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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Synthesis and structural properties of a 2D Zn( II ) dodecahydroxy- closo -dodecaborate coordination polymer

Here, in this work, we discuss the synthesis and characterization of a 2D coordination polymer composed of a dianionic perhydroxylated boron cluster, [B 12 (OH) 12 2– ], coordinated to Zn( II )—the first example of a transition metal-coordinated [B 12 (OH) 12 ] 2– compound. This material was synthesized via cation exchange from the starting cesium salt and then subjected to rigorous characterization prior to and after thermal activation. Numerous techniques, including XRD, FTIR, SEM, TGA, and solid-state NMR revealed a 2D coordination polymer composed of sheets of Zn( II ) ions intercalated between planes of boron clusters. The as-synthesized material was then evacuated of solvent via thermal treatment, and atomic-level changes from this transformation were elucidated through a combination of 1D and 2D solid-state NMR analyses of 11 B and 1 H nuclei, suggesting the full removal of coordinated solvent molecules. Evidence also suggested that [B 12 (OH) 12 2– ] can adjust its coordination to Zn( II ) in the solid-state through hemilability of its numerous –OH ligands.

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

Development of Operando Nuclear Magnetic Resonance Capabilities for Solid-State Battery Research

Mechanistic information regarding solid-solid interfaces in solid-state batteries remains elusive as its observation requires a non-destructive operando technique. Such a technique does not currently exist. Solid-state nuclear magnetic resonance (NMR) is uniquely suited to address this challenge as it is sensitive to chemistry, structure, and dynamics and can measure buried interfaces. However solid-state NMR requires high speed spinning of the sample at the ‘magic angle’ (MAS) to obtain adequate resolution. The metallic current collectors in a battery are detrimental to spinning in magnetic fields as they generate eddy currents which prevent spinning and dampen the NMR signal. Furthermore, the spinning nature of the MAS NMR experiment requires a wireless means of charging for operando capabilities. These challenges were addressed in this research and operando MAS NMR enabled by optical wireless charging was demonstrated. By limiting the size of the metallic components, we were able to spin a sample holder with electrical leads and a solid-state battery up to a few kilohertz, fast enough for high-resolution NMR. We achieved wireless charging by attaching a photovoltaic cell to the head of the NMR rotor and used a laser to transmit power to the photovoltaic cell. Demonstration of the optical wireless charging was performed by polarizing a liquid electrolyte during an operando MAS NMR measurement. This novel capability is a transformative technique for investigating the mechanistic electrochemical processes in solid-state samples.

25 ENERGY STORAGE↗
DOE OSTI2025

Polymer connectivity governs electrophotocatalytic activity in the solid state

The reductive functionalization of inert substrates such as chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging strategy to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is limited by poor stability and mechanistic ambiguity. Here, in this work, we demonstrate heterogeneous electrophotocatalysis using redox-active rylene diimide polymers for the reduction of chloroarenes. We find that the electrophotocatalytic activity varies dramatically as a function of the rylene diimide and the redox-inactive polymer backbone. In particular, a flexible, non-conjugated perylenediimide polymer outperforms all other tested electrophotocatalysts. Transient absorption spectroscopy reveals that precomplexation between the doubly reduced perylenediimide and the haloarene substrate is key to productive catalysis. Overall, this work highlights heterogeneous electrophotocatalysis using insoluble redox-active organic materials and provides critical structure–property insights into solid-state electrophotocatalytic activity, informing the development of next-generation materials for sustainable synthesis.

electrocatalysis↗
DOE OSTI2025

Chemically Recyclable Polyester Thermosets from Activated Adipic Acid and Renewable Polyols

This study outlines a method for producing chemically recyclable crosslinked polyesters using renewable polyols-glycerol and sorbitol-combined with adipic acid (AA), which is transformed/activated into a polyanhydride mixture prior to use. A three-step procedure has been designed: 1) an acid-catalyzed reaction of AA with nontoxic isopropenyl acetate or acetic anhydride to form a crosslinking mixture (CLM) made of adipic-acetic mixed polyanhydrides; 2) a solvent- and additive-free process where glycerol or sorbitol, or a combination thereof, is reacted with the CLM to achieve a prepolymer, and 3) a casting/molding of the liquid viscous prepolymer to yield a thermoset as the end product. Different thermosets (eight examples) are prepared by changing the reagents ratio. These solids are thoroughly characterized by tensile tests, DMA, high-resolution magic angle spinning and solid-state NMR, thermal gravimetric analysis, DSC, and fourier transformed infra red (FT-IR) spectroscopy. The formation of cross-linked polyesters is confirmed in all cases, but mechanical properties varied significantly from one specimen to another. Interestingly, a tensile strength up to 18 MPa-approximately an order of magnitude higher than similar polymers-is achieved when sorbitol and the CLM are used in a 1:1 wt% ratio. The chemical recycle of the resulting polymers is achieved via methanolysis with quantitative recovery of the monomeric units.

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

Ligand-Free Processable Perovskite Semiconductor Ink

We report traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs 2 TeX 6 (X = Cl - , Br - , I - ) in polar aprotic solvents, leading to the stabilization of isolated [TeX 6 ] 2- octahedral anions and free Cs + cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multifunctional inks with the ability to reversibly transform between the liquid ink and the solid-state perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, spraying or painting, and stamping, highlighting the crucial role of solvated octahedral complexes toward the rapid formation of phase-pure perovskite structures in ambient conditions.

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

Silicon Nitride Surface Enabled Propane Dehydrogenation Catalyzed by Supported Organozirconium

Mesoporous silicon nitride (Si 3 N 4 ) is a nontraditional support for the chemisorption of organometallic complexes with the potential for enhancing catalytic activity through features such as the increased Lewis basicity of nitrogen for heterolytic bond activation, increased ligand donor strength, and metal–ligand orbital overlap. In this report tetrabenzyl zirconium (ZrBn 4 ) was chemisorbed on Si 3 N 4 , and the resulting supported organometallic species was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Dynamic Nuclear Polarization-enhanced Solid State Nuclear Magnetic Resonance (DNP-SSNMR), and X-ray Absorption Spectroscopy (XAS). Based on the hypothesis that the nitride might enable facile heterolytic C–H bond activation along the Zr–N bond, this material was found to be a highly active (1.53 mol propene mol Zr –1 h –1 at 450 °C) and selective (99% to propylene) catalyst for propane dehydrogenation. In contrast, the homologous silica supported complex exhibited negligible activity under these conditions.

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

Decoding Antenna Behavior in Metal—Organic Frameworks

Metal–organic frameworks (MOFs) define a solid-state platform for developing artificial photosystems. Efficient anisotropic exciton migrations in these frameworks entail “antenna behavior” that can power up the distal interior reaction centers (RC), driving charge separation between donor-acceptor pairs. Reminiscent of the natural light-harvesting complex, such processes can achieve high quantum yield by exploiting the vast interior surface of the porous crystallites. It is important to understand the optimum positioning of the RC site relative to the anisotropic exciton migration path within these frameworks. The efficiency of such antenna behavior is probed here through Stern–Volmer (SV) type analysis with a series of node-anchored redox quenchers, ferrocene-carboxylate, ferrocene acetate, and dinitrobenzoate. Decoding various intrinsic processes, this work constructs a revised SV formalism in solid assembly that hosts ultrafast anisotropic exciton migration to account for the intrinsic exciton hopping rate from the extrinsic electron transfer rate, and the dimension of effective quenching. In conclusion, this transformative understanding can be applied to other relevant solid-state assemblies.

Saha, Bapan [Southern Illinois University, Carbond↗
DOE OSTI2020

Experimental and theoretical evidence for hydrogen doping in polymer solution-processed indium gallium oxide

The field-effect electron mobility of aqueous solution-processed indium gallium oxide (IGO) thin-film transistors (TFTs) is significantly enhanced by polyvinyl alcohol (PVA) addition to the precursor solution, a >70-fold increase to 7.9 cm 2 /Vs. To understand the origin of this remarkable phenomenon, microstructure, electronic structure, and charge transport of IGO:PVA film are investigated by a battery of experimental and theoretical techniques, including In K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS); resonant soft X-ray scattering (R-SoXS); ultraviolet photoelectron spectroscopy (UPS); Fourier transform-infrared (FT-IR) spectroscopy; time-of-flight secondary-ion mass spectrometry (ToF-SIMS); composition-/processing-dependent TFT properties; high-resolution solid-state 1 H, 71 Ga, and 115 In NMR spectroscopy; and discrete Fourier transform (DFT) analysis with ab initio molecular dynamics (MD) liquid-quench simulations. The 71 Ga{ 1 H} rotational-echo double-resonance (REDOR) NMR and other data indicate that PVA achieves optimal H doping with a Ga···H distance of ~3.4 Å and conversion from six- to four-coordinate Ga, which together suppress deep trap defect localization. This reduces metal-oxide polyhedral distortion, thereby increasing the electron mobility. Finally, hydroxyl polymer doping thus offers a pathway for efficient H doping in green solvent-processed metal oxide films and the promise of high-performance, ultra-stable metal oxide semiconductor electronics with simple binary compositions.

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

High-fidelity topochemical polymerization in single crystals, polycrystals, and solution aggregates

Topochemical polymerization (TCP) emerges as a leading approach for synthesizing single crystalline polymers, but is traditionally restricted to transformations in solid-medium. The complexity in achieving single-crystal-to-single-crystal (SCSC) transformations due to lattice disparities and the untapped potential of performing TCP in a liquid medium with solid-state structural fidelity present unsolved challenges. Herein, by using X-rays as the primary means to overcome crystal disintegration, we reveal the details of SCSC transformation during the TCP of chiral azaquinodimethane (AQM) monomers through in situ crystallographic analysis while spotlighting a rare metastable crystalline phase. Complementary in situ investigations of powders and thin films provide critical insights into the side-chain dependent polymerization kinetics of solid-state reactions. Furthermore, we enable TCP of AQM monomers in a liquid medium via an antisolvent-reinforced aggregated state, yielding polymer nanofibers with high crystallinity akin to that of solid-state. This study testifies high structural precision of TCP performed in different states and media, offering critical insights into the synthesis of processable nanostructured polymers with desired structural integrity.

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

High-Performance CO 2 Capture from Air by Harnessing the Power of CaO- and Superbase-Ionic-Liquid-Engineered Sorbents

Direct air capture (DAC) of CO 2 by solid porous materials represents an attractive “negative emission” technology. However, state-of-the-art sorbents based on supported amines still suffer from unsolved high energy consumption and stability issues. For this work, taking clues from the CO 2 interaction with superbase-derived ionic liquids (SILs), high-performance and tunable sorbents in DAC of CO 2 was developed by harnessing the power of CaO- and SIL-engineered sorbents. Deploying mesoporous silica as the substrate, a thin CaO layer was first introduced to consume the surface-OH groups, and then active sites with different basicities (e. g., triazolate and imidazolate) were introduced as a uniformly distributed thin layer. The as-obtained sorbents displayed high CO 2 uptake capacity via volumetric (at 0.4 mbar) and breakthrough test (400 ppm CO 2 source), rapid interaction kinetics, facile CO 2 releasing, and stable sorption/desorption cycles. Operando diffuse reflectance infrared Fourier transformation spectroscopy (DRIFTS) analysis under simulated air atmosphere and solid-state NMR under 13 CO 2 atmosphere demonstrated the critical roles of the SIL species in low-concentration CO 2 capture. The fundamental insights obtained in this work provide guidance on the development of high-performance sorbents in DAC of CO 2 by leveraging the combined advantages of porous solid scaffolds and the unique features of CO 2 -philic ionic liquids.

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

Burn Intensity Drives the Alteration of Phenolic Lignin to (Poly) Aromatic Hydrocarbons as Revealed by Pyrolysis Gas Chromatography–Mass Spectrometry (Py-GC/MS)

High-intensity wildfires alter the chemical composition of organic matter, which is expected to be distinctly different from low-intensity prescribed fires. In this study, we used pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), in conjunction with solid-state 13 C nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, to assess chemical alterations from three wildfires and a long-term frequent prescribed fire site. Our results showed that black ash formed under moderate intensity burns contained less aromatic (ArH), polyaromatic hydrocarbon (PAH), and nitrogen-containing compounds (Ntg) but more lignin (LgC) and phenol compounds (PhC), compared to white ash formed under high intensity burns. Both 13 C NMR and FT-IR confirmed a higher relative percentage of carboxyl carbon in white ash, indicating the potential for higher water solubility and more mobile carbon, relative to black ash. Compared to wildfires, ash from low-intensity prescribed fire contained less ArH, PAH, and Ntg and more LgC and PhC. Controlled laboratory burning trials indicated that organic matter alteration was sensitive to the burn temperature, but not related to the fuel type (pine vs fir) nor oxygen absence/presence at high burn temperatures. This study concludes that higher burn temperatures resulted in higher (poly)aromatic carbon/nitrogen and lower lignin/phenol compounds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Assembly of Uranyl Peroxides from Ball Milled Solids

Mechanochemistry enables transformations of highly insoluble materials such as uranium dioxide or the mineral studtite [(UO 2 )(O 2 )(H 2 O) 2 ]·(H 2 O) 2 into uranyl triperoxide compounds that can subsequently assemble into hydroxide-bridged uranyl peroxide dimers in the presence of lithium hydroxide. Dissolution of these solids in water yields uranyl peroxide nanoclusters including U 24 , Li 24 [(UO 2 )(O 2 )(OH)] 24 . Insoluble uranium solids can transform into highly soluble uranyl peroxide phases in the solid state with miniscule quantities of water. Furthermore, such reactions are potentially applicable to uranium processing in the front and back end of the nuclear fuel cycle.

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

Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry

Olefin metathesis is a broadly employed reaction with applications that range from fine chemicals to materials and petrochemicals. The design and investigation of olefin metathesis catalysts have been ongoing for over half a century, with advancements made in terms of activity, stability, and selectivity. Immobilization of organometallic complexes onto solid supports such as silica or alumina is a promising strategy for catalyst heterogenization, often resulting in increased activity and stability. Consequently, a broad range of early transition metal catalysts bearing alkyl, oxide/alkoxide, and amide ligands have been grafted onto silica and their reactivities investigated. In this paper, we report a series of silica-supported tungsten and molybdenum dimers (X 3 M≡MX 3, where M = W and Mo; X = neopentyl, tert-butoxide, and dimethyl amide) and their reactivities toward catalytic olefin metathesis. Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR), diffuse reflectance infrared Fourier transform (DRIFT), UV resonance Raman, and X-ray absorption (XAS) spectroscopies suggest that upon heterogenization the dimers bind to the surface in a monopodal fashion, with the M≡M triple bond remaining intact. These structural assignments were further corroborated by density functional theory (DFT) calculations. While the homogeneous dimer counterparts are inert, the supported low-valent alkyl W and Mo dimers become active for the disproportionative self-metathesis of propylene to ethylene and butenes and 4-nonene to 4-octene and 5-decene under mild conditions. The lack of activity observed for the free and supported tert-butoxide and dimethyl amide dimers likely suggests that the neopentyl groups are necessary for the formation of a putative alkylidene active species. The difference in reactivity between the free and supported dimers could be explained either by the lowering of the activation barrier of the complex through the electronic effects of the surface or by site isolation of catalytically relevant reactive intermediates.

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

Evaluation of Common Thermoplastic Polymers in High-Pressure Cycling Hydrogen Under Ambient and Cold Environments as Applicable to the Hydrogen Infrastructure

Thermoplastic polymers are required to perform unfailingly under stringent conditions of changing pressures (35 MPa to 70 MPa) and temperatures (-40°C to +85°C) in storage and fueling operations. Although diffusivity in glassy polymers appear to be an order of magnitude lower than elastomers, polymer microstructural attributes such as degree of crystallinity and presence of polar and non-polar groups on the main chain with and without branching can play a substantial role in influencing their behaviors in hydrogen environments. In the work described here, the effect of high-pressure hydrogen cycling on PEEK, PTFE, PA11, HDPE, POM (and different commercial grades of these polymers) under ambient and cold (-40°C) conditions is addressed. Ex-situ characterization for polymer changes included density measurements for impact of hydrogen retention, hardness changes using nanoindentation, storage modulus and glass transition changes using dynamic mechanical and thermal analysis (DMTA), degree of crystallization with Differential Scanning Calorimetry (DSC) and tensile testing following ASTM D412. In other evaluations, solid-state nuclear magnetic resonance (NMR), attenuated total reflectance Fourier transform infra-red spectroscopy (ATRFTIR), X-ray diffraction (XRD), and X-ray CT results are presented. The overall impact of these evaluations is to establish a technical basis for the behaviors of common thermoplastics in cycling hydrogen environments under ambient and cold temperatures while establishing the relationship between polymer structure-based properties and hydrogen transport effects.

Menon, Nalini C.↗
DOE OSTI2022

Post-Marcus Theory and Simulation of Interfacial Charge Transfer Dynamics in Organic Semiconducting Materials (Final Report)

The research program developed, validated and applies predictive computational protocols for calculating charge transfer (CT) rates in complex molecular systems, including molecular dyads and triads in liquid solution and solid-state organic semiconducting (OSC) materials. We have established a transformative computational scheme that goes beyond widely used simplifications, to achieve realistic descriptions of CT processes. The approach properly addresses the contribution of molecular environment at ambient conditions to CT processes. Our approach achieves unique insight on investigated CT processes in relevant experimental efforts. The collaborative team included three principal investigators (PIs), with complimentary expertise in classical molecular dynamics simulations and data science (Cheung), state-of-the-art electronic structure calculations (Dunietz), and cutting-edge theory and simulation techniques for modeling energy, charge and coherence transfer dynamics in molecular systems (Geva).

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

Chemical Vapor Transformation of Lithium Metal: Mechanism and Enhanced Stability

Constructing a stable solid electrolyte interface (SEI) with high productivity and scalability is essential for the practical application of thin Li metal anodes. Here, in this work, we report a chemical vapor transformation (CVT) strategy in which Li metal is exposed to trimethylaluminum (TMA), inducing a rapid and spontaneous surface reaction that forms a robust, multilayered SEI. In situ quartz crystal microbalance (QCM) and quadrupole mass spectrometry (QMS), combined with ex situ X-ray photoelectron spectroscopy (XPS), UV Raman spectroscopy, and density functional theory (DFT) calculations, reveal that TMA removes the native passivation layer, reacts with Li metal, and drives a coupled bulk-surface transformation involving Li–Al interdiffusion. The resulting SEI exhibits a chemically graded structure consisting of an inner Li–Al alloy and an outer amorphous carbon layer formed via demethylation and ligand-exchange pathways. This modified surface exhibits significantly enhanced stability compared to that of bare Li in electrochemical cycling using liquid and solid-state electrolytes. This work unveils a unique surface-mediated bulk transformation mechanism for lithium metal and establishes CVT as a scalable and fundamentally distinct approach for the interfacial engineering of reactive metals.

Li metal↗
DOE OSTI2020

Large room-temperature elastocaloric effect in a bulk polycrystalline Ni-Ti-Cu-Co alloy with low isothermal stress hysteresis

Creation of high-performance advanced elastocaloric materials is essential for the execution of elastocaloric refrigeration that can be an environment-friendly and high-efficiency substitute for the widely used traditional vapor-compression cooling technology. Here we have developed a bulk polycrystalline Ni-Ti-Cu-Co shape memory alloy exhibiting large elastocaloric effect, low stress hysteresis and room temperature working temperature, all of which are of great importance to and urgently demanded for high-efficiency room-temperature elastocaloric refrigeration. This newly developed (Ni 42.5 Ti 50 Cu 7.5 ) 99 Co 1 alloy shows a large room-temperature elastocaloric effect with directly measured adiabatic temperature change up to -14.4 K during unloading. The stress hysteresis of the isothermal superelastic stress-strain curve is as low as 60 MPa when the maximum tensile strain is 2.7%. Owing to the large elastocaloric effect and low stress hysteresis, a very high coefficient of performance up to 19 is achieved on the material level. This newly developed (Ni 42.5 Ti 50 Cu 7.5 ) 99 Co 1 alloy is a robust candidate for efficient elastocaloric refrigeration. Advanced in-situ synchrotron high-energy X-ray diffraction technique was employed to reveal the phase transformation sequence and to accurately determine the crystal structure of different phases, based on which the lattice compatibility between the transforming phases was evaluated and the phase transformation strain was predicted, providing in-depth fundamental understanding of the martensitic transformation in this newly developed alloy. This work could be useful for designing high-performance elastocaloric materials for solid-state cooling applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Understanding Instability in Formamidinium Lead Halide Perovskites: Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

Transformative and reconstructive reactions impart significant structural changes at particle boundaries of hybrid perovskites, which influence environmental stability and optoelectronic properties of these materials. Here, we investigate the moisture-induced transformative reactions in formamidinium based perovskites FAPbX 3 (X=I, Br) and show that the ambient stability of these materials can be adjusted from a few hours to several months. For FAPbI 3 , roles of water vapor, particle size, and light illumination on the kinetic pathways of the cubic (a) transformation to the hexagonal (d) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence and solid-state NMR spectroscopy techniques. The grain and sub-grain boundaries exhibit different α→δ-FAPbI 3 phase transformation kinetics. Our study suggests that the dynamic transformation involves the local water-induced dissolution of the cubic phase occurring at the crystal surfaces followed by precipitation of the hexagonal phase. Insights into structures and dynamics of a kinetically trapped α-|δ-FAPbI 3 are obtained by 1 H, 2 H, and 207 Pb ssNMR spectroscopy.

36 MATERIALS SCIENCE↗