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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Thermal stability and coalescence dynamics of exsolved metal nanoparticles at charged perovskite surfaces

Exsolution reactions enable the synthesis of oxide-supported metal nanoparticles, which are desirable as catalysts in green energy conversion technologies. It is crucial to precisely tailor the nanoparticle characteristics to optimize the catalysts’ functionality, and to maintain the catalytic performance under operation conditions. We use chemical (co)-doping to modify the defect chemistry of exsolution-active perovskite oxides and examine its influence on the mass transfer kinetics of Ni dopants towards the oxide surface and on the subsequent coalescence behavior of the exsolved nanoparticles during a continuous thermal reduction treatment. Nanoparticles that exsolve at the surface of the acceptor-type fast-oxygen-ion-conductor SrTi 0.95 Ni 0.05 O 3–δ (STNi) show a high surface mobility leading to a very low thermal stability compared to nanoparticles that exsolve at the surface of donor-type SrTi 0.9 Nb 0.05 Ni 0.05 O 3–δ (STNNi). Our analysis indicates that the low thermal stability of exsolved nanoparticles at the acceptor-doped perovskite surface is linked to a high oxygen vacancy concentration at the nanoparticle-oxide interface. For catalysts that require fast oxygen exchange kinetics, exsolution synthesis routes in dry hydrogen conditions may hence lead to accelerated degradation, while humid reaction conditions may mitigate this failure mechanism.

25 ENERGY STORAGE↗
DOE OSTI2020

Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems

Lead sulfide (PbS) quantum dots (QDs) have shown promising performance as a sensitizer in infrared-to-visible photon upconversion systems. To investigate the key design rules, we compare three PbS-sensitized upconversion systems using three mediator molecules with the same tetracene triplet acceptor at different distances from the QD. Using transient absorption spectroscopy, we directly measure the triplet energy-transfer rates and efficiencies from the QD to the mediator and from the mediator to the emitter. With increasing distance between the mediator and PbS QD, the efficiency of the first triplet energy transfer from the QD to the mediator decreases because of a decrease in the rate of this triplet energy-transfer step, while the efficiency of the second triplet energy transfer from the mediator to the emitter increases because of a reduction in the QD-induced mediator triplet state decay. The latter effect is a result of the slow rate constant of the second triplet energy-transfer process, which is 3 orders of magnitude slower than the diffusion-limited value. The combined results lead to a net decrease of the steady-state upconversion quantum yield with distance, which could be predicted by our kinetic model. Our result shows that the QD/mediator interface affects both the first and second triplet energy transfer processes in the photon upconversion system, and the QD/mediator distance has an opposite effect on the efficiencies of the first and second triplet energy transfer. Lastly, these findings provide important insight for the further rational improvement of the overall efficiency of QD-based upconversion systems.

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

Surface fluctuating hydrodynamics methods for the drift-diffusion dynamics of particles and microstructures within curved fluid interfaces

Here we introduce fluctuating hydrodynamics approaches on surfaces for capturing the drift-diffusion dynamics of particles and microstructures immersed within curved fluid interfaces of spherical shape. We take into account the interfacial hydrodynamic coupling, traction coupling with the surrounding bulk fluid, and thermal fluctuations. For fluid-structure interactions, we introduce Immersed Boundary Methods (IBM) and related Stochastic Eulerian-Lagrangian Methods (SELM) for curved surfaces. We use these approaches to investigate the statistics of surface fluctuating hydrodynamics and microstructures. For velocity autocorrelations, we find characteristic power-law scalings $τ^{-1}, τ^{-2}$, and plateaus can emerge. This depends on the physical regime associated with the geometry, surface viscosity, and bulk viscosity. This differs from the characteristic $τ^{-3/2}$ scaling for bulk three dimensional fluids. We develop theory explaining these observed power-laws associated with time-scales for dissipation within the fluid interface and coupling to the surrounding fluid. We then use our introduced methods to investigate a few example systems and roles of hydrodynamic coupling and thermal fluctuations including for the kinetics of passive particles and active microswimmers in curved fluid interfaces.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Self-mixing in microtubule-kinesin active fluid from nonuniform to uniform distribution of activity

Active fluids have applications in micromixing, but little is known about the mixing kinematics of systems with spatiotemporally-varying activity. To investigate, UV-activated caged ATP is used to activate controlled regions of microtubule-kinesin active fluid and the mixing process is observed with fluorescent tracers and molecular dyes. At low Péclet numbers (diffusive transport), the active-inactive interface progresses toward the inactive area in a diffusion-like manner that is described by a simple model combining diffusion with Michaelis-Menten kinetics. At high Péclet numbers (convective transport), the active-inactive interface progresses in a superdiffusion-like manner that is qualitatively captured by an active-fluid hydrodynamic model coupled to ATP transport. Results show that active fluid mixing involves complex coupling between distribution of active stress and active transport of ATP and reduces mixing time for suspended components with decreased impact of initial component distribution. This work will inform application of active fluids to promote micromixing in microfluidic devices.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Programming interfacial energetic offsets and charge transfer in β-Pb 0.33 V 2 O 5 /quantum-dot heterostructures: Tuning valence-band edges to overlap with midgap states

Here, semiconductor heterostructures for solar energy conversion interface light-harvesting semiconductor nanoparticles with wide-band-gap semiconductors that serve as charge acceptors. In such heterostructures, the kinetics of charge separation depend on the thermodynamic driving force, which is dictated by energetic offsets across the interface. A recently developed promising platform interfaces semiconductor quantum dots (QDs) with ternary vanadium oxides that have characteristic midgap states situated between the valence and conduction bands. In this work, we have prepared CdS/β-Pb 0.33 V 2 O 5 heterostructures by both linker-assisted assembly and surface precipitation and contrasted these materials with CdSe/β-Pb 0.33 V 2 O 5 heterostructures prepared by the same methods. Increased valence-band (VB) edge onsets in X-ray photoelectron spectra for CdS/β-Pb 0.33 V 2 O 5 heterostructures relative to CdSe/β-Pb 0.33 V 2 O 5 heterostructures suggest a positive shift in the VB edge potential and, therefore, an increased driving force for the photoinduced transfer of holes to the midgap state of β-Pb 0.33 V 2 O 5 . This approach facilitates a ca. 0.40 eV decrease in the thermodynamic barrier for hole injection from the VB edge of QDs suggesting an important design parameter. Transient absorption spectroscopy experiments provide direct evidence of hole transfer from photoexcited CdS QDs to the midgap states of β-Pb 0.33 V 2 O 5 NWs, along with electron transfer into the conduction band of the β-Pb 0.33 V 2 O 5 NWs. Hole transfer is substantially faster and occurs at <1-ps time scales, whereas completion of electron transfer requires 5—30 ps depending on the nature of the interface. The differentiated time scales of electron and hole transfer, which are furthermore tunable as a function of the mode of attachment of QDs to NWs, provide a vital design tool for designing architectures for solar energy conversion. More generally, the approach developed here suggests that interfacing semiconductor QDs with transition-metal oxide NWs exhibiting intercalative midgap states yields a versatile platform wherein the thermodynamics and kinetics of charge transfer can be systematically modulated to improve the efficiency of charge separation across interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Dynamic interface rearrangement in LaFeO 3 / n - SrTiO 3 heterojunctions

Thin-film synthesis methods that have developed over the past decades have unlocked emergent interface properties ranging from conductivity to ferroelectricity. However, our attempts to exercise precise control over interfaces are constrained by a limited understanding of growth pathways and kinetics. In this paper, we demonstrate that shuttered molecular beam epitaxy induces rearrangements of atomic planes at a polar/nonpolar junction of LaFeO 3 (LFO)/n-SrTiO 3 (STO) depending on the substrate termination. Surface characterization confirms that substrates with two different (TiO 2 and SrO) terminations were prepared prior to LFO deposition; however, local electron-energy-loss spectroscopy measurements of the final heterojunctions show a predominantly LaO/TiO 2 interfacial junction in both cases. Ab initio simulations suggest that the interfaces can be stabilized by trapping extra oxygen (in LaO/TiO 2 ) and forming oxygen vacancies (in FeO 2 /SrO), which points to different growth kinetics in each case and may explain the apparent disappearance of the FeO 2 /SrO interface. Finally, we conclude that judicious control of deposition time scales can be used to modify growth pathways, opening new avenues to control the structure and properties of interfacial systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Revealing the Influence of Binding Motifs on Electron Transfer and Recombination Kinetics for CdSe Quantum Dots Functionalized with a Modified Viologen

Anchoring of molecules to the surfaces of semiconductor nanocrystals (NCs) presents an opportunity to leverage the precise synthetic tunability of molecular function and the remarkable light harvesting properties of NCs to drive photochemical reactions. However, charge transfer between the two species depends not only on the energy level alignments but also on the details of their binding interactions, which are difficult to probe. Here, in this work, we characterize the binding between CdSe quantum dots (QDs) and a new phosphonated derivative of the electron acceptor methyl viologen, designed to attach to the QD surface via the phosphonate group. We use isothermal titration calorimetry to probe the thermodynamics of the QD–molecule interaction and use the parameters determined therein to analyze transient absorption spectroscopy measurements of forward and back electron transfer from QDs to the viologen. We find that the ligand-like phosphonate binding leads to an electron-transfer rate constant that is 3 orders of magnitude smaller than that for the face-on binding of the bipyridine ring of methyl viologen. Back electron transfer is also significantly slower in the derivative. Interestingly, a minor fraction of the phosphonated derivative also binds in the face-on configuration, with similar forward and back electron transfer kinetics as methyl viologen. Numerical simulations show that the ligand-like binding will lead to significantly improved quantum yields of photocatalysis over a wide range of reaction rates. By independently characterizing binding thermodynamics and charge transfer kinetics, this work reveals how the complexities underlying electron transfer at the NC–molecule interface determine photocatalytic outcomes. This work also represents a step toward controlling forward and back electron transfer kinetics via rational molecular design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

A thermal NO(x) prediction model - Scalar computation module for CFD codes with fluid and kinetic effects

A thermal NO(x) prediction model is developed to interface with a CFD, k-epsilon based code. A converged solution from the CFD code is the input to the postprocessing model for prediction of thermal NO(x). The model uses a decoupled analysis to estimate the equilibrium level of (NO(x))e which is the constant rate limit. This value is used to estimate the flame (NO(x)) and in turn predict the rate of formation at each node using a two-step Zeldovich mechanism. The rate is fixed on the NO(x) production rate plot by estimating the time to reach equilibrium by a differential analysis based on the reaction: O + N2 = NO + N. The rate is integrated in the nonequilibrium time space based on the residence time at each node in the computational domain. The sum of all nodal predictions yields the total NO(x) level.

Mcbeath, Giorgio↗
DOE OSTI2026

Phase Transformation Enables Stable Cycling and Fast Charging of Cation-Disordered Rocksalt Cathodes

Developing high-capacity, long-life cathodes is critical to overcome the energy limitations of current Li-ion batteries. In this work, we report a Li-excess cation-disordered rocksalt (DRX) cathode, Li 1.167 Mn0.7Ti 0.133 O 1.8 F 0.2 (M 0.7 F 0.2 ), which demonstrates excellent electrochemical performance. This cathode delivers a capacity approaching 250 mAh g –1 and maintains 200 mAh g –1 over 200 cycles with an average discharge voltage of 3.1 V at 2 V cutoff. The formation of a spinel-like phase during cycling enables fast charging, achieving over 240 mAh g –1 at 2C for 100 cycles. Combined X-ray absorption spectroscopy and transmission electron microscopy reveal reversible electrochemical redox processes and stable Mn local structures during 2 V discharge. These results highlight the potential of DRX cathodes for next-generation Li-ion batteries and provide insights into strategies to overcome kinetic limitations and optimize the cathode-electrolyte interface.

25 ENERGY STORAGE↗
NASA NTRSDate not supplied

CFD Modeling of Phase Change and Pressure Drop during Violent Sloshing of Cryogenic Fluid in a Small-Scale Tank

This paper presents the development of a two-phase CFD model that is used to study sloshing of a cryogenic fluid (LN2) undergoing phase change generated by lateral acceleration and its effects on the ensuing heat and mass transfer and pressure drop in a small-scale tank. In this model the interface is captured using the volume-of-fluid (VOF) method [1]. Kinetic-theory based Schrage relation [2] is used for calculating phase change mass transfer at the liquid-vapor interface. Computational results are compared to the data provided by a non-isothermal sloshing experiment with phase change conducted by the University of Tokyo and JAXA in 2018 using liquid Nitrogen in a transparent tank. The effect of different thicknesses of a liquid temperature stratification layer created at the interface on the pressure drop during sloshing was studied experimentally. CFD results for interface movement and tank pressure are presented and compared in this paper to experimental data for the cases with the smallest and largest liquid temperature stratification thickness.

phase change↗
DOE OSTI2016

Instability of surface electron cyclotron TM-modes influenced by non-monochromatic alternating electric field

The influence of non-monochromaticity of an external alternating electric field on excitation of TM eigenmodes at harmonics of the electron cyclotron frequency is considered here. These TM-modes propagate along the plasma interface in a metal waveguide. An external static constant magnetic field is oriented perpendicularly to the plasma interface. The problem is solved theoretically using the kinetic Vlasov-Boltzmann equation for description of plasma particles motion and the Maxwell equations for description of the electromagnetic mode fields. The external alternating electric field is supposed to be a superposition of two waves, whose amplitudes are different and their frequencies correlate as 2:1. An infinite set of equations for electric field harmonics of these modes is derived with the aid of nonlinear boundary conditions. This set is solved using the wave packet approach consisting of the main harmonic frequency and two nearest satellite temporal harmonics. Analytical studies of the obtained set of equations allow one to find two different regimes of parametric instability, namely, enhancement and suppression of the instability. Numerical analysis of the instability is carried out for the three first electron cyclotron harmonics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

TUMME: Tsinghua University Minnesota Master Equation program

We report that TUMME is a program for assembling and solving master equations for gas-phase chemical kinetics based on chemically significant eigenmodes. TUMME has interfaces to the Gaussian, Polyrate, and/or MSTor output files that allow the master equation code to obtain the microcanonical flux coefficients needed for the coefficient matrix of the master equation. The flux coefficients for reactions with barriers can be calculated by multi-structural variational transition state theory with small-curvature tunneling (MS-VTST/SCT) or by simpler approximations to this such as conventional transition state theory without tunneling (also called RRKM theory). The flux coefficients for barrierless reactions are provided by a hard-sphere model. TUMME is written in double precision with Python 3; quadruple and octuple precision are also available for some subtasks in C++. The Python code can run in serial or parallel (MP or MPI), and the C++ code can run on a single processor or on multiple processors with OpenMP.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2012

Optimization of KINETICS Chemical Computation Code

NASA JPL has been creating a code in FORTRAN called KINETICS to model the chemistry of planetary atmospheres. Recently there has been an effort to introduce Message Passing Interface (MPI) into the code so as to cut down the run time of the program. There has been some implementation of MPI into KINETICS; however, the code could still be more efficient than it currently is. One way to increase efficiency is to send only certain variables to all the processes when an MPI subroutine is called and to gather only certain variables when the subroutine is finished. Therefore, all the variables that are used in three of the main subroutines needed to be investigated. Because of the sheer amount of code that there is to comb through this task was given as a ten-week project. I have been able to create flowcharts outlining the subroutines, common blocks, and functions used within the three main subroutines. From these flowcharts I created tables outlining the variables used in each block and important information about each. All this information will be used to determine how to run MPI in KINETICS in the most efficient way possible.

planetary atmospheres↗
DOE OSTI2024

Accelerated Zymonic Acid Formation from Pyruvic Acid at the Interface of Aqueous Nanodroplets

To explore the role of the liquid interface in mediating reactivity in small compartments, the formation kinetics of zymonic acid (ZA) is measured in submicron aerosols (average radius = 240 nm) using mass spectrometry. The formation of ZA, from a condensation reaction of two pyruvic acid (PA) molecules, proceeds over days in bulk solutions, while in submicron aerosols, it occurs in minutes. The experimental results are replicated in a kinetic model using an apparent interfacial reaction rate coefficient of krxn = (0.9 ± 0.2) × 10-3 M-1 s-1. The simulation reveals that surface activity of PA coupled with an enhanced interfacial reaction rate drives accelerated ZA formation in aerosols. Experimental and simulated results provide compelling evidence that the condensation reaction of PA occurs exclusively at the aerosol interface with a reaction rate coefficient that is enhanced by 4 orders of magnitude (∼104) relative to what is estimated for macroscale solutions.

Kim, Pyeongeun↗
DOE OSTI2024

Hierarchical Ion Interactions in the Direct Air Capture of CO 2 at Air/Aqueous Interfaces

The direct air capture (DAC) of CO 2 using aqueous solvents is plagued by slow kinetics and interfacial barriers that limit effectiveness in combating climate change. Functionalizing air/aqueous surfaces with charged amphiphiles shows promise in accelerating DAC; however, insight into these interfaces and how they evolve in time remains poorly understood. Specifically, competitive ion interactions between DAC reagents and reaction products feedback onto the interfacial structure, thereby modulating interfacial chemical composition and overall function. In this work, we probe the role of glycine amino acid anions (Gly - ), an effective CO 2 capture reagent, that promotes the organization of cationic oligomers at air/aqueous interfaces. These surfaces are probed with vibrational sum frequency generation spectroscopy and molecular dynamics simulations. Our findings demonstrate that the competition for surface sites between Gly - and captured carbonaceous anions (HCO 3 - , CO 3 2 -, carbamates) drives changes in surface hydration, which in turn tunes oligomer ordering. This phenomenon is related to a hierarchical ordering of anions at the surface that are electrostatically attracted to the surface and their ability to compete for interfacial water. These results point to new ways to tune interfaces for DAC via stratification of ions based on relative surface propensities and specific ion effects.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2 , an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification of the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Computational Investigation of Aqueous Phase Effects on the Dehydrogenation and Dehydroxylation of Polyols over Pt(111)

Prediction of solvation effects on the kinetics of elementary reactions occurring at metal–water interfaces is of high importance for the rational design of catalysts for the biomass and electrocatalysis communities. A lack of knowledge of the reliability of various computational solvation schemes for processes on metal surfaces is currently a limiting factor. Using a multilevel quantum mechanical/molecular mechanical (QM/MM) description of the potential energy surface, we determined characteristic time and length scales for typical free-energy perturbation (FEP) calculations of bond cleavages in ethylene glycol, a sugar surrogate molecule, over Pt(111). Our approach is based on our explicit solvation model for metal surfaces and the repetition of FEP calculations to estimate confidence intervals. Results indicate that aqueous phase effects on the free energies of elementary processes can be determined with 95% confidence intervals from limited configuration space sampling and the fixed charge approximation used in the QM/MM-FEP methodology of smaller 0.1 eV. Next, we computed the initial O–H, C–H, and C–OH bond cleavages in ethylene glycol over Pt(111) in liquid water utilizing two different metal–water interaction potentials. Our calculations predict that aqueous phase effects are small (<0.1 eV) for the C–H bond cleavage and the activation barrier of the C–OH bond cleavage. In contrast, solvation effects are large (>0.35 eV) for the O–H bond cleavage and the reaction free energy of the C–OH bond scission. While the choice of a different Pt–water force field can lead to differences in predicted solvation effects of up to 0.2 eV, the differences are usually smaller (<0.1 eV), and the trends are always the same. In contrast, implicit solvation methods appear to currently not be able to reliably describe solvation effects originating from hydrogen bonding for metal surfaces even qualitatively.

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

Elucidating the Interfacial Barriers in Lanthanide Back-Extraction: From Water to Oil and Back Again

Recovery of critical rare earth elements from complex mixtures has long been realized via solvent extraction, where ions in an aqueous phase are separated into an organic phase using amphiphilic ligands. While a great deal of effort has been placed on understanding this forward reaction, substantial knowledge gaps in the back-extraction process remain. This includes the mechanism of interfacial dissociation and transport back into a highly acidic aqueous phase for further processing. In this work, we connect back-extraction kinetics made in realistic solvent extraction systems to salient interfacial chemistry and structure that represent bottlenecks in the back-extraction of lanthanide ions. We show that the interface between the two liquid phases varies dramatically based on the composition of both phases. Water stretching signals are shown to report on the population of lingering interfacial complexes and are thus used as a reporter of competitive adsorption from excess free ligands in solution for limited interfacial vacancies. We show that excess free ligands, often used to improve forward extractions, set up interfacial blockades inhibiting back-extraction both kinetically and thermodynamically. In conclusion, this insight opens up avenues to tune interfacial properties to facilitate a more dynamic, exchangeable interface to speed up back-extractions while using less energy intensive chemical swings.

Interfaces↗