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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Communication: First-principles evaluation of alkali ion adsorption and ion exchange in pure silica LTA zeolite

Utilizing first-principles calculations, we studied the adsorption of alkali ions in pure silica Linde Type A (LTA) zeolite. The probability of adsorbing alkali ions from solution and the driving force for ion exchange between Na + and other alkali ions at the different adsorption sites were analyzed. From the calculated ion exchange isotherms, we show that it is possible to exchange Na + with K + and Rb + in water, but that is not the case for systems in a vacuum. We additionallly demonstrate that a solvation model should be used for the accurate representation of ion exchange in an LTA and that dispersion interactions should be introduced with care.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Enhanced Ion Adsorption on Mineral Nanoparticles

Classical molecular dynamics simulation was used to study the adsorption of Na + , Ca 2+ , Ba 2+ and Cl-ions on gibbsite edge (1 0 0), basal (0 0 1), and nanoparticle surfaces. The gibbsite nanoparticle consists of both basal and edge surfaces. Simulation results indicate that Na + and Cl - ions adsorb on both (1 0 0) and (0 0 1) surfaces as inner-sphere species (i.e., no water molecules between an ion and the surface). Outer-sphere Cl - ions (i.e., one water molecule between an ion and the surface) were also found on these surfaces. On the (1 0 0) edge, Ca 2+ ions adsorb as inner-sphere and outer-sphere complexes, while on the (0 0 1) surface outer-sphere Ca 2+ ions are the dominant species. Ba 2+ ions were found as inner-sphere and outer-sphere complexes on both surfaces. Calculated ion surface coverages indicate that, for all ions, surface coverages are always higher on the basal surface compared to the edge surface. More importantly, surface coverages for cations on the gibbsite nanoparticle are always higher than those calculated for (1 0 0) and (0 0 1) surfaces. This enhanced ion adsorption behavior for the nanoparticle is due to the significant number of inner-sphere cations found at nanoparticle corners. Outer-sphere cations do not contribute to the enhanced surface coverage. In addition, there is no ion adsorption enhancement observed for the Cl - ion. Our work provides a molecular-scale understanding of the relative significance of ion adsorption onto gibbsite basal versus edge surfaces and demonstrates the corner effect on ion adsorption on nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Comparative isosteric ion adsorption for minerals

A comparative isosteric ion adsorption study for minerals (kaolinite, rutile, and quartz) was performed in aqueous solutions of CaCl2, LaCl3, and Th(NO3)4 in the presence of the neutral salt NaCl. It was observed that the concentration of Ca(2+) ions required to produce a standard reduction in the electrophoretic mobility of mineral particles was always appreciably greater than the concentration required for the Th(4+) ions. The effectiveness of adsorption of the cations differed from particle to particle and showed that ion adsorption on a mineral surface depends, among other things, on the nature of the mineral surface and on the particular adsorbed cation. The number of cation binding sites on mineral surfaces and the electrochemical free energies of cation adsorption were calculated. It was found that the adsorption energy of La(3+) and Th(4+) ions on rutile, kaolinite, and quartz was greater than that of Ca(2+) on these minerals.

Omenyi, Samuel N.↗
DOE OSTI2022

On the mechanisms of ion adsorption to aqueous interfaces: air-water vs. oil-water

The adsorption of ions to water-hydrophobe interfaces influences a wide range of phenomena, including chemical reaction rates, ion transport across biological membranes, and electrochemical and many catalytic processes; hence, developing a detailed understanding of the behavior of ions at water-hydrophobe interfaces is of central interest. Here, we characterize the adsorption of the chaotropic thiocyanate anion (SCN − ) to two prototypical liquid hydrophobic surfaces, water-toluene and water-decane, by surface-sensitive nonlinear spectroscopy and compare the results against our previous studies of SCN − adsorption to the air-water interface. For these systems, we observe no spectral shift in the charge transfer to solvent spectrum of SCN − , and the Gibb’s free energies of adsorption for these three different interfaces all agree within error. We employed molecular dynamics simulations to develop a molecular-level understanding of the adsorption mechanism and found that the adsorption for SCN − to both water-toluene and water-decane interfaces is driven by an increase in entropy, with very little enthalpic contribution. This is a qualitatively different mechanism than reported for SCN − adsorption to the air-water and graphene-water interfaces, wherein a favorable enthalpy change was the main driving force, against an unfavorable entropy change.

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

A study of rare earth ion-adsorption clays: The speciation of rare earth elements on kaolinite at basic pH

Synthesized rare earth ion-adsorption clays (La, Ce, Nd, Dy and Y, ~ 400 ppm each) were prepared from kaolinite at various basic pH in open-air conditions. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma mass spectrometry (ICP-MS) were used to characterize the effect of pH on the adsorption mechanism of rare earth elements (REEs) on kaolinite. The crystal structure of kaolinite by XRD analysis is not altered after REE adsorption, suggesting that REEs are bound to the surface of kaolinite. Elemental analysis by XPS and ICP-MS show that the surface concentration of REEs on kaolinite is pH dependent, and a local maximum of the surface concentration is achieved at pH 10. Three characteristics of the La 3d 5/2 XPS photoemission feature were measured and compared to those of standard La compounds to probe the speciation of REEs, and electrostatically bound hydroxides such as REE(OH) 2 + are identified as the primary species on the surface of kaolinite. Finally, compared to the typical ion-adsorption clays with intrinsic acidic pH, clays synthesized at basic pH exhibit similarly high rare earth ion-exchange efficiency with ammonium sulfate (AS), suggesting that rare earth ion-adsorption clays can exist in both acidic and basic environments.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Equilibria model for pH variations and ion adsorption in capacitive deionization electrodes

Ion adsorption and equilibrium between electrolyte and microstructure of porous electrodes are at the heart of capacitive deionization (CDI) research. Surface functional groups are among the factors which fundamentally affect adsorption characteristics of the material and hence CDI system performance in general. Current CDI-based models for surface charge are mainly based on a fixed (constant) charge density, and do not treat acid-base equilibria of electrode microstructure including so-called micropores. Here, we expand current models by coupling the modified Donnan (mD) model with weak electrolyte acid-base equilibria theory. In our model, surface charge density can vary based on equilibrium constants (pK's) of individual surface groups as well as micropore and electrolyte pH environments. In this initial paper, we consider this equilibrium in the absence of Faradaic reactions. The model shows the preferential adsorption of cations versus anions to surfaces with respectively acidic or basic surface functional groups. We introduce a new parameter we term “chemical charge efficiency” to quantify efficiency of salt removal due to surface functional groups. We validate our model using well controlled titration experiments for an activated carbon cloth (ACC), and quantify initial and final pH of solution after adding the ACC sample. We also leverage inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography (IC) to quantify the final background concentrations of individual ionic species. Our results show a very good agreement between experiments and model. The model is extendable to a wide variety of porous electrode systems and CDI systems with applied potential.

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

Bioleaching ion-unexchangeable rare earth in ion-adsorption type rare earth waste tailing

Ion-adsorption type rare earth ores (IREO) in China serve as the primary source of medium and heavy rare earth globally. With the rapidly growing demand for rare earth elements (REEs) and the dwindling supply of premium IREO, enhancing the recovery of REEs, especially the ion-unexchangeable REEs with ultra-low content and ambiguous speciation from IREO or its tailing, has become a critical trend and challenge. Here, this study identified the occurrences of ion-unexchangeable REEs, primarily detected in Fe-enriched minerals, xenotime, and monazite of IREO using TESCAN integrated mineral analyzer (TIMA) and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) analysis. To extract these elusive REEs, a bioleaching technique utilizing Aspergillus niger (A. niger) metabolites was proposed, achieving a leaching yield of 31.4 wt%. Complementary sequential chemical extraction methods (SCEM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations further elucidate the underlying mechanism, involving the carboxylic acid produced by the metabolic process of microbes that dissolves goethite by disrupting Fe—O bonds and liberating REEs, which complexed with carboxylate (R—COO—), to promote further dissolution. This work offers insight into enhancing the recovery of ion-unexchangeable REEs from IREO or its tailing, paving the way for sustainable and efficient rare earth mining practices.

42 ENGINEERING↗
DOE OSTI2020

Nonclassical Behavior in Competitive Ion Adsorption at a Charged Solid–Water Interface

Ion adsorption at solid-water interfaces is commonly described by interactions between specific surface sites and adsorbed ions in classical models. However, energetic contributions from non-site-specific ion-ion interactions have not been explored systematically. Here, we report non-classical behaviors observed during competitive adsorption between Sr 2+ and Na + /Rb + at the negatively-charged muscovite mica (001)-water interface, revealing apparent controls of adsorbed ion speciation over the interfacial reactivity. In the absence of competing cations, Sr 2+ adsorbs in approximately equivalent proportions of inner-sphere and outer-sphere complexes, whereas it adsorbs predominantly as an outer-sphere complex in the presence of Na + /Rb + . This transformation of adsorbed Sr 2+ speciation significantly decreases its adsorption strength, as indicated by ~15-fold shift in the Sr 2+ adsorption edge concentration, compared to that calculated from a classical Langmuir isotherm model developed based on site-specific interactions. Finally, these observations highlight the importance of non-site-specific interactions in controlling the energetics of chemical reactions at the charged interface.

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

Anisotropic surface potentials induced by competitive ion adsorption enable the synthesis of branched cubic Pt mesocrystals

Creation of complex nanostructured materials through oriented attachment (OA) requires the manipulation of interparticle forces, including electrostatic repulsion, which depends strongly on surface potentials and can be modified through the effect of solution environment on interfacial chemistry. Here we show that time-dependent anisotropies in surface potential driven by competitive ion adsorption can alter facet-selectivity during OA. This phenomenon enables the synthesis of branched cubic Pt mesocrystals. Initially, Pt nanoparticles attach preferentially at their {100} facets to form a well-defined cubic core. Over time, changes in ion adsorption shift the attachment preference to the {111} facets, promoting branch formation. In both stages, anisotropic surface potentials generate electrostatic torques that align the particles prior to attachment. These findings demonstrate a generalizable strategy for directing the architecture of nanomaterials through time-resolved control of interfacial chemistry during OA, offering new pathways for the design of complex mesoscale structures.

Bae, Yuna [Pacific Northwest National Laboratory (↗
DOE OSTI2026

Diethylenetriamine-functionalized graphene oxide: Insights into ion adsorption and applications in rare earth element separation

The growing demand for critical minerals and materials requires atom- and energy-efficient, selective separations to overcome the challenges posed by the similar chemical and physical properties of the rare earth elements (REEs) and their low concentrations in unconventional domestic feedstocks. Here, in this study, we developed diethylenetriamine-functionalized graphene oxide (DETA-GO) as a membrane material for REE adsorption and separation. Synthesis conditions were optimized to maximize nitrogen incorporation while also preserving GO dispersibility for facile membrane fabrication. We investigated the mechanism of amine functionalization, the nitrogen-bonding configurations, the organization of the interlayer transport channels, and the resulting effects on ion and water transport for REE separations. Neat-GO and DETA-GO multilayer laminate membranes were fabricated by vacuum filtration onto polymer supports. To investigate the effects of amine functionalization, the membranes were characterized using scanning electron microscopy, Raman, Fourier transform infrared, and X-ray photoelectron spectroscopy, as well as grazing-incidence X-ray diffraction measurements. Ion permeation experiments with representative lanthanum (La 3+ ) and ytterbium (Yb 3+ ) solutions revealed enhanced ion adsorption and water transport through DETA-GO membranes compared to neat-GO. The strong affinity of the membranes for multivalent REEs was also validated with conductivity and inductively coupled plasma mass spectrometry measurements. Atomistic insight into the role of amine functionalization in modulating nanochannel architecture and long-term stability, optimizing adsorption sites, and regulating REE and water transport was obtained using classical molecular dynamics simulations. Collectively, our joint experimental and theoretical study demonstrates the potential of DETA-GO membranes for selective REE separations, offering insights into ion-binding mechanisms, water-transport properties, and nanochannel optimization for the recovery of critical materials from aqueous feedstocks.

Adsorbent↗
DOE OSTI2023

Elucidating Trivalent Ion Adsorption at Floating Carboxylic Acid Monolayers: Charge Reversal or Water Reorganization?

Here we study the adsorption of trivalent neodymium on floating arachidic acid films at the air–water interface by two complementary surface specific probes, sum frequency generation spectroscopy and X-ray fluorescence near total reflection. In the absence of background ions, neodymium ions compensate for the surface charge of the arachidic acid film at a bulk concentration of 50 μM without any charge reversal. Increasing the bulk concentration to 1 mM does not change the neodymium surface coverage but affects the interfacial water structure significantly. In the presence of a high concentration of NaCl, there is overcharging at 1 mM Nd 3+ , i.e., 30% more Nd 3+ than needed to compensate for the surface charge. These results show that the total coverage of neodymium ions is not enough to describe the complete picture at the interface, and interfacial water and ion coverage needs to be considered together to understand more complex ion adsorption and transport processes.

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

Mechanistic insights into rubidium ion adsorption at the quartz (101) surface from quantum chemical metadynamics

Ion sorption extent and mechanism depend in part on the mineral surface termination, which can be highly complex. Variations in surface functional groups, particularly with defect density and surface roughness, influence mineral reactivity towards solutes. In this work, we investigate the adsorption of a rubidium cation (Rb + ) at pristine and defect quartz (101) surface sites using well-tempered metadynamics, based on simulations with the quantum chemical density-functional tight-binding (DFTB) method. We compare the relative energetics of Rb + adsorption across selected sites for each surface, with nanosecond-level sampling, highlighting similarities between vicinal and geminal silanol sites. We find that the positive Rb + partial atomic charge can increase by as much as 0.5e as it approaches the surface, with implications for modulation of ion adsorption strength and extent at the quartz (101) surface with surface vacancies, silanol coverage, and charge.

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

Prediction of alkaline earth metal ion adsorption on goethite for various background electrolytes with the CD-MUSIC model

As water scarcity drives the use of more saline water sources, contaminant fate and transport models must capture the impact of high concentrations of alkaline earth metal ions (AEMs) and background electrolytes in these more complex waters. By utilizing macroscopic adsorption data from various electrolyte systems, a Charge Distribution – Multisite Complexation (CD-MUSIC) model, capable of incorporating electrolyte adsorption, was able to accurately simulate the adsorption behavior of alkaline earth metal ions onto goethite. The modeling effort was guided by previous spectroscopic and surface complexation modeling of alkaline earth metal adsorption and built on previous CD-MUSIC modeling that accounted for changes in crystal face contributions to the surface site density as a function of specific surface area. Further, the model was constrained to consider only two dominant surface complex species for each metal ion adsorption reaction. These two species were selected from 44 possible species through objective curve fitting of single-solute macroscopic adsorption data. While most of the alkaline earth metal surface complexes formed outer-sphere complexes at the goethite surface, an inner-sphere species was utilized for Mg 2+ . With the surface complex species and equilibrium constants obtained from this study, the calibrated model successfully predicted alkaline earth metal ion adsorption over a wide range of solution and surface conditions; the model predictions encompassed a wide range of pH (5–11), solute/solid ratio (1.37 × 10 -5 – 8.33 × 10 -4 mol -solute /g -solid ), ionic strengths (0.01 M – 0.7 M), and background electrolytes (Na + , Cs + , Rb + , Cl - , and NO 3 - ) using the same crystal face contribution methodology for site density, capacitance values, and surface acidity constants adopted for proton and cadmium adsorption in previous work (Han and Katz, 2019). Model simulations for a range of background water chemistries demonstrated the potential for Mg 2+ to reduce Cd 2+ adsorption to goethite in model seawater and oil- and gas-produced waters.

42 ENGINEERING↗
DOE OSTI2022

Rare earth ion-adsorption clays in the presence of iron at basic pH: Adsorption mechanism and extraction method

In this work, the uptake mechanism and influence of iron (Fe) co-adsorption on the binding of rare-earth elements (REEs) on kaolinite have been investigated. REEs and varying concentrations of Fe were co-adsorbed onto kaolinite at pH 10.5. Inductively coupled plasma mass spectrometry (ICP-MS), powder X-ray diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize how Fe co-adsorption influenced the uptake mechanism of REEs on kaolinite. Elemental analysis by ICP-MS revealed that the REE concentrations on kaolinite were unaffected by the presence of Fe. Crystal structure of kaolinite, determined by PXRD, was not altered after REE and Fe co-adsorption. XPS suggests that the adsorbed Fe is in the form of FeOOH, while the greatly attenuated REE XPS signals upon Fe co-adsorption implies that REEs are encapsulated by Fe species. Based on these results, we conclude that FeOOH layers were formed on top of REEs on the surface of kaolinite. Synthesized REE-Fe-kaolinite samples respond poorly to ion-exchange leaching, indicating that Fe is detrimental to the REE ion-exchange efficiency. The inhibition of ion-exchange REE extraction appears to be due to the passivating FeOOH layers. In contrast to ion-exchange methods, reductive leaching was found to dissolve the FeOOH passivating layers and liberate REEs such that they became available for ion-exchange leaching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Modelling and Optimization of Uranium (VI) Ions Adsorption Onto Nano-ZnO/Chitosan Bio-composite Beads with Response Surface Methodology (RSM)

Nano-ZnO-chitosan bio-composite beads were prepared for the sorption of UO{sub 2}{sup 2+} from aqueous media. The resulting nano-ZnO/CTS bio-composite beads were characterized by TEM, XRD etc. The sorption of UO{sub 2}{sup 2+} by bio-composite beads was optimized using RSM. The correlation between four variables was modelled and studied. According to RSM data, correlation coefficients (R{sup 2} = 0.99) and probability F-values (F = 2.24 × 10{sup − 10}) show that the model fits the experimental data well. Adsorption capacity for nano-ZnO/CTS bio-composite beads was obtained at 148.7 mg/g under optimum conditions. The results indicate that nano-ZnO/CTS bio-composite beads are appropriate for the adsorption of UO{sub 2}{sup 2+} ions from aqueous media. Also, the suitability of adsorption values to adsorption isotherms was researched and thermodynamic data were calculated.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Effects of ion adsorption on graphene oxide films and interfacial water structure: A molecular-scale description

Herein we discuss graphene oxide as a promising, emerging separation material, as it is durable, dispersible in water, and has naturally forming functional groups. Bulk studies using graphene oxide flakes have demonstrated impressive metal adsorption. However, little interfacial information about water and metal organization near graphene oxide is available. A mechanistic understanding of water and ions interactions with graphene oxide films is critical toward advanced separations, including improved sorption efficiency and membrane regeneration. We study metal ion and local water organization near graphene oxide thin films formed at the air/water interface. These films are not typical membranes and allow us to determine nanoscale information about the graphene oxide-water interface. We accomplish this with x-ray reflectivity (XR), x-ray fluorescence near total reflection (XFNTR), and vibrational sum frequency generation spectroscopy (SFG). These interface-specific techniques provide the electron density profile normal to the interface, number of adsorbed ions, and information about the orientational ordering and hydrogen-bonding network of interfacial water, respectively. Via XFNTR and SFG, we find that trivalent yttrium ions preferentially adsorb to graphene oxide and affect its structure, compared to divalent strontium and monovalent cesium ions. Two different interfacial water populations can be described, based on their hydrogen bonding strength, and the adsorbed ions affect these populations differently. These results provide fundamental information about ion and water organization at the interface and help address the large computational-experimental agreement gap for graphene oxide systems. Additionally, they are relevant for improved soft-scaffold graphene oxide membranes and downstream applications.

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

Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

With the understanding that sorption in porous carbon electrodes is crucial to many environmental and energy technologies, such as capacitive deionization (CDI), supercapacitor energy storage, and activated carbon filters. In each of these examples, a practical model that can describe ion electrosorption kinetics is highly desirable for accelerating material design. Here, we proposed a multiscale model to study the ion electrosorption kinetics in porous carbon electrodes by combining quantum mechanical simulations with continuum approaches. Our model integrates the Butler-Volmer (BV) equation for sorption kinetics and a continuously stirred tank reactor (CSTR) formulation with atomistic calculations of ion hydration and ion-pore interactions based on density functional theory (DFT). We validated our model experimentally by using ion mixtures in a flow-through electrode CDI device and developed an in-line UV absorption system to provide unprecedented resolution of individual ions in the separation process. We showed that the multiscale model captures unexpected experimental phenomena that cannot be explained by the traditional ion electrosorption theory. The proposed multiscale framework provides a viable approach for modeling separation processes in systems where pore sizes and ion hydration effects strongly influence the sorption kinetics, which can be leveraged to explore possible strategies for improving carbon-based and, more broadly, pore-based technologies

36 MATERIALS SCIENCE↗