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At least 145 records · Page 8

All sources NASA NTRS DOE OSTI

DOE OSTI2026

Tabulated data for Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. We demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents. This is the tabulated data for the paper

biorefining↗

DOE OSTI2026

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

biorefining↗

DOE OSTI2025

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. Here, we demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

09 BIOMASS FUELS↗

DOE OSTI2025

Analysis of semivolatile organics in liquid radioactive residue using sorptive stir bar and solvent back-extraction

Current methods for semivolatiles analysis in radioactive samples can produce large volumes of radioactive solvent residue. A method utilizing stir-bar sorptive extraction has been explored in this work for its applicability to radioactive waste samples. This low solvent analytical method may accelerate remediation, minimize hazardous solvent waste, and reduce exposure risk to workers. Organic compounds (polyaromatic hydrocarbons, chlorinated aromatics, and phenolic compounds) were chosen as surrogates for common Liquid Waste System (LWS) contaminants at Savannah River Site (Aiken, SC). Stir-bar extraction parameters (extraction time, matrix modification, and effective pH range) and solvent back extraction parameters (solvent type, volume, and extraction time) were optimized experimentally for the chosen compounds. Affinity of the stir-bar extraction polymer to radionuclides Cs-137 and Am-241 was observed to determine radionuclide concentration effects. The stir-bar method achieved mean recovery of 100 ± 0.7% (1σ), relative to 114 ± 7% using solvent extraction, while reducing weekly method hands-on time by 93.4% and solvent volume consumption by 99.3%. Sensitivity was improved by 378% in simulated tank waste and 278% in real-world LWS matrix, relative to solvent extraction. This work has produced a safe and optimized method for the low solvent analysis of organics in legacy radioactive tank waste by stir-bar sorptive extraction.

GC-MS↗

NASA NTRS1956

Development of Craze and Impact Resistance in Glazing Plastics by Multiaxial Stretching

The loss of strength of cast polymethyl methacrylate plastic as a result of crazing is of considerable importance to the aircraft industry. Because of the critical need for basic information on the nature of crazing and the effects of various treatments and environmental conditions on its incidence and magnitude, an investigation of this phenomenon was undertaken. The following factors were examined: (1) the effect of stress-solvent crazing on tensile strength of polymethyl methacrylate; (2) the critical stress and strain for onset of crazing at various temperatures; (3) the effect of molecular weight on crazing; and (4) the effect of multiaxial stretching on crazing of polymethyl methacrylate and other acrylic glazing materials.

Kline, G M↗

DOE OSTI2024

Efficient and Robust Dynamic Crosslinking for Compatibilizing Immiscible Mixed Plastics through In Situ Generated Singlet Nitrenes

Abstract Creating a sustainable economy for plastics demands the exploration of new strategies for efficient management of mixed plastic waste. The inherent incompatibility of different plastics poses a major challenge in plastic mechanical recycling, resulting in phase‐separated materials with inferior mechanical properties. Here, this study presents a robust and efficient dynamic crosslinking chemistry that effectively compatibilizes mixed plastics. Composed of aromatic sulfonyl azides, the dynamic crosslinker shows high thermal stability and generates singlet nitrene species in situ during solvent‐free melt‐extrusion, effectively promoting C─H insertion across diverse plastics. This new method demonstrates successful compatibilization of binary polymer blends and model mixed plastics, enhancing mechanical performance and improving phase morphology. It holds promise for managing mixed plastic waste, supporting a more sustainable lifecycle for plastics.

Chemistry↗

DOE OSTI2025

Developing aqueous solubilizing agents as an alternative to solvent extraction

Here, advancing separations science is important for the entire field of chemistry. One partitioning technique that would benefit from improvement is solvent extraction. Despite its effective and widespread use, the method suffers from some problems: generation of flammable organic waste, lengthy process times, and safety concerns associated with contacting organic solvents with acidic aqueous solutions. We developed an alternative separation method inspired by solvent extraction that side-steps those issues. Toward this end, we identified that the functionality of an extractant (an agent used in solvent extraction to pull analytes from the aqueous phase into the organic phase) would change if it was modified for water solubility. In this alternative scenario, the extractant transforms into an “aqueous solubilizing agent.” We discovered that adding this aqueous solubilizing agent alongside a precipitating agent caused the contaminants to precipitate, but not the analyte. This separation concept was demonstrated within the bounds of one of the most difficult partitioning problems, separating minor actinides (Am 3+ ) from lanthanides (Ln 3+ ). We discovered that the (HSO 3 Ph) 4 BTP (aq) aqueous solubilizing agent prevented Am 3+ (aq) from precipitating with Ln 3+ (aq) when f-element precipitating agents (NaF (aq) or HF (aq) ) were added. This separation boasts impressive Am 3+ (aq) recovery yield (90 ± 2 %), near quantitative Ln 3+ (aq) removal, and high separation factors [>3000, Am 3+ (aq) vs. Nd 3+ (aq) ]. It seems likely – given the large number of candidate extractants that could be modified for aqueous solubility and the numerous combinations of existing solubilizing and precipitating agents – that this alternative approach could be used broadly in place of solvent extraction and solve other important separation problems.

(HSO3Ph)4BTP(aq)↗

NASA NTRS1993

Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

Benjamin, Ilan↗

NASA NTRS1975

Effect of polymer properties and adherend surfaces on adhesion

The surface properties associated with good adhesive joints were evaluated in terms of application of adhesive bonding in aerospace technology. The physical and chemical nature was determined of Ti and Al adherend surfaces after various surface treatments, and the effects on fracture surfaces of high temperature aging, and variations in amide, anhydride, and solvent during polymer synthesis. The effects were characterized of (1) high temperature during shear strength testing, (2) fiber-reinforced composites as adherends, (3) acid/base nature of adherends, (4) aluminum powder adhesive filler, and (5) bonding pressure.

Dwight, D. W.↗

DOE OSTI2026

Synergistic Solvent-Surface Interactions Enable Alkyne Semihydrogenation at Palladium

Enabling higher yield and better selectivity for fine-chemical synthesis through heterogeneous catalysis is intricately linked to the interplay of active sites, reaction conditions, and mass transfer influence provided by the catalyst. Alkyne semihydrogenation is ubiquitous in the production of bulk chemicals in the pharmaceutical, polymer, or fine-chemical industries, but product selectivity remains a major challenge. Here, in this study, we demonstrate that the design of catalysts encompassing nickel (Ni) foams as contiguous monolith supports, decorated with ultralow loading of Pd/PdO x nanoparticles on a carbonized polydopamine interface and tuned with a thin layer of Al 2 O 3 , in conjunction with an optimized reaction environment leads to highly selective alkyne semihydrogenation. The reactions demonstrate good functional group tolerance and applicability to flow reactor systems. Combined computational and experimental studies are presented to describe the synergistic effect between the solvent-surface interaction and the degree of Pd surface reduction that are necessary to promote this selectivity. The system highlights the opportunity for catalyst-solvent codesign as a benign alternative to more complex reactants featuring extrinsic poisons or less-favored dopants.

atomic layer deposition↗

DOE OSTI2025

Indium Tin-Doped Oxide Interactions with Solvent Radiolysis Products

Transparent conductive oxides (TCOs), such as indium tin-doped oxide (ITO), are ubiquitous as components of electronics and are ideal electrode substrates for catalysis, energy transformation reactions, and energy storage applications. Recently, researchers have recognized their effectiveness as electrode materials for manipulating actinide oxidation states in solution. Despite their popularity as electrode materials, prior studies focused extensively on the direct radiolysis of TCO materials in air and rarely examined these effects within a solution, limiting our fundamental understanding of the interactions between solvent radiolysis products and these substrates in high radiation environments. Here, in this study, we characterize the effects of solvent radiolysis products—arising from the gamma irradiation of water, aqueous nitric acid solutions, and n-dodecane—on the composition, surface speciation, and band structure of ITO thin films on a glass substrate as a function of absorbed dose using UV-visible spectroscopy, scanning electron microscopy, photoelectrochemistry, and X-ray photoelectron spectroscopy. Our work demonstrates that mesoporous thin film electrodes of ITO exposed to gamma radiation in each solvent accumulate defects and exhibit solvent and dose dependent changes to their surface and interfacial properties. These electrodes maintain their electrochemical function and improve their photoelectrochemical performance up to at least 100 kGy of accumulated gamma dose, confirming their utility in solvents exposed to ionizing radiation fields.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Reactive CO 2 capture and mineralization of magnesium hydroxide to produce hydromagnesite with inherent solvent regeneration

Valorization of multiple low value streams including CO 2 emissions and magnesium-hydroxide bearing mine tailings to produce magnesium carbonate through reactive CO 2 capture and mineralization provides a less explored opportunity to manage several gigatons of CO 2 emissions. To resolve the feasibility of converting magnesium hydroxide to magnesium carbonate through reactive CO 2 capture and mineralization, CO 2 capture solvents such as sodium glycinate are harnessed to capture CO 2 and react directly with Mg(OH) 2 to produce hydromagnesite (Mg 5 [(CO 3 )4(OH) 2 ]·4H 2 O). This approach eliminates the energy-intensive step of producing high purity CO 2 associated with regenerating the solvent, and redissolving CO 2 to produce magnesium carbonate. Interestingly, while temperatures below 50 °C facilitate CO 2 capture, the mineralization kinetics are slow. However, at higher temperatures, accelerated carbon mineralization is favored by the faster kinetics of Mg(OH) 2 dissolution and precipitation of magnesium carbonate. Reacting Mg(OH) 2 at 90 °C with 15 wt% solids in the presence of 2.5 M sodium glycinate after 3 hours under well-stirred conditions results in an extent of carbon mineralization of 75.5%. The theoretical maximum extent of carbon mineralization when hydromagnesite is formed is 80%. Pre-loading CO 2 on the solvent is also an effective approach to ensure that sufficient CO2 is available for reactive CO 2 capture and mineralization, particularly when dilute CO 2 and N 2 mixtures are used. Higher extents of carbon mineralization are associated with an increase in the particle size and a reduction in the cumulative pore volume. These insights unlock the feasibility of harnessing reactive CO 2 capture and mineralization as a pathway to convert magnesium-hydroxide bearing resources into industrially relevant magnesium carbonate products.

Reactive CO2↗

DOE OSTI2025

Methods for Carbon Mass Closure in Polyolefin Hydrocracking

Heterogeneous catalytic hydrocracking of polyolefins is a promising approach for the processing of postconsumer plastics, but product quantification methods remain inconsistent across the literature. In systems that generate a large fraction of vapor-phase products, typical product capture methods can result in large carbon balance deficits, exceeding 50%, compromising reported yields and selectivities. Here, we identify the major sources of product loss and develop enhanced capture methods to improve the quantification accuracy. Seven supplemental techniques were evaluated, targeting either increased vapor recovery (by increasing the volatility or system volume) or enhanced retention in the liquid phase (by decreasing volatility). Among these, a flow collection approach using a continuous helium sweep and downstream gas sampling bag capture yielded the highest recovery, achieving a 96 ± 9.2% carbon balance closure. We show that the efficacy of these methods is strongly dependent on product distribution. In general, solvent addition was most effective when condensable species dominate the product distribution, while flow collection was preferred when both condensable species and light gases are present in high concentrations. These results highlight the need for method-specific workup strategies and demonstrate that no single protocol is universally optimal. We provide general guidelines for selecting and implementing robust product capture techniques, enabling accurate yield and selectivity determinations in polyolefin hydrocracking systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer

The rate of charge transfer within a discrete donor–acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, N, while holding geometry, coupling, and driving forces constant. The [Ru(L) 3−N (OH) N ] 2+ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-tert-butyl-6-(1-methyl-1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV 2+ ), the transient Ru(III) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (λ m ) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Functionalized benzylamines from commercial kraft lignin

Benzylamines are key intermediates in pharmaceuticals, agrochemicals, and polymers, but their conventional production relies on benzyl chloride - a petroleum-derived compound with high toxicity and energy demands. Lignin, accounting for up to 30% of plant biomass, is the largest renewable source of aromatic carbon on Earth. However, its highly complex and recalcitrant structure poses a major barrier to efficient conversion into high-value chemicals. Here, in this study, we developed a catalytic approach to convert commercial kraft lignin into phenolic benzylamines through selective depolymerization and subsequent functionalization. We systematically evaluated the effects of three alcohol solvents, formic acid (FA), and a ruthenium-on‑carbon (Ru/C) catalyst on monophenol yield and selectivity. Up to 6.5 wt% monophenol yield was achieved using methanol (MeOH), FA, and Ru/C at 300 °C for 2 h. Quantum thermodynamic simulations based on the COSMO-RS model confirmed the superior solvation and reactivity of the MeOH + FA system, rationalizing observed product yield. The purified monophenolic products, primarily guaiacol and alkyl guaiacols, were then converted into functionalized benzylamines with >90% yield via a multicomponent Mannich reaction under mild conditions. Techno economic analysis (TEA) and life cycle assessment (LCA) underscore the importance of improving lignin depolymerization yields and expanding biorefinery scale. Solvent-only configurations outperform other options in both cost and emissions, with the methanol-only case performing the best ($\$$105 /kg and 26 kg CO 2e /kg) at a large-scale facility. This study establishes a scalable, bio-based pathway for producing benzylamines from commercial kraft lignin, advancing lignin valorization and offering a sustainable alternative to produce petrochemical-based benzylamines.

Catalytic reduction↗

DOE OSTI2024

Modeling hyperbranched polymer formation via ATRP using dissipative particle dynamics

Hyperbranched polymers (HBPs) offer distinguishing, advantageous properties that arise from their distinctive complex topology. One of the effective approaches to the synthesis of hyperbranched structures involves the use of a branching initiator (inibramer) that is activated only after incorporation into a polymer chain. There remain, however, challenges in determining and characterizing the structures of the synthesized HBPs. Dissipative particle dynamics (DPD) was used to probe the effects of inibramer concentration, solvent concentration, and inibramer reactivity on the kinetics, molecular weight, and dispersity of HBPs. Additionally, DPD allows for direct observation of branched structures, which was not possible in previously reported Monte Carlo type simulations. It was found that higher inibramer concentrations led to faster monomer consumption while forming more dendritic structures with fewer defects. Additionally, high dispersities characteristic of HBP systems were found to originate from asymmetric propagation rates between inibramer-inibramer and inibramer-monomer reactions.

Biswas, Santidan↗

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 OSTI2026

Transition from Vehicular to Structural Ionic Transport in Electrified Alkali Aqueous Solutions

A molecular understanding of the solvation and dynamics of ions under static electric fields is crucial for modelling a wide range of natural and technological processes. Yet, traditional simulation methods suffer from a trade-off that has to be made between accuracy and statistical convergence. To bridge this gap, herein we extend our recently introduced Perturbed Neural Network Potential Molecular Dynamics (PNNP MD) approach to investigate the solvation structures and ionic transport mechanisms of electrified alkali cationic solutions. We obtain ionic conductivities for Li+, Na+ and Cs+ from the field dependence of the ionic current density in good agreement with experiment. Surprisingly, the migration mechanism is found to be strikingly different for the three ions despite their similar ionic conductivities. While Li+ conducts predominantly through vehicular migration of a stable 4-fold coordinated ion at all field strengths, Cs+ conducts strictly through a structural diffusion mechanism, where 9-12 transient first shell water coordination bonds are broken and renewed. Notably, aqueous Na+ emerges as a “Goldilocks” ion: its ion-water interactions are strong enough to maintain distinct 5-6 fold coordination shells at zero field (unlike Cs+) yet labile enough to be strongly perturbed by electric fields (unlike Li+). As a consequence, we observe an electric field-induced transition from vehicular to structural ionic transport for Na+ that is accompanied by a marked increase in the ionic current density. Our results imply that the conductance mechanism of ions with moderate ion-solvent interactions can be effectively tuned by external electric fields.

Joll, Kit↗