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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water

Efficient removal of pertechnetate (TcO4 -) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4 - anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stable zirconium based metalorganic framework can adsorb perrhenate (ReO4 -) anions, a non-radioactive surrogate for TcO4 -, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4 - (surrogate for TcO4 -) molecule within the framework.

Banerjee, Debasis↗
DOE OSTI2019

Dynamics of Water Molecules and Ions in Concentrated Lithium Chloride Solutions Probed with Ultrafast 2D IR Spectroscopy

Water and ion dynamics in concentrated LiCl solutions were studied using ultrafast 2D IR spectroscopy with the methyl thiocyanate (MeSCN) CN stretch as the vibrational probe. The IR absorption spectrum of MeSCN has two peaks, one peak for water associated with the nitrogen lone pair of MeSCN (W) and the other peak corresponding to Li + associated with the lone pair (L). To extract the spectral diffusion (structural dynamics) of W and L species, we developed a method that isolates the peak of interest by subtracting the 2D Gaussian proxies of multiple interfering peaks. Center line slope data (normalized frequency–frequency correlation function) for 2D bands from the W and L are fit with triexponential functions. The fastest component (1.1–1.6 ps) is assigned to local hydrogen bond length fluctuations. The intermediate timescale (~4.0 ps) corresponds to the hydrogen bond network rearrangement. The slowest component decays in ~40 ps and corresponds to ion pair and ion cluster dynamics. The very similar W and L spectral diffusion indicates that the motions of the water and ions are strongly coupled. Orientational relaxations of the W and L species were extracted using a new method to eliminate the effects of overlapping peaks. The results show that MeSCN bound to water undergoes orientational relaxation significantly faster than MeSCN bound to Li + . The orientational and spectral diffusion results are compared. In conclusion, a Stark coupling model is used to extract the root mean square average electric field caused by the ion clouds along the CN moiety as a function of concentration.

14 SOLAR ENERGY↗
DOE OSTI2015

Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water and ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Understanding Structure, Metal Distribution, and Water Adsorption in Mixed-Metal MOF-74

We present a joint computational and experimental study of Mg–Ni-MOF-74 and Mg–Cd-MOF-74 to gain insight into the mixing of metals and understand how metal mixing affects the structure of the undercoordinated open-metal sites. Our calcula tions predict that metal mixing is energetically preferred in these materials. Recent experimental work has demonstrated that Mg–Ni-MOF-74 shows a much greater surface area retention in the presence of water than Mg-MOF-74. To probe this effect, we study H2O adsorption in Mg–Ni-MOF-74, finding that the adsorption en ergetics and electronic structure do not change significantly at the metal sites when compared to Mg-MOF-74 and Ni-MOF-74, respectively. We conclude that the in creased stability of Mg–Ni-MOF-74 is a result of a M–O bond length distortion in mixed-metal MOF-74, consistent with recent work on the stability of MOF-74 under water exposure.

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

Probing Hydrogen-Bonding Interactions of Water Molecules Adsorbed on Silica, Sodium Calcium Silicate, and Calcium Aluminosilicate Glasses

Vibrational sum frequency generation (SFG) spectroscopy was used to study how hydrogen bonding interactions of physisorbed water layers vary with the glass composition and surface condition. Three different glass materials were used: amorphous silica (fused quartz), sodium calcium silicate (also called soda lime silica), and calcium aluminosilicate (boron-/fluorine-free E-glass). Two different surface conditions were compared: (i) a mechanically polished, fire-polished, and then annealed surface and (ii) an acid-leached surface (pH 1, 90 °C, 24 h). Compositional and structural information obtained by X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and attenuated total reflection infrared spectroscopy were correlated with SFG spectral features. The temperature dependence of SFG spectral features revealed that regardless of the glass composition, the glass surface is free of physisorbed water at 250 °C, and during cooling in ambient air, it starts absorbing water at a temperature corresponding to a relative humidity of 1–2%. Humidity-controlled SFG measurements at room temperature showed that the hydrogen bonding interactions of water physisorbed on the glass surface cleaned with UV/O 3 are quite different depending on the glass composition and surface preparation history. This finding will be useful in understanding how surface properties of different glasses are altered by humidity in ambient air.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Heterogeneous Nucleation and Growth of Barium Sulfate at Organic–Water Interfaces: Interplay between Surface Hydrophobicity and Ba 2+ Adsorption

Barium sulfate (BaSO4) is a common scale-forming mineral in natural and engineered systems, yet the rates and mechanisms of heterogeneous BaSO4 nucleation are not understood. To address these, we created idealized interfaces on which to study heterogeneous nucleation rates and mechanisms, which also are good models for organic–water interfaces: self-assembled thin films terminated with different functional groups (i.e., -COOH, -SH, or mixed -SH & COOH) coated on glass slides. BaSO4 precipitation on coatings from Barite-supersaturated solutions (saturation index, SI, = 1.1) was investigated using grazing-incidence small-angle X-ray scattering. After reaction for 1 h, a little amount of BaSO4 formed on hydrophilic bare and -COOH coated glasses. Meanwhile, BaSO4 nucleation was significantly promoted on hydrophobic -SH and mixed -SH & COOH coatings. This is because substrate hydrophobicity likely affected the interfacial energy and hence thermodynamic favorability of heterogeneous nucleation. The heterogeneous BaSO4 nucleation and growth kinetics were found to be affected by the amount of Ba2+ adsorption onto the substrate and incipient BaSO4 nuclei. The importance of Ba2+ adsorption was further corroborated by the finding that precipitation rate increased under [Ba2+]/[SO42–] concentration ratios >1. These observations suggest that thermodynamic favorability for nucleation is governed by substrate–water interfacial energy, while given favorable thermodynamics, the rate is governed by ion attachment to substrates and incipient nuclei.

barite↗
DOE OSTI2019

Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO 2 (110) Surfaces: Alkali Promotion of Water Dissociation and Production of H 2

The addition of potassium atoms to Cu(111) and Cu/TiO 2 (110) surfaces substantially enhances the rate for water dissociation and the production of hydrogen through the water–gas shift reaction (WGS, CO + H 2 O → H 2 + CO 2 ). In the range of temperatures investigated, 550–625 K, Cu/K/TiO 2 (110) exhibits a WGS activity substantially higher than those of K/Cu(111), Cu(111), and Cu/ZnO(000$\bar{1}$) systems used to model an industrial Cu/ZnO catalyst. The apparent activation energy for the WGS drops from 18 Kcal/mol on Cu(111) to 12 Kcal/mol on K/Cu(111) and 6 Kcal/mol on Cu/K/TiO 2 (110). The results of density functional calculations show that K adatoms favor the thermochemistry for water dissociation on Cu(111) and Cu/TiO 2 (110) with the cleavage of an O–H bond occurring at room temperature. Furthermore, at the Cu/K/TiO 2 interface, there is a synergy, and this system has a unique ability to dissociate the water molecule and catalyze hydrogen production through the WGS process. Therefore, when optimizing a regular catalyst, it is essential to consider mainly the effects of an alkali promoter on the metal–oxide interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Stable Water Isotopes Reveal Effects of Intermediate Disturbance and Canopy Structure on Forest Water Cycling

Forests play an important role in the climate system and link water fluxes between the land surface and the atmosphere. Here we compare water vapor isotopes in two adjacent forest sites in the northern lower peninsula of Michigan to understand the effects of intermediate disturbance and canopy structure on forest water cycling. One site is dominated by aspen and birch and has a thick, closed canopy. All of the aspen and birch were killed at the second site. As a result, the disturbed site has a more open-canopy structure. From our comparison, we found that both the species of tree and the spacing around trees are important controls on forest water cycling. With more space between trees, air mixes more freely into the canopy, which dries the forest air. Alternatively, air may be poorly mixed within and above thick, closed canopies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

A Unified Framework to Reconcile Different Approaches of Modeling Transpiration Response to Water Stress: Plant Hydraulics, Supply Demand Balance, and Empirical Soil Water Stress Function

Plant responses to water stress is a major uncertainty to predicting terrestrial ecosystem sensitivity to drought. Different approaches have been developed to represent plant water stress. Empirical approaches (the empirical soil water stress (or Beta) function and the supply-demand balance scheme) have been widely used for many decades; more mechanistic based approaches, that is, plant hydraulic models (PHMs), were increasingly adopted in the past decade. However, the relationships between them—and their underlying connections to physical processes—are not sufficiently understood. This limited understanding hinders informed decisions on the necessary complexities needed for different applications, with empirical approaches being mechanistically insufficient, and PHMs often being too complex to constrain. Here we introduce a unified framework for modeling transpiration responses to water stress, within which we demonstrate that empirical approaches are special cases of the full PHM, when the plant hydraulic parameters satisfy certain conditions. We further evaluate their response differences and identify the associated physical processes. Finally, we propose a methodology for assessing the necessity of added complexities of the PHM under various climatic conditions and ecosystem types, with case studies in three typical ecosystems: a humid Midwestern cropland, a semi-arid evergreen needleleaf forest, and an arid grassland. Notably, Beta function overestimates transpiration when VPD is high due to its lack of constraints from hydraulic transport and is therefore insufficient in high VPD environments. With the unified framework, we envision researchers can better understand the mechanistic bases of and the relationships between different approaches and make more informed choices.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water

Compared to the vapour phase, liquid-phase heterogeneous catalysis provides additional degrees of freedom for reaction engineering, but the multifaceted solvent effects complicate analysis of the reaction mechanism. Here, using furfural as an example, we reveal the important role of water-mediated protonation in a typical hydrogenation reaction over a supported Pd catalyst. Depending on the solvent, we have observed different reaction orders with respect to the partial pressure of H 2 , as well as distinct selectivity towards hydrogenation of the conjugated C=O and C=C double bonds. Free energy calculations show that H 2 O participates directly in the kinetically relevant reaction step and provides an additional channel for hydrogenation of the aldehyde group, in which hydrogen bypasses the direct surface reaction via a hydrogen-bonded water network. In conclusion, this solution-mediated reaction pathway shows the potential role of the solvent for tuning the selectivity of metal-catalysed hydrogenation when charge separation on the metal surface is feasible.

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

Large-scale experimental validation of thermochemical water-splitting oxides discovered by defect graph neural networks

Thermochemical water-splitting (TCH) based on 2-step thermal redox cycles in metal oxides is a promising approach to generating H 2 , but state-of-the-art (SOTA) CeO 2 has several practical limitations, which has motivated continued materials discovery efforts in this field. Here, in this study, we improve upon a SOTA defect graph neural network (dGNN) surrogate model's oxygen vacancy predictions and combine them with materials project phase diagrams to down-select and discover structurally diverse, experimentally known metal oxides whose TCH performance was previously unknown. Amongst twelve candidates selected based on our high-throughput screening and down-selection criteria, we achieved ∼80% accuracy in identifying materials with stable redox cycling and hydrogen production in stagnation flow reactor water-splitting experiments. Closer to 100% accuracy can be achieved if higher-accuracy, hybrid DFT-predicted vacancy formation energies were computed and used in lieu of the most uncertain dGNN-based screening predictions, as they correct false positives to true negatives. Notably, two discovered candidates, Sr 3 PrMn 2 O 8 and Ba 2 Fe 2 O 5 , display hydrogen yields greater than CeO 2 under specific redox conditions. In conclusion, these results demonstrate our ability to computationally predict and experimentally validate promising candidate TCH materials that have the potential to compete with CeO 2 .

08 HYDROGEN↗
DOE OSTI2014

Modeling Interfacial Glass-Water Reactions: Recent Advances and Current Limitations

Describing the reactions that occur at the glass-water interface and control the development of the altered layer constitutes one of the main scientific challenges impeding existing models from providing accurate radionuclide release estimates. Radionuclide release estimates are a critical component of the safety basis for geologic repositories. The altered layer (i.e., amorphous hydrated surface layer and crystalline reaction products) represents a complex region, both physically and chemically, sandwiched between two distinct boundaries pristine glass surface at the inner most interface and aqueous solution at the outer most interface. Computational models, spanning different length and time-scales, are currently being developed to improve our understanding of this complex and dynamic process with the goal of accurately describing the pore-scale changes that occur as the system evolves. These modeling approaches include geochemical simulations [i.e., classical reaction path simulations and glass reactivity in allowance for alteration layer (GRAAL) simulations], Monte Carlo simulations, and Molecular Dynamics methods. Finally, in this manuscript, we discuss the advances and limitations of each modeling approach placed in the context of the glass-water reaction and how collectively these approaches provide insights into the mechanisms that control the formation and evolution of altered layers.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Effect of Light Water Reactor Water Environments on the Fatigue Life of Reactor Materials

The American Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel Code (Code) provides rules for the design of Class 1 components of nuclear power plants. Figures I-9.1 through I-9.6 of Appendix I to Section III of the Code specify fatigue design curves for applicable structural materials. However, the Code design curves do not explicitly address the effects of light water reactor (LWR) water environments. Existing fatigue strain-vs.-life (ε-N) laboratory data illustrate potentially significant effects of LWR water environments on the fatigue resistance of pressure vessel and piping steels. Extensive studies have been conducted at Argonne National Laboratory and elsewhere since 1990 to investigate the effects of LWR environments on the fatigue life of piping and pressure vessel steels. This article summarizes the results of these studies. Existing fatigue ε-N data were evaluated to identify the various material, environmental, and loading conditions that influence fatigue crack initiation; a methodology for estimating fatigue lives as a function of these parameters was developed. The effects were incorporated into the ASME Code Section III fatigue evaluations in terms of an environmental correction factor, F en , which is defined as the ratio of fatigue life in air at room temperature to the fatigue life in the LWR water environment at reactor operating temperatures. Available fatigue data were used to develop fatigue design curves for carbon and low-alloy steels, austenitic stainless steels, and nickel-chromium-iron (NiCr-Fe) alloys and their weld metals in air at room temperature. A review of the Code Section III fatigue adjustment factors of 2 on strain and 20 on life is also presented and the possible conservatism inherent in the choice of these adjustment factors is evaluated. A brief description of potential effects of neutron irradiation on fatigue crack initiation for these structural materials is also presented.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗