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At least 379 records · Page 21

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NASA NTRS2017

Synthesis of Amino Acid Precursors with Organic Solids in Planetesimals with Liquid Water

Amino acids are important ingredients of life that would have been delivered to Earth by extraterrestrial sources, e.g., comets and meteorites. Amino acids are found in aqueously altered carbonaceous chondrites in good part in the form of precursors that release amino acids after acid hydrolysis. Meanwhile, most of the organic carbon (greater than 70 weight %) in carbonaceous chondrites exists in the form of solvent insoluble organic matter (IOM) with complex macromolecular structures. Complex macromolecular organic matter can be produced by either photolysis of interstellar ices or aqueous chemistry in planetesimals. We focused on the synthesis of amino acids during aqueous alteration, and demonstrated one-pot synthesis of a complex suite of amino acids simultaneously with IOM via hydrothermal experiments simulating the aqueous processing

Kebukawa, Y↗

DOE OSTI2026

Cooperative Lanthanide Solvation in an Ionic Liquid for Critical Materials Separations

Effectively separating critical materials, including intra-lanthanide separations, is crucial for meeting growing application demands. Liquid–liquid extraction (LLE) is the industry standard for lanthanide separations, where the selectivity can depend on small changes in metal coordination. In this work, we investigate representative lanthanide Eu coordination with a neutral malonamide extractant in an imidazolium bistriflimide ionic liquid (IL) solvent. Through systematic titrations of the water and extractant and under extraction conditions, we observe surprising cooperative Eu solvation with the IL anion and extractant. Time-resolved fluorescence spectroscopy measurements show strong extractant coordination in water-saturated IL. Lifetime measurements show no water coordination, and extended X-ray fine structure spectroscopy data provide a coordination number of 10. Molecular dynamics simulations confirm this coordination number and reveal IL anion coordination in the final Eu complex, even though it is ordinarily a significantly weaker ligand compared to water. The lack of water in the final extracted complex and IL anion coordination potentially explain the increased extraction in LLE systems using ILs, as evidenced by higher distribution ratios for cation exchange extraction, despite the energetic cost of cation transfer to the aqueous phase. These results highlight the opportunities for tuning metal coordination to drive extraction in unique solvent systems.

Carr, Amanda J.↗

DOE OSTI2021

Application of Sequential Design of Experiments (SDoE) to Large Pilot-Scale Solvent-Based CO2 Capture Process at Technology Centre Mongstad (TCM)

The United States Department of Energy’s Carbon Capture Simulation for Industry Impact (CCSI2) program has developed a framework for sequential design of experiments (SDoE) that aims to maximize knowledge gained from budget- and schedule-limited pilot scale testing. SDoE was applied to the planning and execution of campaigns for testing CO2 capture systems at pilot-scale in order to optimally allocate resources available for the testing. In this methodology, a stochastic process model is developed by quantifying the parametric uncertainty in submodels of interest; for a solvent-based CO2 capture system, these may include physical properties and equipment performance submodels (e.g., mass transfer, interfacial area). This uncertainty is propagated through the full process model, over variable operating conditions, for estimating the resulting uncertainty in key model outputs (e.g., percentage of CO2 capture, solvent regeneration energy requirement). In developing a data collection plan, the predicted output uncertainty is incorporated into an algorithm that seeks simultaneously to select process operating conditions for which the predicted uncertainty is relatively high and to ensure that the entire space of operation is well represented. This test plan is then used to guide operation of the pilot plant at varying steady-state conditions, with resulting process data incorporated into the existing model using Bayesian inference to refine parameter distributions. The updated stochastic model, with reduced parametric uncertainty from data collected, is then used to guide additional data collection, thus the sequential nature of the experimental design. The SDoE process was implemented at the pilot test unit (12 MWe in scale) at Norway’s Technology Centre Mongstad (TCM) in a summer 2018 test campaign with aqueous monoethanolamine (MEA). During the test campaign, the varied operating conditions included the flowrates of circulated solvent, flue gas, and reboiler steam and the CO2 concentration in the flue gas. The process data were used to update probability distributions of mass transfer and interfacial area parameters of a stochastic process model developed by the CCSI2 team. Two iterations of the SDoE process were executed, resulting in the uncertainty in model predicted CO2 capture percentage decreasing by an average of 58.0 ± 4.7% over the full input space of interest. This work demonstrates the potential of the SDoE process for model refinement through reduction in process model parametric uncertainty, and ultimately risk in scale-up, in CO2 capture technology performance.

carbon capture↗

DOE OSTI2026

Mechanistic mass transfer in hollow fiber membrane solvent extraction for bio-based isobutanol

Membrane solvent extraction (MSE) has emerged as a promising method for selectively recovering bioproducts from complex aqueous streams. Bio-isobutanol, a next-generation feedstock for biofuel, remains challenging to recover because of its low concentration and the presence of inhibitory substances. This study explores the potential of hollow fiber (HF) MSE for bio-isobutanol recovery and systematically examines the coupled effects of fiber packing, shell-side flow dynamics, and aqueous chemistry on performance. A resistance-in-series model is applied to understand mass transfer in the HF MSE modules, quantify local resistances, and validate overall performance. The results show that increasing the fiber packing provides a larger interfacial area but induces poor flow distribution and channeling, hindering effective isobutanol transport. Meanwhile, increasing the shell-side velocity improves isobutanol recovery due to reductions in the boundary layer thickness. The presence of salts, added to mimic fermentation broth, increases the partition coefficient through salting-out effects, further improving isobutanol flux. A modified correlation for the shell-side mass transfer coefficient (k s,ϕ+v ), integrating geometric and hydrodynamic effects, was developed and validated. The proposed model achieves highly predictive accuracy (r 2 = 0.9808) across a wide range of conditions, outperforming previous models. The findings provide mechanistic insight into the interaction of geometric packing, hydrodynamics, and chemistry in governing mass transfer in HF MSE. Overall, this work demonstrates the potential of HF MSE for efficient bio-isobutanol recovery and also provides practical guidelines on critical factors (packing fraction, partition coefficient, and shell-side velocity), aiding in the design and scaling of MSE systems for resource recovery.

Aqueous chemistry↗

DOE OSTI2025

X-ray absorption spectroscopy of lanmodulin-derived peptides bound to rare earth elements

A sustainable and robust supply chain of rare earth elements (REEs) is necessary to meet our consumer, national security and clean energy goals. However, current intra-REE separation technologies (e.g. solvent extraction) are costly and carry a heavy environmental burden. Therefore, the development of new aqueous based ligands that are selective for individual REEs will be integral in future REE production systems. To develop these ligands, an understanding of how ligand coordination structure relates to selectivity is imperative. We used X-ray absorption spectroscopy (XAS) to observe the local structure around four lanthanide (Ln) ions (La, Ce, Pr and Nd) complexed by water and several relevant chelating ligands [lanmodulin EF-hand 1 peptides (LanM1), ethylenediaminetetraacetic acid (EDTA), aminotris(methylenephosphonic acid) (ATMP) and citric acid]. To collect these liquid-phase XAS spectra, we developed a new flow cell that prevents bubble interference and beam damage to the samples. In the X-ray absorption near-edge structure (XANES), we observed energy shifts in the white line, white line broadening and differences in the white line intensity of different Ln–ligand complexes between ligands. In the extended X-ray absorption fine structure (EXAFS), we distinguished differences in peak intensity and distance between coordinating ligands. Differences in the local coordination structure between Ln–LanM1 peptide complexes were more subtle compared with the other ligands (La–water, La–EDTA, La–ATMP and La–citric acid complexes). Further XANES and EXAFS studies, in combination with modelling and other techniques, could greatly improve our structural knowledge of how these aqueous ligands bind Ln ions and how they can be used to design more selective ligands for more efficient and sustainable REE separations.

EDTA↗

DOE OSTI2020

Ternary Phase Diagram of Water/Bio-Oil/Organic Solvent for Bio-Oil Fractionation

Separating bio-oil by fractionation with different chemical composition is a critical step to refine these oils and obtain high value products. Cold-water precipitation of pyrolytic lignin from bio-oil is the most common approach used. However, the obtained aqueous phase from this method still contain phenols, is diluted and difficult to use. In this study, the use of liquid-liquid extraction with different solvents (1-butanol, ethyl acetate, 1-octanol, dichloromethane, toluene, and hexane) for the separation of targeted molecules (lignin oligomers, sugars, acetic acid) is explored. Ternary phase diagrams for the organic solvent/water/bio-oil are reported. The partition coefficient of compounds of interest (both light and heavy fraction) is reported for the liquid-liquid equilibrium zone. When using butanol as solvent, the highest separation factor of total phenols over total sugars was observed. Furthermore, our results provide information to design L-L separation units with the capacity to selectively recover targeted molecules from pyrolysis oils.

09 BIOMASS FUELS↗

DOE OSTI2025

Vibroacoustic Process Monitoring of 5-Stage Centrifugal Contactors

Vibroacoustic monitoring was investigated to aid in informing process operators with parameters regarding aqueous separation techniques. These techniques have a wide range of applications including nuclear fuel reprocessing. A small-scale solvent extraction system was set up with five magnetic drive contactors and two piston pumps to collect realistic operation. Vibration sensors were placed on three of the contactors and both pumps, and a microphone was placed near the system. Contactor rotational speed and pump flow rate were varied with known values to compare against measured vibroacoustic signatures. Spectral analysis allowed for the determination of contactor rotational speed and the ratio of organic to aqueous flow rate, an important parameter for ensuring optimal extraction. Vibration metrics such as kurtosis and crest factor provided additional details regarding individual rotational speeds and have potential in examination of faults for predictive maintenance. Overall, results indicate the capability of vibroacoustic monitoring to improve operator awareness and process outcomes.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Oxadiazole derivatives as stable anolytes for >3 V non-aqueous redox flow battery

Effective utilization of energy from renewable sources such as wind and solar requires the development of long duration energy storage (LDES) systems that can accommodate intermittent energy accrual. One option under investigation is the use of a redox flow battery (RFB). A significant amount of work has explored aqueous RFB systems with a variety of inorganic and organic carriers. However, moving to a nonaqueous solvent such as acetonitrile (MeCN) for RFB provides a much larger electrochemical window, which could lead to increased energy density if properly utilized. Here, in this work, we investigate a series of 2,5-diphenyl-1,3,4-oxadiazole (DiPhenOx) derivatives as anolytes for a redox flow battery. DiPhenOx has a low voltage redox event that, while reversible by cyclic voltammetry, was determined to be irreversible during bulk electrolysis. To improve cycling performance, we introduced various ester and cyano groups to the phenyl rings of DiPhenOx using molecular engineering. We characterized these derivatives spectroscopically and electrochemically to assess their feasibility for flow battery applications. The ester derivatives with the best cycling performance were tested in a flow cell vs. ferrocene, 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) and thianthrene, which resulted in ~2 V, ~3 V and ~3 V redox flow batteries, respectively.

25 ENERGY STORAGE↗

DOE OSTI2023

Acoustic Signatures of Solvent Extraction Processes [Poster and Paper]

Data from four low-frequency acoustic sensors were used to investigate potential acoustic characteristics of centrifugal contactor, aqueous pump, and organic pump activity during the experiment. Three of the four sensors were Gem Infrasound Loggers (Anderson, et al. 2018) with serial numbers 190, 189, and 188. They will hereafter be referred to as GEM190, GEM189, and GEM188, respectively. The fourth acoustic sensor was a Raspberry Shake & Boom (Raspberry Shake 2017), which will hereafter be referred to as the RS&B. All four sensors record audio at a sampling rate of 100 Hz, allowing analysis of signals with characteristic frequencies up to 50 Hz.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Influence of Metal Ion Complexation on the Radiolytic Longevity of Butyramide Extractants under Direct Dissolution Process Conditions

The direct dissolution of voloxidized used nuclear fuel (UNF) into an organic solution–comprised of diluent and specialized extractants–poses a promising alternative to the traditional liquid–liquid solvent extraction approach to reprocessing UNF. However, moving to direct dissolution removes the presence of a concentrated nitric acid aqueous phase, which has been shown to significantly influence the radiolytic longevity of extractants in conventional extraction flowsheets. Given the limited knowledge of radiation effects under direct dissolution conditions, here we present a time-resolved and dose-accumulation study on the impact of direct dissolution conditions on the radiolytic longevity of two candidate butyramide extractants, N,N-di(2-ethylhexyl) butyramide (DEHBA) and N,N-di(2-ethylhexyl)isobutyramide (DEHiBA), in pre-equilibrated n-dodecane solvent in the presence and absence of process-relevant metal ions, specifically, uranium and rhenium. Loss G(DEHBA) and G(DEHiBA) values were found to be comparable to each other, with an average of 0.37 ± 0.02 μmol J –1 , and to previous data from the γ irradiation of DEHBA and DEHiBA under conventional solvent extraction conditions. Rhenium, and by extension technetium, extraction had a modest decrease (~10%) in the overall radiolytic stability of DEHiBA only, despite >2× observed increases in chemical kinetic reactivity of the corresponding complexes with the n-dodecane radical cation. Uranium loading, on the other hand, significantly improved the lifetime of both ligands (>30%) under γ irradiation, with a greater stabilization observed for DEHBA over DEHiBA. The observed radioprotective effect afforded by uranium loading is fortuitous for the longevity of direct dissolution solvent.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

NASA NTRS1995

Evaluation of control parameters for Spray-In-Air (SIA) aqueous cleaning for shuttle RSRM hardware

HD-2 grease is deliberately applied to Shuttle Redesigned Solid Rocket Motor (RSRM) D6AC steel hardware parts as a temporary protective coating for storage and shipping. This HD-2 grease is the most common form of surface contamination on RSRM hardware and must be removed prior to subsequent surface treatment. Failure to achieve an acceptable level of cleanliness (HD-2 calcium grease removal) is a common cause of defect incidence. Common failures from ineffective cleaning include poor adhesion of surface coatings, reduced bond performance of structural adhesives, and failure to pass cleanliness inspection standards. The RSRM hardware is currently cleaned and refurbished using methyl chloroform (1,1,1-trichloroethane). This chlorinated solvent is mandated for elimination due to its ozone depleting characteristics. This report describes an experimental study of an aqueous cleaning system (which uses Brulin 815 GD) as a replacement for methyl chloroform. Evaluation of process control parameters for this cleaner are discussed as well as cleaning mechanisms for a spray-in-air process.

Davis, S. J.↗

DOE OSTI2025

Probing the influence of ion-pairing on ligand-field excited-state dynamics

Exploration of the photophysical and photochemical properties of transition metal complexes has driven ground-breaking advancements in solar energy conversion technologies, including photoredox catalysis. While significant research has been devoted to understanding excited state properties of second- and third-row transition metal complexes, earth-abundant first-row metal complexes have received comparatively little attention in this context until very recently. In particular, the role of ion-pairing – which has been identified as a potentially significant factor for Ir(III)-based photosensitizers – has not been examined with regard to its influence on the ligand-field excited states that dominate much of first-row photophysics. A key challenge in studying ion-pair interactions lies in quantifying the extent and nature of ion-pairing, particularly in non-aqueous media where the vast majority of photophysical studies are performed. Cobalt(III) polypyridyl complexes provide an attractive platform to address such questions due to their demonstrated potential for applications in photoredox catalysis involving ligand-field excited states. In the present study, we prepared a cobalt(III) polypyridyl complex, [Co(4,4′-OMebpy) 3 ](BAr F 4 ) 3 (where 4,4′-OMebpy is 4,4′-dimethoxy-2,2′-bipyridine and BAr F 4 is tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) to probe ion-pairing in non-aqueous solutions. Specifically, analysis of data acquired from both variable-temperature diffusion ordered spectroscopy (DOSY) NMR and 1-D rotating-frame nuclear Overhauser effect (ROE) experiments allowed us to identify and differentiate between solvent-separated ion pairs in high-dielectric media and contact ion pairs in a low-dielectric solvent. Time-resolved absorption spectroscopy was then used to measure ground-state recovery dynamics under these varying conditions of ion-pairing, the results of which revealed an increase in excited-state lifetime for contact ion-pairs that we suggest arises from a reduction in outer-sphere reorganization energy relative to conditions which favored solvent-separated ion pairs. We believe this study demonstrates that one can leverage broadly available NMR-based methods to understand ion-pairing in non-aqueous solutions, which in turn can provide a microscopic picture of intermolecular interactions that can impact the photophysical properties of transition metal-based chromophores.

Ghosh, Atanu [Michigan State University, East Lans↗

DOE OSTI2021

Nuclear quantum effects on the quasiparticle properties of the chloride anion aqueous solution within the GW approximation

Photoelectron spectroscopy experiments in ionic solutions reveal important electronic structure information, in which the interaction between hydrated ions and water solvent can be inferred. Based on many-body perturbation theory with GW approximation, we theoretically compute the quasiparticle electronic structure of chloride anion solution, which is modeled by path-integral abinitio molecular dynamics simulation by taking account the nuclear quantum effects (NQEs). The electronic levels of hydrated anion as well as water are determined and compared with the recent experimental photoelectron spectra. It is found that NQEs improve the agreement between theoretical prediction and experiment because NQEs effectively weaken the hybridization of the between the Cl – anion and water. Furthermore, our study indicates that NQEs plays a small but non-negligible role in predicting the electronic structure of the aqueous solvation of ions of the Hofmeister series.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Direct Extraction of Sodium Hydroxide by Calix[4]pyrrole-Based Ion-Pair Receptors

Here, described in this work, are calix[4]pyrrole-based ion-pair receptors, cis/trans-1 and cis/trans-2, designed for the extraction of sodium hydroxide. An X-ray diffraction analysis of a single crystal of the cis-1·NaOH isomer isolated from a mixture of cis/trans-1 revealed a unique dimeric supramolecular structure. An average dimer in toluene-d 8 solution was inferred on the basis of diffusion-ordered spectroscopy (DOSY). Support for the proposed stoichiometry came from density functional theory (DFT) calculations. The structural stability of the dimeric cis-1·NaOH complex in toluene solution was further confirmed by ab initio molecular dynamics (AIMD) simulation with explicit representation of solvent. Under conditions of liquid–liquid extraction (LLE), purified receptors cis- and trans-2 were both found to remove NaOH from a pH 11.01 aqueous source phase into toluene with extraction efficiencies (E%) of 50–60% when used equimolar to NaOH. However, in all cases, precipitation was observed. Complexities associated with precipitation could be avoided by immobilization of the receptors onto a chemically inert poly(styrene) resin by means of solvent impregnation. The use of solvent-impregnated resins (SIRs) eliminated precipitation in solution while retaining the extraction efficiency toward NaOH. This allowed both the pH and salinity of the alkaline source phase to be lowered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Additive‐Free Aqueous MXene Inks for Thermal Inkjet Printing on Textiles

Abstract Direct printing of functional inks onto flexible substrates allows for scalable fabrication of wearable electronics. However, existing ink formulations for inkjet printing require toxic solvents and additives, which make device fabrication more complex, limit substrate compatibility, and hinder device performance. Even water‐based carbon or metal nanoparticle inks require supplemental surfactants, binders, and cosolvents to produce jettable colloidal suspensions. Here, a general approach is demonstrated for formulating conductive inkjet printable, additive‐free aqueous Ti 3 C 2 T x MXene inks for direct printing on various substrates. The rheological properties of the MXene inks are tuned by controlling the Ti 3 C 2 T x flake size and concentration. Ti 3 C 2 T x ‐based electrical conduits and microsupercapacitors (MSCs) are printed on textile and paper substrates by optimizing the nozzle geometry for high‐resolution inkjet printing. The chemical stability and electrical properties of the printed devices are also studied after storing the devices for six months under ambient conditions. Current collector‐free, textile‐based MSCs show areal capacitance values up to 294 mF cm −2 (2 mV s −1 ) in poly(vinyl alcohol)/sulfuric acid gel electrolyte, surpassing reported printed MXene‐based MSCs and inkjet‐printed MSCs using other 2D nanomaterials. This work is an important step toward increasing the functional capacity of conductive inks and simplifying the fabrication of wearable textile‐based electronics.

Uzun, Simge↗

DOE OSTI2023

Probing Complex Chemical Processes at the Molecular Level with Vibrational Spectroscopy and X-ray Tools

Understanding the origins of structure and bonding at the molecular level in complex chemical systems spanning magnitudes in length and time is of paramount interest in physical chemistry. Here, we have coupled vibrational spectroscopy and X-ray based techniques with a series of microreactors and aerosol beams to tease out intricate and sometimes subtle interactions, such as hydrogen bonding, proton transfer, and noncovalent interactions. This allows for unraveling the self-assembly of arginine-oleic acid complexes in an aqueous solution and growth processes in a metal–organic framework. Terahertz and infrared spectroscopy provide an intimate view of the hydrogen-bond network and associated phase changes with temperature in neopentyl glycol. The hydrogen-bond network in aqueous glycerol aerosols and levels of protonation of nicotine in aqueous aerosols are visualized. Future directions in probing the hydrogen-bond networks in deep eutectic solvents and organic frameworks are described, and we suggest how X-ray scattering coupled to X-ray spectroscopy can offer insight into the reactivity of organic aerosols.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Understanding the Influence of Water-Soluble Compounds from Unpretreated Corn Stover Pellets on Enzymatic Hydrolysis of Cellulose

Aqueous extractives are minor and non-structural compounds in biomass that can be extracted using solvents, while contributing significantly to lignocellulose characteristics. Yet their roles in enzyme-mediated processing of lignocellulosic biomass remain elusive. Here, we examine the composition and features of extractives derived from untreated pelleted corn stover as well as their effects on enzymatic hydrolysis. Unlike the observations described in previous reports, we find that water extractable material improves the enzymatic hydrolysis of extractive-free stover by 67% with a glucose yield increase from 12% to 20% with 6 FPU cellulase per g glucan, whereas the enzyme activities are diminished when using microcrystalline cellulose as a substrate. The different behavior of corn stover and microcrystalline cellulose is likely attributed to the presence of lignin, which may interact with inhibitory compounds such as phenolics, mitigating the detrimental impacts of soluble inhibitors or insoluble lignin or both. These findings advance our fundamental understanding of the intrinsic behavior of extractives and help to optimize the schemes for efficient and cost-competitive enzymatic conversion of lignocellulose.

09 BIOMASS FUELS↗

DOE OSTI2025

Direct Extraction of Uranium-Lanthanide Oxides in Tributyl Phosphate

Abstract Direct extraction of used nuclear fuel (UNF) in an organic solution could be more efficient than the previous practice with aqueous solutions. However, the UNF would need to be treated via voloxidiation before being processed using solvent extraction. The voloxidation process can form oxide and/or nitrate compounds. This work investigated the dissolution of uranium/lanthanide oxides in 30 vol % TBP diluted in dodecane (pre-equilibrated with 4 M nitric acid) in a glass reactor with air sparging to ascertain the uranium/lanthanide oxide dissolution behavior prior to scaling the process. The uranium/lanthanide oxides were prepared by co-precipitating uranium/lanthanide nitrates with hydroxide and then calcined to form a mixed oxide. While the relative concentrations of the lanthanides are not representative of used nuclear fuel, the neodymium and erbium allowed ease of tracking dissolution with visible spectroscopy. Cerium was used as a surrogate for plutonium. The dissolution rate of the oxides was similar but incomplete. A miniscule amount of cerium, as cerium oxide, took several months to slowly dissolve; however, when co-precipitated with uranium and other lanthanides, a significant amount of cerium dissolved readily.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗