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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH 4 and increase the selectivity toward C 5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becoming insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C 5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and dissociation.

Johnson, Gregory R.↗
DOE OSTI2015

GeP and (Ge{sub 1−x}Sn{sub x})(P{sub 1−y}Ge{sub y}) (x≈0.12, y≈0.05): Synthesis, structure, and properties of two-dimensional layered tetrel phosphides

GeP and Sn-doped GeP were synthesized from elements in bismuth and tin flux, respectively. The layered crystal structures of these compounds were characterized by single crystal X-ray diffraction. Both phosphides crystallize in a GaTe structure type in the monoclinic space group C2/m (No. 12) with GeP: a=15.1948(7) Å, b=3.6337(2) Å, c=9.1941(4) Å, β=101.239(2)°; Ge{sub 0.93(3)}P{sub 0.95(1)}Sn{sub 0.12(3)}: a=15.284(9) Å, b=3.622(2) Å, c=9.207(5) Å, β=101.79(1)°. The crystal structure of GeP consists of 2-dimensional GeP layers held together by weak electron lone pair interactions between the phosphorus atoms that confine the layer. Each layer is built of Ge–Ge dumbbells surrounded by a distorted antiprism of phosphorus atoms. Sn-doped GeP has a similar structural motif, but with a significant degree of disorder emphasized by the splitting of all atomic positions. Resistivity measurements together with quantum-chemical calculations reveal semiconducting behavior for the investigated phosphides. - Graphical abstract: Layered phosphides GeP and Sn-doped GeP were synthesized from elements in bismuth and tin flux, respectively. The crystal structure of GeP consists of 2-dimensional GeP layers held together by weak electron lone pair interactions between the phosphorus atoms that confine the layer. Sn-doped GeP has a similar structural motif with a significant degree of disorder emphasized by the splitting of all atomic positions. Resistivity measurements together with quantum-chemical calculations reveal semiconducting behavior for the investigated phosphides. - Highlights: • GeP crystallizes in a layered crystal structure. • Doping of Sn into GeP causes large structural distortions. • GeP is narrow bandgap semiconductor. • Sn-doped GeP exhibits an order of magnitude higher resistivity due to disorder.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

The U{sup 5+} compound Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24}: Synthesis, structure, and electronic properties

Black crystals of Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} have been made by direct combination of BaS, Ag, U, and S at 1273 K. This compound crystallizes in a new structure type in the space group C{sub 4v}{sup 10}−I4cm of the tetragonal system with four formula units in a cell with lattice constants a=13.9189(6) Å and c=23.7641(11) Å (V=4604(5) Å{sup 3}). Multiphoton Luminescence Spectroscopy measurements are consistent with the noncentrosymmetric nature of the structure. In the structure each U atom is octahedrally coordinated by six S atoms, whereas three of the five crystallographically independent Ag atoms are tetrahedrally coordinated to four S atoms, another has a seesaw coordination to four S atoms, and the last has a triangular coordination to three S atoms. The overall structure consists of the three-dimensional stacking of the US{sub 6}, AgS{sub 4}, and AgS{sub 3} polyhedra to leave channels in which Ba atoms reside. Based on the values of the U–S interatomic distances, the compound Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} contains U{sup 5+} and charge balance is achieved with the formal oxidation states of 9 Ba{sup 2+}, 10 Ag{sup 1+}, 4 U{sup 5+} and 24 S{sup 2−}. DFT calculations predict an antiferromagnetic ground state and a band gap of 2.1 eV. Resistivity measurements indicate that the compound is a semiconductor with a complex activation mechanism and activation energies ranging from 0.03(1) eV to 0.08(1) eV. - Graphical abstract: General view of the Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} structure. - Highlights: • Black crystals of Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} have been made by direct combination of BaS, Ag, U, and S at 1273 K. • Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} contains U{sup 5+} and charge balance is achieved with 9 Ba{sup 2+}, 10 Ag{sup 1+}, 4 U{sup 5+}, and 24 S{sup 2−}. • DFT calculations predict an antiferromagnetic ground state and a band gap of 2.1 eV. • The compound is a semiconductor with activation energies ranging from 0.03(1) eV to 0.08(1) eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis, crystal structures, and physical properties of the new Zintl phases A{sub 21}Zn{sub 4}Pn{sub 18} (A=Ca, Eu; Pn=As, Sb)—Versatile arrangements of [ZnPn{sub 4}] tetrahedra

Four new Zintl phases, Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18} and Eu{sub 21}Zn{sub 4}Sb{sub 18} have been synthesized by metal flux reactions. Their structures have been established from single-crystal X-ray diffraction. Despite the similar chemical makeup and the identical formulae, the structures of the four compounds are not the same—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18} and Eu{sub 21}Zn{sub 4}As{sub 18} crystallize in the monoclinic space group C2/m (No. 12, Z=4) with the β-Ca{sub 21}Mn{sub 4}Sb{sub 18} structure type, while Eu{sub 21}Zn{sub 4}Sb{sub 18} adopts the Ba{sub 21}Cd{sub 4}Sb{sub 18} structure type with the orthorhombic space group Cmce (No. 64, Z=8). Both structures are based on ZnAs{sub 4} or ZnSb{sub 4} tetrahedra, linked in slightly different ways, and Ca{sup 2+} and Eu{sup 2+} cations that fill the space between them. The structural relationships between the title compounds and other known ternary phases with intricate structures are discussed. Electrical resistivity measurement on single-crystalline Eu{sub 21}Zn{sub 4}Sb{sub 18} suggests an intrinsic semiconductor behavior with a band gap of ca. 0.2 eV. The temperature dependent DC magnetization measurement on the same material indicates Curie–Weiss paramagnetism in the high-temperature regime, and a spontaneous antiferromagnetic ordering below 8 K. The calculated effective moments of Eu confirm the divalent Eu{sup 2+} ground state, as expected from the Zintl–Klemm concept. - Graphical abstract: The four new Zintl phases—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18}—crystallize in two structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. - Highlights: • Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18} are new compounds in the respective ternary phase diagrams. • They form with structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. • For both structures, the valence electron count follows the Zintl–Klemm rules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis, crystal structure, optical, and electronic study of the new ternary thorium selenide Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2}

The compound Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} has been synthesized by solid-state methods at 1173 K. Its crystal structure features one-dimensional chains of {sup 1}{sub ∞}[Th(Se){sub 3}(Se{sub 2}){sub 2}{sup 6−}] separated by Ba{sup 2+} cations. Each Th atom in these chains is coordinated to two Se–Se single-bonded pairs and four Se atoms to give rise to a pseudooctahedral geometry around Th. The Th–Se distances are consistent with Th{sup 4+} and hence charge balance of Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is achieved as 3×Ba{sup 2+}, 1×Th{sup 4+}, 3×Se{sup 2−}, and 2×Se{sub 2}{sup 2−}. From optical measurements the band gap of Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is 1.96(2) eV. DFT calculations indicate that the compound is a semiconductor. - Graphical abstract: Local coordination environment of Th atoms in the Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} structure. - Highlights: • Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} has been synthesized by solid-state methods at 1173 K. • The structure features chains of {sup 1}{sub ∞}[Th(Se){sub 3}(Se{sub 2}){sub 2}{sup 6−}] separated by Ba{sup 2+} cations. • Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is a semiconductor with a band gap of 1.96(2) eV.

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

Synthesis, structure, and magnetic characterization of Cr{sub 4}US{sub 8}

The compound Cr{sub 4}US{sub 8} has been synthesized at 1073 K and its crystal structure has been determined at 100 K. The structure is modulated with a two-fold commensurate supercell. The subcell may be indexed in an orthorhombic cell but weak supercell reflections lead to the monoclinic superspace group P2{sub 1}/c(α0γ)0s with two Cr sites, one U site, and four S sites. The structure comprises a three-dimensional framework of CrS{sub 6} octahedra with channels that are partially occupied by U atoms. Each U atom in these channels is coordinated by eight S atoms in a bicapped trigonal-prismatic arrangement. The magnetic behavior of Cr{sub 4}US{sub 8} is complex. At temperatures above ~120 K at all measured fields, there is little difference between field-cooled and zero field-cooled data and χ(T) decreases monotonously with temperature, which is reminiscent of the Curie–Weiss law. At lower temperatures, the temperature dependence of χ(T) is complex and strongly dependent on the magnetic field strength. - Graphical abstract: Structure of Cr{sub 4}US{sub 8} viewed down the a axis. - Highlights: • At 1073 K Cr{sub 4}US{sub 8} was synthesized and at 100 K its crystal structure was determined. • The 3D structure comprises CrS{sub 6} octahedra with channels partially occupied by U. • The magnetic behavior of Cr{sub 4}US{sub 8} is complex.

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

Synthesis, crystal structure, and magnetic properties of quaternary iron selenides: Ba{sub 2}FePnSe{sub 5} (Pn=Sb, Bi)

Two new barium iron pnictide–selenides, Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, were synthesized by a high-temperature solid-state route and their crystal structures were determined using single crystal X-ray diffraction. Both compounds are isomorphic to the high pressure phase Ba{sub 3}FeS{sub 5} and crystallize in the orthorhombic space group Pnma (No. 62) with cell parameters of a=12.603(2)/12.619(2) Å, b=9.106(1)/9.183(1) Å, c=9.145(1)/9.123(1) Å and Z=4 for Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, respectively. According to differential scanning calorimetry, Ba{sub 2}FePnSe{sub 5} compounds exhibit high thermal stability and melt congruently at 1055(5) K (Pn=Sb) and 1105(5) K (Pn=Bi). Magnetic characterizations reveal strong antiferromagnetic nearest-neighbor interactions in both compounds resulting in an antiferromagnetic ordering at 58(1) K for Ba{sub 2}FeSbSe{sub 5} and 79(2) K for Ba{sub 2}FeBiSe{sub 5}. The magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Graphical abstract: In Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} the magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Highlights: • New compounds Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} have been synthesized. • The crystal structure was determined by single crystal X-ray diffraction. • Both compounds melt congruently at temperatures above 1000 K. • Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} exhibit AFM ordering at 58 K (Sb) and 70 K (Bi). • Magnetic exchange between Fe{sup 3+} is mediated by either Se–Sb(Bi)–Se or Se–Ba–Se bridges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Synthesis and characterization of metastable, 20 nm-sized Pna2{sub 1}-LiCoPO{sub 4} nanospheres

The majority of research activities on LiCoPO{sub 4} are focused on the phospho-olivine (space group Pnma), which is a promising high-voltage cathode material for Li-ion batteries. In contrast, comparably little is known about its metastable Pna2{sub 1} modification. Herein, we present a comprehensive study on the structure–property relationships of 15–20 nm Pna2{sub 1}-LiCoPO{sub 4} nanospheres prepared by a simple microwave-assisted solvothermal process. Unlike previous reports, the results indicate that the compound is non-stoichiometric and shows cation-mixing with Co ions on the Li sites, which provides an explanation for the poor electrochemical performance. Co L{sub 2,3}-edge X-ray absorption spectroscopic data confirm the local tetrahedral symmetry of Co{sup 2+}. Comprehensive studies on the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and in situ powder X-ray diffraction show an exothermic phase transition to olivine Pnma-LiCoPO{sub 4} at 527 °C. The influence of the atmosphere and the particle size on the thermal stability is also investigated. - Graphical abstract: Blue nano-sized Pna2{sub 1}-LiCoPO{sub 4,} featuring tetrahedrally-coordinated Co{sup 2+}, was synthesized in a rapid one-step microwave-assisted solvothermal process. The phase relation between this metastable and the stable polymorph was analyzed and electrochemical properties are discussed. - Highlights: • Preparation of uniform 15–20 nm nanospheres of metastable Pna2{sub 1}-LiCoPO{sub 4} polymorph. • Structure redetermination shows cation-mixing (Co blocking Li sites). • In situ investigation of phase transformation to olivine Pnma-LiCoPO{sub 4} at 527 °C. • Pna2{sub 1}-LiCoPO{sub 4} reemerges as a stable high-temperature phase above 800 °C. • X-ray absorption spectroscopy confirms local tetrahedral symmetry (T{sub d} Co{sup 2+}).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Facile, One-Step Synthesis for Core–Shell Perovskite Materials via Molten Salt

Core–shell La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF)–La 0.8 Sr 0.2 MnO 3 (LSM) heterostructure crystalline materials have been synthesized in a simple, one-step feeding method via a KNO 3 molten salt solvent. Two-phase perovskite composites can be synthesized in times as short as 10 minutes and is demonstrated for the first time in a molten salt. Further, a combination of X-ray diffraction and S/TEM energy dispersive X-ray spectroscopy has been utilized to confirm the formation of an LSM shell on LSCF cores in all samples when adjusting dwell time, core size, weight ratio between core and shell precursors, and weight ratio of powder to salt. Specifically, decreasing the LSCF core size increases core–shell yield. Smaller cores introduce a greater density of facets on the crystal surface and provide more favorable sites for LSM heterogeneous nucleation.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Graphene and nano-diamond synthesis in expansions of molten liquid carbon

Despite their widespread use in high-pressure experiments, little is known about the physical and chemical properties of carbon-containing materials as they expand and cool to ambient conditions. As a result, interpretation of experiments can rely on use of unconstrained models with poor accuracy for the ensuing equation of state properties and final chemical products. To this end, we use quantum simulations to study the free expansion and cooling of carbon from metallic liquid states achieved during shock compression. Expansions from three different sets of shock conditions yielded of a variety of chain and ring structures. We then quantify the relative amounts of graphite-like and diamond-like particles formed during cooling and equilibration. Here, we observe that for all cases, graphene sheets are the majority product formed with more extreme initial conditions producing increasingly larger amounts of diamond particles. Our results can address key needs for future meso-scale models of experiments, where knowledge of material properties and chemical end products can have a pronounced effect on interpreting experimental observables.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Enhanced power factor of higher manganese silicide via melt spin synthesis method

We report on the thermoelectric properties of the Higher Manganese Silicide MnSi₁.₇₅ (HMS) synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describe the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5x10²⁰ cm⁻³ at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper; the maximum value is superior to those reported in the literatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

High pressure synthesis of amorphous TiO{sub 2} nanotubes

Amorphous TiO{sub 2} nanotubes with diameters of 8-10 nm and length of several nanometers were synthesized by high pressure treatment of anatase TiO{sub 2} nanotubes. The structural phase transitions of anatase TiO{sub 2} nanotubes were investigated by using in-situ high-pressure synchrotron X-ray diffraction (XRD) method. The starting anatase structure is stable up to ∼20GPa, and transforms into a high-density amorphous (HDA) form at higher pressure. Pressure-modified high- to low-density transition was observed in the amorphous form upon decompression. The pressure-induced amorphization and polyamorphism are in good agreement with the previous results in ultrafine TiO{sub 2} nanoparticles and nanoribbons. The relationship between the LDA form and α-PbO{sub 2} phase was revealed by high-resolution transmission electron microscopy (HRTEM) study. In addition, the bulk modulus (B{sub 0} = 158 GPa) of the anatase TiO{sub 2} nanotubes is smaller than those of the corresponding bulks and nanoparticles (180-240 GPa). We suggest that the unique open-ended nanotube morphology and nanosize play important roles in the high pressure phase transition of TiO{sub 2} nanotubes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Controlled synthesis of Eu{sup 2+} and Eu{sup 3+} doped ZnS quantum dots and their photovoltaic and magnetic properties

Eu-doped ZnS quantum dots (QDs) have been synthesized by wet-chemical method and found to form in zinc blende (cubic) structure. Both Eu{sup 2+} and Eu{sup 3+} doped ZnS can be controllably synthesized. The Eu{sup 2+} doped ZnS QDs show broad photoluminescence emission peak around 512 nm, which is from the Eu{sup 2+} intra-ion transition of 4f{sup 6}d{sup 1} – 4f{sup 7}, while the Eu{sup 3+} doped samples exhibit narrow emission lines characteristic of transitions between the 4f levels. The investigation of the magnetic properties shows that the Eu{sup 3+} doped samples exhibit signs of ferromagnetism, on the other hand, Eu{sup 2+} doped samples are paramagnetic of Curie-Weiss type. The incident photon to electron conversion efficiency is increased with the Eu doping, which suggests the QD solar cell efficiency can be enhanced by Eu doping due to widened absorption windows. This is an attractive approach to utilize benign and environmentally friendly wide band gap ZnS QDs in solar cell technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

GAS PHASE SYNTHESIS OF (ISO)QUINOLINE AND ITS ROLE IN THE FORMATION OF NUCLEOBASES IN THE INTERSTELLAR MEDIUM

Nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) have been proposed to play a key role in the astrochemical evolution of the interstellar medium, yet the formation mechanisms of even their simplest prototypes—quinoline and isoquinoline—remain elusive. Here, we reveal a novel concept that under high temperature conditions representing circumstellar envelopes of carbon stars, (iso)quinoline can be synthesized via the reaction of pyridyl radicals with two acetylene molecules. The facile gas phase formation of (iso)quinoline in circumstellar envelopes defines a hitherto elusive reaction class synthesizing aromatic structures with embedded nitrogen atoms that are essential building blocks in contemporary biological-structural motifs. Once ejected from circumstellar shells and incorporated into icy interstellar grains in cold molecular clouds, these NPAHs can be functionalized by photo processing forming nucleobase-type structures as sampled in the Murchison meteorite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗