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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 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Tuning the Kinetic Water Stability and Adsorption Interactions of Mg-MOF-74 by Partial Substitution with Co or Ni

Varying amounts of Co and Ni were substituted into the metal–organic framework Mg-MOF-74 via a one-pot solvothermal reaction, and the effects of these substitutions on CO 2 adsorption and kinetic water stability properties were examined. Based on elemental analyses, Co and Ni are more favorably incorporated into the MOF-74 framework from solution than Mg. In addition, reaction temperature more strongly impacts the final metal composition in these mixed-metal (MM) MOF-74 structures than does the reaction solvent composition. Single-component CO 2 adsorption isotherms were measured for the MM-MOF-74 systems at 5, 25, and 45 °C, and isosteric heats of adsorption were calculated. These results suggest that CO 2 adsorption properties can be adjusted by partial metal substitution. Water adsorption isotherms were also measured for the MM-MOF-74 samples, with powder X-ray diffraction patterns and Brunauer–Emmett–Teller surface areas measured both before and after water exposure. Results show that Mg-MOF-74 can gain partial kinetic water stability by the incorporation of Ni 2+ or Co 2+ metal ions that are less vulnerable to hydrolysis than Mg 2+ . Finally, of particular note, Mg–Ni-MM-MOF-74 shows a significant increase in water stability when incorporating as little as 16 mol % Ni into the Mg-MOF-74 structure.

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

Kinetic Studies of Acid Hydrolysis of Food Waste-Derived Saccharides

Starch saccharified glucose from food waste can be an important precursor for renewable chemicals and fuels. Despite numerous studies on hydrolysis of biomass, detailed kinetic studies and associated models of hydrolysis are lacking. We investigated the kinetics of glycosidic bond scission of malto-oligosaccharides in lithium bromide acidified molten salt hydrate (AMSH) medium and estimated rate parameters from experimental data. Our data support the hypothesis that the terminal, nonreducing bonds hydrolyze faster than the interior and terminal-reducing C–O bonds. Next, we extended the model to simulate the hydrolysis of linear and cyclic saccharides of varying degree of polymerization and of potato starch. We characterize starch using X-ray diffraction (XRD) and light scattering methods. The model is in excellent agreement with the experimentally determined concentrations of glucose and other oligosaccharides. Finally, the chain length of saccharides is found to be directly related to their hydrolysis rate constant, but inversely proportional to the glucose formation rate constant

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

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH) 3 and Ce(OH) 2 molecules and Ce(OH) 2 + cation as major products. Additional minor products were identified as the Ce(OH) 4 , HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D 2 O 2 , D 2 , and 18 O 2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH) 3 and of the Ce(OH) 2 + cation increase on UV ($λ$ > 220 nm) photolysis, while Ce(OH) 2 , Ce(OH) 4 , and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH) 4 , is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

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

Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba 3 Ln 2 O 5 Cl 2

Single crystals of a new family of layered lanthanide oxychlorides, Ba 3 Ln 2 O 5 Cl 2 (Ln = Gd–Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/ mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)–4.4541(1) Å and c = 24.5108(7)–24.8448(9) Å. Ba 3 Ln 2 O 5 Cl 2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba 2 Ln 2 O 5 formed by corner-connected LnO 5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl 2 . A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. Finally, the synthesis of this family suggests a route to other potential multianion phases.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Experimental and Theoretical Comparison of Transition-Metal and Actinide Tetravalent Schiff Base Coordination Complexes

A series of homoleptic tetravalent transition-metal and actinide Schiff-base coordination complexes, ML 2 {M = Zr, Hf, Th, U; L = N,N'-bis[(4,4'-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes create the opportunity for comparing a series of complexes containing metal cations in the formal IV+ oxidation state by structural, spectroscopic, and theoretical analysis that also incorporate the previously reported Ce(IV) and Pu(IV) analogues. X-ray crystallographic analysis reveals that all complexes are isomorphous and feature a co-facial ligand geometry. TD-DFT and other quantum mechanical methods were used to explore bonding differences across between the complexes, and resulting calculated absorbance spectra for ML 2 are in good agreement with the experimental data. The computational results also suggest that U(IV) and Pu(IV) analogs have more covalent character in their bonding than found with the other metal cations reported here.

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

Electronic, Magnetic, and Theoretical Characterization of (NH 4 ) 4 UF 8 , a Simple Molecular Uranium(IV) Fluoride

The simple system of tetraammonium octafluorouranate is employed to derive a fundamental understanding of the uranium–fluorine interaction. The structure is composed of isolated molecules, enabling a detailed examination of the U 4+ (ƒ 2 ) ion. Characterization of single-crystals by X-ray diffraction, absorption spectroscopy, and magnetic analysis up to 45 T is combined with extensive theoretical treatment by CASSCF. The influence of different active spaces and representations of the structure is examined in the context of the experimental evidence. The Interacting Quantum Atoms method (IQA) is used to examine the nature of the U–F bond, concluding that there is a non-negligible degree of covalent character (9% of the total bond energy) in [UF8] 4- . For the structural and theoretical reasons discussed herein, it is proposed that the structure of (NH 4 ) 4 UF 8 may be appropriately employed as a benchmark compound for future theoretical characterization of U(IV).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2019

Tailored Perovskite Waste Forms for Plutonium Trapping

Perovskite ceramics have been extensively studied as host matrixes for radionuclide entrapment for nuclear waste disposal. As an expansion of these investigations, cerium, neodymium, and plutonium were incorporated into a perovskite phase, ACu 3 FeTi 3 O 12 (A = Nd, Ce, Pu), using sol–gel methods under oxidizing and reducing atmospheres. The targeted materials contained varying levels of Ce 3+ and Nd 3+ on the A site, yielding potential compositions of Nd 1–x Ce x Cu 3 FeTi 3 O 12 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.8). However, interrogation of these materials shows that the maximum Ce 3+ loading is achieved near x ≈ 0.2. A single composition with plutonium was targeted, Nd 0.9 Pu 0.1 Cu 3 FeTi 3 O 12 , in order to properly model more realistic loading levels for a repository-destined material. These compounds were characterized using powder X-ray diffraction with Rietveld refinements of the structures and by a variety of spectroscopic techniques. Finally, the data suggest that, in order to achieve Pu 3+ substitution onto the A sites in the Nd 0.9 Pu 0.1 Cu 3 FeTi 3 O 12 , a reducing atmosphere must be employed. Otherwise, the redox activity of plutonium results in substitution onto multiple sites in the material as well as the formation of secondary phases such as TiO 2 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2015

Electroosmotic Flow Rectification in Membranes with Asymmetrically Shaped Pores: Effects of Current and Pore Density

We have recently demonstrated a new electrokinetic phenomenon—electroosmotic flow rectification in membranes with asymmetrically shaped pores. Flow rectification means that at constant driving force the flow rate in one direction through the membrane is faster than the flow rate in the opposite direction. EOF rectification could be of practical use in microfluidic devices incorporating porous membranes, but additional research is required. As such, we explore here the effects of two key experimental variables—current density used to drive flow through the membrane and membrane pore density—on EOF rectification. We have found that the extent of EOF rectification, as quantified by the rectification ratio, increases with increasing current density. In contrast, the rectification ratio decreases with increasing membrane pore density. We propose explanations for these results based on simple EOF and membrane-transport theories.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗