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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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Grafting-To and From for Multiplexed Chemical-Warfare-Agent Responsive Polymer Brushes

Surface-tethered polymers have important applications in functional polymer coatings, particularly for the development of chemically responsive surfaces. Here, we combined the traditional grafting-to and grafting-from methods to create a new surface grafting strategy, termed grafting-to and from, using surface-initiated ring-opening metathesis polymerization (SI-ROMP). In this method, poly(pentafluorophenyl methacrylate) is grafted to an amine terminated surface. Surplus reactive esters after reaction with surface amines render this polymer a connecting or tie layer that can be further reacted to provide dense ROMP initiation sites. This amplification of grafting sites results in thick and environmentally stable polymer brushes upon SI-ROMP. With the goal of developing polymer-grafted breathable membranes that autonomously react to multiple chemical warfare agents (CWAs), we demonstrate the benefit of this method by employing amine reactive monomers in the grafting-from step. This enables diverse postsynthetic functionalization for the facile screening of chemical motifs to enhance response capabilities to mustard blister agents. Surface-tethered triarylmethanol-containing polymers with four distinct functional groups are prepared and challenged with the vapor of 2-chloroethyl ethyl sulfide (CEES), a simulant of mustard agent, in humid air. Importantly, hydroxyl groups effectively improve CWA response and the resulting polymer brushes show chain collapse after both CEES and diethylchlorophosphate (DCP) treatment. Our results illustrate that the grafting-to and from method can be used to grow functional and robust polymer coatings for various applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Site-Selective Atomic Layer Deposition at Thermally Generated Surface Oxygen Vacancies on Rutile TiO 2

Unique atomic arrangements (i.e., defects) on material surfaces may exhibit distinctive reactivity that affords opportunities for selective surface chemistry exclusively at those sites. While theoretically appealing, site-selective atomic layer deposition (ALD) processes remain largely unrealized experimentally. Here we provide evidence for site-selective ALD that exclusively targets oxygen vacancies thermally generated at the surface of TiO 2 single crystals. High-resolution in situ ellipsometry reveals the nucleation behavior of dimethylaluminum isopropoxide (DMAI) and water at process conditions precisely tuned for selective hydroxylation of surface defects. An island growth model for nucleation and atomic force microscopy (AFM) imaging are consistent with a site-selective growth mechanism that depends on the surface oxygen vacancy density. This approach to direct ALD reactions at defective surface sites may provide future opportunities for targeted remediation of electronically imperfect interfaces.

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

Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

The fabrication of polymer-MOF composite gels holds great potential to provide emergent properties for drug delivery, environmental remediation, and catalysis. To leverage the full potential of these composites, we investigated how the presence and chemistry of polymers impact MOF formation within the composites and, in turn, how MOFs impact polymer gelation. We show that polymers with a high density of strongly metal-binding carboxylic acids inhibit MOF formation; however, reducing the density of carboxylic acids or substituting them with weaker metal-binding hydroxyl groups permits both MOF formation and gelation within composites. Preparing composites with poly(ethylene glycol) (PEG), which does not bind MOF zirconium (Zr)-oxo clusters, and observing gelation suggests that MOFs can entrap polymer chains to create cross-links in addition to cross-linking them through polymer-Zr-oxo interactions. Both simulations and experiments show composite hydrogels formed with poly(vinyl alcohol) (PVA) to be more stable than those made with PEG, which can reptate through MOF pores upon heating. We demonstrate the generalizability of this composite formation process across different Zr-based MOFs (UiO-66, NU-901, UiO-67, and MOF-525) and by spin-coating gels into conformable films. PVA-UiO-66 composite hydrogels demonstrated high sorption and sustained release of methylene blue relative to the polymer alone (3× loading, 28× slower release), and PVA-MOF-525 composite hydrogels capably sorb the therapeutic peptide Angiotensin 1–7. By understanding the influence of polymer-MOF interactions on the structure and properties of composite gels, this work informs and expands the design space of this emerging class of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration

Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlO x infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnO x infiltration, especially one that is initiated by AlO x priming, has not received much attention because highly reactive hydroxyl groups generated by AlO x -priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnO x VPI. Here, we interrogate the ZnO x infiltration mechanism in AlO x -primed poly(methyl methacrylate) (PMMA) in comparison to the control AlO x -only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlO x network can quickly saturate the AlO x infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnO x infiltration using divalent DEZ precursor, once activated via AlO x -priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlO x -priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnO x .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Exploring the Role of Inorganic and Organic Interfaces on CO 2 and CH 4 Partitioning: Case Study of Silica, Illite, Calcite, and Kerogen Nanopores on Gas Adsorption and Nanoscale Transport Behaviors

The adsorption, partitioning, and diffusion of CO 2 and CH 4 in organic–inorganic pores composed of kerogen with silica, illite, or calcite are studied using density functional theory and classical molecular dynamics simulations. The adsorption and partitioning behavior of CO 2 and CH 4 molecules is found to be a function of chemistry of the solid interface, pore size, and surface area. CO 2 molecules are preferentially adsorbed compared to CH 4 molecules on silica, illite, calcite, and kerogen surfaces due to significant contributions of electrostatic interactions with the atoms of the associated surfaces. CO 2 and CH 4 molecules display higher adsorption energy on calcite and silica compared to those on illite and kerogen because of enhanced interactions with the positively charged calcium ions on the calcite surface and the hydroxyl group (-OH) on the silica surface. Enhanced internal nanopores and the availability of adsorption active sites in illite and kerogen matrices aid in higher partitioning of the gas molecules into these pores. CO 2 has a significant influence on the clustering and swelling of kerogen fragments compared to CH 4 . Higher CO 2 adsorption on inorganic and kerogen surfaces results in lower overall self-diffusivities compared to CH 4 . This study illustrates surface and pore size controls on the adsorption, partitioning, and self-diffusivities of CO 2 and CH 4 at conditions relevant for subsurface energy applications. The chemistry of the surfaces along with the availability of internal pores and active adsorption sites influences the adsorption behavior of gases. Our results suggest that CO 2 stored in depleted gas reservoirs may preferentially inhabit nanoconfined pores.

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

Probing the Core–Shell Organization of Nanoconfined Methane in Cylindrical Silica Pores Using In Situ Small-Angle Neutron Scattering and Molecular Dynamics Simulations

Determining the structure of nanoconfined fluids is essential for predicting the fate of these fluids in subsurface geologic formations with nanoporous features and for engineering novel nanoporous materials for storing compressed gases. In this study, we probe the structure of nanoconfined methane at pressures in the range of 15–100 bar using in situ small-angle neutron scattering (SANS) measurements and molecular dynamics (MD) simulations. The structure of methane is probed in MCM-41 and SBA-15 with cylindrical pores and diameters of 3.3 and 6.8 nm, respectively. In situ SANS measurements and MD simulations showed that the confined methane molecules are organized in a core–shell structure, with the shell arising from the adsorption of methane molecules on the silica surface. The shell thicknesses of the adsorbed deuterated methane (CD4) molecules in MCM-41 obtained by SANS measurements are 1.4 ± 0.5, 2.1 ± 0.1, 3.2 ± 0.8, 4.0 ± 0.3, and 6.0 ± 0.7 Å at equilibrated pressures of 15.6, 35.6, 55.5, 73.3, and 95.7 bar, respectively. The shell thicknesses of the adsorbed CD4 layer in SBA-15 pores are 2.7 ± 0.5, 4.3 ± 0.7, 6.6 ± 0.7, 10.2 ± 0.3, and 14.6 ± 0.8 Å at equilibrated pressures of 15.5, 32.7, 52.4, 70, and 99.5 bar, respectively. These experimental results are in close agreement with the results predicted from MD simulations. Adsorption of methane molecules on the silica surfaces is primarily driven by van der Waals interactions between the methane molecules and the hydroxyl groups on the silica surface, while electrostatic interactions play a minor role. In conclusion, the experimental and simulation approaches described in this study provide fundamental insights into the organization of confined gases using methane as a specific example in the context of compressed fluid storage in natural and engineered materials for adaptive energy use.

03 NATURAL GAS↗
DOE OSTI2021

Experimental and Kinetic Modeling Study of 3-Methyl-2-butenol (Prenol) Oxidation

Longer chain alcohols with 4–5 carbon atoms are attractive alternative fuels as they can be derived from biological sources and since their combustion leads to lower exhaust gas levels of NO x and soot compared to commercial fossil fuels. The auto-ignition behavior of fuels that contain both a hydroxyl group and a C=C double bond in their molecular structure is not well established in the literature. Understanding the influence of these functional groups on the ignition behavior of fuels is critical in the development of tailor-made fuels for advanced combustion engines. In this study, ignition delay times of an unsaturated alcohol, 3-methyl-2-butenol (prenol), are measured using a high-pressure shock tube and a rapid compression machine at pressures of 15 and 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 in “air” in the temperature range 600–1400 K. Furthermore, a detailed kinetic model is developed and validated using the new experimental data in this study. In addition, speciation data in a jet-stirred reactor, ignition delay times, and laminar burning velocities available in the literature were also used to validate the new kinetic model. Fuel flux and sensitivity analyses are performed using this new model to determine the important fuel consumption pathways and critical reactions that affect the reactivity of prenol.

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

Impacts of Hydrogen Bond Donor Structures in Phenolic Aldehyde Deep Eutectic Solvents on Pretreatment Efficiency

As a green solvent for biomass processing, deep eutectic solvents (DESs) have shown effectiveness in biomass processing. Here, in this study, phenolic aldehydes with different numbers of methoxy groups, including 4-hydroxybenzaldehyde (HBA, no methoxy), vanillin (VA, monomethoxy), and syringaldehyde (SA, dimethoxy) were employed to synthesize DESs with choline chloride (ChCl). The presence of methoxy groups in the hydrogen bond donor structure affected DES properties, as well as biomass pretreatment performance. The high thermal stability of phenolic aldehyde DESs was shown with over 225 °C onset temperature. The hydrogen bond donor with one aldehyde and one hydroxyl group at the para position without a methoxy group (ChCl-HBA) showed the highest xylan removal and delignification, reaching 59.3 and 88.0%, respectively, leading to the highest enzymatic hydrolysis yield. Sonication after pretreatment further enhanced the hydrolysis yields, achieving 83.3% glucan conversion and 50.1% xylan conversion. In the lignin-rich fraction, the recovered lignin showed a low weight–average molecular weight under 2100 g/mol with a relatively uniform molecular weight dispersity below 1.5. This study provides insights into how the chemical structure of hydrogen bond donors in DESs affects biomass processing and paves the way for designing effective lignin-derived DES in future biorefinery processes.

09 BIOMASS FUELS↗
DOE OSTI2021

Facet-Dependent Photodegradation of Methylene Blue by Hematite Nanoplates in Visible Light

The expression of specific crystal facets in different nanostructures is known to play a vital role in determining the sensitivity toward photodegradation of organics, which can generally be ascribed to differences in surface structure and energy. Herein, we report the synthesis of hematite nanoplates with controlled relative exposure of basal (001) and edge (012) facets, enabling us to establish direct correlation between surface structure and the photocatalytic degradation efficiency of methylene blue (MB) in the presence of hydrogen peroxide. MB adsorption experiments showed that the capacity on (001) is about three times larger than on (012), and this is supported by density functional theory calculations suggesting adsorption energies about 1.5 times higher. However, this alone cannot explain the observed MB photodegradation rate, which is around 14.5 times faster on (001) than (012). The enhancement we attribute to a higher availability of photoelectron accepting surface Fe3+ sites on the (001) facet. This facilitates more efficient iron valence cycling and the heterogeneous photo-Fenton reaction yielding MB-oxidizing hydroxyl radicals at the surface. Our findings help establish a rational basis for design and optimization of hematite nanostructures as photocatalysts for environmental remediation.

Zong, Meirong↗
DOE OSTI2023

Surface Processes Control the Fate of Reactive Oxidants Generated by Electrochemical Activation of Hydrogen Peroxide on Stainless-Steel Electrodes

Low-cost stainless-steel electrodes can activate hydrogen peroxide (H 2 O 2 ) by converting it into a hydroxyl radical ( • OH) and other reactive oxidants. At an applied potential of +0.020 V, the stainless-steel electrode produced • OH with a yield that was over an order of magnitude higher than that reported for other systems that employ iron oxides as catalysts under circumneutral pH conditions. Decreasing the applied potential at pH 8 and 9 enhanced the rate of H 2 O 2 loss by shifting the process to a reaction mechanism that resulted in the formation of an Fe(IV) species. Significant metal leaching was only observed under acidic pH conditions (i.e., at pH <6), with the release of dissolved Fe and Cr occurring as the thickness of the passivation layer decreased. Despite the relatively high yield of • OH production under circumneutral pH conditions, most of the oxidants were scavenged by the electrode surface when contaminant concentrations comparable to those expected in drinking water sources were tested. The stainless-steel electrode efficiently removed trace organic contaminants from an authentic surface water sample without contaminating the water with Fe and Cr. With further development, stainless-steel electrodes could provide a cost-effective alternative to other H 2 O 2 activation processes, such as those by ultraviolet light.

42 ENGINEERING↗
DOE OSTI2023

(Fe, Cr)(OH) 3 Coprecipitation in Solution and on Soil: Roles of Surface Functional Groups and Solution pH

The simultaneous precipitation of (Fe, Cr)(OH) 3 nanoparticles in solution (homogeneous) and on soil surfaces (heterogeneous), which controls Cr transport in soil and aquatic systems, was quantified for the first time in the presence of model surfaces, i.e., bare and natural organic matter (NOM)-coated SiO 2 and Al 2 O 3 . Various characterization techniques were combined to explore the surface-ion-precipitate interactions and the controlling mechanisms. (Fe, Cr)(OH) 3 accumulation on negatively charged SiO 2 was mainly governed by electrostatic interactions between hydrolyzed ion species or homogeneous (Fe, Cr)(OH) 3 and surfaces. The elevated pH through protonation of Al 2 O 3 surface hydroxyls resulted in higher Cr/Fe ratios in both homogeneous and heterogeneous coprecipitates. Here, due to ignorable NOM adsorption onto SiO 2 , the amounts of (Fe, Cr)(OH) 3 precipitates on bare/NOM-SiO 2 were similar; contrarily, attributed to favored NOM adsorption onto Al 2 O 3 and consequently carboxyl association with metal ions or (Fe, Cr)(OH) 3 nanoparticles, remarkably more heterogeneous precipitates harvested on NOM-Al 2 O 3 than bare-Al 2 O 3 . With the same solution supersaturation, the total amounts of homogeneous and heterogeneous precipitates were similar irrespective of the substrate type. With lower pH, decreased electrostatic forces between substrates and precipitates shifted (Fe, Cr)(OH) 3 distribution from heterogeneous to homogeneous phases. The quantitative knowledge of (Fe, Cr)(OH) 3 distribution and the controlling mechanisms can assist in better Cr sequestration in natural and engineered settings.

(Fe, Cr)(OH)3 distribution↗
DOE OSTI2023

Surface Functional Groups Affect Iron (Hydr)oxide Heterogeneous Nucleation: Implications for Membrane Scaling

Because of its favorable thermodynamics and fast kinetics, heterogeneous solid nucleation on membranes triggers early-stage mineral scaling. Iron (hydr)oxide, a typical membrane scale, initially forms as nanoparticles that interact with surface functional groups on membranes, but these nanoscale phenomena are difficult to observe in real time. In this study, we utilized in situ grazing incidence small angle X-ray scattering and ex situ atomic force microscopy to examine the heterogeneous nucleation of iron (hydr)oxide on surface functional groups commonly used in membranes, including hydroxyl (OH), carboxyl (COOH), and fluoro (F) groups. We found that, compared to nucleation on hydrophilic OH- and COOH-surfaces, the high hydrophobicity of an F-modified surface significantly reduced the extents of both heterogeneously and homogeneously formed iron (hydr)oxide nucleation. Moreover, on the OH-surface, the high functional group density of 0.76 nmol/cm 2 caused faster heterogeneous nucleation than that on a COOH-surface, with a density of 0.28 ± 0.04 nmol/cm 2 . The F-surface also had the highest heterogeneous nucleation energy barrier (26 ± 0.6 kJ/mol), followed by COOH- (23 ±0.8 kJ/mol) and OH- (20 ± 0.9 kJ/mol) surfaces. The kinetic and thermodynamic information provided here will help us better predict the rates and extents of early-stage scaling of iron (hydr)oxide nanoparticles in membrane processes. Finally, this work provides both kinetic and thermodynamic information about iron (hydr)oxide nucleation controlled by membrane-related functional groups (OH, COOH, and F).

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

Effects of Halides on Organic Compound Degradation during Plasma Treatment of Brines

Plasma has been proposed as an alternative strategy to treat organic contaminants in brines. Chemical degradation in these systems is expected to be partially driven by halogen oxidants, which have been detected in halide-containing solutions exposed to plasma. In this study, we characterized specific mechanisms involving the formation and reactions of halogen oxidants during plasma treatment. Here, we first demonstrated that addition of halides accelerated the degradation of a probe compound known to react quickly with halogen oxidants (i.e., para -hydroxybenzoate) but did not affect the degradation of a less reactive probe compound (i.e., benzoate). This effect was attributed to the degradation of para-hydroxybenzoate by hypohalous acids, which were produced via a mechanism involving halogen radicals as intermediates. We applied this mechanistic insight to investigate the impact of constituents in brines on reactions driven by halogen oxidants during plasma treatment. Bromide, which is expected to occur alongside chloride in brines, was required to enable halogen oxidant formation, consistent with the generation of halogen radicals from the oxidation of halides by hydroxyl radical. Other constituents typically present in brines (i.e., carbonates, organic matter) slowed the degradation of organic compounds, consistent with their ability to scavenge species involved during plasma treatment.

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

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (˙OH), singlet molecular oxygen ( 1 O 2 *), and triplet excited states of organic compounds ( 3 C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase ˙OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with ˙OH, 1 O 2 *, and 3 C* in cloud droplets and aerosol liquid water. Here, we investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Further, our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

09 BIOMASS FUELS↗
DOE OSTI2024

Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene

Organic molecules in the environment oxidatively degrade by a variety of free radical, microbial, and biogeochemical pathways. A significant pathway is heterogeneous autoxidation, in which degradation occurs via a network of carbon and oxygen centered free radicals. Recently, we found evidence for a new heterogeneous autoxidation mechanism of squalene that is initiated by hydroxyl (OH) radical addition to a carbon–carbon double bond and apparently propagated through pathways involving Criegee Intermediates (CI) produced from β-hydroxy peroxy radicals (β-OH-RO 2 •). It remains unclear, however, exactly how CI are formed from β-OH-RO 2 •, which could occur by a unimolecular or bimolecular pathway. Combining kinetic models and multiphase OH oxidation measurements of squalene, we evaluate the kinetic viability of three mechanistic scenarios. Scenario 1 assumes that CI are formed by the unimolecular bond scission of β-OH-RO 2 •, whereas Scenarios 2 and 3 test bimolecular pathways of β-OH-RO 2 • to yield CI. Scenario 1 best replicates the entire experimental data set, which includes effective uptake coefficients vs [OH] as well as the formation kinetics of the major products (i.e., aldehydes and secondary ozonides). Finally, although the unimolecular pathway appears to be kinetically viable, future high-level theory is needed to fully explain the mechanistic relationship between CI and β-OH-RO 2 • in the condensed phase.

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

Scale-Up of a Two-Stage Cu-Catalyzed Alkaline-Oxidative Pretreatment of Hybrid Poplar

A two-stage alkaline-oxidative pretreatment of hybrid poplar was investigated at scale (20 L reactor volume) with the goals of understanding how reaction conditions as well as interstage mechanical refining impact downstream process responses. The pretreatment comprises a first stage of alkaline delignification (alkaline pre-extraction) followed by a second delignification stage employing Cu-catalyzed alkaline hydrogen peroxide with supplemental O 2 (O 2 -enhanced Cu-AHP). Increasing pre-extraction severity (i.e., temperature and alkali loading) and pre-treatment oxidation (increasing H 2 O 2 loading) were found to increase mass and lignin solubilization in each stage. Lignin recovered from the first stage was subjected to oxidative depolymerization and led to aromatic monomer yields as high as 23.0% by mass. As a result, lignins recovered from the second stage Cu-AHP pretreatment liquors were shown to exhibit aliphatic hydroxyl contents more than six-fold higher than for a typical hardwood kraft lignin, indicating these lignins could serve as a biobased polyol for a range of polyurethane applications.

09 BIOMASS FUELS↗
DOE OSTI2025

Structurally Driven Selective Adsorption of Hydrocarbons by Metal Substitution in Isostructural Rare-Earth Metal–Organic Frameworks

The design and realization of highly selective nanoporous materials are necessary to target critical separations across industries. By leveraging pore size, pore shape, and linker functionalization, the design of nanoporous solid adsorbents will enable the rapid production of energy efficient separation materials for high-value gas mixtures. This study uses a combination of modeling, synthesis, and gas adsorption testing to investigate a new class of small-pore isostructural rare-earth (RE) 2,5-dihydroxyterephthalic acid (DOBDC) metal–organic frameworks (MOFs) (RE: Pr-, Gd-, Er-, Yb; DOBDC = 2,5-dihydroxyterephthalic acid) and their adsorption selectivity for acetylene/ethylene mixtures. Density functional theory simulations identified that selective binding of acetylene over ethylene in the Gd-, Er-, and Yb-DOBDC MOFs was due to hydrogen-bonding between acetylene and the linker hydroxyl. Adsorption experiments validated the computational results by identifying mechanisms that control the acetylene/ethylene adsorption selectivity and high acetylene adsorption. Furthermore, dynamic column breakthrough experiments with the Gd-DOBDC MOF validated the simulations and indicated that ethylene can be separated from acetylene in a mixture containing 1 vol % acetylene and 39 vol % ethylene (balance argon). In conclusion, the results highlight the complexity of gas binding in functional porous materials and how combining modeling and experiment enables a fundamental understanding of gas–framework interactions that can be leveraged for the design of future separation materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Extraction, Characterization, and Stability Studies of Bistriazinyl-Derived Carboxylic Acids

Separation of An(III) and Ln(III) ions will benefit the recycling of used nuclear fuel (UNF). For this purpose, many ligands have been tested over the years, and several separation processes have been successfully demonstrated on the laboratory scale. Current research aims at the development of new ligands that are built only with carbon, hydrogen, oxygen, and nitrogen (CHON), as they can be incinerated completely without secondary waste production. Here, we tested a new class of water-soluble ligands, the bistriazinyl-octa-carboxylic acids. One member, in particular, 2,6-bis-[5,6-di(3,4-dicarboxyphenyl)-1,2,4- triazin-3-yl]-pyridine (BTPOA), was found to be suitable for the selective separation of Am(III) and Cm(III) ions from Ln(III) ions and may act as a CHON alternative to its sulfonated analogue (SO 3 -Ph-BTP). BTPOA exhibited good extraction results and a high selectivity for Am(III) over Eu(III) ions. This ligand’s complexation of metal ions was further studied using potentiometric spectroscopy, as well as time-resolved laser-induced spectroscopy with Cm(III) and Eu(III) in aqueous HClO 4 and HNO 3 media. Conditional stability constants of each formed species were determined. In the HClO 4 system, Cm(III) formed three species (1:1, 1:2, and 1:3) through the stepwise addition of a single BTPOA molecule. On the other hand, in HNO 3 , Cm(III) formed two 1:2 complexes and one 1:3 complex, while the stepwise formation of three species was observed for Eu(III). The stability constants are comparable to the values for SO 3 -Ph-BTP. The radiolytic behavior of BTPOA was also investigated using electron pulse irradiation measurements to determine absolute rate coefficients (k) under ambient temperature conditions for the reaction of BTPOA with typical UNF reprocessing radical radiolysis products the hydrated electron (e aq − , k = (1.60 ± 0.02) × 10 10 M −1 s −1 ), the hydrogen atom (H • , k = (2.17 ± 0.03) × 10 9 M −1 s −1 ), and hydroxyl ( • OH, k = (6.95 ± 0.06) × 10 9 M −1 s −1 ) and nitrate (NO 3 • , k = (0.37 ± 0.02) × 10 7 M −1 s−1) radicals. These rate coefficients indicate that the radiolytic longevity of BTPOA should increase with HNO 3 concentration, owing to the consumption of e aq − /H • , by nitrate anions, and the replacement of • OH by the less reactive NO 3 • .

Diaz Gomez, Laura [Forschungszentrum Juelich (Germ↗