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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Disentangling interlayer confinement and pore surface adsorption in functionalized smectites for tunable ethylene gas capture

Smectite-based adsorbents are increasingly being studied as sustainable packaging materials for scavenging ethylene, a plant hormone that accelerates fruit ripening. However, the mechanisms governing their uptake and retention remain poorly understood. Here, to tackle this question we systematically investigate ethylene gas-solid interactions in pristine, acid-activated, and choline-functionalized montmorillonites using a complementary combination of structural, gravimetric, and spectroscopic techniques, including inelastic neutron scattering. We experimentally distinguish ethylene populations associated with interlayer confinement, mesopore, and external surface adsorption. We show that chemical functionalization distinctly controls adsorption pathways: acid activation enhances total uptake by generating mesoporous adsorption sites and promoting partial interlayer intercalation, yielding capacities comparable to those of leading smectite-based adsorbents, while choline functionalization promotes preferential confinement and stabilization of guest molecules within the interlayer galleries. Advanced spectroscopic analysis provides molecular-level insight into confinement environments and interaction strengths. We also establish clear structure-property relationships by correlating uptake values derived from independent techniques, linking chemical modification, accessible adsorption domains, and retention behavior. These findings provide general design principles for tuning gas-solid interactions in functionalized layered silicates and highlight their potential as adaptable platforms for sustainable ethylene gas capture and selective adsorption technologies.

Ethylene adsorption mechanism↗
DOE OSTI2022

Electrochemical reactivity of atomic and molecular species under solid-state confinement

The nanoconfinement of electrochemically-active guest species in host solid state electrode materials provides opportunities to tune mass transport between the bulk electrolyte and inner surface of the electrode, enhance electron-transfer rates, and/or improve the stability and dispersion of active material. Here, this review summarizes recent experimental and theoretical electrochemical studies of three types of nanoconfined guest species: (1) ion adsorption of electrolyte ions, (2) confined redox-active molecules, and (3) electrocatalytic reactions of confined ions/solvents and catalytic particles. The examples discussed in this review illustrate how the confinement of guest species within enclosed spaces with nanoscale dimensions – such as pores, pockets, channels, and interlayers – can lead to improved electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2016

The micro-environmental impact of volatile organic compound emissions from large-scale assemblies of people in a confined space

Large-scale assemblies of people in a confined space can exert significant impacts on the local air chemistry due to human emissions of volatile organics. Variations of air-quality in such small scale can be studied by quantifying fingerprint volatile organic compounds (VOCs) such as acetone, toluene, and isoprene produced during concerts, movie screenings, and sport events (like the Olympics and the World Cup). This review summarizes the extent of VOC accumulation resulting from a large population in a confined area or in a small open area during sporting and other recreational activities. Apart from VOCs emitted directly from human bodies (e.g., perspiration and exhaled breath), those released indirectly from other related sources (e.g., smoking, waste disposal, discharge of food-waste, and use of personal-care products) are also discussed. Although direct and indirect emissions of VOCs from human may constitute <1% of the global atmospheric VOCs budget, unique spatiotemporal variations in VOCs species within a confined space can have unforeseen impacts on the local atmosphere to lead to acute human exposure to harmful pollutants.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Bridging adsorption behavior of confined CH 4 -CO 2 binary mixtures across scales

An accurate understanding of the competitive adsorption of CH 4 -CO 2 binary mixtures in nano-confined systems is critical for engineering CO 2 storage in shale gas reservoirs. Due to difficulties in making reliable experimental observations in nano-scale, atomistic simulations (ASs), such as the Grand Canonical Monte Carlo (GCMC) method, provide a viable approach to studying the adsorption behavior of confined fluids. ASs are, however, limited in the size of the compositional domain due to the high computational cost. This work proposes a framework that combines AS and the lattice Boltzmann (LB) method to bridge the physics of confined fluids across scales. The Peng–Robinson equation of state (PR-EoS) produces fugacity coefficients, which serve as input for conducting multi-component GCMC simulations. These GCMC simulations explore the competitive adsorption behavior of CH 4 -CO 2 in nano-slits at various composition, pressure, and channel-width conditions. Both components generate adsorption layers with high densities near the walls with CO 2 preferentially adsorbing compared to CH 4 on the organic walls of carbon sheets. At the mesoscale, a pseudopotential model represents the intermolecular forces in multi-component, multiple-relaxation-time LB simulations. The LB simulations are in good agreement with the GCMC results, allowing us to obtain values for tunable LB parameters. We then extend the use of LB to simulate adsorption behavior in complex networks with nano-sized channels. The phase behavior and fluid properties in the complex geometries of nano-channels differ from nano-slits and bulk systems. Furthermore, the bridging of physics from GCMC (microscale) to LB (mesoscale) via the macroscale PR-EoS connects the adsorption behavior of binary systems across scales.

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

Neutron diffraction illustrates residual stress behavior of welded alloys used as radioactive confinement boundary

Corrosion-resistant welded alloys are frequently used as a leak-tight boundary in critical applications that require confinement of hazardous and/or radioactive substances, including an increasing population of spent nuclear fuel (SNF) canisters. The behavior of residual stresses generated as a result of irregular elastic–plastic deformation during processes such as welding is one of today's key issues to a full understanding of the aging mechanisms that may compromise the confinement boundary. Whether such processes and any subsequent weld repairs, not subjected to post-weld heat treatment, would negatively affect the initial material by introducing through-thickness tensile stresses remains an open question. Here we report the first residual stress measurements using neutron diffraction on the welded joints of a SNF canister. We found significant tensile residual stresses in the as welded sample, indicating that initiation and through-thickness growth of cracks may be possible. Following repair, we observed a stress redistribution and introduction of beneficial compressive stresses. We anticipate our results will improve understanding of confinement susceptibility to aging and guide improvements in repair techniques.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Surfactant-thermal method to synthesize a new Zn(II)-trimesic MOF with confined Ru(bpy){sub 3}{sup 2+} complex

A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy){sub 3}{sup 2+} (RuBpy) complex by using surfactant PEG 400 as reaction medium. The RuBpy molecules were encapsulated between the 2-D sheets in ZJU-100. ZJU-100 showed bathochromic shift in the steady-state emission spectrum and increased emission lifetimes relative to RuBpy molecules. The extended lifetime is attributed to the reduced nonradiative decay rate due to the stabilization of RuBpy within the rigid MOF framework. These results represent the first example of MOF with confined complex synthesized by surfactant, indicating that the surfactant-thermal method could offer exciting opportunities for preparing new MOFs host/guest materials with novel structures and interesting luminescent properties. - Graphical abstract: A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy){sub 3}{sup 2+} (RuBpy) complex by using surfactant PEG 400 as reaction medium. - Highlights: • Surfactant-thermal synthesis of crystalline metal-organic framework host/guest materials. • RuBpy molecules were encapsulated between the 2-D sheets of MOFs. • Extended lifetime is observed due to the stabilization of RuBpy within the rigid MOF framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Effective Schottky barrier lowering of Ni silicide/p-Si(100) using an ytterbium confinement structure for high performance n-type MOSFETs

A simple but effective rare earth metal (RE) confinement structure is demonstrated to suppress surface accumulation of Yb generally encountered in the RE metal incorporated Ni silicide system. The confinement structure is realized by inserting a Ti diffusion barrier layer between Yb and Ni layers. Yb atoms can be constrained in a specified reaction region during silicidation as evidenced by Auger electron spectroscopy and cross-section transmission electron microscopy analysis. The RE metal confinement structure provides a complementary metal-oxide-semiconductor compatible approach for further Schottky barrier height engineering and is a promising method for future technology nodes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Integration of high confinement, high poloidal beta plasma with dual radiated power and detachment controls for divertor protection and ELM suppression

Divertor detachment without serious core confinement quality loss in DIII-D’s high poloidal β scenario has been combined with impurity-induced ELM mitigation without disruption. Use of Ne previously granted access to a detached, non-ELMing regime that retained high confinement quality due to stimulation of Internal Transport Barrier (ITB) growth, but suffered from on-going core fuel dilution and high disruptivity. Excess Ne accumulation in the core plasma has now been avoided by feeding back core radiated power ($P_{rad}$) measurements to control Ne seeding, rather than using attachment fraction ($A_{frac}$) control with Ne; this also reduces disruptivity. At the same time, N 2 seeding is used in a feedback loop with $A_{frac}$ measurements, which previously posed low disruption risk. In this way, the effect of Ne in the core is managed while avoiding excess seeding, and N 2 acts to correct for any excess heat exhaust that might interfere with detachment. The average Ne flow rate was 38% of what was used in pure Ne $A_{frac}$ control, plus average N 2 flow that was 43% of pure N 2 $A_{frac}$ control, even while meeting an even deeper detachment target. Meanwhile, a steep pressure gradient in the core plasma reduces sensitivity to impurity-induced degradation of the pedestal and reasonable confinement quality was maintained despite operational challenges that blocked formation of an ITB in these experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Study of the nature of the confinement in the GlueX experiment

Confinement is a fundamental property of quantum chromodynamics (QCD) associated with the unique role of the gluonic field responsible for binding quarks in hadrons. Understanding the role of gluons in the confinement of quarks is one of the most tantalizing topics in modern particle physics to be explored. The new experiment GlueX has been recently constructed at Jefferson Lab. The experiment was designed to search for hybrid mesons with exotic quantum numbers using a beam of linearly polarized photons incident on a liquid hydrogen target. The spectrum of these states and their mass splitting from normal mesons may yield information on confinement. In addition, these observations in combination with detailed chromodynamics calculations such as on the Lattice can provide important tests for our understanding of the role of gluons. The production of exotic mesons is expected to be enhanced in p interactions, where the experimental data is very limited. We present the description of the GlueX detector, beam line, and first results of the commissioning with photon beam.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries

Electrochemical measurements conducted in confined volumes provide a powerful and direct means to address scientific questions at the nexus of nanoscience, biotechnology, and chemical analysis. How are electron transfer and ion transport coupled in confined volumes and how does understanding them require moving beyond macroscopic theories? Also, how do these coupled processes impact electrochemical detection and processing? We address these questions by studying a special type of confined-volume architecture, the nanopore electrode array, or NEA, which is designed to be commensurate in size with physical scaling lengths, such as the Debye length, a concordance that offers performance characteristics not available in larger scale structures. The experiments described here depend critically on carefully constructed nanoscale architectures that can usefully control molecular transport and electrochemical reactivity. We begin by considering the experimental constraints that guide the design and fabrication of zero-dimensional nanopore arrays with multiple embedded electrodes. These zero-dimensional structures are nearly ideal for exploring how permselectivity and unscreened ion migration can be combined to amplify signals and improve selectivity by enabling highly efficient redox cycling. Our studies also highlight the benefits of arrays, in that molecules escaping from a single nanopore are efficiently captured by neighboring pores and returned to the population of active redox species being measured, benefits that arise from coupling ion accumulation and migration. These tools for manipulating redox species are well-positioned to explore single molecule and single particle electron transfer events through spectroelectrochemistry, studies which are enabled by the electrochemical zero-mode waveguide (ZMW), a special hybrid nanophotonic/nanoelectronic architecture in which the lower ring electrode of an NEA nanopore functions both as a working electrode to initiate electron transfer reactions and as the optical cladding layer of a ZMW. Furthermore, while the work described here is largely exploratory and fundamental, we believe that the development of NEAs will enable important applications that emerge directly from the unique coupled transport and electron-transfer capabilities of NEAs, including in situ molecular separation and detection with external stimuli, redox-based electrochemical rectification in individually encapsulated nanopores, and coupled sorters and analyzers for nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Unraveling the Growth Mechanism of Strongly Confined CsPbBr 3 Perovskite Quantum Dots under Thermodynamic Equilibrium Control

Size-confined lead halide perovskite quantum dots (PQDs) are promising materials for optoelectronic devices. Large quantities of PQDs with high ensemble uniformity are often needed for device fabrication. The thermodynamic-equilibrium-controlled synthesis can produce PQDs with good size and shape uniformity. Unfortunately, scaling up this synthesis often produces unwanted perovskite nanoplatelets (NPLs). To date, the PQD and NPL growth mechanism under thermodynamic equilibrium control remains unexplored. We discovered that the growth of size-confined CsPbBr 3 PQDs is mediated by ultrasmall (~ 2.4 nm) metastable nanoclusters. These nanoclusters can eventually grow into PQDs when sufficient Cs-precursors are provided. Otherwise, the unreacted nanoclusters will self-assemble and fuse into NPLs during the synthesis and/or PQD purification. Furthermore, by controlling the homogeneous growth of nanoclusters, strongly confined (≤ 5 nm) PQDs with high size uniformity can be produced at the gram scale.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Confining Liquids inside Carbon Nanotubes: Accelerated Molecular Dynamics with Spliced, Soft-Core Potentials and Simulated Annealing

Understanding emergent phenomena of fluids under physical confinement requires the development of advanced tools for rapid and accurate simulation of their physiochemical properties. Simulating liquid molecules commensurate in size with the nanoscale enclosures that confine them is a key challenge. In this work, we demonstrate an accelerated molecular dynamics simulation technique that combines soft-core potentials (SCP) and simulated annealing (SA) to analyze confined liquids. This integrated SCP/SA method relies on a new spliced soft-core potential (SSCP), which enables tunable accuracy with respect to the target hard-core potential (HCP). SCP/SA enables the packing of enclosures with bulk material in a controlled, thermodynamically consistent manner. The enhanced SSCP accuracy is a critical feature of SCP/SA, enabling a smooth transition between the SCP and the HCP at a desired SCP hardness. We applied SCP/SA to the problem of filling a carbon nanotube (CNT) in periodic boundary conditions with a popular ionic liquid (IL), 1- butyl-3-methylimidazolium hexafluorophosphate $[\text{BMIM}^+][\text{PF}^–_6]$. We performed a series of triplicate simulations on systems with varying CNT diameter and charge to demonstrate SCP/SA’s versatility. Beyond this IL/CNT system, the SCP/SA simulation framework has a broad range of potential applications, not limited to nanoscale enclosures and interfaces, including both solid-state and biological systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Consequences of Convex Nanopore Chemistry on Confined Water Dynamics

A basic understanding of confined water is crucial for developing selective ion transport and water purification membranes, yet the roles of nanopore geometry and functionality on confined water dynamics remain unresolved. We discuss the synthesis of perdeuterated ionic alkylsulfonate amphiphiles and their water-induced self-assembly into lyotropic liquid crystal (LLC) mesophases with well-defined, convex, sulfonate-lined nanopores. Quasielastic neutron scattering (QENS) measurements demonstrate that the water self-diffusion coefficients within these sulfonate-lined convex nanopores depend on the hydration level and amphiphile counterion identity (H + , K + , NMe 4 + ). The consistency of the observed counterion-dependent water dynamics trends with those of carboxylate LLCs is rationalized on the basis of similarities in the counterion spatial distributions in the water-filled channels, which we deduce from electron density maps derived from small-angle X-ray scattering (SAXS) analyses. These findings indicate that water diffusion is systematically faster in sulfonate-lined nanopores as compared to carboxylate-lined pores due to weaker water interactions with the softer and more hydrophobic–SO 3 – functionalities. These molecular-level insights into the relationships between convex pore wall chemical functionalities, hydrated counterions, and confined water diffusion may inform future development of new nanoporous media.

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

Water-Assisted Proton Transport in Confined Nanochannels

Hydrated excess protons under hydrophobic confinement are a critical component of charge transport behavior and reactivity in nanoporous materials and biomolecular systems. In this study, excess proton confinement effects are computationally investigated for sub-2 nm hydrophobic nanopores by varying the diameters (d = 0.81, 0.95, 1.09, 1.22, 1.36, 1.63, and 1.90 nm), lengths (l ~3 and ~5 nm), curvature, and chirality of cylindrical carbon nanotube (CNT) nanopores. CNTs with a combination of different diameter segments are also explored. The spatial distribution of water molecules under confinement is diameter-dependent; however, proton solvation and transport are consistently found to occur in the water layer adjacent to the pore wall, showing an “amphiphilic” character of the hydrated excess proton hydronium-like structure. The proton transport free energy barrier also decreases significantly as the nanopore diameter increases and proton transport becomes almost barrierless in the d > 1 nm nanopores. Among the nanopores studied, the Zundel cation (H 5 O 2 + ) is populated only in the d = 0.95 nm CNT (7,7) nanopore. The presence of the hydrated excess proton and K + inside the CNT (7,7) nanopore induces a water density increase by 40 and 20%, respectively. The K + transport through CNT nanopores is also consistently higher in the free energy barrier than proton transport. Interestingly, the evolution of excess protonic charge defect distribution reveals a “frozen” single water wire configuration in the d = 0.81 nm CNT (6,6) nanopore (or segment), through which hydrated excess protons can only shuttle via the Grotthuss mechanism. Vehicular diffusion becomes relevant to proton transport in the “flat” free energy regions and in the wider nanopores, where protons do not primarily shuttle in the axial direction.

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

Extremely Slow Diffusion of Gold Nanoparticles under Confinement in Mesoporous Silica

Here, we report an X-ray photon correlation spectroscopy (XPCS) study of the mobility of colloidal gold nanoparticles with a diameter of approximately 4 nm in glycerol under confinement within the channels of SBA-15 mesoporous silica with pore diameters of approximately 6 and 12 nm. The XPCS correlation functions result from an effective heterodyne signal due to the mixing of the coherent scattering from the nanoparticles and the mesoporous silica. Over the range of wave vectors and hence length scales probed, the nanoparticle dynamics are well described by one-dimensional diffusion. The nanoparticle diffusivity varies with temperature in a manner expected based on the temperature-dependent viscosity of glycerol; however, the magnitudes of the diffusion coefficients are several orders of magnitude smaller than those of the nanoparticles in bulk glycerol. We consider mechanisms that might contribute to this reduction in diffusivity including enhancement in hydrodynamic drag under confinement, effects of nanoparticle adsorption to the pore walls, and slowing structural dynamics in glycerol due to the combination of the nanometer-scale confinement and the presence of the nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Confinement-Controlled Rearrangements in Dioxolane Upgrading on H-ZSM-5 Revealed by Periodic DFT

Zeolitic Brønsted acid sites catalyze carbocation rearrangements central to upgrading biomass-derived oxygenates. Here we elucidate the mechanism of dioxolane conversion to methyl ethyl ketone and isobutanal on H-ZSM-5 using periodic density functional theory on the MFI model, complemented by ab initio molecular dynamics to probe confinement effects. Dioxolane adsorption at the Brønsted site is followed by protonation-assisted ring opening to form an oxocarbenium intermediate stabilized by the deprotonated framework. From this common intermediate, selectivity is governed by two competing rearrangements, namely, the 1,2-hydride shift with a free-energy barrier of 18.05 kcal mol –1 at 498 K leading toward MEK, and the 1,2-methyl shift with a higher barrier of 25.40 kcal mol –1 leading toward isobutanal. The hydride-shift channel is kinetically preferred over the methyl-shift channel, lowering the isobutanal/MEK ratio below the 3:1 limit expected for equal branching. Adsorption thermodynamics further indicate stronger stabilization of MEK than isobutanal within ZSM-5 channels, suggesting that confinement-controlled binding can bias product distributions in addition to intrinsic rearrangement barriers. These results highlight how Brønsted acidity and pore confinement jointly shape the rearrangement landscape in MFI zeolites.

adsorption↗
DOE OSTI2019

Directed Pore Uptake and Phase Separation of Surfactant Solutions under Confinement

The ability of a porous material to uptake and release molecules is determined by the thermodynamic state of preadsorbed surfactants in pore space. Yet, the effect of spatial confinement on the thermodynamic state of the surfactants is poorly understood. In this study, we use a combination of small-angle neutron scattering experiments and all-atom molecular dynamics simulations to develop a better understanding of the effect of confinement on self-assembly and temperature-induced liquid–liquid phase separation of surfactant solutions. Here, we study the demixing of a model nonionic surfactant triethyleneglycol monohexyl ether (C 6 E 3 ) in tubular nanopores of the SBA-15 silica material (pore diameter of 8.6 nm). We find that the nonionic surfactants display an enhanced in situ aggregation behavior in silica pores upon increasing the temperature above the lower critical solution temperature (LCST). The surfactant molecules directly bound to the pore walls act as anchor sites for subsequent adsorption, resulting in the increased uptake of nonanchored surfactants upon increasing temperature and driving an increase in the size of assemblies. The nonanchored surfactant molecules can be released into a bulk solvent by decreasing the temperature below LCST. This ability of C 6 E 3 surfactant allows reversible partitioning of secondary molecules (here dye) dissolved in the cores of surfactant micelles between the pore space and bulk solvent. The findings presented in the article provide fundamental insights into the surfactant assembly in confinement, which is crucial in the development of new multiresponsive materials for isolating and recovering molecules.

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

Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C 30 H 62 Alkane by OH

Here, we examine in a simple organic aerosol the transition between heterogeneous chemistry under well-mixed conditions to chemistry under interfacial confinement. A single reaction mechanism, shown to reproduce observed OH oxidation chemistry for liquid and semisolid C 30 H 62 , is used in reaction-diffusion simulations to explore reactivity over a broad viscosity range. The results show that when internal mixing of the aerosol is fast and the particle interface is enriched in C-H groups, ketone and alcohol products, formed via peroxy radical disproportionation, predominate. As viscosity increases the reactions become confined to a shell at the gas-aerosol interface. The confinement is accompanied by emergence of acyloxy reaction pathways that are particularly active when the shell is 1 nm or less. We quantify this trend using a reaction-diffusion index, allowing the parts of the mechanism that control reactivity as viscosity increases to be identified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗