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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on Ce4Cu3(SO)4 by Materials Project

Ce4Cu3(SO)4 crystallizes in the tetragonal I-42m space group. The structure is three-dimensional. Ce3+ is bonded in a 4-coordinate geometry to four equivalent S2- and four O2- atoms. There are two shorter (3.11 Å) and two longer (3.12 Å) Ce–S bond lengths. All Ce–O bond lengths are 2.33 Å. There are two inequivalent Cu+1.33+ sites. In the first Cu+1.33+ site, Cu+1.33+ is bonded to four equivalent S2- atoms to form edge-sharing CuS4 tetrahedra. All Cu–S bond lengths are 2.38 Å. In the second Cu+1.33+ site, Cu+1.33+ is bonded to four equivalent S2- atoms to form a mixture of corner and edge-sharing CuS4 tetrahedra. All Cu–S bond lengths are 2.38 Å. S2- is bonded in a 3-coordinate geometry to four equivalent Ce3+ and three Cu+1.33+ atoms. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded to four equivalent Ce3+ atoms to form a mixture of corner and edge-sharing OCe4 tetrahedra. In the second O2- site, O2- is bonded to four equivalent Ce3+ atoms to form a mixture of corner and edge-sharing OCe4 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Nd12Cu6O25 by Materials Project

Nd12Cu6O25 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are six inequivalent Nd3+ sites. In the first Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Nd–O bond distances ranging from 2.30–2.91 Å. In the second Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Nd–O bond distances ranging from 2.35–2.69 Å. In the third Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Nd–O bond distances ranging from 2.38–2.77 Å. In the fourth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Nd–O bond distances ranging from 2.31–2.79 Å. In the fifth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Nd–O bond distances ranging from 2.28–2.96 Å. In the sixth Nd3+ site, Nd3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Nd–O bond distances ranging from 2.32–2.80 Å. There are three inequivalent Cu+2.33+ sites. In the first Cu+2.33+ site, Cu+2.33+ is bonded to six O2- atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 0–9°. There are a spread of Cu–O bond distances ranging from 1.88–2.37 Å. In the second Cu+2.33+ site, Cu+2.33+ is bonded in a distorted square co-planar geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.88–2.63 Å. In the third Cu+2.33+ site, Cu+2.33+ is bonded to six O2- atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 2–9°. There are a spread of Cu–O bond distances ranging from 1.89–2.31 Å. There are thirteen inequivalent O2- sites. In the first O2- site, O2- is bonded to four Nd3+ and two equivalent Cu+2.33+ atoms to form distorted ONd4Cu2 octahedra that share corners with two equivalent ONd4Cu2 octahedra, a cornercorner with one ONd4 tetrahedra, an edgeedge with one ONd4Cu2 octahedra, and faces with two equivalent ONd4Cu2 octahedra. The corner-sharing octahedral tilt angles are 2°. In the second O2- site, O2- is bonded in a 3-coordinate geometry to five Nd3+ and one Cu+2.33+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to five Nd3+ and one Cu+2.33+ atom. In the fourth O2- site, O2- is bonded to four Nd3+ and two equivalent Cu+2.33+ atoms to form a mixture of distorted corner, edge, and face-sharing ONd4Cu2 octahedra. The corner-sharing octahedral tilt angles are 2°. In the fifth O2- site, O2- is bonded to four Nd3+ atoms to form ONd4 tetrahedra that share corners with three ONd4Cu2 octahedra, corners with two equivalent ONd4 tetrahedra, and edges with two equivalent ONd4 tetrahedra. The corner-sharing octahedra tilt angles range from 50–65°. In the sixth O2- site, O2- is bonded in a 6-coordinate geometry to five Nd3+ and one Cu+2.33+ atom. In the seventh O2- site, O2- is bonded in a 6-coordinate geometry to four Nd3+ and two Cu+2.33+ atoms. In the eighth O2- site, O2- is bonded in a 5-coordinate geometry to three Nd3+ and two equivalent Cu+2.33+ atoms. In the ninth O2- site, O2- is bonded in a 6-coordinate geometry to five Nd3+ and one Cu+2.33+ atom. In the tenth O2- site, O2- is bonded to four Nd3+ and two Cu+2.33+ atoms to form distorted ONd4Cu2 octahedra that share corners with two equivalent ONd4 tetrahedra, edges with two equivalent ONd4Cu2 octahedra, and faces with two equivalent ONd4Cu2 octahedra. In the eleventh O2- site, O2- is bonded in a 6-coordinate geometry to five Nd3+ and one Cu+2.33+ atom. In the twelfth O2- site, O2- is bonded in a 3-coordinate geometry to four Nd3+ and one Cu+2.33+ atom. In the thirteenth O2- site, O2- is bonded to four equivalent Nd3+ and two equivalent Cu+2.33+ atoms to form a mixture of distorted edge and face-sharing ONd4Cu2 octahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Photoelectrochemical Nitrogen Reduction to Ammonia on Cupric and Cuprous Oxide Photocathodes

Photoelectrochemical N 2 reduction enables the production of NH 3 under ambient conditions using water as the hydrogen source. Furthermore, by utilizing solar energy, photoelectrochemical N 2 reduction can significantly reduce the energy input required for N 2 reduction. In this study, photoelectrochemical N 2 production was investigated using CuO and Cu 2 O photocathodes that are known to be poorly catalytic for water reduction, the major reaction competing with N 2 reduction. When tested under simulated solar illumination with isotopically labeled 15 N 2 in 0.1 M KOH solution, the CuO and Cu 2 O photocathodes produced 15 NH 3 with a Faradaic efficiency of 17% and 20% at 0.6 V and 0.4 V vs. RHE, respectively. These potentials are significantly more positive than the thermodynamic reduction potential of N 2 , which demonstrates how the use of photoexcited electrons in the CuO and Cu 2 O photocathodes can reduce the energy input required for NH 3 production. Here, the use of photoexcited electrons in these photocathodes for N 2 reduction, water reduction, and photocorrosion was carefully examined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Materials Data on Cu4(PO4)3 by Materials Project

Cu4(PO4)3 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. there are three inequivalent Cu+2.25+ sites. In the first Cu+2.25+ site, Cu+2.25+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 1.96–2.58 Å. In the second Cu+2.25+ site, Cu+2.25+ is bonded to five O2- atoms to form distorted CuO5 trigonal bipyramids that share corners with five PO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.90–2.26 Å. In the third Cu+2.25+ site, Cu+2.25+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There is two shorter (1.90 Å) and two longer (1.92 Å) Cu–O bond length. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four equivalent CuO5 trigonal bipyramids. There is two shorter (1.52 Å) and two longer (1.62 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three equivalent CuO5 trigonal bipyramids. There are a spread of P–O bond distances ranging from 1.52–1.61 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+2.25+ and one P5+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to two Cu+2.25+ and one P5+ atom. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.25+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to one Cu+2.25+ and one P5+ atom. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to two Cu+2.25+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.25+ and one P5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effective one-band models for the one-dimensional cuprate Ba 2-x Sr x CuO 3+δ

In this work, we consider a multiband Hubbard model H m for Cu and O orbitals in Ba 2-x Sr x CuO 3+δ similar to the three-band model for two-dimensional cuprates. The hopping parameters are obtained from maximally localized Wannier functions derived from ab initio calculations. Using the cell perturbation method, we derive both a generalized t–J model H tJ and a one-band Hubbard model H H to describe the low-energy physics of the system. H tJ has the advantage of having a smaller relevant Hilbert space, facilitating numerical calculations, while additional terms should be included in H H to accurately describe the multiband physics of H m . Using H tJ and the density matrix renormalization group method, we calculate the wave-vector-resolved photoemission and discuss the relevant features in comparison with recent experiments. In agreement with previous calculations, we find that the addition of an attractive nearest-neighbor interaction of the order of the nearest-neighbor hopping shifts the weight from the 3k F to the holon-folding branch. Kinetic effects also contribute to this process.

1-dimensional systems↗
DOE OSTI2025

CO 2 Adsorption and Hydrogenation on Inverse InO x /Cu(111) Catalysts: Active Role of the Oxide–Metal Interface

The direct conversion of carbon dioxide (CO 2 ) into methanol via hydrogenation is essential for industrial applications. Recent studies on catalysts that contain an inverse oxide/metal configuration have shown very good catalytic performance for the CO 2 hydrogenation to methanol process. Here, in this study, we investigated the behavior of indium oxide-Cu(111) interfaces under pure CO 2 and CO 2 /H 2 mixtures using synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). Initially, a single layer of copper oxide (Cu x O) was grown on the Cu(111) surface by controlled oxidation. On this surface, indium was deposited at room temperature. Oxygen atoms transferred from Cu x O/Cu(111) to the indium metal upon deposition, forming In-O-Cu bonds and active interfaces. Although Cu(111) is not very active for the binding and activation of CO 2 , the formed InO x -Cu(111) interfaces had no problem adsorbing and dissociating the molecule at room temperature. Reaction of CO 2 with H 2 on InO x -Cu(111) yielded surface-bound H 3 CO, CO 2 δ− , CO 3 , and CH x species that are typical intermediates in the production of methanol and other oxygenates. The InO x -Cu(111) interface underwent dynamic chemical changes under reaction conditions, forming In-Cu alloys at low indium coverages (< 0.05 monolayer), while at higher indium coverages a mixture of an In-Cu and InO x was detected in XPS. These findings indicate that InO x /In-Cu interfaces can play a key role in processes aimed at the trapping and valorization of CO 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Magnetic and structural properties of the solid solution CuAl 2(1–x) Ga 2x O 4

CuAl 2 O 4 is a ternary oxide spinel with Cu 2+ ions (s = 1/2) primarily populating the A-site diamond sublattice. The compound is reported to display evidence of spin glass behavior but possess a non-frozen magnetic ground state below the transition temperature. On the other hand, the spinel CuGa 2 O 4 displays spin glass behavior at ~ 2.5 K with Cu 2+ ions more readily tending to the B-site pyrochlore sublattice. Therefore, we investigate the magnetic and structural properties of the solid solution CuAl 2(1-x) Ga 2x O 4 examining the evolution of the magnetic behavior as Al 3+ is replaced with a much larger Ga 3+ ion. Our results show that the Cu 2+ ions tend to migrate from tetrahedral to octahedral sites as the Ga 3+ ion concentration increases, resulting in a concomitant change in the glassy magnetic properties of the solution. Results indicate glassy behavior for much of the solution with a general trend towards decreasing magnetic frustration as the Cu 2+ ion shifts to the B-site. However, the x = 0.1 and 0.2 members of the system do not show glassy behavior down to our measurement limit (1.9 K) suggesting a delayed spin glass transition. We suggest that these two members are additional candidates for investigation to access highly frustrated exotic quantum states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Reductive Depolymerization of Lignin to Aromatic Compounds over Promoted Nickel Catalysts in Sub– and Supercritical Methanol

The use of γ-Al 2 O 3 -supported Ni catalysts promoted with either Cu or Fe was investigated for the reductive catalytic fractionation (RCF) of hybrid poplar in methanol at 200 and 250 °C. The effectiveness of lignin depolymerization was quantified in terms of the lignin oil production, the quantity and distribution of identifiable monomers present in the lignin oil, and the yield of residual solids. All of the Ni-based catalysts tested provided improved yields of lignin oil and monomers, along with reduced char formation, relative to blank (sans catalyst) runs. The highest monomer yield of 51 % was obtained at 250 °C over a 20 wt.% Ni-5 wt.% Cu/Al 2 O 3 catalyst, the improved performance obtained through Cu promotion being attributed to the ability of Cu to facilitate NiO reduction, resulting in an increased amount of Ni 0 on the catalyst surface and, consequently, improved hydrogenation activity. Finally, the main monomers formed were propanol-, propyl- and propenyl-substituted guaiacol and syringol, the S/G ratio of the products corresponding closely to that in the native lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2010

Rocket-Plume Spectroscopy Simulation for Hydrocarbon-Fueled Rocket Engines

The UV-Vis spectroscopic system for plume diagnostics monitors rocket engine health by using several analytical tools developed at Stennis Space Center (SSC), including the rocket plume spectroscopy simulation code (RPSSC), to identify and quantify the alloys from the metallic elements observed in engine plumes. Because the hydrocarbon-fueled rocket engine is likely to contain C2, CO, CH, CN, and NO in addition to OH and H2O, the relevant electronic bands of these molecules in the spectral range of 300 to 850 nm in the RPSSC have been included. SSC incorporated several enhancements and modifications to the original line-by-line spectral simulation computer program implemented for plume spectral data analysis and quantification in 1994. These changes made the program applicable to the Space Shuttle Main Engine (SSME) and the Diagnostic Testbed Facility Thruster (DTFT) exhaust plume spectral data. Modifications included updating the molecular and spectral parameters for OH, adding spectral parameter input files optimized for the 10 elements of interest in the spectral range from 320 to 430 nm and linking the output to graphing and analysis packages. Additionally, the ability to handle the non-uniform wavelength interval at which the spectral computations are made was added. This allowed a precise superposition of wavelengths at which the spectral measurements have been made with the wavelengths at which the spectral computations are done by using the line-by-line (LBL) code. To account for hydrocarbon combustion products in the plume, which might interfere with detection and quantification of metallic elements in the spectral region of 300 to 850 nm, the spectroscopic code has been enhanced to include the carbon-based combustion species of C2, CO, and CH. In addition, CN and NO have spectral bands in 300 to 850 nm and, while these molecules are not direct products of hydrocarbon-oxygen combustion systems, they can show up if nitrogen or a nitrogen compound is present as an impurity in the propellants and/or these can form in the boundary layer as a result of interaction of the hot plume with the atmosphere during the ground testing of engines. Ten additional electronic band systems of these five molecules have been included into the code. A comprehensive literature search was conducted to obtain the most accurate values for the molecular and the spectral parameters, including Franck-Cordon factors and electronic transition moments for all ten band systems. For each elemental transition in the RPSSC, six spectral parameters - Doppler broadened line width at half-height, pressure-broadened line width at half-height, electronic multiplicity of the upper state, electronic term energy of the upper state, Einstein transition probability coefficient, and the atomic line center - are required. Input files have been created for ten elements of Ni, Fe, Cr, Co, Cu, Ca, Mn, Al, Ag, and Pd, which retain only relatively moderate to strong transitions in 300 to 430 nm spectral range for each element. The number of transitions in the input files is 68 for Ni; 148 for Fe; 6 for Cr; 87 for Co; 1 for Ca; 3 for Mn; 2 each for Cu, Al, and Ag; and 11 for Pd.

Tejwani, Gopal D.↗
DOE OSTI2023

Rational Design and Reticulation of Infinite qbe Rod Secondary Building Units into Metal–Organic Frameworks through a Global Desymmetrization Approach for Inverse C 3 H 8 /C 3 H 6 Separation

Abstract The development of reticular chemistry has enabled the construction of a large array of metal–organic frameworks (MOFs) with diverse net topologies and functions. However, dominating this class of materials are those built from discrete/finite secondary building units (SBUs), yet the designed synthesis of frameworks involving infinite rod‐shaped SBUs remain underdeveloped. Here, by virtue of a global linker desymmetrization approach, we successfully targeted a novel Cu‐MOF (Cu‐ASY) incorporating infinite Cu‐carboxylate rod SBUs with its structure determined by micro electron diffraction (MicroED) crystallography. Interestingly, the rod SBU can be simplified as a unique cylindric sphere packingqbetubule made of [4 3 .6 2 ] tiles, which further connect the tritopic linkers to give a newly discovered 3,5‐connectedgfcnet. Cu‐ASY is a permanent ultramicroporous material featuring 1D channels with highly inert surfaces and shows a preferential adsorption of propane (C 3 H 8 ) over propene (C 3 H 6 ). The efficiency of C 3 H 8 selective Cu‐ASY is validated by multicycle breakthrough experiments, giving C 3 H 6 productivity of 2.2 L/kg. Density functional theory (DFT) calculations reveal that C 3 H 8 molecules form multiple C−H⋅⋅⋅π and atypical C−H⋅⋅⋅ H−C van der Waals interactions with the inner nonpolar surfaces. This work therefore highlights the linker desymmetrization as an encouraging and intriguing strategy for achieving unique MOF structures and properties.

Chemistry↗
DOE OSTI2020

Materials Data on Sr7LaCu4(BiO3)8 by Materials Project

Sr7LaCu4(BiO3)8 is Pb (Zr_0.50 Ti_0.48) O_3-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are seven inequivalent Sr2+ sites. In the first Sr2+ site, Sr2+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Sr–O bond distances ranging from 2.48–3.05 Å. In the second Sr2+ site, Sr2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Sr–O bond distances ranging from 2.40–2.79 Å. In the third Sr2+ site, Sr2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Sr–O bond distances ranging from 2.41–2.94 Å. In the fourth Sr2+ site, Sr2+ is bonded to six O2- atoms to form distorted SrO6 pentagonal pyramids that share corners with two BiO5 square pyramids, a cornercorner with one CuO5 trigonal bipyramid, and a cornercorner with one BiO5 trigonal bipyramid. There are a spread of Sr–O bond distances ranging from 2.42–2.87 Å. In the fifth Sr2+ site, Sr2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Sr–O bond distances ranging from 2.48–3.11 Å. In the sixth Sr2+ site, Sr2+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Sr–O bond distances ranging from 2.32–3.17 Å. In the seventh Sr2+ site, Sr2+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Sr–O bond distances ranging from 2.50–2.78 Å. La3+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of La–O bond distances ranging from 2.33–2.80 Å. There are four inequivalent Cu+1.75+ sites. In the first Cu+1.75+ site, Cu+1.75+ is bonded in a 3-coordinate geometry to three O2- atoms. There are two shorter (1.88 Å) and one longer (2.33 Å) Cu–O bond lengths. In the second Cu+1.75+ site, Cu+1.75+ is bonded in a linear geometry to two O2- atoms. There is one shorter (1.80 Å) and one longer (1.87 Å) Cu–O bond length. In the third Cu+1.75+ site, Cu+1.75+ is bonded to five O2- atoms to form distorted CuO5 trigonal bipyramids that share a cornercorner with one SrO6 pentagonal pyramid, a cornercorner with one BiO5 trigonal bipyramid, and an edgeedge with one BiO5 square pyramid. There are a spread of Cu–O bond distances ranging from 1.96–2.62 Å. In the fourth Cu+1.75+ site, Cu+1.75+ is bonded in a linear geometry to two O2- atoms. There is one shorter (1.84 Å) and one longer (1.86 Å) Cu–O bond length. There are eight inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to five O2- atoms to form distorted BiO5 trigonal bipyramids that share a cornercorner with one SrO6 pentagonal pyramid, a cornercorner with one CuO5 trigonal bipyramid, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.22–2.72 Å. In the second Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Bi–O bond distances ranging from 2.13–2.92 Å. In the third Bi3+ site, Bi3+ is bonded in a 3-coordinate geometry to three O2- atoms. There are one shorter (2.12 Å) and two longer (2.20 Å) Bi–O bond lengths. In the fourth Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Bi–O bond distances ranging from 2.16–2.83 Å. In the fifth Bi3+ site, Bi3+ is bonded to five O2- atoms to form distorted BiO5 square pyramids that share a cornercorner with one SrO6 pentagonal pyramid, a cornercorner with one BiO5 square pyramid, an edgeedge with one CuO5 trigonal bipyramid, and an edgeedge with one BiO5 trigonal bipyramid. There are a spread of Bi–O bond distances ranging from 2.19–2.62 Å. In the sixth Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Bi–O bond distances ranging from 2.14–2.99 Å. In the seventh Bi3+ site, Bi3+ is bonded to five O2- atoms to form distorted BiO5 square pyramids that share a cornercorner with one SrO6 pentagonal pyramid and a cornercorner with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.20–2.67 Å. In the eighth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Bi–O bond distances ranging from 2.19–2.69 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to one Sr2+, one La3+, and two Bi3+ atoms. In the second O2- site, O2- is bonded to four Sr2+ and one Bi3+ atom to form OSr4Bi trigonal bipyramids that share a cornercorner with one OSr3CuBi2 octahedra, a cornercorner with one OSr3Bi tetrahedra, a cornercorner with one OSr2CuBi2 trigonal bipyramid, and an edgeedge with one OSr2Bi3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 56°. In the third O2- site, O2- is bonded in a 6-coordinate geometry to three Sr2+, one La3+, and two Bi3+ atoms. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to one Sr2+, one Cu+1.75+, and two Bi3+ atoms. In the fifth O2- site, O2- is bonded to two Sr2+ and three Bi3+ atoms to form distorted OSr2Bi3 trigonal bipyramids that share a cornercorner with one OSr2CuBi2 trigonal bipyramid, an edgeedge with one OSr4Bi trigonal bipyramid, and a faceface with one OSr3CuBi2 octahedra. In the sixth O2- site, O2- is bonded in a 5-coordinate geometry to two Sr2+ and three Bi3+ atoms. In the seventh O2- site, O2- is bonded to two Sr2+, one Cu+1.75+, and two Bi3+ atoms to form distorted OSr2CuBi2 trigonal bipyramids that share corners with two OSr4Bi trigonal bipyramids and an edgeedge with one OSr3Bi tetrahedra. In the eighth O2- site, O2- is bonded in a 5-coordinate geometry to three Sr2+, one Bi3+, and one O2- atom. The O–O bond length is 1.52 Å. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Sr2+, one Cu+1.75+, and two Bi3+ atoms. In the tenth O2- site, O2- is bonded in a 4-coordinate geometry to one La3+, one Cu+1.75+, and two Bi3+ atoms. In the eleventh O2- site, O2- is bonded in a 5-coordinate geometry to three Sr2+ and two Bi3+ atoms. In the twelfth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Sr2+ and one Cu+1.75+ atom. In the thirteenth O2- site, O2- is bonded to three Sr2+ and one Bi3+ atom to form distorted OSr3Bi tetrahedra that share a cornercorner with one OSr3CuBi2 octahedra, a cornercorner with one OSr4Bi trigonal bipyramid, and an edgeedge with one OSr2CuBi2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 28°. In the fourteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Sr2+, one Bi3+, and one O2- atom. In the fifteenth O2- site, O2- is bonded in a 4-coordinate geometry to one Sr2+, one Cu+1.75+, and two Bi3+ atoms. In the sixteenth O2- site, O2- is bonded in a 5-coordinate geometry to two Sr2+, one Cu+1.75+, and two Bi3+ atoms. In the seventeenth O2- site, O2- is bonded to three Sr2+, one Cu+1.75+, and two Bi3+ atoms to form distorted OSr3CuBi2 octahedra that share a cornercorner with one OSr3Bi tetrahedra, a cornercorner with one OSr4Bi trigonal bipyramid, and a faceface with one OSr2Bi3 trigonal bipyramid. In the eighteenth O2- site, O2- is bonded in a 5-coordinate geometry to two Sr2+, one La3+, one Cu+1.75+, and one Bi3+ atom. In the nineteenth O2- site, O2- is bonded in a 5-coordinate geometry to one Sr2+, one La3+, one Cu+1.75+, and two Bi3+ atoms. In the twentieth O2- site, O2- is bonded in a trigonal planar geometry to one Sr2+ and two Bi3+ atoms. In the twenty-first O2- site, O2- is bonded in a 4-coordinate geometry to one Sr2+, one Cu+1.75+, and two Bi3+ atoms. In the twenty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Sr2+, one La3+, and one Bi3+ atom. In the twenty-third O2- site, O2- is bonded in a 4-coordinate geometry to one Sr2+, one La3+, one Cu+1.75+, and one Bi3+ atom. In the twenty-fourth O2- site, O2- is bonded in a distorted T-shaped geometry to one Sr2+ and two Bi3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Fe3(CuS5)2 by Materials Project

Fe3(CuS5)2 is pyrite-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.22–2.31 Å. In the second Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.22–2.31 Å. In the third Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.26–2.33 Å. In the fourth Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.22–2.30 Å. In the fifth Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with four CuS6 octahedra and corners with eight FeS6 octahedra. The corner-sharing octahedra tilt angles range from 60–67°. There are a spread of Fe–S bond distances ranging from 2.26–2.34 Å. In the sixth Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 61–68°. There are a spread of Fe–S bond distances ranging from 2.22–2.31 Å. In the seventh Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.25–2.35 Å. In the eighth Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.25–2.35 Å. In the ninth Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with four CuS6 octahedra and corners with eight FeS6 octahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.26–2.33 Å. In the tenth Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with four FeS6 octahedra, corners with eight CuS6 octahedra, and corners with two SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are two shorter (2.25 Å) and four longer (2.28 Å) Fe–S bond lengths. In the eleventh Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with six FeS6 octahedra, corners with six CuS6 octahedra, and a cornercorner with one SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.26–2.33 Å. In the twelfth Fe3+ site, Fe3+ is bonded to six S+1.20- atoms to form FeS6 octahedra that share corners with four FeS6 octahedra, corners with eight CuS6 octahedra, and a cornercorner with one SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 60–68°. There are a spread of Fe–S bond distances ranging from 2.22–2.32 Å. There are eight inequivalent Cu+1.50+ sites. In the first Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with two equivalent CuS6 octahedra, corners with ten FeS6 octahedra, and a cornercorner with one SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 64–68°. There are a spread of Cu–S bond distances ranging from 2.38–2.47 Å. In the second Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with two equivalent CuS6 octahedra, corners with ten FeS6 octahedra, and corners with two SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 64–69°. There are a spread of Cu–S bond distances ranging from 2.39–2.48 Å. In the third Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with four equivalent CuS6 octahedra, corners with eight FeS6 octahedra, and corners with four SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 64–70°. There are a spread of Cu–S bond distances ranging from 2.39–2.48 Å. In the fourth Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with four CuS6 octahedra, corners with eight FeS6 octahedra, and corners with four SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 64–69°. There are four shorter (2.39 Å) and two longer (2.46 Å) Cu–S bond lengths. In the fifth Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with two equivalent CuS6 octahedra, corners with ten FeS6 octahedra, and corners with two SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 64–69°. There are a spread of Cu–S bond distances ranging from 2.37–2.47 Å. In the sixth Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with two equivalent CuS6 octahedra, corners with ten FeS6 octahedra, and corners with two SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 63–69°. There are a spread of Cu–S bond distances ranging from 2.36–2.47 Å. In the seventh Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with four CuS6 octahedra, corners with eight FeS6 octahedra, and corners with three SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 63–69°. There are a spread of Cu–S bond distances ranging from 2.38–2.48 Å. In the eighth Cu+1.50+ site, Cu+1.50+ is bonded to six S+1.20- atoms to form CuS6 octahedra that share corners with four equivalent CuS6 octahedra, corners with eight FeS6 octahedra, and corners with four SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 63–70°. There are four shorter (2.39 Å) and two longer (2.46 Å) Cu–S bond lengths. There are forty inequivalent S+1.20- sites. In the first S+1.20- site, S+1.20- is bonded in a 3-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.20 Å. In the second S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.15 Å. In the third S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.17 Å. In the fourth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.20 Å. In the fifth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.14 Å. In the sixth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to three Fe3+ and one S+1.20- atom. The S–S bond length is 2.20 Å. In the seventh S+1.20- site, S+1.20- is bonded to one Fe3+, two Cu+1.50+, and one S+1.20- atom to form distorted SFeCu2S tetrahedra that share a cornercorner with one FeS6 octahedra, corners with two CuS6 octahedra, and corners with six SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 69–80°. The S–S bond length is 2.09 Å. In the eighth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.14 Å. In the ninth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.16 Å. In the tenth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.11 Å. In the eleventh S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to three Fe3+ and one S+1.20- atom. The S–S bond length is 2.19 Å. In the twelfth S+1.20- site, S+1.20- is bonded to two Fe3+, one Cu+1.50+, and one S+1.20- atom to form distorted SFe2CuS tetrahedra that share a cornercorner with one FeS6 octahedra, corners with two CuS6 octahedra, and corners with two SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 72–81°. The S–S bond length is 2.11 Å. In the thirteenth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to one Fe3+, two Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.10 Å. In the fourteenth S+1.20- site, S+1.20- is bonded to one Fe3+, two Cu+1.50+, and one S+1.20- atom to form distorted SFeCu2S tetrahedra that share a cornercorner with one FeS6 octahedra, corners with two CuS6 octahedra, and corners with three SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 70–79°. The S–S bond length is 2.07 Å. In the fifteenth S+1.20- site, S+1.20- is bonded to one Fe3+, two Cu+1.50+, and one S+1.20- atom to form distorted SFeCu2S tetrahedra that share a cornercorner with one FeS6 octahedra, corners with two CuS6 octahedra, and corners with seven SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 69–80°. The S–S bond length is 2.08 Å. In the sixteenth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.16 Å. In the seventeenth S+1.20- site, S+1.20- is bonded to two Fe3+, one Cu+1.50+, and one S+1.20- atom to form distorted SFe2CuS tetrahedra that share a cornercorner with one FeS6 octahedra, corners with two CuS6 octahedra, and a cornercorner with one SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 72–81°. The S–S bond length is 2.11 Å. In the eighteenth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.15 Å. In the nineteenth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to one Fe3+, two Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.12 Å. In the twentieth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to one Fe3+, two Cu+1.50+, and one S+1.20- atom. The S–S bond length is 2.09 Å. In the twenty-first S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. In the twenty-second S+1.20- site, S+1.20- is bonded to one Fe3+, two Cu+1.50+, and one S+1.20- atom to form distorted SFeCu2S tetrahedra that share a cornercorner with one FeS6 octahedra, corners with two CuS6 octahedra, and corners with three SFeCu2S tetrahedra. The corner-sharing octahedra tilt angles range from 70–79°. In the twenty-third S+1.20- site, S+1.20- is bonded to two Fe3+, one Cu+1.50+, and one S+1.20- atom to form distorted SFe2CuS tetrahedra that share a cornercorner with one FeS6 octahedra, corners with two CuS6 octahedra, and corners with two SFe2CuS tetrahedra. The corner-sharing octahedra tilt angles range from 72–82°. In the twenty-fourth S+1.20- site, S+1.20- is bonded in a 4-coordinate geometry to two Fe3+, one Cu+1.50+, and one S+1.20- atom. In the tw

36 MATERIALS SCIENCE↗
DOE OSTI2021

The multi-optics high-resolution absorption x-ray spectrometer (HiRAXS) for studies of materials under extreme conditions

We report the development of a high-resolution spectrometer for extended x-ray absorption fine structure (EXAFS) studies of materials under extreme conditions. A curved crystal and detector in the spectrometer are replaceable such that a single body is employed to perform EXAFS measurements at different x-ray energy intervals of interest. Two configurations have been implemented using toroidal crystals with Ge 311 reflection set to provide EXAFS at the Cu K-edge (energy range 8.9–9.8 keV) and Ge 400 reflection set to provide EXAFS at the Ta L3-edge (9.8–10.7 keV). Key performance characteristics of the spectrometer were found to be consistent with design parameters. The data generated at the National Ignition Facility have shown an ≃3 eV spectral resolution for the Cu K-edge configuration and ≃6 eV for the Ta L3-edge configuration.

Stoupin, S. (ORCID:0000000226225270)↗
DOE OSTI2022

A Study of Support Effects for the Water-Gas-Shift Reaction over Cu

The water–gas-shift (WGS) reaction was studied on a series of supported Cu catalysts in which the MgAl 2 O 4 (MAO) support was modified by depositing ZnO, CeO 2 , Mn2O 3 and CoO using Atomic Layer Deposition (ALD). Addition of Cu by one ALD cycle gave rise to catalysts with nominally 1-wt% Cu. A 1.1-wt% Cu/MAO catalyst prepared by ALD exhibited twice the dispersion but ten times the WGS activity of a 1-wt% Cu/MAO catalyst prepared by impregnation, implying that the reaction is structure sensitive. However, Cu catalysts prepared with the ZnO, CeO 2 , and Mn 2 O 3 films showed negligible differences from that of the Cu/MAO catalyst, implying that these oxides did not promote the reaction. Cu catalysts prepared on the CoO film showed a slightly lower activity, possibly due to alloy formation. The implications of these results for the development of better WGS catalysts is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Materials Data on Sr3La21Zn2(Cu5O24)2 by Materials Project

Sr3La21Zn2(Cu5O24)2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are three inequivalent Sr sites. In the first Sr site, Sr is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of Sr–O bond distances ranging from 2.44–3.03 Å. In the second Sr site, Sr is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of Sr–O bond distances ranging from 2.48–3.01 Å. In the third Sr site, Sr is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of Sr–O bond distances ranging from 2.46–2.96 Å. There are twenty-one inequivalent La sites. In the first La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.25–3.14 Å. In the second La site, La is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.46–3.24 Å. In the third La site, La is bonded in a 4-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.31–3.20 Å. In the fourth La site, La is bonded in a 2-coordinate geometry to eight O atoms. There are a spread of La–O bond distances ranging from 2.34–2.76 Å. In the fifth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.27–3.27 Å. In the sixth La site, La is bonded in a 9-coordinate geometry to eight O atoms. There are a spread of La–O bond distances ranging from 2.37–2.79 Å. In the seventh La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.26–3.27 Å. In the eighth La site, La is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of La–O bond distances ranging from 2.39–2.76 Å. In the ninth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.28–3.18 Å. In the tenth La site, La is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.32–3.20 Å. In the eleventh La site, La is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.34–3.20 Å. In the twelfth La site, La is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of La–O bond distances ranging from 2.39–2.80 Å. In the thirteenth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.25–3.12 Å. In the fourteenth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.27–3.16 Å. In the fifteenth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.32–3.21 Å. In the sixteenth La site, La is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.36–3.22 Å. In the seventeenth La site, La is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.33–3.10 Å. In the eighteenth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.36–3.22 Å. In the nineteenth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.31–3.20 Å. In the twentieth La site, La is bonded in a 2-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.30–3.26 Å. In the twenty-first La site, La is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of La–O bond distances ranging from 2.34–3.19 Å. There are ten inequivalent Cu sites. In the first Cu site, Cu is bonded to six O atoms to form distorted CuO6 octahedra that share corners with four equivalent ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–13°. There are a spread of Cu–O bond distances ranging from 1.89–2.51 Å. In the second Cu site, Cu is bonded to six O atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 4–11°. There are a spread of Cu–O bond distances ranging from 1.93–2.47 Å. In the third Cu site, Cu is bonded to six O atoms to form distorted CuO6 octahedra that share corners with four equivalent ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 3–18°. There are a spread of Cu–O bond distances ranging from 1.90–2.56 Å. In the fourth Cu site, Cu is bonded to six O atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 4–11°. There are a spread of Cu–O bond distances ranging from 1.93–2.51 Å. In the fifth Cu site, Cu is bonded to six O atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 7–11°. There are a spread of Cu–O bond distances ranging from 1.95–2.46 Å. In the sixth Cu site, Cu is bonded to six O atoms to form distorted corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 2–15°. There are a spread of Cu–O bond distances ranging from 1.94–2.53 Å. In the seventh Cu site, Cu is bonded to six O atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 5–10°. There are a spread of Cu–O bond distances ranging from 1.95–2.44 Å. In the eighth Cu site, Cu is bonded to six O atoms to form corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 7–11°. There are a spread of Cu–O bond distances ranging from 1.92–2.44 Å. In the ninth Cu site, Cu is bonded to six O atoms to form distorted corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 2–15°. There are a spread of Cu–O bond distances ranging from 1.93–2.53 Å. In the tenth Cu site, Cu is bonded to six O atoms to form distorted corner-sharing CuO6 octahedra. The corner-sharing octahedra tilt angles range from 5–10°. There are a spread of Cu–O bond distances ranging from 1.91–2.48 Å. There are two inequivalent Zn sites. In the first Zn site, Zn is bonded to six O atoms to form ZnO6 octahedra that share corners with four equivalent CuO6 octahedra. The corner-sharing octahedra tilt angles range from 7–13°. There are a spread of Zn–O bond distances ranging from 1.98–2.44 Å. In the second Zn site, Zn is bonded to six O atoms to form distorted ZnO6 octahedra that share corners with four equivalent CuO6 octahedra. The corner-sharing octahedra tilt angles range from 3–18°. There are a spread of Zn–O bond distances ranging from 1.98–2.52 Å. There are forty-eight inequivalent O sites. In the first O site, O is bonded in a 6-coordinate geometry to one Sr, three La, and two Cu atoms. In the second O site, O is bonded in a 6-coordinate geometry to five La and one Zn atom. In the third O site, O is bonded in a 2-coordinate geometry to five La and one Cu atom. In the fourth O site, O is bonded in a 6-coordinate geometry to four La, one Cu, and one Zn atom. In the fifth O site, O is bonded to four La, one Cu, and one Zn atom to form distorted face-sharing OLa4ZnCu octahedra. In the sixth O site, O is bonded in a 6-coordinate geometry to one Sr, three La, and two Cu atoms. In the seventh O site, O is bonded in a 2-coordinate geometry to five La and one Zn atom. In the eighth O site, O is bonded in a 2-coordinate geometry to four La and one Cu atom. In the ninth O site, O is bonded in a 5-coordinate geometry to five La and one Cu atom. In the tenth O site, O is bonded in a 2-coordinate geometry to four La and one Cu atom. In the eleventh O site, O is bonded to four La, one Cu, and one Zn atom to form distorted face-sharing OLa4ZnCu octahedra. In the twelfth O site, O is bonded in a 6-coordinate geometry to four La, one Cu, and one Zn atom. In the thirteenth O site, O is bonded in a 6-coordinate geometry to four La, one Cu, and one Zn atom. In the fourteenth O site, O is bonded to four La, one Cu, and one Zn atom to form distorted face-sharing OLa4ZnCu octahedra. In the fifteenth O site, O is bonded in a 6-coordinate geometry to two equivalent Sr, three La, and one Cu atom. In the sixteenth O site, O is bonded in a 5-coordinate geometry to one Sr, four La, and one Cu atom. In the seventeenth O site, O is bonded in a 2-coordinate geometry to four La and one Cu atom. In the eighteenth O site, O is bonded in a 5-coordinate geometry to five La and one Zn atom. In the nineteenth O site, O is bonded to one Sr, three La, and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OSrLa3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 2–4°. In the twentieth O site, O is bonded to one Sr, three La, and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OSrLa3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 2–4°. In the twenty-first O site, O is bonded to four La, one Cu, and one Zn atom to form distorted face-sharing OLa4ZnCu octahedra. In the twenty-second O site, O is bonded in a 6-coordinate geometry to four La, one Cu, and one Zn atom. In the twenty-third O site, O is bonded in a 5-coordinate geometry to five La and one Cu atom. In the twenty-fourth O site, O is bonded in a 6-coordinate geometry to five La and one Cu atom. In the twenty-fifth O site, O is bonded in a 5-coordinate geometry to two equivalent Sr, two La, and one Cu atom. In the twenty-sixth O site, O is bonded in a 6-coordinate geometry to five La and one Zn atom. In the twenty-seventh O site, O is bonded to four La and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OLa4Cu2 octahedra. The corner-sharing octahedra tilt angles range from 0–4°. In the twenty-eighth O site, O is bonded to four La and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OLa4Cu2 octahedra. The corner-sharing octahedra tilt angles range from 0–4°. In the twenty-ninth O site, O is bonded to one Sr, three La, and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OSrLa3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 2–4°. In the thirtieth O site, O is bonded to one Sr, three La, and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OSrLa3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 2–4°. In the thirty-first O site, O is bonded in a 6-coordinate geometry to two equivalent Sr, three La, and one Cu atom. In the thirty-second O site, O is bonded in a 6-coordinate geometry to one Sr, four La, and one Cu atom. In the thirty-third O site, O is bonded in a 5-coordinate geometry to five La and one Cu atom. In the thirty-fourth O site, O is bonded in a 5-coordinate geometry to five La and one Cu atom. In the thirty-fifth O site, O is bonded to one Sr, three La, and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OSrLa3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 0–5°. In the thirty-sixth O site, O is bonded to one Sr, three La, and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OSrLa3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 0–5°. In the thirty-seventh O site, O is bonded to four La and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OLa4Cu2 octahedra. The corner-sharing octahedra tilt angles range from 0–4°. In the thirty-eighth O site, O is bonded to four La and two Cu atoms to form a mixture of distorted corner, edge, and face-sharing OLa4Cu2 octahedra. The corner-sharing octahedra tilt angles range from 0–4°. In the thirty-ninth O site, O is bonded in a 6-coordinate geometry to two equivalent Sr, three La, and one Cu atom. In the fortieth O site, O is bonded in a 6-coordinate geometry to one Sr, four La, and one Cu atom. In the forty-first O site, O is bonded in a 5-coordinate geometry to two equivalent Sr, three

36 MATERIALS SCIENCE↗
DOE OSTI2026

Impact of Salt Chemistry and Interlayer Architecture on Solid Electrolyte Interphase Composition and Performance

Reversible lithium metal anodes require interphases that are chemically stable, mechanically robust, and compatible with scalable processing. Here, we use slot-die-coated, salt-rich PEO interlayers to design SEI nanolayers on Cu current collectors and isolate how salt anion chemistry controls interphase composition and lithium plating/stripping behavior in architectures relevant to Li plating and anode-free cells. Mesoscale modeling shows that dendrite initiation at SEI defects is governed by a tradeoff among interphase thickness, ionic conductivity, and stiffness through defect-driven current focusing, motivating controlled formation from thin precursor layers. Using UHV-transferred XPS and ToF-SIMS depth profiling after controlled Li deposition, we find that fluorinated sulfonylimide salts (LiTFSI, LiFSI) form mixed inorganic/organic interphases containing LiF and PEO-derived alkoxides, with LiFSI producing a more LiF-dominant Li-facing surface than LiTFSI under identical conditions. In contrast, LiNO 3 -containing interlayers yield a comparatively thick nitrate-derived interphase that reduces upon Li contact to an N-rich inorganic layer (Li–N/N 3− , LiN x O y ). In Cu| |Li cells, these designed interlayers reduce interfacial resistance and improve Coulombic efficiency (CE) and critical current density (CCD) relative to uncoated controls, with LiFSI- and LiNO 3 -based interlayers providing the highest CE/CCD. Overall, the results demonstrate a manufacturing-relevant approach to engineer SEI nanolayers by salt chemistry, providing pathways to improve reversible lithium metal anodes while reducing reliance on LiTFSI.

anion chemistry↗
DOE OSTI2024

Microstructure analysis and machinability of additively manufactured A205 aluminum with heat treatments

A205 aluminum is one of the few high-strength aluminum alloys discovered for additive manufacturing (AM). The microstructure and heat treatment effects of AM A205 vary from those of its cast form, indicating possible differences in machinability during post-processing. Here, the objective of this research is to determine these variations of AM A205 and their effects on machinability using the cast condition as the baseline. As built and two heat-treated conditions (solution treatment and age hardening) were applied and compared in terms of their microstructures, micro-hardness, and machinability including vibration, specific cutting energy, chip morphology, and surface finish. The effects of print orientations on machinability were tested as well and found to be insignificant. AM as built had a higher hardness and slightly better machinability than its cast as built cast counterpart due to a smaller grain size (1 µm vs. 15 µm), eutectic θ-Al 2 Cu lattice and a fine, homogeneous TiB 2 distribution. The solution treatment dissolved this θ-Al 2 Cu lattice and increased the grain size (3 µm) which decreased the hardness, increased the ductility seen in the chips, and reduced the overall machinability. The presence of θ’-Al 2 Cu precipitates improved the machinability of aged AM A205. In addition, it was found that A205 exhibited both ductile and brittle behavior depending on the cutting speed, thus producing different machinability. The speed dependency is related to the material condition and heat treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2022

PdCu Electrocatalysts for Selective Nitrate and Nitrite Reduction to Nitrogen

Electrocatalytic conversion of nitrate in waste can enable efficient waste remediation (NO 3 - to N 2 ) or waste valorization (NO 3 - to NH 4 + ) depending on the selectivity of the catalyst. Palladium and copper electrocatalysts typically exhibit ideal nitrate and nitrite binding properties, allowing for effective destruction of nitrate. However, rational steering of selectivity through material design remains a critical challenge for PdCu electrocatalyst. Here, we use the electrochemical underpotential deposition method to synthesize palladium nanocube electrocataysts with controlled copper surface coverage (e.g., partial and full copper coatings). We then examine the potential for NO 3 - destruction (conversion) and NO 2 - reduction reaction. We identify that partial copper-coated Pd nanocubes not only effectively facilitate the reduction of 95% of NO 3 - but also increase the reduction of NO 2 - to N 2 with 89% selectivity over 20 consecutive cycles (80 h). We also show that under these conditions, the Pd(100) surface facet is exposed. Complete copper-covered Pd nanocubes effectively facilitate the reduction of ~99% of NO 3 - . Complete coverage of copper; however, prevented exposure of Pd(100) surface facet, promoting the selective reduction of NO 2 - to NH 4 + with a 70% selectivity over 20 consecutive cycles (80 h). Density functional theory (DFT) calculations show that NO 3 - and NO 2 - adsorb more strongly on the Cu(100) surface compared to the Pd(100) surface, while the NO* intermediate generated from NO 3 - or NO 2 - reduction adsorbs more strongly on the Pd surface. Furthermore, barrier calculations show that NO* can readily migrate from the Cu domain to the Pd domain and that the N–N coupling barrier on Pd is significantly diminished at high NO* coverage. Together, these results suggest that the high N 2 selectivity observed on the PdCu electrocatalyst is caused by the spillover of NO* from the Cu domains to the Pd domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗