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DOE OSTI2020

Materials Data on Cu(CO2)4 by Materials Project

Cu(C2O4)2 crystallizes in the monoclinic P2_1/c space group. The structure is two-dimensional and consists of one Cu(C2O4)2 sheet oriented in the (1, 0, 0) direction. Cu2+ is bonded in an octahedral geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 2.07–2.54 Å. There are two inequivalent C+3.50+ sites. In the first C+3.50+ site, C+3.50+ is bonded in a bent 150 degrees geometry to two O2- atoms. Both C–O bond lengths are 1.22 Å. In the second C+3.50+ site, C+3.50+ is bonded in a linear geometry to two O2- atoms. Both C–O bond lengths are 1.18 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu2+ and one C+3.50+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cu2+ and one C+3.50+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cu2+ and one C+3.50+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one C+3.50+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li6CoCu3(PO4)4 by Materials Project

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

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CuH6(CO2)4 by Materials Project

CuH6(CO2)4 crystallizes in the orthorhombic Pbca space group. The structure is three-dimensional. Cu2+ is bonded in an octahedral geometry to six O2- atoms. There are a spread of Cu–O bond distances ranging from 1.97–2.52 Å. There are two inequivalent C2+ sites. In the first C2+ site, C2+ is bonded in a trigonal planar geometry to one H1+ and two O2- atoms. The C–H bond length is 1.10 Å. There is one shorter (1.23 Å) and one longer (1.33 Å) C–O bond length. In the second C2+ site, C2+ is bonded in a trigonal planar geometry to one H1+ and two O2- atoms. The C–H bond length is 1.10 Å. There is one shorter (1.27 Å) and one longer (1.28 Å) C–O bond length. There are three inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one C2+ atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one C2+ atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.73 Å) H–O bond length. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one Cu2+ and one C2+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to one Cu2+ and one C2+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one C2+ and one H1+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Cu2+, one C2+, and one H1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on RbCoCuS2 by Materials Project

RbCoCuS2 is alpha bismuth trifluoride-derived structured and crystallizes in the tetragonal I-4m2 space group. The structure is three-dimensional. Rb1+ is bonded in a body-centered cubic geometry to eight equivalent S2- atoms. All Rb–S bond lengths are 3.46 Å. Co2+ is bonded to four equivalent S2- atoms to form CoS4 tetrahedra that share corners with four equivalent CoS4 tetrahedra and edges with four equivalent CuS4 tetrahedra. All Co–S bond lengths are 2.28 Å. Cu1+ is bonded to four equivalent S2- atoms to form CuS4 tetrahedra that share corners with four equivalent CuS4 tetrahedra and edges with four equivalent CoS4 tetrahedra. All Cu–S bond lengths are 2.28 Å. S2- is bonded in a 4-coordinate geometry to four equivalent Rb1+, two equivalent Co2+, and two equivalent Cu1+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on SrCuH4(CO2)4 by Materials Project

CuSr(HCOO)4 crystallizes in the monoclinic P2/c space group. The structure is one-dimensional and consists of four hydrogen molecules and two SrCuH2(CO2)4 ribbons oriented in the (1, 0, 0) direction. In each SrCuH2(CO2)4 ribbon, Sr2+ is bonded in a distorted hexagonal planar geometry to six O2- atoms. There are a spread of Sr–O bond distances ranging from 2.49–2.51 Å. Cu2+ is bonded in an L-shaped geometry to two equivalent O2- atoms. Both Cu–O bond lengths are 1.94 Å. There are two inequivalent C2+ sites. In the first C2+ site, C2+ is bonded in a distorted water-like geometry to one H1+ and one O2- atom. The C–H bond length is 1.10 Å. The C–O bond length is 1.63 Å. In the second C2+ site, C2+ is bonded in a distorted bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.32 Å) C–O bond length. H1+ is bonded in a single-bond geometry to one C2+ atom. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to two C2+ atoms. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Sr2+ and one O2- atom. The O–O bond length is 1.37 Å. In the third O2- site, O2- is bonded in a distorted single-bond geometry to one Sr2+, one Cu2+, and one O2- atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Sr2+ and one C2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on SrCuH4(CO2)4 by Materials Project

CuSr(HCOO)4 crystallizes in the monoclinic P2/c space group. The structure is three-dimensional. Sr2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Sr–O bond distances ranging from 2.45–2.78 Å. Cu2+ is bonded in a distorted square co-planar geometry to four O2- atoms. There is two shorter (1.96 Å) and two longer (1.98 Å) Cu–O bond length. There are two inequivalent C2+ sites. In the first C2+ site, C2+ is bonded in a trigonal planar geometry to one H1+ and two O2- atoms. The C–H bond length is 1.11 Å. There is one shorter (1.26 Å) and one longer (1.28 Å) C–O bond length. In the second C2+ site, C2+ is bonded in a trigonal planar geometry to one H1+ and two O2- atoms. The C–H bond length is 1.11 Å. There is one shorter (1.25 Å) and one longer (1.29 Å) C–O bond length. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one C2+ atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one C2+ atom. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu2+ and one C2+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Sr2+, one Cu2+, and one C2+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Sr2+ and one C2+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Sr2+ and one C2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on SrCuH4(CO2)4 by Materials Project

CuSr(HCOO)4 crystallizes in the monoclinic P2/c space group. The structure is one-dimensional and consists of two CuSr(HCOO)4 ribbons oriented in the (1, 0, 0) direction. Sr2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Sr–O bond distances ranging from 2.36–2.78 Å. Cu2+ is bonded in an L-shaped geometry to two equivalent O2- atoms. Both Cu–O bond lengths are 1.95 Å. There are two inequivalent C2+ sites. In the first C2+ site, C2+ is bonded in a distorted water-like geometry to one H1+ and one O2- atom. The C–H bond length is 1.10 Å. The C–O bond length is 1.70 Å. In the second C2+ site, C2+ is bonded in a distorted bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.32 Å) C–O bond length. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one C2+ atom. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one Sr2+, one H1+, and one O2- atom. The O–O bond length is 1.52 Å. In the second O2- site, O2- is bonded in a 1-coordinate geometry to one Sr2+ and one C2+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to two C2+ atoms. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Sr2+, one Cu2+, and one O2- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on KCo3Cu(AsO4)3 by Materials Project

KCo3Cu(AsO4)3 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. K1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of K–O bond distances ranging from 2.67–3.00 Å. There are two inequivalent Co2+ sites. In the first Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six AsO4 tetrahedra, an edgeedge with one CoO6 octahedra, and an edgeedge with one CoO6 pentagonal pyramid. There are a spread of Co–O bond distances ranging from 2.03–2.18 Å. In the second Co2+ site, Co2+ is bonded to six O2- atoms to form distorted CoO6 pentagonal pyramids that share corners with six AsO4 tetrahedra and edges with two equivalent CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.10–2.21 Å. Cu2+ is bonded in a square co-planar geometry to four O2- atoms. There is two shorter (1.95 Å) and two longer (1.97 Å) Cu–O bond length. There are two inequivalent As5+ sites. In the first As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with four equivalent CoO6 octahedra and corners with two equivalent CoO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 38–61°. There are a spread of As–O bond distances ranging from 1.71–1.75 Å. In the second As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with four equivalent CoO6 octahedra and corners with two equivalent CoO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 60–62°. There is two shorter (1.73 Å) and two longer (1.75 Å) As–O bond length. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to one Co2+, one Cu2+, and one As5+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Co2+ and one As5+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, two Co2+, and one As5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, two Co2+, and one As5+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Co2+, one Cu2+, and one As5+ atom. In the sixth O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent K1+, one Co2+, and one As5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Co7CuAs4(HO5)4 by Materials Project

Co7CuAs4(HO5)4 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are five inequivalent Co2+ sites. In the first Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with four AsO4 tetrahedra, a cornercorner with one CuO5 trigonal bipyramid, corners with three CoO5 trigonal bipyramids, and edges with two equivalent CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.08–2.26 Å. In the second Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with four AsO4 tetrahedra, a cornercorner with one CuO5 trigonal bipyramid, corners with three CoO5 trigonal bipyramids, and edges with two equivalent CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.08–2.29 Å. In the third Co2+ site, Co2+ is bonded to five O2- atoms to form CoO5 trigonal bipyramids that share corners with four CoO6 octahedra, corners with four AsO4 tetrahedra, and an edgeedge with one CuO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 55–65°. There are a spread of Co–O bond distances ranging from 2.02–2.11 Å. In the fourth Co2+ site, Co2+ is bonded to five O2- atoms to form CoO5 trigonal bipyramids that share corners with four CoO6 octahedra, corners with four AsO4 tetrahedra, and an edgeedge with one CoO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 55–65°. There are a spread of Co–O bond distances ranging from 2.01–2.09 Å. In the fifth Co2+ site, Co2+ is bonded to five O2- atoms to form CoO5 trigonal bipyramids that share corners with four CoO6 octahedra, corners with four AsO4 tetrahedra, and an edgeedge with one CoO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 54–66°. There are a spread of Co–O bond distances ranging from 2.02–2.09 Å. Cu2+ is bonded to five O2- atoms to form CuO5 trigonal bipyramids that share corners with four CoO6 octahedra, corners with four AsO4 tetrahedra, and an edgeedge with one CoO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 54–62°. There are a spread of Cu–O bond distances ranging from 1.98–2.08 Å. There are four inequivalent As5+ sites. In the first As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with four CoO6 octahedra, corners with two CoO5 trigonal bipyramids, and corners with two equivalent CuO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 56–64°. There is three shorter (1.73 Å) and one longer (1.74 Å) As–O bond length. In the second As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with four CoO6 octahedra and corners with four CoO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 56–65°. There is one shorter (1.72 Å) and three longer (1.73 Å) As–O bond length. In the third As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with four CoO6 octahedra, a cornercorner with one CuO5 trigonal bipyramid, and corners with three CoO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 56–64°. There is two shorter (1.72 Å) and two longer (1.73 Å) As–O bond length. In the fourth As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with four CoO6 octahedra, a cornercorner with one CuO5 trigonal bipyramid, and corners with three CoO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 57–63°. There are a spread of As–O bond distances ranging from 1.72–1.74 Å. There are four inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.97 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.97 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to one Co2+, one Cu2+, and one As5+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two Co2+ and one As5+ atom. In the third O2- site, O2- is bonded in a trigonal planar geometry to two Co2+ and one As5+ atom. In the fourth O2- site, O2- is bonded in a trigonal planar geometry to two Co2+ and one As5+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Co2+ and one As5+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Co2+ and one As5+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to one Co2+, one Cu2+, and one As5+ atom. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Co2+, one Cu2+, and one As5+ atom. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Co2+ and one As5+ atom. In the tenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Co2+ and one As5+ atom. In the eleventh O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Co2+ and one As5+ atom. In the twelfth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Co2+ and one As5+ atom. In the thirteenth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Co2+, one Cu2+, and one H1+ atom. In the fourteenth O2- site, O2- is bonded in a distorted single-bond geometry to three Co2+ and one H1+ atom. In the fifteenth O2- site, O2- is bonded in a distorted single-bond geometry to three Co2+ and one H1+ atom. In the sixteenth O2- site, O2- is bonded in a distorted single-bond geometry to three Co2+ and one H1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CaV4Co(CuO6)2 by Materials Project

CaCu2CoV4O12 crystallizes in the orthorhombic Immm space group. The structure is three-dimensional. Ca2+ is bonded to twelve O2- atoms to form CaO12 cuboctahedra that share faces with eight equivalent VO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.58–2.63 Å. V+4.50+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six equivalent VO6 octahedra and faces with two equivalent CaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 37–39°. There is two shorter (1.94 Å) and four longer (1.97 Å) V–O bond length. Co2+ is bonded in a distorted square co-planar geometry to four equivalent O2- atoms. All Co–O bond lengths are 2.02 Å. There are two inequivalent Cu1+ sites. In the first Cu1+ site, Cu1+ is bonded in a square co-planar geometry to four equivalent O2- atoms. All Cu–O bond lengths are 1.97 Å. In the second Cu1+ site, Cu1+ is bonded in a square co-planar geometry to four equivalent O2- atoms. All Cu–O bond lengths are 1.98 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, two equivalent V+4.50+, and one Cu1+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one Ca2+, two equivalent V+4.50+, and one Co2+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, two equivalent V+4.50+, and one Cu1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Understanding the effect of density functional choice and van der Waals treatment on predicting the binding configuration, loading, and stability of amine-grafted metal organic frameworks

Metal organic frameworks (MOFs) are crystalline, three-dimensional structures with high surface areas and tunable porosities. Made from metal nodes connected by organic linkers, the exact properties of a given MOF are determined by node and linker choice. MOFs hold promise for numerous applications, including gas capture and storage. M2(4,4′-dioxidobiphenyl-3,3′-dicarboxylate)—henceforth simply M2(dobpdc), with M = Mg, Mn, Fe, Co, Ni, Cu, or Zn—is regarded as one of the most promising structures for CO2 capture applications. Further modification of the MOF with diamines or tetramines can significantly boost gas species selectivity, a necessity for the ultra-dilute CO2 concentrations in the direct-air capture of CO2. There are countless potential diamines and tetramines, paving the way for a vast number of potential sorbents to be probed for CO2 adsorption properties. The number of amines and their configuration in the MOF pore are key drivers of CO2 adsorption capacity and kinetics, and so a validation of computational prediction of these quantities is required to suitably use computational methods in the discovery and screening of amine-functionalized sorbents. In this work, we study the predictive accuracy of density functional theory and related calculations on amine loading and configuration for one diamine and two tetramines. In particular, we explore the Perdew–Burke–Ernzerhof (PBE) functional and its formulation for solids (PBEsol) with and without the Grimme-D2 and Grimme-D3 pairwise corrections (PBE+D2/3 and PBEsol+D2/3), two revised PBE functionals with the Grimme-D2 and Grimme-D3 pairwise corrections (RPBE+D2/3 and revPBE+D2/3), and the nonlocal van der Waals correlation (vdW-DF2) functional. We also investigate a universal graph deep learning interatomic potential’s (M3GNet) predictive accuracy for loading and configuration. These results allow us to identify a useful screening procedure for configuration prediction that has a coarse component for quick evaluation and a higher accuracy component for detailed analysis. Our general observation is that the neural network-based potential can be used as a high-level and rapid screening tool, whereas PBEsol+D3 gives a completely qualitatively predictive picture across all systems studied, and can thus be used for high accuracy motif predictions. We close by briefly exploring the predictions of relative thermal stability for the different functionals and dispersion corrections.

Chemistry↗
DOE OSTI2022

Grain Boundary‐Derived Cu + /Cu 0 Interfaces in CuO Nanosheets for Low Overpotential Carbon Dioxide Electroreduction to Ethylene

Abstract Electrochemical CO 2 reduction reaction can be used to produce value‐added hydrocarbon fuels and chemicals by coupling with clean electrical energy. However, highly active, selective, and energy‐efficient CO 2 conversion to multicarbon hydrocarbons, such as C 2 H 4 , remains challenging because of the lack of efficient catalysts. Herein, an ultrasonication‐assisted electrodeposition strategy to synthesize CuO nanosheets for low‐overpotential CO 2 electroreduction to C 2 H 4 is reported. A high C 2 H 4 Faradaic efficiency of 62.5% is achieved over the CuO nanosheets at a small potential of −0.52 V versus a reversible hydrogen electrode, corresponding to a record high half‐cell cathodic energy efficiency of 41%. The selectivity toward C 2 H 4 is maintained for over 60 h of continuous operation. The CuO nanosheets are prone to in situ restructuring during CO 2 reduction, forming abundant grain boundaries (GBs). Stable Cu + /Cu 0 interfaces are derived from the low‐coordinated Cu atoms in the reconstructed GB regions and act as highly active sites for CO 2 reduction at low overpotentials. In situ Raman spectroscopic analysis and density functional theory computation reveal that the Cu + /Cu 0 interfaces offer high *CO surface coverage and lower the activation energy barrier for *CO dimerization, which, in synergy, facilitates CO 2 reduction to C 2 H 4 at low overpotentials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CuH2(CO2)2 by Materials Project

Cu(HCOO)2 crystallizes in the orthorhombic Pbca space group. The structure is two-dimensional and consists of two Cu(HCOO)2 sheets oriented in the (0, 0, 1) direction. Cu2+ is bonded in a 4-coordinate geometry to one C2+ and three O2- atoms. The Cu–C bond length is 1.92 Å. There are a spread of Cu–O bond distances ranging from 1.99–2.11 Å. There are two inequivalent C2+ sites. In the first C2+ site, C2+ is bonded in a bent 120 degrees geometry to one Cu2+ and two O2- atoms. There is one shorter (1.22 Å) and one longer (1.35 Å) C–O bond length. In the second C2+ site, C2+ is bonded in a trigonal planar geometry to one H1+ and two O2- atoms. The C–H bond length is 1.11 Å. There is one shorter (1.25 Å) and one longer (1.30 Å) C–O bond length. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one C2+ atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a water-like geometry to one C2+ and one H1+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu2+ and one C2+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one C2+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu2+ and one C2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Insights into the methanol synthesis mechanism via CO 2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio

In this study, we evaluated aspects of the CO 2 hydrogenation mechanism, correlating structure-activity relationships of Cu-ZnO-ZrO 2 catalysts prepared by one-pot surfactant-assisted co-precipitation with different surfactant ratios. Identifying the CO 2 hydrogenation pathway intermediates is key to controlling the reaction selectivity. Experimental evidence shows that the CO 2 is dissociating into CO* and O* onto the surface of the Cu-ZnO-ZrO 2 catalyst. The adsorption and dissociation of CO2 were evidenced by a combination of in situ ambient-pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Fourier Transform Infrared Spectroscopy (FTIR) with a transmission cell. AP-XPS showed that the catalysts are composed of a Cu 2+ , Zr 3+ , and Zr 4+ mixture and two kinds of Zn 2+ species. After the H 2 reduction process, only Cu 2+ was reduced to Cu0. The Zn and Zr species were oxidized by the dissociated O* species. In situ transmission FTIR showed that CO was adsorbed onto the Cu+/0 sites. The catalyst with the higher surfactant molar ratio exhibited the highest CO 2 conversion close to the equilibrium conversion, as well as a good methanol formation rate.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Planar defect-driven electrocatalysis of CO 2 -to-C 2 H 4 conversion

The selectivity towards a specific C 2+ product, such as ethylene (C 2 H 4 ), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO 2 ) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. In this work, we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO 2 -to-C 2 H 4 conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (–0.50 ~ –0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C 2 H 4 and a partial current density of 217 mA cm –2 at –0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C 2 H 4 and a partial current density of 87 mA cm –2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C 2+ products, especially C 2 H 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2025

CO2 upgrading into bioproducts using a two-step abiotic–biotic system

The valorization of CO2 to chemicals beyond C1-2 products is receiving significant interest; however, the direct electrosynthesis of Cn molecules (n > 4) remains a challenge. Here, we present a two-step abiotic-biotic system for upgrading CO2 into the biopolymer, poly(3-hydroxybutyrate). In the electrolysis system, CO2 is converted into C2 oxygenates using a Cu-Ag tandem electrocatalyst. The electrolysis process generates a liquid stream containing ~ 200 mM acetate in a bio-compatible electrolyte. This electrosynthesized acetate is then fed to a bioreactor, where the substrate is upgraded by Cupriavidus necator to biopolymer with a maximum rate of 32 ± 3.5 mg L-1 h-1. We further demonstrate the purification of the resulting biopolymer into a powder. The high productivity of the abiotic-biotic system demonstrates its feasibility for sustainable chemical manufacturing.

CO2 upgrading↗
DOE OSTI2020

Materials Data on CoCu2(BO3)2 by Materials Project

Cu2CoB2O6 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Co2+ is bonded to six O2- atoms to form edge-sharing CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.09–2.30 Å. There are two inequivalent Cu2+ sites. In the first Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.92–2.61 Å. In the second Cu2+ site, Cu2+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.88–2.45 Å. There are two inequivalent B3+ sites. In the first B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.36 Å) and one longer (1.42 Å) B–O bond length. In the second B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.34–1.44 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to one Co2+, two equivalent Cu2+, and one B3+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent Co2+, one Cu2+, and one B3+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to one Co2+, two equivalent Cu2+, and one B3+ atom. In the fourth O2- site, O2- is bonded to two equivalent Co2+ and two Cu2+ atoms to form corner-sharing OCo2Cu2 tetrahedra. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent Cu2+ and one B3+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Cu2+ and two B3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Switching CO 2 Electroreduction Selectivity Between C 1 and C 2 Hydrocarbons on Cu Gas-Diffusion Electrodes

We report that regulating the selectivity toward a target hydrocarbon product is still the focus of CO 2 electroreduction. Here, we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C 1 or C 2 hydrocarbons. The selectivity toward C 2 H 4 progressively increases, while CH 4 decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas-diffusion electrode with the highest Cu δ+ /Cu 0 ratio favors the pathways of hydrogenation to form CH 4 with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm -2 at -0.83 V vs RHE. At 2.0 V, the Cu gas-diffusion electrode with the lowest Cu δ+ /Cu 0 ratio prefers C–C coupling to form C 2+ products with Faradaic efficiency topping 80.1% at -0.75 V vs RHE, where the Faradaic efficiency of C 2 H 4 accounts for 46.4% and the partial current density of C 2 H 4 achieves 279 mA cm -2 . This work demonstrates that the selectivity from CH 4 to C 2 H 4 is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.

36 MATERIALS SCIENCE↗