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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

About the Barriers to Reaction of CCl4 with HFeOH and FeCl2

The reactivity of iron nanoparticles in aqueous environments has received considerable attention due to their potential utilization in environmental remediation technologies. As part of a broader program aiming at an improved understanding of the mechanisms involved in the degradation of harmful chlorocarbons, joint experimental and computational studies of model systems were initiated. We previously reported on the reaction of one and two Fe atoms reactions with carbon tetrachloride (CCl4) in direct mimic of “atom-dropping” experiments, with insights into the formation of novel iron-carbon-chlorine complexes, their structures and possible reaction mechanisms. Increasing the level of complexity, we report here on the modeling of the reaction of HFeOH and CCl4 as companion research of recent ultra high vacuum experiments of the reaction of Fe with water and CCl4. HFeOH is a stable molecular species formed in the reaction of Fe with H2O. Experimentally the (Fe, H2O, CCl4) system showed no reactivity up to the desorption temperature of CCl4. Electron correlated CCSD(T) calculations (at DFT(B3LYP) optimized structures) indicated an energy barrier to reactivity of 24.5 kcal/mol following the formation of a stable ( 7.5 kcal/mol) long-range precursor complex. This finding is consistent with the lack of experimentally detected reaction products. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Partial high-resolution structure of phosphorylated and non-phosphorylated leucine-rich amelogenin protein adsorbed to hydroxyapatite

The formation of biogenic materials requires the interaction of organic molecules with the mineral phase. In forming enamel, the amelogenin proteins contribute to the mineralization of hydroxyapatite (HAp). Leucine-rich amelogenin protein (LRAP) is a naturally occurring splice variant of amelogenin that comprises amelogenin’s predicted HAp binding domains. We determined the partial structure of phosphorylated and non-phosphorylated LRAP variants bound to HAp using combined solid-state NMR (ssNMR) and ssNMR-biased computational structure prediction. The ssNMR measurements indicate a largely extended structure for both variants, though some measurements are consistent with a partially helical N-terminal segment. Structure prediction was biased using 21 ssNMR measurements at five HAp crystal faces. The predicted fold of LRAP is similar at all HAp faces studied, regardless of phosphorylation. LRAP’s predicted structure is relatively extended with a helix-turn-helix motif in the N-terminal domain and some helix in the C-terminal domain. The N-terminal domain of the phosphorylated variant binds HAp more tightly than the N-terminal domain of the non-phosphorylated variant. Both variants are predicted to preferentially bind the {010} HAp crystal face providing further evidence that amelogenins block crystal growth on the a and b faces to allow elongated crystals in the c-axis. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2011

Effects of La2O3 on the Mixed Higher Alcohols Synthesis from Syngas over Co Catalysts: A Combined Theoretical and Experimental Study

The promoting role of lanthanum oxide (La{sub 2}O{sub 3}) in the catalytic synthesis of mixed higher (C{sub 2}-C{sub 6}) alcohols from syngas on Co-based catalysts was investigated using a combination of in situ and ex situ X-ray diffraction (XRD), photoelectron spectroscopy (XPS), catalyst reactivity performance studies, and ab initio molecular dynamics (AIMD) simulations. XRD measurements show that doping with La (0.5 wt %) onto activated carbon (AC) supported Co catalyst enhances the Co{sub 2}C phase formation, whereas the Co{sub 2}C phase formation is largely suppressed on alumina supported Co catalyst. A strong correlation of the selectivity toward alcohols with the ratio of Co{sub 2}C/Co particles present in the catalysts was observed. AIMD simulations suggest that on AC supports La exists as an oxide phase in the form of small clusters in the vicinity of Co particles. It was found that Co{sub 2}C formation is energetically favorable, especially for smaller Co particles because of the formation of surface carbide. Theoretical mechanistic studies indicate that oxygenated hydrocarbons can be formed on these catalysts by multiple routes involving the formation of CH{sub x}O and CH{sub x}CO species at the interface between the La{sub 2}O{sub 3} phase and Co/Co{sub 2}C. A detailed comparison with previous findings in the literature as well as discussion of the implications of these results upon the improvement of the selectivity of these catalysts toward higher alcohols is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Laser Spectroscopic and Theoretical Studies of Encapsulation Complexes of Calix[4]arene

The complexes between the host calix[4]arene (C4A) and various guest molecules such as NH3, N2, CH4, and C2H2 have been investigated via experimental and theoretical methods. The S1-S0 electronic spectra of these guest-host complexes are observed by mass-selected resonant two-photon ionization (R2PI) and laser induced fluorescence (LIF) spectroscopy. The infrared (IR) spectra of the complexes formed in molecular beams are obtained by IR-UV double resonance (IR-UV DR) and IR photodissociation (IRPD) spectroscopy. The supramolecular structures of the complexes are investigated by electronic structure methods (density functional and second order perturbation theory). The current results for the various molecular guests are put in perspective with the previously reported ones for the C4A-Rare Gas (Rg) (Phys. Chem. Chem. Phys. 2007, 126, 141101) and C4A-H2O complexes (J. Phys. Chem. A, 2010, 114, 2967). The electronic spectra of the complexes of C4A with N2, CH4 and C2H2 exhibit red-shifts of similar magnitudes with the ones observed for the C4A-Rg complexes, whereas the complexes of C4A with H2O and NH3 show much larger red-shifts. Most of the IR-UV DR spectra of the complexes, except for C4A-C2H2, show a broad hydrogen bonded OH stretching band with a peak at ~3160 cm-1. The analysis of the experimental results, in agreement with the ones resulted from the electronic structure calculations, suggest that C4A preferentially forms endo-complexes with all the guest species reported in this study. We discuss the similarities and differences of the structures, binding energies and the nature of the interaction between the C4A host and the various guest species. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy

08 HYDROGEN↗
DOE OSTI2011

Vapor-liquid Coexistence Curves for Methanol and Methane using Dispersion-Corrected Density Functional Theory

First principles Monte Carlo simulations in the Gibbs and isobaric-isothermal ensembles were performed to map the vapor-liquid coexistence curves (VLCC) of methanol and methane described by Kohn-Sham density functional theory using the Becke-Lee-Yang-Parr (BLYP) exchange and correlation functionals with the Grimme correction term for dispersive (D2) interactions. The simulations indicate that the BLYP-D2 description underpredicts the saturated vapor densities and overpredicts the saturated liquid densities and critical and boiling temperatures for both compounds. Although the deviations are quite large, these results present a significant improvement over the BLYP functional without the correction term which misses the experimental results by a larger extent in the opposite direction. With the D2 correction, an increase in the basis set does not lead to significant changes in the VLCC properties. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

03 NATURAL GAS↗
DOE OSTI2011

Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water

Molecular-level insight into the dissociation of nitric acid in water is obtained from photoelectron X-ray spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from N1s binding energy shifts of HNO3(aq) as a function of concentration, and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO3(aq) and dissociated NO3-(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO3 interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO3 and water. We suggest that the driving force behind the more structured solvent configuration of HNO3 is the overlap of nitric acid solvent shells that sets in around 4 M concentration. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

08 HYDROGEN↗
DOE OSTI2011

Does Nitric Acid Dissociate at the Aqueous Solution Surface?

Nitric acid is a prevalent component of atmospheric aerosols, and the extent of nitric acid dissociation at aqueous interfaces is relevant to its role in heterogeneous atmospheric chemistry. Several experimental and theoretical studies have suggested that the extent of dissociation of nitric acid near aqueous interfaces is less than in bulk solution. Here, dissociation of HNO3 at the surface of aqueous nitric acid is quantified using X-ray photoelectron spectroscopy of the nitrogen local electronic structure. The relative amounts of undissociated HNO3(aq) and dissociated NO3-(aq) are identified by the distinguishable N1s core-level photoelectron spectra of the two species, and we determine the degree of dissociation, αint, in the interface (the first ~3 layers of solution) as a function of HNO3 concentration. Our measurements show that dissociation is decreased by approximately 20% near the solution interface compared with bulk, and furthermore that dissociation occurs even in the top-most solution layer. The experimental results are supported by first-principles MD simulations, which show that hydrogen-bonds between HNO3 and water molecules at the solution surface stabilize the molecular form at low concentration, in analogy to the stabilization of molecular HNO3 that occurs in bulk solution at high concentration. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

Understanding Vibrational Anharmonicity and Phonon Dispersion in Solid Ammonia Borane

We compute the hydrogen vibrational spectra for bulk ammonia borane (NH3BH3) using harmonic and anharmonic methodologies as well as quantifying dispersive effects to determine their influence on the resulting spectra. Even at 10K the accounting of anharmonic effects on the IINS signal are more significant than approximations introduced by sampling and interpolating a finite simulation cell to capture dispersion effects. We compare our computed anharmonic power spectrum with IINS spectral measurements and find excellent agreement. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences and Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

08 HYDROGEN↗
DOE OSTI2011

Surface Chemistry of Trimethyl Phosphate on α-Fe2O3

The chemistry of trimethyl phosphate (TMP) was examined on the (012) crystallographic face of hematite (α-Fe2O3) using temperature programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), static secondary ion mass spectrometry (SSIMS) and Auger electron spectroscopy (AES). TMP binds to Fe3+ sites on the clean α-Fe2O3(012) surface through lone pairs on the P=O oxygen atom. A small portion of adsorbed TMP desorbs without decomposition, however, the majority of adsorbed TMP decomposes in a two step process on the clean surface. The first step, occurring at or below room temperature (RT), likely involves displacement or substitution of one –OCH3 group to form surface methoxy groups and adsorbed dimethyl phosphate (DMP). In the second step, DMP decomposes above 500 K to a 1:1 ratio of gaseous methanol and formaldehyde with phosphate left on the surface. Identification of these steps was confirmed using the chemistry of methanol on the clean surface. Coadsorption of TMP and water led to a small degree of hydrolysis between these two molecules in the multilayer, but no significant change in the chemistry on the surface. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

10 SYNTHETIC FUELS↗
DOE OSTI2012

First-Principles Prediction of Intermediate Products in the Decomposition of Metal Amidoboranes

The non-volatile products remaining after the thermal decomposition of metal amidoboranes ([M]n+[NH2BH3] - , M = alkali or alkaline metal atom) are amorphous and incompletely characterized increasing the complexity of devising regeneration strategies for these potential hydrogen storage materials. Utilizing the combined prototype electrostatic ground state search (PEGS) and density-functional theory (DFT) methodology (PEGS+DFT), we have searched for crystal structures of possible intermediate phases with [NHBH2] - , [NBH] - , [N3H2B3H3] - , and polymer-M[NHBH2] anion groups in the decomposition of lithium amidoborane (LiAB) and calcium amidoborane (CaAB). All these potential reaction products are calculated to be significantly endothermic, in contrast to the experimentally measured nearly thermo neutral values [3 to 5 kJ/(mol H2) in LiAB and 3.5 kJ/(mol H2) in CaAB] suggesting that there are alternative products formed. The dianion group [NHBHNHBH3] 2- has recently been suggested to form in the decomposition of a calcium amidoborane complex in solution. In LiAB and CaAB, we use PEGS+DFT calculations to predict intermediate metal-dianion compounds, and the static H2 release enthalpy is 27.4 kJ/(mol H2) in LiAB and 27.3 kJ/(mol H2) in CaAB, respectively. Introducing vibrational effects by phonon calculations, the enthalpies are shifted down by a roughly constant amount, _25 kJ/(mol H2) at 0 K and _22 kJ/(mol H2) at 300 K. Thus, our theoretical H2 release enthalpies agree with the experimentally measured nearly thermo-neutral data in the decomposition of LiAB and CaAB. This agreement supports the existence of the dianion phases as products in the decomposition of metal amidoboranes. Then, using the dianion compound as an intermediate in the decomposition of MAB, we further study the stability trends of a series of MAB (M=Li, Na, K, Ca), and find that the reaction enthalpies generally obey the following trend: The amidoborane becomes more stable, i.e., MAB stability increases as the metal cation moves down in the periodic table along a given column (LiAB>NaAB>KAB), or as metal cation moves to the left along a given row (KAB>CaAB). T.A. acknowledges the Fuel Cell Technology Program at USDOE, Office of Energy Efficiency and Renewable Energy. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Toward an Understanding of the Specific Ion Effect using Density Functional Theory

Here we use first-principles molecular dynamics simulations, in which the forces are obtained "on the fly" from electronic structure calculations based on density functional theory, to determine the intrinsic propensity of the hydroxide anion for the air-water interface. We find that the hydroxide anion is stabilized by about 0.5 kcal/mol at the air-water interface vs. in bulk water, and we predict, therefore, that the population of the ion is enhanced roughly twofold at the interface. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Site Competition During Coadsorption of Acetone with Methanol and Water on TiO2(110)

The competitive interaction between acetone and two solvent molecules (methanol and water) for surface sites on rutile TiO2(110) was studied using temperature programmed desorption (TPD). On a vacuum reduced TiO2(110) surface, which possessed ~5% oxygen vacancy sites, excess methanol displaced preadsorbed acetone molecules to weakly bound and physisorbed desorption states below 200 K, whereas acetone was stabilized to 250 K against displacement by methanol on an oxidized surface through formation of an acetone-diolate species. These behaviors of acetone differ from the competitive interactions between acetone and water in that acetone is less susceptible to displacement by water. Examination of acetone+methanol and acetone+water multilayer combinations shows that acetone is more compatible in water-ice films than in methanol-ice films, presumably because water has greater potential as a hydrogen-bond donor than does methanol. Acetone molecules displaced from the TiO2(110) surface by water are more likely to be retained in the near-surface region, having a greater opportunity to revisit the surface, than when methanol is used as a coadsorbate. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

10 SYNTHETIC FUELS↗
DOE OSTI2012

Direct in Situ Observation of Nanoparticle Synthesis in a Liquid Crystal Surfactant Template

Controlled synthesis of nanostructures is essential for many applications, from energy storage/generation and catalysis to semiconductor and biomedical devices. Normally, nanostructures are characterized after synthesis and growth mechanisms are assumed. Here we show the first direct observation of nanoparticle synthesis in a liquid crystal surfactant template using an electron microscope fluid stage. The nanoparticles first sinter (to ~5nm), then grow connections to each other around the micelles to form clusters. Upon reaching a critical size (>10-15nm), the clusters become highly mobile in the template, displacing micelles to form spherical nanoparticles. This ability to observe and understand fundamental growth mechanisms on the nanoscale in real time and in aqueous environments will impact every branch of nanoscience where precise control over nanostructure is essential. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2011

Experimental and Digital Modeling Studies of the Electrochemical Oxidation of the Metal Anion [CpW(CO)2(IMes)]- and the 17-Electron Metal Radical CpW(CO)2(IMes)•. Kinetics and Thermodynamics of Capture and Release of MeCN by a Metal Radical and a Metal Cation

The electrochemistry of [CpW(CO)2(IMes)] [K(18 crown 6)]+ (Cp = η5-C5H5, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), CpW(CO)2(IMes)•, and [CpW(CO)2(IMes)(MeCN)]+PF6 were studied by cyclic voltammetry in MeCN (0.2 M nBu4N+BF4 ). The tungsten anion [CpW(CO)2(IMes)]- showed a fully reversible one-electron oxidation with E½ = 1.65 V vs. Cp2Fe+/0. Oxidation of the resultant 17-electron radical CpW(CO)2(IMes)• was irreversible at all scan rates, affording the 18-electron solvent adduct [CpW(CO)2(IMes)(MeCN)]+. Reduction of [CpW(CO)2(IMes)(MeCN)]+ proceeded with loss of coordinated MeCN, and was followed by a second reduction to generate [CpW(CO)2(IMes)]-. Simultaneous digital simulation of voltammograms of [CpW(CO)2(IMes)]- and CpW(CO)2(IMes)• over a range of scan rates and concentrations gave estimates for E° of 0.491(2) V for the [CpW(CO)2(IMes)]+/• couple and 1.92 V for the [CpW(CO)2(IMes)(MeCN)]+/• couple. The neutral 19-electron radical complex CpW(CO)2(IMes)(MeCN)• is a stronger reducing agent (by 1.42 V) than the unsolvated 17-electron radical CpW(CO)2(IMes)•. Binding of MeCN by the unsolvated 16-electron cation [CpW(CO)2(IMes)]+ is exergonic with Keq = 1.2 × 1011 M 1 for [CpW(CO)2(IMes)]+ + MeCN [CpW(CO)2(IMes)(MeCN)]+. Expulsion of the MeCN ligand from the 19-electron complex CpW(CO)2(IMes)(MeCN)• is also exergonic, with Keq = 1.2 × 1013 M for CpW(CO)2(IMes)(MeCN)• CpW(CO)2(IMes)• + MeCN. Experimental and simulated cyclic voltammograms also account for the chemical reduction of the metal cation [CpW(CO)2(IMes)(MeCN)]+ by the metal anion [CpW(CO)2(IMes)]-, which ultimately produces two equivalents of the metal-centered radical CpW(CO)2(IMes)• This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Effects of Phosphine-Carbene Substitutions on the Electrochemical and Thermodynamic Properties of Nickel Complexes

Nickel(II) complexes containing chelating N-heterocyclic carbene-phosphine ligands ([NiL2](BPh4)2, for which L = [MeIm(CH2)2PR2]) have been synthesized for the purpose of studying how this class of ligand effects the electrochemical properties compared to the nickel bis- diphosphine analogues. The nickel complexes were synthesized and characterized by x-ray crystallography and electrochemical methods. Based on the half wave potentials (E1/2), substitution of an NHC for one of the phosphines in a diphoshine ligand results in shifts in potential to 0.6 V to 1.2 V more negative than the corresponding nickel bis-diphosphine complexes. These quantitative results highlight the substantial effect that NHC ligands can have upon the electronic properties of the metal complexes. BRG, JCL, and AMA acknowledge the support by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MLH acknoledges the support of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

carbene↗
DOE OSTI2012

Electron Tomography: Seeing Atoms in Three Dimensions

Our eyes - a parallel lens system - have the phenomenal ability to observe and "reconstruct" the three-dimensional world, relaying a 3-D image to our brains. Imaging of the nanoworld is best done with electrons rather than photons because of their lower wavelengths and higher resolution. The advent of aberration-correction has led to transmission electron microscopes with sub-Angstrom resolution that can resolve single atoms. Yet, no matter what detector is used, the resulting images are only two-dimensional projections of three-dimensional objects. Electron tomography is a technique that allows reconstruction of the three-dimensional structure and morphology of nanomaterials from such projections. X-ray tomography has been used in many branches of science for nearly half a century, and in the biological sciences electron tomography has been a powerful tool for understanding ultrastructure. However, for many years crystalline materials posed a challenge to electron tomography because diffraction contrast (a change in intensity in the image at particular crystal orientations) creates artifacts in the 3-D reconstruction. In 2003, with advances in scanning transmission electron microscopy, Midgley and colleagues obtained the first electron tomograms of crystalline materials. Shortly thereafter, Arslan et al. showed that the spatial resolution could be improved to 1 nm in all three spatial dimensions and visualized the formation of faceted 3.5-nm quantum dots embedded in a Si matrix. However, with that work existing reconstruction algorithms appeared to have reached their limit. To attain a resolution of 1 nm, a total of 140 images over ±78 degrees of tilt were needed. Writing in Nature Materials, Goris et al. now report a novel algorithm for 3-D reconstruction of the atomic structure of free-standing Au nanorods, using only four projection images. I.A. acknowledges collaboration with J.D. Roehling, K.J. Batenburg, B.C. Gates and A. Katz for Figure 1, supported in part by the DOE BES DE-SC0005822, and in part by the LDRD program at PNNL. The Pacific Northwest National Laboratory is operated by Battelle under contract DE-AC05-76RL01830.

Arslan, Ilke↗