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At least 649 records · Page 36
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DOE OSTI2020

Materials Data on CrFe3Cu2(PO4)6 by Materials Project

CrFe3Cu2(PO4)6 crystallizes in the trigonal R3 space group. The structure is three-dimensional. Cr6+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.93 Å) and three longer (1.98 Å) Cr–O bond length. There are three inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six PO4 tetrahedra. There are three shorter (1.94 Å) and three longer (2.06 Å) Fe–O bond lengths. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six PO4 tetrahedra. There are three shorter (1.95 Å) and three longer (2.08 Å) Fe–O bond lengths. In the third Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six PO4 tetrahedra. There are three shorter (1.93 Å) and three longer (2.07 Å) Fe–O bond lengths. There are two inequivalent Cu+1.50+ sites. In the first Cu+1.50+ site, Cu+1.50+ is bonded in a 6-coordinate geometry to six O2- atoms. There are three shorter (2.21 Å) and three longer (2.23 Å) Cu–O bond lengths. In the second Cu+1.50+ site, Cu+1.50+ is bonded in a 6-coordinate geometry to six O2- atoms. All Cu–O bond lengths are 2.19 Å. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one CrO6 octahedra and corners with three FeO6 octahedra. The corner-sharing octahedra tilt angles range from 24–50°. There are a spread of P–O bond distances ranging from 1.53–1.57 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one CrO6 octahedra and corners with three FeO6 octahedra. The corner-sharing octahedra tilt angles range from 28–49°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Cu+1.50+, and one P5+ atom. In the third O2- site, O2- is bonded in a bent 150 degrees geometry to one Cr6+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Cu+1.50+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Cr6+, one Cu+1.50+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Cu+1.50+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on TiFe3Cu2(PO4)6 by Materials Project

TiFe3Cu2(PO4)6 crystallizes in the trigonal R3 space group. The structure is three-dimensional. Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.89 Å) and three longer (2.03 Å) Ti–O bond length. There are three inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.93 Å) and three longer (2.06 Å) Fe–O bond length. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six PO4 tetrahedra. There are three shorter (1.94 Å) and three longer (2.08 Å) Fe–O bond lengths. In the third Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six PO4 tetrahedra. There are three shorter (1.94 Å) and three longer (2.06 Å) Fe–O bond lengths. There are two inequivalent Cu+2.50+ sites. In the first Cu+2.50+ site, Cu+2.50+ is bonded in a 6-coordinate geometry to six O2- atoms. There are three shorter (2.19 Å) and three longer (2.22 Å) Cu–O bond lengths. In the second Cu+2.50+ site, Cu+2.50+ is bonded in a 6-coordinate geometry to six O2- atoms. All Cu–O bond lengths are 2.18 Å. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one TiO6 octahedra and corners with three FeO6 octahedra. The corner-sharing octahedra tilt angles range from 23–50°. There are a spread of P–O bond distances ranging from 1.52–1.56 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one TiO6 octahedra and corners with three FeO6 octahedra. The corner-sharing octahedra tilt angles range from 28–49°. There are a spread of P–O bond distances ranging from 1.52–1.57 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Cu+2.50+, and one P5+ atom. In the third O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Cu+2.50+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+, one Cu+2.50+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Cu+2.50+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2022

BiCuI 4 (Pyridine) 5 a neutral ligand-supported compound of BiI 3 and CuI

Reaction of equimolar pyridine (Py) solutions BiI 3 and CuI produces the Py-supported 1:1 bimetallic complex BiCuI 4 (Py) 5 in quantitative yield. The title complex is only the second neutral complex to feature Cu–I–Bi bridging and shows an octahedral trans-[BiI 4 (Py) 2 ] unit joined to a distorted tetrahedral CuI(Py) 3 unit by an iodide bridge. The complex shows low thermal stability, decomposing under modest heating or vacuum to produce a mixture of BiI 3 and CuI. Thus, it is a potential entry/precursor to BiI 3 /CuI chemistry. Natural Localized Molecular Orbital (NLMO) calculations were performed to analyze the nature of the Cu–I–Bi bonds, revealing that the title compound lies on the cusp of being [Cu(Py) 3 ] + [BiI 4 (Py) 2 ] – . Diffuse reflectance spectroscopy measurements show a strong absorption band with an optical bandgap energy of 1.94 eV. Theoretical density of states (DOS) and time-dependent density functional theory (TD-DFT) experiments to map the electronic structure assign the primary electronic transition as a mixed halide/metal-to-ligand charge transfer between Cu–I–Bi donor orbitals and Py π* acceptor orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermodynamics of the Metal Carbonates and Bicarbonates of Mn, Co, Ni, Cu, and Zn Relevant to Mineral Energetics

The gas phase heats of formation of ground-state MCO 3 , M(HCO 3 ) 2 , and M(HCO 3 )(OH), where M = Mn, Co, Ni, Cu, and Zn, have been predicted using the correlated molecular orbital theory at the CCSD(T) level extrapolated to the complete basis set limit using the Feller–Peterson–Dixon (FPD) approach. Cohesive energies of the carbonates were predicted based on the calculated gas phase and experimental solid heats of formation. Coulombic dissociation energies (CDEs) between metal cations and anions show a near-linear correlation with Shannon metal cation atomic radii, yet no correlation is found with the hardness of these cations. The total reaction dissociation energies (TRDEs) of transition metals are higher than their CDEs for the di-bicarbonates, in contrast to those for Mg and Ca based on our prior work. In addition to differences in the energies needed to prepare the transition metal dications, electron donation from the ligands to the 3d orbitals of open-shell transition metal dications from lone pairs of adjacent O atoms also plays a role. No electron donation from the ligands to the fully occupied 3d orbitals of Zn and Cd was found. Decomposition energies for generating MO, CO 2 , and/or H 2 O were calculated. Gas phase metal exchange energies only partially correlate with the electrochemical series for M(s) → M 2+( aq). The FPD heats of formation were used to benchmark a range of density functional theory exchange–correlation functionals, including those commonly used in solid-state mineral calculations. None of the functionals provided chemical accuracy agreement (±1 kcal/mol) with the FPD results. So, the best agreement with the FPD results is predicted for the $\tau$-HCTH functional with an average unsigned error of 8.3 kcal/mol.

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

Materials Data on Rb3(Cu4Se3)2 by Materials Project

Rb3(Cu4Se3)2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 7-coordinate geometry to seven Se2- atoms. There are a spread of Rb–Se bond distances ranging from 3.46–3.74 Å. In the second Rb1+ site, Rb1+ is bonded in a body-centered cubic geometry to eight Se2- atoms. There are four shorter (3.53 Å) and four longer (3.55 Å) Rb–Se bond lengths. There are four inequivalent Cu+1.12+ sites. In the first Cu+1.12+ site, Cu+1.12+ is bonded in a 3-coordinate geometry to three Se2- atoms. There are one shorter (2.37 Å) and two longer (2.57 Å) Cu–Se bond lengths. In the second Cu+1.12+ site, Cu+1.12+ is bonded to four Se2- atoms to form a mixture of edge and corner-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.47–2.71 Å. In the third Cu+1.12+ site, Cu+1.12+ is bonded in a trigonal planar geometry to three Se2- atoms. There are two shorter (2.44 Å) and one longer (2.45 Å) Cu–Se bond lengths. In the fourth Cu+1.12+ site, Cu+1.12+ is bonded in a 4-coordinate geometry to four Se2- atoms. There are a spread of Cu–Se bond distances ranging from 2.38–2.68 Å. There are three inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a 8-coordinate geometry to four Rb1+ and four Cu+1.12+ atoms. In the second Se2- site, Se2- is bonded in a 8-coordinate geometry to four Rb1+ and four Cu+1.12+ atoms. In the third Se2- site, Se2- is bonded in a 9-coordinate geometry to three equivalent Rb1+ and six Cu+1.12+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li6CoCu3(PO4)4 by Materials Project

Li6CoCu3(PO4)4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent LiO4 tetrahedra, corners with four PO4 tetrahedra, and corners with two equivalent LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.92–2.51 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent LiO4 tetrahedra, corners with four PO4 tetrahedra, and corners with two equivalent LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.92–2.51 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 trigonal pyramids that share a cornercorner with one CoO6 octahedra, corners with four PO4 tetrahedra, corners with two equivalent LiO4 trigonal pyramids, and an edgeedge with one CoO6 octahedra. The corner-sharing octahedral tilt angles are 74°. There are a spread of Li–O bond distances ranging from 1.92–2.04 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 trigonal pyramids that share a cornercorner with one CoO6 octahedra, corners with four PO4 tetrahedra, corners with two equivalent LiO4 trigonal pyramids, and an edgeedge with one CoO6 octahedra. The corner-sharing octahedral tilt angles are 72°. There are a spread of Li–O bond distances ranging from 1.91–2.02 Å. In the fifth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two equivalent LiO4 tetrahedra, corners with four PO4 tetrahedra, and corners with two equivalent LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.89–2.06 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two equivalent LiO4 tetrahedra, corners with four PO4 tetrahedra, and corners with two equivalent LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.89–2.06 Å. Co2+ is bonded to six O2- atoms to form distorted CoO6 octahedra that share corners with four PO4 tetrahedra, corners with two LiO4 trigonal pyramids, an edgeedge with one PO4 tetrahedra, and edges with two LiO4 trigonal pyramids. There are a spread of Co–O bond distances ranging from 2.08–2.32 Å. There are three inequivalent Cu+1.33+ sites. In the first Cu+1.33+ site, Cu+1.33+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.97–2.31 Å. In the second Cu+1.33+ site, Cu+1.33+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.97–2.41 Å. In the third Cu+1.33+ site, Cu+1.33+ is bonded in a 3-coordinate geometry to three O2- atoms. There are two shorter (1.96 Å) and one longer (2.15 Å) Cu–O bond lengths. There are four inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one CoO6 octahedra, corners with four LiO4 tetrahedra, and corners with four LiO4 trigonal pyramids. The corner-sharing octahedral tilt angles are 54°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one CoO6 octahedra, corners with four LiO4 trigonal pyramids, and an edgeedge with one CoO6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO4 tetrahedra and corners with four LiO4 trigonal pyramids. There are a spread of P–O bond distances ranging from 1.51–1.58 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent CoO6 octahedra, corners with two LiO4 tetrahedra, and corners with four LiO4 trigonal pyramids. The corner-sharing octahedra tilt angles range from 46–48°. There are a spread of P–O bond distances ranging from 1.55–1.58 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co2+, and one P5+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two Li1+, one Cu+1.33+, and one P5+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Cu+1.33+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Cu+1.33+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Co2+, one Cu+1.33+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Co2+, one Cu+1.33+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Cu+1.33+, and one P5+ atom. In the eighth O2- site, O2- is bonded to two Li1+, one Cu+1.33+, and one P5+ atom to form distorted corner-sharing OLi2CuP trigonal pyramids. In the ninth O2- site, O2- is bonded in a bent 120 degrees geometry to one Cu+1.33+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a 2-coordinate geometry to one Co2+ and one P5+ atom. In the eleventh O2- site, O2- is bonded to two Li1+, one Cu+1.33+, and one P5+ atom to form distorted corner-sharing OLi2CuP trigonal pyramids. In the twelfth O2- site, O2- is bonded to two Li1+, one Cu+1.33+, and one P5+ atom to form distorted corner-sharing OLi2CuP trigonal pyramids. In the thirteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co2+, and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co2+, and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a trigonal planar geometry to two Li1+ and one P5+ atom. In the sixteenth O2- site, O2- is bonded to two Li1+, one Cu+1.33+, and one P5+ atom to form distorted corner-sharing OLi2CuP trigonal pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li3Cr3(CuO6)2 by Materials Project

Li3Cr3(CuO6)2 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a distorted see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.97–2.07 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two CuO6 octahedra, corners with four CrO4 tetrahedra, and an edgeedge with one CuO6 octahedra. The corner-sharing octahedra tilt angles range from 61–72°. There are a spread of Li–O bond distances ranging from 1.99–2.09 Å. In the third Li1+ site, Li1+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 2.02–2.21 Å. There are three inequivalent Cr6+ sites. In the first Cr6+ site, Cr6+ is bonded to four O2- atoms to form CrO4 tetrahedra that share corners with four CuO6 octahedra and corners with two equivalent LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 29–47°. There are a spread of Cr–O bond distances ranging from 1.67–1.70 Å. In the second Cr6+ site, Cr6+ is bonded to four O2- atoms to form CrO4 tetrahedra that share corners with four CuO6 octahedra and a cornercorner with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 25–51°. There are a spread of Cr–O bond distances ranging from 1.64–1.72 Å. In the third Cr6+ site, Cr6+ is bonded to four O2- atoms to form CrO4 tetrahedra that share corners with four CuO6 octahedra and a cornercorner with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 46–50°. There are a spread of Cr–O bond distances ranging from 1.64–1.72 Å. There are two inequivalent Cu+1.50+ sites. In the first Cu+1.50+ site, Cu+1.50+ is bonded to six O2- atoms to form CuO6 octahedra that share a cornercorner with one LiO4 tetrahedra, corners with six CrO4 tetrahedra, and an edgeedge with one LiO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.97–2.34 Å. In the second Cu+1.50+ site, Cu+1.50+ is bonded to six O2- atoms to form CuO6 octahedra that share a cornercorner with one LiO4 tetrahedra and corners with six CrO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.96–2.22 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cr6+ and one Cu+1.50+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom. In the fourth O2- site, O2- is bonded in a distorted tetrahedral geometry to two Li1+, one Cr6+, and one Cu+1.50+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom. In the seventh O2- site, O2- is bonded in a bent 150 degrees geometry to one Cr6+ and one Cu+1.50+ atom. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+, one Cr6+, and one Cu+1.50+ atom. In the ninth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom. In the twelfth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Cr6+, and one Cu+1.50+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on MnCu8Sb3S13N6 by Materials Project

MnN6Cu8Sb3S13 crystallizes in the cubic F-43c space group. The structure is three-dimensional and consists of eight MnN6 clusters and one Cu8Sb3S13 framework. In each MnN6 cluster, Mn7+ is bonded in an octahedral geometry to six equivalent N+1.67- atoms. All Mn–N bond lengths are 1.84 Å. N+1.67- is bonded in a single-bond geometry to one Mn7+ atom. In the Cu8Sb3S13 framework, there are two inequivalent Cu+1.75+ sites. In the first Cu+1.75+ site, Cu+1.75+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three equivalent SbS4 tetrahedra, corners with four CuS4 trigonal pyramids, and edges with three equivalent CuS4 trigonal pyramids. There are three shorter (2.26 Å) and one longer (2.58 Å) Cu–S bond lengths. In the second Cu+1.75+ site, Cu+1.75+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three equivalent SbS4 tetrahedra, corners with four CuS4 trigonal pyramids, and edges with three equivalent CuS4 trigonal pyramids. There are three shorter (2.26 Å) and one longer (2.57 Å) Cu–S bond lengths. Sb5+ is bonded to four equivalent S2- atoms to form SbS4 tetrahedra that share corners with eight CuS4 trigonal pyramids. All Sb–S bond lengths are 2.43 Å. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded in a 3-coordinate geometry to two Cu+1.75+ and one Sb5+ atom. In the second S2- site, S2- is bonded in a body-centered cubic geometry to eight Cu+1.75+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on FeCu8Sb3S13N6 by Materials Project

FeN6Cu8Sb3S13 crystallizes in the cubic F-43c space group. The structure is three-dimensional and consists of eight FeN6 clusters and one Cu8Sb3S13 framework. In each FeN6 cluster, Fe3+ is bonded in an octahedral geometry to six equivalent N+1.67- atoms. All Fe–N bond lengths are 1.85 Å. N+1.67- is bonded in a single-bond geometry to one Fe3+ atom. In the Cu8Sb3S13 framework, there are two inequivalent Cu+2.25+ sites. In the first Cu+2.25+ site, Cu+2.25+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three equivalent SbS4 tetrahedra, corners with four CuS4 trigonal pyramids, and edges with three equivalent CuS4 trigonal pyramids. There are three shorter (2.27 Å) and one longer (2.57 Å) Cu–S bond lengths. In the second Cu+2.25+ site, Cu+2.25+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three equivalent SbS4 tetrahedra, corners with four CuS4 trigonal pyramids, and edges with three equivalent CuS4 trigonal pyramids. There are three shorter (2.26 Å) and one longer (2.58 Å) Cu–S bond lengths. Sb5+ is bonded to four equivalent S2- atoms to form SbS4 tetrahedra that share corners with eight CuS4 trigonal pyramids. All Sb–S bond lengths are 2.42 Å. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded in a 3-coordinate geometry to two Cu+2.25+ and one Sb5+ atom. In the second S2- site, S2- is bonded in a body-centered cubic geometry to eight Cu+2.25+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu8NiSb3S13N6 by Materials Project

NiN6Cu8Sb3S13 crystallizes in the cubic F-43c space group. The structure is three-dimensional and consists of eight nickel ammine bromide molecules and one Cu8Sb3S13 framework. In the Cu8Sb3S13 framework, there are two inequivalent Cu+2.12+ sites. In the first Cu+2.12+ site, Cu+2.12+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three equivalent SbS4 tetrahedra, corners with four CuS4 trigonal pyramids, and edges with three equivalent CuS4 trigonal pyramids. There are three shorter (2.26 Å) and one longer (2.60 Å) Cu–S bond lengths. In the second Cu+2.12+ site, Cu+2.12+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three equivalent SbS4 tetrahedra, corners with four CuS4 trigonal pyramids, and edges with three equivalent CuS4 trigonal pyramids. There are three shorter (2.26 Å) and one longer (2.58 Å) Cu–S bond lengths. Sb5+ is bonded to four equivalent S2- atoms to form SbS4 tetrahedra that share corners with eight CuS4 trigonal pyramids. All Sb–S bond lengths are 2.42 Å. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded in a 3-coordinate geometry to two Cu+2.12+ and one Sb5+ atom. In the second S2- site, S2- is bonded in a body-centered cubic geometry to eight Cu+2.12+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Interpreting the Operando XANES of Surface-Supported Subnanometer Clusters: When Fluxionality, Oxidation State, and Size Effect Fight.

X-ray absorption near edge structure (XANES) spectroscopy is widely used for operando catalyst characterization. We show that, for highly fluxional supported nanoclusters, the customary extraction of the oxidation state of the metal from the XANES data by fitting to the bulk standards is highly questionable. The XANES signatures as well as the apparent oxidation state for such clusters arise from a complex combination of many factors, and not only from the chemical composition in reaction conditions (e.g., oxygen content in oxidizing atmosphere). The thermally accessible isomerization and population of several structurally distinct cluster forms, cluster-support interaction, and intrinsic size effects all impact the metal oxidation state and XANES signal. We demonstrate this on copper oxide clusters with different compositions, Cu4Ox(x = 2-5) and Cu5Oy (y = 3, 5), deposited on amorphous alumina and ultrananocrystalline diamond, for which we computed the XANES spectra and compare the results to the experiment. We show in addition that fitting the experimental spectrum to calculated spectra of supported clusters can, in contrast, provide good agreement and insight into the spectrum-composition-structure relation. Experimental XANES interpreted using the proposed fitting scheme shows the partial reduction of Cu oxide clusters at rising temperatures, and pinpoints the specific stoichiometries that dominate in the ensemble of cluster states as the temperature changes.

Zandkarimi, Borna↗
DOE OSTI2020

Materials Data on BaCuO6 by Materials Project

(BaCuO4)4(Ba2Cu2O9)2(O2)7 crystallizes in the triclinic P1 space group. The structure is two-dimensional and consists of seven hydrogen peroxide molecules; one Ba2Cu2O9 sheet oriented in the (0, 0, 1) direction; and one BaCuO4 sheet oriented in the (0, 0, 1) direction. In the Ba2Cu2O9 sheet, there are four inequivalent Ba sites. In the first Ba site, Ba is bonded in a 6-coordinate geometry to six O atoms. There are a spread of Ba–O bond distances ranging from 2.67–2.82 Å. In the second Ba site, Ba is bonded in a 6-coordinate geometry to nine O atoms. There are a spread of Ba–O bond distances ranging from 2.61–3.49 Å. In the third Ba site, Ba is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of Ba–O bond distances ranging from 2.63–3.22 Å. In the fourth Ba site, Ba is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of Ba–O bond distances ranging from 2.61–2.90 Å. There are four inequivalent Cu sites. In the first Cu site, Cu is bonded in a rectangular see-saw-like geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.79–1.81 Å. In the second Cu site, Cu is bonded in a rectangular see-saw-like geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.77–2.03 Å. In the third Cu site, Cu is bonded in a rectangular see-saw-like geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.78–1.97 Å. In the fourth Cu site, Cu is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.77–1.90 Å. There are eighteen inequivalent O sites. In the first O site, O is bonded in a distorted trigonal planar geometry to two Ba and one Cu atom. In the second O site, O is bonded in a single-bond geometry to one Ba and one O atom. The O–O bond length is 1.23 Å. In the third O site, O is bonded in a trigonal non-coplanar geometry to two Ba and one Cu atom. In the fourth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the fifth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the sixth O site, O is bonded in a 1-coordinate geometry to two Ba, one Cu, and one O atom. The O–O bond length is 1.40 Å. In the seventh O site, O is bonded in a single-bond geometry to one O atom. In the eighth O site, O is bonded in a 1-coordinate geometry to one Ba, one Cu, and one O atom. The O–O bond length is 1.38 Å. In the ninth O site, O is bonded in a 3-coordinate geometry to two Ba and one Cu atom. In the tenth O site, O is bonded in a single-bond geometry to one Ba and one Cu atom. In the eleventh O site, O is bonded in a 3-coordinate geometry to two Ba and one Cu atom. In the twelfth O site, O is bonded in a 2-coordinate geometry to two Ba, one Cu, and one O atom. In the thirteenth O site, O is bonded in a distorted single-bond geometry to two Ba and one Cu atom. In the fourteenth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the fifteenth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the sixteenth O site, O is bonded in a 1-coordinate geometry to two Ba, one Cu, and one O atom. In the seventeenth O site, O is bonded in a 1-coordinate geometry to two Ba and one Cu atom. In the eighteenth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the BaCuO4 sheet, there are four inequivalent Ba sites. In the first Ba site, Ba is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of Ba–O bond distances ranging from 2.67–2.95 Å. In the second Ba site, Ba is bonded in a 5-coordinate geometry to six O atoms. There are a spread of Ba–O bond distances ranging from 2.56–3.25 Å. In the third Ba site, Ba is bonded in a 7-coordinate geometry to seven O atoms. There are a spread of Ba–O bond distances ranging from 2.62–2.84 Å. In the fourth Ba site, Ba is bonded in a 7-coordinate geometry to seven O atoms. There are a spread of Ba–O bond distances ranging from 2.60–3.05 Å. There are four inequivalent Cu sites. In the first Cu site, Cu is bonded in a rectangular see-saw-like geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.78–1.82 Å. In the second Cu site, Cu is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.76–1.92 Å. In the third Cu site, Cu is bonded in a rectangular see-saw-like geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.78–1.82 Å. In the fourth Cu site, Cu is bonded in a rectangular see-saw-like geometry to four O atoms. There are a spread of Cu–O bond distances ranging from 1.78–1.83 Å. There are sixteen inequivalent O sites. In the first O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the second O site, O is bonded in a distorted single-bond geometry to one Ba and one Cu atom. In the third O site, O is bonded in a 1-coordinate geometry to two Ba and one Cu atom. In the fourth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the fifth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the sixth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the seventh O site, O is bonded in a distorted single-bond geometry to two Ba and one Cu atom. In the eighth O site, O is bonded in a distorted trigonal planar geometry to two Ba and one Cu atom. In the ninth O site, O is bonded in a single-bond geometry to two Ba and one Cu atom. In the tenth O site, O is bonded in a 1-coordinate geometry to one Cu and one O atom. The O–O bond length is 1.35 Å. In the eleventh O site, O is bonded in a distorted trigonal non-coplanar geometry to two Ba and one Cu atom. In the twelfth O site, O is bonded in a 1-coordinate geometry to one Ba, one Cu, and one O atom. In the thirteenth O site, O is bonded in a 1-coordinate geometry to two Ba and one Cu atom. In the fourteenth O site, O is bonded in a distorted single-bond geometry to two Ba and one Cu atom. In the fifteenth O site, O is bonded in a 1-coordinate geometry to two Ba and one Cu atom. In the sixteenth O site, O is bonded in a trigonal non-coplanar geometry to two Ba and one Cu atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Mg3Cu9(SiO3)16 by Materials Project

Mg3Cu9(SiO3)16 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are two inequivalent Mg2+ sites. In the first Mg2+ site, Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with six SiO4 tetrahedra. There are a spread of Mg–O bond distances ranging from 2.01–2.38 Å. In the second Mg2+ site, Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with six SiO4 tetrahedra. There are a spread of Mg–O bond distances ranging from 2.01–2.33 Å. There are five inequivalent Cu+2.89+ sites. In the first Cu+2.89+ site, Cu+2.89+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.82–1.89 Å. In the second Cu+2.89+ site, Cu+2.89+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.82–1.89 Å. In the third Cu+2.89+ site, Cu+2.89+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.83–1.89 Å. In the fourth Cu+2.89+ site, Cu+2.89+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.82–1.88 Å. In the fifth Cu+2.89+ site, Cu+2.89+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with six SiO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.97–2.42 Å. There are eight inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MgO6 octahedra and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. There are a spread of Si–O bond distances ranging from 1.62–1.66 Å. In the second Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two MgO6 octahedra and corners with two SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 41–54°. There are a spread of Si–O bond distances ranging from 1.63–1.66 Å. In the third Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two MgO6 octahedra and corners with two SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 41–54°. There are a spread of Si–O bond distances ranging from 1.63–1.66 Å. In the fourth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MgO6 octahedra and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. There are a spread of Si–O bond distances ranging from 1.62–1.66 Å. In the fifth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MgO6 octahedra and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. There are a spread of Si–O bond distances ranging from 1.62–1.65 Å. In the sixth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MgO6 octahedra, a cornercorner with one CuO6 octahedra, and corners with two SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 43–54°. There is three shorter (1.64 Å) and one longer (1.66 Å) Si–O bond length. In the seventh Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MgO6 octahedra, a cornercorner with one CuO6 octahedra, and corners with two SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 42–54°. There are a spread of Si–O bond distances ranging from 1.63–1.68 Å. In the eighth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one CuO6 octahedra and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. There are a spread of Si–O bond distances ranging from 1.62–1.68 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the third O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the eighth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+2.89+ and one Si4+ atom. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the eleventh O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+2.89+ and one Si4+ atom. In the twelfth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the thirteenth O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the fourteenth O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the fifteenth O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the sixteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the seventeenth O2- site, O2- is bonded in a bent 150 degrees geometry to two Si4+ atoms. In the eighteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Cu+2.89+ and one Si4+ atom. In the nineteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.89+ and one Si4+ atom. In the twentieth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+2.89+ and one Si4+ atom. In the twenty-first O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the twenty-second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mg2+, one Cu+2.89+, and one Si4+ atom. In the twenty-third O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+2.89+ and one Si4+ atom. In the twenty-fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.89+ and one Si4+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CaCu10Te4(As2O17)2 by Materials Project

CaCu10Te4(As2O17)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with two equivalent AsO4 tetrahedra and edges with two equivalent CuO5 square pyramids. There are a spread of Ca–O bond distances ranging from 2.24–2.43 Å. There are five inequivalent Cu+2.20+ sites. In the first Cu+2.20+ site, Cu+2.20+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.83–2.23 Å. In the second Cu+2.20+ site, Cu+2.20+ is bonded to five O2- atoms to form CuO5 trigonal bipyramids that share corners with four CuO5 square pyramids, corners with two AsO4 tetrahedra, and a cornercorner with one CuO5 trigonal bipyramid. There are a spread of Cu–O bond distances ranging from 1.91–2.14 Å. In the third Cu+2.20+ site, Cu+2.20+ is bonded to five O2- atoms to form distorted CuO5 square pyramids that share corners with two AsO4 tetrahedra, corners with two equivalent CuO5 trigonal bipyramids, an edgeedge with one CaO6 octahedra, and an edgeedge with one CuO5 square pyramid. There are a spread of Cu–O bond distances ranging from 1.83–2.53 Å. In the fourth Cu+2.20+ site, Cu+2.20+ is bonded to five O2- atoms to form distorted CuO5 square pyramids that share corners with three AsO4 tetrahedra, corners with two equivalent CuO5 trigonal bipyramids, and an edgeedge with one CuO5 trigonal bipyramid. There are a spread of Cu–O bond distances ranging from 1.88–2.68 Å. In the fifth Cu+2.20+ site, Cu+2.20+ is bonded to five O2- atoms to form distorted CuO5 trigonal bipyramids that share corners with two AsO4 tetrahedra, a cornercorner with one CuO5 trigonal bipyramid, and an edgeedge with one CuO5 square pyramid. There are a spread of Cu–O bond distances ranging from 1.82–2.08 Å. There are two inequivalent As5+ sites. In the first As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with two CuO5 square pyramids and corners with two CuO5 trigonal bipyramids. There are a spread of As–O bond distances ranging from 1.70–1.76 Å. In the second As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share a cornercorner with one CaO6 octahedra, corners with three CuO5 square pyramids, and corners with two CuO5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 59°. There are a spread of As–O bond distances ranging from 1.72–1.75 Å. There are two inequivalent Te6+ sites. In the first Te6+ site, Te6+ is bonded in a 5-coordinate geometry to three O2- atoms. There is one shorter (1.83 Å) and two longer (2.00 Å) Te–O bond length. In the second Te6+ site, Te6+ is bonded in a 4-coordinate geometry to three O2- atoms. There are a spread of Te–O bond distances ranging from 1.82–2.00 Å. There are seventeen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.20+ and one Te6+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Cu+2.20+ and one As5+ atom. In the third O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+2.20+ and one As5+ atom. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.20+ and one Te6+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.20+ and one Te6+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.20+ and one As5+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.20+ and one Te6+ atom. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Cu+2.20+ atoms. In the ninth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Cu+2.20+ and one As5+ atom. In the tenth O2- site, O2- is bonded in a 2-coordinate geometry to one Cu+2.20+ and one As5+ atom. In the eleventh O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ca2+, one Cu+2.20+, and one As5+ atom. In the twelfth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ca2+ and one Te6+ atom. In the thirteenth O2- site, O2- is bonded in a bent 120 degrees geometry to one Cu+2.20+ and one As5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu+2.20+ and one As5+ atom. In the fifteenth O2- site, O2- is bonded in a single-bond geometry to one Cu+2.20+ atom. In the sixteenth O2- site, O2- is bonded in a single-bond geometry to one Cu+2.20+ atom. In the seventeenth O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, one Cu+2.20+, and one Te6+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Kinetic control of phase evolution and defect-mediated recombination in AACVD-grown copper antimony sulphide thin films

Copper antimony sulphide (CAS) is a multinary chalcogenide semiconductor in which small deviations from stoichiometry can drive phase competition and strong defect-mediated modulation of optoelectronic properties. However, the systematic roles of copper precursor fraction and deposition time in governing phase evolution, off-stoichiometry, and recombination dynamics in aerosol-assisted chemical vapour deposition (AACVD)-grown undoped CAS thin films remain insufficiently understood. In this work, undoped CAS thin films were deposited by AACVD using Cu(dedtc)2 and Sb(dedtc)3 single-source precursors at 550 °C and a carrier gas flow rate of 150 sccm, while the Cu(dedtc)2 mole fraction (x = 0.15 – 0.55) and deposition time (1 – 2 hours) were systematically varied to probe how growth kinetics influence phase composition, microstructure, and defect-mediated optical properties without post-deposition annealing or extrinsic doping. Increasing copper precursor content drives phase evolution toward tetrahedrite-dominant CAS films at intermediate Cu(dedtc)2 mole fractions, with the film deposited at x = 0.35 exhibiting the strongest tetrahedrite character within the parameter space examined. The films are also copper-rich, antimony-poor, and sulphur-deficient, consistent with off-stoichiometric growth and intrinsic defect formation, plausibly including copper interstitials, Cu-on-Sb antisites, and sulphur vacancies. These growth-dependent compositional deviations are accompanied by tunable indirect optical bandgaps of approximately 1.60 – 2.18 eV and weak visible photoluminescence governed by defect-mediated recombination. Time-resolved photoluminescence reveals bi-exponential decay behaviour with lifetimes of approximately 0.1 – 3.6 ns, with emission dominated by slower donor–acceptor pair recombination and a smaller contribution from faster trap-assisted pathways. Collectively, these results establish an explicit kinetic process–structure–defect–property relationship for AACVD-grown CAS thin films and provide a growth–structure–property framework relevant to future optimization of CAS-based optoelectronic and energy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ba(Cu2As)4 by Materials Project

Ba(Cu2As)4 crystallizes in the tetragonal I4/m space group. The structure is three-dimensional. Ba2+ is bonded in a body-centered cubic geometry to eight equivalent As3- atoms. All Ba–As bond lengths are 3.43 Å. There are two inequivalent Cu+1.25+ sites. In the first Cu+1.25+ site, Cu+1.25+ is bonded in a 3-coordinate geometry to three equivalent As3- atoms. There are one shorter (2.44 Å) and two longer (2.51 Å) Cu–As bond lengths. In the second Cu+1.25+ site, Cu+1.25+ is bonded in a 4-coordinate geometry to four equivalent As3- atoms. There are a spread of Cu–As bond distances ranging from 2.43–2.60 Å. As3- is bonded in a 9-coordinate geometry to two equivalent Ba2+ and seven Cu+1.25+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Mn6Al31Cu2 by Materials Project

Mn6Cu2Al31 crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. there are four inequivalent Mn sites. In the first Mn site, Mn is bonded in a 12-coordinate geometry to twelve Al atoms. There are a spread of Mn–Al bond distances ranging from 2.49–2.94 Å. In the second Mn site, Mn is bonded in a 10-coordinate geometry to ten Al atoms. There are a spread of Mn–Al bond distances ranging from 2.49–2.74 Å. In the third Mn site, Mn is bonded in a distorted cuboctahedral geometry to twelve Al atoms. There are a spread of Mn–Al bond distances ranging from 2.44–2.81 Å. In the fourth Mn site, Mn is bonded in a 9-coordinate geometry to nine Al atoms. There are a spread of Mn–Al bond distances ranging from 2.40–2.53 Å. Cu is bonded in a 12-coordinate geometry to one Cu and eleven Al atoms. The Cu–Cu bond length is 2.68 Å. There are a spread of Cu–Al bond distances ranging from 2.50–2.89 Å. There are thirteen inequivalent Al sites. In the first Al site, Al is bonded in a 1-coordinate geometry to three Mn and ten Al atoms. There are a spread of Al–Al bond distances ranging from 2.66–3.07 Å. In the second Al site, Al is bonded in a distorted linear geometry to two equivalent Mn and six Al atoms. There are two shorter (2.86 Å) and four longer (3.05 Å) Al–Al bond lengths. In the third Al site, Al is bonded in a 2-coordinate geometry to two Mn and nine Al atoms. There are two shorter (2.73 Å) and two longer (2.90 Å) Al–Al bond lengths. In the fourth Al site, Al is bonded in a 12-coordinate geometry to two Mn, two equivalent Cu, and eight Al atoms. There are a spread of Al–Al bond distances ranging from 2.54–2.87 Å. In the fifth Al site, Al is bonded in a 10-coordinate geometry to three Mn and seven Al atoms. There are one shorter (2.45 Å) and four longer (2.67 Å) Al–Al bond lengths. In the sixth Al site, Al is bonded in a 2-coordinate geometry to two Mn, one Cu, and ten Al atoms. There are a spread of Al–Al bond distances ranging from 2.62–2.95 Å. In the seventh Al site, Al is bonded in a 3-coordinate geometry to one Mn, two equivalent Cu, and ten Al atoms. There are four shorter (2.75 Å) and one longer (3.00 Å) Al–Al bond lengths. In the eighth Al site, Al is bonded in a 2-coordinate geometry to two Mn and nine Al atoms. There are one shorter (2.73 Å) and two longer (2.93 Å) Al–Al bond lengths. In the ninth Al site, Al is bonded in a 3-coordinate geometry to one Mn, two equivalent Cu, and six Al atoms. All Al–Al bond lengths are 2.94 Å. In the tenth Al site, Al is bonded in a 12-coordinate geometry to three Mn and nine Al atoms. There are one shorter (2.74 Å) and one longer (2.95 Å) Al–Al bond lengths. In the eleventh Al site, Al is bonded in a distorted linear geometry to two equivalent Cu and six Al atoms. Both Al–Al bond lengths are 2.78 Å. In the twelfth Al site, Al is bonded in a 2-coordinate geometry to one Mn, one Cu, and five Al atoms. In the thirteenth Al site, Al is bonded in a 3-coordinate geometry to three Mn, one Cu, and nine Al atoms. The Al–Al bond length is 2.84 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Controlled hydrogenation of a biomass-derived platform chemical formed by aldol-condensation of 5-hydroxymethyl furfural (HMF) and acetone over Ru, Pd, and Cu catalysts

Her we report that we studied the hydrogenation at temperatures from 313–393 K of a biomass-derived platform molecule, 5-hydroxymethyl furfural (HMF)-acetone-HMF (HAH) over Pd, Ru, and Cu based catalysts. HAH was selectively hydrogenated to produce partially-hydrogenated monomers (PHAH) over Cu and Ru catalysts and to fully-hydrogenated HAH monomers (FHAH) over the Ru catalyst. Pd based catalysts yielded a mixture of partially and fully hydrogenated monomers. Lumped reaction kinetics models were employed to quantify the kinetic behavior for hydrogenation over Ru, Cu, and Pd catalysts. The 5-step pathway exhibited over Pd and Ru catalysts consists of both series and parallel reaction steps, where HAH is both converted to fully hydrogenated products sequentially via series reactions of partially hydrogenated intermediates, as well as converted directly in parallel reactions to form the fully hydrogenated products. In contrast, the 3-step pathway over the Cu catalyst consists only of the consecutive reaction steps, where the final product was formed via series reactions of intermediate products. Additionally, reaction over the Cu catalyst did not hydrogenate the furan rings of the HAH molecule and yielded a different final product than those hydrogenation over Pd and Ru catalysts. Batch conditions are determined for each hydrogenated product that give the highest yields in both batch and plug flow reactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗