics Groups. The most important parameter to match between design simulations and construction regarding these concrete compositions is the density. Next in importance is the fraction of iron and hydrogen in the mixture.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Solution combustion synthesis of iron-based alumina catalysts for dehydrogenation of fossil fuels

Microwave-assisted thermocatalytic dehydrogenation of fossil fuels has been proposed as a method for hydrogen production with no CO2 emissions. The byproduct is carbon, which has a commercial value. Iron-based alumina nanocomposites are promising catalysts for this process as they both absorb microwave radiation and catalyze the dehydrogenation. In addition, they may have magnetic properties, which could be used for their separation from the carbon byproduct. Solution combustion synthesis (SCS) is an attractive technique for the fabrication of iron-based alumina nanocomposites because it can produce high specific surface area oxides in a facile manner. However, the effects of the heating mode, the fuel, and the iron/aluminum ratio on the combustion synthesis behavior and the product properties have not been studied yet. In the present work, the iron-based alumina nanocomposites were obtained by SCS using a hotplate, a muffle furnace, and a microwave oven. The initial mixtures were aqueous solutions of iron nitrate, aluminum nitrate, and an organic fuel. The concentrations of the two nitrates were varied in proportion to Fe:Al molar ratios of 1:2, 1:1, and 2:1. Two fuels were tested: citric acid and glycine. The combustion was less vigorous when citric acid was used as the fuel, which is explained by the lower exothermicity of the reaction. X-ray diffraction analysis of the products confirmed the formation of complex oxides of Fe and Al, specifically it detected hercynite and magnetite phases. Brunauer-Emmett-Teller surface area analysis has shown that the powders obtained using citric acid have specific surface areas as high as 276 m2/g, significantly higher than those obtained using glycine. Muffle furnace and hotplate heating led to comparable specific surface areas, while microwave heating resulted in significantly lower specific surface areas. The magnetic properties of the products increase with increasing the Fe/Al molar ratio from 1:2 (no response to a magnetic field) to 1:1 (weak response) and 2:1 (strong response).

solution combustion synthesis, nanoscale oxides, f↗
DOE OSTI2021

Analysis of the Ion Conversion Mechanisms in the Effluent of Atmospheric Pressure Plasma Jets in Ar with Admixtures of O 2 , H 2 O and Air

Ionic species in atmospheric pressure plasma jets (APPJs) play an important role in plasmasurface and plasma-liquid interactions, nonetheless, they have not received the same attention as their neutral reactive species counterparts. In this work, a molecular beam mass spectrometer (MBMS) was used to characterize the ion compositions in the effluent of an APPJ operating in ambient air for different feed gases including Ar + O 2 , Ar + air and Ar + H 2 O mixtures inspired by gas compositions used for biomedical applications. Changes in compositions of positive and negative ions as a function of nozzle-to-substrate distance along the plasma plume were analyzed and compared with a pseudo-1D plug flow model. Positive and negative ions were detected up to distances of 12 mm from the visible plasma plume tip. The measurements enable to follow the ion conversion pathways in the effluent of the APPJs as a function of distance from the nozzle. The trends in ion yield obtained from a pseudo-1D plug flow model showed generally a good agreement with the experimentally observed trends after addition of ionic reactions to the previously reported reaction set but also some distinctive differences were observed. The dominant positive ions in the far effluent are water ion clusters, the most stable ion for all gas mixtures investigated, while a large variety of negative ions was found for different gas mixtures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole

Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N-donor f-element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz), 5-amino-tetrazole (5-NH 2 -HTetaz), and 1,2,3-triazole (1,2,3-HTriaz) in 1 : 1 and 1 : 3 ratios with CeCl 3 ⋅ 7H 2 O, [C 2 mim] 3 [CeCl 6 ] ([C 2 mim] + =1-ethyl-2-methylimidazolium), and Ce(NO 3 ) 3 ⋅ 6H 2 O. Although unsuccessful in our goal, structural analysis revealed that neutral 4-NH 2 -1,2,4-Triaz is structure directing via η 2 μ 2 κ 2 bridging, with the formation of the dinuclear complexes [Ce 2 Cl 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (H 2 O) 8 ]Cl 4 ⋅ 4H 2 O, [Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (4-NH 2 -1,2,4-Triaz) 2 (Cl) 6 ], and [4-NH 2 -1,2,4-HTriaz][Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 2 (μ 2 -NO 3 )(NO 3 ) 6 (H 2 O) 2 ]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 2 (μ 3 -Cl) 2 (Cl) 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ] ⋅ 7H 2 O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N-donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non-oxo coordinating anions in the M 6 X 8 core, and the first reported Ce(III) hexanuclear complex of this type.

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

Surface functionality and formation mechanisms of carbon and graphene quantum dots

Graphene quantum dots (GQDs) and Carbon dots (C-dots) have been widely studied in recent years due to their structural and optoelectrical properties. These properties have prompted the exploration of the role of these carbon-based materials in many potential applications. This includes solar cells, photodetectors, bioimaging, sensors, batteries and drug delivery. These properties and applications of GQDs and C-dots are highly dependent on their size, shape and surface functionality. In this work, GQDs and C-dots mixtures have been synthesized by an inexpensive wet chemical method by varying the synthesis temperature from 85°, 100° to 115 °C. The surface functionalities of the synthesized carbon-based materials were investigated by several analytical methods. We discovered a higher degree of oxidation at higher temperatures. The mechanism of formation of different sized GQDs and C-dots with different functionalities have been explained with the help of XPS and NEXAFS analysis. The influence of size and surface functionalities on the optical properties of these nanomaterials is analyzed by UV–Vis and PL spectroscopic techniques. Furthermore, this study demonstrates that physicochemical properties of GQDs and C-dots can be controlled by changing the synthesis temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Bi-fated tendon-to-bone attachment cells are regulated by shared enhancers and KLF transcription factors

The mechanical challenge of attaching elastic tendons to stiff bones is solved by the formation of a unique transitional tissue. Here, we show that murine tendon-to-bone attachment cells are bi-fated, activating a mixture of chondrocyte and tenocyte transcriptomes, under regulation of shared regulatory elements and Krüppel-like factors (KLFs) transcription factors. High-throughput bulk and single-cell RNA sequencing of humeral attachment cells revealed expression of hundreds of chondrogenic and tenogenic genes, which was validated by in situ hybridization and single-molecule ISH. ATAC sequencing showed that attachment cells share accessible intergenic chromatin areas with either tenocytes or chondrocytes. Epigenomic analysis revealed enhancer signatures for most of these regions. Transgenic mouse enhancer reporter assays verified the shared activity of some of these enhancers. Finally, integrative chromatin and motif analyses and transcriptomic data implicated KLFs as regulators of attachment cells. Indeed, blocking expression of both Klf2 and Klf4 in developing limb mesenchyme impaired their differentiation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Technical and Economic Assessment and Gap Analysis of Advanced Nuclear Reactor Integration with a Reference Methanol Synthesis Plant

Efforts continue to identify the most-economic methods to decarbonize several sectors of the United States (U.S.) economy. Industrial processes such as synfuel synthesis and high value commodity chemicals rely heavily on energy-dense and easily stored and transported fossil fuels, which power and feed their operations. Steam methane reforming (SMR) is a widely used process for producing methanol. In this process, methane (CH 4 ) from natural gas (NG) reacts with steam (H 2 O) over a catalyst at high temperatures (700-1,000°C) to produce syngas, a mixture of hydrogen (H 2 ) and carbon monoxide (CO). The syngas is then converted into methanol (CH 3 OH) through a second catalytic reaction. This method is known for being an efficient and commonly employed pathway for industrial methanol production. The high-temperature heat needed for SMR, which is currently used in the natural-gas-to-methanol process, cannot be supplied by small modular nuclear reactor (SMNR) direct heating; the temperatures required for the SMR process exceed those of the main steam produced by near-market high-temperature gas reactors (HTGRs). For the conventional methanol process, this leaves possible nuclear-integration opportunities that include: (1) blending nuclear hydrogen into the SMR NG fuel, or (2) assessing alternative synthesis routes leveraging nuclear capabilities and steam electrolysis outputs. In the reference methanol plant, SMR provides the methanol-synthesis reactor with H 2 and co. In Case (2), the state-of-the-art reverse water gas shift (RWGS) pathway achieves the same, sourcing carbon from an industrial CO 2 source.

08 HYDROGEN↗
DOE OSTI2025

Technical and Economic Assessment and Gap Analysis of Advanced Nuclear Reactor Integration with a Reference Methanol Synthesis Plant

Efforts continue to identify the most-economic methods to decarbonize several sectors of the United States (U.S.) economy. Industrial processes such as synfuel synthesis and high value commodity chemicals rely heavily on energy-dense and easily stored and transported fossil fuels, which power and feed their operations. Steam methane reforming (SMR) is a widely used process for producing methanol. In this process, methane (CH 4 ) from natural gas (NG) reacts with steam (H 2 O) over a catalyst at high temperatures (700°1,000°C) to produce syngas, a mixture of hydrogen (H 2 ) and carbon monoxide (CO). The syngas is then converted into methanol (CH 3 OH) through a second catalytic reaction. This method is known for being an efficient and commonly employed pathway for industrial methanol production. The high-temperature heat needed for SMR, which is currently used in the natural-gas-to-methanol process, cannot be supplied by small modular nuclear reactor (SMNR) direct heating; the temperatures required for the SMR process exceed those of the main steam produced by near-market high-temperature gas reactors (HTGRs). For the conventional methanol process, this leaves possible nuclear-integration opportunities that include: (1) blending nuclear hydrogen into the SMR NG fuel, or (2) assessing alternative synthesis routes leveraging nuclear capabilities and steam electrolysis outputs. In the reference methanol plant, SMR provides the methanol-synthesis reactor with H 2 and co. In Case (2), the state-of-the-art reverse water gas shift (RWGS) pathway achieves the same, sourcing carbon from an industrial CO 2 source.

08 - HYDROGEN↗
DOE OSTI2024

Catabolism of β-5 linked aromatics by Novosphingobium aromaticivorans

ABSTRACT Aromatic compounds are an important source of commodity chemicals traditionally produced from fossil fuels. Aromatics derived from plant lignin can potentially be converted into commodity chemicals through depolymerization followed by microbial funneling of monomers and low molecular weight oligomers. This study investigates the catabolism of the β-5 linked aromatic dimer dehydrodiconiferyl alcohol (DC-A) by the bacterium Novosphingobium aromaticivorans . We used genome-wide screens to identify candidate genes involved in DC-A catabolism. Subsequent in vivo and in vitro analyses of these candidate genes elucidated a catabolic pathway composed of four required gene products and several partially redundant dehydrogenases that convert DC-A to aromatic monomers that can be funneled into the central aromatic metabolic pathway of N. aromaticivorans . Specifically, a newly identified γ-formaldehyde lyase, PcfL, opens the phenylcoumaran ring to form a stilbene and formaldehyde. A lignostilbene dioxygenase, LsdD, then cleaves the stilbene to generate the aromatic monomers vanillin and 5-formylferulate (5-FF). We also showed that the aldehyde dehydrogenase FerD oxidizes 5-FF before it is decarboxylated by LigW, yielding ferulic acid. We found that some enzymes involved in the β-5 catabolism pathway can act on multiple substrates and that some steps in the pathway can be mediated by multiple enzymes, providing new insights into the robust flexibility of aromatic catabolism in N. aromaticivorans . A comparative genomic analysis predicted that the newly discovered β-5 aromatic catabolic pathway is common within the order Sphingomonadales. IMPORTANCE In the transition to a circular bioeconomy, the plant polymer lignin holds promise as a renewable source of industrially important aromatic chemicals. However, since lignin contains aromatic subunits joined by various chemical linkages, producing single chemical products from this polymer can be challenging. One strategy to overcome this challenge is using microbes to funnel a mixture of lignin-derived aromatics into target chemical products. This approach requires strategies to cleave the major inter-unit linkages of lignin to release monomers for funneling into valuable products. In this study, we report newly discovered aspects of a pathway by which the Novosphingobium aromaticivorans DSM12444 catabolizes aromatics joined by the second most common inter-unit linkage in lignin, the β-5 linkage. This work advances our knowledge of aromatic catabolic pathways, laying the groundwork for future metabolic engineering of this and other microbes for optimized conversion of lignin into products.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Direct observation of key aluminum hydroxide prenucleation oligomers for gibbsite nucleation and crystallization in sodium aluminate solution by liquid ToF-SIMS

The mechanism of gibbsite (aluminum hydroxide) crystallization from highly alkaline solutions such as Bayer liquors remains poorly understood, where aluminum (Al) transforms from largely tetrahedrally coordinated aluminate monomers in sodium aluminate solutions into a network of octahedra in gibbsite crystals. A variety of traditional analytical approaches applied to this system do not readily reveal the presence of higher-order oligomeric intermediates. To overcome this limitation, we employed in-situ liquid Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to examine the Al species present in concentrated sodium aluminate solutions favoring crystallization of gibbsite or sodium aluminate. A complex mixture of Al oligomers was found. By comparing the change in the relative concentration of Al oligomers with +1 and -1 charge, we were able to identify three major Al oligomer candidates, iso-tetramers, iso-pentamers, and cyclic-hexamers, for the nucleation and crystallization of gibbsite. The concentrations of iso-tetramers and iso-pentamers significantly surpass those of cyclic-hexamers. Time-dependent in-situ Raman spectroscopy analysis indicated that the appearance of gibbsite coincided with the peak concentration of these oligomers. The Density-functional theory (DFT) calculation suggests that the formation of iso-oligomers is more favorable than that of cyclic-hexamers. The combined results suggest that iso-tetramers and iso-pentamers play the most substantial role in the nucleation and growth of gibbsite in the sodium aluminate solutions. Our findings also suggest that the oligomers that promote gibbsite crystallization are more stable in dilute sodium aluminate solutions, making these solutions particularly suitable for efficient gibbsite crystallization. In conclusion, our study fills a major knowledge gap in understanding Al speciation that leads to the nucleation and crystallization of gibbsite in concentrated sodium aluminate solutions.

Bayer liquor↗
DOE OSTI2023

Crystallographic Study of Product Phases of Carbothermic Reduction and Nitridation of Hafnium Dioxide

Details of the carbothermic reduction/nitridation to synthesize hafnium nitride (HfN) and hafnium carbide (HfC) are scarce in the literature. Therefore, this current study was carried out to evaluate two pathways for synthesizing these two refractory materials: direct nitridation and carbothermic reduction/nitridation. Two mixtures of hafnium dioxide and carbon with C/HfO 2 molar ratios of 2.15 and 3.1 were nitridized directly using flowing nitrogen gas at elevated temperatures (1300–1700 °C). The 3.1 C/HfO 2 molar ratio mixture was also carbothermically reduced under flowing argon gas to synthesize HfC, which was converted into HfN by introducing a nitridation step under both N 2(g ) and N 2(g) -10% H 2(g) . X-ray diffraction results showed the formation of HfN at 1300 and 1400 °C and HfC 1–y N y at ≥1400 °C under direct nitridation of samples using a C/HfO 2 molar ratio of 2.15. These phase analysis data together with lower lattice strain and greater crystallite sizes of HfC 1–y N y that formed at higher temperatures suggested that the HfC 1–y N y phase is preferred over HfN at those temperatures. Carbothermic reduction of 3.1 C/HfO 2 molar ratio samples under an inert atmosphere produced single-phased HfC with no significant levels of dissolved oxygen. In conclusion, carbothermic reduction nitridation made two phases of different carbon levels (HfC 1–y N y and HfC 1–y 'N y ', where y' < y), while direct nitridation produced a single HfC 1–y N y phase under both N 2 and N 2 -10% H 2 cover gas environments.

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

Single-Walled Zeolitic Nanotube–Poly(oxazoline) Nanocomposites as Heterogeneous Catalysts for Acid–Base Cascade Reactions

Zeolites with a unique, 1-dimensional form factor were recently discovered − zeolite nanotubes (ZNTs). Here we describe the synthesis and characterization of NaH-ZNTpoly( oxazoline) composites targeting liquid-phase acid−base cascade catalysis. NaH-ZNT, a one-dimensional zeolite analogue with mesoporosity (3−4 nm) associated with nanotubes and inherent Brønsted acid sites associated with the microporous zeolite domains, is functionalized with poly(oxazoline)-based triblock copolymers with varying molecular weights (3−17 kDa). The composites are characterized using N2 sorption, STEM, FTIR, and elemental analysis, confirming successful grafting and preservation of the zeolite nanotube structure. The composites’ catalytic performance is evaluated through separate acid and base reactions, followed by a combined cascade of a deacetalization−Knoevenagel condensation for the synthesis of chalcone compounds. High initial reaction rates are demonstrated, but modest overall cascade product formation rates are observed, attributed to interactions between Brønsted acid sites and base amine groups that occur in the polymer-grafted systems. Physical mixtures of NaH-ZNT-SH and poly(oxazoline)s, lacking covalent linkages between ZNT and the polymer, support this supposition. This work demonstrates the potential of NaH-ZNT-poly(oxazoline) composites for liquid-phase cascade catalysis for synthesizing compounds of potential medicinal interest, highlighting the benefits of the grafting-to approach as well as the need for further optimization of the catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗