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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Combustion of liquid-fuel droplets in supercritical conditions

A comprehensive analysis of liquid-fuel droplet combustion in both subcritical and supercritical environments has been conducted. The formulation is based on the complete conservation equations for both gas and liquid phases, and accommodates variable thermophysical properties, finite-rate chemical kinetics, and a full treatment of liquid-vapor phase equilibrium at the drop surface. The governing equations and associated interfacial boundary conditions are solved numerically using a fully coupled, implicit scheme with the dual time-stepping integration technique. The model is capable of treating the entire droplet history, including the transition from the subcritical to supercritical state. As a specific example, the combustion of n-pentane fuel droplets in air is studied for pressures in the range of 5-140 atm. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the critical pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure.

Shuen, J. S.↗
DOE OSTI2024

Anomalous proximitized transport in metal/quantum magnet heterostructure Bi 2 Ir 2 O 7 /Yb 2 Ti 2 O 7

Fluctuations of quantum spins play a crucial role in the emergence of exotic magnetic phases and excitations. The lack of the charge degree of freedom in insulating quantum magnets, however, precludes such fluctuations from mediating electronic transport. Here, we show that the quantum fluctuations of a localized frustrated magnet induce strong proximitized charge transport of the conduction electrons in a synthetic heterostructure comprising an epitaxial Bi 2 Ir 2 O 7 ultrathin film on a single crystal of Yb 2 Ti 2 O 7 . The proximity effects are evidenced by the scaling behavior of the Bi 2 Ir 2 O 7 resistance in correspondence with the dynamic scaling of the dynamic spincorrelation function of Yb 2 Ti 2 O 7 , which is a result of quantum fluctuations near a multiphase quantum critical point. The proximitized transport in Bi 2 Ir 2 O 7 can be effectively tuned by a magnetic field through suppressing the quantum spin fluctuations (QSFs) as well as inducing transitions via magnetic anisotropy in Yb 2 Ti 2 O 7 . In this study, we establish a pathway for harnessing QSFs in magnetic insulators with electric transport, offering exciting prospects for potential applications in the realm of quantum spintronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Knowledge of intrinsic properties is of central importance for materials design and assessing suitability for specific applications. Self-assembling block copolymer electrolytes (BCEs) are of great interest for applications in solid-state energy storage devices. A fundamental understanding of ion transport properties, however, is hindered by the difficulty in deconvoluting extrinsic factors, such as defects, from intrinsic factors, such as the presence of interfaces between the domains. Here, we quantify the intrinsic ion transport properties of a model BCE system consisting of poly(styrene-block-ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt using a generalizable strategy of depositing thin films on interdigitated electrodes and self-assembling fully connected parallel lamellar structures throughout the films. Comparison between conductivity in homopolymer poly(ethylene oxide) (PEO)-LiTFSI electrolytes and the analogous conducting material in SEO over a range of salt concentrations (r, molar ratio of lithium ion to ethylene oxide repeat units) and temperatures reveals that between 20% and 50% of the PEO in SEO is inactive. Using mean-field theory calculations of the domain structure and monomer concentration profiles at domain interfaces-both of which vary substantially with salt concentration-the fraction of inactive PEO in the SEO, as derived from conductivity measurements, can be quantitatively reconciled with the fraction of PEO that is mixed with greater than a few volume percent of polystyrene. Despite the detrimental interfacial effects for ion transport in BCEs, the intrinsic conductivity of the SEO studied here (ca. 10 -3 S/cm at 90 degrees C, r = 0.085) is an order of magnitude higher than reported values from bulk samples of similar molecular weight SEO (ca. 10 -4 S/cm at 90 degrees C, r = 0.085). Finally, this work provides motivation and methods for pursuing improved BCE chemical design, interfacial engineering, and processing.

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

Metal Oxide-Induced Instability and Its Mitigation in Halide Perovskite Solar Cells

Halide perovskite solar cells (PSCs) have emerged as a promising photovoltaic technology for sustainable energy solutions due to their impressive power conversion efficiency and a path to be manufactured by low-cost, high-throughput methods. To reach PSCs’ full potential for practical implementation, it is crucial to solving the issues related to its long-term operational stability. Furthermore, given that PSCs consist of many layers of dissimilar materials which form multiple internal interfaces, it is prudent to examine whether there exist interfacial interactions, most importantly between transport layers and perovskite absorbers, that can trigger device performance and instability. In this perspective, we bring to the attention of the PSC research community the lesser-known interfacial degradation of halide perovskites promoted by contact with metal oxide transport layers and highlight the deleterious effects on the PSCs’ performance and stability. We also discuss various mitigation strategies that have shown promises to achieve high-performing and stable PSCs.

14 SOLAR ENERGY↗
DOE OSTI2026

Unveiling the High‐Voltage Reactivity and Gas Evolution With Aluminum‐Based Chloride and Oxychloride Catholytes in Solid‐State Sodium Batteries

All-solid-state sodium batteries (ASSBs) employing halide solid electrolytes (SEs) offer a cost-effective and energy-dense alternative to conventional liquid electrolyte systems. However, their high voltage (>4 V vs. Na/Na + ) performance remains limited by interfacial instability between the cathode active material (CAM) and the SE. We present here the electrochemical and interfacial behaviors of crystalline NaAlCl 4 and amorphous sodium–aluminum–oxychloride (NACO) SEs when combined with NaNi 0.5 Mn 0.5 O 2 cathode. While oxygen incorporation in NACO enhances ionic conductivity by nearly three orders of magnitude relative to NaAlCl 4 , it does not improve high-voltage cycling stability. Cells employing NACO exhibit accelerated capacity fade, increased cell impedance growth, and intrinsic oxygen evolution above 4.5 V vs. Na 3 Sn, as revealed by operando electrochemical mass spectrometry. In contrast, the NaAlCl 4 -based cells show no detectable gas release, underscoring their superior high-voltage stability and safety. Time-of-flight secondary-ion mass spectrometry confirms the formation of Al─O and Ni/Mn─Cl species, respectively, in the SE and CAM, indicating redox-driven anion exchange that contributes to kinetic hindrance of high-voltage phase transitions. The findings establish that while oxygen incorporation enhances ionic transport, it can compromise interfacial stability, suggesting pure chloride SEs may offer a more robust and intrinsically safer pathway for developing high-energy ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Probing Ice-Rule-Breaking Transition in Dy 2 Ti 2 O 7 Thin Film by Proximitized Transport and Magnetic Torque

While the spin-ice state of bulk pyrochlores such as Dy 2⁢ Ti 2 ⁢O 7 and Ho 2⁢ Ti 2 ⁢O 7 has been extensively studied in the past several decades due to its unique degenerate ground state and emergent monopole excitation, whether it survives in the thin-film form remains a mystery. The limited volume of the thin-film sample makes it challenging to study the intrinsic magnetic properties. Here, we synthesized 18-nm-thick Dy 2⁢ Ti 2 ⁢O 7 thin film on yttria-stabilized zirconia with 9.5 mol% Y 2 ⁢O 3 substrate and capped it by a thin conductive Bi 2 ⁢Ir 2 ⁢O 7 layer and performed the proximitized magnetoresistance measurements. Our Letter found that the ice-rule-breaking phase transition survives but with a modified effective nearest-neighbor interaction (𝐽 eff =1.054 K) and distorted Ising spin axes (𝜀 = +0.051) compared to the bulk crystal. Furthermore, the results are supported by the simultaneously measured capacitive torque magnetometry. Our Letter demonstrates that proximitized transport is an effective tool for thin films of insulating frustrated magnets.

Magnetic interactions↗
DOE OSTI2023

Tuned Reactivity at the Lithium Metal–Argyrodite Solid State Electrolyte Interphase

Thin intermetallic Li 2 Te–LiTe 3 bilayer (0.75 µm) derived from 2D tellurene stabilizes the solid electrolyte interphase (SEI) of lithium metal and argyrodite (LPSCl, Li 6 PS 5 Cl) solid-state electrolyte (SSE). Tellurene is loaded onto a standard battery separator and reacted with lithium through single-pass mechanical rolling or transferred directly to SSE surface by pressing. State-of-the-art electrochemical performance is achieved, e.g., symmetric cell stable for 300 cycles (1800 h) at 1 mA cm -2 and 3 mAh cm -2 (25% DOD, 60 µm foil). Cryo-stage focused ion beam (Cryo-FIB) sectioning and Raman mapping demonstrate that the Li 2 Te–LiTe 3 bilayer impedes SSE decomposition. The unmodified Li–LPSCl interphase is electrochemically unstable with a geometrically heterogeneous reduction decomposition reaction front that extends deep into the SSE. Decomposition drives voiding in Li metal due to its high flux to the reaction front, as well as voiding in the SSE due to the associated volume changes. Analysis of cycled SSE found no evidence for pristine (unreacted) lithium metal filaments/dendrites, implying failure driven by decomposition phases with sufficient electrical conductivity that span electrolyte thickness. In conclusion, DFT calculations clarify thermodynamic stability, interfacial adhesion, and electronic transport properties of interphases, while mesoscale modeling examines interrelations between reaction front heterogeneity (SEI heterogeneity), current distribution, and localized chemo-mechanical stresses.

25 ENERGY STORAGE↗
DOE OSTI2022

Ionic Liquid Engineering in Perovskite Photovoltaics

Over the past decade, perovskite photovoltaics have approached other currently available technologies and proven to be the most prospective type of solar cells. Although the many-sided research in this very active field has generated consistent results with regard to their undisputed consistently increasing power conversion efficiency, it also produced several rather contradictory opinions. Among other important details, debate surrounding their proneness to surface degradation and poor mechanical robustness, as well as the environmental footprint of this materials class, remains a moot point. The application of ionic liquids appears as one of the potential remedies to some of these challenges due to their high conductivity, the opportunities for chemical “tuning” of the structure, and relatively lower environmental footprint. This article provides an overview, classification, and applications of ionic liquids in perovskite solar cells. Here, we summarize the use and role of ionic liquids as versatile additives, solvents, and modifiers in perovskite precursor solution, in charge transport layer, and in interfacial and stability engineering. Finally, challenges and the future prospects for the design and/or selection of ionic liquids with a specific profile that meets the requirements for next-generation highly efficient and stable perovskite solar cells are proposed.

14 SOLAR ENERGY↗
DOE OSTI2019

Structure and Thermodynamic Stability of Zeolitic Imidazolate Framework Surfaces

Extensive efforts over the last several decades have focused on the possibility of “crystal engineering” metal–organic framework (MOF) materials with bulk properties tailored toward specific applications. However, beyond their bulk structure, MOF interfaces and surfaces can also play an important role in governing the materials properties relevant to many applications, including both interfacial mass and/or charge transport. We presently examine the diversity of stable surface structures/terminations of zeolitic imidazolate frameworks (ZIFs), a subclass of MOFs, under a variety of conditions that are characteristic of either gas-phase, “post-synthetic” conditions (relevant to many MOF applications) or solution-phase conditions (typical of those used during MOF synthesis). We construct surface phase diagrams to predict the most stable ZIF surface terminations as a function of external parameters (including temperature, adsorbate pressures, and pH), making explicit comparison against prior experimental observations, when possible. Overall, we find that the resulting phase diagrams can be used to explain the results of prior experimental studies of ZIF terminations across a variety of conditions and provide important insights into the factors that govern the structure of ZIF interfaces.

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

Manipulating topological Hall-like signatures by interface engineering in epitaxial ruthenate/manganite heterostructures

Topologically protected non-trivial spin textures (e.g. skyrmions) give rise to a novel phenomenon called the topological Hall effect (THE) and have promising implications in future energy-efficient nanoelectronic and spintronic devices. Here, we have studied the Hall effect in SrRuO 3 /La 0.42 Ca 0.58 MnO 3 (SRO/LCMO) bilayers. Our investigation suggests that pure SRO has hard and soft magnetic characteristics but the anomalous Hall effect (AHE) in SRO is governed by the high coercivity phase. Here, we have shown that the proximity effect of a soft magnetic LCMO on SRO plays a critical role in interfacial magnetic coupling and transport properties in SRO. Upon reducing the SRO thickness in the bilayer, the proximity effect becomes the dominant feature, enhancing the magnitude and temperature range of THE-like signatures. The THE-like features in bilayers can be explained by a diffusive Berry phase transition model in the presence of an emergent magnetic state due to interface coupling. This work provides an alternative understanding of THE-like signatures and their manipulation in SRO-based heterostructures, bilayers and superlattices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Possible unconventional pairing in ( Ca , Sr ) 3 ( Ir , Rh ) 4 Sn 13 superconductors revealed by controlling disorder

Here we study the evolution of temperature-dependent resistivity with added pointlike disorder induced by 2.5 MeV electron irradiation in stoichiometric compositions of the “3-4-13” stannides, (Ca,Sr) 3 (Ir,Rh) 4 Sn 13 . Three of these cubic compounds exhibit a proposed microscopic coexistence of charge density wave (CDW) order and superconductivity (SC), while Ca 3 Rh 4 Sn 13 does not develop CDW order. As expected, the CDW transition temperature T CDW is universally suppressed by irradiation in all three compositions. The superconducting transition temperature, T c , behaves in a more complex manner. In Sr 3 Rh 4 Sn 13 , it increases initially in a way consistent with a direct competition of CDW and SC, but quickly saturates at higher irradiation doses. In the other three compounds, T c is monotonically suppressed by irradiation. The strongest suppression is found in Ca 3 Rh 4 Sn 13 , which does not have CDW order. We further examine this composition by measuring the London penetration depth λ(T), from which we derive the superfluid density. The result unambiguously points to a weak-coupling, full single gap, isotropic superconducting state. Therefore we must explain two seemingly incompatible experimental observations: a single isotropic superconducting gap and a significant suppression of T c by nonmagnetic disorder. We conduct a quantitative theoretical analysis based on a generalized Anderson theorem which points to an unconventional multiband s +– -pairing state where the sign of the order parameter is different on one (or a small subset) of the smaller Fermi surface sheets but remains isotropic and overall fully gapped.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Basic Energy Sciences Roundtable: Foundational Science for Carbon Dioxide Removal Technologies (Brochure)

Basic research to identify and understand the fundamental principles governing carbon dioxide removal processes of capture, conversion, and storage is essential for achieving zero carbon emissions by 2050. In March 2022, the Office of Basic Energy Sciences (BES)—in coordination with the US Department of Energy (DOE) technology Offices of Energy Efficiency and Renewable Energy, Fossil Energy and Carbon Management, and Nuclear Energy—held a roundtable titled, “Foundational Science for Carbon Dioxide Removal Technologies,” to discuss the scientific and technical barriers for CO 2 capture, conversion, and storage. Five priority research opportunities were identified to address these scientific and technical challenges and accelerate progress toward the realization of zero carbon emissions. The PROs are as follows: 1) Master Interfacial Processes of CO2 Transport and Reactivity Across Multiple Length and Time Scales; 2) Create Materials that Simultaneously Exhibit Multiple Properties for CO 2 Capture and Release or Conversion; 3) Discover Unconventional Pathways for Energy-Efficient CO 2 Capture, Release, and Conversion; 4) Control Multiphase Interactions Required for CO 2 Conversion into Minerals and Materials; and 5) Achieve Predictive Understanding of Coupled Processes in Complex Subsurface Geologic Systems for Secure Carbon Storage.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Supercritical droplet combustion and related transport phenomena

An overview of recent advances in theoretical analyses of supercritical droplet vaporization and combustion is conducted. Both hydrocarbon and cryogenic liquid droplets over a wide range of thermodynamic states are considered. Various important high-pressure effects on droplet behavior, such as thermodynamic non-ideality, transport anomaly, and property variation, are reviewed. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the criticl pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure. The influence of droplet size on the burning characteristics is also noted.

Yang, Vigor↗
NASA NTRS1993

Temperature dependence of protein solubility-determination, application to crystallization, and growth kinetics studies

A scintillation method was developed for determinations of the temperature dependence of the solubility, and of nucleation induction times of proteins, in 50-100 mu(l) volumes of solution. Solubility data for lysozyme and horse serum albumin were obtained for various combinations of pH and precipitant concentrations. These data and the nucleation induction information were used for dynamic crystallization control, that is, for the controlled separation of nucleation and growth stages. Individual lysozyme and horse serum albumin crystals were grown in 15-20 mu(l) solution volumes contained in x-ray capillaries. The morphology and kinetics of the growth and dissolution of lysozyme in aqueous solutions with 2.5 percent NaCl and at pH = 4.5 was studied in situ with a depth resolution of 300 A (4 unit cells) by high resolution optical microscopy and digital image processing. The bulk super- or under saturation, sigma, of the solution inside a closed growth cell was controlled by temperature. The growth habit was bound by (110) and (101) faces that grew through layer spreading, although with different growth rate dependencies on supersaturation/temperature. At sigma less than 10 (obtained at higher temperatures) growth was purely kinetic ally controlled, with impurity effects (macrostep formation and kinetic hindrance) becoming significant for sigma less than 2. At sigma greater than 10 (lower temperatures), anisotropies in the interfacial kinetics were more pronounced, with interfacial kinetics and bulk transport becoming equally important to the growth morphology. Growth rates were growth history dependent. The formation of striations (layers of irregularly incorporated solution) was unambiguously correlated with growth temperature variations. Etching exposed dislocations and various high-index faces whose growth morphologies were studied during return to the steady state growth form. Growth steps were observed to originate from two-dimensional nuclei or from outcrops of growth striations, and from dislocations that preferentially formed in growth sector boundaries.

Rosenberger, Franz↗
NASA NTRS1996

Nucleation and Crystallization of Globular Proteins: What we Know and What is Missing

Recently. much progress has been made in understanding the nucleation and crystallization of globular proteins, including the formation of compositional and structural crystal defects, Insight into the interactions of (screened) protein macro-ions in solution, obtained from light scattering, small angle X-ray scattering and osmotic pressure studies. can guide the search for crystallization conditions. These studies show that the nucleation of globular proteins is governed by the same principles as that of small molecules. However, failure to account for direct and indirect (hydrodynamic) protein interactions in the solutions results in unrealistic aggregation scenarios. Microscopic studies of numerous proteins reveal that crystals grow by the attachment of growth units through the same layer-spreading mechanisms as inorganic crystals. Investigations of the growth kinetics of hen-egg-white lysozyme (HEWL) reveal non-steady behavior under steady external conditions. Long-term variations in growth rates are due to changes in step-originating dislocation groups. Fluctuations on a shorter timescale reflect the non-linear dynamics of layer growth that results from the interplay between interfacial kinetics and bulk transport. Systematic gel electrophoretic analyses suggest that most HEWL crystallization studies have been performed with material containing other proteins at percent levels. Yet, sub-percent levels of protein impurities impede growth step propagation and play a role in the formation of structural/compositional inhomogeneities. In crystal growth from highly purified HEWL solutions, however, such inhomogeneities are much weaker and form only in response to unusually large changes in growth conditions. Equally important for connecting growth conditions to crystal perfection and diffraction resolution are recent advances in structural characterization through high-resolution Bragg reflection profiling and X-ray topography.

Rosenberger, F.↗
DOE OSTI2021

High Performance PEFC Electrode Structures

Raytheon Technologies Research Center (RTRC) in collaboration with Ion Power Inc. and the University of Arkansas at Little Rock and the FC-PAD consortium executed a project that: (1) developed comprehensive models of oxygen and proton transport in cathode catalyst layers that provided new insights about losses associated with reducing platinum loading to 0.1 mg/cm 2 , (2) designed, fabricated, characterized, and tested cells featuring carbon-supported catalyst layers with low platinum loadings that met efficiency and power density targets set forth by the Hydrogen and Fuel Cells Technology Office, and (3) designed, fabricated, characterized, and tested novel catalyst structures. The modeling efforts produced eight scientific publications that shared new descriptions of oxygen and proton transport in catalyst layers with the broader technical community. The key physical insights from the models are expressed in straightforward algebraic expressions, facilitating easy adoption by other researchers. The models developed during the project explain why resistance to oxygen transport is inversely proportional to interfacial area of platinum – an observation that eluded quantitative explanation for a decade. The models quantitatively predict polarization when measured morphological parameters and transport properties are input. Membrane-electrode assemblies made during the project met stated goals for current at high voltage and power density at rated voltage for transportation fuel cells at the end of budget period 2. High performance was achieved by developing a diffusion layer with low resistance to oxygen transport and a PtCo/C cathode catalyst layer capable of supporting rapid proton and oxygen transport. The project was subsequently directed to curtail experimental work and focus on modeling during budget period 3. Ion Power Inc. developed new expertise in fabricating catalyst layers containing platinum-cobalt catalysts, and processing very thin membranes. The University of Arkansas at Little Rock developed novel nanocolumnar self-supported thin film electrocatalysts that can be grown on carbon supports using a simple high pressure sputter deposition method. The nanocolumnar microstructure provides adequate surface-to-volume ratio for efficient platinum utilization, and the conformal platinum shell with larger crystal grain sizes covering the carbon support surface may eliminate durability issues associated with catalyst dissolution, agglomeration, and carbon corrosion.

08 HYDROGEN↗
DOE OSTI2021

Effect of time and spatial domains on monolayer 2D material interface thermal conductance measurement using ns ET-Raman

Raman-based approaches to characterizing thermal properties of nanoscale and microscale materials have proven to be powerful experimental methods. Here, this work explores the potential of energy-transport state-resolved Raman (ET-Raman) for the precise determination of interfacial thermal conductance (G) between monolayer 2D materials and their substrates. ET-Raman employs a continuous wave laser and nanosecond (ns) pulsed laser to induce both steady state and transient heating while simultaneously collecting 2D material temperature information from the Raman signal. A 3D numerical model built using the finite volume method simulates the two differentiated thermal transport processes. The simulated temperature rises are compared with experimental Raman temperature information to extract G. In this study, we investigate the temporal effects of the pulse frequency and pulse width of the ns laser on precise characterization of G. By running multiple simulations for a range of pulsed laser frequencies and pulse widths, we determine that ET-Raman is most sensitive to precise interfacial thermal conductance measurements with short pulse widths (~below 20 ns) and with pulsing frequencies that ensure sufficient cooling time between consecutive pulses (~below 500 kHz). We also conclude that substrate thickness and laser spot size play critical roles in heat distribution and subsequent sensitivity to meaningful G measurements. As both laser spot size and SiO 2 substrate thickness decrease, detection of interfacial thermal transport becomes more difficult. These results offer essential guidance in the design of future Raman-based approaches to thermal measurements using pulsed lasers.

2D materials↗
DOE OSTI2025

Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption

The competition between bulk and interfacial phenomena underlies many key processes in complex chemical phenomena and transport. While competitive processes are often framed in a thermodynamic context, opportunities to leverage transient species found away from equilibrium can provide a kinetic handle to achieve unconventional reaction outcomes. In this work, we outfit an iminoguanidinium headgroup capable of selective SO 4 2– complexation with alkyl tails of varying complexity to probe competitive bulk and interfacial reaction pathways and tune kinetic pathways for selective chemical separations. Using sum frequency generation (SFG) vibrational spectroscopy we unexpectedly find that adsorption of ligands to the air–aqueous interface was dramatically slowed down for species with increasingly hydrophobic tails. Underlying this phenomenon, we show that the formation of bulk colloidal species with differing propensities for SO 4 2– inhibited surface adsorption via a kinetic bottleneck in the exchange of molecular extractants with colloidal aggregates. This kinetic effect could open up avenues to access unconventional selectivity via complexation of strongly coordinating species in the bulk phase, allowing for more weakly coordinating species to transport via interfacial mechanisms. Furthermore, this work broadly probes nonequilibrium phenomena in chemical separations that arise through unexpected interfacial events that are neglected in traditional equilibrium descriptions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗