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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,171 records · Page 65
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Quantum chemical topology and natural bond orbital analysis of M–O covalency in M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np)

Covalency is complex yet central to our understanding of chemical bonding, particularly in the actinide series. In this work, we assess covalency in a series of isostructural d and f transition element compounds M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density functional theory in conjunction with the Natural Bond Orbital (NBO), quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) approaches. The IQA exchange–correlation covalency metric is evaluated for the first time for actinides other than uranium, in order to assess its applicability in the 5f series. It is found to have excellent correlation with NBO and QTAIM covalency metrics, making it a promising addition to the computational toolkit for analysing metal–ligand bonding. Our range of metrics agree that the actinide-oxygen bonds are the most covalent of the elements studied, with those of the heavier group 4 elements the least. Within the early actinide series, Th stands apart from the other three elements considered, being consistently the least covalent.

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DOE OSTI2020

First-principles study of CaB 12 H 12 as a potential solid-state conductor for Ca

Calcium dodecahydro-closo-dodecaborate, CaB 12 H 12 , was calculated to have a percolating Ca migration path with low activation barrier (650 meV). The formation of Ca vacancies required for diffusion was calculated to be thermodynamically feasible by substitution of Ca with Al, Bi, or a number of trivalent rare-earth cations.

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DOE OSTI2020

Influence of soluble oligomeric aluminum on precipitation in the Al-KOH-H2O system

The role of oligomeric aluminate (Al(OH)4-) species in the precipitation of aluminum phases such as gibbsite (a-Al(OH)3) from aqueous hydroxide solutions remains unclear and difficult to probe directly, despite its importance to developing accurate predictions of Al solubility in highly alkaline systems. Precipitation in this system entails a transition from predominantly tetrahedrally coordinated Al species in solution to octahedrally coordinated Al in gibbsite. Here we report a quantitative study of dissolved Al in the Al-KOH-H2O system using a combination of molecular spectroscopies. We established a relationship between changes in 27Al NMR chemical shifts and the relative intensity of Raman vibrational bands, indicative of variations in the ensemble speciation of Al in solution, and the formation of unique contact ion pair interactions with the aluminate dimer, Al2O(OH)62 . A strong correlation between the extent of Al oligomerization and the amount of solvated Al was demonstrated by systematically varying the KOH:Al molar ratio. The concentration of dissolved oligomeric Al in solution also directly impacted the particle size and morphology of gibbsite; high concentrations of dimeric Al2O(OH)62-, yielded smaller and more numerous anhedral to subhedral gibbsite particles, while low concentrations yielded fewer and larger euhedral gibbsite platelets. The collective observations suggest a key role of the Al2O(OH)62- dimer in promoting gibbsite precipitation from solution, where the potassium ion-paired dimer possibly catalyzes a more rapid transformation of Al coordination from tetrahedral in solution to octahedral in gibbsite.

Dembowski, Mateusz↗
DOE OSTI2020

Cyclohexene epoxidation with H 2 O 2 in the vapor and liquid phases over a vanadium-based metal–organic framework

A metal–organic framework, MIL-47(V) containing coordinatively saturated V +IV sites linked together by terephthalic linkers, was prepared by a solvothermal method and evaluated as a catalyst in the epoxidation of cyclohexene. We have compared the catalytic activity in the condensed and gas phase oxidation of cyclohexene to discuss the effect of temperature and reaction phase in cyclohexene epoxidation over MIL-47(V). The catalysts were examined for the epoxidation of cyclohexene with H 2 O 2 at 50, 65, 120, and 150 °C. Finally, we observed significant differences in product selectivity between liquid-phase and gas-phase operations and confirmed that the active sites are tightly incorporated into the MOF as node channels and thus resistant to leaching.

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DOE OSTI2020

The high-yield direct synthesis of dimethyl ether from CO 2 and H 2 in a dry reaction environment

Direct dimethyl ether (DME) synthesis from CO 2 and H 2 is considered a promising production route. However, this process is thermodynamically and kinetically restricted by the presence of water as a byproduct. In this study, a water-conduction membrane was incorporated into the direct DME synthesis reactor to generate a dry reaction environment. In the absence of water, the activities of the CO 2 hydrogenation catalyst (CZA) and methanol dehydration catalyst (HZSM-5) were boosted 4- and 10-fold, respectively, and single-pass CO 2 conversion of up to 73.4%, far beyond equilibrium, and DME yields of up to 54.5% were obtained. Moreover, the good protection of the catalysts against fast deactivation was demonstrated.

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DOE OSTI2020

Crystal structure and luminescence properties of lead-free metal halides (C 6 H 5 CH 2 NH 3 ) 3 MBr 6 (M = Bi and Sb)

Organic–inorganic hybrid metal halides have received extensive attention owing to their versatile structures and optoelectronic properties. Herein, we report two lead-free metal halides, (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 [PMA + : (C 6 H 5 CH 2 NH 3 ) + , as the abbreviation of phenylmethylammonium], which possess iso-structural zero-dimensional structures and crystallize in the monoclinic space group P2 1 /c. (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 exhibit optical band gaps of ~3.50 and 3.40 eV, respectively, and density functional theory calculations reveal their indirect bandgap behaviors. Upon 350 and 425 nm excitation, (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 exhibit broadband emission peaking at 510 nm and 625 nm with wide full-widths at half-maximum of ~153 and 175 nm, respectively. The emission mechanism of the metal halides is attributed to self-trapped exciton emission. The relationship between the crystal structure and luminescence intensity is also discussed. Lastly, both metal halides have high decomposition temperatures and are stable for long-term storage under ambient conditions, demonstrating their potential for optoelectronic applications.

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DOE OSTI2021

Steep sulfur gradient in CZTSSe solar cells by H 2 S-assisted rapid surface sulfurization

Sulfur/selenium grading is a widely used optimization strategy in kesterite thin-film solar cells to obtain a bandgap-graded absorber material and to optimize optical and electrical properties of the solar-cell device. In this work, we present a novel approach to introduce a [S]/([S] + [Se]) grading for Cu 2 ZnSn(S,Se) 4 solar cells. In contrast to commonly used methods with slow process dynamics, the presented approach aims to create a fast sulfurization reaction on the surface of pure selenide kesterite absorbers by using highly reactive H 2 S gas and high sulfurization temperatures in a rapid flash-type process. With a combination of X-ray photoelectron spectroscopy, X-ray emission spectroscopy, Raman spectroscopy, and Raman-shallow angle cross sections spectroscopy, we gain depth-varied information on the [S]/([S] + [Se]) ratio and discuss the impact of different process parameter variations on the material and device properties. The results demonstrate the potential of the developed process to generate a steep gradient of sulfur that is confined mainly to the surface region of the absorber film.

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DOE OSTI2022

Evidence for H-bonding interactions to the μ-η 2 :η 2 -peroxide of oxy-tyrosinase that activate its coupled binuclear copper site

The factors that control the diverse reactivity of the μ-η 2 :η 2 -peroxo dicopper(II) oxy-intermediates in the coupled binuclear copper proteins remain elusive. In this study, spectroscopic and computational methods reveal H-bonding interactions between active-site waters and the μ-η 2 :η2-peroxide of oxy-tyrosinase, and define their effects on the Cu(II) 2 O 2 electronic structure and O 2 activation.

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DOE OSTI2022

Full-dimensional quantum studies of vibrational energy transfer dynamics between H 2 O and Ar: theory assessing experiment

In this work we report the first full-dimensional quantum mechanical calculations of the ro-vibrational inelastic scattering dynamics between water molecules and argon atoms on an accurate potential energy surface, using a recently developed time-independent quantum method based on the close-coupling approach. The state-to-state integral cross-sections and rate coefficients show strong observance of gap laws. The calculated thermal rate coefficients for the relaxation of the stretching fundamental states of H 2 O are in good agreement with experimental values, while those for the bending overtone state are approximately five times smaller than the values extracted through a previous kinetic modeling of fluorescence decay data. Our state-specific quantum scattering results suggest the need to reassess the kinetic modeling of the experimental data. This work advanced our understanding of the quantum dynamics of vibrationally inelastic energy transfer processes involving polyatomic molecules.

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DOE OSTI2022

Thermal and concentration effects on 1 H NMR relaxation of Gd 3+ -aqua using MD simulations and measurements

We report gadolinium-based contrast agents are key in clinical MRI for enhancing the longitudinal NMR relativity (r 1 ) of hydrogen nuclei ( 1 H) in water and improving the contrast among different tissues. The importance of MRI in clinical practice cannot be gainsaid, yet the interpretation of MRI relies on models with severe assumptions, reflecting a poor understanding of the molecular-scale relaxation processes. In a step towards building a clearer understanding of the relaxation processes, here we investigate thermal and concentration effects on r 1 of the Gd 3+ -aqua complex using both semi-classical molecular dynamics (MD) simulations and measurements. We follow the MD simulation approach recently introduced by [Singer et al., Phys. Chem. Chem. Phys., 2021, 23, 20974], in which no NMR relaxation model or free-parameter is assumed to predict r 1 , thereby bringing new insights into the physics of r 1 on a molecular scale. We expand the autocorrelation function G(t) in terms of molecular modes and determine the thermal activation energies of the two largest modes, both of which are consistent with the range of literature values for rotational diffusion. We also determine the activation energies for translational diffusion and low-field electron-spin relaxation, both of which are consistent with the literature. Furthermore, we validate the MD simulations at human body temperature and concentrations of the paramagnetic ion used in clinical MRI, and we quantify the uncertainties in both simulations and measurements.

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DOE OSTI2022

Facile synthesis and phase stability of Cu-based Na 2 Cu(SO 4 ) 2 · x H 2 O ( x = 0–2) sulfate minerals as conversion type battery electrodes

Mineral exploration forms a key approach for unveiling functional battery electrode materials. The synthetic preparation of naturally found minerals and their derivatives can aid in designing of new electrodes. Herein, saranchinaite Na 2 Cu(SO 4 ) 2 and its hydrated derivative kröhnkite Na 2 Cu(SO 4 ) 2 ·2H 2 O bisulfate minerals have been prepared using a facile spray drying route for the first time. The phase stability relation during the (de)hydration process was examined synergising in situ X-ray diffraction and thermochemical studies. Kröhnkite forms the thermodynamically stable phase as the hydration of saranchinaite to kröhnkite is highly exothermic (-51.51 ± 0.63 kJ mol -1 ). Structurally, kröhnkite offers a facile 2D pathway for Na+ ion migration resulting in 20 times higher total conductivity than saranchinaite at 60 °C. Both compounds exhibited a conversion redox mechanism for Li-ion storage with the first discharge capacity exceeding 650 mA h g -1 (at 2 mA g -1 vs. Li + /Li) upon discharge up to 0.05 V. Post-mortem analysis revealed that the presence of metallic Cu in the discharged state is responsible for high irreversibility during galvanostatic cycling. This study reaffirms the exploration of Cu-based polyanionic sulfates, which while having limited (de)insertion properties, can be harnessed for conversion-based electrode materials for batteries.

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DOE OSTI2022

Light-mediated aerobic oxidation of C(sp 3 )–H bonds by a Ce(iv) hexachloride complex

A photochemical C(sp 3 )–H oxygenation of alkane and arene substrates catalyzed by [NEt 4 ] 2 [Ce IV Cl 6 ] under mild conditions (1 atm, 25 °C) is described. Time-course studies reveal that the hydrocarbons are oxidized in a stepwise fashion to afford alcohols, aldehydes, ketones, and carboxylic acids. The catalyst resting state, [Ce IV Cl 6 ] 2- , is observed by UV-visible spectroscopy. On/off light-switching experiments, quantum yield measurements, and the absence of a kinetic isotope effect on parallel C–H/C–D functionalization suggest that ligand-to-metal charge transfer of [NEt 4 ] 2 [Ce IV Cl 6 ] to generate Cl˙ is the turnover-limiting step. The involvement of a highly reducing excited-state [NEt 4 ] 3 [Ce III Cl 6 ]* species as well as photo-excited aldehyde, under black light irradiation appears to facilitate the conversion of primary alcohols and aldehydes to carboxylic acids. Remarkably, this approach is found to be capable of direct activation of light alkanes, including methane and ethane.

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DOE OSTI2022

Luminescent 1 H -1,3-benzazaphospholes

2-R-1 H -1,3-Benzazaphospholes (R-BAPs) are an interesting class of fluorescent σ 2 P heterocycles containing PC bonds.

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