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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Downstream Separation of Formic Acid with Anion-Exchange Resin from Electrocatalytic Carbon Dioxide (CO 2 ) Conversion: Adsorption, Kinetics, and Equilibrium Modeling

The electrocatalytic carbon dioxide reduction reaction (CO 2 RR) that produces liquid formic acid (FA) is one potential route to minimize the CO 2 concentration in the atmosphere by utilizing CO 2 as a feedstock. However, one of the main disadvantages of this route is the high energy demand required for purification through conventional distillation. This method of purification has been shown to result in a large carbon footprint in life-cycle analysis (LCA). Therefore, finding an alternative purification technique that can integrate with an electrochemical CO 2 RR process with the potential to lower the carbon footprint would be of great interest. Under the experimental conditions of the CO 2 RR, FA remains in its basic form as the formate anion in the catholyte. Anion exchange resins with their basic properties can separate the formate anion from the catholyte mixture as an alternative to energy intensive distillation. In this work, three anion exchange resins with increasing basicity order: Amberlite IRA-96 < Amberlite IRA-910 < Ambersep 900 are tested to separate FA in the presence of aqueous solution of potassium bicarbonate catholyte with varying levels of resin and FA. Kinetics and equilibrium studies data for the FA adsorption are interpreted using several kinetics and isotherm models. The kinetics data fit well with a pseudo-first-order model at high initial FA concentrations and a pseudo-second-order model at low initial FA concentrations. The experimental data can be best explained with the Freundlich isotherm model. The fitted results show that strongly basic Ambersep 900 is more effective at separating FA, with a maximum adsorption capacity of 336.7 mg/g compared to Amberlite IRA-96 (275.2 mg/g) and Amberlite IRA-910 (209.2 mg/g) in neutral water. However, weakly basic Amberlite IRA-96 (110.8 mg/g) can separate FA more efficiently from potassium bicarbonate catholyte than Amberlite IRA-910 (99.9 mg/g) and Ambersep 900 (40.0 mg/g). As a result, competitive adsorption occurs in the presence of potassium bicarbonate catholyte, but the formic acid adsorption capacity is still sufficient for adequate separation.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2024

Adsorption Equilibrium, Kinetics, and Column Breakthrough Data for Aqueous Solutions of Binary-Acid and Ternary-Acid Mixtures of Acetic Acid, Butyric Acid, and Lactic Acid on IRN-78 Ion-Exchange Resin at Initial pH Levels of ∼3–7 and at 25–55 °C

This work is part of an effort to develop thermophysical property data and models supporting adsorptive process development for organic acid separation from a dilute aqueous solution of fermentation broth. It presents systematic experimental measurements for aqueous-phase adsorption equilibrium, kinetics, and column breakthrough for three binary-acid aqueous mixtures (acetic acid + lactic acid, butyric acid + lactic acid, and acetic acid + butyric acid) and one ternary-acid aqueous mixture (acetic acid + butyric acid + lactic acid) on Amberlite IRN-78 ion-exchange resin. The equilibrium measurements covered broad ranges of the initial acid concentration (100–400 mmol/L), initial pH (∼3–7), and temperature (25–55 °C). The equilibrium data for the binary-acid and ternary-acid aqueous mixtures indicate selective adsorption of lactic acid at initial pH levels of ∼3 and 4, while acetic acid and butyric acid are selectively adsorbed at initial pH levels of 5, 6, and 7. The subsequent kinetics and column breakthrough experiments were performed at 200 mmol/L with equimolar ratios, an initial pH of 6, and 25 °C. In conclusion, the measurements provide essential data sets for rigorous thermodynamic modeling and process simulation of adsorptive separation processes for organic acid separation from fermentation broth.

Adsorption↗
DOE OSTI2021

Stability of Pt Skin Intermetallic Core Catalysts and Adsorption Properties for the Oxygen Reduction Reaction

Density functional theory calculations were used to determine the stability of metal slabs consisting of a Pt surface monolayer and intermetallic supporting layers made from combinations of six transition metal elements (Pt, Fe, Co, Ni, Cu, and Ag), as a model system for Pt skin intermetallic core nanoparticle catalysts. The stability of the slabs is largely determined by strain at the interface of the Pt skin and the subsurface intermetallic, which was described by a lattice matching parameter (r). The surface charge on the Pt skin was found to be correlated with the average electronegativity (EN) of the intermetallic core, so this average EN was used as a descriptor for how the electronic coupling (or ligand effect) affects adsorption energies. A total of 46 slabs were investigated in terms of their stability, from which 10 stable slabs were selected for further studies of adsorbate binding (OOH*, O*, and OH*) that are intermediates in the oxygen reduction reaction (ORR). The correlation between all three adsorption energies and descriptors r and EN was found. Using a linear fit between our descriptors and the calculated adsorption energies, the overpotential for the ORR was obtained as a function of r and EN, from which a volcano plot was produced. The volcano peak was found at r = 0.96 or at EN = 2.025. Interestingly, neither r nor EN was a sufficient single reactivity descriptor as the data points were well off the general trend in both linear fits; this implies that both the strain effect and the ligand effect influence the adsorption energies, although they are partly correlated. The (r, EN) target peak parameters were used to screen over 241 intermetallic combinations of transition metal elements as active ORR activity. In conclusion, this analysis identified 11 intermetallic compounds which can support a Pt skin to have a high predicted ORR activity.

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

Unraveling Electronic Trends in O* and OH* Surface Adsorption in the MO 2 Transition-Metal Oxide Series

Understanding the bond strength of O* and OH* intermediates to metal-oxide surfaces is key to predicting the catalytic activity in oxygen-based electrochemistry. Here, we uncover highly non-linear trends in O* and OH* adsorption energies across the 3d, 4d, and 5d series of MO 2 transition-metal (TM) oxide surfaces computed within Hubbard- U corrected density functional theory (DFT + U ). Investigating the electronic structure with crystal orbital Hamiltonian populations (COHP) of the relevant metal–oxygen bonds reveals that the spin-dependent coupling strength between metal-d and oxygen-2p atomic orbitals together with the extent of filling of bonding and anti-bonding orbitals are the primary contributors to the adsorption energy. Importantly, we show that the integrated COHP obtained purely from bulk calculations is a highly accurate descriptor for surface adsorption energetics that captures trends across the group 5–12 TM oxide series within 0.19–0.36 eV. Our results suggest a pathway to prediction of adsorption energies for an arbitrary metal–ligand catalyst system.

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

Discrimination of Hexane Isomers by Temperature Swing Adsorption in a Rigid Aluminum Metal–Organic Framework

The efficient separation of alkane isomers with similar physicochemical properties remains a persistent challenge for the petrochemical industry. Adsorptive separation using metal− organic frameworks (MOFs) offers an energy-efficient alternative to conventional distillation. Herein, we report temperature swing discrimination of hexane isomers with different degrees of branching using MIL-120, a rigid aluminum pyromellitate-based MOF. MIL-120 features uniform one-dimensional channels with an aperture of ∼5.5 Å. At 30 °C, it selectively adsorbs linear and monobranched hexanes while excluding the dibranched isomer. Upon heating to 120 °C, both mono- and dibranched isomers are completely excluded, whereas linear hexane remains strongly adsorbed. Breakthrough experiments validate the temperature swing separation performance. Adsorption heat analysis combined with ab initio calculations provides a quantitative measure of distinct differences in adsorption enthalpies, binding energies, and diffusion barriers responsible for the observed separation efficiency, highlighting the potential of this MOF for efficient separation of alkane isomers via temperature swing adsorption.

Adsorption↗
DOE OSTI2020

Sequential Ammonia and Carbon Dioxide Adsorption on Pyrolyzed Biomass to Recover Waste Stream Nutrients

Untreated fecal waste in unsewered communities and reactive nitrogen (N) loading from wastewater and urine disposal are important environmental challenges. Through pyrolysis, untreated fecal waste can be converted into amine-rich carbon dioxide (CO 2 ) sorbents, the chemisorption of which tunes the surface chemistry toward ammonia (NH 3 ) uptake. We compared the N-loading potential within amine-rich pyrolyzed human solid waste through exposure to CO 2 followed by NH 3 with the N-loading potential on carboxyl-rich, pyrolyzed oxidized wood using sequential adsorption of isotopically labeled CO 2 and NH 3 . The total N content of pyrolyzed oxidized wood exposed once to NH3 was similar to native, pyrolyzed human solid waste (3.7% compared to 4.6%). However, sorption kinetics and spectroscopic evidence revealed distinct N forms between the two materials affecting subsequent CO 2 and NH 3 uptake. Tertiary amines comprised 70% of N in pyrolyzed waste, compared to only 53% in pyrolyzed oxidized wood. The high heat of adsorption of CO 2 on pyrolyzed human solid waste (50 kJ mol-1) at low concentrations (0.05 mmol CO 2 g -1 ) was indicative of CO 2 reactivity with tertiary amines, consistent with the formation of carbamic acid (Figure S1). Conversely, after exposure to NH 3 , pyrolyzed oxidized wood chemisorbed CO 2 at much higher concentrations (0.7 mmol CO 2 g-1), pointing to primary amines as the active functional moieties. Adsorption kinetics of pyrolyzed oxidized wood revealed continued, albeit diminishing NH 3 uptake with each consecutive CO 2 treatment, averaging 5.9 mmol NH 3 g -1 for the first NH 3 exposure event, and still 3.5 and 2.9 mmol NH 3 g -1 for the second and third. Penetration of 15 NH 3 and 13 CO 2 measured by NanoSIMS reached over 7 µm deep into both materials, explaining the large NH 3 capture. The significantly lower NH 3 adsorption compared to pyrolyzed oxidized wood may be a result of potassium (K) carbonate precipitation precluding a Lewis base interaction between NH 3 and chemisorbed CO 2 , suggested by a 2-fold increase in surface K concentrations after exposure of pyrolyzed human solid waste to CO 2 +NH 3 detected by XPS.

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

Influence of 1-Butene Adsorption on the Dimerization Activity of Single Metal Cations on UiO-66 Nodes

Grafting metal cations to missing linker defect sites in zirconium-based metal–organic frameworks, such as UiO-66, produces a uniquely well-defined and homotopic catalytically active site. We present here the synthesis and characterization of a group of UiO-66-supported metal catalysts, M-UiO-66 (M = Ni, Co, Cu, and Cr), for the catalytic dimerization of alkenes. The hydrogen–deuterium exchange via deuterium oxide adsorption followed by infrared spectroscopy showed that the last molecular water ligand desorbs from the sites after evacuation at 300 °C leading to M(OH)-UiO-66 structures. Adsorption of 1-butene is studied using calorimetry and density functional theory techniques to characterize the interactions of the alkene with metal cation sites that are found active for alkene oligomerization. For the most active Ni-UiO-66, the removal of molecular water from the active site significantly increases the 1-butene adsorption enthalpy and almost doubles the catalytic activity for 1-butene dimerization in comparison to the presence of water ligands. Other M-UiO-66 (M = Co, Cu, and Cr) exhibit 1–3 orders of magnitude lower catalytic activities compared to Ni-UiO-66. The catalytic activities correlate linearly with the Gibbs free energy of 1-butene adsorption. Furthermore, density functional theory calculations probing the Cossee–Arlman mechanism for all metals support the differences in activity, providing a molecular level understanding of the metal site as the active center for 1-butene dimerization.

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

Machine learning using host/guest energy histograms to predict adsorption in metal–organic frameworks: Application to short alkanes and Xe/Kr mixtures

A machine learning (ML) methodology that uses a histogram of interaction energies has been applied to predict gas adsorption in metal–organic frameworks (MOFs) using results from atomistic grand canonical Monte Carlo (GCMC) simulations as training and test data. In this work, the method is first extended to binary mixtures of spherical species, in particular, Xe and Kr. In addition, it is shown that single-component adsorption of ethane and propane can be predicted in good agreement with GCMC simulation using a histogram of the adsorption energies felt by a methyl probe in conjunction with the random forest ML method. Here, the results for propane can be improved by including a small number of MOF textural properties as descriptors. We also discuss the most significant features, which provides physical insight into the most beneficial adsorption energy sites for a given application.

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

Effect of surface properties and polymer chain length on polymer adsorption in solution

In polymer nanoparticle composites (PNCs) with attractive interactions between nanoparticles (NPs) and polymers, a bound layer of the polymer forms on the NP surface, with significant effects on the macroscopic properties of the PNCs. The adsorption and wetting behaviors of polymer solutions in the presence of a solid surface are critical to the fabrication process of PNCs. In this study, we use both classical density functional theory (cDFT) and molecular dynamics (MD) simulations to study dilute and semi-dilute solutions of short polymer chains near a solid surface. Using cDFT, we calculate the equilibrium properties of polymer solutions near a flat surface while varying the solvent quality, surface–fluid interactions, and the polymer chain lengths to investigate their effects on the polymer adsorption and wetting transitions. Using MD simulations, we simulate polymer solutions near solid surfaces with three different curvatures (a flat surface and NPs with two radii) to study the static conformation of the polymer bound layer near the surface and the dynamic chain adsorption process. Additionally, we find that the bulk polymer concentration at which the wetting transition in the poor solvent system occurs is not affected by the difference in surface–fluid interactions; however, a threshold value of surface–fluid interaction is needed to observe the wetting transition. We also find that with good solvent, increasing the chain length or the difference in the surface–polymer interaction relative to the surface–solvent interaction increases the surface coverage of polymer segments and independent chains for all surface curvatures. Finally, we demonstrate that the polymer segmental adsorption times are heavily influenced only by the surface–fluid interactions, although polymers desorb more quickly from highly curved surfaces.

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

Surface coverage dynamics for reversible dissociative adsorption on finite linear lattices

Dissociative adsorption onto a surface introduces dynamic correlations between neighboring sites not found in non-dissociative absorption. We study surface coverage dynamics where reversible dissociative adsorption of dimers occurs on a finite linear lattice. We derive analytic expressions for the equilibrium surface coverage as a function of the number of reactive sites, N, and the ratio of the adsorption and desorption rates. Using these results, we characterize the finite size effect on the equilibrium surface coverage. For comparable N’s, the finite size effect is significantly larger when N is even than when N is odd. Moreover, as N increases, the size effect decays more slowly in the even case than in the odd case. The finite-size effect becomes significant when adsorption and desorption rates are considerably different. These finite-size effects are related to the number of accessible configurations in a finite system where the odd-even dependence arises from the limited number of accessible configurations in the even case. We confirm our analytical results with kinetic Monte Carlo simulations. We also analyze the surface-diffusion case where adsorbed atoms can hop into neighboring sites. As expected, the odd-even dependence disappears because more configurations are accessible in the even case due to surface diffusion.

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

Thermodynamically consistent incorporation of the Langmuir adsorption model into compressible fluctuating hydrodynamics

For a gas–solid interfacial system where chemical species undergo reversible adsorption, we develop a mesoscopic stochastic modeling method that simulates both gas-phase hydrodynamics and surface coverage dynamics by coupling the Langmuir adsorption model with compressible fluctuating hydrodynamics. To this end, we derive a thermodynamically consistent mass–energy update scheme that accounts for how the mass and energy variables in the gas and surface subsystems should be updated according to the changes in the number of molecules of each species in each subsystem due to adsorption and desorption events. By performing a stochastic analysis for the ideal Langmuir model and the full hydrodynamic system, we analytically confirm that our mass–energy update scheme captures thermodynamic equilibrium predicted by equilibrium statistical mechanics. We find that an internal energy correction term is needed, which is attributed to the difference in the mean kinetic energy of gas molecules colliding with the surface from that computed from the Maxwell–Boltzmann distribution. By performing an equilibrium simulation study for an ideal gas mixture of CO and Ar, with CO undergoing reversible adsorption, we validate our overall simulation method and implementation.

Adsorption↗
DOE OSTI2025

Strong adsorption of guanidinium cations to the air–water interface

Combining Deep-UV second harmonic generation spectroscopy with molecular simulations, we confirm and quantify the specific adsorption of guanidinium cations to the air–water interface. Using a Langmuir analysis of measurements at multiple concentrations, we extract the Gibbs free energy of adsorption, finding it larger than typical thermal energies. Molecular simulations clarify the role of polarizability in tuning the thermodynamics of adsorption, and establish the preferential parallel alignment of guanidinium at the air–water interface. As a polyatomic cation, guanidinium represents one of the few examples of a positively charged species to exhibit a propensity for the air-water interface. As such, these results expand on the growing body of work on specific ion adsorption.

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

Multigas Adsorption with Single-Site Cooperativity in a Metal-Organic Framework

Cooperative gas adsorption in metal-organic frameworks (MOFs) is a rare phenomenon that generally involves long-range communication between multiple binding sites. We demonstrate a MOF containing cobalt(II)-methyl sites that selectively and reversibly capture two carbon monoxide (CO) molecules per site, leading to record-high adsorption capacities at ambient temperatures and pressures. Gas adsorption and structural, spectroscopic, and computational analyses support a mechanism in which binding of one CO molecule triggers a spin transition, followed by binding of a second CO molecule and migratory insertion of the first CO molecule into the cobalt-methyl bond to form an acetyl. The greater binding affinity associated with the second CO results in sigmoidal adsorption isotherms, a hallmark of cooperativity and phase-change materials, despite the absence of long-range interactions within the framework.

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

Determining the Adsorption Energetics of 2,3-Butanediol on RuO 2 (110): Coupling First-Principles Calculations With Global Optimizers

As climate change continues to pose a threat to the Earth due to the disrupted carbon cycles and fossil fuel resources remain finite, new sources of sustainable hydrocarbons must be explored. 2,3-butanediol is a potential source to produce butene because of its sustainability as a biomass-derived sugar. Butene is an attractive product because it can be used as a precursor to jet fuel, categorizing this work in the alcohol-to-jet pathway. While studies have explored the conversion of 2,3-butanediol to butene, little is understood about the fundamental reaction itself. We quantify the energetics for three pathways that were reported in the literature in the absence of a catalyst. One of these pathways forms a 1,3-butadiene intermediate, which is a highly exothermic process and thus is unlikely to occur since 2,3-butanediol likely gets thermodynamically trapped at this intermediate. We further determined the corresponding energetics of 2,3-butanediol adsorption on an ensemble of predetermined binding sites when it interacts with a defect-free stoichiometric RuO 2 (110) surface. Within this ensemble of adsorption sites, the most favorable site has 2,3-butanediol covering a Ru 5–coordinated cation. This approach is compared to that obtained using the global optimization algorithm as implemented in the Northwest Potential Energy Surface Search Engine. When using such a global optimization algorithm, we determined a more favorable ground-state structure that was missed during the manual adsorption site testing, with an adsorption energy of -2.61 eV as compared to -2.34 eV when using the ensemble-based approach. We hypothesize that the dehydration reaction requires a stronger chemical bond, which could necessitate the formation of oxygen vacancies. As such, this study has taken the first step toward the utilization of a global optimization algorithm for the rational design of Ru-based catalysts toward the formation of butene from sustainable resources.

09 BIOMASS FUELS↗
NASA NTRS2001

Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Calcium Carbonate/metabolism↗
NASA NTRS2014

Evaluating the Adsorptive Capacities of Chemsorb 1000 and Chemsorb 1425

The Air Revitalization Lab at KSC tested Chemsorb 1000 and 1425, two candidate sorbents for use in future air revitalization technologies being evaluated by the ARREM project. Chemsorb 1000 and 1425 are granular coconut-shell activated carbon sorbents produced by Molecular Products, Inc. that may be used in the TCCS. Chemsorb 1000 is a high grade activated carbon for organic vapor adsorption. In contrast, Chemsorb 1425 is a high-grade impregnated activated carbon for adsorption of airborne ammonia and amines. Chemsorb 1000 was challenged with simulated spacecraft gas streams in order to determine its adsorptive capacities for mixtures of volatile organics compounds. Chemsorb 1425 was challenged with various NH3 concentrations to determine its adsorptive capacity.

Evaluating↗
DOE OSTI2025

A Transferable Force Field for Predicting Adsorption and Diffusion of Water in Cationic Zeolites with Coupled Cluster Accuracy

We present a transferable force field for water in proton-exchanged, alkali (Li, Na, K, Rb, and Cs) metal-exchanged, and alkaline-earth (Mg, Ca, Sr, and Ba) metal-exchanged zeolites. The fitting methodology is based on adsorbate–adsorbent interaction energies obtained from periodic density functional theory calculations and corrected using the coupled-cluster method applied to small model clusters. To ensure an accurate prediction of both adsorption and diffusion properties of water, sets of configurations that sample both adsorption sites and intracrystalline hopping transition states were used in the fitting. The quality of the force field is assessed for a wide range of zeolites with different topologies and chemical compositions, demonstrating good agreement between theoretical predictions and experimental measurements of water adsorption and diffusion.

Adsorption↗
DOE OSTI2024

Data for: Competitive and Cooperative Effects of Chloride on Palladium(II) Adsorption to Iron (Oxyhydr)oxides: Implications for Mobility During Weathering

Data package for manuscript "Competitive and Cooperative Effects of Chloride on Palladium(II) Adsorption to Iron (Oxyhydr)oxides: Implications for Mobility During Weathering" by Emily G. Wright, Xicheng He, Elaine D. Flynn, Daniel E. Giammar, and Jeffrey G. Catalano. The manuscript will be submitted to Geochimica et Cosmochimica Acta. This dataset contains adsorption results from experiments designed to investigate the effect of chloride on Pd(II) adsorption to hematite and 2-line ferrihydrite. This includes lab experiments reacting suspensions of the minerals with various amounts of Pd and chloride at pH 4. We also characterized adsorbed Pd with X-ray absorption fine structure spectroscopy.

58 GEOSCIENCES↗