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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Investigation of Complex Intermediates in Solvent-Mediated Synthesis of Thiophosphate Solid-State Electrolytes

Lithium thiophosphates represent a promising class of solid Li + conductors for all-solid-state batteries. Scalable solvent-mediated synthesis routes for several Li–P–S ternary compounds have been reported, but little is known regarding the reaction mechanism of such pathways. This work demonstrates that solvent-mediated synthesis of lithium thiophosphate solid electrolytes from mixtures of Li 2 S and P 2 S 5 proceeds through a highly soluble P 2 S 6 2– intermediate. This intermediate exhibits virtually the same Raman spectra in several solvents including acetonitrile, methyl acetate, ethyl acetate, ethyl propionate, dimethoxyethane, tetraethylene glycol dimethyl ether, and tetrahydrofuran. Additionally, based on this universal intermediate, a general reaction mechanism is proposed for the solvent-mediated synthesis of several lithium thiophosphates including (LiPS 3 ) n , Li 2 P 2 S 6 , Li 7 P 3 S 11 , and Li 3 PS 4 .

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

Holistic design principles for flow batteries: Cation dependent membrane resistance and active species solubility

Cation dependent resistance of a commercial cation exchange membrane, Nafion™ 212, as well as the solubility of select active materials are investigated, demonstrating practical consequences of cation choice on redox flow battery (RFB) performance. The conductivity of alkali and methyl- or -alcohol substituted ammonium cations through pretreated Nafion™ 212 reveal that cation size is the dominant factor affecting ionic transport. Among the alkali series the resistance increases with larger ionic radii and similarly, with increasing steric bulk through substitution on ammonia. The solubility of ferrocyanide, a commonly used redox flow battery posolyte (or catholyte), as well as iron, cobalt, and chromium metal-organic compounds are determined for the same series of cations. Full cells are assembled using various cation mixtures and membrane pre-treatments to demonstrate practical effects of each variable. Here, we highlight the need to carefully select the correct cations for efficient electrolyte design, since certain cations may lead to high conductivity but low solubility, or vice versa, and provide design principles for RFBs using Nafion™ 212.

25 ENERGY STORAGE↗
DOE OSTI2025

Pd–Methyl Bond Energy─Property Correlations, Noncorrelations, Machine Learning Models, and Application to Polymerization Catalysis

Metal–carbon bonds are a key intermediate in a variety of homogeneous organometallic transformations and often determine the critical thermodynamics and kinetics of catalytic processes. Surprisingly, the influence of different ligands on metal–carbon bond strengths has been largely overlooked. Here, in this study, we evaluated nearly 700 experimental Pd–methyl complexes by calculating their bond dissociation energies using density functional theory (DFT) and compared these bond strengths to several fundamental molecular properties, and this revealed several surprising correlations and noncorrelations. Most surprising was that several fundamental properties, such as the bond length, bond force constant, and bond electron density, have no correlation with bond strength, despite these correlations often holding for main-group compounds. We were indeed able to identify key ligand-dependent chemical features/descriptors that provided a highly accurate machine learning model and provided insight into the general factors that control the Pd–carbon bond strength, such as radical delocalization and nucleophilicity. Insights gained from the Pd–Me bond energy analysis were then applied to CO migratory insertion steps that are part of copolymerization reactions.

binding energy↗
DOE OSTI2022

Conversion of Phenolic Oil from Biomass Pyrolysis into Phenyl Esters

Bio-oil is among the most economical approaches for advanced biofuel production. However, bio-oil faces several challenges including high acidity and viscosity, poor storage, and thermal stability. This study focuses on the upgradation of lignocellulosic (corn stover and yellow pine) bio-oil derived phenolic oil (PO), produced by the autothermal fast pyrolysis, through acid-catalyzed esterification reaction. Our strategy exploits a little recognized chemistry: the Fischer esterification of PO and carboxylic acids into carboxylic acid phenyl esters (CAPE) using Dean Stark distillation. Analyses by the Folin–Ciocalteu method, Karl Fischer titration, gas chromatography flame ionization detector, and the molecular weight determination by gel permeation chromatography suggest the conversion of 50 wt% added phenolics to their corresponding CAPE. The Fourier transform infrared spectroscopy analysis confirmed the formation of new C=O and two C–O stretching bands and decrease in the intensity of phenolic-OH bands in the CAPE. The 13 C NMR analysis supports the formation of CAPE together with some unreacted precursors. A base-catalyzed ester hydrolysis experiment and mass balance calculation show an excellent agreement (within 5% range) of the equivalent weight between the produced ester and the phenyl hexanoate. Brookfield analysis indicates that CAPE has 330-fold lower viscosity than starting PO. Heating values of CAPE were higher than PO, from which they were derived (42.2 and 43.6%, respectively, for PO from pyrolysis of corn stover and yellow pine), while moisture content decreased by 98.3 and 98.7%, respectively. The CAPE, which is a phenolic analogue of methyl esters used in biodiesel, has improved stability compared to PO from which it was derived.

42 ENGINEERING↗
DOE OSTI2023

Interaction of Anisole on Alumina-Supported Ni and Mo Oxide Hydrodeoxygenation Catalysts

The conversion of biomass to transportation fuels and value-added chemicals is a promising method to reduce reliance on fossil fuels. Mo-based catalysts have been shown to be highly active in the hydrodeoxygenation of biomass-derived phenolic compounds. The catalyst active phase, surface species, and the effect of adding additional metals is not comprehensively understood. Here we compare the temperature-dependent adsorption behavior of the model compound anisole 2 on an alumina-supported mixed nickel molybdenum oxide catalyst with two reference catalysts of molybdenum oxide and nickel oxide. Raman spectroscopy showed that the catalysts contain significant amounts of molybdates and molybdoaluminates, in addition to NiMoO 4 in the nickel molybdenum catalyst and MoO 3 in the molybdenum-only catalyst. Using transmission infrared spectroscopy under a controlled environment, we find that anisole chemisorbed largely through the oxygen in the methoxy group to form surface-bound phenoxy and methoxy species on all the catalysts. Ambient pressure X-ray photoelectrons spectroscopy measurements of the catalysts in anisole vapor showed reduced Mo atoms are the binding sites. The surface interaction and removal temperature of these species varied with the metal composition. The MoO x component dominated the adsorption behavior in both MoO x and NiMoO x catalysts. The formation of new aromatics, including methylated rings, depended on Ni composition. Upon adding hydrogen to induce the hydrodeoxygenation of anisole, undesirable polynuclear aromatic species were quickly formed on the Mo-based catalysts. In conclusion, these results suggest that the molybdenum oxide controls the adsorption and reactivity of the surface species, with a cooperative effect by Ni.

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

A polyketide-based biosynthetic platform for diols, amino alcohols and hydroxy acids

Medium- and branched-chain diols and amino alcohols are important industrial solvents, polymer building blocks, cosmetics and pharmaceutical ingredients, yet biosynthetically challenging to produce. Here we present an approach that uses a modular polyketide synthase (PKS) platform for the efficient production of these compounds. This platform takes advantage of a versatile loading module from the rimocidin PKS and nicotinamide adenine dinucleotide phosphate-dependent terminal thioreductases. Reduction of the terminal aldehyde with alcohol dehydrogenases enables the production of diols, oxidation enables the production of hydroxy acids and specific transaminases allow the production of various amino alcohols. Furthermore, replacement of the malonyl-coenzyme A-specific acyltransferase in the extension module with methyl- or ethylmalonyl-coenzyme A-specific acyltransferase enables the production of branched-chain diols, amino alcohols and carboxylic acids in high titres. Use of our PKS platform in Streptomyces albus demonstrated the high tunability and efficiency of the platform.

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

Emergent Chemical Behavior in Mixed Food and Lignocellulosic Green Waste Hydrothermal Liquefaction

Hydrothermal liquefaction (HTL) is a promising strategy for the conversion of energy-dense waste streams to fuels. Mixed-feed HTL aggregates multiple feed streams to achieve greater scales that capitalize on local resources, hence lowering costs. The potential for new pathways and products upon feedstock blending becomes a compounding level of complexity when unlocking emergent chemistries. Here, food and green waste streams were evaluated under HTL conditions (300 °C, 1 h) to understand the effect of feed molecular composition on product distributions and mechanisms. Thousands of emergent chemical compounds were detected via Fourier transform ion cyclotron resonance mass spectrometry, ultimately leading to the emergence of two dominant outcomes. First, the presence of small amounts of food waste into green waste results in substantial decarboxylation and subsequent polymerization to biocrude than chars. Second, in the other limit, small amounts of green waste promote the capping of oxygenates into the biodiesel range, such as with the emergence of fatty acid methyl esters.

09 BIOMASS FUELS↗
DOE OSTI2023

Melt Blending: A Tool to Simplify Plastic Scintillator Synthesis

Plastic scintillators are widely used as radiation detection media in homeland security and nuclear physics applications. Their attributes include low cost, scalability to large detector volumes, and additive compounding to enable additional material and detection features, such as pulse shape discrimination (PSD), gamma-ray spectroscopy, aging resistance, and coincidence timing. However, traditional chemically cured plastic scintillators (CCS) require long reaction times, and hazardous wet chemical procedures performed by specially trained personnel, and can leave residual monomer, resulting in deleterious optical and material properties. Here, we synthesize melt blended scintillators (MBSs) in 2.5 days using easily accessible solid-state compounding of commercially-available poly(styrene) with 30–60 wt% fluorene-based compound “P2” to create monolithic detectors with < 100 ppm residual monomer, in several form factors. Further, the best scintillation performance was recorded for 60 wt% P2 in Styron 665, including gamma-ray light yield 139% of EJ- 200 commercial scintillator and PSD figure of merit (FOM) value of 2.65 at 478 keVee, approaching P2 organic glass scintillator (OGS). The capability of MBS to generate fog-resistant scintillators and poly(methyl methacrylate) (PMMA)-based scintillators for use in challenging environments is also demonstrated.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2020

Pseudomonas sp. Strain 273 Degrades Fluorinated Alkanes

Fluorinated organic compounds have emerged as environmental constituents of concern. We demonstrate that the alkane degrader Pseudomonas sp. strain 273 utilizes terminally monofluorinated C 7 –C 10 alkanes and 1,10-difluorodecane (DFD) as the sole carbon and energy sources in the presence of oxygen. Strain 273 degraded 1-fluorodecane (FD) (5.97 ± 0.22 mM, nominal) and DFD (5.62 ± 0.13 mM, nominal) within 7 days of incubation, and 92.7 ± 3.8 and 90.1 ± 1.9% of the theoretical maximum amounts of fluorine were recovered as inorganic fluoride, respectively. With n-decane, strain 273 attained (3.24 ± 0.14) × 10 7 cells per μmol of carbon consumed, while lower biomass yields of (2.48 ± 0.15) × 10 7 and (1.62 ± 0.23) × 10 7 cells were measured with FD or DFD as electron donors, respectively. The organism coupled decanol and decanoate oxidation to denitrification, but the utilization of (fluoro)alkanes was strictly oxygen-dependent, presumably because the initial attack on the terminal carbon requires oxygen. Fluorohexanoate was detected as an intermediate in cultures grown with FD or DFD, suggesting that the initial attack on the fluoroalkanes can occur on the terminal methyl or fluoromethyl groups. Overall, the findings indicate that specialized bacteria such as Pseudomonas sp. strain 273 can break carbon–fluorine bonds most likely with oxygenolytic enzyme systems and that terminally monofluorinated alkanes are susceptible to microbial degradation. The findings have implications for the fate of components associated with aqueous film-forming foam (AFFF) mixtures.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Lepidopteran mevalonate pathway optimization in Escherichia coli efficiently produces isoprenol analogs for next-generation biofuels

Terpenes constitute the largest class of natural products with over 55,000 compounds with versatile applications including drugs and biofuels. Introducing structural modifications to terpenes through metabolic engineering is an efficient and sustainable way to improve their properties. Here, in this study, we report the optimization of the lepidopteran mevalonate (LMVA) pathway towards the efficient production of isopentenyl pyrophosphate (IPP) analogs as terpene precursors. First, we linked the LMVA pathway to NudB, a promiscuous phosphatase, resulting in the production of the six-carbon analog of 3-methyl-3-buten-1-ol (isoprenol), 3-ethyl-3-buten-1-ol (C6-isoprenol). Using C6-isoprenol as the final product, we then engineered the LMVA pathway by redirecting its upstream portion from a thiolase-dependent pathway to a beta-oxidation pathway. The beta-oxidation LMVA pathway transforms valeric acid, a platform chemical that can be produced from biomass, into C6-isoprenol at a titer of 110.3 mg/L, improved from 5.5 mg/L by the thiolase LMVA pathway, which used propionic acid as a feedstock. Knockout of the E. coli endogenous thiolase genes further improved the C6-isoprenol titer to 390 mg/L, implying efficient production of homo isopentenyl pyrophosphate (HIPP). The beta-oxidation LMVA-NudB pathway also converts butanoic acid and hexanoic acid into isoprenol and isoprenol’s seven-carbon analog, 3-propyl-3-buten-1-ol (C7-isoprenol), respectively, suggesting the beta-oxidation LMVA pathway produces IPP and C7-IPP from the corresponding fatty acids. Fuel property tests revealed the longer chain isoprenol analogs have lower water solubilities, similar or higher energy densities, and comparable research octane number (RON) boosting effects to isopentenols. This work not only optimizes the LMVA pathway, setting the basis for homoterpene biosynthesis to expand terpene chemical space, but provides an efficient pathway to produce isoprenol analogs as next-generation biofuels from sustainable feedstocks.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Crystal Growth, Single Crystal Structure, and Biological Activity of Thiazolo-Pyridine Dicarboxylic Acid Derivatives

Four novel TPDCA derivatives were prepared via a supersaturation method combining TPDCA with water, N-methyl-2-pyrrolidone (NMP), Na(PO 2 H 2 ), and ammonia solution: 2(C 9 H 7 NO 5 S)H 2 O (1), (C 9 H 7 NO 5 S)C 5 H 9 NO (2), (C 9 H 7 NO 5 S)Na(PO 2 H 2 ) (3), and (C 9 H 5 NO 5 S)(NH 4 )2(H 2 O) (4). Their crystal structures were determined by single-crystal X-ray diffraction. Compounds (1) and (2) crystallize in the monoclinic space groups P2 1 and P2 1 /c, respectively, whereas compounds (3) and (4) crystallize in the triclinic space group P1 - . Weak and moderate hydrogen bonds were detected in the four compounds. In the biological tests, (1) and (3) exhibited significant antibacterial activity against Escherichia coli and Staphylococcus aureus; in addition, (1) was cytotoxic against leukemia HL-60 cells with the IC 50 value of 158.5 ± 12.5 μM.

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

Luminescent hybrid halides with various centering metal cations (Zn, Cd and Pb) and diverse structures

Organic–inorganic hybrid metal halides have been extensively studied because of their great potential in optoelectronics. Herein, we report three hybrid metal halides (Bmpip) 2 ZnBr 4 , (Bmpip) 2 CdBr 4 , and (Bmpip) 8 Pb 11 Br 30 (where Bmpip + is 1-butyl-1-methyl-piperidinium, C 10 H 22 N + ). (Bmpip) 2 ZnBr 4 and (Bmpip) 2 CdBr 4 crystallize in the P2 1 /c space group with zero-dimensional crystal structures with [MBr 4 ] 2− (M = Zn, Cd) tetrahedra isolated by Bmpip + . (Bmpip) 8 Pb 11 Br 30 crystallizes in the triclinic space group P$\overline{1}$ with combining macron] with one-dimensional corrugated chains constructed from face-sharing [PbBr 6 ] 4− octahedra. Furthermore, all of the compounds exhibit excellent ambient and thermal stability. Under UV excitation, all three compounds exhibit very broad emissions. Temperature-dependent photoluminescence measurements indicate that the broad emissions of (Bmpip) 2 ZnBr 4 and (Bmpip) 2 CdBr 4 can be attributed to both the organic cations and self-trapped excitons (STEs) and that the emission of (Bmpip) 8 Pb 11 Br 30 is assigned to STEs. Density functional theory calculations reveal that the three compounds adopt a direct band gap. This work enriches our understanding of the structure types of hybrid metal halides while revealing their diverse emission mechanisms.

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

Sooting tendencies of terpenes and hydrogenated terpenes as sustainable transportation biofuels

Terpenes are a diverse group of molecules that are synthesized by plants and microorganisms through combining units of isoprene (2-methyl-1,3-butadiene). They typically contain rings and methyl branches, which gives them high energy densities and low freezing points and makes them appealing candidates for sustainable transportation biofuels. Between the original biosynthesis and upgrading options such as hydrogenation, they have a large degree of freedom of structures, e.g., different carbon skeletons, positions of double bonds, and functional groups. Therefore, structure-property data is needed to downselect potential fuel candidates. Here, we measured the sooting tendencies of 17 C10 monoterpenes and 7 of their hydrogenated analogues. The hydrogenated compounds were custom synthesized, so the quantities were too small for conventional smoke point measurements. Thus, the sooting tendencies were quantified with yield sooting index (YSI), which is based on the soot yield in a fuel-doped non-premixed methane flame. Derived smoke points (DSPs) were estimated from a correlation between YSI and smoke point for other hydrocarbons. The YSI of terpenes and their derivatives varies widely from 85.6 to 248.5. The YSI follows the trend: terpenes > dihydroterpenes > tetrahydroterpenes. The DSPs of all the tetrahydroterpenes and some dihydroterpenes are higher than that of a Jet-A fuel sample, suggesting that they offer soot reduction benefits. Further, the YSIs depend strongly on molecular structure; for example, α-pinene and β-pinene have identical carbon skeletons and differ only in the position of one carbon-carbon double bond, but the YSI of α-pinene is 34% higher than that of β-pinene. Detailed decomposition analysis via density functional theory (DFT) suggests that compared with β-pinene, α-pinene requires fewer steps to form the first aromatic ring and the process is more thermodynamically favorable. The YSI difference between the pinenes is mainly affected by the identity of the products from the dominant decomposition pathways.

09 BIOMASS FUELS↗
DOE OSTI2021

Two-bond 13 C– 13 C spin-coupling constants in saccharides: dependencies on exocyclic hydroxyl group conformation

Seven doubly 13 C-labeled isotopomers of methyl β-D-glucopyranoside, methyl β-D-xylopyranoside, methyl β-D-galactopyranoside, methyl β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside and methyl β-D-galactopyranosyl-(1→4)-β-D-xylopyranoside were prepared, crystallized, and studied by single-crystal X-ray crystallography and solid-state 13 C NMR spectroscopy to determine experimentally the dependence of 2 J C1,C3 values in aldopyranosyl rings on the C1–C2–O2–H torsion angle, θ 2 , involving the C2 carbon of the C1–C2–C3 coupling pathway. Using X-ray crystal structures to determine θ 2 in crystalline samples and by selecting compounds that exhibit a relatively wide range of θ 2 values in the crystalline state, 2 J C1,C3 values measured in crystalline samples were plotted against θ 2 and the resulting plot compared to that obtained from density functional theory (DFT) calculations. For θ 2 values ranging from ~90° to ~240°, very good agreement was observed between the experimental and theoretical plots, providing strong validation of DFT-calculated spin-coupling dependencies on exocyclic C–O bond conformation involving the central carbon of geminal C–C–C coupling pathways. we report that these findings provide new experimental evidence supporting the use of 2 J CCC values as non-conventional spin-coupling constraints in MA'AT conformational modeling of saccharides in solution, and the use of NMR spin-couplings not involving coupled hydroxyl hydrogens as indirect probes of C–O bond conformation. Solvomorphism was observed in crystalline βGal-(1→4)-βGlcOCH 3 wherein the previously-reported methanol solvate form was found to spontaneously convert to a monohydrate upon air-drying, leading to small but discernible conformational changes in, and a new crystalline form of, this disaccharide.

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

Compositions and Formation Mechanisms of Solid-Electrolyte Interphase on Microporous Carbon/Sulfur Cathodes

We report the formation mechanism and compositions of a solid-electrolyte interphase (SEI) on a microporous carbon/sulfur (MC/S) cathode in Li–S batteries using a carbonate-based electrolyte (1 M LiPF 6 in ethylene carbonate (EC)/dimethyl carbonate, v:v = 1:1). Through characterizations using 1D and 2D solution-phase nuclear magnetic resonance spectroscopy, coupled with model chemical reactions and DFT calculations, we have identified two critical roles of Li + in steering the SEI formation. First, the preferential solvation of Li + by EC in the mixed carbonate electrolyte renders EC as the dominant participant in the SEI formation, and second, Li + coordination to the EC carbonyl alters activation barriers and changes the reaction pathways relative to Na + . The main organic components in the SEI are identified as lithium ethylene monocarbonate and lithium methyl carbonate, which are virtually identical to those formed on Li and graphite anodes of lithium-ion batteries but via a different pathway.

25 ENERGY STORAGE↗
DOE OSTI2024

Functional analysis of the methylerythritol phosphate pathway terminal enzymes IspG and IspH from Zymomonas mobilis

ABSTRACT Isoprenoids are a diverse family of compounds that are synthesized from two isomeric compounds, isopentenyl diphosphate and dimethylallyl diphosphate. In most bacteria, isoprenoids are produced from the essential methylerythritol phosphate (MEP) pathway. The terminal enzymes of the MEP pathway IspG and IspH are [4Fe-4S] cluster proteins, and in Zymomonas mobilis, the substrates of IspG and IspH accumulate in cells in response to O 2 , suggesting possible lability of their [4Fe-4S] clusters. Here, we show using complementation assays in Escherichia coli that even under anaerobic conditions, Z. mobilis IspG and IspH are not as functional as their E. coli counterparts, requiring higher levels of expression to rescue viability. A deficit of the sulfur utilization factor (SUF) Fe-S cluster biogenesis pathway did not explain the reduced function of Z. mobilis IspG and IspH since no improvement in viability was observed in E. coli expressing the Z. mobilis SUF pathway or having increased expression of the E. coli SUF pathway. Complementation of single and double mutants with various combinations of Z. mobilis and E. coli IspG and IspH indicated that optimal growth required the pairing of IspG and IspH from the same species. Furthermore, Z. mobilis IspH conferred an O 2 -sensitive growth defect to E. coli that could be partially rescued by co-expression of Z. mobilis IspG. In vitro analysis showed O 2 sensitivity of the [4Fe-4S] cluster of both Z. mobilis IspG and IspH. Altogether, our data indicate an important role of the cognate protein IspG in Z. mobilis IspH function under both aerobic and anaerobic conditions. IMPORTANCE Isoprenoids are one of the largest classes of natural products, exhibiting diversity in structure and function. They also include compounds that are essential for cellular life across the biological world. In bacteria, isoprenoids are derived from two precursors, isopentenyl diphosphate and dimethylallyl diphosphate, synthesized primarily by the methylerythritol phosphate pathway. The aerotolerant Z. mobilis has the potential for methylerythritol phosphate pathway engineering by diverting some of the glucose that is typically efficiently converted into ethanol to produce isoprenoid precursors to make bioproducts and biofuels. Our data revealed the surprising finding that Z. mobilis IspG and IspH need to be co-optimized to improve flux via the methyl erythritol phosphate pathway in part to evade the oxygen sensitivity of IspH.

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

Improving Carbonate-Promoted C–H Carboxylation Using Mesoporous Carbon Supports

C–H carboxylation is an attractive way to utilize CO 2 for chemical production provided that it does not consume resource-intensive reagents. Alkali carbonates dispersed into the pores of mesoporous supports display strongly basic reactivity under CO 2 , allowing them to be used as base promoters for C–H carboxylation of (hetero)arenes in the absence of other reagents or catalysts. Mesoporous oxides are convenient support materials, but only a relatively small fraction of the dispersed carbonate (ca. 10-20%) is converted to carboxylate products when metal oxide supports are used. Here we compare mesoporous oxide and carbon supports and investigate the dependence of carbonate reactivity on pore structure. We show that using mesoporous carbons supports can increase the carbonate conversion by 2–4x when compared to oxide supports. This improved carbonate reactivity is maintained across a variety of mesoporous carbons with different pore structures (ordered vs. disordered) and pore diameters, indicating that the dispersed carbonate is intrinsically more reactive on the surface of a carbon material compared to an oxide surface. Reaction of the carboxylate products with dimethyl carbonate yields isolable methyl esters as the final product and regenerates the dispersed carbonate. We show that mesoporous carbon supports are robust to at least 5 cycles of successive C–H carboxylation and methylation with dimethyl carbonate. Furthermore, understanding how the support structure affects dispersed carbonate reactivity is valuable for advancing C–H carboxylation toward practical application and utilizing these materials in other CO 2 transformations.

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

Functional group effect of chemically modified microcrystalline methyl cellulose on thermoplastic polyurethane composites

Microcrystalline cellulose (MCC) is a promising bio-based filler for lightweight yet mechanically high-performance eco-polymer composites because of its low density and high biocompatibility. However, intermolecular hydrogen bonding among MCC is stronger than the polymer–filler interactions, which deteriorate the mechanical properties of the composites. Herein, we investigated the effects of functional groups on the mechanical properties of composites by scrutinizing chemically modified microcrystalline methyl cellulose (m-MMC) with three different substitution levels of hydroxyl group to hydroxypropyl (HP) group: no-, low-, and high-level substitution (HP-0, HP-low, and HP-high). The degree of HP substitution of m-MMC was quantitatively measured by CP/MAS NMR analysis. The relatively bulky HP groups interrupted the filler–filler intermolecular interactions and reduced the crystallinity and density of m-MMC, as evident from X-ray diffractometer and pycnometer data, respectively. For scalable production of the composites, the m-MMC were compounded with thermoplastic polyurethane (TPU) by a twin-screw extruder at concentrations between 0.5 and 10 wt%. Despite its low filler concentration, the toughness of m-MMC/TPU composites was remarkably enhanced, up to 28% (229.2 to 294.4 MJ/m 3 ) at 0.5 wt% loading of HP-low, owing to the enhanced polymer–filler interactions. In conclusion, the fundamental understanding on structure–property relationships will provide insights for designing of mechanically robust yet eco-friendly polymer composites.

composites↗