Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Cu(IN)4”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

A Molecular Compound for Highly Selective Purification of Ethylene

Purification of C 2 H 4 from an C 2 H 4 /C 2 H 6 mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF 3 ) 2 Bp]Cu} 3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF 3 ) 2 Bp]Cu(C 2 H 4 ). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C 2 H 4 /C 2 H 6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In-situ PXRD provides a “live” picture of the reversible conversion between [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) and the ethylene-free sorbent in the solid-state, driven by the presence or removal of C 2 H 4 . As a result, molecular structures of trinuclear {[(CF 3 ) 2 Bp]Cu} 3 and mononuclear [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) are also presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Trans-Bis(acetato-o)bis(4-methylpyridine-N)copper(II)

The structure of trans-bis(acetato-O)bis(4-methyl- pyridine-N)copper(II), (Cu(C2H302)(sub 2)(C6H7N)(sub 2)), re- ported herein, represents a monomeric parent acetate complex with a distorted square-planar arrangement of acetate and 4-methylpyridine ligands around the Cu atom with the following distances and angles: Cu-N = 2.027 (4) and Cu-O1 = 1.950 (3) A; O1-Cu-N = 89.1 (2) and O1 -Cu-N' = 90.9 (2)deg. The Cu atom resides on a center of inversion. The most important dihedral angles are the angle between the 4-methylpyridine plane and the acetate plane (O1, O2, C21 and C22), 78.2 deg and the angle between the 4-methylpyridine ring and the coordination plane (Cu, N, O1), 31.6 deg.

Jedrzejas, Marek J.↗
DOE OSTI2020

Materials Data on SrCu9Si4 by Materials Project

SrCu9Si4 crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Sr2+ is bonded in a 8-coordinate geometry to eight equivalent Si4- atoms. All Sr–Si bond lengths are 3.39 Å. There are three inequivalent Cu+1.56+ sites. In the first Cu+1.56+ site, Cu+1.56+ is bonded in a 7-coordinate geometry to three Cu+1.56+ and four equivalent Si4- atoms. There are two shorter (2.46 Å) and one longer (2.47 Å) Cu–Cu bond lengths. There are two shorter (2.52 Å) and two longer (2.57 Å) Cu–Si bond lengths. In the second Cu+1.56+ site, Cu+1.56+ is bonded in a 4-coordinate geometry to one Cu+1.56+ and four equivalent Si4- atoms. The Cu–Cu bond length is 2.56 Å. There are a spread of Cu–Si bond distances ranging from 2.41–2.60 Å. In the third Cu+1.56+ site, Cu+1.56+ is bonded in a 12-coordinate geometry to eight Cu+1.56+ and four equivalent Si4- atoms. All Cu–Si bond lengths are 2.44 Å. Si4- is bonded to two equivalent Sr2+, nine Cu+1.56+, and one Si4- atom to form a mixture of distorted corner and face-sharing SiSr2Cu9Si cuboctahedra. The Si–Si bond length is 2.70 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on BaCu9Si4 by Materials Project

BaCu9Si4 crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Ba2+ is bonded in a 8-coordinate geometry to eight equivalent Si4- atoms. All Ba–Si bond lengths are 3.42 Å. There are three inequivalent Cu+1.56+ sites. In the first Cu+1.56+ site, Cu+1.56+ is bonded in a 7-coordinate geometry to three Cu+1.56+ and four equivalent Si4- atoms. There are one shorter (2.48 Å) and two longer (2.50 Å) Cu–Cu bond lengths. There are two shorter (2.54 Å) and two longer (2.58 Å) Cu–Si bond lengths. In the second Cu+1.56+ site, Cu+1.56+ is bonded in a 4-coordinate geometry to one Cu+1.56+ and four equivalent Si4- atoms. The Cu–Cu bond length is 2.57 Å. There are a spread of Cu–Si bond distances ranging from 2.46–2.61 Å. In the third Cu+1.56+ site, Cu+1.56+ is bonded in a 12-coordinate geometry to eight Cu+1.56+ and four equivalent Si4- atoms. All Cu–Si bond lengths are 2.45 Å. Si4- is bonded to two equivalent Ba2+, nine Cu+1.56+, and one Si4- atom to form a mixture of distorted face and corner-sharing SiBa2Cu9Si cuboctahedra. The Si–Si bond length is 2.70 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu9S5 by Materials Project

Cu9S5 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are nine inequivalent Cu+1.11+ sites. In the first Cu+1.11+ site, Cu+1.11+ is bonded in a 3-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.30–2.77 Å. In the second Cu+1.11+ site, Cu+1.11+ is bonded in a 4-coordinate geometry to five S2- atoms. There are a spread of Cu–S bond distances ranging from 2.38–2.91 Å. In the third Cu+1.11+ site, Cu+1.11+ is bonded in a tetrahedral geometry to four S2- atoms. There are one shorter (2.37 Å) and three longer (2.38 Å) Cu–S bond lengths. In the fourth Cu+1.11+ site, Cu+1.11+ is bonded in a 4-coordinate geometry to six S2- atoms. There are a spread of Cu–S bond distances ranging from 2.46–3.14 Å. In the fifth Cu+1.11+ site, Cu+1.11+ is bonded in a distorted trigonal planar geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.28–2.85 Å. In the sixth Cu+1.11+ site, Cu+1.11+ is bonded in a 4-coordinate geometry to five S2- atoms. There are a spread of Cu–S bond distances ranging from 2.38–3.15 Å. In the seventh Cu+1.11+ site, Cu+1.11+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.29–2.75 Å. In the eighth Cu+1.11+ site, Cu+1.11+ is bonded in a 4-coordinate geometry to six S2- atoms. There are a spread of Cu–S bond distances ranging from 2.41–3.10 Å. In the ninth Cu+1.11+ site, Cu+1.11+ is bonded in a distorted trigonal planar geometry to three S2- atoms. There are a spread of Cu–S bond distances ranging from 2.30–2.34 Å. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded in a 9-coordinate geometry to six Cu+1.11+ atoms. In the second S2- site, S2- is bonded in a 9-coordinate geometry to nine Cu+1.11+ atoms. In the third S2- site, S2- is bonded in a 9-coordinate geometry to nine Cu+1.11+ atoms. In the fourth S2- site, S2- is bonded in a 9-coordinate geometry to nine Cu+1.11+ atoms. In the fifth S2- site, S2- is bonded in a distorted hexagonal bipyramidal geometry to eight Cu+1.11+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Structural and physical properties of two distinct 2D lead halides with intercalated Cu( II )

Transition metal cation intercalation between the layers of two-dimensional (2D) metal halides is an underexplored research area. In this work we focus on the synthesis and physical property characterizations of two layered hybrid lead halides: a new compound [Cu(O 2 C–CH 2 –NH 2 ) 2 ]Pb 2 Br 4 and the previously reported [Cu(O 2 C–(CH 2 ) 3 –NH 3 ) 2 ]PbBr 4 . These compounds exhibit 2D layered crystal structures with incorporated Cu 2+ between the metal halide layers, which is achieved by combining Cu(II) and lead bromide with suitable amino acid precursors. The resultant [Cu(O 2 C–(CH 2 ) 3 –NH 3 ) 2 ]PbBr 4 adopts a 2D layered perovskite structure, whereas the new compound [Cu(O 2 C–CH 2 –NH 2 ) 2 ]Pb 2 Br 4 crystallizes with a new structure type based on edge-sharing dodecahedral PbBr5O3 building blocks. [Cu(O 2 C–CH 2 –NH 2 ) 2 ]Pb 2 Br 4 is a semiconductor with a bandgap of 3.25 eV. It shows anisotropic charge transport properties with a semiconductor resistivity of 1.44 × 10 10 Ω cm (measured along the a-axis) and 2.17 × 10 10 Ω cm (along the bc-plane), respectively. The fabricated prototype detector based on this material showed response to soft low-energy X-rays at 8 keV with a detector sensitivity of 1462.7 μCGy –1 cm –2 , indicating its potential application for ionizing radiation detection. Finally, these encouraging results are discussed together with the results from density functional theory calculations, optical, magnetic, and thermal property characterization experiments.

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

Materials Data on Ba6Cu34S27 by Materials Project

Ba6Cu34S27 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Ba–S bond distances ranging from 3.17–3.76 Å. In the second Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Ba–S bond distances ranging from 3.18–3.54 Å. In the third Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Ba–S bond distances ranging from 3.15–3.41 Å. In the fourth Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Ba–S bond distances ranging from 3.16–3.40 Å. In the fifth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Ba–S bond distances ranging from 3.17–3.73 Å. In the sixth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Ba–S bond distances ranging from 3.17–3.46 Å. There are thirty-four inequivalent Cu+1.24+ sites. In the first Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of distorted edge and corner-sharing CuS4 trigonal pyramids. There are a spread of Cu–S bond distances ranging from 2.25–2.93 Å. In the second Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of distorted edge and corner-sharing CuS4 trigonal pyramids. There are a spread of Cu–S bond distances ranging from 2.24–2.81 Å. In the third Cu+1.24+ site, Cu+1.24+ is bonded in a trigonal non-coplanar geometry to three S2- atoms. There are a spread of Cu–S bond distances ranging from 2.26–2.38 Å. In the fourth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.33–2.43 Å. In the fifth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.31–2.46 Å. In the sixth Cu+1.24+ site, Cu+1.24+ is bonded in a trigonal non-coplanar geometry to three S2- atoms. There are a spread of Cu–S bond distances ranging from 2.26–2.36 Å. In the seventh Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.31–2.39 Å. In the eighth Cu+1.24+ site, Cu+1.24+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.24–2.97 Å. In the ninth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.33–2.43 Å. In the tenth Cu+1.24+ site, Cu+1.24+ is bonded in a trigonal non-coplanar geometry to three S2- atoms. There are a spread of Cu–S bond distances ranging from 2.25–2.38 Å. In the eleventh Cu+1.24+ site, Cu+1.24+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.26–3.02 Å. In the twelfth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 trigonal pyramids. There are a spread of Cu–S bond distances ranging from 2.27–2.54 Å. In the thirteenth Cu+1.24+ site, Cu+1.24+ is bonded in a 3-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.27–2.95 Å. In the fourteenth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.30–2.47 Å. In the fifteenth Cu+1.24+ site, Cu+1.24+ is bonded in a distorted trigonal planar geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.24–3.00 Å. In the sixteenth Cu+1.24+ site, Cu+1.24+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.25–2.87 Å. In the seventeenth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.32–2.39 Å. In the eighteenth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.32–2.39 Å. In the nineteenth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of distorted edge and corner-sharing CuS4 trigonal pyramids. There are a spread of Cu–S bond distances ranging from 2.25–2.88 Å. In the twentieth Cu+1.24+ site, Cu+1.24+ is bonded in a 3-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.29–2.93 Å. In the twenty-first Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.30–2.51 Å. In the twenty-second Cu+1.24+ site, Cu+1.24+ is bonded in a distorted trigonal planar geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.24–3.02 Å. In the twenty-third Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 trigonal pyramids. There are a spread of Cu–S bond distances ranging from 2.26–2.54 Å. In the twenty-fourth Cu+1.24+ site, Cu+1.24+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.24–3.04 Å. In the twenty-fifth Cu+1.24+ site, Cu+1.24+ is bonded in a trigonal non-coplanar geometry to three S2- atoms. There are a spread of Cu–S bond distances ranging from 2.25–2.38 Å. In the twenty-sixth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.32–2.45 Å. In the twenty-seventh Cu+1.24+ site, Cu+1.24+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.25–2.96 Å. In the twenty-eighth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.30–2.39 Å. In the twenty-ninth Cu+1.24+ site, Cu+1.24+ is bonded in a distorted trigonal non-coplanar geometry to three S2- atoms. There are a spread of Cu–S bond distances ranging from 2.26–2.37 Å. In the thirtieth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.31–2.46 Å. In the thirty-first Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.32–2.41 Å. In the thirty-second Cu+1.24+ site, Cu+1.24+ is bonded in a trigonal non-coplanar geometry to three S2- atoms. There are a spread of Cu–S bond distances ranging from 2.26–2.37 Å. In the thirty-third Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of distorted edge and corner-sharing CuS4 trigonal pyramids. There are a spread of Cu–S bond distances ranging from 2.24–2.82 Å. In the thirty-fourth Cu+1.24+ site, Cu+1.24+ is bonded to four S2- atoms to form a mixture of distorted edge and corner-sharing CuS4 trigonal pyramids. There are a spread of Cu–S bond distances ranging from 2.25–2.93 Å. There are twenty-seven inequivalent S2- sites. In the first S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the second S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the third S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the fourth S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the fifth S2- site, S2- is bonded in a 8-coordinate geometry to two Ba2+ and six Cu+1.24+ atoms. In the sixth S2- site, S2- is bonded in a 7-coordinate geometry to three Ba2+ and four Cu+1.24+ atoms. In the seventh S2- site, S2- is bonded in a 7-coordinate geometry to two Ba2+ and five Cu+1.24+ atoms. In the eighth S2- site, S2- is bonded in a 7-coordinate geometry to three Ba2+ and four Cu+1.24+ atoms. In the ninth S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the tenth S2- site, S2- is bonded in a distorted octahedral geometry to three Ba2+ and three Cu+1.24+ atoms. In the eleventh S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the twelfth S2- site, S2- is bonded in a 7-coordinate geometry to two Ba2+ and five Cu+1.24+ atoms. In the thirteenth S2- site, S2- is bonded in a 2-coordinate geometry to three Ba2+ and two Cu+1.24+ atoms. In the fourteenth S2- site, S2- is bonded in a distorted water-like geometry to three Ba2+, two Cu+1.24+, and one S2- atom. The S–S bond length is 2.16 Å. In the fifteenth S2- site, S2- is bonded in a 7-coordinate geometry to two Ba2+ and five Cu+1.24+ atoms. In the sixteenth S2- site, S2- is bonded in a 6-coordinate geometry to five Ba2+ and one S2- atom. In the seventeenth S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the eighteenth S2- site, S2- is bonded in a distorted octahedral geometry to three Ba2+ and three Cu+1.24+ atoms. In the nineteenth S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the twentieth S2- site, S2- is bonded in a 7-coordinate geometry to three Ba2+ and four Cu+1.24+ atoms. In the twenty-first S2- site, S2- is bonded in a 7-coordinate geometry to two Ba2+ and five Cu+1.24+ atoms. In the twenty-second S2- site, S2- is bonded in a 7-coordinate geometry to three Ba2+ and four Cu+1.24+ atoms. In the twenty-third S2- site, S2- is bonded in a 8-coordinate geometry to two Ba2+ and six Cu+1.24+ atoms. In the twenty-fourth S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the twenty-fifth S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the twenty-sixth S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms. In the twenty-seventh S2- site, S2- is bonded in a 7-coordinate geometry to one Ba2+ and six Cu+1.24+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Co8Cu7(MoO4)12 by Materials Project

Co8Cu7(MoO4)12 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are eight inequivalent Mo6+ sites. In the first Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with two CuO6 octahedra and corners with three CoO6 octahedra. The corner-sharing octahedra tilt angles range from 26–58°. There are a spread of Mo–O bond distances ranging from 1.79–1.85 Å. In the second Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with two CuO6 octahedra and corners with three CoO6 octahedra. The corner-sharing octahedra tilt angles range from 26–60°. There is two shorter (1.79 Å) and two longer (1.85 Å) Mo–O bond length. In the third Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share a cornercorner with one CuO6 octahedra and corners with three CoO6 octahedra. The corner-sharing octahedra tilt angles range from 19–59°. There are a spread of Mo–O bond distances ranging from 1.75–1.86 Å. In the fourth Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share a cornercorner with one CuO6 octahedra and corners with three CoO6 octahedra. The corner-sharing octahedra tilt angles range from 45–60°. There are a spread of Mo–O bond distances ranging from 1.75–1.86 Å. In the fifth Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share a cornercorner with one CuO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 44–63°. There are a spread of Mo–O bond distances ranging from 1.73–1.86 Å. In the sixth Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share a cornercorner with one CuO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 16–63°. There are a spread of Mo–O bond distances ranging from 1.73–1.85 Å. In the seventh Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with two CuO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 21–63°. There are a spread of Mo–O bond distances ranging from 1.77–1.85 Å. In the eighth Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with two CuO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 21–63°. There are a spread of Mo–O bond distances ranging from 1.76–1.84 Å. There are four inequivalent Co2+ sites. In the first Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one CoO6 octahedra, corners with six MoO4 tetrahedra, and edges with two equivalent CoO6 octahedra. The corner-sharing octahedral tilt angles are 56°. There are a spread of Co–O bond distances ranging from 2.07–2.21 Å. In the second Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one CoO6 octahedra, corners with six MoO4 tetrahedra, and edges with two equivalent CoO6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of Co–O bond distances ranging from 2.05–2.19 Å. In the third Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one CoO6 octahedra, corners with six MoO4 tetrahedra, and edges with two equivalent CoO6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are a spread of Co–O bond distances ranging from 2.05–2.16 Å. In the fourth Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one CoO6 octahedra, corners with six MoO4 tetrahedra, and edges with two equivalent CoO6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are a spread of Co–O bond distances ranging from 2.04–2.16 Å. There are seven inequivalent Cu+1.14+ sites. In the first Cu+1.14+ site, Cu+1.14+ is bonded in a 4-coordinate geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 2.05–2.60 Å. In the second Cu+1.14+ site, Cu+1.14+ is bonded in a 4-coordinate geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 2.05–2.60 Å. In the third Cu+1.14+ site, Cu+1.14+ is bonded in a 4-coordinate geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 2.05–2.62 Å. In the fourth Cu+1.14+ site, Cu+1.14+ is bonded in a 4-coordinate geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 2.04–2.62 Å. In the fifth Cu+1.14+ site, Cu+1.14+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with six MoO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 2.07–2.24 Å. In the sixth Cu+1.14+ site, Cu+1.14+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with six MoO4 tetrahedra and faces with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 2.11–2.26 Å. In the seventh Cu+1.14+ site, Cu+1.14+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with six MoO4 tetrahedra and faces with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 2.10–2.28 Å. There are twenty-eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Mo6+ and one Cu+1.14+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Mo6+ and one Cu+1.14+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the fifth O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+, one Co2+, and one Cu+1.14+ atom. In the sixth O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+, one Co2+, and one Cu+1.14+ atom. In the seventh O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+, one Co2+, and one Cu+1.14+ atom. In the eighth O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+, one Co2+, and one Cu+1.14+ atom. In the ninth O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+ and two equivalent Co2+ atoms. In the tenth O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+ and two equivalent Co2+ atoms. In the eleventh O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+ and two equivalent Co2+ atoms. In the twelfth O2- site, O2- is bonded in a trigonal planar geometry to one Mo6+ and two equivalent Co2+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted linear geometry to one Mo6+ and one Cu+1.14+ atom. In the fourteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Mo6+ and one Cu+1.14+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the sixteenth O2- site, O2- is bonded in a 1-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the seventeenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms. In the eighteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms. In the nineteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms. In the twentieth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms. In the twenty-first O2- site, O2- is bonded in a 2-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the twenty-second O2- site, O2- is bonded in a 2-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the twenty-third O2- site, O2- is bonded in a 2-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the twenty-fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Mo6+ and two Cu+1.14+ atoms. In the twenty-fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms. In the twenty-sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms. In the twenty-seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms. In the twenty-eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mo6+ and two Co2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Employing Long-Range Inductive Effects to Modulate Metal-to-Ligand Charge Transfer Photoluminescence in Homoleptic Cu(I) Complexes

Four Cu(I) bis(phenanthroline) photosensitizers formulated from a new ligand structural motif (Cu1-Cu4) coded according to their 2,9-substituents, were synthesized, structurally characterized, and fully evaluated using steady-state and time-resolved absorption and photoluminescence (PL) measurements as well as electrochemistry. The 2,9-disubstituted-3,4,7,8-tetramethyl-1,10-phenanthroline ligands feature the following six-membered ring systems prepared through photochemical synthesis: 4,4-dimethylcyclohexyl (1), tetrahydro-2H-pyran-4-yl (2), tetrahydro-2H-thiopyran-4-yl (3), and 4,4-difluorocyclohexyl (4). Universally, these Cu(I) metal-to-ligand charge transfer (MLCT) chromophores display excited state lifetimes on the microseconds time scale at room temperature, including the three longest-lived homoleptic cuprous phenanthroline excited states measured to date in deaerated CH 2 Cl 2 , τ = 2.5 to 4.3 μs. This series of molecules also feature high PL quantum efficiencies (ΦPL = 5.3 to 12% in CH 2 Cl 2 ). Temperature-dependent PL lifetime experiments confirmed that all these molecules exhibit reverse intersystem crossing and display thermally activated delayed PL from a 1 MLCT excited state lying slightly above the 3 MLCT state, 1050 – 1490 cm -1 . Ultrafast and conventional transient absorption measurements confirmed that the PL originates from the MLCT excited state, which remains sterically arrested, preventing an excessive flattening distortion even when dissolved in Lewis basic CH 3 CN. Combined PL and electrochemical data provided evidence that Cu1-Cu4 are highly potent photoreductants (E ox * = -1.73 to -1.62 V vs. Fc +/o in CH 3 CN), whose potentials are altered solely based on which heteroatoms or substituents are resident on the 2,9-appended ring derivatives. It is proposed that long-range electronic inductive effects are responsible for the systematic modulation observed in the PL spectra, excited state lifetimes, as well as the ground state absorption spectra and redox potentials. Cu1-Cu4 quantitatively follow the energy gap law, correlating well with structurally related cuprous phenanthrolines and are also shown to triplet photosensitize the excited states of 9,10-diphenylanthracene with bimolecular rate constants ranging from 1.61 to 2.82 × 10 8 M –1 s –1 . Furthermore, the ability to tailor both photophysical and electrochemical properties using long-range inductive effects imposed by the 2,9-ring platforms advocates new directions for future MLCT chromophore discovery.

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

Materials Data on LiCu3(CO3)3 by Materials Project

LiCu3(CO3)3 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with two equivalent CuO4 tetrahedra and edges with two equivalent LiO5 trigonal bipyramids. There are a spread of Li–O bond distances ranging from 1.99–2.23 Å. In the second Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 2.00–2.25 Å. In the third Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 2.00–2.28 Å. There are nine inequivalent Cu+1.67+ sites. In the first Cu+1.67+ site, Cu+1.67+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.88–2.40 Å. In the second Cu+1.67+ site, Cu+1.67+ is bonded in a 4-coordinate geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.94–2.59 Å. In the third Cu+1.67+ site, Cu+1.67+ is bonded in a 4-coordinate geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.93–2.55 Å. In the fourth Cu+1.67+ site, Cu+1.67+ 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 1.90–2.17 Å. In the fifth Cu+1.67+ site, Cu+1.67+ is bonded to four O2- atoms to form corner-sharing CuO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.92–2.21 Å. In the sixth Cu+1.67+ site, Cu+1.67+ is bonded to four O2- atoms to form distorted CuO4 tetrahedra that share corners with two equivalent CuO4 tetrahedra and corners with two equivalent LiO5 trigonal bipyramids. There are a spread of Cu–O bond distances ranging from 1.94–2.23 Å. In the seventh Cu+1.67+ site, Cu+1.67+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.96–2.19 Å. In the eighth Cu+1.67+ site, Cu+1.67+ is bonded to four O2- atoms to form distorted corner-sharing CuO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.94–2.13 Å. In the ninth Cu+1.67+ site, Cu+1.67+ is bonded to four O2- atoms to form corner-sharing CuO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.89–2.26 Å. There are nine inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.28 Å) and one longer (1.32 Å) C–O bond length. 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 1.27–1.31 Å. In the third 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 1.27–1.33 Å. In the fourth 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 1.27–1.33 Å. In the fifth 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 1.29–1.31 Å. In the sixth 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 1.28–1.33 Å. In the seventh C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.28 Å) and one longer (1.32 Å) C–O bond length. In the eighth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.28 Å) and one longer (1.32 Å) C–O bond length. In the ninth 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 1.28–1.32 Å. There are twenty-seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted water-like geometry to two Cu+1.67+ and one C4+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the third O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two equivalent Cu+1.67+, and one C4+ atom. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent Cu+1.67+ and one C4+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to two Cu+1.67+ and one C4+ atom. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent Li1+, one Cu+1.67+, and one C4+ atom. In the eighth O2- site, O2- is bonded to two equivalent Li1+, one Cu+1.67+, and one C4+ atom to form distorted OLi2CuC tetrahedra that share corners with six OLiCu2C tetrahedra and an edgeedge with one OLi2CuC tetrahedra. In the ninth O2- site, O2- is bonded to two equivalent Li1+, one Cu+1.67+, and one C4+ atom to form distorted corner-sharing OLi2CuC tetrahedra. In the tenth O2- site, O2- is bonded to two equivalent Li1+, one Cu+1.67+, and one C4+ atom to form distorted OLi2CuC tetrahedra that share corners with six OLiCu2C tetrahedra and an edgeedge with one OLi2CuC tetrahedra. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to two Cu+1.67+ and one C4+ atom. In the twelfth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the thirteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the fourteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the fifteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu+1.67+ and one C4+ atom. In the sixteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu+1.67+ and one C4+ atom. In the seventeenth O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Cu+1.67+ and one C4+ atom. In the eighteenth O2- site, O2- is bonded to one Li1+, two equivalent Cu+1.67+, and one C4+ atom to form distorted corner-sharing OLiCu2C tetrahedra. In the nineteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu+1.67+ and one C4+ atom. In the twentieth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the twenty-first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the twenty-second O2- site, O2- is bonded to two equivalent Li1+, one Cu+1.67+, and one C4+ atom to form distorted OLi2CuC tetrahedra that share corners with six OLiCu2C tetrahedra and an edgeedge with one OLi2CuC tetrahedra. In the twenty-third O2- site, O2- is bonded in a distorted water-like geometry to one Cu+1.67+ and one C4+ atom. In the twenty-fourth O2- site, O2- is bonded to two equivalent Li1+, one Cu+1.67+, and one C4+ atom to form distorted OLi2CuC tetrahedra that share corners with six OLiCu2C tetrahedra and an edgeedge with one OLi2CuC tetrahedra. In the twenty-fifth O2- site, O2- is bonded in a bent 120 degrees geometry to one Cu+1.67+ and one C4+ atom. In the twenty-sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu+1.67+ and one C4+ atom. In the twenty-seventh O2- site, O2- is bonded to one Li1+, two equivalent Cu+1.67+, and one C4+ atom to form distorted corner-sharing OLiCu2C tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Off-stoichiometric semiconductors Cu 1.33+x Zn 1.33-x In 1.33 Se 4 (x = 0, 0.1, 0.2 and 0.3): Synthesis, structure, and thermal and electrical properties

The synthesis, structure, and temperature dependent thermal and electrical properties of off-stoichiometric polycrystalline modified zinc blende quaternary chalcogenides Cu 1.33+x Zn 1.33-x In 1.33 Se 4 , where x = 0, 0.1, 0.2 and 0.3, are investigated. Temperature-dependent electrical properties reveal these compositions to be semiconductors with alteration of the carrier concentration and electrical transport via stoichiometric variation. The thermal conductivity is low for all specimens and intrinsic to these materials. First principles calculations are also reported in establishing a fundamental investigation that illustrates the large variation in stoichiometry that is possible in these materials. This stoichiometric variation results in the observed variation of the transport properties. Overall, the results presented reveal fundamental structure-property relationships in these quaternary chalcogenides, and provides a basis for further research into the viability for large stoichiometric variation in other materials that are of interest for technological applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 four equivalent BiS5 square pyramids, corners with two equivalent CuS4 tetrahedra, and an edgeedge with one BiS5 square pyramid. There are a spread of Cu–S bond distances ranging from 2.29–2.36 Å. In the second Cu+1.50+ site, Cu+1.50+ is bonded in a distorted trigonal planar geometry to four S2- atoms. There are a spread of Cu–S bond distances ranging from 2.23–3.06 Å. In the third Cu+1.50+ site, Cu+1.50+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three equivalent BiS6 octahedra, corners with two equivalent CuS4 trigonal pyramids, and edges with two equivalent CuS4 trigonal pyramids. The corner-sharing octahedra tilt angles range from 2–77°. There are a spread of Cu–S bond distances ranging from 2.26–2.61 Å. In the fourth Cu+1.50+ site, Cu+1.50+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with two equivalent BiS6 octahedra, a cornercorner with one BiS5 square pyramid, corners with two equivalent CuS4 tetrahedra, and an edgeedge with one BiS6 octahedra. The corner-sharing octahedral tilt angles are 30°. There are a spread of Cu–S bond distances ranging from 2.27–2.41 Å. There are four inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to five S2- atoms to form distorted BiS5 square pyramids that share corners with five CuS4 tetrahedra, edges with two equivalent BiS5 square pyramids, and an edgeedge with one CuS4 tetrahedra. There are a spread of Bi–S bond distances ranging from 2.61–3.07 Å. In the second Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to seven S2- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.44 Å. In the third 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 2.69–3.13 Å. In the fourth Bi3+ site, Bi3+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with two equivalent CuS4 tetrahedra, corners with three equivalent CuS4 trigonal pyramids, edges with four equivalent BiS6 octahedra, and an edgeedge with one CuS4 tetrahedra. There are a spread of Bi–S bond distances ranging from 2.73–3.01 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 in a 4-coordinate geometry to one Cu+1.50+ and three Bi3+ atoms. In the fourth S2- site, S2- is bonded in a 6-coordinate geometry to three Cu+1.50+ and three Bi3+ atoms. In the fifth S2- site, S2- is bonded to three equivalent Cu+1.50+ and three Bi3+ atoms to form distorted edge-sharing SCu3Bi3 octahedra. 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 5-coordinate geometry to five Bi3+ atoms. In the eighth S2- site, S2- is bonded in a 4-coordinate geometry to three Cu+1.50+ and one S2- atom. The S–S bond length is 2.15 Å. In the ninth S2- site, S2- is bonded in a 4-coordinate geometry to one Cu+1.50+, two equivalent Bi3+, and one S2- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Observation of an Intermediate to H 2 Binding in a Metal–Organic Framework

Coordinatively unsaturated metal sites within certain zeolites and metal–organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H 2 at the trigonal pyramidal Cu + sites in the metal–organic framework Cu I -MFU- 4 l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. Here, the activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu + coordination environment that enhances p-backbonding with H 2 . Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

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

Materials Data on Cu19Se11 by Materials Project

Cu19Se11 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are nineteen inequivalent Cu+1.16+ sites. In the first Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form corner-sharing CuSe4 trigonal pyramids. There are a spread of Cu–Se bond distances ranging from 2.38–2.55 Å. In the second Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form distorted corner-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.35–2.63 Å. In the third Cu+1.16+ site, Cu+1.16+ is bonded in a 2-coordinate geometry to two equivalent Se2- atoms. There are one shorter (2.47 Å) and one longer (2.53 Å) Cu–Se bond lengths. In the fourth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form distorted corner-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.42–2.60 Å. In the fifth Cu+1.16+ site, Cu+1.16+ is bonded to one Cu+1.16+ and four Se2- atoms to form CuCuSe4 tetrahedra that share corners with nine CuSe4 tetrahedra and edges with three equivalent CuCu3Se4 tetrahedra. The Cu–Cu bond length is 2.51 Å. There are a spread of Cu–Se bond distances ranging from 2.41–2.54 Å. In the sixth Cu+1.16+ site, Cu+1.16+ is bonded in a 3-coordinate geometry to four Cu+1.16+ and six Se2- atoms. There are one shorter (2.50 Å) and two longer (2.51 Å) Cu–Cu bond lengths. There are a spread of Cu–Se bond distances ranging from 2.51–3.23 Å. In the seventh Cu+1.16+ site, Cu+1.16+ is bonded to three equivalent Cu+1.16+ and four Se2- atoms to form distorted CuCu3Se4 tetrahedra that share corners with three equivalent CuSe4 tetrahedra and edges with nine CuCuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.47–2.56 Å. In the eighth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form corner-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.42–2.49 Å. In the ninth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form a mixture of corner and edge-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.51–2.54 Å. In the tenth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form a mixture of corner and edge-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.45–2.51 Å. In the eleventh Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form a mixture of corner and edge-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.35–2.53 Å. In the twelfth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form a mixture of distorted corner and edge-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.57–2.67 Å. In the thirteenth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form a mixture of corner and edge-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.41–2.57 Å. In the fourteenth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form distorted corner-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.56–2.66 Å. In the fifteenth Cu+1.16+ site, Cu+1.16+ is bonded to four Se2- atoms to form a mixture of corner and edge-sharing CuSe4 tetrahedra. There are a spread of Cu–Se bond distances ranging from 2.44–2.57 Å. In the sixteenth Cu+1.16+ site, Cu+1.16+ is bonded in a 3-coordinate geometry to three Se2- atoms. There are a spread of Cu–Se bond distances ranging from 2.69–2.90 Å. In the seventeenth Cu+1.16+ site, Cu+1.16+ is bonded in a distorted trigonal non-coplanar geometry to three equivalent Se2- atoms. There are one shorter (2.44 Å) and two longer (2.47 Å) Cu–Se bond lengths. In the eighteenth Cu+1.16+ site, Cu+1.16+ is bonded in a 2-coordinate geometry to three equivalent Se2- atoms. There are a spread of Cu–Se bond distances ranging from 2.65–3.03 Å. In the nineteenth Cu+1.16+ site, Cu+1.16+ is bonded in a 3-coordinate geometry to four Se2- atoms. There are a spread of Cu–Se bond distances ranging from 2.46–2.97 Å. There are eleven inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a 8-coordinate geometry to eight Cu+1.16+ atoms. In the second Se2- site, Se2- is bonded to four Cu+1.16+ atoms to form corner-sharing SeCu4 trigonal pyramids. In the third Se2- site, Se2- is bonded in a distorted hexagonal planar geometry to six Cu+1.16+ atoms. In the fourth Se2- site, Se2- is bonded in a 4-coordinate geometry to four Cu+1.16+ atoms. In the fifth Se2- site, Se2- is bonded in a 5-coordinate geometry to seven Cu+1.16+ atoms. In the sixth Se2- site, Se2- is bonded in a 4-coordinate geometry to seven Cu+1.16+ atoms. In the seventh Se2- site, Se2- is bonded to four Cu+1.16+ atoms to form corner-sharing SeCu4 tetrahedra. In the eighth Se2- site, Se2- is bonded in a 7-coordinate geometry to seven Cu+1.16+ atoms. In the ninth Se2- site, Se2- is bonded in a body-centered cubic geometry to eight Cu+1.16+ atoms. In the tenth Se2- site, Se2- is bonded in a 7-coordinate geometry to eight Cu+1.16+ atoms. In the eleventh Se2- site, Se2- is bonded in a 3-coordinate geometry to ten Cu+1.16+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ce2Ga5Cu3 by Materials Project

Ce2Cu3Ga5 crystallizes in the tetragonal P-4m2 space group. The structure is three-dimensional. Ce is bonded in a 12-coordinate geometry to six Cu and ten Ga atoms. There are four shorter (3.29 Å) and two longer (3.34 Å) Ce–Cu bond lengths. There are a spread of Ce–Ga bond distances ranging from 3.22–3.34 Å. There are three inequivalent Cu sites. In the first Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent Ce and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.45 Å. In the second Cu site, Cu is bonded to four equivalent Ce and eight Ga atoms to form distorted CuCe4Ga8 cuboctahedra that share corners with four equivalent CuCe4Ga8 cuboctahedra, faces with four equivalent CuCe4Ga8 cuboctahedra, and faces with four equivalent GaCe4Ga4Cu4 cuboctahedra. There are four shorter (2.52 Å) and four longer (2.99 Å) Cu–Ga bond lengths. In the third Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent Ce and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.45 Å. There are three inequivalent Ga sites. In the first Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent Ce, two equivalent Cu, and three Ga atoms. There are one shorter (2.48 Å) and two longer (2.52 Å) Ga–Ga bond lengths. In the second Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent Ce, four Cu, and one Ga atom. In the third Ga site, Ga is bonded to four equivalent Ce, four equivalent Cu, and four equivalent Ga atoms to form GaCe4Ga4Cu4 cuboctahedra that share corners with four equivalent GaCe4Ga4Cu4 cuboctahedra, faces with four equivalent CuCe4Ga8 cuboctahedra, and faces with four equivalent GaCe4Ga4Cu4 cuboctahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on La2Ga5Cu3 by Materials Project

La2Cu3Ga5 crystallizes in the tetragonal P-4m2 space group. The structure is three-dimensional. La is bonded in a 12-coordinate geometry to six Cu and ten Ga atoms. There are four shorter (3.33 Å) and two longer (3.37 Å) La–Cu bond lengths. There are a spread of La–Ga bond distances ranging from 3.30–3.37 Å. There are three inequivalent Cu sites. In the first Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent La and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.49 Å. In the second Cu site, Cu is bonded to four equivalent La and eight Ga atoms to form distorted CuLa4Ga8 cuboctahedra that share corners with four equivalent CuLa4Ga8 cuboctahedra, faces with four equivalent CuLa4Ga8 cuboctahedra, and faces with four equivalent GaLa4Ga4Cu4 cuboctahedra. There are four shorter (2.55 Å) and four longer (3.06 Å) Cu–Ga bond lengths. In the third Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent La and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.49 Å. There are three inequivalent Ga sites. In the first Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent La, two equivalent Cu, and three Ga atoms. There are one shorter (2.54 Å) and two longer (2.55 Å) Ga–Ga bond lengths. In the second Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent La, four Cu, and one Ga atom. In the third Ga site, Ga is bonded to four equivalent La, four equivalent Cu, and four equivalent Ga atoms to form GaLa4Ga4Cu4 cuboctahedra that share corners with four equivalent GaLa4Ga4Cu4 cuboctahedra, faces with four equivalent CuLa4Ga8 cuboctahedra, and faces with four equivalent GaLa4Ga4Cu4 cuboctahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Pr2Ga5Cu3 by Materials Project

Pr2Cu3Ga5 crystallizes in the tetragonal P-4m2 space group. The structure is three-dimensional. Pr is bonded in a 12-coordinate geometry to six Cu and ten Ga atoms. There are four shorter (3.30 Å) and two longer (3.35 Å) Pr–Cu bond lengths. There are a spread of Pr–Ga bond distances ranging from 3.26–3.35 Å. There are three inequivalent Cu sites. In the first Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent Pr and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.46 Å. In the second Cu site, Cu is bonded to four equivalent Pr and eight Ga atoms to form distorted CuPr4Ga8 cuboctahedra that share corners with four equivalent CuPr4Ga8 cuboctahedra, faces with four equivalent CuPr4Ga8 cuboctahedra, and faces with four equivalent GaPr4Ga4Cu4 cuboctahedra. There are four shorter (2.52 Å) and four longer (3.02 Å) Cu–Ga bond lengths. In the third Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent Pr and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.46 Å. There are three inequivalent Ga sites. In the first Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent Pr, two equivalent Cu, and three Ga atoms. There are one shorter (2.51 Å) and two longer (2.52 Å) Ga–Ga bond lengths. In the second Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent Pr, four Cu, and one Ga atom. In the third Ga site, Ga is bonded to four equivalent Pr, four equivalent Cu, and four equivalent Ga atoms to form GaPr4Ga4Cu4 cuboctahedra that share corners with four equivalent GaPr4Ga4Cu4 cuboctahedra, faces with four equivalent CuPr4Ga8 cuboctahedra, and faces with four equivalent GaPr4Ga4Cu4 cuboctahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Sm2Ga5Cu3 by Materials Project

Sm2Cu3Ga5 crystallizes in the tetragonal P-4m2 space group. The structure is three-dimensional. Sm is bonded in a 12-coordinate geometry to six Cu and ten Ga atoms. There are four shorter (3.27 Å) and two longer (3.36 Å) Sm–Cu bond lengths. There are a spread of Sm–Ga bond distances ranging from 3.21–3.36 Å. There are three inequivalent Cu sites. In the first Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent Sm and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.45 Å. In the second Cu site, Cu is bonded to four equivalent Sm and eight Ga atoms to form distorted CuSm4Ga8 cuboctahedra that share corners with four equivalent CuSm4Ga8 cuboctahedra, faces with four equivalent CuSm4Ga8 cuboctahedra, and faces with four equivalent GaSm4Ga4Cu4 cuboctahedra. There are four shorter (2.53 Å) and four longer (2.98 Å) Cu–Ga bond lengths. In the third Cu site, Cu is bonded in a 4-coordinate geometry to four equivalent Sm and four equivalent Ga atoms. All Cu–Ga bond lengths are 2.45 Å. There are three inequivalent Ga sites. In the first Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent Sm, two equivalent Cu, and three Ga atoms. There are one shorter (2.48 Å) and two longer (2.53 Å) Ga–Ga bond lengths. In the second Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent Sm, four Cu, and one Ga atom. In the third Ga site, Ga is bonded to four equivalent Sm, four equivalent Cu, and four equivalent Ga atoms to form GaSm4Ga4Cu4 cuboctahedra that share corners with four equivalent GaSm4Ga4Cu4 cuboctahedra, faces with four equivalent CuSm4Ga8 cuboctahedra, and faces with four equivalent GaSm4Ga4Cu4 cuboctahedra.

36 MATERIALS SCIENCE↗