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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Determination of Infinite Dilution Activity Coefficients of Molecular Solutes in Ionic Liquids and Deep Eutectic Solvents by Factorization-Machine-Based Neural Networks

Widely known as “green solvents,” ionic liquids (ILs) and deep eutectic solvents (DESs) have been used as substitutes for traditional organic solvents in separation science. To achieve better separations using ILs and DESs, this work aimed to predict the infinite dilution activity coefficients (IDACs) of molecular solutes in these solvents with the state-of-the-art factorization-machine-based neural network (DeepFM). DeepFM combines the benefits of factorization machines and deep neural networks to learn both low-order and high-order interactions among features. The IDAC prediction model was established with 52,372 experimental IDAC datapoints including 260 solvents (252 ILs and 8 DESs) and 112 molecular solutes collected at various temperatures from 288.15 to 428.15 K. Chemical information describing the ILs, DESs, and molecular solutes was included in the IDAC prediction model, including chemical functional groups, molecular weights, and Abraham solvation parameters. The IDAC prediction model showed an improved accuracy compared with alternative models; additionally, DESs were included in the IDAC prediction model for the first time. Here, the model will reduce the energy and resources needed to optimize the selection of ILs and DESs for specific separations, which will promote the development of these green solvents for sustainable chemical processes.

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

Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes

High-valent nonheme Fe IV –oxido species are key intermediates in biological oxidation, and their properties are proposed to be influenced by the unique microenvironments present in protein active sites. Microenvironments are regulated by noncovalent interactions, such as hydrogen bonds (H-bonds) and electrostatic interactions; however, there is little quantitative information about how these interactions affect crucial properties of high valent metal–oxido complexes. To address this knowledge gap, we introduced a series of Fe IV –oxido complexes that have the same S = 2 spin ground state as those found in nature and then systematically probed the effects of noncovalent interactions on their electronic, structural, and vibrational properties. The key design feature that provides access to these complexes is the new tripodal ligand [poat] 3– , which contains phosphinic amido groups. An important structural aspect of [Fe IV poat(O)] - is the inclusion of an auxiliary site capable of binding a Lewis acid (LA II ); we used this unique feature to further modulate the electrostatic environment around the Fe–oxido unit. Experimentally, studies confirmed that H-bonds and LA II s can interact directly with the oxido ligand in Fe IV –oxido complexes, which weakens the Fe=O bond and has an impact on the electronic structure. Additionally, we found that relatively large vibrational changes in the Fe–oxido unit correlate with small structural changes that could be difficult to measure, especially within a protein active site. Our work demonstrates the important role of noncovalent interactions on the properties of metal complexes, and that these interactions need to be considered when developing effective oxidants.

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

Magnetic ordering through itinerant ferromagnetism in a metal-organic framework

In this report, the materials that combine magnetic order with other desirable physical attributes could find transformative applications in spintronics, quantum sensing, low-density magnets and gas separations. Among potential multifunctional magnetic materials, metal-organic frameworks, in particular, bear structures that offer intrinsic porosity, vast chemical and structural programmability, and the tunability of electronic properties. Nevertheless, magnetic order within metal-organic frameworks has generally been limited to low temperatures, owing largely to challenges in creating a strong magnetic exchange. Here we employ the phenomenon of itinerant ferromagnetism to realize magnetic ordering at T C = 225 K in a mixed-valence chromium(II/III) triazolate compound, which represents the highest ferromagnetic ordering temperature yet observed in a metal-organic framework. The itinerant ferromagnetism proceeds through a double-exchange mechanism, which results in a barrierless charge transport below the Curie temperature and a large negative magnetoresistance of 23% at 5 K. These observations suggest applications for double-exchange-based coordination solids in the emergent fields of magnetoelectrics and spintronics.

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

Relativistic self-consistent G W : Exact two-component formalism with one-electron approximation for solids

We present a formulation of relativistic self-consistent GW for solids based on the exact two-component formalism with one-electron approximation (X2C1e) and nonrelativistic Coulomb interactions. Our theory allows us to study scalar relativistic effects, spin-orbit coupling, and the interplay of relativistic effects with electron correlation without adjustable parameters. Our all-electron implementation is fully ab initio and does not require a pseudopotential constructed from atomic calculations. We examine the effect of the X2C1e approximation by comparison to the established four-component formalism and reach an excellent agreement. The simplicity of X2C1e enables the construction of higher order theories, such as embedding theories, on top of perturbative calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2020

On-chip spectroscopic sensors with optical fringe suppression

An on-chip spectroscopic sensor includes a tunable diode laser. A laser driver for drives the tunable diode laser. An analyte test cavity receives a chemical sample and exposes the received chemical sample to light from the tunable diode laser. An optical detector detects light emerging from the analyte test cavity as a result of the laser exposure. A spectral analyzer determines a spectrum of the emerging light, matches and removes one or more known optical fringe patterns from the determined spectrum, and determines a composition or concentration of the chemical sample from the optical fringe pattern-removed spectrum.

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

Pore space partition of metal-organic frameworks for gas storage and separation

Pore space partition (PSP) concept is a synthetic design concept and can also serve as a structure analysis method useful for next-step synthetic planning and execution. PSP provides an integrated chemistry-topology-focused tool to design new materials platforms. While PSP is no less effective for making large-pore materials, the growing importance of small-molecule gas storage and separation for green-energy applications provides impetus for developing small-pore materials for which the PSP strategy is uniquely suited. Currently, the best embodiment of the PSP concept is the partitioned-acs (pacs) platform in which both fine or coarse adjustments to the building blocks have sparked a transformation of a prototype framework into a huge and continuously expanding family of chemically robust materials with controllable pore metrics and functionalities suitable for tailored applications. The pacs compositional diversity results from the platform’s intrinsic multi-module nature, geometric flexibility and tolerance towards individual module variations, and mutual structure-directing effects among various modules, all of which combine to enable the molecular-level uniform co-assemblies of chemical components rarely seen together elsewhere. Here, in this contribution, we present an overview of different pore space engineering methods and how different MOF materials have contributed to important advances in chemical stability, industrial gas storage and gas separation. In particular, we will focus on synthetic assembly of the pacs system, highlighting the differences of pacs materials from other MOF platforms and advantages of pacs materials in enhancing various MOF properties.

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

Strong anharmonicity dictates ultralow thermal conductivities of type-I clathrates

Type-I clathrate solids have attracted significant interest due to their ultralow thermal conductivities and sub- sequent promise for thermoelectric applications, yet the mechanisms underlying these properties are not well understood. Here, we extend the framework of vibrational dynamical mean-field theory (VDMFT) to calculate temperature-dependent thermal transport properties of solids using a many-body Green’s function approach. When applied to a coarse-grained description of 𝑋 8 Ga 16 Ge 30 , where 𝑋= Ba, Sr, we find that nonresonant scattering between cage acoustic modes and rattling modes leads to a reduction of acoustic phonon lifetimes and thus thermal conductivities. Moreover, we find that the moderate temperature dependence of conductivities above 300 K, which is consistent with experimental measurements, cannot be reproduced by textbook perturbation theory calculations, which predict a 𝑇 −1 dependence. Therefore, we suggest that nonperturbative anharmonic effects, including four- and higher-phonon scattering processes, are responsible for the ultralow thermal conductivities of type-I clathrates.

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

Harvest Initiated Volatile Organic Compound Emissions from In-Field Tall Wheatgrass

While crop and grassland usage continues to increase, the full diversity of plant-specific volatile organic compounds (VOCs) emitted from these ecosystems, including their implications for atmospheric chemistry and carbon cycling, remains poorly understood. It is particularly important to investigate VOCs in the context of potential biofuels: aside from the implications of largescale land use, harvest may shift both the flux and speciation of emitted VOCs. To this point, we evaluate the diversity of VOCs emitted both pre and postharvest from “Alkar” tall wheatgrass (Thinopyrum ponticum), a candidate biofuel that exhibits greater tolerance to frost and saline land compared to other grass varieties. Mature plants grown under field conditions (n = 6) were sampled for VOCs both pre- and postharvest (October 2022). Via hierarchical clustering of emitted VOCs from each plant, we observe distinct “volatilomes” (diversity of VOCs) specific to the pre- and postharvest conditions despite plant-to-plant variability. In total, 50 VOCs were found to be unique to the postharvest tall wheatgrass volatilome, and these unique VOCs constituted a significant portion (26%) of total postharvest signal. While green leaf volatiles (GLVs) dominate the speciation of postharvest emissions (e.g., 54% of unique postharvest VOC signal was due to 1-penten-3-ol), we demonstrate novel postharvest VOCs from tall wheatgrass that are under characterized in the context of carbon cycling and atmospheric chemistry (e.g., 3-octanone). Continuing evaluations will quantitatively investigate tall wheatgrass VOC fluxes, better informing the feasibility and environmental impact of tall wheatgrass as a biofuel.

09 BIOMASS FUELS↗
DOE OSTI2024

Above‐T g Annealing Benefits in Nanoparticle‐Stabilized Carbon Molecular Sieve Membrane Pyrolysis for Improved Gas Separation

Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol-gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource-H 2 separation processes.

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

Membrane Strategies for Water Electrolysis

Hydrogen holds great promise as a clean energy resource to help the global carbon-free energy goal. Here, green hydrogen production from renewable energy-powered water electrolysis can decarbonize hard-to-abate industries and transport applications. Ion-exchange membranes are an essential component of membrane-based water electrolysis, enabling high hydrogen production efficiency through a zero-gap configuration. While perfluorosulfonic acids are the standard polymer electrolyte membrane material, research efforts for membrane alternatives have increased over the years to drive down the cost of electrolyzers and improve devices’ durability without sacrificing performance and efficiency. Here we present our perspectives on acidic, alkaline, and bipolar membranes for water electrolyzers and discuss future research directions to develop advanced membranes for green hydrogen production technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

An improved data structure for AVIRIS-type imaging spectrometer measurements

Imaging spectrometers, such as the Airborne Visible/Infrared Imaging (AVIRIS), measure spectra in the region from 400 to 2500 nm at nominally 10-nrn sampling. This gives approximately 200 continuous spectral channels of data for every spatial element measured. These spectroscopic measurements are used to determine the composition and infer processes of the Earth system through spectroscopy analysis. Spectroscopic analysis is based on the physics, chemistry, and biology revealed through the interaction of energy with matter recorded in each measured spectrum

Perez, Rosa M.↗
DOE OSTI2021

Interpretation of multiple solutions in fully iterative GF2 and GW schemes using local analysis of two-particle density matrices

Due to the presence of non-linear equations, iterative Green’s function methods can result in multiple different solutions even for simple molecular systems. In contrast to the wave-function methods, a detailed and careful analysis of such molecular solutions was not performed before. In this work, we use two-particle density matrices to investigate local spin and charge correlators that quantify the charge resonance and covalent characters of these solutions. When applied within the unrestricted orbital set, spin correlators elucidate the broken symmetry of the solutions, containing necessary information for building effective magnetic Hamiltonians. Based on GW and GF2 calculations of simple molecules and transition metal complexes, we construct Heisenberg Hamiltonians, four-spin-four-center corrections, and biquadratic spin–spin interactions. These Hamiltonian parameterizations are compared to previous wave-function calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2021

Synthesis and Characterization of Fe(III)-Fe(II)- Mg- Al Smectite Solid Solutions and Implications for Planetary Science

This study demonstrates the synergies and limits of multiple measurement types for the detection of smectite chemistry and oxidation state on planetary surfaces to infer past geochemical conditions. Smectite clay minerals are common products of water-rock interactions throughout the solar system, and their detection and characterization provides important clues about geochemical conditions and past environments if sufficient information about their composition can be discerned. Here, we synthesize and report on the spectroscopic properties of a suite of smectite samples that span the intermediate compositional range between Fe(II), Fe(III), Mg, and Al end-member species using bulk chemical analyses, X-ray diffraction, Vis/IR reflectance spectroscopy, UV and green-laser Raman spectroscopy, and Mössbauer spectroscopy. Our data show that smectite composition and the oxidation state of octahedral Fe can be reliably identified in the near infrared on the basis of combination and fundamental metal-OH stretching modes between 2.1–2.9 μm, which vary systematically with chemistry. Smectites dominated by Mg or Fe(III) have spectrally distinct fundamental and combination stretches, whereas Al-rich and Fe(II)-rich smectites have similar fundamental minima near 2.76 μm, but have distinct combination M-OH features between 2.24 and 2.36 μm. We show that with expanded spectral libraries that include intermediate composition smectites and both Fe(III) and Fe(II) oxidation states, more refined characterization of smectites from MIR data is now possible, as the position of the 450 cm–1 absorption shifts systematically with octahedral Fe content, although detailed analysis is best accomplished in concert with other characterization methods. Our data also provide the first Raman spectral libraries of smectite clays as a function of chemistry, and we demonstrate that Raman spectroscopy at multiple excitation wavelengths can qualitatively distinguish smectite clays of different structures and can enhance interpretation by other types of analyses. Our sample set demonstrates how X-ray diffraction can distinguish between dioctahedral and trioctahedral smectites using either the (02,11) or (06,33) peaks, but auxiliary information about chemistry and oxidation state aids in specific identifications. Finally, the temperature-dependent isomer shift and quadrupole splitting in Mössbauer data are insensitive to changes in Fe content but reliability differentiates Fe within the smectite mineral structure.

Valerie K Fox↗