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At least 1,009 records · Page 56

Selecting Adsorbents to Separate Diverse Near-Azeotropic Chemicals

Industrial separations of near-azeotropic chemicals, species with very similar boiling points, are energy- and capital-intensive. Adsorption-based processes can energy-efficiently separate near-azeotropic mixtures provided suitable adsorbent materials can be found. Among the full diversity of industry-relevant molecules, millions of these mixtures exist, meaning that discovery of mixture-specific adsorbents by direct experiment is infeasible. We show that vast numbers of adsorbents and adsorbing molecules can be explored in a powerful way by coupling atomistic simulations with machine learning. This concept is demonstrated by describing the adsorption of ~54000 industry-relevant chemicals in an experimentally derived set of thousands of metal–organic framework materials. Here, our results identify thousands of near-azeotropic mixtures that can be efficiently separated using adsorption and open possibilities for creating adsorption processes for complex mixtures with many components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating 3,4-bis(3-nitrofurazan-4-yl)furoxan detonation with a rapidly tuned density functional tight binding model

In this work, we describe a machine learning approach to rapidly tune density functional tight binding models for the description of detonation chemistry in organic molecular materials. Resulting models enable simulations on the several 10s of ps scales characteristic to these processes, with “quantum-accuracy.” We use this approach to investigate early shock chemistry in 3,4-bis(3-nitrofurazan-4-yl)furoxan, a hydrogen-free energetic material known to form onion-like nanocarbon particulates following detonation. We find that the ensuing chemistry is significantly characterized by the formation of large C x N y O z species, which are likely precursors to the experimentally observed carbon condensates. Beyond utility as a means of investigating detonation chemistry, the present approach can be used to generate quantum-based reference data for the development of full machine-learned interatomic potentials capable of simulation on even greater time and length scales, i.e., for applications where characteristic time scales exceed the reach of methods including Kohn–Sham density functional theory, which are commonly used for reference data generation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photophysics in emerging photovoltaics

Emerging photovoltaic technologies continue to march forward with power conversion efficiencies of lead halide perovskite solar cells (PSCs) nearing 26%, perovskite-Si tandems now exceeding the single junction detailed balance limit of 33%, and organic solar cells (OSCs) showing efficiencies nearing 20%. Yet, some of the photophysics underpinning PSCs and OSCs remain unresolved. A better understanding will enable more efficient and photostable solar cells and optoelectronic devices in the future. Here, this special issue collects the latest cutting-edge research in the photophysics of PSCs and OSCs, contributed by experts on spectroscopy, theory, device physics, and materials science.

14 SOLAR ENERGY↗

Data from : "Warming promotes loss of subsoil carbon through accelerated degradation of plant-derived organic matter". Blodgett warming experiment

This dataset contains data used for the paper: Warming promotes loss of subsoil carbon through accelerated degradation of plant-derived organic matter. Soil Biology and Biochemistry 156, 108185. doi:10.1016/j.soilbio.2021.108185On April 2018 (after 4.5 years of warming), we collected O-horizon (organic horizon) material and soil core down to 90 cm depth from a whole-soil warming experiment in a mixed-coniferous temperate forest, located at the University of California Blodgett experimental forest in the foothills of the Sierra Nevada, CA USA. The goal was to assess how 4.5 years of +4 °C whole-soil warming affected the quantity and quality of soil organic matter. Cores were collected from 6 experimental plots (three replicated blocks); samples were collected in 10 cm increments from 0 to 90 cm depth.This dataset contains a compressed (.zip) archive of the data used for this manuscript. The dataset includes files in .xlsx format, which can be accessed and processed using MS Excel or R. Carbon and nitrogen concentrations, as well as stable carbon isotope composition ((δ13C) and solvent extractable lipid biomarker (alkanoic acids and alkanes) data are provided as processed data files. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy data are provided as raw output and processed data files.The dataset files "Blodgett_warming_Data" and "Blodgett_warming_raw_data.xlsx" were updated on July 7, 2021. The following updates were made: (1) specification of the units of measurements in the dataset (the unit of measurement was missing in some parameters) and (2) the column name "pulled depth" was changed to "pooled depth" in the updated data files.

54 ENVIRONMENTAL SCIENCES↗

Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors

Amidate-based ligands (N-(tert-butyl)isobutyramide, ITA) bind κ 2 to form homoleptic, 8-coordinate complexes with tetravalent 237 Np (Np(ITA) 4 , 1-Np) and 242 Pu (Pu(ITA) 4 , 1-Pu). These compounds complete an isostructural series from Th, U–Pu and allow for the direct comparison between many of the early actinides with stable tetravalent oxidation states by nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction (SCXRD). The molecular precursors are subjected to controlled thermolysis under mild conditions with the exclusion of exogenous air and moisture, facilitating the removal of the volatile organic ligands and ligand byproducts. The preformed metal–oxygen bond in the precursor, as well as the metal oxidation state, are maintained through the decomposition, forming fully stoichiometric, oxidation-state pure NpO 2 and PuO 2 . Powder X-ray diffraction (PXRD), scanning transmission electron microscopy (STEM), and energy dispersive X-ray spectroscopy (EDS) elemental mapping supported the evaluation of these high-purity materials. This chemistry is applicable to a wide range of metals, including actinides, with accessible tetravalent oxidation states, and provides a consistent route to analytical standards of importance to the field of nuclear nonproliferation, forensics, and fundamental studies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Surpassing the Organic Cathode Performance for Lithium-Ion Batteries with Robust Fluorinated Covalent Quinazoline Networks

Organic electrode materials have promising application prospects in energy storage, but issues including rapid capacity fading and poor power capacity restrict their practical applications. In this study, nanoporous fluorinated covalent quinazoline networks (F-CQNs) were constructed by condensation of fluorinated aromatic aminonitrile precursors via an ionothermal pathway. Precise control of the reaction parameters afforded F-CQN-1-600 material featuring high surface area, permanent porosity, high nitrogen content (23.49 wt %), extended π-conjugated architecture, layered structure, and bipolar combination of benzene and tricycloquinazoline. Synergy among these unique properties leads to a good performance as a cathode source for lithium-ion batteries (LIBs) in terms of high capacity (250 mA h g –1 at 0.1 A g –1 ), high rate capability (105 mA h g –1 at 5.0 A g –1 ), and impressive cycling stability (95.8% retention rate after 2000 cycles at 2.0 A g –1 together with a high Coulombic efficiency of 99.95%), surpassing most of the previous organic cathode counterparts.

25 ENERGY STORAGE↗

Selection of an Alternate Biocide for the ISS Internal Thermal Control System Coolant, Phase 2

The ISS (International Space Station) ITCS (Internal Thermal Control System) includes two internal coolant loops that utilize an aqueous based coolant for heat transfer. A silver salt biocide had previously been utilized as an additive in the coolant formulation to control the growth and proliferation of microorganisms within the coolant loops. Ground-based and in-flight testing demonstrated that the silver salt was rapidly depleted, and did not act as an effective long-term biocide. Efforts to select an optimal alternate biocide for the ITCS coolant application have been underway and are now in the final stages. An extensive evaluation of biocides was conducted to down-select to several candidates for test trials and was reported on previously. Criteria for that down-select included: the need for safe, non-intrusive implementation and operation in a functioning system; the ability to control existing planktonic and biofilm residing microorganisms; a negligible impact on system-wetted materials of construction; and a negligible reactivity with existing coolant additives. Candidate testing to provide data for the selection of an optimal alternate biocide is now in the final stages. That testing has included rapid biocide effectiveness screening using Biolog MT2 plates to determine minimum inhibitory concentration (amount that will inhibit visible growth of microorganisms), time kill studies to determine the exposure time required to completely eliminate organism growth, materials compatibility exposure evaluations, coolant compatibility studies, and bench-top simulated coolant testing. This paper reports the current status of the effort to select an alternate biocide for the ISS ITCS coolant. The results of various test results to select the optimal candidate are presented.

Wilson, Mark E.↗

Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State

In the solid state the properties of organic radicals depend heavily on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4- dimethoxyphenylene), and outline how its bisradical dicationic redox state associates with the methyl viologen radical cation (MV •+ ) to give a trisradical tricationic inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid-state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments with a range of guests reveal that the methoxy substituents on the para-xylenyl do not influence significantly of the binding affinity of the cyclophane for small neutral guests, whereas the affinity decreases by an order of magnitude for larger radical cationic guests such as MV •+ . X-Ray diffraction reveals that the solid- state structures of the tricationic trisradical complexes to be a discrete entity with weak intermolecular orbital overlap between the neighboring complexes. Transient nutation EPR experiment and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap within the complex, while the quartet-state spin configuration is higher in energy and so is inaccessible at ambient temperature. The superconducting quantum interference device (SQUID) measurement reveals that trisradical tricationic complexes interact antiferromagnetically (J/k = - 2.33 K) and form a 1D Heisenberg antiferromagnetic chain along the a-axis in the crystal. Furthermore, these results offer new insights into the design and synthesis of organic magnetic materials based on host-guest inclusion complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum Sieving for Isotopic Separations of Gases Using Porous Materials─30 Years of Progress

Here, this paper reviews theoretical and experimental efforts to establish microporous materials that can be used to separate isotopologues of molecular gases such as H 2 and D 2 . Emphasis is placed on use of simplified models to highlight the quantum phenomena that make these separations possible. In equilibrium adsorption, differences in zero point energy in the adsorbed states of molecules favor binding of heaver isotopologues (e.g. D 2 relative to H 2 ). Experimental data showing this effect was reported as early as 1933, but the theoretical work of Beenakkers et al. in 1995 [Chem. Phys. Lett. 232 (1995) 379-382] spurred modern efforts to develop materials with strong so-called quantum sieving. In porous materials where the transition state for molecular diffusion is more strongly confined than the energy minima associated with equilibrium adsorption, differences in zero point energies between these two sites can lead to isotopic differences in molecular diffusivities. This effect favors diffusion of heavier species (e.g. D 2 ) relative to lighter species (e.g. H 2 ). This so-called kinetic quantum sieving has been observed experimentally in porous carbons and in porous organic cage materials. We show that quantum tunneling, which favors hopping of lighter species across energy barriers, diminishes the strength of kinetic quantum sieving but that it appears to make only a small contribution to the net molecular diffusivities in many porous materials of practical interest.

Sholl, David S. [Oak Ridge National Laboratory (OR↗

Thresholds of Temperature and Time for Mars Sample Return: Final Report of The Mars Sample Return Temperature-Time Tiger Team

The time-temperature tiger team (T4) was chartered by NASA and ESA to evaluate the risks to the scientific return of the MSR samples if they are exposed to temperatures between +30 and +60 ⁰C for different amounts of time. This team consists of 13 scientists, who were selected based on their scientific background to represent the scientific disciplines that are expected to be the ones that will be the most affected if such heating were to happen. The expertise of the team will help to understand whether exposing the MSR samples to temperatures between +30 and +60 ⁰C will pose any risk to the sample integrity and therefore, to future scientific investigations. Key processes identified by the T4 were: the release of volatiles by desorption and sublimation and release from condensed phases (interiors, decomposition, dehydration); chemical reactions including gas-gas and gas-solid; deliquescence of hygroscopic salts; acid/base interactions (potential for extreme pH conditions); aqueous redox reactions, isotopic exchange (aqueous phases, minerals, gasses, organic phases); condensation and freezing (in the after-heating cooling phase) and interactions with the sample tube materials. There is potential for multiple interactions and overlapping effects. For inorganic materials and the records they represent, over both long time scales (hours to days) and short time scales (minutes to hours) no temperature excursion above +30 °C could be accommodated without loss of science (Figure 1.1). While there will be some robust constituents (feldspars, quartz, pyroxenes, etc.) that are unaffected, there will also be some less robust constituents (salts, phyllosilicates, radicals, etc.) that are affected across all temperature ranges ≤60 °C. For organic materials, in particular organic biosignatures, the risks reflect that preservation is reliant on a number of processes, and a change in one component within a sample tube can affect another. For organic materials, over long timescales of hours to days no temperature excursion above +30 °C could be accommodated without loss of science, but over shorter time scales (minutes to hours), raising the temperature to 40 °C could be manageable without major disruption to science, whereas temperatures above 40 °C would lead to significant losses. The consideration of these findings by the MSR team will help to maintain the fidelity of samples returned from Mars in the future and maximize scientific return when analyzed in Earth laboratories.

Mark A Sephton↗

Comprehensive view of microscopic interactions between DNA-coated colloids

Abstract The self-assembly of DNA-coated colloids into highly-ordered structures offers great promise for advanced optical materials. However, control of disorder, defects, melting, and crystal growth is hindered by the lack of a microscopic understanding of DNA-mediated colloidal interactions. Here we use total internal reflection microscopy to measure in situ the interaction potential between DNA-coated colloids with nanometer resolution and the macroscopic melting behavior. The range and strength of the interaction are measured and linked to key material design parameters, including DNA sequence, polymer length, grafting density, and complementary fraction. We present a first-principles model that screens and combines existing theories into one coherent framework and quantitatively reproduces our experimental data without fitting parameters over a wide range of DNA ligand designs. Our theory identifies a subtle competition between DNA binding and steric repulsion and accurately predicts adhesion and melting at a molecular level. Combining experimental and theoretical results, our work provides a quantitative and predictive approach for guiding material design with DNA-nanotechnology and can be further extended to a diversity of colloidal and biological systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Iodine Close Packing in Hybrid Halide Bismuth(III) and Antimony(III) Semiconductors: (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10

Simple features in complex hybrid inorganic–organic crystalline materials provide opportunities for targeted discovery of materials with desired optoelectronic properties. In this study, we report the structure and optoelectronic properties of isostructural (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10 . The crystal structures are characterized by corner-connected metal-iodide octahedral chains that form a cubic close-packed iodine inorganic framework. Variable temperature UV–visible diffuse reflectance spectroscopy reveals stark contrasts in the onset of absorption and color changes between the [MX6]3– based structures, due to differences in the interaction of the (NH 3 (CH 2 ) 7 NH 3 ) 2+ organic ammonium cation and the iodine packing of the inorganic framework. Density functional theory (DFT) calculations reveal flat bands reflective of the pseudo-1D crystal structure. Dark microwave conductivity (DMC) and time-resolved microwave conductivity (TRMC) reveal an excitonic character with long carrier lifetimes, consistent with the electronically confined octahedral chains. Comparison of the structural features with those of other diammonium-containing crystals reveals that diammoniumheptane can substitute into structures, displacing inorganic octahedra while retaining a close-packed anion framework. This provides a means for targeting new hybrid materials in which “vacancy-ordering” provides a crystal chemical approach for targeting desirable optoelectronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlled Pyrolysis: A Robust Scalable Composite Recycling Technology

The reinforced composites industry is facing significant challenges in handling the scrap composite material from automobile manufacturing, the wind turbine industry, and others. The fibers in the material, whether they be carbon, glass, or other materials have commercial value if they can be recovered successfully. Successfully means the fibers are clean with no sizing or other binders and have adequate strength and physical properties that would allow them to be economically reprocessed into valuable product. The composites recycling project was an industry-collaborative effort to develop a composite recycling technology using controlled pyrolysis. Through the recycling of scrap and end-of-life (EOL) cured composite materials, this pilot study was intended to create a business case by realizing a cost-effective means for recycling EOL and production scrap composite materials, ultimately reducing the volume of composite materials destined for landfill. The project was led by the Institute for Advanced Composites Manufacturing Innovation (IACMI), the American Composites Manufacturers Association (ACMA), Oak Ridge National Laboratory (ORNL), Continental Structural Plastics (CSP) a Teijin Group Company, CHZ Technologies, and A. Schulman with support from Owens Corning, John Deere, General Electric (GE), Ashland LLC, and Plastics Europe (CEFIC). The team studied and tested CHZ Technologies’ controlled pyrolysis system, known as the Thermolyzer TM , which operates on a scalable basis to convert organic polymer materials into a clean synthesis gas and char containing the recoverable carbon and glass fiber reinforcement. The recoverable energy contained in the input polymers creates the synthesis gas that can be used to provide heat to the Thermolyzer TM primary reactor in a sustainable manner. That is, once the Thermolyzer TM is started with a small amount of external natural gas, the synthesis gas that is created from the polymers will continue to operate the burners so long as feedstock is supplied. The reinforcing fiber materials remaining in the solid phase char were separated and cleaned for re-use in other polymer systems based on the retained properties of the fibers. The study created reports (attached in the appendix) on the Mass and Energy Balances, syngas analytics, VOC assessment, yield analysis and other analytics necessary for a Techno-Economic Analysis (TEA) to quantify the economic impact of the recovery and sustainable re-use of the carbon and glass fibers. The process consisted of 4 steps: Selection of 4 samples of cured composite waste materials from project partners interested in materials recycling and recovering the reinforcing fibers for best case re-use. The materials included glass fiber (GF) polyester/vinyl ester automotive SMC from CSP, GF epoxy balsa/PVC foam wind blades from GE, carbon fiber (CF) epoxy wind blade laminated spar caps from GE, and GF/CF epoxy hybrid assembly from John Deere. Processing the waste composite samples into 1-2” shreds. Packaging the shredded composites into bulk sacks on international shipping pallets for shipment to KUG in Forst (Lausitz), Germany. Pyrolysis of the shredded composites under controlled conditions designed for each polymer system. Collecting samples of the gas and char for analysis. Shipping the char containing the CF/GF back to the US for the next steps of testing the fibers and developing protocols for sustainable re-use of the fibers in composite applications.

36 MATERIALS SCIENCE↗

First-Principles Study of Ferroelectric and Optical Properties in Derivatives of Thiourea

Organic ferroelectric materials in the form of molecular crystals are promising alternatives to well-known ferroelectric perovskite oxides due to their structural flexibility, tunability, and ease of processing. First-principles density functional theory calculations combined with group theory analyses are employed in this work to discuss polar nature of a class of derivatives of thiourea: CH 4 N 2 A where A = O, S, Se, and Te. Further, optical properties in the UV range along with thermodynamic and dynamic stability of such materials are also evaluated in the study. We find that CH 4 N 2 Te with bandgap energy of ~3.33 eV shows large spontaneous polarization of P = 10.92 μC/cm 2 . The electronic and optical properties become tunable under strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multiwalled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be repurposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

solid state devices↗

Hierarchical Epoxy Structures via Tunable Polymerization-Induced Phase Separation Combined with Additive Manufacturing

Polymerization-induced phase separation (PIPS) allows for the control of thermoset morphologies and properties, enabling the tuning of domain sizes and thermomechanical response. However, its use in generating substructural features in additively manufactured materials has been limited. In this work, we combine epoxy PIPS with UV curable acrylate and rheological modifiers to print nano- to macro-phase separating materials via a two-step, dual-cure approach. This method enables direct ink write printing of hierarchical structures with both controlled morphologies through phase separation and macroscale architecture through print design. We find that formulations for phase-separating materials require judicious incorporation of additives to enable printability and to provide sufficient green strength. Atomic force microscopy-nano infrared mapping reveals tunable, reticulated nano- to micron-scale domains of the resultant multiphase materials and their morphology changes due to additives, resulting in alterations to thermomechanical and tensile properties. Shape memory behavior is also demonstrated through multimaterial additive manufacturing of epoxies with functionally graded internal morphology using active mixing techniques, highlighting this method’s ability to fabricate complex architectures with controlled morphologies and thermomechanical response.

Van Meter, Kylie E [Organic Materials Science, San↗

Novel Materials, Processing, and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multi-walled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be re-purposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

thin films↗