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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 1,099 records · Page 61

Superacid-promoted synthesis of highly porous hypercrosslinked polycarbazoles for efficient CO 2 capture

A superacid-promoted “knitting” strategy has been developed for the generation of a novel family of hypercrosslinked nanoporous polycarbazoles for efficient CO 2 capture. Using trifluoromethanesulfonic acid, a Brønsted superacid, we demonstrate the facile and rapid synthesis of highly porous polycarbazoles with BET surface areas as high as 1688 m 2 g –1 , and capable of adsorbing 3.5 mmol g –1 of CO 2 at 298 K and 1 bar. This impressive result bestows the material with the highest CO 2 uptake capacity for all nanoporous carbazolic polymers and ranks among the best by known porous organic polymers under this condition. In conclusion, this innovative approach affords a metal-free alternative to Friedel–Crafts alkylation, and may open up new possibilities for the rational design and synthesis of new hypercrosslinked nanoporous organic networks for carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Universal Solvent Viscosity Reduction via Hydrogen Bonding Disruptors

Liquid Ion Solutions LLC (DBA RoCo Global) in partnership with Carnegie Mellon University and Carbon Capture Scientific LLC, has performed lab-scale development and evaluation of novel additives that lower the viscosity of water-lean amine solvents for post-combustion carbon dioxide capture. This project focuses on developing additives that minimize the formation of long-range electrostatic and hydrogen bonding (HB) networks, decreasing the solvent viscosity, improving diffusion, and improving the process economics. The project objectives included: 1) performing computer simulation to understand the molecular interactions of the additive molecules in water-lean CO 2 capture solvents, 2) design and synthesis of HB disruptors additives, 3) performance testing with additive molecules on model amine solvents, and 4) demonstration of the effectiveness of the optimized additives in the presence of synthetic flue gas. To meet the abovementioned objectives, the project team utilized a holistic approach that combines molecular simulation, experimental testing, and economic analysis studies. The project team developed ab initio molecular model and then perform computer simulation to develop relationship between hydrogen bonding, viscosity, and performed quantitative analysis of additive on the viscosity of the solvent. The team completed computational comparative study on a range of organic functional groups such as ethers, esters, cyclic carbonates, alkanes, and ammonium salts for their effect on viscosity gaining key insights into molecular interactions and the impact of various functional groups and molecular shapes on viscosity. Assisted with molecular simulation insights, the project team conducted additive synthesis and testing, including a proof-of-concept study, additive screening, optimization, and synthetic flue gas testing. The experimental proof-of-concept study proved that the hydrogen bonding acceptors result in significant decrease of viscosities. Detailed additive screening (exploring various functionalities and molecular structures) has been performed. Several promising additives showed excellent reduction in viscosity (30-41%) at 5% additive loading, and over 50% viscosity reduction at 10% additive loading for the model solvents. The team also performed complex screening studies on additive loadings and mixing effect among additives using the design of experiments. Based on multiple screening experiments, one additive-solvent candidate was down-selected for synthetic flue gas testing. A 100-hour continuous absorption/desorption study was conducted under simulated flue gas using a lab-scale continuous capture and separation system. No degradation (for both solvent and additive) was observed based on the GC results of the solvent samples collected from the continuous study. The team conducted preliminary engineering analyses and cost-benefit analyses to quantify the potential economic benefits of the additive approach for solvent viscosity reduction. Based on the experimental data, CO 2 capture cost savings from the capital and operating cost savings are estimated at $\$$4.7/tonne and $\$$0.3/tonne CO 2 captured, respectively. Considering the additive cost, the net benefit is estimated to be between $\$$4.32~$\$$4.86/tonne CO 2 captured.

20 FOSSIL-FUELED POWER PLANTS↗

Overstepping Löwenstein’s Rule—A Route to Unique Aluminophosphate Frameworks with Three-Dimensional Salt-Inclusion and Ion-Exchange Properties

The synthesis of four non-Löwenstein uranyl aluminophosphates, [Cs13Cl5][(UO2)3Al2O(PO4)6], Rb7[Al2O(PO4)3][(UO2)6O4(PO4)2], Cs3[Al2O(PO4)3][(UO2)3O2], and Rb3[Al2O(PO4)3][(UO2)3O2], the first uranyl phosphate salt-inclusion material [Cs4Cs4Cl][(UO2)4(PO4)5], and a related structure Cs4[UO2Al2(PO4)4], all prepared by molten flux methods, is reported. All compounds are discussed from the point of view of their structural features favoring, in some cases, ion-exchange properties. Löwenstein’s rule, well known in the realm of zeolites, aluminosilicate, and aluminophosphate minerals, describes the tendency of tetrahedra (Al, P, Si, and Ge) linked by an oxygen bridge to be of two different elements resulting in the avoidance of Al–O–Al bonds. Zeolites and related aluminosilicate/aluminophosphate minerals are traditionally formed under relatively mild temperatures, where zeolites are synthesized using the hydrothermal synthetic technique. Few exceptions to Löwenstein’s rule are known among aluminophosphates, and four of the five exceptions are synthesized under either high temperature or high pressure methods. For that reason, the high-temperature flux synthesis of four new non-Löwenstein uranyl aluminophosphates realizes a unique synthetic approach to forming the new pyroaluminate-based building block, [Al2O(PO4)6]14–, that can be easily obtained and employed for the construction of new porous structures.

nuclear, materials and chemistry by design, synthe↗

Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation

Abstract Design and synthesis of porous solids employing both reversible coordination chemistry and reversible covalent bond formation is described. The combination of two different linkage modes in a single material presents a link between two distinct classes of porous materials as exemplified by metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). This strategy, in addition to being a compelling material‐discovery method, also offers a platform for developing a fundamental understanding of the factors influencing the competing modes of assembly. We also demonstrate that even temporary formation of reversible connections between components may be leveraged to make new phases thus offering design routes to polymorphic frameworks. Moreover, this approach has the striking potential of providing a rich landscape of structurally complex materials from commercially available or readily accessible feedstocks.

Dutta, Ananya↗

Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation

Abstract Design and synthesis of porous solids employing both reversible coordination chemistry and reversible covalent bond formation is described. The combination of two different linkage modes in a single material presents a link between two distinct classes of porous materials as exemplified by metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). This strategy, in addition to being a compelling material‐discovery method, also offers a platform for developing a fundamental understanding of the factors influencing the competing modes of assembly. We also demonstrate that even temporary formation of reversible connections between components may be leveraged to make new phases thus offering design routes to polymorphic frameworks. Moreover, this approach has the striking potential of providing a rich landscape of structurally complex materials from commercially available or readily accessible feedstocks.

Dutta, Ananya↗

Materials Science of Electrodes and Interfaces for High-Performance Organic Photovoltaics

The science of organic photovoltaic (OPV) cells has made dramatic advances over the past three years with power conversion efficiencies (PCEs) now reaching ~12%. The upper PCE limit of light-to-electrical power conversion for single-junction OPVs as predicted by theory is ~23%. With further basic research, the vision of such devices, composed of non-toxic, earth-abundant, readily easily processed materials replacing/supplementing current-generation inorganic solar cells may become a reality. Organic cells offer potentially low-cost, roll-to-roll manufacturable, and durable solar power for diverse in-door and out-door applications. Importantly, further gains in efficiency and durability, to that competitive with inorganic PVs, will require fundamental, understanding-based advances in transparent electrode and interfacial materials science and engineering. This team-science research effort brought together an experienced and highly collaborative interdisciplinary group with expertise in hard and soft matter materials chemistry, materials electronic structure theory, solar cell fabrication and characterization, microstructure characterization, and low temperature materials processing. We addressed in unconventional ways critical electrode-interfacial issues underlying OPV performance -- controlling band offsets between transparent electrodes and organic active-materials, addressing current loss/leakage phenomena at interfaces, and new techniques in cost-effective low temperature and large area cell fabrication. The research foci were: 1) Theory-guided design and synthesis of advanced crystalline and amorphous transparent conducting oxide (TCO) layers which test our basic understanding of TCO structure-transport property relationships, and have high conductivity, transparency, and tunable work functions but without (or minimizing) the dependence on indium. 2) Development of theory-based understanding of optimum configurations for the interfaces between oxide electrodes/interfacial layers and OPV active layer organic molecules/polymers. 3) Exploration and perfection of new processing strategies and cell architectures for the next-generation, large-area flexible OPVs. The goal has been to develop for the solar energy community the fundamental scientific understanding needed to design, fabricate, prototype, and ultimately test high-efficiency cells incorporating these new concepts. We achieved success in all of these directions.

14 SOLAR ENERGY↗

Electro-Optically Active Monomers: Synthesis and Characterization of Thin Films of Liquid Crystalline Substituted Polyacetylenes

The overall objective of this study was the description of the behavior of mesogen substituted acetylene monomers and polymers in monolayer films at the air/water interface and as multilayer films including the formation of such films. Fundamental knowledge to be gained would include the effect of balancing hydrophilic and hydrophobic tendencies in a molecule more complex than the classical fatty acids or lipids. The effect of molecular shape on the packing and thus the ultimate stability of monolayers formed from these new molecules was explored. The work takes on the challenge of preorienting monomers in well-ordered arrays prior to attempting polymerization with the hope that order would be preserved in any resulting polymer. New knowledge gained with regard to the acetylenic monomers includes processing of the acetylene monomer into multi-layer films, followed by the design and synthesis of a second generation of improved monomer structure for superior LBK film transfer properties. A third generation of acetylenic monomer was synthesized which approaches more closely the goal of solid state polymerization of these materials. A parallel study took a different approach. The materials are pre-formed poly(phenylene-acetylene) polymers so questions about reactivity are mute. The materials are a variation on the well-known hairy-rod polymers with regard to their Langmuir film-forming properties. Overall, the goal was to demonstrate that these polymers could be processed into NLO materials with novel polar order.

Duran, R. S.↗

Renewable Epoxy Thermosets from Fully Lignin-Derived Triphenols

A series of fully renewable triphenols (TPs) with various number of methoxy group substituents (n = 0–6) were synthesized using lignin-derived phenols (guaiacol and 2,6-dimethoxyphenol) and aldehydes (4-hydroxybenzaldehyde, vanillin, and syringaldehyde). The structural evolution from TPs to epoxy thermosets was followed by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. Thermomechanical properties of the resulting epoxy thermosets were investigated by dynamic mechanical analysis (DMA), tensile analysis (TA), and thermogravimetric analysis (TGA). Increasing the content of methoxy groups decreased the glass transition temperature (132–118 °C) and glassy modulus (2.7–2.2 GPa). Thermal stability of high-methoxy-content thermosets was reduced due to electron-donating effects and higher oxygen content. Conversions and isolated yields of TPs significantly decreased as the number of methoxy substituents increased, which markedly determined the feasibility of TPs as precursors for polymers. This work widens the synthesis route of fully lignin-derived polyphenols, yielding polymers with thermomechanical properties comparable to bisphenol A (BPA) based materials. Finally, evaluation of methoxy substitution provides insight for the selection of lignin-derived monomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Density Ultra-small Clusters and Single-Atom Fe Sites Embedded in Graphitic Carbon Nitride (g-C 3 N 4 ) for Highly Efficient Catalytic Advanced Oxidation Processes

Ultra-small metal clusters have attracted great attention owing to their superior catalytic performance and extensive application in heterogeneous catalysis. However, the synthesis of high-density metal clusters is very challenging due to their facile aggregation. In this work, one-step pyrolysis was used to synthesize ultra-small clusters and single-atom Fe sites embedded in graphitic carbon nitride with high density (iron loading up to 18.2 wt %), evidenced by high-angle annular dark field-scanning transmission electron microscopy, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and 57 Fe Mössbauer spectroscopy. The catalysts exhibit enhanced activity and stability in degrading various organic samples in advanced oxidation processes. The drastically increased metal site density and stability provide useful insights into the design and synthesis of cluster catalysts for practical application in catalytic oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Loss of ferulate 5-hydroxylase leads to Mediator-dependent inhibition of soluble phenylpropanoid biosynthesis in Arabidopsis

Phenylpropanoids are phenylalanine-derived specialized metabolites and include important structural components of plant cell walls, such as lignin and hydroxycinnamic acids, as well as ultraviolet and visible light-absorbing pigments, such as hydroxycinnamate esters (HCEs) and anthocyanins. Previous work has revealed a remarkable degree of plasticity in HCE biosynthesis, such that most Arabidopsis (Arabidopsis thaliana) mutants with blockages in the pathway simply redirect carbon flux to atypical HCEs. In contrast, the ferulic acid hydroxylase1 (fah1) mutant accumulates greatly reduced levels of HCEs, suggesting that phenylpropanoid biosynthesis may be repressed in response to the loss of FERULATE 5-HYDROXYLASE (F5H) activity. Here, we show that in fah1 mutant plants, the activity of HCE biosynthetic enzymes is not limiting for HCE accumulation, nor is phenylpropanoid flux diverted to the synthesis of cell wall components or flavonol glycosides. We further show that anthocyanin accumulation is also repressed in fah1 mutants and that this repression is specific to tissues in which F5H is normally expressed. Finally, we show that repression of both HCE and anthocyanin biosynthesis in fah1 mutants is dependent on the MED5a/5b subunits of the transcriptional coregulatory complex Mediator, which are similarly required for the repression of lignin biosynthesis and the stunted growth of the phenylpropanoid pathway mutant reduced epidermal fluorescence8. Taken together, these observations show that the synthesis of HCEs and anthocyanins is actively repressed in a MEDIATOR-dependent manner in Arabidopsis fah1 mutants and support an emerging model in which MED5a/5b act as central players in the homeostatic repression of phenylpropanoid metabolism.

09 BIOMASS FUELS↗

Rationally Designed 2D Covalent Organic Framework with a Brick-Wall Topology

In this paper, we report the design and synthesis of an imine-based two-dimensional covalent organic framework (2D COF) with a novel brick-wall topology by judiciously choosing a tritopic T-shaped building block and a ditopic linear linker. Unlike the main body of COF frameworks reported to-date, which consists of higher-symmetry 2D topologies, the unconventional layered brick-wall topology have only been proposed but never been realized experimentally. The brick-wall structure was characterized by powder X-ray diffraction analysis, FT-IR, solid state 13 C NMR spectroscopy, nitrogen, and carbon oxide adsorption-desorption measurements as well as theoretical simulations. Lastly, our present work opens the door to the design of novel 2D COFs and will broaden the scope of emerging COF materials.

36 MATERIALS SCIENCE↗

Development of the Safe and Broad‐Spectrum Aldehyde and Ketoamide Mpro inhibitors Derived from the Constrained α, γ‐AA Peptide Scaffold

Abstract SARS‐CoV‐2 is still wreaking havoc all over the world with surging morbidity and high mortality. The main protease (M pro ) is essential in the replication of SARS‐CoV‐2, enabling itself an active target for antiviral development. Herein, we reported the design and synthesis of a new class of peptidomimetics‐constrained α, γ‐AA peptides, based on which a series of aldehyde and ketoamide inhibitors of the M pro of SARS‐CoV‐2 were prepared. The lead compounds showed excellent inhibitory activity in the FRET‐based M pro enzymatic assay not only for the M pro of SARS‐CoV‐2 but also for SARS‐CoV and MERS‐CoV, along with HCoVs like HCoV‐OC43, HCoV‐229E, HCoV‐NL63 and HKU1. The X‐ray crystallographic results demonstrated that our compounds form a covalent bond with the catalytic Cys145. They also demonstrated effective antiviral activity against live SARS‐CoV‐2. Overall, the results suggest that α, γ‐AA peptide could be a promising molecular scaffold in designing novel M pro inhibitors of SARS‐CoV‐2 and other coronaviruses.

Chemistry↗

Quantum Fast Approximate Synthesis Tool (QFAST) v1.0.0

We present QFAST, a quantum synthesis tool designed to produce short circuits and to scale well in practice. Our contributions are: 1) a novel representation of circuits able to encode placement and topology; 2) a hierarchical approach with an iterative refinement formulation that combines "coarse-grained" fast optimization during circuit structure search with a good, but slower, optimization stage only in the final circuit instantiation stage. When compared against state-of-the-art techniques, although not optimal, QFAST can generate much shorter circuits for "time dependent evolution" algorithms used by domain scientists. We also show the composability and tunability of our formulation in terms of circuit depth and running time. For example, we show how to generate shorter circuits by plugging in the best available third party synthesis algorithm at a given hierarchy level. Composability enables portability across chip architectures, which is missing from the available approaches.

Younis, Ed↗

Diffusion-controlled alloying of single-phase multi-principal transition metal carbides with high toughness and low thermal diffusivity

Multicomponent alloying has displayed extraordinary potential for producing exceptional structural and functional materials. Consequently, the synthesis of single-phase, multi-principal covalent compounds remains a challenge. Here, we present a diffusion-controlled alloying strategy for the realization of covalent multi-principal transition metal carbides (MPTMCs) with a single face-centered cubic phase. The increased interfacial diffusion promoted by the addition of a nonstoichiometric compound leads to rapid formation of the single phase at much lower sintering temperature. Direct atomic-level observations via scanning transmission electron microscopy demonstrate that MPTMCs are composed of a single phase with a random distribution of all cations, which holds the key to the unique combinations of improved fracture toughness, superior Vickers hardness, and extremely lower thermal diffusivity achieved in MPTMCs. Conclusively, the present discovery provides a promising approach toward the design and synthesis of next-generation high-performance materials.

36 MATERIALS SCIENCE↗

Role of a Modulator in the Synthesis of Phase-Pure NU-1000

NU-1000 is a robust, mesoporous metal–organic framework (MOF) with hexazirconium nodes ([Zr 6 O 16 H 16 ] 8+ , referred to as oxo–Zr 6 nodes) that can be synthesized by combining a solution of ZrOCl 2 ·8H 2 O and a benzoic acid modulator in N,N-dimethylformamide with a solution of linker (1,3,6,8-tetrakis(p-benzoic acid)pyrene, referred to as H 4 TBAPy) and by aging at an elevated temperature. Typically, the resulting crystals are primarily composed of NU-1000 domains that crystallize with a more dense phase that shares structural similarity with NU-901, which is an MOF composed of the same linker molecules and nodes. Density differences between the two polymorphs arise from the differences in the node orientation: in NU-1000, the oxo–Zr 6 nodes rotate 120° from node to node, whereas in NU-901, all nodes are aligned in parallel. Considering this structural difference leads to the hypothesis that changing the modulator from benzoic acid to a larger and more rigid biphenyl-4-carboxylic acid might lead to a stronger steric interaction between the modulator coordinating on the oxo–Zr6 node and misaligned nodes or linkers in the large pore and inhibit the growth of the more dense NU-901-like material, resulting in phase-pure NU-1000. Side-by-side reactions comparing the products of synthesis using benzoic acid or biphenyl-4-carboxylic acid as a modulator produce structurally heterogeneous crystals and phase-pure NU-1000 crystals. It can be concluded that the larger and more rigid biphenyl-4-carboxylate inhibits the incorporation of nodes with an alignment parallel to the neighboring nodes already residing in the crystal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗