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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on CuSnO12 by Materials Project

CuSnO4(O2)4 crystallizes in the tetragonal P4_2/nnm space group. The structure is one-dimensional and consists of eight hydrogen peroxide molecules and two CuSnO4 ribbons oriented in the (0, 0, 1) direction. In each CuSnO4 ribbon, Cu is bonded in a 12-coordinate geometry to four equivalent O atoms. All Cu–O bond lengths are 2.10 Å. Sn is bonded in a 4-coordinate geometry to four equivalent O atoms. All Sn–O bond lengths are 2.32 Å. O is bonded in a 3-coordinate geometry to one Cu, one Sn, and one O atom. The O–O bond length is 1.44 Å.

36 MATERIALS SCIENCE↗
NASA NTRS1988

Thermal expansion behavior of randomly oriented short carbon fiber reinforced copper composites

Several experiments were carried out on Cu composites with random orientation of short C fibers. The composite with random orientation of short C fibers swelled due to the elastic deformation of the fiber skeleton above 573 K. In a 3-D isotropic composite, the Cu matrix softened above 573 K and was fractured by the repulsive force of C fibers which were elastically deformed and released during heating. Swelling of the composite occurred when the fiber content was greater than or = 20 volume percent or the fiber length exceeded 0.5 millimeters. The addition of carbide-forming elements such as Ti was effective in preventing the swelling.

Kuniya, Keiichi↗
DOE OSTI2020

Materials Data on Cu5(Si2O7)2 by Materials Project

Cu5(Si2O7)2 crystallizes in the orthorhombic Pbca space group. The structure is three-dimensional. there are three inequivalent Cu+2.40+ sites. In the first Cu+2.40+ site, Cu+2.40+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 1.91–2.61 Å. In the second Cu+2.40+ site, Cu+2.40+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 1.93–2.63 Å. In the third Cu+2.40+ site, Cu+2.40+ is bonded in a distorted square co-planar geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.91–1.95 Å. There are two inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded to four O2- atoms to form corner-sharing SiO4 tetrahedra. There are a spread of Si–O bond distances ranging from 1.62–1.65 Å. In the second Si4+ site, Si4+ is bonded to four O2- atoms to form corner-sharing SiO4 tetrahedra. There is three shorter (1.64 Å) and one longer (1.66 Å) Si–O bond length. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Si4+ atoms. In the second O2- site, O2- is bonded in a trigonal non-coplanar geometry to two equivalent Cu+2.40+ and one Si4+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to three Cu+2.40+ and one Si4+ atom. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu+2.40+ 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 three Cu+2.40+ and one Si4+ atom. In the seventh O2- site, O2- is bonded in a trigonal non-coplanar geometry to three Cu+2.40+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu8Ge5C4(S2N)8 by Materials Project

Cu8Ge5S16(CN2)4 crystallizes in the tetragonal P4_2/mmc space group. The structure is three-dimensional and consists of eight cyanamide molecules and one Cu8Ge5S16 framework. In the Cu8Ge5S16 framework, Cu+1.50+ is bonded in a trigonal planar geometry to three S2- atoms. All Cu–S bond lengths are 2.23 Å. There are three inequivalent Ge4+ sites. In the first Ge4+ site, Ge4+ is bonded to four S2- atoms to form edge-sharing GeS4 tetrahedra. There are two shorter (2.25 Å) and two longer (2.26 Å) Ge–S bond lengths. In the second Ge4+ site, Ge4+ is bonded to four S2- atoms to form edge-sharing GeS4 tetrahedra. All Ge–S bond lengths are 2.26 Å. In the third Ge4+ site, Ge4+ is bonded in a tetrahedral geometry to four equivalent S2- atoms. All Ge–S bond lengths are 2.26 Å. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu+1.50+ and one Ge4+ atom. In the second S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Cu+1.50+ and one Ge4+ atom. In the third S2- site, S2- is bonded in an L-shaped geometry to two equivalent Ge4+ atoms. In the fourth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu+1.50+ and one Ge4+ atom. In the fifth S2- site, S2- is bonded in an L-shaped geometry to two equivalent Ge4+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiCu2(CO3)2 by Materials Project

LiCu2(CO3)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Li1+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.94–2.00 Å. There are two inequivalent Cu+1.50+ sites. In the first Cu+1.50+ site, Cu+1.50+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.90–2.41 Å. In the second Cu+1.50+ site, Cu+1.50+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.90–2.27 Å. There are two inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.31 Å. In the second C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.31 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, two equivalent Cu+1.50+, and one C4+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Cu+1.50+, and one C4+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one Cu+1.50+ and one C4+ atom. In the fourth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Li1+, one Cu+1.50+, and one C4+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Cu+1.50+ and one C4+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Cu+1.50+, and one C4+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu5(PO6)2 by Materials Project

Cu5(PO6)2 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are three inequivalent Cu+2.80+ sites. In the first Cu+2.80+ site, Cu+2.80+ is bonded in a square co-planar geometry to four O2- atoms. There is two shorter (1.87 Å) and two longer (1.94 Å) Cu–O bond length. In the second Cu+2.80+ site, Cu+2.80+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.88–1.91 Å. In the third Cu+2.80+ site, Cu+2.80+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with four equivalent PO4 tetrahedra and edges with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.86–2.47 Å. P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four equivalent CuO6 octahedra. The corner-sharing octahedra tilt angles range from 49–66°. There are a spread of P–O bond distances ranging from 1.51–1.60 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one Cu+2.80+ and one P5+ atom. In the second O2- site, O2- is bonded in a trigonal non-coplanar geometry to three Cu+2.80+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to three Cu+2.80+ atoms. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Cu+2.80+ and one P5+ atom. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to two Cu+2.80+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Cu+2.80+ and one P5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiCuPCO7 by Materials Project

LiCuCPO7 crystallizes in the monoclinic P2_1 space group. The structure is three-dimensional. Li is bonded in a 6-coordinate geometry to six O atoms. There are a spread of Li–O bond distances ranging from 1.98–2.51 Å. Cu is bonded to six O atoms to form CuO6 octahedra that share corners with four equivalent PO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.92–2.07 Å. C is bonded in a trigonal planar geometry to three O atoms. There is one shorter (1.24 Å) and two longer (1.31 Å) C–O bond length. P is bonded to four O atoms to form PO4 tetrahedra that share corners with four equivalent CuO6 octahedra. The corner-sharing octahedra tilt angles range from 45–51°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. There are seven inequivalent O sites. In the first O site, O is bonded in a 3-coordinate geometry to one Li, one Cu, and one P atom. In the second O site, O is bonded in a 3-coordinate geometry to one Li, one Cu, and one C atom. In the third O site, O is bonded in a 3-coordinate geometry to one Li, one Cu, and one C atom. In the fourth O site, O is bonded in a distorted bent 120 degrees geometry to one Cu and one P atom. In the fifth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Cu, and one P atom. In the sixth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Cu, and one P atom. In the seventh O site, O is bonded in a bent 150 degrees geometry to one Li and one C atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu4Bi4S9 by Materials Project

Cu4Bi4S9 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are four inequivalent Cu+1.50+ sites. In the first Cu+1.50+ site, Cu+1.50+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with two equivalent BiS5 square pyramids and corners with two equivalent CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.29–2.33 Å. In the second Cu+1.50+ site, Cu+1.50+ is bonded to four S2- atoms to form distorted CuS4 tetrahedra that share corners with four equivalent BiS6 octahedra, corners with two equivalent BiS5 square pyramids, corners with two equivalent CuS4 tetrahedra, an edgeedge with one BiS6 octahedra, and edges with two equivalent CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 38–41°. There are a spread of Cu–S bond distances ranging from 2.30–2.91 Å. In the third Cu+1.50+ site, Cu+1.50+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.24–2.73 Å. In the fourth Cu+1.50+ site, Cu+1.50+ is bonded to four S2- atoms to form distorted CuS4 tetrahedra that share corners with two equivalent BiS6 octahedra, corners with two equivalent BiS5 square pyramids, and corners with two equivalent CuS4 tetrahedra. The corner-sharing octahedral tilt angles are 70°. There are a spread of Cu–S bond distances ranging from 2.24–2.40 Å. There are four inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with six CuS4 tetrahedra, edges with four equivalent BiS6 octahedra, and an edgeedge with one CuS4 tetrahedra. There are a spread of Bi–S bond distances ranging from 2.70–3.22 Å. In the second Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Bi–S bond distances ranging from 2.67–3.11 Å. In the third Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Bi–S bond distances ranging from 2.61–3.07 Å. In the fourth Bi3+ site, Bi3+ is bonded to five S2- atoms to form distorted BiS5 square pyramids that share corners with six CuS4 tetrahedra and edges with two equivalent BiS5 square pyramids. There are a spread of Bi–S bond distances ranging from 2.66–2.86 Å. There are nine inequivalent S2- sites. In the first S2- site, S2- is bonded to two Cu+1.50+ and two equivalent Bi3+ atoms to form corner-sharing SCu2Bi2 tetrahedra. In the second S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Cu+1.50+ and three Bi3+ atoms. In the third S2- site, S2- is bonded to one Cu+1.50+ and three Bi3+ atoms to form distorted corner-sharing SCuBi3 tetrahedra. In the fourth S2- site, S2- is bonded in a 5-coordinate geometry to three Cu+1.50+ and two Bi3+ atoms. In the fifth S2- site, S2- is bonded in a 2-coordinate geometry to three equivalent Cu+1.50+ and four Bi3+ atoms. In the sixth S2- site, S2- is bonded in a 1-coordinate geometry to one Cu+1.50+ and four Bi3+ atoms. In the seventh S2- site, S2- is bonded in a 4-coordinate geometry to one Cu+1.50+, two equivalent Bi3+, and one S2- atom. The S–S bond length is 2.12 Å. In the eighth S2- site, S2- is bonded in a 3-coordinate geometry to three equivalent Bi3+ atoms. In the ninth S2- site, S2- is bonded in a 4-coordinate geometry to three Cu+1.50+ and one S2- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Crystal Structure and Properties of Layered Pnictides BaCuSi2Pn3 (Pn = P, As)

Two novel layered compounds BaCuSi 2 Pn 3 (Pn = P, As) adopting new structure types are reported. As revealed by single-crystal X-ray diffraction, both compounds are composed of unique Cu–Si–Pn layers featuring CuPn 3 and Si 2 Pn 6 structural motifs found in other archetypal pnictide materials. The stacking of the isostructural Cu–Si–Pn layers is different for phosphide and arsenide compounds. Synthesis from elements aided by in situ synchrotron powder X-ray diffraction resulted in the obtainment of bulk powders with a minimized amount of admixtures. Experimentally measured physical properties of BaCuSi 2 As 3 unexpectedly showed metal-like behavior at temperatures above 15 K, despite the fact that density functional theory calculations predict a small band gap of 0.4 eV. BaCuSi 2 As 3 exhibits ultralow thermal conductivity, which can be explained by the combination of a layered crystal structure with alternating covalent and ionic bonding, which feature rattling of Cu atoms similar to that in tetrahedrites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Mechanisms and site requirements for NO and NH 3 oxidation on Cu/SSZ-13

Two series of Cu/SSZ-13 catalysts were synthesized via aqueous solution and solid-state ion exchange using SSZ-13 supports of varying Si/Al ratios. The isolated and multinuclear Cu content of these catalysts were determined by H 2 temperature programmed reduction (H 2 -TPR). Multinuclear Cu in these catalysts, including in situ Cu- dimers formed from ZCu II OH coupling and permanent CuO clusters, are active species for dry NO oxidation. NH 3 oxidation on these catalysts follows an internal SCR (i-SCR) mechanism, i.e., a portion of NH 3 is first oxidized to NO, then NO is selectively reduced by the remaining NH 3 to N 2 . NH 3 oxidation displays distinct kinetic behavior below ~300 °C and above ~400 °C. At low temperature the results indicate that NH 3 -solvated mobile Cu-ions are the active centers. CuO clusters, when present, also contribute to the low temperature activity by catalyzing NH 3 oxidation to NO. At high temperature, in situ Cu-dimers and CuO clusters catalyze NH 3 oxidation to NO, and isolated Cu-ions catalyze SCR to realize the cascade turnovers. For both NO and NH 3 oxidation, Cu-dimers balanced by framework charges of close proximity appear to be more active than Cu-dimers balanced by distant framework charges. However, the former Cu-dimers are less stable than the latter and tend to split into monomers in the presence of vicinal Brønsted acid sites. Via density functional theory (DFT) calculations, the i-SCR mechanism for low temperature NH 3 oxidation, i.e., the energetic favorability for the involvement of the NO intermediate, is justified. Furthermore, the DFT results also agree with experimental data that the formation of Cu-dimers from ZCu II OH dimerization is essential for NH 3 oxidation at high temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2015

Consideration of Conductive Motor Winding Materials at Room and Elevated Temperatures

A brief history of conductive motor winding materials is presented, comparing various metal motor winding materials and their properties in terms of conductivity, density and cost. The proposed use of carbon nanotubes (CNTs) and composites incorporating CNTs is explored as a potential way to improve motor winding conductivity, density, and reduce motor size which are important to electric aircraft technology. The conductivity of pure Cu, a CNT yarn, and a dilute Cu-CNT composite was measured at room temperature and at several temperatures up to 340 C. The conductivity of the Cu-CNT composite was about 3 percent lower than pure copper's at all temperatures measured. The conductivity of the CNT yarn was about 200 times lower than copper's, however, the yarn's conductivity dropped less with increasing temperature compared to Cu. It is believed that the low conductivity of the yarn is due primarily to high interfacial resistances and the presence of CNTs with low, semiconductor like electrical properties (s-CNT). It is believed the conductivity of the CNT-Cu composite could be improved by not using s-CNT, and instead using only CNTs with high, metallic like electrical properties (m-CNT); and by increasing the vol% m-CNTs.

yarns↗
DOE OSTI2025

Dynamic Features of Cu-Ceria Interface under CO 2 Hydrogenation to Methanol

It is generally accepted that metal–support interaction is very important for the hydrogenation of CO 2 to methanol, but little has been revealed about the feature of interfacial active sites under real reaction conditions since there are only limited techniques that can be applied under high-pressure conditions. Here, in this work, by combining multiple in situ and operando techniques on a model Cu/ceria catalyst, we have tracked Cu and ceria sites for methanol formation. Under the reaction condition, it is found that upon reaching the reaction temperature, oxidized Cu species in the as-synthesized catalyst immediately change into metallic Cu species. Following this, it is the gradual formation of methanol, the changing rate of which coincides with the formation of a unique Ce 3+ species. The combined experimental results and density functional theory (DFT) calculations have determined that the formed Ce 3+ sites driven by the reaction conditions are bound to hydrides, adsorbed carbonate species, and interfacial active Cu sites. The Cu-ceria interaction in this complex moiety is weak and can be easily disturbed with reaction environment variations, leading to dynamic changes at the interface upon the hydrogenation of active carbonate intermediates, which are precursors for the formation of methanol. The formation of this unique Cu–Ce 3+ interface and its dynamicity lead to an increase of methanol selectivity from less than 20% to 60%. These results suggest that reactant-derived species (H – and carbonate in this work) can be essential components of the active center with the functions of manipulating the metal−oxide interaction and directing reaction pathways.

CO2 hydrogenation to methanol↗
DOE OSTI2021

Maturation of Rhodobacter capsulatus Multicopper Oxidase CutO Depends on the CopA Copper Efflux Pathway and Requires the cutF Product

Copper (Cu) is an essential cofactor required for redox enzymes in all domains of life. Because of its toxicity, tightly controlled mechanisms ensure Cu delivery for cuproenzyme biogenesis and simultaneously protect cells against toxic Cu. Many Gram-negative bacteria contain extracytoplasmic multicopper oxidases (MCOs), which are involved in periplasmic Cu detoxification. MCOs are unique cuproenzymes because their catalytic center contains multiple Cu atoms, which are required for the oxidation of Cu 1+ to the less toxic Cu 2+ . Hence, Cu is both substrate and essential cofactor of MCOs. Here, we investigated the maturation of Rhodobacter capsulatus MCO CutO and its role in periplasmic Cu detoxification. A survey of CutO activity of R. capsulatus mutants with known defects in Cu homeostasis and in the maturation of the cuproprotein cbb 3 -type cytochrome oxidase ( cbb 3 -Cox) was performed. This revealed that CutO activity is largely independent of the Cu-delivery pathway for cbb 3 -Cox biogenesis, except for the cupric reductase CcoG, which is required for full CutO activity. The most pronounced decrease of CutO activity was observed with strains lacking the cytoplasmic Cu chaperone CopZ, or the Cu-exporting ATPase CopA, indicating that CutO maturation is linked to the CopZ-CopA mediated Cu-detoxification pathway. Our data demonstrate that CutO is important for cellular Cu resistance under both aerobic and anaerobic growth conditions. CutO is encoded in the cutFOG operon, but only CutF, and not CutG, is essential for CutO activity. No CutO activity is detectable when cutF or its putative Cu-binding motif are mutated, suggesting that the cutF product serves as a Cu-binding component required for active CutO production. Bioinformatic analyses of CutF-like proteins support their widespread roles as putative Cu-binding proteins for several Cu-relay pathways. Our overall findings show that the cytoplasmic CopZ-CopA dependent Cu detoxification pathway contributes to providing Cu to CutO maturation, a process that strictly relies on cutF .

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Acetate formation on metals via CH 4 carboxylation by CO 2 : A DFT study

Here, density functional theory calculations have been performed to investigate CH 4 activation and coupling to CO 2 forming C 2 carboxylates such as acetate on the close-packed (111) or (0001) surfaces of ten mid-to-late transition and coinage metals (Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au). Consistent with the literature, the activation energy (E a ) for the initial C-H bond scission in CH 4 is mild, being ca. 1 eV or less on all but the coinage metals, of which Ag exhibits the highest E a at 2.13 eV, followed by Au and Cu. E a for the CH 3 -CO 2 coupling step is 0.8 ~ 1.1 eV on Co, Ru, Rh, and Ag, 1.2 ~ 1.5 eV on Ni, Cu, Pd, and Ir, and 1.8 ~ 2.1 eV on Pt and Au. While the two E a are comparable for several metals in terms of DFT total energies, free energy analysis indicates CH 3 -CO 2 coupling to be much more rate-limiting than CH 4 activation. Overcoming it would require over 800 K even on the most active of the metals considered, Ru, which makes the formation of acetate not feasible on the monometallic metal surfaces. Instead, we propose that single atom alloys based on early transition metals doped into a host metal such as Ni(111) could be viable catalysts. The dopant sites serve to stabilize the transition state of C-C coupling while Ni sites continue to activate CH 4 , thereby significantly lowering the required temperature for acetate formation.

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

Molecular Structure of Copper and μ-Oxodiiron Octafluorocorrole Derivatives: Insights into Ligand Noninnocence

Single-crystal X-ray structures were obtained for the copper and μ-oxodiiron complexes of 2,3,7,8,12,13,17,18-octafluoro-5,10,15-triphenylcorrole, hereafter denoted as Cu[F 8 TPC] and {Fe[F 8 TPC]} 2 O. A comparison with the crystal structures of other undecasubstituted Cu corroles, including those with H, Ar, Br, I, and CF 3 as β-substituents, showed that the degree of saddling increases in the order: H ≲ F < Ar ≲ Br ≲ I < CF 3 . In other words, Cu[F 8 TPC] is marginally more saddled than β-unsubstituted Cu triarylcorroles, but substantially less saddled than Cu undecaarylcorroles, β-octabromo-meso-triarylcorroles, and β-octaiodo-meso-triarylcorroles, and far less saddled than Cu β-octakis(trifluoromethyl)-meso-triarylcorroles. As for {Fe[F 8 TPC]} 2 O, the moderate quality of the structure did not allow us to draw firm conclusions in regard to bond length alternations in the corrole skeleton and hence also the question of ligand noninnocence. The Fe-O bond distances, 1.712(8) and 1.724(8), however, are essentially identical to those observed for {Fe[TPFPC]} 2 O, where TPFPC 3- is the trianion of 5,10,15-tris(pentafluorophenyl)corrole, suggesting that a partially noninnocent electronic structural description may be applicable for both compounds.

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

Materials Data on Ti3FeCu2(PO4)6 by Materials Project

Ti3FeCu2(PO4)6 crystallizes in the trigonal R3 space group. The structure is three-dimensional. there are three inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.91 Å) and three longer (2.03 Å) Ti–O bond length. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.90 Å) and three longer (2.00 Å) Ti–O bond length. In the third Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.90 Å) and three longer (2.03 Å) Ti–O bond length. 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 (2.07 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 (2.22 Å) and three longer (2.28 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. There are three shorter (2.27 Å) and three longer (2.29 Å) Cu–O bond lengths. 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 FeO6 octahedra and corners with three TiO6 octahedra. The corner-sharing octahedra tilt angles range from 22–47°. There are a spread of P–O bond distances ranging from 1.54–1.56 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one FeO6 octahedra and corners with three TiO6 octahedra. The corner-sharing octahedra tilt angles range from 23–45°. There are a spread of P–O bond distances ranging from 1.51–1.56 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+, one Cu+1.50+, and one P5+ atom. In the third O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+, one Cu+1.50+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Cu+1.50+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+, one Cu+1.50+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ti3CrCu2(PO4)6 by Materials Project

Ti3CrCu2(PO4)6 crystallizes in the trigonal R3 space group. The structure is three-dimensional. there are three inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.91 Å) and three longer (2.02 Å) Ti–O bond length. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.91 Å) and three longer (2.00 Å) Ti–O bond length. In the third Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.90 Å) and three longer (2.03 Å) Ti–O bond length. Cr3+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six PO4 tetrahedra. There is three shorter (1.95 Å) and three longer (2.02 Å) Cr–O bond length. 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 (2.24 Å) and three longer (2.28 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. There are three shorter (2.28 Å) and three longer (2.29 Å) Cu–O bond lengths. 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 TiO6 octahedra. The corner-sharing octahedra tilt angles range from 23–45°. There is two shorter (1.54 Å) and two longer (1.55 Å) P–O bond length. 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 TiO6 octahedra. The corner-sharing octahedra tilt angles range from 24–44°. There are a spread of P–O bond distances ranging from 1.51–1.56 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+, one Cu+1.50+, and one P5+ atom. In the third O2- site, O2- is bonded in a bent 150 degrees geometry to one Cr3+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+, one Cu+1.50+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Cr3+, one Cu+1.50+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+, one Cu+1.50+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom.

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