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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Programmable heating and quenching for efficient thermochemical synthesis

Conventional thermochemical syntheses by continuous heating under near-equilibrium conditions face critical challenges in improving the synthesis rate, selectivity, catalyst stability and energy efficiency, owing to the lack of temporal control over the reaction temperature and time, and thus the reaction pathways. As an alternative, we present a non-equilibrium, continuous synthesis technique that uses pulsed heating and quenching (for example, 0.02 s on, 1.08 s off) using a programmable electric current to rapidly switch the reaction between high (for example, up to 2,400 K) and low temperatures. The rapid quenching ensures high selectivity and good catalyst stability, as well as lowers the average temperature to reduce the energy cost. Using CH4 pyrolysis as a model reaction, our programmable heating and quenching technique leads to high selectivity to value-added C2 products (>75% versus <35% by the conventional non-catalytic method and versus <60% by most conventional methods using optimized catalysts). Our technique can be extended to a range of thermochemical reactions, such as NH 3 synthesis, for which we achieve a stable and high synthesis rate of about 6,000 μmol g Fe –1 h –1 at ambient pressure for >100 h using a non-optimized catalyst. Furthermore, this study establishes a new model towards highly efficient non-equilibrium thermochemical synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Energy Efficient Formaldehyde Synthesis by Direct Hydrogenation of Carbon Monoxide in Functionalized Metal–Organic Frameworks

Formaldehyde (CH 2 O) is a highly versatile platform chemical with an annual production of over 30 megatons. The current most widely used industrial method for formaldehyde synthesis is very energy intensive and plagued with significant exergy losses. We propose a highly efficient heterogeneous nanoporous catalyst capable of direct hydrogenation of CO to CH 2 O followed by condensation of CH 2 O from a mixture of CO and H 2 , which are non-condensable gases. The key to this synthesis is a Lewis Pair (LP) functionalized metal-organic framework (MOF) heterogeneous porous catalyst. We have computed reaction pathways, barriers, and uncertainties for CO hydrogenation on a LP functionalized MOF using various density functional theory (DFT) methods and high-level ab initio methods. We have assessed the uncertainties in the energetics inherent in the DFT functionals. Here, we predict that the thermodynamics of CH 2 O synthesis will be enhanced relative to gas phase synthesis and more importantly, will not be equilibrium limited because the barrier to product desorption from the MOF is much lower than the barrier for the reverse reaction. Hence, the product will be continuously removed from the process, facilitating very high overall conversion rates. Our proposed process will dramatically improve the sustainability of CH 2 O synthesis.

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

Mechanistic insight of KBiQ 2 (Q = S, Se) using panoramic synthesis towards synthesis-by-design

Solid-state synthesis has historically focused on reactants and end products; however, knowledge of reaction pathways, intermediate phases and their formation may provide mechanistic insight of solid-state reactions. With an increased understanding of reaction progressions, design principles can be deduced, affording more predictive power in materials synthesis. In pursuit of this goal, in situ powder X-ray diffraction is employed to observe crystalline phase evolution over the course of the reaction, thereby constructing a “panoramic” view of the reaction from beginning to end. We conducted in situ diffraction studies in the K–Bi–Q (Q = S, Se) system to understand the formation of phases occurring in this system in the course of their reactions. Powder mixtures of K 2 Q to Bi 2 Q 3 in 1:1 and 1.5:1 ratios were heated to 800 °C or 650 °C, while simultaneously collecting diffraction data. Three new phases, K 3 BiS 3 , β-KBiS 2 , and β-KBiSe 2 , were discovered. Panoramic synthesis showed that K 3 BiQ 3 serves an important mechanistic role as a structural intermediate in both chalcogen systems (Q = S, Se) in the path to form the KBiQ 2 structure. Thermal analysis and calculations at the density functional theory (DFT) level show that the cation-ordered β-KBiQ 2 polymorphs are the thermodynamically stable phase in this compositional space, while Pair Distribution Function (PDF) analysis shows that all α-KBiQ 2 structures have local disorder due to stereochemically active lone pair expression of the bismuth atoms. The formation of the β-KBiQ 2 structures, both of which crystallize in the α-NaFeO 2 structure type, show a boundary where the structure can be disordered or ordered with regards to the alkali metal and bismuth. A cation radius tolerance for six-coordinate cation site sharing of ($\frac{r^+}{r^{3+}}$) ~ 1.3 is proposed. The mechanistic insight the panoramic synthesis technique provides in the K–Bi–Q system is progress towards the overarching goal of synthesis-by-design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Theory-Guided Synthesis of a Metastable Lead-Free Piezoelectric Polymorph

Many technologically critical materials are metastable under ambient conditions, yet the understanding of how to rationally design and guide the synthesis of these materials is limited. This paper presents an integrated approach that targets a metastable lead-free piezoelectric polymorph of SrHfO 3 . First-principles calculations predict that the previous experimentally unrealized, metastable P4mm phase of SrHfO 3 should exhibit a direct piezoelectric response (d 33 ) of 36.9 pC N -1 (compared to d 33 = 0 for the ground state). Combining computationally optimized substrate selection and synthesis conditions lead to the epitaxial stabilization of the polar P4mm phase of SrHfO 3 on SrTiO 3 . The films are structurally consistent with the theory predictions. A ferroelectric-induced large signal effective converse piezoelectric response of 5.2 pm V -1 for a 35 nm film is observed, indicating the ability to predict and target multifunctionality. Finally, this illustrates a coupled theory-experimental approach to the discovery and realization of new multifunctional polymorphs.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Cavitation and radicals drive the sonochemical synthesis of functional polymer spheres

Sonochemical synthesis can lead to a dramatic increase in the kinetics of formation of polymer spheres (templates for carbon spheres) compared to the modified Stöber silica method applied to produce analogous polymer spheres. Reactive molecular dynamics simulations of the sonochemical process indicate a significantly enhanced rate of polymer sphere formation starting from resorcinol and formaldehyde precursors. The associated chemical reaction kinetics enhancement due to sonication is postulated to arise from the localized lowering of atomic densities, localized heating, and generation of radicals due to cavitation collapse in aqueous systems. This dramatic increase in reaction rates translates into enhanced nucleation and growth of the polymer spheres. The results are of broad significance to understanding mechanisms of sonication induced synthesis as well as technologies utilizing polymers spheres.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures

Recent advances in theoretical structure prediction methods and high-throughput computational techniques are revolutionizing experimental discovery of the thermodynamically stable inorganic materials. Metastable materials represent a new frontier for these studies, since even simple binary non-ground state compounds of common elements may be awaiting discovery. However, there are significant research challenges related to non-equilibrium thin film synthesis and crystal structure predictions, such as small strained crystals in the experimental samples and energy minimization based theoretical algorithms. Here, we report on experimental synthesis and characterization, as well as theoretical first-principles calculations of a previously unreported mixed-valent binary tin nitride. Thin film experiments indicate that this novel material is N-deficient SnN with tin in the mixed II/IV valence state and a small low-symmetry unit cell. Theoretical calculations suggest that the most likely crystal structure has the space group 2 (SG2) related to the distorted delafossite (SG166), which is nearly 0.1 eV/atom above the ground state SnN polymorph. This observation is rationalized by the structural similarity of the SnN distorted delafossite to the chemically related Sn{sub 3}N{sub 4} spinel compound, which provides a fresh scientific insight into the reasons for growth of polymorphs of metastable materials. In addition to reporting on the discovery of the simple binary SnN compound, this paper illustrates a possible way of combining a wide range of advanced characterization techniques with the first-principle property calculation methods, to elucidate the most likely crystal structure of the previously unreported metastable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extended structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Lastly, our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.

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

Large Single Crystals of V 1– x Mo x O 2 from a Two-Step Chemical Vapor Transport Synthesis

This article details the synthesis of single crystals with the chemical formulas V 1-x Mo x O 2 ( 0 ≤ x ≤ 0.6) using the chemical vapor transport method at high temperatures (850 to 950 °C). These compounds are of interest due to the special relationship between their structure and electronic properties. Understanding this relationship will help guide future efforts in designing energy-saving devices. While some of these compounds have been synthesized before, this is the first time their synthesis has been reported for such a wide range of compounds in the form of bulk single crystals. The single crystal form is required for detailed characterization of the compounds. The materials were characterized chemically and structurally in order to validate the precise chemical compositions that were reported. Characterization methods included x-ray diffraction, inductively-coupled plasma atomic emission spectroscopy, and electron dispersive spectroscopy. The synthesis method is tunable, and the introduction of multiple steps both overcome the previous chemical challenges precluding synthesis of high molybdenum content crystals and allow for the creation of larger single crystals that were otherwise possible. The crystals synthesized this way are suitable for specialized measurements for determining the precise physical properties and atomic structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Synthesis of Ultra-incompressible sp 3 -Hybridized Carbon Nitride with 1:1 Stoichiometry

Search of materials with C-N composition hold a great promise in creating materials which would rival diamond hardness due to the very strong and relatively low-ionic C-N bond. Early experimental and theoretical works on C-N compounds were based on structural similarity with binary A 3 B 4 structural types; however, the synthesis of C 3 N 4 remains elusive. Here we explored an unbiased synthesis from the elemental materials at high pressures and temperatures. Using in situ synchrotron X-ray diffraction and Raman spectroscopy we demonstrate the synthesis of highly incompressible Pnnm CN compound with sp 3 hybridized carbon above 55 GPa and 7000 K. This result is supported by first principles evolutionary search, which finds that Pnnm CN is the most stable compound above 10.9 GPa. On pressure release below 6 GPa the synthesized CN compound amorphizes reattaining its 1:1 stoichiometry as confirmed by Energy-Dispersive X-ray Spectroscopy. Here, this work underscores the importance of understanding of novel high-pressure chemistry rules and it opens a new route for synthesis of superhard materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Synthesis of 1 nm Pd Nanoparticles in a Microfluidic Reactor: Insights from in Situ X ray Absorption Fine Structure Spectroscopy and Small-Angle X ray Scattering

In this paper we show that the temporal separation of nucleation and growth is not a necessary condition for the colloidal synthesis of monodisperse nanoparticles. The synthesis mechanism of Pd nanoparticles was determined by in situ XAFS and SAXS in a microfluidic reactor capable of millisecond up to an hour time resolution. The SAXS results showed two autocatalytic growth phases, a fast growth phase followed by a very slow growth phase. The steady increase in the number of particles throughout the two growth phases indicates the synthesis is limited by slow continuous nucleation. The transition from fast to slow growth was caused by rapid increase in bonding with the capping agent as shown by XAFS. Based on this fundamental understanding of the synthesis mechanism, we show that 1 nm monodisperse Pd nanoparticles can be synthesized at low temperature using a strong binding capping agent such as trioctylphosphine (TOP).

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Synthesis and characterization of rare-earth-free magnetic manganese bismuth nanocrystals

Earth abundant manganese bismuth (MnBi) has long been of interest due to its largemagnetocrystalline anisotropy and high energy density for advanced permanent magnet applications. However, solution synthesis of MnBi phase is challenging due to the reduction potential mismatch between Mn and Bi elements. In this study, we show a versatile MnBi synthesis method involving the metal co-reduction followed by thermal annealing. The magnetically hard MnBi crystalline phase is then exchange coupled with magnetically soft cobalt coating. Our processing approach offers a promising strategy for manufacturing rare-earth-free magnetic nanocrystals.

Shen, J↗
DOE OSTI2017

Synthesis and structure of synthetically pure and deuterated amorphous (basic) calcium carbonates

It is generally believed that H 2 O and OH - are the key species stabilizing and controlling amorphous calcium carbonate “polyamorph” forms, and may in turn control the ultimate crystallization products during synthesis and in natural systems. Yet, the locations and hydrogen-bonding network of these species in ACC have never been measured directly using neutron diffraction. In this paper, we report a synthesis route that overcomes the existing challenges with respect to yield quantities and deuteration, both of which are critically necessary for high quality neutron studies.

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

Computationally aided, entropy-driven synthesis of highly efficient and durable multi-elemental alloy catalysts

Multi-elemental alloy nanoparticles (MEA-NPs) hold great promise for catalyst discovery in a virtually unlimited compositional space. However, rational and controllable synthesize of these intrinsically complex structures remains a challenge. Here, we report the computationally aided, entropy-driven design and synthesis of highly efficient and durable catalyst MEA-NPs. The computational strategy includes prescreening of millions of compositions, prediction of alloy formation by density functional theory calculations, and examination of structural stability by a hybrid Monte Carlo and molecular dynamics method. Selected compositions can be efficiently and rapidly synthesized at high temperature (e.g., 1500 K, 0.5 s) with excellent thermal stability. We applied these MEA-NPs for catalytic NH 3 decomposition and observed outstanding performance due to the synergistic effect of multi-elemental mixing, their small size, and the alloy phase. We anticipate that the computationally aided rational design and rapid synthesis of MEA-NPs are broadly applicable for various catalytic reactions and will accelerate material discovery.

36 MATERIALS SCIENCE↗