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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 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

A new method for determining the CO to H2 conversion factor for translucent clouds

In this paper we describe a new technique for obtaining the conversion factor between the molecular hydrogen column density and the CO(J = 1-0) integrated antenna temperature. This factor, typically known as X(sub CO) is often to be of order a few times 10(exp 20)/sq cm/K km/s) for the molecular clouds in the Galaxy and is one of the primary means of determining the molecular cloud mass from CO observations. However, for the low-extinction interstellar clouds known as the translucent molecular clouds, estimates of X(sub CO) vary by up to a factor of 60 depending on the object and techniques employed to calibrate X(sub CO). Since the cloud mass is directly proportional to X(sub CO) uncertainties in mass estimates of translucent clouds can be more than an order of magnitude. We calibrate the H2 content in translucent clouds by using the linear relationship between the CH and H2 column densities. The CH column density is readily determined from observations of the CH ground-state hyperfine main-line transition at 3335 MHz. Using CH as a surrogate tracer for H2 and CO(J = 1-0) observations of a sample of translucent and dark molecular clouds, we find a wide variation in values for X(sub CO). For translucent clouds, X(sub CO) ranges from 0.3 to 6.8 x 10(exp 20) and for dark clouds the values range from 0.8 to 8.6. Although the average values for both types of cloud are similar to the canonical value determined for the Galactic molecular cloud ensemble (2-4 x 10(exp 20)), the scatter in individual X(sub CO) values may indicate that X(sub CO) for a given translucent cloud cannot be determined a priori and must be obtained for each cloud so that a reliable mass determination may be made.

Magnani, L.↗
DOE OSTI2024

Online Monitoring of Catalytic Processes by Fiber-Enhanced Raman Spectroscopy

An innovative solution for real-time monitoring of reactions within confined spaces, optimized for Raman spectroscopy applications, is presented. This approach involves the utilization of a hollow-core waveguide configured as a compact flow cell, serving both as a conduit for Raman excitation and scattering and seamlessly integrating into the effluent stream of a cracking catalytic reactor. The analytical technique, encompassing device and optical design, ensures robustness, compactness, and cost-effectiveness for implementation into process facilities. Notably, the modularity of the approach empowers customization for diverse gas monitoring needs, as it readily adapts to the specific requirements of various sensing scenarios. As a proof of concept, the efficacy of a spectroscopic approach is shown by monitoring two catalytic processes: CO 2 methanation (CO 2 + 4H 2 → CH 4 + 2H 2 O) and ammonia cracking (2NH 3 → N 2 + 3H 2 ). Leveraging chemometric data processing techniques, spectral signatures of the individual components involved in these reactions are effectively disentangled and the results are compared to mass spectrometry data. This robust methodology underscores the versatility and reliability of this monitoring system in complex chemical environments.

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

Impact of Hydroxyl Functionalization and Unsaturation on Linear Poly(ethylene- co -vinyl alcohol)

Functionalization of C═C in unsaturated polyolefins by hydroboration/oxidation successfully generates linear poly(ethylene-co-vinyl alcohol) (LEVOH) polymers. This postpolymerization modification expands upon previously reported chemistry to control the extent of functionalization through reagent stoichiometry. Partial functionalization (24–92% of C═C) of polycyclooctene produces materials with both C═C in the backbone and pendant OH and subsequent hydrogenation generate a LEVOH. We explore the thermal, structural, surface, and adhesive properties of these LEVOH and the partially unsaturated intermediate and find they are impacted by both the extent of OH incorporation and saturation. The presence of C═C significantly reduces the melting temperature and crystallinity while increasing surface polarity and adhesive strength compared with saturated polymers at equivalent functionalization. Furthermore, this investigation demonstrates linear analogs of EVOH with a wide range of properties tuned by extent of hydroxylation and presence of unsaturation.

Crystal structure↗
DOE OSTI2025

Sustainable Shape Memory Elastomers with Reduced Melt Viscosity and Enhanced Stiffness

Melt reactive processing of lignin with nitrile rubber is a promising approach to synthesizing shape memory materials. The strong intramolecular interactions in lignin macromolecular structures, caused by π–π stacking in aromatic rings and hydrogen bonding, often result in large phase separation or low miscibility with rubbers. In this study, we investigated the chemical and molecular characteristics, as well as the stiffness and complex viscosity, of modified kraft lignin melt-reacted with an acrylonitrile/butadiene copolymer containing 41% acrylonitrile (NBR41). To enhance the macromolecular compatibility of kraft lignin with NBR41, kraft lignin was cross-linked with poly(propylene glycol) diglycidyl ether (PPDE) and trimethylolpropane triglycidyl ether (TTE), both rich in epoxy reactive groups capable of forming chemical bonds with hydroxyl and carboxyl groups. Here, our findings demonstrate that the modification of kraft lignin with PPDE and TTE resulted in significantly increased stiffness of the composites. The elastic modulus of NBR41-Kraft lignin-PPDE and NBR41-Kraft lignin-TTE increased by 82 and 162%, respectively. Both the yield strength and Young’s modulus of these two samples showed dramatic improvements. Specifically, the yield strength and Young’s modulus of NBR41-Kraft lignin-TTE increased nearly 4 and 3-fold, respectively, compared to the control sample. Interestingly, despite significant improvements in mechanical properties, the viscosity of NBR41-Kraft lignin-PPDE was substantially lower than that of the control sample. At 210 °C and an angular frequency of 1 rad/s, the complex viscosity of NBR41-Kraft lignin was approximately 100.25 ± 4.77 kPa·s, while that of NBR41-Kraft lignin-PPDE was significantly lower at 56 ± 0.93 kPa·s. These findings were validated through Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic mechanical analysis, thermal characterization, rheological tests, and quasi-elastic neutron scattering techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

An IUE survey of interstellar H I Ly alpha absorption. 2: Interpretations

We present an analysis of interstellar neutral hydrogen column densities obtained from archival Ly alpha absorption line data toward the complete sample of B2 and hotter stars observed at high spectral resolution with the IUE satellite. The full sample includes 554 stars and more than doubles the number of lines of sight previously observed. Many of the B2 and B1.5 stars exhibit contamination from stellar Ly alpha absorption, and were excluded from the subsequent analysis. The final working sample includes 393 stars. We present statistical averages for a number of quantities derived for the sample. The stars range in distance from 0.12 to 11 kpc with an average distance of 2.1 kpc. Values for average sight-line density range from 0.017 to 8.62 atoms cm(exp -3), with an overall average of 0.23 atoms cm(exp -3). Neutral hydrogen and dust are well correlated, with N(H I)/E(B - V) = 4.93 x 10(exp 21) cm(exp -2) mag(exp -1), and N(H I)/E(Bump) = 2.17 x 10(exp 21) cm(exp -2) mag(exp -1). There is an increase in the H I to dust ratios for the densest sight lines. Evidently, the H I to dust ratios in dense clouds are higher than in the lower density medium between the clouds and in interarm directions. The effect is probably an indication of dust modification in the dense clouds. The H I to dust ratios are approx. 17% smaller for the sight lines to O stars compared to the ratios found toward B stars. We have identified sight lines with anomalously large and small values of N(H I)/E(B - V) and H(H I)/E(Bump). Some of these sight lines are well-known examples of peculiar extinction (i.e., HD 147933 and HD 37061 (NU Ori)). Others are less well known and may provide important new examples of regions with highly modified dust. The number of stars with anomalously low H I to dust ratios is disproportionately larger than the number of stars with anomalously high H I to dust ratios. The distribution of the gas away form the Galactic plane for the sample of objects is complex. For the subset of 375 stars whose lines of sight have a statistically low probablility of intersecting a large cloud, the distribution may be roughly approximated by an exponential density distribution, with a midplane density of 0.366 atoms cm(exp -3), a scale height of 195 pc, and a random logarithmic scattering parameter sigma (sub p) of 0.159 dex. For the same sample of stars, interstellar dust is found to be confined closer to the plane than the H I, with (E(B - V)/r)(sub 0) = 0.257 mag kpc(exp -1), scale height h = 152 pc, and sigma(sub p) = 0.263 dex. The dust distribution is more inhomogeneous than the gas distribution. The observed distribution of H I away from the Galactic plane can also be fitted with a two-component exponential model including the effects of patchiness. Unfortunately, the foreground contamination produced by the cloudy and more confined component of H I makes it difficult to estimate the scale height of the extended component without invoking an independent estimate of its midplane density. Assuming n(sub 2)(0) = 0.16 cm(exp -3) from the Copernicus satellite H I/H(sub 2) survey, we obtain n(sub 1)(0) = 0.247 cm(exp -3), h(sub 1) = 73 PC, and h(sub 2) + 357 pc.

Diplas, Athanassios↗
NASA NTRS2002

A Proposed Model for Protein Crystal Nucleation and Growth

How does one take a molecule, strongly asymmetric in both shape and charge distribution, and assemble it into a crystal? We propose a model for the nucleation and crystal growth process for tetragonal lysozyme, based upon fluorescence, light, neutron, and X-ray scattering data, size exclusion chromatography experiments, dialysis kinetics, AFM, and modeling of growth rate data, from this and other laboratories. The first species formed is postulated to be a 'head to side' dimer. Through repeating associations involving the same intermolecular interactions this grows to a 4(sub 3) helix structure, that in turn serves as the basic unit for nucleation and subsequent crystal growth. High salt attenuates surface charges while promoting hydrophobic interactions. Symmetry facilitates subsequent helix-helix self-association. Assembly stability is enhanced when a four helix structure is obtained, with each bound to two neighbors. Only two unique interactions are required. The first are those for helix formation, where the dominant interaction is the intermolecular bridging anion. The second is the anti-parallel side-by-side helix-helix interaction, guided by alternating pairs of symmetry related salt bridges along each side. At this stage all eight unique positions of the P4(sub3)2(sub 1),2(sub 1) unit cell are filled. The process is one of a) attenuating the most strongly interacting groups, such that b) the molecules begin to self-associate in defined patterns, so that c) symmetry is obtained, which d) propagates as a growing crystal. Simple and conceptually obvious in hindsight, this tells much about what we are empirically doing when we crystallize macromolecules. By adjusting the growth parameters we are empirically balancing the intermolecular interactions, preferentially attenuating the dominant strong (for lysozyme the charged groups) while strengthening the lesser strong (hydrophobic) interactions. In the general case for proteins the lack of a singularly defined association pathway may lead to formation of multiple species, i.e., amorphous precipitation. Weak interactions, such as hydrogen bonds, are promiscuous, serving to strengthen rather than define specific interactions. Participation in an interaction sequesters that surface from subsequent interactions, and we expect the strongest bonds to form first. This model, its basis, how it fits into the currently understood osmotic second virial coefficient approach to crystallization, and what it suggests will be discussed.

Pusey, Marc↗
DOE OSTI2021

Isotopic and vibrational-level dependence of H 2 dissociation by electron impact

The low-energy electron-impact dissociation of molecular hydrogen has been a source of disagreement between various calculations and measurements for decades. Excitation of the ground state of H 2 into the dissociative b 3 $Σ$$$^{+}_{u}$ state is now well understood, with the most recent measurements being in excellent agreement with the molecular convergent close-coupling (MCCC) calculations of both integral and differential cross sections [Zawadzki et al., Phys. Rev. A 98, 062704 (2018)]. However, in the absence of similar measurements for vibrationally excited or isotopically substituted H 2 , cross sections for dissociation of these species must be determined by theory alone. We have identified large discrepancies between MCCC calculations and the recommended R-matrix cross sections for dissociation of vibrationally excited H 2 , D 2 , T 2 , HD, HT, and DT [Trevisan et al., Plasma Phys. Contr. Fusion 44 1263 (2002); Plasma Phys. Contr. Fusion 44, 2217 (2002)], with disagreement in both the isotope effect and dependence on initial vibrational level. Furthermore, we investigate the source of the discrepancies, and discuss the consequences for plasma models, which have incorporated the previously recommended data.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. The report below summarizes the work done at UC Davis, which is complemented by work done at BYU (Woodfield) and Virginia Tech (Ross).

36 MATERIALS SCIENCE↗
DOE OSTI2022

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. This research was a collaboration between UC Davis (A. Navrotsky) BYU (B. Woodfield) and Virginia Tech (N. Ross).

36 MATERIALS SCIENCE↗
DOE OSTI2022

Conditional H I Mass Functions and the H I -to-halo Mass Relation in the Local Universe

We present a new H I mass estimator that relates log 10 (M HI /M * ) to a linear combination of four galaxy properties: stellar surface mass density, color index u - r, stellar mass, and concentration index, with the scatter of individual galaxies around the mean H I mass modeled with a Gaussian distribution function. We calibrate the estimator using the xGASS sample, including both H I detection and nondetection, and constrain the model parameters through Bayesian inferences. Tests with mock catalogs demonstrate that our estimator provides unbiased H I masses for optical samples like SDSS. We apply our estimator to the SDSS spectroscopic sample to estimate the H I mass function (HIMF) of local galaxies, as well as the conditional H I mass function in galaxy groups and the H I –halo mass relation. Our HIMF agrees with the ALFALFA measurements at M HI ≳ 5 × 10 9 M ⊙ , but with higher amplitude and a steeper slope at lower masses. We show that this discrepancy is caused primarily by the cosmic variance, which is corrected for the SDSS sample but not for ALFALFA. The total CHIMFs for all halo masses can be described by a single Schechter function, while those of central galaxies show a double-Gaussian profile. The total H I mass in a group increases monotonically with halo mass, but for central galaxies, the H I mass shows weak dependence on halo mass when M h ≳ 10 12 M ⊙ . The observed H I –halo mass relation is not reproduced by current hydrodynamic simulations and semianalytic models of galaxy formation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Techniques for studying materials under extreme states of high energy density compression

The properties of materials under extreme conditions of pressure and density are of key interest to a number of fields, including planetary geophysics, materials science, and inertial confinement fusion. In geophysics, the equations of state of planetary materials, such as hydrogen and iron, under ultrahigh pressure and density provide a better understanding of their formation and interior structure [Celliers et al., “Insulator-metal transition in dense fluid deuterium,” Science 361, 677–682 (2018) and Smith et al., “Equation of state of iron under core conditions of large rocky exoplanets,” Nat. Astron. 2, 591–682 (2018)]. The processes of interest in these fields occur under conditions of high pressure (100 GPa–100 TPa), high temperature (>3000 K), and sometimes at high strain rates (>103 s−1) depending on the process. With the advent of high energy density (HED) facilities, such as the National Ignition Facility (NIF), Linear Coherent Light Source, Omega Laser Facility, and Z, these conditions are reachable and numerous experimental platforms have been developed. To measure compression under ultrahigh pressure, stepped targets are ramp-compressed and the sound velocity, measured by the velocity interferometer system for any reflector diagnostic technique, from which the stress-density of relevant materials is deduced at pulsed power [M. D. Knudson and M. P. Desjarlais, “High-precision shock wave measurements of deuterium: Evaluation of exchange-correlation functionals at the molecular-to-atomic transition,” Phys. Rev. Lett. 118, 035501 (2017)] and laser [Smith et al., “Equation of state of iron under core conditions of large rocky exoplanets,” Nat. Astron. 2, 591–682 (2018)] facilities. To measure strength under high pressure and strain rates, experimenters measure the growth of Rayleigh–Taylor instabilities using face-on radiography [Park et al., “Grain-size-independent plastic flow at ultrahigh pressures and strain rates,” Phys. Rev. Lett. 114, 065502 (2015)]. The crystal structure of materials under high compression is measured by dynamic x-ray diffraction [Rygg et al., “X-ray diffraction at the national ignition facility,” Rev. Sci. Instrum. 91, 043902 (2020) and McBride et al., “Phase transition lowering in dynamically compressed silicon,” Nat. Phys. 15, 89–94 (2019)]. Medium range material temperatures (a few thousand degrees) can be measured by extended x-ray absorption fine structure techniques, Yaakobi et al., “Extended x-ray absorption fine structure measurements of laser-shocked V and Ti and crystal phase transformation in Ti,” Phys. Rev. Lett. 92, 095504 (2004) and Ping et al., “Solid iron compressed up to 560 GPa,” Phys. Rev. Lett. 111, 065501 (2013), whereas more extreme temperatures are measured using x-ray Thomson scattering or pyrometry. This manuscript will review the scientific motivations, experimental techniques, and the regimes that can be probed for the study of materials under extreme HED conditions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Reversible CO 2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex

Abstract The authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir 3 H 6 ( μ 3 ‐H)(PN) 3 ] 2+ ( 2‐H , PN = (2‐pyridyl)CH 2 PBu t 2 ). Despite its unusual stability to unsaturated organics, electrophiles, and even CF 3 SO 3 D, they find that complex 2‐H catalyzes hydrogenation of CO 2 to formate (TON Ir = 9600) and reverse formic acid dehydrogenation (TON Ir = 54 400). The hydrogenation operates via a reactive intermediate [Ir 3 H 4 ( μ ‐H) 4 (PN) 3 ] + ( 5 ). Neutron crystallography and DFT‐supported neutron vibrational spectroscopy of 2‐H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir 3 H 7 core. Stoichiometric oxidation of 2‐H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra‐ and pentanuclear clusters [Ir 3 H 6 ( μ 3 ‐AuPPh 3 )(PN) 3 ] 2+ ( 2‐Au ) and [Ag{Ir 2 H 4 ( μ ‐OAc)(PN) 2 } 2 ] 3+ ( 6 ) are generated using AuPPh 3 + and AgOAc, respectively. Further oxidation to class [Ir 2 H 3 ( μ ‐X) 2 (PN) 2 ] + is possible with AgOAc, Hg(OAc) 2 , or I 2 . Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir 2 Cl 4 ( μ ‐Cl) 2 (PN) 2 ] ( 11 ).

Cherepakhin, Valeriy [Loker Hydrocarbon Research I↗
DOE OSTI2024

Catalytic Water Electrolysis by Co–Cu–W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co–Cu–W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co 2+ (octahedral), Cu + / 2+ (tetrahedral/square-planar), and W 6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co 3+ and Cu 0 are the active catalytic sites involved in the OER and HER, respectively, while Cu 2+ and W 6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co–Cu–W MMO system. In conclusion, these results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co 3+ hydroperoxide, whose formation is accompanied by changes in the Cu–O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

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

Structural reversibility of Cu doped NU-1000 MOFs under hydrogenation conditions

The metal-organic framework (MOF), NU-1000, and its metalated counterparts have found proof-of-concept application in heterogeneous catalysis and hydrogen storage amongst others. A vapor-phase technique, akin to atomic layer deposition (ALD), is used to selectively deposit divalent Cu ions on oxo, hydroxo-bridged hexa-zirconium(IV) nodes capped with terminal –OH and -OH 2 ligands. Subsequent reaction with steam yields node-anchored, CuII-oxo,hydroxo clusters. We find that cluster installation via AIM (= ALD In MOFs) is accompanied by an expansion of MOF mesopore (channel) diameter . We investigated the behavior of the cluster-modified material, termed Cu-AIM-NU-1000, to heat treatment up to 325 °C, at atmospheric pressure with a low flow of H2 into the reaction cell. The response under these conditions revealed two important results: (1) Above 200 °C, the initially installed few-metal-ion clusters reduce to neutral Cu atoms. The neutral atoms migrate from the nodes and aggregate into Cu nanoparticles. While the size of particles formed in the MOF interior is constrained by the width of mesopores (ca. 3 nm), those formed on the exterior surface of the MOF can grow as large as ca. 8 nm. (2) Reduction and release of Cu atoms from the MOFs nodes is accompanied NU-1000 undergoes dynamic structural transformation as it reverts back to its original dimension following the release. These results show while the MOF framework itself remains intact at 325 °C in an H 2 atmosphere, the small, AIM-installed Cu II -oxo,hydroxo clusters are stable with respect to reduction and conversion to metallic nanoparticles only up to ~200 °C.

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

Orientation-dependent enhanced ionization in acetylene revealed by ultrafast cross-polarized pulse pairs

We investigate the orientation dependence of enhanced ionization (EI) during strong-field-driven nuclear motion in acetylene (C 2 ⁢H 2 ). Here, we both initiate and probe molecular dynamics in acetylene with intense 6-fs cross-polarized pulse pairs, separated by a variable delay. Following multiple ionization by the first pulse, acetylene undergoes simultaneous elongation of the carbon-carbon and carbon-hydrogen bonds, enabling further ionization by the second pulse and the formation of a very highly charged state, [C 2 ⁢H 2 ] 6+ . At small interpulse delays (< 20 fs), this enhancement occurs when the molecule is aligned to the probe pulse. Conversely, at large delays (> 40 fs), formation of [C 2 ⁢H 2 ] 6+ occurs when the molecule is aligned to the pump pulse. By analyzing the polarization and time dependence of sequentially ionized [C 2 ⁢H 2 ] 6+ , we resolve two transient alignments that both contribute to a large increase in the multiple ionization yield. In conclusion, this cross-polarized pulse pair scheme uniquely enables selective probing of deeply bound orbitals, providing new insights on orientation-dependent EI in highly charged hydrocarbons.

Atomic & molecular clusters↗
NASA NTRS2018

Cryogenic Selective Surfaces

There are many challenges involved in deep-space exploration, but several of these can be mitigated, or even solved, by the development of a coating that reflects most of the Sun’s energy, yet still provides far-infrared heat emission. Such a coating would allow non-heat-generating objects in space to reach cryogenic temperatures without using an active cooling system. This would benefit deep-space sensors that require low temperatures, such as the James Webb Telescope focal plane array. It would also allow the use of superconductors in deep space, which could lead to magnetic energy storage rings, lossless power delivery, or perhaps a large-volume magnetic shield against galactic cosmic radiation. However, perhaps the most significant enablement achieved from such a coating would be the long-term, deep space storage of cryogenic liquids, such as liquid oxygen (LOX). In our Phase I NIAC study, we realized that a combination of scattering particles and a silver backing could yield a highly effective, very broadband, reflector that could potentially reflect more than 99.9% of the Sun’s irradiant power. We developed a sophisticated model of this reflector and theoretically showed that cryogenic temperatures could be achieved in deep space at one astronomical unit (1 AU) from the Sun. We showed how this new reflector could minimize heat conduction into the cryogenic tanks by coating the tank support struts. We then modelled a strawman architecture for a mission to Mars, using a coated LOX tank, coated struts, and infrared shields, to show that with our new coating it would be possible to maintain liquid oxygen passively. As a result of this work a patent application was generated and a paper published in Optics Letters. Our Phase II NIAC study had two primary goals, to develop a rigid version of the cryogenic selective surface proposed in Phase I and to test its performance in a simulated deep space environment. During the first year of the project the work concentrated on developing rigid tiles of BaF2, leading to tiles as large as 4 inches in diameter that transmitted very little visible light. In addition, during the first year a simulated deep space environment was created using a vacuum chamber and cryocooler. Using this facility, we showed that our BaF2 tiles absorbed less than ¼% of 375 nm radiation, a significant milestone for the work. During the second year of the project, we continued to develop the BaF2 tiles and we put significant effort into the construction of a deep space environment where we could project simulated solar radiation onto a sample. In the spring of 2018, we conducted our first solar simulator test with BaF2 and saw about 3.6% absorption. This is better than the state-of-the-art, but disappointing since predictions were for much lower absorption. We, erroneously, attributed this absorption to water retention by the BaF2, and decided to change materials. We considered several oxides and settled on yttrium oxide (Y2O3) for further development, because it is broadband, lightweight, has high index, and is hydrophobic. In July 2018 we conducted our first test of a rigid tile of Y2O3 in the simulated deep space environment and saw significant absorption again. We then realized that the issue was not water, but mid-wave radiation passing through the tile and being absorbed by the temperature sensor and the varnish used to hold it in place. We wrapped the sensor in silver foil, re-ran the test, and saw much lower absorption; only 1.1%. We then re-ran the BaF2 tile and saw 1.4% absorption. These values are almost adequate to maintain LOX in deep space, but we suspect that there are still issues in our test apparatus; we suspect thermocouple wires may be absorbing radiation. Further, post-NIAC, testing will better determine the performance of our new solar reflector. In order to restrict the size of this report, we will only briefly describe topics that we have previously published, allowing us to devote more time to new material. So minimal material will be devoted to modeling the material and deep space cryogenic storage, while longer sections will cover our material development, simulated deep space testing, and new applications. The Launch Service Program (LSP) requested that we explore ways to use this new coating to maintain LOX in low Earth Orbit and that work is described. In addition, the Nuclear Thermal Propulsion (NTP) Program asked us to explore ways to reduce the heat load for liquid hydrogen, resulting in the development of a spray-on version of the coating that should significantly improve in-space multi-layer insulation performance.

Robert C. Youngquist,↗
DOE OSTI2025

Capturing Ring Opening in Photoexcited Enolic Acetylacetone upon Hydrogen Bond Dissociation by Ultrafast Electron Diffraction

Photoinduced biological and chemical reactions are often based on key structural transformations of a molecule driven across multiple electronic states. Acetylacetone (AcAc) is a prototypical system for complex chemical pathways involving several conical intersections (CI) and singlet–triplet intersystem crossings (ISC) characterized by distinct geometries. In the gas phase, AcAc is predominantly in a planar ring-like enolic form stabilized by a strong intramolecular O–H···O hydrogen bond. Following excitation into the S 2 (ππ*) state at 266 nm, acetylacetone undergoes rapid internal conversion followed by intersystem crossing. Such relaxation pathways are associated with structural changes including ring opening, deplanarization, and bond elongation. In this work, ultrafast electron diffraction (UED) at the SLAC MeV-UED setup is employed as a direct structural probe with a time resolution of 160 fs. Together with trajectory surface hopping simulations, analysis of the UED data provides a new perspective on the early time nuclear dynamics in acetylacetone. Specifically, AcAc is observed to undergo ring opening, deplanarization, and bond elongation all within the first 700 fs after photoexcitation. The monitored dynamics is associated mainly with the nuclear motion on the S 1 potential energy surface, formed after very rapid transfer from S 2 to S 1 , allowing AcAc to reach the conical intersection to intersystem crossing. Such time scales of nuclear motion are contrasted with the time scales of electronic transitions in AcAc that were previously characterized with spectroscopic methods, specifically internal conversion (<100 fs) and intersystem crossing (∼1.5 ps).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗