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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Structural and electronic properties of the first iridium containing mixed B-site spinel oxide: Cu [ Ir 1.5 Cu 0.5 ] O 4

Geometrically frustrated systems populated with large spin-orbit coupled ions are an ideal setting for the exploration of novel exotic states of matter. In this study we present an example of iridium on a mixed B-site spinel oxide structure: Cu [ Ir 1.498 ( 2 ) Cu 0.502 ( 2 ) ] O 4 . Synchrotron XRD refinements reveal a face-centered-cubic structure with space group F d 3 ¯ m and mixed Cu-Ir site disorder within the B 2 O 4 rocksalt substructure. Electrical properties reveal a metallic state within the 50–600-K range with a Kondo effect at T < 50 K . X-ray absorption spectroscopy (XAS) measurements show a mixed Cu 1 + / 2 + and Ir 3 + / 4 + charge partitioned picture, which suggests a metallic/band description with reduced on-site Coulomb interactions. Spin-glass-like freezing is seen at T g = 49 K , and the hysteresis behavior for T > T g resembles that of a strongly frustrated magnet. DFT calculations show sizable hybridization between the Cu 3 d and Ir 5 d states with an effective mixed Ir 3 + / 4 + charge partitioned picture, supporting the electronic and XAS results.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

The electrochemical lithiation and delithiation of the layered oxysulfide Sr 2 MnO 2 Cu 4-δ S 3 has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X-ray absorption and 7 Li NMR spectroscopy, together with a range of electrochemical experiments. Sr 2 MnO 2 Cu 4-δ S 3 consists of [Sr 2 MnO 2 ] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu 4-δ S 3 ] (δ ≈ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li 4 S 3 slabs and Cu + is reduced and extruded as metallic particles. For the initial 2-3% of the first discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn 2.5+ is reduced to Mn 2+ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn 2+ to Mn 2.5+ . However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in the removal of most of the Li, little reinsertion of Cu, and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure-property investigation will promote the design of new functional electrodes with improved device performance.

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

Effect of the Chemical States of Copper on Methanol Decomposition and Oxidation

Here, the decomposition and oxidation reactions of CH 3 OH over metallic Cu(100) and Cu 2 O-covered Cu(100) surfaces are studied using a combination of in-situ ambient-pressure X-ray photoelectron spectroscopy, Auger electron spectroscopy, and density functional theory calculations. We identify the sequential chemical transformation pathways from bond cleavage to the formation of intermediates and final products under operational conditions. Accumulative surface adsorption of CH 3 O species on metallic Cu(100) impedes the decomposition of CH 3 OH. Co-dosing on metallic Cu(100) with low pressures of 1·10 -4 Torr CH 3 OH + 1·10 -4 Torr O 2 results in partial oxidation of CH 3 OH, where the chemisorbed O ads reduces surface sites available for CH 3 O adsorption, decreasing the surface activity for CH 3 OH decomposition. In contrast, the Cu 2 O overlayer formed under the elevated pressures of 0.33 Torr CH 3 OH + 0.66 Torr O 2 promotes the total oxidation of CH 3 OH into the final products of CO 2 and H 2 O, arising from the active reaction 2 between lattice O within Cu 2 O and intermediates of CH 3 O, CH 2 O, HCOO, and CO. Despite the more favorable O-H bond scission, C-O bond scission also occurs to result in surface accumulation of CH x on metallic Cu(100), blocking active sites for decomposition reactions of CH 3 OH and CH 3 O. By comparison, the CH x species on the Cu 2 O-covered Cu(100) undergo oxidation into CO 2 and H 2 O with lattice O in the Cu 2 O overlayer, thereby freeing active sites for the total oxidation of CH 3 OH. These results highlight the distinct roles of metallic Cu and Cu 2 O in the pathways of CH 3 OH decomposition and oxidation reactions, offering practical insights for the design of Cu-based catalysts with tailored reactivity and selectivity.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Local structure of Sr 2 CuO 3.3 , a 95 K cuprate superconductor without CuO 2 planes

The local structure of the highly “overdoped” 95 K superconductor Sr 2 CuO 3.3 determined by Cu K X-ray absorption fine structure (XAFS) at 62 K in magnetically oriented samples shows that 1) the magnetization is perpendicular to the c axis; 2) at these levels of precision the Cu sublattice is tetragonal in agreement with the crystal structure; the O sublattice has 3) continuous -Cu-O- chains that orient perpendicular to an applied magnetic field; 4) approximately half-filled -Cu-O- chains that orient parallel to this field; 5) a substantial number of apical O vacancies; 6) O ions at some apical positions with expanded Cu-O distances; and 7) interstitial positions that imply highly displaced Sr ions. These results contradict the universally accepted features of cuprates that require intact CuO 2 planes, magnetization along the c axis, and a termination of the superconductivity when the excess charge on the CuO 2 Cu ions exceeds 0.27. These radical differences in charge and structure demonstrate that this compound constitutes a separate class of Cu-O–based superconductors in which the superconductivity originates in a different, more complicated structural unit than CuO 2 planes while retaining exceptionally high transition temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1988

Heavy metal toxicity as a kill mechanism in impact caused mass extinctions

Heavy metals that are known to be toxic exist in carbonaceous chrondrites at abundances considerably in excess to that of the terrestrial crust. An impactor of relatively undifferentiated cosmic matter would inject into the terrestrial environment large quantities of toxic elements. The abundances of toxic metals found in the Allende CV carbonaceous chondrite and the ratio of meteoritic abundance to crustal abundance are: Cr, 3630 PPM, 30X; Co, 662 PPM, 23X; ni, 13300 PPm, 134X; se, 8.2 PPM, 164X; Os, 0.828 PPM, 166X. The resulting areal density for global dispersal of impactor derived heavy metals and their dilution with terrestrial ejecta are important factors in the determination of the significance of impactor heavy metal toxicity as a kill mechanism in impact caused mass extinctions. A 10 km-diameter asteroid having a density of 3 gram per cu cm would yield a global areal density of impact dispersed chondritic material of 3 kg per square meter. The present areal density of living matter on the terrestrial land surface is 1 kg per square meter. Dilution of impactor material with terrestrial ejecta is determined by energetics, with the mass of ejecta estimated to be in the range of 10 to 100 times that of the mass of the impactor. Because a pelagic impact would be the most likely case, the result would be a heavy metal rainout.

Wdowiak, T. J.↗
DOE OSTI2021

Effect of Cu on the passivity of Ti–xCu (x = 0, 3 and 5 wt%) alloy in phosphate-buffered saline solution within the framework of PDM-II

The effect of copper content on the passivity of Ti–xCu alloys in a phosphate-buffered saline electrolyte (pH 7.4), in the steady-state condition, was examined using potentiostatic polarization, electrochemical impedance spectroscopy, and Mott-Schottky analysis. The study demonstrates that the oxide layer forms on the Ti–xCu alloys surface have n-type semiconducting character, and the steady-state thickness of the oxide layer is observed linearly and depends on the applied potential. The study observations are in line with the predictions of the Point Defect Model (PDM-II), which provides a physiochemically realistic description of the oxide layer formation on Ti–xCu alloys. The observations reveal that the Cu additions result in a decrease in the charge transfer resistance and capacitances associated with the hydroxide and barrier layer, an increase in the donor density, and reduce the electrochemical resistance of the Ti–xCu alloys. The study also exhibits that the decrease in the steady-state current density after the initial addition of 3 wt% of Cu is attributed to the progressive substitution of copper on the cation sublattice of the film resulting in enhanced electrostatic interaction between the immobilized copper $Cu^{x'}_{Ti}$, and the mobile cation interstitials $Cu^{+}_{i}$, which carries the excess current over and that conveyed by oxygen vacancies $V^{••}_o$ in the barrier layer. Moreover, it is also observed that over a hundred-year implant period, about 0.006 cm (0.06 mm) of Ti–3Cu alloy is predicted to lose due to steady-state corrosion in the PBS solution under the given set of conditions, it is further seen that, as the Cu amount increased from 3 wt% to 5 wt% in the Ti–xCu alloys, the steady-state corrosion rate decreases.

Electrochemical Impedance Spectroscopy↗
DOE OSTI2025

Heterogeneous and Framework-Bound Copper Species Contribute to Catalytic Partial Methane Oxidation in Cu–Chabazite Zeolites

The relationship between continuous partial methane oxidation (PMO) rates and Cu site speciation in Cu-CHA zeolite catalysts is explored through differential rate measurements across a series of samples of varying compositions combined with density functional theory, first-principles thermodynamics, and statistical models that characterize Cu speciation. Under continuous PMO conditions (573 K, 0.07 kPa O 2 , 3 kPa H 2 O), Cu ions are shown to anchor to the CHA framework in both monomeric (Z 2 Cu and Z 2 CuH 2 O) and dimeric (O- and OH-bridged Cu) forms that are sensitive to the identity of the local framework anchoring site. Consequently, across the studied compositional range, Cu-CHA catalysts are predicted to contain a mixture of monomeric and dimeric Cu sites. Cu-normalized CH 3 OH formation rates extrapolated to zero conversion reflect contributions from multiple site types. Predicted CH 3 OH formation rates indicate that the Cu site reactivity toward CH 4 is influenced by zeolite composition and is likely limited by the reduction half-cycle.

03 NATURAL GAS↗
DOE OSTI2020

Materials Data on Cu3OF5 by Materials Project

Cu3OF5 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Cu+2.33+ sites. In the first Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuO2F4 octahedra and edges with two CuF6 octahedra. The corner-sharing octahedra tilt angles range from 45–56°. The Cu–O bond length is 1.82 Å. There are a spread of Cu–F bond distances ranging from 1.91–2.33 Å. In the second Cu+2.33+ site, Cu+2.33+ is bonded to two O2- and four F1- atoms to form a mixture of distorted edge and corner-sharing CuO2F4 octahedra. The corner-sharing octahedra tilt angles range from 43–56°. There is one shorter (1.86 Å) and one longer (1.96 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 1.98–2.33 Å. In the third Cu+2.33+ site, Cu+2.33+ is bonded to six F1- atoms to form CuF6 octahedra that share corners with eight CuO2F4 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 41–58°. There are a spread of Cu–F bond distances ranging from 1.88–2.34 Å. In the fourth Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form distorted CuOF5 octahedra that share corners with eight CuOF5 octahedra and edges with two CuO2F4 octahedra. The corner-sharing octahedra tilt angles range from 41–57°. The Cu–O bond length is 1.96 Å. There are a spread of Cu–F bond distances ranging from 1.97–2.37 Å. In the fifth Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuOF5 octahedra and edges with two CuO2F4 octahedra. The corner-sharing octahedra tilt angles range from 45–58°. The Cu–O bond length is 1.86 Å. There are a spread of Cu–F bond distances ranging from 1.97–2.21 Å. In the sixth Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuO2F4 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 44–57°. The Cu–O bond length is 1.83 Å. There are a spread of Cu–F bond distances ranging from 1.88–2.35 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to three Cu+2.33+ atoms. In the second O2- site, O2- is bonded in a trigonal planar geometry to three Cu+2.33+ atoms. There are ten inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the second F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the third F1- site, F1- is bonded in a trigonal planar geometry to three Cu+2.33+ atoms. In the fourth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the sixth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the seventh F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the eighth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the ninth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the tenth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Oxygen-atom transfer photochemistry of a molecular copper bromate complex

Here, we report the synthesis and oxygen-atom transfer (OAT) photochemistry of [Cu(tpa)BrO 3 ]ClO 4 . In situ spectroscopy and in crystallo experiments indicate OAT proceeds from a Cu–O fragment generated by sequential Cu–O bond cleavage and OAT from BrO x to [Cu(tpa)] + . Furthermore, these results highlight synthetic opportunities in M–O photochemistry and demonstrate the utility of in crystallo experiments to evaluating photochemical reaction mechanisms.

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

Materials Data on In3Cu7 by Materials Project

Cu7In3 is Bergman Structure: Mg32(Al,Zn)49 Bergman-derived structured and crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are fifteen inequivalent Cu sites. In the first Cu site, Cu is bonded to eight Cu and four In atoms to form corner-sharing CuIn4Cu8 cuboctahedra. There are a spread of Cu–Cu bond distances ranging from 2.51–2.66 Å. There are two shorter (2.70 Å) and two longer (2.79 Å) Cu–In bond lengths. In the second Cu site, Cu is bonded to eight Cu and four In atoms to form CuIn4Cu8 cuboctahedra that share corners with two equivalent CuIn4Cu8 cuboctahedra and faces with two equivalent CuIn5Cu7 cuboctahedra. There are a spread of Cu–Cu bond distances ranging from 2.56–2.69 Å. There are two shorter (2.68 Å) and two longer (2.75 Å) Cu–In bond lengths. In the third Cu site, Cu is bonded in a 4-coordinate geometry to eight Cu and five In atoms. There are a spread of Cu–Cu bond distances ranging from 2.49–2.91 Å. There are a spread of Cu–In bond distances ranging from 2.74–3.07 Å. In the fourth Cu site, Cu is bonded in a 12-coordinate geometry to six Cu and six In atoms. There are a spread of Cu–Cu bond distances ranging from 2.62–2.82 Å. There are a spread of Cu–In bond distances ranging from 2.73–3.03 Å. In the fifth Cu site, Cu is bonded to seven Cu and five In atoms to form distorted CuIn5Cu7 cuboctahedra that share corners with two equivalent CuIn4Cu8 cuboctahedra, an edgeedge with one CuIn5Cu7 cuboctahedra, and a faceface with one CuIn4Cu8 cuboctahedra. There are a spread of Cu–Cu bond distances ranging from 2.57–2.71 Å. There are a spread of Cu–In bond distances ranging from 2.72–2.95 Å. In the sixth Cu site, Cu is bonded in a 3-coordinate geometry to eight Cu and five In atoms. There are a spread of Cu–Cu bond distances ranging from 2.58–3.01 Å. There are a spread of Cu–In bond distances ranging from 2.72–3.12 Å. In the seventh Cu site, Cu is bonded in a 12-coordinate geometry to seven Cu and five In atoms. There are a spread of Cu–Cu bond distances ranging from 2.55–3.11 Å. There are a spread of Cu–In bond distances ranging from 2.67–2.90 Å. In the eighth Cu site, Cu is bonded in a 12-coordinate geometry to nine Cu and four In atoms. There are a spread of Cu–Cu bond distances ranging from 2.60–3.12 Å. There are a spread of Cu–In bond distances ranging from 2.65–2.93 Å. In the ninth Cu site, Cu is bonded in a distorted q6 geometry to eight Cu and four In atoms. There are a spread of Cu–Cu bond distances ranging from 2.55–2.70 Å. There are a spread of Cu–In bond distances ranging from 2.77–2.97 Å. In the tenth Cu site, Cu is bonded in a 12-coordinate geometry to six Cu and six In atoms. There are a spread of Cu–Cu bond distances ranging from 2.58–2.95 Å. There are a spread of Cu–In bond distances ranging from 2.70–2.97 Å. In the eleventh Cu site, Cu is bonded in a 4-coordinate geometry to nine Cu and four In atoms. There are one shorter (2.62 Å) and one longer (2.63 Å) Cu–Cu bond lengths. There are a spread of Cu–In bond distances ranging from 2.66–2.90 Å. In the twelfth Cu site, Cu is bonded in a 12-coordinate geometry to eight Cu and four In atoms. The Cu–Cu bond length is 2.57 Å. There are a spread of Cu–In bond distances ranging from 2.79–2.90 Å. In the thirteenth Cu site, Cu is bonded in a 11-coordinate geometry to six Cu and five In atoms. There are a spread of Cu–In bond distances ranging from 2.61–2.83 Å. In the fourteenth Cu site, Cu is bonded in a 11-coordinate geometry to six Cu and five In atoms. There are a spread of Cu–In bond distances ranging from 2.63–2.76 Å. In the fifteenth Cu site, Cu is bonded in a distorted q6 geometry to eight Cu and four In atoms. There are a spread of Cu–In bond distances ranging from 2.80–2.93 Å. There are six inequivalent In sites. In the first In site, In is bonded in a 12-coordinate geometry to eleven Cu and one In atom. The In–In bond length is 3.13 Å. In the second In site, In is bonded in a 9-coordinate geometry to eleven Cu atoms. In the third In site, In is bonded in a 12-coordinate geometry to eleven Cu atoms. In the fourth In site, In is bonded in a 12-coordinate geometry to eleven Cu atoms. In the fifth In site, In is bonded in a 12-coordinate geometry to eleven Cu atoms. In the sixth In site, In is bonded in a 11-coordinate geometry to eleven Cu atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on In4Cu9 by Materials Project

Cu9In4 is gamma-brass-like structured and crystallizes in the cubic P-43m space group. The structure is three-dimensional. there are six inequivalent Cu sites. In the first Cu site, Cu is bonded in a 11-coordinate geometry to six Cu and five In atoms. There are a spread of Cu–Cu bond distances ranging from 2.54–2.98 Å. There are a spread of Cu–In bond distances ranging from 2.67–2.73 Å. In the second Cu site, Cu is bonded in a 4-coordinate geometry to seven Cu and six In atoms. There are one shorter (2.60 Å) and two longer (2.80 Å) Cu–Cu bond lengths. There are a spread of Cu–In bond distances ranging from 2.67–2.98 Å. In the third Cu site, Cu is bonded in a 2-coordinate geometry to nine Cu and four equivalent In atoms. There are a spread of Cu–Cu bond distances ranging from 2.63–2.80 Å. All Cu–In bond lengths are 2.89 Å. In the fourth Cu site, Cu is bonded in a 3-coordinate geometry to nine Cu and four In atoms. All Cu–Cu bond lengths are 2.63 Å. There are three shorter (2.61 Å) and one longer (3.24 Å) Cu–In bond lengths. In the fifth Cu site, Cu is bonded in a distorted q6 geometry to nine Cu and three equivalent In atoms. All Cu–Cu bond lengths are 2.55 Å. All Cu–In bond lengths are 2.79 Å. In the sixth Cu site, Cu is bonded to six Cu and six In atoms to form distorted face-sharing CuIn6Cu6 cuboctahedra. There are three shorter (2.73 Å) and three longer (2.77 Å) Cu–In bond lengths. There are two inequivalent In sites. In the first In site, In is bonded in a 11-coordinate geometry to eleven Cu atoms. In the second In site, In is bonded in a 9-coordinate geometry to ten Cu atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ga4Cu9 by Materials Project

Cu9Ga4 is gamma-brass-like structured and crystallizes in the cubic P-43m space group. The structure is three-dimensional. there are six inequivalent Cu sites. In the first Cu site, Cu is bonded in a 9-coordinate geometry to nine Cu and four equivalent Ga atoms. There are a spread of Cu–Cu bond distances ranging from 2.49–2.76 Å. All Cu–Ga bond lengths are 2.75 Å. In the second Cu site, Cu is bonded in a 11-coordinate geometry to six Cu and five Ga atoms. There are a spread of Cu–Cu bond distances ranging from 2.52–2.79 Å. There are a spread of Cu–Ga bond distances ranging from 2.53–2.61 Å. In the third Cu site, Cu is bonded in a 12-coordinate geometry to six Cu and six Ga atoms. All Cu–Cu bond lengths are 2.67 Å. There are three shorter (2.57 Å) and three longer (2.62 Å) Cu–Ga bond lengths. In the fourth Cu site, Cu is bonded in a 12-coordinate geometry to nine Cu and three equivalent Ga atoms. There are three shorter (2.58 Å) and three longer (2.60 Å) Cu–Cu bond lengths. All Cu–Ga bond lengths are 2.59 Å. In the fifth Cu site, Cu is bonded in a 3-coordinate geometry to nine Cu and three equivalent Ga atoms. All Cu–Ga bond lengths are 2.48 Å. In the sixth Cu site, Cu is bonded in a 4-coordinate geometry to seven Cu and six Ga atoms. The Cu–Cu bond length is 2.51 Å. There are four shorter (2.54 Å) and two longer (2.83 Å) Cu–Ga bond lengths. There are two inequivalent Ga sites. In the first Ga site, Ga is bonded in a 9-coordinate geometry to nine Cu atoms. In the second Ga site, Ga is bonded in a 11-coordinate geometry to eleven Cu atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu6OF11 by Materials Project

Cu6OF11 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Cu+2.17+ sites. In the first Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 45–54°. There are a spread of Cu–F bond distances ranging from 1.91–2.37 Å. In the second Cu+2.17+ site, Cu+2.17+ is bonded to one O2- and five F1- atoms to form distorted CuOF5 octahedra that share corners with eight CuF6 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 43–58°. The Cu–O bond length is 2.07 Å. There are a spread of Cu–F bond distances ranging from 1.95–2.43 Å. In the third Cu+2.17+ site, Cu+2.17+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuOF5 octahedra and edges with two CuF6 octahedra. The corner-sharing octahedra tilt angles range from 43–56°. The Cu–O bond length is 1.85 Å. There are a spread of Cu–F bond distances ranging from 1.93–2.36 Å. In the fourth Cu+2.17+ site, Cu+2.17+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuF6 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 44–56°. The Cu–O bond length is 1.87 Å. There are a spread of Cu–F bond distances ranging from 1.96–2.29 Å. In the fifth Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form CuF6 octahedra that share corners with eight CuF6 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 47–56°. There are a spread of Cu–F bond distances ranging from 1.94–2.35 Å. In the sixth Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form CuF6 octahedra that share corners with eight CuOF5 octahedra and edges with two CuF6 octahedra. The corner-sharing octahedra tilt angles range from 49–58°. There are a spread of Cu–F bond distances ranging from 1.92–2.36 Å. O2- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. There are eleven inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the second F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the fourth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the sixth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the seventh F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the eighth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the ninth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the tenth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the eleventh F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu3OF5 by Materials Project

Cu3OF5 is zeta iron carbide-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Cu+2.33+ sites. In the first Cu+2.33+ site, Cu+2.33+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 46–56°. There are a spread of Cu–F bond distances ranging from 1.91–2.30 Å. In the second Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form distorted CuOF5 octahedra that share corners with eight CuF6 octahedra and edges with two CuO2F4 octahedra. The corner-sharing octahedra tilt angles range from 40–58°. The Cu–O bond length is 1.96 Å. There are a spread of Cu–F bond distances ranging from 1.95–2.35 Å. In the third Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuOF5 octahedra and edges with two CuF6 octahedra. The corner-sharing octahedra tilt angles range from 40–54°. The Cu–O bond length is 1.81 Å. There are a spread of Cu–F bond distances ranging from 1.92–2.34 Å. In the fourth Cu+2.33+ site, Cu+2.33+ is bonded to two O2- and four F1- atoms to form CuO2F4 octahedra that share corners with eight CuF6 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 41–55°. There is one shorter (1.89 Å) and one longer (1.94 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 2.02–2.18 Å. In the fifth Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuF6 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 44–56°. The Cu–O bond length is 1.87 Å. There are a spread of Cu–F bond distances ranging from 1.95–2.23 Å. In the sixth Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuOF5 octahedra and edges with two CuF6 octahedra. The corner-sharing octahedra tilt angles range from 45–58°. The Cu–O bond length is 1.85 Å. There are a spread of Cu–F bond distances ranging from 1.91–2.35 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to three Cu+2.33+ atoms. In the second O2- site, O2- is bonded in a trigonal planar geometry to three Cu+2.33+ atoms. There are ten inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the second F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the fourth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the sixth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the seventh F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the eighth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the ninth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.33+ atoms. In the tenth F1- site, F1- is bonded in a trigonal planar geometry to three Cu+2.33+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu6OF11 by Materials Project

Cu6OF11 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Cu+2.17+ sites. In the first Cu+2.17+ site, Cu+2.17+ is bonded to one O2- and five F1- atoms to form distorted CuOF5 octahedra that share corners with eight CuOF5 octahedra and edges with two CuF6 octahedra. The corner-sharing octahedra tilt angles range from 40–60°. The Cu–O bond length is 1.84 Å. There are a spread of Cu–F bond distances ranging from 1.91–2.42 Å. In the second Cu+2.17+ site, Cu+2.17+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuOF5 octahedra and edges with two CuF6 octahedra. The corner-sharing octahedra tilt angles range from 43–58°. The Cu–O bond length is 1.84 Å. There are a spread of Cu–F bond distances ranging from 1.93–2.39 Å. In the third Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 43–58°. There are a spread of Cu–F bond distances ranging from 1.91–2.41 Å. In the fourth Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form CuF6 octahedra that share corners with eight CuF6 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 47–57°. There are a spread of Cu–F bond distances ranging from 1.93–2.35 Å. In the fifth Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form CuF6 octahedra that share corners with eight CuF6 octahedra and edges with two CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 40–55°. There are a spread of Cu–F bond distances ranging from 1.90–2.41 Å. In the sixth Cu+2.17+ site, Cu+2.17+ is bonded to one O2- and five F1- atoms to form a mixture of distorted edge and corner-sharing CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 40–60°. The Cu–O bond length is 1.99 Å. There are a spread of Cu–F bond distances ranging from 1.95–2.49 Å. O2- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. There are eleven inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the second F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the third F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the fourth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the sixth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the seventh F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the eighth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the ninth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the tenth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the eleventh F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Homologous Alkali Metal Copper Rare-Earth Chalcogenides A 2 Cu 2 n Ln 4 Q 7+ n ( n = 1, 2, 3)

Twenty-seven new members of the A 2 Cu 2n Ln 4 Q 7+n (A = Cs, Rb; Ln = La-Nd, Sm, Gd-Yb; Q = S, Se) homologous series were synthesized in one of three structural types (indicated by n = 1, 2, 3). All the compounds contained 3D frameworks with alkali-metal-containing tunnels. For each increment in n, one Cu 2 Q was added, which was incorporated into the framework as an edge-sharing tetrahedron by replacing a square planar chalcogenide site. High-throughput DFT calculations predicted many of the phases to be thermodynamically stable. These predictions were compared with the synthesis results for the phases formed in each composition space. In the syntheses, heavier lanthanides showed a preference to start forming the n = 3 ACu 3 Ln 2 Q 5 , which is consistent with the predictions. RbCuNd 2 Se 4 and RbCuTb 2 Se 4 were found to be thermally stable under vacuum at temperatures up to 1000 °C. Optical measurements revealed band gaps of 1.55(5) and 1.62(5) eV for CsCuCe 2 Se 4 and RbCuTb 2 Se 4 , respectively, and a work function of 4.83(5) eV for CsCuPr 2 Se 4 . Additionally, some n = 3 ACu 3 Ln 2 Qs compounds exhibit a negative phonon mode because of a copper atom coordination, which may distort to a trigonal planar geometry at sufficiently low temperatures. The dynamic instabilities and the predicted distortion in the copper tetrahedra for the n = 3 ACu 3 Ln 2 Q 5 compounds were found to have a linear relationship with the atomic number of the lanthanides and the electronegativity of the lanthanides. In conclusion, the A 2 Cu 2 n Ln 4 Q 7+n compounds can potentially find application as high-temperature thermoelectric materials and other semiconductors.

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

Materials Data on Cu6OF11 by Materials Project

Cu6OF11 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Cu+2.17+ sites. In the first Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 43–54°. There are a spread of Cu–F bond distances ranging from 1.91–2.34 Å. In the second Cu+2.17+ site, Cu+2.17+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share corners with eight CuF6 octahedra and edges with two equivalent CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 46–57°. The Cu–O bond length is 1.82 Å. There are a spread of Cu–F bond distances ranging from 1.92–2.37 Å. In the third Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 45–56°. There are four shorter (1.92 Å) and two longer (2.35 Å) Cu–F bond lengths. In the fourth Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 47–54°. There are a spread of Cu–F bond distances ranging from 1.94–2.31 Å. In the fifth Cu+2.17+ site, Cu+2.17+ is bonded to two equivalent O2- and four F1- atoms to form distorted CuO2F4 octahedra that share corners with eight CuF6 octahedra and edges with two equivalent CuO2F4 octahedra. The corner-sharing octahedra tilt angles range from 43–57°. There is one shorter (1.88 Å) and one longer (2.07 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 1.97–2.45 Å. In the sixth Cu+2.17+ site, Cu+2.17+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 46–54°. There are a spread of Cu–F bond distances ranging from 1.93–2.28 Å. O2- is bonded in a trigonal planar geometry to three Cu+2.17+ atoms. There are eleven inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the second F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the fourth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the fifth F1- site, F1- is bonded in a 2-coordinate geometry to three Cu+2.17+ atoms. In the sixth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the seventh F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the eighth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the ninth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.17+ atoms. In the tenth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms. In the eleventh F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.17+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu3OF5 by Materials Project

Cu3OF5 is zeta iron carbide-derived structured and crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are four inequivalent Cu+2.33+ sites. In the first Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form a mixture of edge and corner-sharing CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 41–57°. The Cu–O bond length is 1.87 Å. There are a spread of Cu–F bond distances ranging from 1.96–2.19 Å. In the second Cu+2.33+ site, Cu+2.33+ is bonded to one O2- and five F1- atoms to form a mixture of edge and corner-sharing CuOF5 octahedra. The corner-sharing octahedra tilt angles range from 41–57°. The Cu–O bond length is 1.87 Å. There are a spread of Cu–F bond distances ranging from 1.92–2.35 Å. In the third Cu+2.33+ site, Cu+2.33+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 46–53°. There are a spread of Cu–F bond distances ranging from 1.85–2.33 Å. In the fourth Cu+2.33+ site, Cu+2.33+ is bonded to two equivalent O2- and four F1- atoms to form a mixture of edge and corner-sharing CuO2F4 octahedra. The corner-sharing octahedra tilt angles range from 46–52°. Both Cu–O bond lengths are 1.97 Å. There are two shorter (1.97 Å) and two longer (2.03 Å) Cu–F bond lengths. O2- is bonded in a trigonal planar geometry to three Cu+2.33+ atoms. There are five inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.33+ atoms. In the second F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the fourth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu+2.33+ atoms.

36 MATERIALS SCIENCE↗