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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 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Greenlighting Photoelectrochemical Oxidation of Water by Iron Oxide

Hematite (alpha-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematites modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form. Notably, the effects are most pronounced for charges photogenerated by photons with energy comparable to the band gap for excitation of Fe(3d) -> Fe(3d) transitions (i.e., green photons). Additionally, at the optimum Ti substitution level the lifetimes of surface-localized holes, competent for water oxidation, are extended. Together these changes explain an overall improvement in photoelectrochemical performance, especially enhanced internal quantum efficiencies, observed upon Ti(IV) incorporation.

absorbed photon-to-current conversion efficiency (↗
DOE OSTI2016

Progress in the Analysis of Complex Atmospheric Particles

This manuscript presents an overview on recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surfaces interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multi-modal chemical characterization of particles with both molecular and lateral specificity. When combined, they provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore environmental effects of air-surface interactions.

Aerosol↗
DOE OSTI2019

Organic-Mineral Interfacial Chemistry Drives Heterogeneous Nucleation of Sr-Rich (Bax, Sr1-x)SO4 from Undersaturated Solution

Sr-bearing marine barite [(Bax, Sr1-x)SO4] cycling has been widely used to reconstruct geochemical evolutions of paleoenvironments. However, an understanding of barite precipitation in the ocean, which is globally undersaturated with respect to barite, is missing. Moreover, the reason for the occurrence of higher Sr content in marine barites than expected for classical crystal growth processes remains unknown. Field data analyses suggested that organic molecules may regulate the formation and composition of marine barites; however, the specific organic–mineral interactions are unclear. Using in situ grazing incidence small-angle X-ray scattering (GISAXS), size and total volume evolutions of barite precipitates on organic films were characterized. The results show that barite forms on organic films from undersaturated solutions. Moreover, from a single supersaturated solution with respect to barite, Sr-rich barite nanoparticles formed on organics, while micrometer-size Sr-poor barites formed in bulk solutions. Ion adsorption experiments showed that organic films can enrich cation concentrations in the adjacent solution, thus increasing the local supersaturation and promoting barite nucleation on organic films, even when the bulk solution was undersaturated. The Sr enrichment in barites formed on organic films was found to be controlled by solid-solution nucleation rates; instead, the Sr-poor barite formation in bulk solution was found to be controlled by solid-solution growth rates. This study provides a mechanistic explanation for Sr-rich marine barite formation and offers insights for understanding and controlling the compositions of solid solutions by separately tuning their nucleation and growth rates via the unique chemistry of solution–organic interfaces.

Deng, Ning↗
DOE OSTI2022

Insights into Sorption and Molecular Transport of Aqueous Glucose into Zeolite Nanopores

Liquid-phase heterogeneous catalysis using zeolites is important for biomass conversion to fuels and chemicals. There is a substantial body of work on gas-phase sorption in zeolites with different topologies; however, studies investigating the diffusion of complex molecules in liquid medium into zeolitic nanopores are scarce. Here, we present a molecular dynamics study to understand the sorption and diffusion of aqueous β-d-glucose into β-zeolite silicate at T = 395 K and P = 1 bar. Through 2-μs-long molecular dynamics trajectories, we reveal the role of the solvent, the kinetics of the pore filling, and the effect of the water model on these properties. We find that the glucose and water loading is a function of the initial glucose concentration. Although the glucose concentration increases monotonically with the initial glucose concentration, the water loading exhibits a nonmonotonic behavior. At the highest initial concentration (~20 wt %), we find that the equilibrium loading of glucose is approximately five molecules per unit cell and displays a weak dependence on the water model. Glucose molecules follow a single-file diffusion in the nanopores due to confinement. Here, the dynamics of glucose and water molecules slows significantly at the interface. The average residence time for glucose molecules is an order of magnitude larger than that in the bulk solution, while it is about twice as large for the water molecules. Our simulations reveal critical molecular details of the glucose molecule’s local environment inside the zeolite pore relevant to catalytic conversion of biomass to valuable chemicals.

09 BIOMASS FUELS↗
DOE OSTI2015

Sailing into uncharted waters: recent advances in the in situ monitoring of catalytic processes in aqueous environments

Catalysis in aqueous environments is attracting enormous interest. Many characterization methods are well established at gas-solid interfaces and a majority of the surface-science approaches were historically limited to model surfaces and vacuum conditions. However, practical scenarios with complex catalyst structures, elevated temperatures and pressures, as well as the presence of two or more condensed phases, can pose significant challenges to these techniques, particularly for catalysts at their dynamic working states. In such contexts, this review highlights the advances over the past five years in the in situ and real-time detection of catalytic processes and related phenomena in aqueous media, ideally under realistic conditions. We underline latest technical innovations, describe novel chemistries that are made accessible by recently developed toolboxes, and discuss future directions of in situ and time-resolved analytical approaches applicable to aqueous phase catalysis.

Heterogeneous catalysis, in situ, time-resolved, s↗
DOE OSTI2026

Embedded Ferroelectric Nanoclusters can drive Polarization Reversal in a Non-Ferroelectric Polar Film via the Proximity Effect

Heterogeneous nucleation from defects dominates the electric field required for polarization switching of ferroelectrics. Here, we consider the switching of a nominally non-switchable polar thin film of AlN due to the proximity effect arising from embedded ferroelectric nanoclusters of Al 1-x Sc x N. Using a Landau-Ginzburg-Devonshire thermodynamic approach and finite element modeling, we study the influence of nanocluster shape on polarization switching and domain nucleation emerging in AlN. The ferroelectric nanocluster boundary is modeled as a thin layer transitioning from Al 1-x Sc x N to AlN. We analyze the conditions under which polarization switching in the AlN film occurs at coercive fields significantly lower than its dielectric breakdown field. In the presence of spike-like Al 1-x Sc x N nanoclusters, the proximity effect enables switching of the spontaneous polarization in AlN and significantly reduces the corresponding coercive field. The internal field, which is depolarizing inside the AlN (due to its larger spontaneous polarization) and polarizing within the ferroelectric Al 1-x Sc x N nanoclusters (due to its smaller spontaneous polarization), lowers the potential barrier in the clusters and nucleates nanodomains at the Al 1-x Sc x N-AlN interface, forming localized regions of reversed polarization. Proximity effect can thus provide a pathway towards "thawing" previously "frozen" ferroelectrics through engineered nucleation for memory, actuation and optical technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Condensed Phase Deactivation of Solid Brønsted Acids in the Dehydration of Fructose to Hydroxymethylfurfural

Catalyst deactivation resulting from the hydrothermal leaching of sulfonic acid residues and the deposition of carbonaceous residues was studied using condensed phase flow reactor experiments along with state-of-the-art solid-state NMR. Several commercially available sulfonic acid-containing heterogeneous Brønsted acids were compared by measuring the rates of sulfonic acid breakdown at hydrothermal flow conditions of 160 °C. Amberlyst 45 was found to show higher hydrothermal stability when compared to both Nafion and Amberlyst 15, with <10% loss in acidity after 48 h. The dehydration reaction of fructose to hydroxymethylfurfural (HMF) was used as a model system to compare deactivation rates from carbon deposition (fouling) to those from sulfur leaching, and deactivation from fouling was shown to be dramatically faster than that from sulfonic acid leaching alone. Fouling rates were then investigated in greater detail by comparing the influence of several factors including reactant, solvent, residence time, and feed concentration. The only successful approach to minimize fouling was the use of a polar aprotic solvent [dimethyl sulfoxide (DMSO)] with dilute (50 mM) reactant streams. In aqueous systems, operating the reactor in a regime with low conversion conditions (short residence times) does not significantly improve the longevity of the catalyst. Spent catalysts were characterized using 13C solid-state NMR spectroscopy enhanced by dynamic nuclear polarization. Additionally, in situ 1H and 13C high-resolution magic angle spinning (HR-MAS) solid-state NMR spectroscopies were used to investigate the solvent influence at the catalyst interface. The HR-MAS NMR studies showed that in polar aprotic solvents, the increased acidity leads to greater selectivity toward HMF; more importantly, that the dehydration products do not readily adhere to the surface in DMSO, in contrast to their behavior in water. The results demonstrate that more active and longer-lived acid catalysts could be obtained by tuning the solvent and surface polarity to allow for efficient desorption of products, thereby reducing the catalyst deactivation that occurs due to fouling.

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

A simplified CFD approach for modeling mass transport in catalytic open-cell foams

A simplified macroscopic CFD approach is presented to model mass transport including chemical reactions in washcoated open-cell foams. The foam is treated as a porous medium. Species conversion during chemical reactions is modeled using appropriate source terms based on reaction rate expressions and modified to account for the mass transport resistances occurring at the fluid-washcoat interfaces and within the washcoat layers. As example, the catalytic CO oxidation over platinum is studied. The simulation results show good agreement with experimental data from literature. A parametric study on washcoat parameters, such as thickness, tortuosity, porosity, and size, is carried out. Increasing the washcoat thickness from 5 to 100 µm or decreasing the tortuosity to porosity ratio from 5 to 20 decreases the CO conversion by 10 %. The proposed model is found to be reliable and has the advantage of lower computational cost, making it a suitable tool for foam-based catalytic reactor design.

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

Nanosecond Freezing of Water at High Pressures: Nucleation and Growth near the Metastability Limit

The fundamental study of phase transition kinetics has motivated experimental methods toward achieving the largest degree of undercooling possible, more recently culminating in the technique of rapid, quasi-isentropic compression. This approach has been demonstrated to freeze water into the high-pressure ice VII phase on nanosecond timescales, with some experiments undergoing heterogeneous nucleation while others, in apparent contradiction, suggest a homogeneous nucleation mode. We show through a combination of theory, simulation, and analysis of experiments that these seemingly contradictory results are in agreement when viewed from the perspective of classical nucleation theory. We find that, perhaps surprisingly, classical nucleation theory is capable of accurately predicting the solidification kinetics of ice VII formation under an extremely high driving force ( | Δ μ / k B T | ≈ 1 ) but only if amended by two important considerations: (i) transient nucleation and (ii) separate liquid and solid temperatures. Finally, this is the first demonstration of a model that is able to reproduce the experimentally observed rapid freezing kinetics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Electrolyte Engineering Stabilizes Photoanodes Decorated with Molecular Catalysts

Molecular catalysts are promising oxygen evolution promoters in conjunction with photoanodes for solar water splitting. Maintaining the stability of both photoabsorber and cocatalyst is still a prime challenge, with many efforts tackling this issue through sophisticated material designs. Such approaches often mask the importance of the electrode-electrolyte interface and overlook easily tunable system parameters, such as the electrolyte environment, to improve efficiency. We provide a systematic study on the activity-stability relationship of a prominent Fe 2 O 3 photoanode modified with Ir molecular catalysts using in situ mass spectroscopy. After gaining detailed insights into the dissolution behavior of the Ir cocatalyst, a comprehensive pH study is conducted to probe the impact of the electrolyte on the performance. An inverse trend in Fe and Ir stability is found, with the best activity-stability synergy obtained at pH 9.7. The results bring awareness to the overall photostability and electrolyte engineering when advancing catalysts for solar water splitting.

14 SOLAR ENERGY↗
DOE OSTI2024

Inverse design of pore wall chemistry and topology through active learning of surface group interactions

Design of next-generation membranes requires a nanoscopic understanding of the effect of biologically inspired heterogeneous surface chemistries and topologies (roughness) on local water and solute behavior. In particular, the rejection of small, neutral solutes, such as boric acid, poses a heretofore unsolved challenge. In prior work, a computational inverse design technique using an evolutionary optimization successfully uncovered new surface design strategies for optimized transport of water over solutes in smooth, model pores consisting of two surface chemistries. However, extending such an approach to more complex (and realistic) scenarios involving many surface chemistries as well as surface roughness is challenging due to the expanded design space. In this work, we develop a new approach that uses active learning to optimize in a reduced feature space of surface group interactions, finding parameters that lead to their assembly into ordered, optimal patterns. This approach rapidly identifies novel surface functionalizations that maximize the difference in water and boric acid transport through the nanopore. Moreover, we find that the roughness of the nanopore wall, independent of its chemistry, can be leveraged to enhance transport selectivity: oscillations in the pore wall diameter optimally inhibit boric acid transport by creating energetic wells from which the solute must escape to transport down the pore. Furthermore, this proof-of-concept demonstrates the potential for active learning strategies, in concert with molecular simulations, to rapidly navigate complex design spaces of aqueous interfaces and is promising as a tool for engineering water-mediated surface interactions for a broad range of applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Fundamental Investigations into the Properties and Performance of Advanced Materials

Intelligent engineering designs require an accurate understanding of material behavior, since any uncertainties or gaps in knowledge must be counterbalanced with heightened factors of safety, leading to overdesign. Therefore, building better structures and pushing the performance of new components requires an improved understanding of the thermomechanical response of advanced materials under service conditions. This dissertation provides fundamental investigations of several advanced materials: thermoset polymers, a common matrix material for fiber-reinforced composites and nanocomposites; aluminum alloy 7075-T6 (AA7075-T6), a high-performance aerospace material; and ceramic matrix composites (CMCs), an advanced composite for extreme-temperature applications. To understand matrix interactions with various interfaces and nanoinclusions at their fundamental scale, the properties of thermoset polymers are studied at the atomistic scale. An improved proximity-based molecular dynamics (MD) technique for modeling the crosslinking of thermoset polymers is carefully established, enabling realistic curing simulations through its ability to dynamically and probabilistically perform complex topology transformations. The proximity-based MD curing methodology is then used to explore damage initiation and the local anisotropic evolution of mechanical properties in thermoset polymers under uniaxial tension with an emphasis on changes in stiffness through a series of tensile loading, unloading, and reloading experiments. Aluminum alloys in aerospace applications often require a fatigue life of over 109 cycles, which is well over ii the number of cycles that can be practically tested using conventional fatigue testing equipment. In order to study these high-life regimes, a detailed ultrasonic cycle fatigue study is presented for AA7075-T6 under fully reversed tension-compression loading. The geometric sensitivity, frequency effects, size effects, surface roughness effects, and the corresponding failure mechanisms for ultrasonic fatigue across different fatigue regimes are investigated. Finally, because CMCs are utilized in extreme environments, oxidation plays an important role in their degradation. A multiphysics modeling methodology is thus developed to address the complex coupling between oxidation, mechanical stress, and oxygen diffusion in heterogeneous carbon fiber-reinforced CMC microstructures.

Schichtel, Jacob J.↗
DOE OSTI2015

Solid-liquid work of adhesion of coarse-grained models of n-hexane on graphene layers derived from the conditional reversible work method

We address the question of how reducing the number of degrees of freedom modifies the interfacial thermodynamic properties of heterogeneous solid-liquid systems. We consider the example of n-hexane interacting with multi-layer graphene which we model both with fully atomistic and coarse-grained (CG) models. The CG models are obtained by means of the conditional reversible work (CRW) method. The interfacial thermodynamics of these models is characterized by the solid-liquid work of adhesion W{sub SL} calculated by means of the dry-surface methodology through molecular dynamics simulations. We find that the CRW potentials lead to values of W{sub SL} that are larger than the atomistic ones. Clear understanding of the relationship between the structure of n-hexane in the vicinity of the surface and W{sub SL} is elucidated through a detailed study of the energy and entropy components of W{sub SL}. We highlight the crucial role played by the solid-liquid energy fluctuations. Our approach suggests that CG potentials should be designed in such a way that they preserve the range of solid-liquid interaction energies, but also their fluctuations in order to preserve the reference atomistic value of W{sub SL}. Our study thus opens perspectives into deriving CG interaction potentials that preserve the thermodynamics of solid-liquid contacts and will find application in studies that intend to address materials driven by interfaces.

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

Suppressing CO formation in low-temperature methanol steam reforming via Ce-modified CuZnGa layered oxide catalysts

Cu-based layered double hydroxides (LDHs) are widely recognized as effective catalysts for low-temperature methanol steam reforming, yet achieving high hydrogen productivity together with near-complete suppression of CO formation remains challenging. Here, we report the synthesis and evaluation of a series of CuZnGa LDH-derived catalysts and Ce-modified analogues prepared via an aqueous miscible organic method, which enables high metal dispersion and precise structural control. The optimized CuZnGa catalyst exhibits a hydrogen production rate of 16.9 µmol H 2 ·g cat −1 ·s −1 at 180 °C with an H 2 /CO ratio exceeding 3500, outperforming many state-of-the-art low-temperature systems. Importantly, the incorporation of small amounts of Ce further suppresses CO formation while maintaining high hydrogen productivity. Combined spectroscopic characterization and density functional theory calculations reveal that Ce is incorporated into the LDH lattice by substituting Ga 3+ sites up to a critical threshold, beyond which highly dispersed CeO x species are formed. These species provide mobile lattice oxygen that participates in a Mars-van Krevelen-type pathway, selectively oxidizing CO and suppressing the reverse water-gas shift reaction. This study establishes a clear relationship between Ce speciation, oxygen mobility, and catalytic selectivity in LDH-derived systems. The resulting catalysts demonstrate the potential of interface-engineered Cu-based materials for efficient low-temperature hydrogen production with minimal CO contamination.

09 BIOMASS FUELS↗
DOE OSTI2024

Programmable nanowrinkle-induced room-temperature exciton localization in monolayer WSe2

Abstract Localized states in two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been the subject of intense study, driven by potential applications in quantum information science. Despite the rapidly growing knowledge surrounding these emitters, their microscopic nature is still not fully understood, limiting their production and application. Motivated by this challenge, and by recent theoretical and experimental evidence showing that nanowrinkles generate strain-localized room-temperature emitters, we demonstrate a method to intentionally induce wrinkles with collections of stressors, showing that long-range wrinkle direction and position are controllable with patterned array design. Nano-photoluminescence (nano-PL) imaging combined with detailed strain modeling based on measured wrinkle topography establishes a correlation between wrinkle properties, particularly shear strain, and localized exciton emission. Beyond the array-induced wrinkles, nano-PL spatial maps further reveal that the strain environment around individual stressors is heterogeneous due to the presence of fine wrinkles that are less deterministic. At cryogenic temperatures, antibunched emission is observed, confirming that the nanocone-induced strain is sufficiently large for the formation of quantum emitters. At 300 K, detailed nanoscale hyperspectral images uncover a wide range of low-energy emission peaks originating from the fine wrinkles, and show that the states can be tightly confined to regions <10 nm, even in ambient conditions. These results establish a promising potential route towards realizing room temperature quantum emission in 2D TMDC systems.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the S N 2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the S N 2 reaction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗