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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Elucidating the Influence of Metal Surface Composition on Organic Adsorbate Binding Using Active Particle Dynamics

The adsorption strengths of organic compounds on metal surfaces are sensitive to the metal composition, and they play a central role in many catalytic reactions, helping to control the coverage of the reactant and altering the overall reaction rate. While adsorption energies are straightforward to measure and calculate in vacuum and gas-phase environments, adsorption energetics can be dramatically altered by the presence of solvent in liquid-phase reactions. However, the effects of metal composition on binding strengths in a liquid environment are less well understood, primarily due to the difficulty of accurate in situ measurements of organic binding on metal surfaces in the liquid phase. Here, we utilize the motion of active particles in water to probe the adsorption energies of an organic adsorbate (furfural) on a range of metal surfaces (pure Pd, pure Pt, and four PdAu alloy compositions) to elucidate the effect of metal composition. Janus particles with catalytic caps of particular metal compositions all exhibited active motion resulting from consumption of H 2 O 2 ; adsorbate binding was inferred through the decrease in the velocity of active motion and was modeled by a Langmuir adsorption isotherm. The measured adsorption affinities were used to extract the adsorption enthalpy of furfural on the different metals. The Pd surface was found to bind furfural more strongly than the Pt surface by some 10 kJ/mol. Furthermore, the adsorption of furfural on the alloys was found to increase monotonically in magnitude with Pd content. As a result, the data reported herein aid the development of accurate understanding of organic adsorption in the presence of solvent and the role of the metal surface in tuning adsorption strengths to optimize catalytic processes in the liquid phase.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Spatiotemporal and Statistical Mapping of Transition Metal Equilibria in Alkaline Media

Transition metal dissolution and redeposition (D/R) kinetics in alkaline media play a critical role in various chemical and electrochemical processes. Competitive reaction kinetics between different transition metals can modulate individual metal behavior in these processes. To date, these phenomena have remained largely unmeasured, and even when captured, they are difficult to statistically characterize due to their dynamic nature, simultaneous occurrence, and spatially heterogeneous nature. Here, in this study, we develop a statistical analysis framework based on in situ and operando X-ray fluorescence microscopy (XFM) to investigate the relative D/R kinetics of multiple transition metals in alkaline media. By employing statistical analysis, we quantify the spatial distribution of D/R species and assess the rate at which the system reaches equilibrium under varying reaction conditions. We show that pH does not simply change the rate of dissolution and redeposition, but reorganizes the cross-element kinetic correlations among Ni, Fe, and Mn and accelerates the spatial equilibration of D/R events, as quantified through correlation analysis, reaction-rate estimation, probability function distributions, and texture-based monitoring statistics. Additionally, we demonstrate how modifying the solvent environment can influence D/R kinetics, providing a pathway for tuning materials synthesis and process optimization. Our study offers valuable insights into the complex interplay between different transition metals and provides a reliable statistical framework for spatial analysis of diverse imaging data sets, enabling deeper extraction of latent information across multiple modalities.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Uncovering the binding nature of thiocyanate in contact ion pairs with lithium ions

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN–) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN– binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S–C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency–frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Lastly, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs.

25 ENERGY STORAGE↗
DOE OSTI2022

Preliminary Result from the Dissolution of Neodymium and Erbium Oxide in a Tributyl Phosphate Solvent

This work demonstrated that visible absorbance spectroscopy can track the dissolution of neodymium and erbium oxide in an organic solution containing tributyl phosphate and nitrates. The formation of an aqueous phase was unexpected but an important phenomenon to consider when developing a metal oxide dissolution in organic solution flowsheet. Since the metal oxide appeared to completely dissolve into either the organic or newly formed aqueous phase, dissolution (extraction) rates should be easier to determine.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Comparing π‐complexation capabilities of ionic liquids containing silver(I) and copper(I) ions by headspace single drop microextraction in combination with high‐performance liquid chromatography

Selective π‐complexation capabilities of silver(I) and copper(I) ions can be effectively facilitated in ionic liquids. To understand the effects of environmental factors that influence the π‐complexation of these metal ions with analytes, techniques that employ small volumes of ionic liquid that can be readily analyzed are desired. In this study, headspace single drop microextraction coupled with HPLC is used to investigate a diverse set of environmental factors on the metal ion‐mediated complexation with aromatic compounds in ionic liquid media. Silver(I) and copper(I) bis[(trifluoromethyl)sulfonyl]imide salts were both studied by dissolving them in the 1‐decyl‐3‐methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ionic liquid and employing the mixture as extraction media for aromatic compounds. Water and acetonitrile within the sample solution were observed to interfere with the complexation of silver(I) ions and aromatic compounds, while ethylene glycol and triethylene glycol did not. The temperature and extraction times were optimized to fully facilitate the π‐complexation capabilities of metal ions in ionic liquid media. Partition coefficients between the sample headspace and metal ion were determined using a three‐phase equilibria model. Although no discernable difference in analyte partitioning between the headspace and ionic liquid solvent was observed, analyte partition coefficients to silver(I) ion tended to be greater compared to copper(I) ion.

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

Sustainable Synthesis of NiMo Alloy Nanoparticles for Hydrogen Evolution Catalysis Using a Recyclable Ionic Liquid Solvent

Advancing the sustainability of nanoparticle electrocatalyst synthesis requires reducing solvent waste without compromising catalytic performance. Here, we report a rapid, microwave‐assisted colloidal synthesis of NiMo alloy nanoparticles in the ionic liquid 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM‐NTf 2 ), which serves as both reaction medium and recyclable solvent. NiMo nanoparticles with tunable compositions were obtained within 1 min at 230 °C, with Ni 0.86 Mo 0.14 giving the highest activity toward the hydrogen evolution reaction (HER), achieving an onset potential of −129 mV, an overpotential at 10 mA cm −2 of −290 mV versus RHE in acidic electrolyte, and >99% Faradaic efficiency. The ionic liquid was recovered and purified via aqueous NH 4 OH extraction, removing over 99% of residual Mo species, and reused for up to five successive syntheses. Nanoparticles prepared in recycled BMIM‐NTf 2 retained comparable crystallinity, morphology, and catalytic activity, with stable HER performance over 45 h of electrolysis. These results demonstrate that ionic liquid recycling can improve the sustainability of the preparation of NiMo nanoparticle electrocatalysts while preserving performance and material integrity.

bimetallic alloy↗
DOE OSTI2023

Cost details from front-end engineering design of piperazine with the advanced stripper

This Front-End Engineering Design (FEED) was funded by the U.S. Department of Energy (DOE) to estimate the cost to capture and compress 90% of the CO 2 from an existing natural gas combined cycle (NGCC) in Denver City, Texas, USA. The FEED used the PZAS (Piperazine with the Advanced Stripper) 2G amine scrubbing technology developed and modeled by The University of Texas at Austin. This FEED is unique in providing more public cost details than other FEEDs funded by DOE. The primary objective of the FEED was to provide a comprehensive estimate for the total installed cost of the capture plant. The estimated capital cost of NGCC at the Mustang Station is $\$727$ million for a capacity of 460 MW and 1.6 million tonnes CO 2 /yr. This includes a contingency of $\$104.6$ million and a contractor’s profit of $\$60.1$ million. The total direct field cost is $\$384.1$ million. With an optimistic fuel value of $\$3$/MMBtu, the estimated cost of capture varies from $\$85$/t at 4% IRR/85% load to $\$170$/t at 10% IRR/52% load. Air cooling is technically feasible but expensive. The air cooling systems for the water wash and pump-around intercooling account for 23.4% of the direct cost. The gas-fired boilers represent only 4% of the direct costs, but steam extraction would reduce energy cost, free up cooling water, and reduce the direct costs of processing additional flue gas and CO 2 from the boilers. The absorbers represent 9.6% of the direct cost in this FEED with no direct contact cooler and only 7.6 m of packing. Furthermore, the solvent cross exchangers are less expensive than expected (2.5% of direct costs). Doubling the number of these exchangers could reduce the heat duty from 3.0 to 2.5 GJ/t CO 2 .

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

Probing surface-adsorbate interactions through active particle dynamics

Adsorbate molecules present in a reaction mixture may bind to and block catalytic sites. Measurement of the surface coverage of these molecules via adsorption isotherms is critical for modeling and design of catalytic reactions on surfaces. However, it is challenging to measure isotherms in solution in a way that is directly relevant to catalytic activity under reaction conditions, particularly since adsorbates may bind with an enormous range of surface affinity parameters. Here we used the motion of self-propelled catalytic Janus particles, which employ the decomposition of hydrogen peroxide fuel as a propulsion mechanism, to determine the effective surface coverage of thioglycerol, furfural, and ethanol on a platinum surface as a function of concentration in aqueous solution by measuring the decrease in active motion due to the blocking of active sites. For strongly adsorbing thioglycerol, this effective coverage was compared and contrasted to the total adsorbed amount measured using inductively-coupled plasma analysis. Demonstrating the broad applicability of this approach, the surface affinity of the three adsorbates spanned more than four orders of magnitude. For each species, the adsorbate-mediated attenuation of active motion occurred over a wide concentration range and was well-described by a Langmuir isotherm. The strongly interacting thioglycerol had the highest affinity towards the surface (K a = 15.5 ± 4.3 mM –1 ) and fully deactivated the active particle motion at surface saturation. Furfural had an intermediate affinity (K a = 0.42 ± 0.07 mM –1 ) but did not fully block H 2 O 2 access to the surface at apparent saturation, consistent with a maximum fractional surface coverage of θ max = 0.67. Ethanol exhibited even lower affinity (K a = 0.0025 ± 2x10 -4 mM –1 ) and its coverage saturated at only θ max = 0.38. Analysis of isotherms at elevated temperatures enabled direct extraction of the enthalpies of adsorption. The degree of surface coverage at adsorbate saturation appeared to correlate with the relative energies of adsorption for the different adsorbate species and was consistent with adsorbate saturation of one of multiple active site populations towards H 2 O 2 decomposition. Furthermore, computational investigations into solvent effects on furfural adsorption showed good quantitative agreement with the experimental results. This work leverages unique properties of active particles to explore fundamental catalysis questions and demonstrates a novel paradigm for significant and experimentally accessible multidisciplinary research.

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

Life‐Cycle Assessment Considerations for Batteries and Battery Materials

Abstract Rechargeable batteries are necessary for the decarbonization of the energy systems, but life‐cycle environmental impact assessments have not achieved consensus on the environmental impacts of producing these batteries. Nonetheless, life cycle assessment (LCA) is a powerful tool to inform the development of better‐performing batteries with reduced environmental burden. This review explores common practices in lithium‐ion battery LCAs and makes recommendations for how future studies can be more interpretable, representative, and impactful. First, LCAs should focus analyses of resource depletion on long‐term trends toward more energy and resource‐intensive material extraction and processing rather than treating known reserves as a fixed quantity being depleted. Second, future studies should account for extraction and processing operations that deviate from industry best‐practices and may be responsible for an outsized share of sector‐wide impacts, such as artisanal cobalt mining. Third, LCAs should explore at least 2–3 battery manufacturing facility scales to capture size‐ and throughput‐dependent impacts such as dry room conditioning and solvent recovery. Finally, future LCAs must transition away from kg of battery mass as a functional unit and instead make use of kWh of storage capacity and kWh of lifetime energy throughput.

25 ENERGY STORAGE↗
DOE OSTI2023

Charge transfer as a mechanism for chlorophyll fluorescence concentration quenching

Highly concentrated solutions of chlorophyll display rapid fluorescence quenching. The same devastating energy loss is not seen in photosynthetic light-harvesting antenna complexes, despite the need for chromophores to be in close proximity to facilitate energy transfer. A promising, though unconfirmed mechanism for the observed quenching is energy transfer from an excited chlorophyll monomer to a closely associated chlorophyll pair that subsequently undergoes rapid nonradiative decay to the ground state via a short-lived intermediate charge-transfer state. In this work, we make use of newly emerging fast methods in quantum chemistry to assess the feasibility of this proposed mechanism. We calculate rate constants for the initial charge separation, based on Marcus free-energy surfaces extracted from molecular dynamics simulations of solvated chlorophyll pairs, demonstrating that this pathway will compete with fluorescence (i.e., drive quenching) at experimentally measured quenching concentrations. We show that the rate of charge separation is highly sensitive to interchlorophyll distance and the relative orientations of chromophores within a quenching pair. We discuss possible solvent effects on the rate of charge separation (and consequently the degree of quenching), using the light-harvesting complex II (LH2) protein from rps. acidophila as a specific example of how this process might be controlled in a protein environment. Crucially, we reveal that the LH2 antenna protein prevents quenching, even at the high chlorophyll concentrations required for efficient energy transfer, by restricting the range of orientations that neighboring chlorophyll pairs can adopt.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Understanding slurry formulations to guide solution-processing of solid electrolytes

Scalable processing of thin solid electrolytes is crucial for engineering solid-state batteries with practical energy densities. To leverage existing battery production infrastructure, pathways for solution processing of solid electrolyte films must be investigated. Here, roll-to-roll compatible film preparation of aluminum-doped lithium lanthanum zirconate oxide was studied. Four slurry configurations accounting for different solvent properties and solid loadings were evaluated to investigate the ternary interactions within the dispersions. Rheological and coating stability analyses were carried out on the processed slurries. The analysis and characterization indicated that improved component interactions within the ethanol/toluene system result in homogenized distribution of the particles, binder, and plasticizer, and enable the extraction of free-standing thin films with thicknesses of 20 μm and large area (>15 in. 2 ). The drawbacks and opportunities of several protocols for high temperature sintering of the dried green films were investigated. This study highlights the importance of engineering dispersions during the development of processing protocols for solid electrolytes and provides guidelines for the best practices that can be leveraged for solution processing–based fabrications for a wide range of solid electrolyte materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Gas-phase stability of large lanthanide:diglycolamide clusters evaluated using collision-induced dissociation

Efficient utilization of long-term deep geologic storage repositories is critical for the large-scale deployment of nuclear energy. As the minor actinides (americium and curium) are the largest contributor to the decay heat of used nuclear fuel after a few hundred years, their removal from used fuel prior to disposal can significantly increase the amount of waste that can be stored in a given volume. The development of ligands that can effectively separate the minor actinides from other components of used nuclear fuel are crucial to efficient utilization of geological storage repositories. N,N,N’,N’-tetraoctyl diglycolamide (TODGA) is a promising extractant for the separation of lanthanides and the minor actinides from other components of used nuclear fuel. While the use of TODGA in f-element separations has been investigated in process-based formulations, gas-phase metal ion cluster experiments enable the study of covalent interactions in reprocessing systems absent from solvent effects. Exploring fundamental differences in lanthanide-ligand covalent interactions can impact the development and implementation of actinide-lanthanide separation systems in nuclear fuels reprocessing. In this study, lanthanide-TODGA clusters were synthesized in the gas-phase and identified using mass spectrometry fragmentation experiments. Large europium and samarium clusters were identified that contained up to 8 and 10 bound TODGA ligands, respectively; this was surprising due to the size and multidentate binding that is normal for TODGA. In addition, while smaller clusters showed evidence of sequential ligand fragmentation, larger clusters displayed the loss of neutral TODGA with applied collision voltage. Interestingly, the voltage required for this removal decreased as more TODGA ligands were bound to the metal, suggesting that the metal coordination sphere was becoming more saturated and TODGA ligands were more weakly bound as the clusters got larger.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

A Method for Obtaining Liquid–Solid Adsorption Rates from Molecular Dynamics Simulations: Applied to Methanol on Pt(111) in H 2 O

Adsorption is an important step in heterogeneous catalysis as it predetermines how many reactant molecules can participate in a surface reaction per unit time. While the rate of adsorption processes is well studied in gas–solid adsorption in both theory and experiment, such rates are still not well studied for liquid–solid adsorption. This is partly because the ever-changing configurations of liquid-phase solvent molecules impede the ability to study a molecule approaching a surface from a liquid phase by either experiment or theory. In this work, we develop a method using molecular dynamics (MD) simulations to study the rate of adsorption in liquid–solid adsorption processes. Specifically, we use MD to model the diffusion of a methanol molecule in aqueous solvent and its adsorption to a Pt(111) surface. We find that by approximating the solute motion as following the same displacement rates as a random walk model, the adsorbed and non-adsorbed states of the methanol molecule near the Pt(111) surface can be discerned and quantified. In particular, this methodology enables extracting a sticking coefficient and a macroscopically relatable adsorption rate. This method can be applied to arbitrary types of reactants and surfaces, as well as different liquid environments, thus providing a general tool for predicting quantitative adsorption rates of liquid–solid adsorption systems.

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

Phase-Selective Fractionation of Lignocellulosic Biomass Using a Lignin-Based Hydrophobic Deep Eutectic Solvent Biphasic System

Lignocellulose fractionation is a critical step in biomass valorization. Herein, we report a hydrophobic deep eutectic solvent (HDES)-mediated biphasic fractionation strategy that enables the simultaneous and selective separation of cellulose, hemicellulose, and lignin in a single process. Lignin-derived HDESs composed of thymol and 2,6-dimethoxyphenol (syringol) were combined with an acidic aqueous phase to create a water-HDES biphasic system, in which lignin was preferentially extracted into the HDES phase, hemicellulose-derived sugars were selectively solubilized in the aqueous phase, and cellulose was retained in the solid residue. Using wheat straw and poplar wood as representative herbaceous and woody biomass feedstocks, the HDES-acid system exhibited strong synergistic effects, achieving delignification up to 69.8% and xylan removal up to 93.6%. Structural characterization confirmed effective disruption of the lignocellulosic matrix and increased cellulose accessibility, resulting in markedly enhanced enzymatic saccharification, with glucose yields up to 96.2% for wheat straw. This work demonstrates a sustainable and efficient HDES-based biphasic fractionation platform that enables phase-selective separation of major lignocellulosic components and provides a foundation for further development of closed-loop biorefinery processes.

09 BIOMASS FUELS↗
DOE OSTI2023

Combustion synthesis of Eu 2 O 3 nanomaterials with tunable phase composition and morphology

Combustion reactions in europium nitrate – acetylacetone – 2-methoxyethanol solutions and gels were investigated to produce europium (III) oxide (Eu 2 O 3 ) nanocrystalline materials and thin films. Thermal analyses of solutions indicated that the 2-methoxyethanol solvent also acts as a fuel in the absence of acetylacetone. Adding acetylacetone increases the overall heat of the reaction. Thermal analysis results revealed that the slow oxidation of unburned hydrocarbon residues follows the primary combustion reaction. Time-temperature profile measurements of the bulk combustion synthesis process in air and nitrogen atmospheres enabled the extraction of the maximum reaction temperature and the heating and cooling rates in the combustion zone. Several direct correlations exist between measured combustion parameters and the phase composition of the products. Combustion in air results in mixed-phase cubic and monoclinic nanocrystalline Eu 2 O 3 . Increasing the acetylacetone concentration in solutions increases the synthesis temperature and decreases the quantity of cubic Eu 2 O 3 . Here, the reaction of solutions in a nitrogen atmosphere or diluted with Eu 2 O 3 provides control of the product phase composition and reduces the quantity of the monoclinic phase. Transmission electron microscopy imaging shows that the Eu 2 O 3 end products are highly porous aggregates of nanocrystalline particles. Electrospraying of reactive solutions onto different substrates followed by short annealing makes the preparation of Eu 2 O 3 materials with diverse morphologies possible.

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

Big Data Analysis and Technical Review of Regeneration for Carbon Capture Processes

Carbon capture remains an integral technology to mitigate pollution from one of the most prevalent greenhouse gases. CO 2 desorption/absorbent regeneration for both solid- and liquid-based systems is widely recognized as an energy-intensive and costly process operation. Consequently, tremendous work was devoted towards developing new absorbents and regeneration processes to promote their economic feasibility for extensive implementation. In this review, we broadly and deeply review more than 10,000 papers and extract the hidden trends of carbon capture and absorbents regeneration in the past few decades, using a novel data-mining analysis technique. We comprehensively analyzed an array of recent absorbent regeneration methods utilized in post-combustion, pre-combustion, carbon capture from industrial point sources, and direct air carbon capture, with an emphasis on sorbent and solvent-based techniques. In conclusion, advanced regeneration methods in these techniques were illustrated and discussed, followed by recommendations for further research efforts.

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

Verification Testing of OLI Systems Mixed Solvent Electrolyte Model for the Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 ) System to High Ionic Strength at 25°C

This technical report summarizes model verification results and summary statistics for 41 evaporite mineral solubility cases evaluated by Savannah River National Laboratory using OLI Systems’ aqueous electrolyte thermodynamic modeling software. The 41 verification cases containing a total of 60 solubility curves comprise mineral solubility data from low to high ionic strength at 25°C for the eight-component system Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 O as reported by Harvie et al. (1984). Thermodynamic calculations were executed using OLI Systems’ Stream Analyzer computation module within the OLI Studio software platform (Ver. 11.0, Rev. 11.0.1.9). The Mixed Solvent Electrolyte (MSE) thermodynamic framework was chosen for this investigation because of its superiority in modeling high ionic-strength inorganic salt solutions and actinide redox chemistry and solubility, both of which are relevant to the geological repository conditions at the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Mineral solubility data in various inorganic salt solutions were digitized and extracted from figures generated by Harvie et al. (1984). For each of the 60 solubility curves, a case-specific chemistry model and input file were generated in OLI Studio using OLI Stream Analyzer and the MSE (H 3 O + ion) public databank provided by OLI Systems. Model simulation results were exported to Microsoft Excel to calculate summary statistics and to generate graphs comparing the OLI model predictions to the solubility data. Summary statistics include residuals (model – data) and concordance (accuracy × precision, where precision is indicated by the Pearson correlation coefficient and accuracy accounts for bias and scale differential). Private databanks were not developed, and activity coefficient model regressions were not performed to improve OLI model fits to the data. Of the 41 model verification plots, 83% have a mean of the percent residuals less than or equal to 25%. Similarly, 75% display a concordance greater than or equal to 0.75. Only seven of the 41 verification plots fail to show good agreement between the model and data. Of these seven, three are relevant to the WIPP repository because they involve the Mg-OH-Cl-SO 4 -CO 3 aqueous system. The remaining four address salt solubilities at the pH extremes (strong acid and strong base). It should be noted that in two of the three Mg-OH-Cl-SO 4 -CO 3 system cases, the regressed Harvie et al. (1984) solubility curve also deviated from the data. Lack of agreement between the OLI model-predicted solubility curves and the data is attributable to one or more of the following: specific solid species are not included in the OLI MSE databank; there is significant variation among the different solubility datasets chosen by Harvie et al. (1984); the OLI MSE model’s thermodynamic parameters were determined using different solubility datasets; and the activity coefficient parameters for certain relevant ion-ion and ion-molecule pairs have not been optimized via data regression. Two recommendations for future work are to (1) evaluate solubility data for the Mg-OH-Cl-SO 4 -CO 3 system at high ionic strength and, if necessary, develop a private OLI MSE database that includes missing species and, where necessary, regressed standard state properties and interaction parameters; (2) perform similar verification testing of the OLI model for actinide solubility data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

QM Investigation of Rare Earth Ion Interactions with First Hydration Shell Waters and Protein-Based Coordination Models

Here, conventional methods for extracting rare earth metals (REMs) from mined mineral ores are inefficient, expensive, and environmentally damaging. Recent discovery of lanmodulin (LanM), a protein that coordinates REMs with high-affinity and selectivity over competing ions, provides inspiration for new REM refinement methods. Here, we used quantum mechanical (QM) methods to investigate trivalent lanthanide cation (Ln 3+ ) interactions with coordination systems representing bulk solvent water and protein binding sites. Energy decomposition analysis (EDA) showed differences in the energetic components of Ln 3+ interaction with representatives of solvent (water, H 2 O) and protein binding sites (acetate, CH 3 COO – ), highlighting the importance of accurate description of electrostatics and polarization in computational modeling of REM interactions with biological and bioinspired molecules. Relative binding free energies were obtained for Ln 3+ with coordination complexes originating from binding sites in PDB structures of a lanthanum binding peptide (PDB entry 7CCO) and LanM, with explicit consideration of the first hydration shell waters, according to quasi-chemical theory (QCT). Beyond the first shell, the bulk solvent environment was represented with an implicit continuum model. Ln 3+ interactions with (H 2 O) 9 and both binding site models became more favorable, moving down the periodic series. This trend was more pronounced with the protein binding site models than with water, resulting in affinity increasing with periodic number, except for the last REM, Lu 3+ , which bound less favorably than the preceding element, Yb 3+ . Using the truncated 7CCO binding site model, the magnitude and trend of the experimental Ln 3+ relative binding free energies for the whole 7CCO peptide were reproduced. Conversely, the previously reported experimental data for LanM show a preference for the earlier lanthanides; this is likely due to longer-range interactions and cooperative effects, which are not represented by the reduced models. Using the truncated 7CCO binding site model, the magnitude and trend of the experimental Ln 3+ relative binding free energies for the whole 7CCO peptide were reproduced. In contrast to the previously reported experimental data for LanM, the peptide preferentially binds the earlier lanthanides. This difference likely arises due to longer-range interactions and cooperative effects not represented by the peptide. Further investigation of Ln 3+ interactions with whole proteins using polarizable molecular mechanics models with explicit solvent is warranted to understand the influence of longer-ranged interactions, cooperativity, and bulk solvent. Nevertheless, the present work provides new insights into Ln 3+ interactions with biomolecules and presents an effective computational platform for designing specific single-site REM binding peptides more efficiently.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗