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DOE OSTI2020

Materials Data on Zn(CuO2)2 by Materials Project

Zn(CuO2)2 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are twelve inequivalent Cu3+ sites. In the first Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with three CuO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.96–2.09 Å. In the second Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with three equivalent CuO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.96–2.07 Å. In the third Cu3+ site, Cu3+ is bonded to four O2- atoms to form CuO4 tetrahedra that share corners with six CuO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 55–60°. There are a spread of Cu–O bond distances ranging from 1.92–1.94 Å. In the fourth Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four CuO4 tetrahedra, edges with three CuO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.93–2.03 Å. In the fifth Cu3+ site, Cu3+ is bonded to four O2- atoms to form CuO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CuO6 octahedra. The corner-sharing octahedra tilt angles range from 55–63°. There are a spread of Cu–O bond distances ranging from 1.88–1.97 Å. In the sixth Cu3+ site, Cu3+ is bonded to four O2- atoms to form CuO4 tetrahedra that share corners with six CuO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 55–60°. There are a spread of Cu–O bond distances ranging from 1.89–1.93 Å. In the seventh Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with six CuO4 tetrahedra, edges with two equivalent CuO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.93–2.04 Å. In the eighth Cu3+ site, Cu3+ is bonded to four O2- atoms to form CuO4 tetrahedra that share corners with six CuO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–60°. There are a spread of Cu–O bond distances ranging from 1.90–1.94 Å. In the ninth Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five CuO4 tetrahedra, edges with three CuO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.94–2.09 Å. In the tenth Cu3+ site, Cu3+ is bonded to four O2- atoms to form CuO4 tetrahedra that share corners with six CuO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–61°. There are a spread of Cu–O bond distances ranging from 1.92–1.97 Å. In the eleventh Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with three equivalent CuO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.96–2.05 Å. In the twelfth Cu3+ site, Cu3+ is bonded to four O2- atoms to form CuO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CuO6 octahedra. The corner-sharing octahedra tilt angles range from 54–63°. There are a spread of Cu–O bond distances ranging from 1.89–1.99 Å. There are eight inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CuO6 octahedra. The corner-sharing octahedra tilt angles range from 56–61°. There is one shorter (1.97 Å) and three longer (1.98 Å) Zn–O bond length. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three CuO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six CuO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.11 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CuO6 octahedra. The corner-sharing octahedra tilt angles range from 57–61°. There is three shorter (1.99 Å) and one longer (2.00 Å) Zn–O bond length. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four CuO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five CuO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.06–2.12 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CuO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four equivalent CuO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.06–2.11 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CuO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CuO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.06–2.14 Å. In the seventh Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five CuO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five CuO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.11 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CuO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CuO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.12 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Cu3+ and two Zn2+ atoms. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cu3+ and two Zn2+ atoms. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Cu3+ atoms. In the fifth O2- site, O2- is bonded to two Cu3+ and two Zn2+ atoms to form a mixture of distorted corner and edge-sharing OZn2Cu2 trigonal pyramids. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Cu3+ and two Zn2+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Cu3+ and two Zn2+ atoms. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the seventeenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Cu3+ and two Zn2+ atoms. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Cu3+ and two Zn2+ atoms. In the nineteenth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to two equivalent Cu3+ and two Zn2+ atoms. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the twenty-first O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the twenty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Cu3+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Cu3+ and one Zn2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(NiO2)2 by Materials Project

Zn(NiO2)2 is Sylvanite-like structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are sixteen inequivalent Ni3+ sites. In the first Ni3+ site, Ni3+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with three NiO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four NiO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.78–2.21 Å. In the second Ni3+ site, Ni3+ is bonded to six O2- atoms to form distorted NiO6 octahedra that share corners with three equivalent NiO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four NiO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.69–2.22 Å. In the third Ni3+ site, Ni3+ is bonded to six O2- atoms to form distorted NiO6 octahedra that share corners with three NiO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four NiO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.73–2.35 Å. In the fourth Ni3+ site, Ni3+ is bonded to four O2- atoms to form NiO4 tetrahedra that share corners with six NiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 43–68°. There are a spread of Ni–O bond distances ranging from 1.78–2.11 Å. In the fifth Ni3+ site, Ni3+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four NiO4 tetrahedra, edges with three NiO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.75–2.22 Å. In the sixth Ni3+ site, Ni3+ is bonded to four O2- atoms to form NiO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine NiO6 octahedra. The corner-sharing octahedra tilt angles range from 45–70°. There are a spread of Ni–O bond distances ranging from 1.81–2.12 Å. In the seventh Ni3+ site, Ni3+ is bonded to four O2- atoms to form NiO4 tetrahedra that share corners with six NiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 44–66°. There are a spread of Ni–O bond distances ranging from 1.72–2.05 Å. In the eighth Ni3+ site, Ni3+ is bonded to six O2- atoms to form distorted NiO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four NiO4 tetrahedra, edges with three NiO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.77–2.28 Å. In the ninth Ni3+ site, Ni3+ is bonded to six O2- atoms to form distorted NiO6 octahedra that share corners with six NiO4 tetrahedra, edges with two equivalent NiO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.75–2.29 Å. In the tenth Ni3+ site, Ni3+ is bonded to four O2- atoms to form NiO4 tetrahedra that share corners with six NiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 44–69°. There are a spread of Ni–O bond distances ranging from 1.77–2.10 Å. In the eleventh Ni3+ site, Ni3+ is bonded to six O2- atoms to form distorted NiO6 octahedra that share corners with six NiO4 tetrahedra, edges with two equivalent NiO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.76–2.22 Å. In the twelfth Ni3+ site, Ni3+ is bonded to six O2- atoms to form distorted NiO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five NiO4 tetrahedra, edges with three NiO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.72–2.36 Å. In the thirteenth Ni3+ site, Ni3+ is bonded to six O2- atoms to form NiO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five NiO4 tetrahedra, edges with three NiO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.82–2.19 Å. In the fourteenth Ni3+ site, Ni3+ is bonded to four O2- atoms to form NiO4 tetrahedra that share corners with six NiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 45–68°. There are a spread of Ni–O bond distances ranging from 1.78–2.11 Å. In the fifteenth Ni3+ site, Ni3+ is bonded to six O2- atoms to form distorted NiO6 octahedra that share corners with three equivalent NiO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four NiO6 octahedra. There are a spread of Ni–O bond distances ranging from 1.70–2.20 Å. In the sixteenth Ni3+ site, Ni3+ is bonded to four O2- atoms to form NiO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine NiO6 octahedra. The corner-sharing octahedra tilt angles range from 46–71°. There are a spread of Ni–O bond distances ranging from 1.81–2.11 Å. There are eight inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine NiO6 octahedra. The corner-sharing octahedra tilt angles range from 47–69°. There are a spread of Zn–O bond distances ranging from 1.82–2.15 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with three NiO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six NiO6 octahedra. There are a spread of Zn–O bond distances ranging from 1.85–2.35 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine NiO6 octahedra. The corner-sharing octahedra tilt angles range from 46–71°. There are a spread of Zn–O bond distances ranging from 1.83–2.14 Å. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four NiO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five NiO6 octahedra. There are a spread of Zn–O bond distances ranging from 1.85–2.31 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six NiO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four NiO6 octahedra. There are a spread of Zn–O bond distances ranging from 1.83–2.28 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with six NiO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four NiO6 octahedra. There are a spread of Zn–O bond distances ranging from 1.80–2.35 Å. In the seventh Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five NiO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five NiO6 octahedra. There are a spread of Zn–O bond distances ranging from 1.86–2.36 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with six NiO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four NiO6 octahedra. There are a spread of Zn–O bond distances ranging from 1.81–2.35 Å. There are thirty-two inequivalent O2- sites. In the first O2- site, O2- is bonded to two Ni3+ and two Zn2+ atoms to form distorted corner-sharing OZn2Ni2 tetrahedra. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two Ni3+ and two Zn2+ atoms. In the third O2- site, O2- is bonded in a 4-coordinate geometry to two Ni3+ and two Zn2+ atoms. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to four Ni3+ atoms. In the sixth O2- site, O2- is bonded to two Ni3+ and two Zn2+ atoms to form distorted corner-sharing OZn2Ni2 tetrahedra. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Ni3+ and one Zn2+ atom. In the ninth O2- site, O2- is bonded in a 4-coordinate geometry to two Ni3+ and two Zn2+ atoms. In the tenth O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Ni3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded to three Ni3+ and one Zn2+ atom to form distorted corner-sharing OZnNi3 tetrahedra. In the thirteenth O2- site, O2- is bonded to two Ni3+ and two Zn2+ atoms to form distorted corner-sharing OZn2Ni2 tetrahedra. In the fourteenth O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the fifteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ni3+ and two Zn2+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Ni3+ and one Zn2+ atom. In the seventeenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ni3+ and two Zn2+ atoms. In the eighteenth O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the nineteenth O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the twentieth O2- site, O2- is bonded to two Ni3+ and two Zn2+ atoms to form distorted corner-sharing OZn2Ni2 tetrahedra. In the twenty-first O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the twenty-second O2- site, O2- is bonded in a 4-coordinate geometry to two Ni3+ and two Zn2+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ni3+ and two Zn2+ atoms. In the twenty-fourth O2- site, O2- is bonded to two Ni3+ and two Zn2+ atoms to form distorted corner-sharing OZn2Ni2 tetrahedra. In the twenty-fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ni3+ and two Zn2+ atoms. In the twenty-sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Ni3+ and one Zn2+ atom. In the twenty-seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Ni3+ and one Zn2+ atom. In the twenty-eighth O2- site, O2- is bonded in a 4-coordinate geometry to two Ni3+ and two Zn2+ atoms. In the twenty-ninth O2- site, O2- is bonded in a 4-coordinate geometry to four Ni3+ atoms. In the thirtieth O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the thirty-first O2- site, O2- is bonded in a 4-coordinate geometry to three Ni3+ and one Zn2+ atom. In the thirty-second O2- site, O2- is bonded to three Ni3+ and one Zn2+ atom to form distorted corner-sharing OZnNi3 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(SbO2)2 by Materials Project

Zn(SbO2)2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded in a distorted T-shaped geometry to three O2- atoms. There is two shorter (1.93 Å) and one longer (1.94 Å) Zn–O bond length. In the second Zn2+ site, Zn2+ is bonded in a distorted trigonal pyramidal geometry to four O2- atoms. There are a spread of Zn–O bond distances ranging from 1.95–2.06 Å. In the third Zn2+ site, Zn2+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Zn–O bond distances ranging from 1.89–2.16 Å. In the fourth Zn2+ site, Zn2+ is bonded in a 4-coordinate geometry to five O2- atoms. There are a spread of Zn–O bond distances ranging from 2.02–2.71 Å. In the fifth Zn2+ site, Zn2+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Zn–O bond distances ranging from 1.98–2.02 Å. In the sixth Zn2+ site, Zn2+ is bonded in a distorted see-saw-like geometry to four O2- atoms. There are a spread of Zn–O bond distances ranging from 1.99–2.16 Å. There are twelve inequivalent Sb3+ sites. In the first Sb3+ site, Sb3+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Sb–O bond distances ranging from 1.98–2.72 Å. In the second Sb3+ site, Sb3+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are a spread of Sb–O bond distances ranging from 1.98–2.01 Å. In the third Sb3+ site, Sb3+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Sb–O bond distances ranging from 1.98–2.00 Å. In the fourth Sb3+ site, Sb3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Sb–O bond distances ranging from 2.05–2.72 Å. In the fifth Sb3+ site, Sb3+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Sb–O bond distances ranging from 1.97–2.70 Å. In the sixth Sb3+ site, Sb3+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are a spread of Sb–O bond distances ranging from 1.98–2.13 Å. In the seventh Sb3+ site, Sb3+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are two shorter (2.00 Å) and one longer (2.02 Å) Sb–O bond lengths. In the eighth Sb3+ site, Sb3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Sb–O bond distances ranging from 2.03–2.71 Å. In the ninth Sb3+ site, Sb3+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Sb–O bond distances ranging from 2.01–2.41 Å. In the tenth Sb3+ site, Sb3+ is bonded in a 3-coordinate geometry to three O2- atoms. There are a spread of Sb–O bond distances ranging from 1.98–2.07 Å. In the eleventh Sb3+ site, Sb3+ is bonded in a distorted T-shaped geometry to three O2- atoms. There is one shorter (1.97 Å) and two longer (2.00 Å) Sb–O bond length. In the twelfth Sb3+ site, Sb3+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are a spread of Sb–O bond distances ranging from 1.96–2.01 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one Sb3+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Zn2+ and two Sb3+ atoms. In the third O2- site, O2- is bonded in a distorted T-shaped geometry to two Zn2+ and one Sb3+ atom. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to one Zn2+ and three Sb3+ atoms. In the fifth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two Zn2+ and one Sb3+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Zn2+ and two Sb3+ atoms. In the seventh O2- site, O2- is bonded in a bent 120 degrees geometry to two Sb3+ atoms. In the eighth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Zn2+ and two Sb3+ atoms. In the ninth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two Zn2+ and one Sb3+ atom. In the tenth O2- site, O2- is bonded in a trigonal non-coplanar geometry to one Zn2+ and two Sb3+ atoms. In the eleventh O2- site, O2- is bonded in a bent 120 degrees geometry to two Sb3+ atoms. In the twelfth O2- site, O2- is bonded in a bent 120 degrees geometry to two Sb3+ atoms. In the thirteenth O2- site, O2- is bonded in a 3-coordinate geometry to two Zn2+ and two Sb3+ atoms. In the fourteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Zn2+ and two Sb3+ atoms. In the fifteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one Sb3+ atom. In the sixteenth O2- site, O2- is bonded in a trigonal planar geometry to one Zn2+ and two Sb3+ atoms. In the seventeenth O2- site, O2- is bonded in a water-like geometry to two Sb3+ atoms. In the eighteenth O2- site, O2- is bonded in a 2-coordinate geometry to three Sb3+ atoms. In the nineteenth O2- site, O2- is bonded in a trigonal non-coplanar geometry to one Zn2+ and two Sb3+ atoms. In the twentieth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two Zn2+ and one Sb3+ atom. In the twenty-first O2- site, O2- is bonded in a bent 150 degrees geometry to two Sb3+ atoms. In the twenty-second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Zn2+ and one Sb3+ atom. In the twenty-third O2- site, O2- is bonded in a distorted trigonal planar geometry to one Zn2+ and two Sb3+ atoms. In the twenty-fourth O2- site, O2- is bonded in a bent 120 degrees geometry to two Sb3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(SbO2)2 by Materials Project

Zn(SbO2)2 crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are eight inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded in a trigonal planar geometry to three O2- atoms. There are two shorter (1.96 Å) and one longer (2.09 Å) Zn–O bond lengths. In the second Zn2+ site, Zn2+ is bonded to five O2- atoms to form distorted ZnO5 trigonal bipyramids that share corners with two equivalent SbO5 square pyramids, a cornercorner with one SbO4 trigonal pyramid, and edges with three SbO5 square pyramids. There are a spread of Zn–O bond distances ranging from 2.02–2.25 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form distorted ZnO4 trigonal pyramids that share corners with two equivalent SbO5 square pyramids. There are a spread of Zn–O bond distances ranging from 1.94–2.50 Å. In the fourth Zn2+ site, Zn2+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Zn–O bond distances ranging from 1.92–2.13 Å. In the fifth Zn2+ site, Zn2+ is bonded to five O2- atoms to form ZnO5 square pyramids that share corners with two equivalent SbO6 octahedra, corners with two equivalent SbO4 tetrahedra, and edges with two equivalent SbO6 octahedra. The corner-sharing octahedral tilt angles are 69°. There are a spread of Zn–O bond distances ranging from 2.07–2.16 Å. In the sixth Zn2+ site, Zn2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Zn–O bond distances ranging from 2.08–2.63 Å. In the seventh Zn2+ site, Zn2+ is bonded to five O2- atoms to form distorted ZnO5 trigonal bipyramids that share corners with two equivalent SbO4 trigonal pyramids and an edgeedge with one SbO5 square pyramid. There are a spread of Zn–O bond distances ranging from 1.97–2.20 Å. In the eighth Zn2+ site, Zn2+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are one shorter (1.95 Å) and three longer (2.05 Å) Zn–O bond lengths. There are twelve inequivalent Sb3+ sites. In the first Sb3+ site, Sb3+ is bonded to five O2- atoms to form distorted SbO5 square pyramids that share a cornercorner with one SbO5 square pyramid, a cornercorner with one ZnO5 trigonal bipyramid, a cornercorner with one ZnO4 trigonal pyramid, a cornercorner with one SbO4 trigonal pyramid, edges with two SbO5 square pyramids, and an edgeedge with one ZnO5 trigonal bipyramid. There are a spread of Sb–O bond distances ranging from 2.11–2.59 Å. In the second Sb3+ site, Sb3+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are two shorter (2.00 Å) and one longer (2.01 Å) Sb–O bond lengths. In the third Sb3+ site, Sb3+ is bonded to four O2- atoms to form distorted SbO4 tetrahedra that share corners with four equivalent SbO6 octahedra and corners with two equivalent ZnO5 square pyramids. The corner-sharing octahedra tilt angles range from 56–60°. There are a spread of Sb–O bond distances ranging from 1.96–2.63 Å. In the fourth Sb3+ site, Sb3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Sb–O bond distances ranging from 2.01–2.73 Å. In the fifth Sb3+ site, Sb3+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. All Sb–O bond lengths are 1.99 Å. In the sixth Sb3+ site, Sb3+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are one shorter (1.96 Å) and two longer (2.10 Å) Sb–O bond lengths. In the seventh Sb3+ site, Sb3+ is bonded to six O2- atoms to form distorted SbO6 octahedra that share a cornercorner with one ZnO5 square pyramid, corners with two equivalent SbO4 tetrahedra, edges with two equivalent SbO6 octahedra, and an edgeedge with one ZnO5 square pyramid. There are a spread of Sb–O bond distances ranging from 2.08–2.74 Å. In the eighth Sb3+ site, Sb3+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Sb–O bond distances ranging from 2.02–2.23 Å. In the ninth Sb3+ site, Sb3+ is bonded in a distorted see-saw-like geometry to four O2- atoms. There are a spread of Sb–O bond distances ranging from 2.05–2.32 Å. In the tenth Sb3+ site, Sb3+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Sb–O bond distances ranging from 1.98–2.81 Å. In the eleventh Sb3+ site, Sb3+ is bonded to five O2- atoms to form distorted SbO5 square pyramids that share corners with two equivalent SbO4 trigonal pyramids, edges with two equivalent SbO5 square pyramids, and edges with two ZnO5 trigonal bipyramids. There are a spread of Sb–O bond distances ranging from 2.04–2.54 Å. In the twelfth Sb3+ site, Sb3+ is bonded to four O2- atoms to form SbO4 trigonal pyramids that share corners with four SbO5 square pyramids and corners with three ZnO5 trigonal bipyramids. There are a spread of Sb–O bond distances ranging from 1.99–2.13 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to two Zn2+ and two Sb3+ atoms. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Zn2+ and two equivalent Sb3+ atoms. In the third O2- site, O2- is bonded in a trigonal non-coplanar geometry to three Sb3+ atoms. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to two Sb3+ atoms. In the fifth O2- site, O2- is bonded in a distorted T-shaped geometry to two Zn2+ and one Sb3+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Zn2+ and two Sb3+ atoms. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to one Zn2+ and three Sb3+ atoms. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to one Zn2+ and three Sb3+ atoms. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Zn2+ and three Sb3+ atoms. In the tenth O2- site, O2- is bonded to two Zn2+ and two Sb3+ atoms to form a mixture of distorted edge and corner-sharing OZn2Sb2 tetrahedra. In the eleventh O2- site, O2- is bonded in a trigonal non-coplanar geometry to one Zn2+ and two equivalent Sb3+ atoms. In the twelfth O2- site, O2- is bonded in a 3-coordinate geometry to one Zn2+ and two Sb3+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Zn2+ and three Sb3+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Zn2+ and two equivalent Sb3+ atoms. In the fifteenth O2- site, O2- is bonded in a 1-coordinate geometry to one Zn2+ and three Sb3+ atoms. In the sixteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Zn2+ and three Sb3+ atoms. In the seventeenth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Zn2+ and two Sb3+ atoms. In the eighteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Zn2+ and two Sb3+ atoms. In the nineteenth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Zn2+ and two equivalent Sb3+ atoms. In the twentieth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Sb3+ atoms. In the twenty-first O2- site, O2- is bonded in a trigonal non-coplanar geometry to one Zn2+ and two equivalent Sb3+ atoms. In the twenty-second O2- site, O2- is bonded in a 3-coordinate geometry to three Sb3+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted trigonal planar geometry to one Zn2+ and two Sb3+ atoms. In the twenty-fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Zn2+ and one Sb3+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(PO3)2 by Materials Project

Zn(PO3)2 is quartz (alpha)-derived structured and crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are two inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with four PO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.94–1.98 Å. In the second Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with four PO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.94–1.98 Å. There are four inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent ZnO4 tetrahedra and corners with two PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.49–1.62 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent ZnO4 tetrahedra and corners with two PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.50–1.62 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two ZnO4 tetrahedra and corners with two PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.49–1.62 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two ZnO4 tetrahedra and corners with two PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.50–1.61 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Zn2+ and one P5+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Zn2+ and one P5+ atom. In the third O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two P5+ atoms. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to two P5+ atoms. In the fifth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two P5+ atoms. In the sixth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two P5+ atoms. In the seventh O2- site, O2- is bonded in a bent 150 degrees geometry to one Zn2+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a bent 150 degrees geometry to one Zn2+ and one P5+ atom. In the ninth O2- site, O2- is bonded in a bent 150 degrees geometry to one Zn2+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Zn2+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a bent 150 degrees geometry to one Zn2+ and one P5+ atom. In the twelfth O2- site, O2- is bonded in a bent 150 degrees geometry to one Zn2+ and one P5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2021

An Anode-Free Zn–MnO 2 Battery

Aqueous Zn-based batteries are attractive because of the low cost and high theoretical capacity of the Zn metal anode. However, the Zn-based batteries developed so far utilize an excess amount of Zn (i.e., thick Zn metal anode), which decreases the energy density of the whole battery. In this study, we demonstrate an anode-free design (i.e., zero-excess Zn), which is enabled by employing a nanocarbon nucleation layer. Electrochemical studies show that this design allows for uniform Zn electrodeposition with high efficiency and stability over a range of current densities and plating capacities. Using this anode-free configuration, we showcase a Zn–MnO 2 battery prototype, showing 68.2% capacity retention after 80 cycles. Our anode-free design opens a new direction for implementing aqueous Zn-based batteries in energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Stabilizing Zinc Anode Reactions by Polyethylene Oxide Polymer in Mild Aqueous Electrolytes

Abstract Zn dendrites growth and poor cycling stability are significant challenges for rechargeable aqueous Zn batteries. Zn metal deposition‐dissolution in aqueous electrolytes is typically determined by Zn anode–electrolyte interfaces. In this work, the role of a long‐chain polyethylene oxide (PEO) polymer as a multifunctional electrolyte additive in stabilizing Zn metal anodes is reported. PEO molecules suppress Zn 2+ ion transfer kinetics and regulate Zn 2+ ion concentration in the vicinity of Zn anodes through interactions between ether groups of PEO and Zn 2+ ions. The suppressed Zn 2+ ion transfer kinetics and homogeneous Zn 2+ ion distribution at the interface promotes dendrite‐free homogeneous Zn deposition. In addition, electrochemically inert PEO molecules adsorbed onto Zn anodes can protect the anode surfaces from H 2 generation and, thereby, enhance their electrochemical stability. Stable cycling over 3000 h and high reversibility (Coulombic efficiency > 99.5%) of Zn anodes is demonstrated in 1 m ZnSO 4 electrolyte with 0.5 wt% PEO. This finding provides helpful insights into the mechanism of Zn metal anodes stabilization by low‐cost multifunctional polymer electrolyte additives that stabilize interfacial reactions.

Jin, Yan↗
DOE OSTI2020

Zincate-Blocking-Functionalized Polysulfone Separators for Secondary Zn–MnO 2 Batteries

Alkaline zinc–manganese dioxide (Zn–MnO 2 ) batteries are well suited for grid storage applications because of their inherently safe, aqueous electrolyte and established materials supply chain, resulting in low production costs. With recent advances in the development of Cu/Bi-stabilized birnessite cathodes capable of the full 2-electron capacity equivalent of MnO 2 (617 mA h/g), there is a need for selective separators that prevent zincate (Zn(OH) 4 ) 2– transport from the anode to the cathode during cycling, as this electrode system fails in the presence of dissolved zinc. In this work, we present the synthesis of N-butylimidazolium-functionalized polysulfone (NBI-PSU)-based separators and evaluate their ability to selectively transport hydroxide over zincate. We then examine their impact on the cycling of high depth of discharge Zn/(Cu/Bi–MnO 2 ) batteries when inserted in between the cathode and anode. Initially, we establish our membranes’ selectivity by performing zincate and hydroxide diffusion tests, showing a marked improvement in zincate-blocking (D Zn (cm 2 /min): 0.17 ± 0.04 × 10 –6 for 50-PSU, our most selective separator vs 2.0 ± 0.8 × 10 –6 for Cellophane 350P00 and 5.7 ± 0.8 × 10 –6 for Celgard 3501), while maintaining similar crossover rates for hydroxide (D OH (cm 2 /min): 9.4 ± 0.1 × 10 –6 for 50-PSU vs 17 ± 0.5 × 10 –6 for Cellophane 350P00 and 6.7 ± 0.6 × 10 –6 for Celgard 3501). We then implement our membranes into cells and observe an improvement in cycle life over control cells containing only the commercial separators (cell lifetime extended from 21 to 79 cycles).

crossover↗
DOE OSTI2020

Materials Data on Zn(BrN)2 by Materials Project

(N2)Zn(Br)2 crystallizes in the orthorhombic Imma space group. The structure is zero-dimensional and consists of four diaminozinc molecules and eight hydrobromic acid molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Synaptic Zn2+ potentiates the effects of cocaine on striatal dopamine neurotransmission and behavior

Abstract Cocaine binds to the dopamine (DA) transporter (DAT) to regulate cocaine reward and seeking behavior. Zinc (Zn 2+ ) also binds to the DAT, but the in vivo relevance of this interaction is unknown. We found that Zn 2+ concentrations in postmortem brain (caudate) tissue from humans who died of cocaine overdose were significantly lower than in control subjects. Moreover, the level of striatal Zn 2+ content in these subjects negatively correlated with plasma levels of benzoylecgonine, a cocaine metabolite indicative of recent use. In mice, repeated cocaine exposure increased synaptic Zn 2+ concentrations in the caudate putamen (CPu) and nucleus accumbens (NAc). Cocaine-induced increases in Zn 2+ were dependent on the Zn 2+ transporter 3 (ZnT3), a neuronal Zn 2+ transporter localized to synaptic vesicle membranes, as ZnT3 knockout (KO) mice were insensitive to cocaine-induced increases in striatal Zn 2+ . ZnT3 KO mice showed significantly lower electrically evoked DA release and greater DA clearance when exposed to cocaine compared to controls. ZnT3 KO mice also displayed significant reductions in cocaine locomotor sensitization, conditioned place preference (CPP), self-administration, and reinstatement compared to control mice and were insensitive to cocaine-induced increases in striatal DAT binding. Finally, dietary Zn 2+ deficiency in mice resulted in decreased striatal Zn 2+ content, cocaine locomotor sensitization, CPP, and striatal DAT binding. These results indicate that cocaine increases synaptic Zn 2+ release and turnover/metabolism in the striatum, and that synaptically released Zn 2+ potentiates the effects of cocaine on striatal DA neurotransmission and behavior and is required for cocaine-primed reinstatement. In sum, these findings reveal new insights into cocaine’s pharmacological mechanism of action and suggest that Zn 2+ may serve as an environmentally derived regulator of DA neurotransmission, cocaine pharmacodynamics, and vulnerability to cocaine use disorders.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Zinc Speciation and Propane Dehydrogenation in Zn/H-ZSM-5 Catalysts

Zn/H-ZSM-5 catalysts have been frequently investigated for propane dehydrogenation (PDH); however, the active site remains unresolved due to the complexity of the system. We employed in situ FTIR spectroscopy and a kinetics method to correlate the Zn speciation and PDH activity in Zn/H-ZSM-5 with two Si/Al ratios (15 and 39) and a range of Zn/Al ratios (0–1.7). Incremental additions of zinc show that Zn 2+ sites are preferentially formed on H-ZSM-5 over a fraction of paired Al sites followed by [Zn-O-Zn] 2+ and [ZnOH] + sites and then ZnO x clusters. The [Zn-OH] + and [Zn-O-Zn] 2+ sites in H-ZSM-5 are more active and selective than isolated Zn 2+ for PDH. [Zn-OH] + species sublimate over time on stream, leading to catalyst deactivation, while [Zn-O-Zn] 2+ species are stable even after high-temperature reduction (750 °C for 60 min). Three distinct Zn sites ([Zn-O-Zn] 2+ , Zn 2+ , and [ZnOH] + ) show a similar propane reaction order (close to 1) and H 2 reaction order (close to 0). Combined with the lack of Zn hydride when propane flows over the catalyst at 550 °C, it is concluded that propane adsorption and dissociation is a rate-determining step and H 2 desorption is fast. This work indicates that the preparation of H-ZSM-5 with abundant Al pairs may be a strategy to form stable and selective Zn/H-ZSM-5 catalysts for propane dehydrogenation. Furthermore, it is also highlighted that examining the effect of both metal/Al ratios and Al distribution of the zeolite is crucial in identifying the metal cations in metal–zeolite systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Rational design of a genetically encoded NMR zinc sensor

Elucidating the biochemical roles of the essential metal ion, Zn 2+ , motivates detection strategies that are sensitive, selective, quantitative, and minimally invasive in living systems. Fluorescent probes have identified Zn 2+ in cells but complementary approaches employing nuclear magnetic resonance (NMR) are lacking. Recent studies of maltose binding protein (MBP) using ultrasensitive 129 Xe NMR spectroscopy identified a switchable salt bridge which causes slow xenon exchange and elicits strong hyperpolarized 129 Xe chemical exchange saturation transfer (hyper-CEST) NMR contrast. To engineer the first genetically encoded, NMR-active sensor for Zn 2+ , we converted the MBP salt bridge into a Zn 2+ binding site, while preserving the specific xenon binding cavity. The zinc sensor (ZS) at only 1 μM achieved ‘turn-on’ detection of Zn 2+ with pronounced hyper-CEST contrast. This made it possible to determine different Zn 2+ levels in a biological fluid via hyper-CEST. ZS was responsive to low-micromolar Zn 2+ , only modestly responsive to Cu 2+ , and nonresponsive to other biologically important metal ions, according to hyper-CEST NMR spectroscopy and isothermal titration calorimetry (ITC). Protein X-ray crystallography confirmed the identity of the bound Zn 2+ ion using anomalous scattering: Zn 2+ was coordinated with two histidine side chains and three water molecules. Penta-coordinate Zn 2+ forms a hydrogen-bond-mediated gate that controls the Xe exchange rate. Metal ion binding affinity, 129 Xe NMR chemical shift, and exchange rate are tunable parameters via protein engineering, which highlights the potential to develop proteins as selective metal ion sensors for NMR spectroscopy and imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Expanding the Zinc Precursor Toolbox: A Comparative Study of Precursors for Thermal ALD of ZnO Thin Films

Atomic layer deposition (ALD) of zinc oxide (ZnO) has been widely researched using diethyl zinc (DEZ)-based methods. The significant importance of thin films of ZnO as transparent conductive oxides (TCO) in optoelectronic devices and photovoltaics warrants examining alternative Zn precursors for ZnO ALD as potential replacements for the pyrophoric DEZ. In this study, we investigated three alternative Zn precursors: Zn(EEKI)2, Zn(DMP)2, ZnEt(HMDS), in the process development for high-quality ZnO thin films and compared them to DEZ. The ALD processes were studied using in situ spectroscopic ellipsometry. The properties of the ALD ZnO films were characterized using ex situ X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry and nuclear reaction analysis (RBS/NRA), X-ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and ultraviolet-visible (UV/Vis) spectrophotometry. These measurements confirmed the formation of pure, stoichiometric, and polycrystalline ZnO films using all four Zn precursors. Although the selected precursors are chemically diverse Zn compounds, they all yielded saturating ALD processes and high-quality ZnO thin films at 200 °C. This study highlights the potential benefits of alternative zinc precursors in designing ALD processes for ZnO thin films.

Obenlüneschloß, Jorit↗
DOE OSTI2024

Thermal transport in Yb-based 1-2-20 materials

Abstract Lattice thermal-transport properties of heavy-fermion YbT 2 Zn 20 -based (T = Co, Rh, and Ir) 1-2-20 compounds are calculated with the single-mode relaxation-time approximation and the full solution of the linearized phonon Boltzmann transport equation from first-principles anharmonic phonon calculations. We predict low lattice thermal conductivity κ L with a maximum value of ∼ 24.16 · K at 85.14 K, 137.29 · K at 9.67 K, and 23.55 · K at 67.50 K and ∼ 12.02, 40.04, and 10.30 · K at room temperature for YbCo 2 Zn 20 , YbRh 2 Zn 20 , and YbIr 2 Zn 20 , respectively. Based on the analysis of the cumulative κ L as a function of the phonon mean free path and the frequency-dependent joint density of states at various temperatures, we attribute the low κ L to a rattling mode with an average characteristic rattling frequency that enhanced phonon scattering processes, which reduced the phonon mean free paths, suppressed the phonon lifetime, and enhanced the probability of three-phonon scattering events. The predicted low κ L , especially in YbCo 2 Zn 20 and YbIr 2 Zn 20 , makes them promising candidate materials for thermoelectric applications and thermal management.

Physics↗
DOE OSTI2021

Zinc binding alters the conformational dynamics and drives the transport cycle of the cation diffusion facilitator YiiP

YiiP is a secondary transporter that couples Zn 2+ transport to the proton motive force. Structural studies of YiiP from prokaryotes and Znt8 from humans have revealed three different Zn 2+ sites and a conserved homodimeric architecture. These structures define the inward-facing and outward-facing states that characterize the archetypal alternating access mechanism of transport. To study the effects of Zn 2+ binding on the conformational transition, we use cryo-EM together with molecular dynamics simulation to compare structures of YiiP from Shewanella oneidensis in the presence and absence of Zn 2+ . To enable single-particle cryo-EM, we used a phage-display library to develop a Fab antibody fragment with high affinity for YiiP, thus producing a YiiP/Fab complex. To perform MD simulations, we developed a nonbonded dummy model for Zn 2+ and validated its performance with known Zn 2+ -binding proteins. Using these tools, we find that, in the presence of Zn 2+ , YiiP adopts an inward-facing conformation consistent with that previously seen in tubular crystals. After removal of Zn 2+ with high-affinity chelators, YiiP exhibits enhanced flexibility and adopts a novel conformation that appears to be intermediate between inward-facing and outward-facing states. This conformation involves closure of a hydrophobic gate that has been postulated to control access to the primary transport site. Comparison of several independent cryo-EM maps suggests that the transition from the inward-facing state is controlled by occupancy of a secondary Zn 2+ site at the cytoplasmic membrane interface. This work enhances our understanding of individual Zn 2+ binding sites and their role in the conformational dynamics that govern the transport cycle.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Tuning the Kinetics of Zinc-Ion Insertion/Extraction in V 2 O 5 by In Situ Polyaniline Intercalation Enables Improved Aqueous Zinc-Ion Storage Performance

Rechargeable zinc-ion batteries (ZIBs) are emerging as a promising alternative for Li-ion batteries. However, the developed cathodes suffer from sluggish Zn 2+ diffusion kinetics, leading to poor rate capability and inadequate cycle life. Herein, an in situ polyaniline (PANI) intercalation strategy is developed to facilitate the Zn 2+ (de)intercalation kinetics in V 2 O 5 . In this way, a remarkably enlarged interlayer distance (13.90 Å) can be constructed alternatively between the V-O layers, offering expediting channels for facile Zn 2+ diffusion. Importantly, the electrostatic interactions between the Zn 2+ and the host O 2- , which is another key factor in hindering the Zn 2+ diffusion kinetics, can be effectively blocked by the unique π-conjugated structure of PANI. As a result, the PANI-intercalated V 2 O 5 exhibits a stable and highly reversible electrochemical reaction during repetitive Zn 2+ insertion and extraction, as demonstrated by in situ synchrotron X-ray diffraction and Raman studies. Further first-principles calculations clearly reveal a remarkably lowered binding energy between Zn 2+ and host O 2- , which explains the favorable kinetics in PANI-intercalated V 2 O 5 . Benefitting from the above, the overall electrochemical performance of PANI-intercalated V 2 O 5 electrode is remarkable improved, exhibiting excellent high rate capability of 197.1 mAh g -1 at current density of 20 A g -1 with capacity retention of 97.6% over 2000 cycles.

36 MATERIALS SCIENCE↗
NASA NTRS1981

Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

Bridson, P. K.↗