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Results for “Liquid adsorption”

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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280 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Understanding Self-Assembly and the Stabilization of Liquid/Liquid Interfaces: The Importance of Ligand Tail Branching and Oil-Phase Solvation

Organophosphorus-based ligands represent a versatile set of solvent extraction reagents whose chemical makeup plays an important role in extraction mechanism. We hypothesize that the branching of the extractant hydrophobic tail and its oil-phase solvation affect the liquid/liquid interfacial structure. Understanding the structure mediated adsorption and interfacial ordering becomes key in designing ligands with enhanced selectivity and efficiency for targeted extractions. We employed vibrational sum frequency generation spectroscopy and interfacial tension measurements to extract thermodynamic adsorption energies, map interfacial ordering, and rationalize disparate behaviors of model di-(2-ethylhexyl) phosphoric acid and dioctyl phosphoric acid ligands at the hexadecane water interface. With increased surface loading, ligands with branched hydrophobic tails formed stable interfaces at much lower concentrations than those observed for ligands with linear alkyl tails. The lack of an oil phase and associated solvation results in markedly different interfacial properties, and thus measurements made at air/liquid surfaces cannot be assumed to correlate with the processes occurring at buried liquid/liquid interfaces. Here, we attribute these differences in the surface mediated self-assembly to key variations in hydrophobic interactions and tail solvation taking place in the oil phase demonstrating that interactions in both the polar and nonpolar phases are essential to understand self-assembly and function.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Literature Review Investigating Adsorbents for Mercury Removal from Salt Batch Feed Material

The Savannah River Site (SRS) Liquid Waste System (LWS) contains mercury that originated from decades of canyon processing where it was used as a catalyst for dissolving aluminum cladding of reactor fuel. Since the start of radioactive operations, the Salt Waste Processing Facility (SWPF) has experienced processing difficulties due to the presence of mercury-laden solids. In response to these challenges, Savannah River National Laboratory (SRNL) has been requested by Savannah River Mission Completion (SRMC)/Salt Waste Processing Facility (SWPF) personnel to perform a literature review to assess the feasibility of chemical strikes to salt waste-containing tanks at the SRS as an option to reduce mercury introduction into SWPF. The literature review should evaluate known technologies and chemistries for decreasing mercury concentration and the anticipated efficacy of each technology on various mercury species known to exist in SRS waste.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

A coarse-grained model of clay colloidal aggregation and consolidation with explicit representation of the electrical double layer

The aggregation of clay minerals in liquid water exemplifies colloidal self-assembly in nature. These negatively charged aluminosilicate platelets interact through multiple mechanisms with different sensitivities to particle shape, surface charge, aqueous chemistry, and interparticle distance and exhibit complex aggregation structures. Experiments have difficulty resolving the associated colloidal assemblages at the scale of individual particles. Conversely, all-atom molecular dynamics (MD) simulations provide detailed insight on clay colloidal interaction mechanisms, but they are limited to systems containing a few particles. We develop a new coarse-grained (CG) model capable of representing assemblages of hundreds of clay particles with accuracy approaching that of MD simulations, at a fraction of the computational cost. Our CG model is parameterized based on MD simulations of a pair of smectite clay particles in liquid water. A distinctive feature of our model is that it explicitly represents the electrical double layer (EDL), i.e., the cloud of charge-compensating cations that surrounds the clay particles. Our model captures the simultaneous importance of long-range colloidal interactions (i.e., interactions consistent with simplified analytical models, already included in extant clay CG models) and short-range interactions such as ion correlation and surface and ion hydration effects. The resulting simulations correctly predict, at low solid-water ratios, the existence of ordered arrangements of parallel particles separated by water films with a thickness up to ~10 nm and, at high solid-water ratios, the coexistence of crystalline and osmotic swelling states, in agreement with experimental observations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Chemical Potential Driven Reorganization of Anions between Stern and Diffuse Layers at the Air/Water Interface

We report ion adsorption and transfer at charged interfaces play key roles in various industrial and environmental processes. Molecular scale details of ion-ion, ion-water, and ion-surface interactions are still debated. Complex ions, such as SCN - and SeCN - , are particularly interesting due to their unexpected adsorption trends. Here, we combine vibrational sum frequency generation (VSFG) spectroscopy and surface-sensitive synchrotron X-ray studies to provide a detailed description of SeCN - adsorption at a floating charged monolayer. Polarimetry studies show that the average orientation of SeCN - anions with respect to the surface normal decreases from 45° to 22° with the increasing KSeCN concentration. Interfacial SeCN - coverage saturates at very low bulk concentrations, but their orientational organization, distribution between Stern and diffuse layers, and effects on the hydrogen-bonding network of the interfacial water continue to change with increasing bulk KSeCN concentration. These results show that the increasing chemical potential may lead to further reorganization of the adsorbed ions, even though the total interfacial ion population does not change. The reorganization of the interfacial ions and the water may be very important in chemical separations of heavy metals, where metal-anion complexes drive the selective ion transfer at aqueous interfaces.

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

The Role of Interfaces and Charge for Chemical Reactivity in Microdroplets

A wide variety of reactions are reported to be dramatically accelerated in aqueous microdroplets, making them a promising platform for environmentally clean chemical synthesis. However, to fully utilize the microdroplets for accelerating chemical reactions requires a fundamental understanding of how microdroplet chemistry differs from that of a homogeneous phase. Here, in this work, we provide our perspective on recent progress to this end, both experimentally and theoretically. We begin by reviewing the many ways in which microdroplets can be prepared, creating water/hydrophobic interfaces that have been frequently implicated in microdroplet reactivity due to preferential surface adsorption of solutes, persistent electric fields, and their acidity or basicity. These features of the interface interplay with specific mechanisms proposed for microdroplet reactivity, including partial solvation, possible gas phase channels, and the presence of highly reactive intermediates. We especially highlight the role of droplet charge and associated electric fields, which appears to be key to understanding how certain reactions, like the formation of hydrogen peroxide and reduced transition metal complexes, are thermodynamically possible in microdroplets. Lastly, we emphasize opportunities for theoretical advances and suggest experiments that would greatly enhance our understanding of this fascinating subject.

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

Factors Determining Selectivity of Acid- and Base-Catalyzed Self- and Cross-Condensation of Acetone and Cyclopentanone

In a combined kinetics and density functional theory (DFT) study, we have explored several factors that affect the selectivity of acid- and base-catalyzed self- and cross-aldol condensation of acetone (ACE) and cyclopentanone (CPO). These factors include competitive adsorption, molecular structure, and electron polarization of the two ketones on the catalyst surface. Here, kinetic analysis shows that on MgO, self-condensation of both ACE and CPO is limited by the initial unimolecular enolization step. Accordingly, CPO exhibits a higher self-condensation rate than ACE due to the more favorable α-C–H abstraction by the basic O site. The thermodynamic parameters derived from the kinetic analysis indicate that under cross-condensation reaction conditions, the MgO surface fraction covered by CPO is significantly higher than that covered by ACE. Therefore, the product distribution is dominated by [CPO]-activated products ([CPO]CPO + [CPO]ACE). Also, for a given enolate (indicated as [CPO] or [ACE]), the higher surface coverage of CPO leads to enhanced C–C coupling with CPO as the electrophile ([CPO]CPO > [CPO]ACE; [ACE]CPO > [ACE]ACE). By contrast, for both acid catalysts investigated, the rate-limiting step is the bimolecular C–C coupling, with aspects of this step depending on the density of acid sites. That is, on the high-acid-density MCM-41-SO 3 H catalyst, condensation follows a bimolecular dual-site mechanism (Langmuir–Hinshelwood model). On this catalyst surface, the ACE coverage is higher than that of CPO, which causes a higher selectivity for those products in which ACE is the electrophile ([CPO]ACE > [CPO]CPO; [ACE]ACE > [ACE]CPO). Steric hindrance is another factor that affects selectivity in the same way, favoring products in which the electrophile is ACE since it presents a lower steric hindrance to C–C coupling than CPO. Therefore, the same sequence of products is obtained for the low-acid-density MCM-41-SO 3 H catalyst, which proceeds on a single-acid site with the other molecule in the liquid phase (Eley–Rideal model). In this case, the electrophile coverage is not relevant, but the steric hindrance is, yielding the same trend as above ([CPO]ACE > [CPO]CPO; [ACE]ACE > [ACE]CPO).

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

Asphaltene-induced spontaneous emulsification: Effects of interfacial co-adsorption and viscoelasticity

Asphaltenes are a class of high molecular weight aromatic compounds found in crude oil. They adsorb onto toluene-water interfaces and induce a spontaneous emulsification phenomenon, whereby stable water-in-oil emulsions form without the need of an external energy input. This work aims to control and understand the factors affecting spontaneous droplet formation in the presence of asphaltene adsorption. This is particularly useful for crude oil refining, where the presence of a stable emulsion hampers the efficiency of downstream processing operations. We explore the effect of the addition of copolymers designed as crude oil flow improvers as a means to control the extent of emulsion formation. We find that the polymers competitively adsorb onto the toluene-water interface and diminish spontaneous emulsification. Additionally, we conduct fluorescence microscopy experiments and measurements of the interfacial energy to determine the mechanism of spontaneous emulsification in asphaltene systems. We conclude that an emulsion forms via the diffusion of molecular water into the oil phase and subsequent binding with asphaltene aggregates, leading to the nucleation of micrometer-sized water droplets. We find that the polymer forms complexes with the dissolved asphaltenes, possibly hampering the ability of diffused water to bind to the asphaltenes and reducing the extent of spontaneous emulsification. Finally, we investigate the role of interfacial shear and dilatational viscoelasticity to better understand which fundamental interfacial properties are important in the emulsification of asphaltene-laden systems. We find that the rate of formation of an interfacial microstructural network is inversely correlated with the extent and rate of spontaneous emulsification.

42 ENGINEERING↗
DOE OSTI2025

Prediction of hydration energies of adsorbates at Pt(111) and liquid water interfaces using machine learning

Aqueous phase heterogeneous catalysis is important to various industrial processes, including biomass conversion, Fischer–Tropsch synthesis, and electrocatalysis. Accurate calculation of solvation thermodynamic properties is essential for modeling the performance of catalysts for these processes. Explicit solvation methods employing multiscale modeling, e.g., involving density functional theory and molecular dynamics have emerged for this purpose. Although accurate, these methods are computationally intensive. This study introduces machine learning (ML) models to predict solvation thermodynamics for adsorbates on a Pt(111) surface, aiming to enhance computational efficiency without compromising accuracy. In particular, ML models are developed using a combination of molecular descriptors and fingerprints and trained on previously published water–adsorbate interaction energies, energies of solvation, and free energies of solvation of adsorbates bound to Pt(111). These models achieve root mean square error values of 0.09 eV for interaction energies, 0.04 eV for energies of solvation, and 0.06 eV for free energies of solvation, demonstrating accuracy within the standard error of multiscale modeling. Feature importance analysis reveals that hydrogen bonding, van der Waals interactions, and solvent density, together with the properties of the adsorbate, are critical factors influencing solvation thermodynamics. Furthermore, these findings suggest that ML models can provide rapid and reliable predictions of solvation properties. This approach not only reduces computational costs but also offers insights into the solvation characteristics of adsorbates at Pt(111)–water interfaces.

Adsorption↗
DOE OSTI2022

CO 2 Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

Superbase-derived task-specific ionic liquids (STSILs) represent one of the most attractive and extensively studied systems in carbon capture via chemisorption, in which the obtained CO 2 uptake capacity has a strong relationship with the basicity of the anions. High energy input in desorption and side reactions caused by the strong basicity of the anions are still unsolved issues. The development of other customized STSILs leveraging an alternative driving force to achieve efficient CO 2 chemisorption/desorption is highly desirable yet challenging. Here, in this work, carbanion-derived STSILs were developed for efficient CO 2 chemisorption via a carboxylic acid formation pathway. The STSIL with the deprotonated malononitrile molecule ([MN]) as the anion exhibited much higher CO 2 uptake capacity than the one derived from 2-methylmalononitrile ([MMN]). Notably, this trend was opposite to their basicity ([MN] < [MMN]). Detailed characterization of the products, supported by density functional theory simulations of spectra and calculations of the reaction energetics, demonstrated that carboxylic acid was formed upon reacting with CO 2 via proton transfer in [MN]-derived STSILs but not in the case of [MMN] due to lack of an α-H. The preference of the carboxylic acid product over carboxylate formation was driven by the extended conjugation among the central sp 2 carbon, the as-formed carboxylic acid, and the two nitrile groups. The achievements made in this work provide an alternative design principle of STSILs by leveraging the extended conjugation in the CO 2 -integrated product.

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

Identification and quantification of distinct active sites in Hf-Beta zeolites for transfer hydrogenation catalysis

Despite the significant progress made in characterizing different framework heteroatom sites that exist in Lewis acidic zeolites with probe molecule adsorption and spectroscopy, methods to reliably quantify site counts remain indefinite and have been primarily limited to Sn and Ti Lewis acid sites. Here, methods to quantify framework Lewis acidic Hf 4+ sites in zeolite Beta (Hf-Beta) with two Lewis base titrants (pyridine, deuterated acetonitrile) were developed using infrared (IR) spectroscopy. Lewis acid site counts for Hf-Beta zeolites were validated by measuring integrated molar extinction coefficients (IMECs; ε, cm μmol –1 ) on Sn-Beta zeolites using identical Lewis base titrants to benchmark site counts with established literature procedures to quantify Lewis acid sites in Beta zeolites from IR spectra. Highlighting the importance of benchmarking active site counts against well-established experimental protocols, IMECs of CD 3 CN bound to open (ε(Sn; 2316 cm –1 ): 1.80 ± 0.25) and closed (ε(Sn; 2308 cm –1 ): 3.76 ± 0.33) Sn sites were ~1.8x larger than those previously reported while total Lewis acid site counts agreed with those measured by pyridine (ε(Sn; 1451 cm –1 ): 1.58 ± 0.16) on six different Sn-Beta zeolites. IMECs measured for IR peaks reflecting pyridine bound to Lewis acidic Hf sites (ε(Hf; 1448 cm –1 ): 1.54 ± 0.21) and CD 3 CN bound to open (ε(Hf; 2313 cm –1 ): 2.40 ± 0.22) and closed (ε(Hf; 2307 cm –1 ): 3.55 ± 0.41) Hf sites, gave similar counts for the total number of Lewis acidic sites across six Hf-Beta zeolites (Si/Hf = 100–413). Consistent with previous reports with Sn-Beta catalysts where open Sn sites are responsible for catalytic turnover, apparent first and zero-order MPVO rate constants (0.01–1 M cyclohexanone in 2-butanol; per total Hf, 373 K) correlated with the total number of open Hf sites, per total Hf, but not with the total number of closed Hf sites or total Lewis acid site counts. Measured initial MPVO rates (0.1 M cyclohexanone in 2-butanol, per open Hf, 373 K) were ~25x higher on hydrophobic Hf-Beta-F than on hydrophilic Hf-Beta-OH zeolites. Overall, the apparent first-order MPVO rate constants (2-butanol solvent, per open Hf, 373 K) were ~6x higher on Hf-Beta-F than on Hf-Beta-OH zeolites. The characterization methods reported here enable normalization of MPVO turnover rates on Sn- and Hf-Beta zeolites by their number of open sites. Finally, this enables performing quantitative rate comparisons across Lewis acid zeolites of varying active site identity, solvation, and pore topology used in liquid-phase catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗