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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Role of SaPCR2 in Zn Uptake in the Root Elongation Zone of the Zn/Cd Hyperaccumulator Sedum alfredii

Zn pollution is a potential toxicant for agriculture and the environment. Sedum alfredii is a Zn/Cd hyperaccumulator found in China and has been proven as a useful resource for the phytoremediation of Zn-contaminated sites. However, the molecular mechanism of Zn uptake in S. alfredii is limited. In this study, the function of SaPCR2 on Zn uptake in S. alfredii was identified by gene expression analysis, yeast function assays, Zn accumulation and root morphology analysis in transgenic lines to further elucidate the mechanisms of uptake and translocation of Zn in S. alfredii. The results showed that SaPCR2 was highly expressed in the root elongation zone of the hyperaccumulating ecotype (HE) S. alfredii, and high Zn exposure downregulated the expression of SaPCR2 in the HE S. alfredii root. The heterologous expression of SaPCR2 in yeast suggested that SaPCR2 was responsible for Zn influx. The overexpression of SaPCR2 in the non-hyperaccumulating ecotype (NHE) S. alfredii significantly increased the root uptake of Zn, but did not influence Mn, Cu or Fe. SR-μ-XRF technology showed that more Zn was distributed in the vascular buddle tissues, as well as in the cortex and epidermis in the transgenic lines. Root morphology was also altered after SaPCR2 overexpression, and a severe inhibition was observed. In the transgenic lines, the meristematic and elongation zones of the root were lower compared to the WT, and Zn accumulation in meristem cells was also reduced. These results indicate that SaPCR2 is responsible for Zn uptake, and mainly functions in the root elongation zone. This research on SaPCR2 could provide a theoretical basis for the use of genetic engineering technology in the modification of crops for their safe production and biological enhancement.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Ultrafast Metal Electrodeposition Revealed by In Situ Optical Imaging and Theoretical Modeling towards Fast–Charging Zn Battery Chemistry

Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Importantly, understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast-charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn 2+ -ion diffusion. Moreover, steady-state Zn metal plating/ stripping with Coulombic efficiency above 99 % is achieved at 10-100 mA cm -2 in a reasonably high concentration (3 M) ZnSO 4 electrolyte. Significantly, a long-term cycling-stable Zn metal electrode is realized with a depth of discharge of 66.7% under 50 mA cm -2 in both Zn || Zn symmetrical cells and MnO 2 || Zn full cells.

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

Materials Data on Zn(HO)2 by Materials Project

Zn(OH)2 crystallizes in the triclinic P1 space group. The structure is one-dimensional and consists of two Zn(OH)2 ribbons oriented in the (1, 0, 0) direction. In one of the Zn(OH)2 ribbons, there are three inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.96–2.04 Å. In the second Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.93–2.06 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.95–2.06 Å. There are six 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 0.97 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.01 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.01 Å. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. In the sixth 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 six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to two Zn2+ and one H1+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one H1+ atom. In the third O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Zn2+ and one H1+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Zn2+ and one H1+ atom. In the sixth O2- site, O2- is bonded in a distorted single-bond geometry to two Zn2+ and one H1+ atom. In one of the Zn(OH)2 ribbons, there are three inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.95–2.03 Å. In the second Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.92–2.03 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.93–2.06 Å. There are six 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 O2- atom. The H–O bond length is 0.97 Å. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the fifth 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 sixth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one H1+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to two Zn2+ and one H1+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the sixth O2- site, O2- is bonded in a 1-coordinate geometry to two Zn2+ and one H1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(HO)2 by Materials Project

Zn(OH)2 crystallizes in the triclinic P1 space group. The structure is one-dimensional and consists of two Zn(OH)2 ribbons oriented in the (1, 0, 0) direction. In one of the Zn(OH)2 ribbons, there are three inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.93–2.06 Å. In the second Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.94–2.04 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.92–2.06 Å. There are six 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 0.99 Å. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.01 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the fifth 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 sixth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to two Zn2+ and one H1+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one H1+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one H1+ atom. In one of the Zn(OH)2 ribbons, there are three inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.95–2.02 Å. In the second Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.93–2.04 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form corner-sharing ZnO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.94–2.08 Å. There are six 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 0.99 Å. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. In the fifth 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 sixth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to two Zn2+ and one H1+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one H1+ atom. In the third O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Zn2+ and one H1+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zn2+ and one H1+ atom. In the sixth O2- site, O2- is bonded in a distorted single-bond geometry to two Zn2+ and one H1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(FeO2)2 by Materials Project

ZnFe2O4 is Spinel-like structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twenty inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three equivalent FeO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with three FeO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.01–2.09 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.10 Å. In the third Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.11 Å. In the fourth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three equivalent FeO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.00–2.09 Å. In the fifth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.98–2.10 Å. In the sixth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 55–60°. There are a spread of Fe–O bond distances ranging from 1.92–1.97 Å. In the seventh Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.96–2.14 Å. In the eighth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three equivalent FeO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.02–2.08 Å. In the ninth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with five ZnO6 octahedra and corners with seven FeO6 octahedra. The corner-sharing octahedra tilt angles range from 51–61°. There are a spread of Fe–O bond distances ranging from 1.91–1.96 Å. In the tenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four FeO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.10 Å. In the eleventh Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 54–59°. There is two shorter (1.92 Å) and two longer (1.95 Å) Fe–O bond length. In the twelfth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four FeO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.10 Å. In the thirteenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, edges with three FeO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.98–2.04 Å. In the fourteenth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with six FeO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–60°. There are a spread of Fe–O bond distances ranging from 1.90–1.96 Å. In the fifteenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, edges with two FeO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.95–2.02 Å. In the sixteenth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with four ZnO6 octahedra and corners with eight FeO6 octahedra. The corner-sharing octahedra tilt angles range from 53–60°. There are a spread of Fe–O bond distances ranging from 1.89–2.01 Å. In the seventeenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, edges with two FeO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.97–2.02 Å. In the eighteenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five FeO4 tetrahedra, edges with two FeO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.00–2.10 Å. In the nineteenth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with six FeO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 55–59°. There are a spread of Fe–O bond distances ranging from 1.88–1.99 Å. In the twentieth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with five ZnO6 octahedra and corners with seven FeO6 octahedra. The corner-sharing octahedra tilt angles range from 54–59°. There are a spread of Fe–O bond distances ranging from 1.89–1.95 Å. There are ten inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with four ZnO6 octahedra and corners with eight FeO6 octahedra. The corner-sharing octahedra tilt angles range from 55–60°. There are a spread of Zn–O bond distances ranging from 1.96–2.02 Å. In the second Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–59°. There are a spread of Zn–O bond distances ranging from 1.97–1.99 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 FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–61°. There are a spread of Zn–O bond distances ranging from 1.97–2.03 Å. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.09–2.13 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.06–2.14 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six FeO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.18 Å. In the seventh Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four FeO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.08–2.14 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six FeO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.17 Å. In the ninth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five FeO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.01–2.20 Å. In the tenth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five FeO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.02–2.19 Å. There are forty inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Fe3+ atoms. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to three Fe3+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Fe3+ atoms. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the seventeenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the nineteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Fe3+ atoms. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the twenty-first O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twenty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twenty-third O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twenty-fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the twenty-sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twent

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(FeO2)2 by Materials Project

ZnFe2O4 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are fifteen inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with two equivalent ZnO6 octahedra and corners with ten FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–59°. There are a spread of Fe–O bond distances ranging from 1.93–1.97 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.00–2.11 Å. In the third Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three equivalent FeO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.02–2.10 Å. In the fourth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–58°. There are a spread of Fe–O bond distances ranging from 1.93–1.99 Å. In the fifth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.00–2.12 Å. In the sixth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three equivalent FeO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.03–2.08 Å. In the seventh Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–58°. There are a spread of Fe–O bond distances ranging from 1.93–1.99 Å. In the eighth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.00–2.11 Å. In the ninth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three equivalent FeO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.03–2.08 Å. In the tenth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 57–59°. There are a spread of Fe–O bond distances ranging from 1.93–1.98 Å. In the eleventh Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent FeO4 tetrahedra, corners with four ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.02–2.11 Å. In the twelfth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three equivalent FeO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.03–2.09 Å. In the thirteenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share a cornercorner with one FeO4 tetrahedra, corners with five ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.03–2.11 Å. In the fourteenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share a cornercorner with one FeO4 tetrahedra, corners with five ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.02–2.11 Å. In the fifteenth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six ZnO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.00–2.11 Å. There are ten inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share a cornercorner with one ZnO6 octahedra and corners with eleven FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–60°. There are one shorter (1.99 Å) and three longer (2.01 Å) Zn–O bond lengths. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.10–2.15 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 FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–59°. There are a spread of Zn–O bond distances ranging from 1.98–2.03 Å. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.10–2.14 Å. In the fifth Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 57–59°. There are a spread of Zn–O bond distances ranging from 1.98–2.03 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three FeO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.10–2.14 Å. In the seventh Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–60°. There are a spread of Zn–O bond distances ranging from 1.96–2.03 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with two equivalent FeO4 tetrahedra, corners with four ZnO4 tetrahedra, and edges with six FeO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.09–2.14 Å. In the ninth Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share a cornercorner with one ZnO6 octahedra and corners with eleven FeO6 octahedra. The corner-sharing octahedra tilt angles range from 57–62°. There are a spread of Zn–O bond distances ranging from 1.98–2.04 Å. In the tenth Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with two equivalent ZnO6 octahedra and corners with ten FeO6 octahedra. The corner-sharing octahedra tilt angles range from 55–61°. There are a spread of Zn–O bond distances ranging from 1.98–2.04 Å. There are thirty inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the second O2- site, O2- is bonded to three Fe3+ and one Zn2+ atom to form a mixture of distorted edge and corner-sharing OZnFe3 trigonal pyramids. In the third O2- site, O2- is bonded to four Fe3+ atoms to form a mixture of distorted edge and corner-sharing OFe4 trigonal pyramids. In the fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the seventh O2- site, O2- is bonded to three Fe3+ and one Zn2+ atom to form a mixture of distorted edge and corner-sharing OZnFe3 trigonal pyramids. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Fe3+ and two Zn2+ atoms. In the ninth O2- site, O2- is bonded to four Fe3+ atoms to form a mixture of distorted edge and corner-sharing OFe4 trigonal pyramids. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the thirteenth O2- site, O2- is bonded to three Fe3+ and one Zn2+ atom to form distorted edge-sharing OZnFe3 trigonal pyramids. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Fe3+ and two Zn2+ atoms. In the fifteenth O2- site, O2- is bonded to four Fe3+ atoms to form a mixture of distorted edge and corner-sharing OFe4 trigonal pyramids. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the seventeenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the eighteenth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to two equivalent Fe3+ and two Zn2+ atoms. In the nineteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Fe3+ and two Zn2+ atoms. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the twenty-first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Fe3+ atoms. In the twenty-second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twenty-third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Fe3+ and two Zn2+ atoms. In the twenty-fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Fe3+ atoms. In the twenty-sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Fe3+ and two Zn2+ atoms. In the twenty-seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Fe3+ and one Zn2+ atom. In the twenty-eighth O2- site, O2- is bonded to three Fe3+ and one Zn2+ atom to form a mixture of distorted edge and corner-sharing OZnFe3 trigonal pyramids. In the twenty-ninth O2- site, O2- is bonded to three Fe3+ and one Zn2+ atom to form a mixture of distorted edge and corner-sharing OZnFe3 trigonal pyramids. In the thirtieth O2- site, O2- is bonded to three Fe3+ and one Zn2+ atom to form distorted edge-sharing OZnFe3 trigonal pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Integrated three-dimensional characterization of reactive phase formation and coarsening during isothermal annealing of metastable Zn–3Mg–4Al eutectic

Microstructural instabilities associated with a metastable lamellar eutectic when exposed to an elevated temperature were analyzed in a Zn-3Mg-4Al alloy as a model system. X-ray diffraction and scanning electron microscopy showed that annealing at a temperature 43 K below the equilibrium eutectic temperature converted the metastable ternary MgZn 2 /η-Zn/β-ZnAl eutectic to a stable mixture of Mg 2 Zn 11 /η-Zn/α-Al. 3D EBSD suggested that supersaturation of η-Zn with Mg and Al eased difficulties in nucleation of Mg 2 Zn 11 and α-Al at the MgZn 2 /η-Zn phase interfaces. Quasi-in-situ X-ray nanotomography revealed that a reactive diffusion process prevailed in an early stage of annealing leading to rapid consumption of MgZn 2 for growth of Mg 2 Zn 11 and concomitant thinning and pinch-off of η-Zn lamellae. The reactive diffusion process also brought about significant and quantifiable changes in the topological characteristics of the η-Zn phase at remarkably shorter time scales compared to Rayleigh instability and Ostwald ripening mechanisms. Overall, the present results provide fresh insights on the short-term annealing effects on metastable eutectics, with relevance to structural evolution in additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2021

DFT Mechanism Studies: Biomimetic 1,4-NADH Chemoselective, Co-factor Regeneration with [Cp*Rh(bpy)H] + , in Tandem with the Biocatalysis Pathways of a Core Model of the (HLADH)-Zn(II) Mediated Enzyme, in the Enantioselective Reduction of Achiral Ketones to Chiral S-Alcohols

In this study, Quantum Chemical (QC) calculations, utilizing Density Functional Theory (DFT), were performed to investigate the mechanistic aspects of the chemoselective catalyzed reaction of [Cp*Rh(bpy)H] + with the biomimetic NAD + analogues, N-benzylnicotinamide triflate, 1, and β-nicotinamide ribose-5'-methyl phosphate, 2, in the conversion to their 1,4-NADH analogues, 1,4-dihydro-N-benzylnicotinamide, 4, and β-1,4-dihydronicotinamide-5'-ribose methyl phosphate, 5. This reaction was in tandem with the 1,4-NADH dependent HLADH-Zn(II)- catalyzed reduction of achiral ketones to chiral S-alcohols. The [Cp*Rh(bpy)H] + complex, and not its equilibrium tautomer, [η 4 -Cp*HRh(bpy)] + , was found to control the hydride transfer during the biomimetic NAD + /1,4-NADH conversion, through the non-covalent interactions of the biomimetic co-factors with [Cp*Rh(bpy)H] + . The thermodynamics and kinetics for the chiral reduction of the Zn(II) bound ketones, 2-pentanone and 4-phenyl-2-butanone, with co-factor, 4, catalyzed by Zn(SCH 3 ) 2 (Imidazole), a core model of the Zn(II)-based catalytic center of HLADH, was also investigated by the evaluation of two possible reaction pathways: (1) formation of a ZnH from the C4-H hydride transfer of co-factor, 4, followed by reaction of the postulated ZnH with the bound 2-pentanone or 4-phenyl-2-butanone substrate, and (2), the direct C4-H transfer to the bound achiral ketone substrates, to provide the dominant chiral alcohols, S-2-pentanol or S-4-phenyl-2-butanol. The latter pathway was found most viable, and DFT calculations also revealed an essential η 2 -coordination of the 5,6 double bond of co-factor, 4, to the HLADH-Zn(II) metal ion center, upon imidazole decomplexation, providing an asymmetric differentiation of S-η 2 -5,6-1,4-NADH-Zn(II) binding. A proposed new paradigm for the Zn(II)'s non-innocent role in the HLADH-Zn(II) biocatalysis reduction mechanism, for enantioselective hydride transfer to a Zn(II) bound ketone, providing S-alcohols.

1,4 NADH co-factors↗
DOE OSTI2020

Materials Data on Zn(AgO2)2 by Materials Project

Zn(AgO2)2 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are twelve inequivalent Ag3+ sites. In the first Ag3+ site, Ag3+ is bonded to six O2- atoms to form AgO6 octahedra that share corners with three AgO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four AgO6 octahedra. There are a spread of Ag–O bond distances ranging from 2.10–2.26 Å. In the second Ag3+ site, Ag3+ is bonded to six O2- atoms to form AgO6 octahedra that share corners with three equivalent AgO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four AgO6 octahedra. There are a spread of Ag–O bond distances ranging from 2.10–2.27 Å. In the third Ag3+ site, Ag3+ is bonded to four O2- atoms to form AgO4 tetrahedra that share corners with six AgO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 57–65°. There are a spread of Ag–O bond distances ranging from 2.19–2.26 Å. In the fourth Ag3+ site, Ag3+ is bonded to six O2- atoms to form AgO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four AgO4 tetrahedra, edges with three AgO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Ag–O bond distances ranging from 2.08–2.29 Å. In the fifth Ag3+ site, Ag3+ is bonded to four O2- atoms to form AgO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine AgO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Ag–O bond distances ranging from 2.09–2.21 Å. In the sixth Ag3+ site, Ag3+ is bonded to four O2- atoms to form AgO4 tetrahedra that share corners with six AgO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–65°. There are a spread of Ag–O bond distances ranging from 2.17–2.20 Å. In the seventh Ag3+ site, Ag3+ is bonded to six O2- atoms to form AgO6 octahedra that share corners with six AgO4 tetrahedra, edges with two equivalent AgO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ag–O bond distances ranging from 2.08–2.15 Å. In the eighth Ag3+ site, Ag3+ is bonded to four O2- atoms to form AgO4 tetrahedra that share corners with six AgO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–64°. There are a spread of Ag–O bond distances ranging from 2.11–2.18 Å. In the ninth Ag3+ site, Ag3+ is bonded to six O2- atoms to form AgO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five AgO4 tetrahedra, edges with three AgO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Ag–O bond distances ranging from 2.07–2.20 Å. In the tenth Ag3+ site, Ag3+ is bonded to four O2- atoms to form AgO4 tetrahedra that share corners with six AgO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 57–65°. There are a spread of Ag–O bond distances ranging from 2.16–2.20 Å. In the eleventh Ag3+ site, Ag3+ is bonded to six O2- atoms to form AgO6 octahedra that share corners with three equivalent AgO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four AgO6 octahedra. There are a spread of Ag–O bond distances ranging from 2.11–2.32 Å. In the twelfth Ag3+ site, Ag3+ is bonded to four O2- atoms to form AgO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine AgO6 octahedra. The corner-sharing octahedra tilt angles range from 58–64°. There are one shorter (2.13 Å) and three longer (2.21 Å) Ag–O bond lengths. 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 AgO6 octahedra. The corner-sharing octahedra tilt angles range from 50–62°. There are a spread of Zn–O bond distances ranging from 1.99–2.07 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three AgO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six AgO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.15–2.17 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 AgO6 octahedra. The corner-sharing octahedra tilt angles range from 53–60°. There are a spread of Zn–O bond distances ranging from 2.00–2.07 Å. 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 AgO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five AgO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.10–2.23 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six AgO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four equivalent AgO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.08–2.18 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six AgO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four AgO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.20 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 AgO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five AgO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.06–2.23 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six AgO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four AgO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.09–2.20 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ag3+ and two Zn2+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Ag3+ and two Zn2+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Ag3+ and one Zn2+ atom. In the fourth O2- site, O2- is bonded to four Ag3+ atoms to form a mixture of distorted corner and edge-sharing OAg4 trigonal pyramids. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ag3+ and two Zn2+ atoms. In the sixth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 tetrahedra that share a cornercorner with one OZnAg3 tetrahedra, corners with two OZnAg3 trigonal pyramids, edges with two OZnAg3 tetrahedra, and an edgeedge with one OAg4 trigonal pyramid. In the seventh O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 tetrahedra that share corners with six OZn2Ag2 tetrahedra and corners with four OZnAg3 trigonal pyramids. In the eighth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 tetrahedra that share corners with two equivalent OZnAg3 tetrahedra, a cornercorner with one OAg4 trigonal pyramid, edges with two equivalent OZnAg3 tetrahedra, and an edgeedge with one OAg4 trigonal pyramid. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Ag3+ and one Zn2+ atom. In the tenth O2- site, O2- is bonded to two Ag3+ and two Zn2+ atoms to form distorted OZn2Ag2 tetrahedra that share corners with seven OZn2Ag2 tetrahedra, corners with four OZnAg3 trigonal pyramids, an edgeedge with one OZn2Ag2 tetrahedra, and edges with two OZnAg3 trigonal pyramids. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Ag3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded to two Ag3+ and two Zn2+ atoms to form distorted OZn2Ag2 tetrahedra that share corners with five OZnAg3 tetrahedra, corners with two OZnAg3 trigonal pyramids, an edgeedge with one OZn2Ag2 tetrahedra, and an edgeedge with one OZnAg3 trigonal pyramid. In the thirteenth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 trigonal pyramids that share corners with six OZn2Ag2 tetrahedra, corners with six OZnAg3 trigonal pyramids, edges with two equivalent OZn2Ag2 tetrahedra, and an edgeedge with one OZnAg3 trigonal pyramid. In the fourteenth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 trigonal pyramids that share corners with five OZnAg3 tetrahedra, a cornercorner with one OAg4 trigonal pyramid, and edges with two equivalent OZn2Ag2 tetrahedra. In the fifteenth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 trigonal pyramids that share corners with seven OZn2Ag2 tetrahedra, corners with four OZnAg3 trigonal pyramids, edges with two equivalent OZn2Ag2 tetrahedra, and an edgeedge with one OZnAg3 trigonal pyramid. In the sixteenth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 trigonal pyramids that share corners with six OZn2Ag2 tetrahedra, corners with six OZnAg3 trigonal pyramids, edges with two equivalent OZn2Ag2 tetrahedra, and an edgeedge with one OZnAg3 trigonal pyramid. In the seventeenth O2- site, O2- is bonded to two Ag3+ and two Zn2+ atoms to form distorted OZn2Ag2 tetrahedra that share corners with six OZn2Ag2 tetrahedra, corners with six OZnAg3 trigonal pyramids, an edgeedge with one OZn2Ag2 tetrahedra, and an edgeedge with one OZnAg3 trigonal pyramid. In the eighteenth O2- site, O2- is bonded to two Ag3+ and two Zn2+ atoms to form distorted OZn2Ag2 tetrahedra that share corners with six OZn2Ag2 tetrahedra, corners with six OZnAg3 trigonal pyramids, an edgeedge with one OZn2Ag2 tetrahedra, and edges with two OZnAg3 trigonal pyramids. In the nineteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Ag3+ and two Zn2+ atoms. In the twentieth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 trigonal pyramids that share corners with six OZn2Ag2 tetrahedra, corners with five OZnAg3 trigonal pyramids, edges with two equivalent OZn2Ag2 tetrahedra, and an edgeedge with one OZnAg3 trigonal pyramid. In the twenty-first O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 trigonal pyramids that share corners with six OZn2Ag2 tetrahedra, corners with six OZnAg3 trigonal pyramids, and edges with two equivalent OZn2Ag2 tetrahedra. In the twenty-second O2- site, O2- is bonded to four Ag3+ atoms to form distorted OAg4 trigonal pyramids that share corners with five OZn2Ag2 tetrahedra, corners with two equivalent OZnAg3 trigonal pyramids, edges with two equivalent OZnAg3 tetrahedra, and an edgeedge with one OZnAg3 trigonal pyramid. In the twenty-third O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 tetrahedra that share corners with five OZn2Ag2 tetrahedra, corners with two OZnAg3 trigonal pyramids, an edgeedge with one OZnAg3 tetrahedra, and edges with two OAg4 trigonal pyramids. In the twenty-fourth O2- site, O2- is bonded to three Ag3+ and one Zn2+ atom to form distorted OZnAg3 trigonal pyramids that share corners with six OZn2Ag2 tetrahedra, corners with three OZnAg3 trigonal pyramids, edges with two equivalent OZnAg3 tetrahedra, and an edgeedge with one OAg4 trigonal pyramid.

36 MATERIALS SCIENCE↗
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(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(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(MoO2)2 by Materials Project

Zn(MoO2)2 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are twelve inequivalent Mo3+ sites. In the first Mo3+ site, Mo3+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with three MoO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.14–2.19 Å. In the second Mo3+ site, Mo3+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with three equivalent MoO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.15–2.19 Å. In the third Mo3+ site, Mo3+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with six MoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 45–65°. There are a spread of Mo–O bond distances ranging from 2.09–2.12 Å. In the fourth Mo3+ site, Mo3+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four MoO4 tetrahedra, edges with three MoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.14–2.19 Å. In the fifth Mo3+ site, Mo3+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine MoO6 octahedra. The corner-sharing octahedra tilt angles range from 48–64°. There are three shorter (2.09 Å) and one longer (2.12 Å) Mo–O bond lengths. In the sixth Mo3+ site, Mo3+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with six MoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 41–67°. There are three shorter (2.10 Å) and one longer (2.11 Å) Mo–O bond lengths. In the seventh Mo3+ site, Mo3+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with six MoO4 tetrahedra, edges with two equivalent MoO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.15–2.18 Å. In the eighth Mo3+ site, Mo3+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with six MoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 45–65°. There are a spread of Mo–O bond distances ranging from 2.08–2.14 Å. In the ninth Mo3+ site, Mo3+ is bonded to six O2- atoms to form MoO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five MoO4 tetrahedra, edges with three MoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.15–2.19 Å. In the tenth Mo3+ site, Mo3+ is bonded to four O2- atoms to form distorted MoO4 tetrahedra that share corners with six MoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 44–67°. There are a spread of Mo–O bond distances ranging from 2.09–2.13 Å. In the eleventh Mo3+ site, Mo3+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with three equivalent MoO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.15–2.19 Å. In the twelfth Mo3+ site, Mo3+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine MoO6 octahedra. The corner-sharing octahedra tilt angles range from 50–64°. There are three shorter (2.09 Å) and one longer (2.13 Å) Mo–O bond lengths. 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 MoO6 octahedra. The corner-sharing octahedra tilt angles range from 49–60°. There are a spread of Zn–O bond distances ranging from 2.05–2.09 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three MoO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six MoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.14–2.21 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 MoO6 octahedra. The corner-sharing octahedra tilt angles range from 48–61°. There are a spread of Zn–O bond distances ranging from 2.05–2.10 Å. 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 MoO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five MoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.14–2.18 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six MoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four equivalent MoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.14–2.21 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six MoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four MoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.14–2.20 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 MoO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five MoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.13–2.21 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six MoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four MoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.15–2.23 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mo3+ and two Zn2+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Mo3+ and two Zn2+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Mo3+ atoms. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mo3+ and two Zn2+ atoms. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mo3+ and two Zn2+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mo3+ and two Zn2+ atoms. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the seventeenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mo3+ and two Zn2+ atoms. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mo3+ and two Zn2+ atoms. In the nineteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Mo3+ and two Zn2+ atoms. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the twenty-first O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the twenty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Mo3+ atoms. In the twenty-third O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Mo3+ and one Zn2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(WO2)2 by Materials Project

Zn(WO2)2 is Ilmenite-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are twelve inequivalent W3+ sites. In the first W3+ site, W3+ is bonded to six O2- atoms to form WO6 octahedra that share corners with two equivalent WO4 tetrahedra, corners with three ZnO4 tetrahedra, a cornercorner with one WO4 trigonal pyramid, edges with two equivalent ZnO6 octahedra, and edges with four WO6 octahedra. There are a spread of W–O bond distances ranging from 2.15–2.23 Å. In the second W3+ site, W3+ is bonded to six O2- atoms to form WO6 octahedra that share corners with three equivalent WO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four WO6 octahedra. There are two shorter (2.16 Å) and four longer (2.18 Å) W–O bond lengths. In the third W3+ site, W3+ is bonded to four O2- atoms to form distorted WO4 trigonal pyramids that share corners with six WO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 37–80°. There are a spread of W–O bond distances ranging from 2.00–2.48 Å. In the fourth W3+ site, W3+ is bonded to six O2- atoms to form WO6 octahedra that share a cornercorner with one WO4 tetrahedra, corners with two equivalent ZnO4 tetrahedra, corners with three WO4 trigonal pyramids, edges with three WO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of W–O bond distances ranging from 2.12–2.20 Å. In the fifth W3+ site, W3+ is bonded to four O2- atoms to form WO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine WO6 octahedra. The corner-sharing octahedra tilt angles range from 51–73°. There are a spread of W–O bond distances ranging from 2.04–2.29 Å. In the sixth W3+ site, W3+ is bonded in a trigonal planar geometry to three O2- atoms. There are two shorter (2.02 Å) and one longer (2.10 Å) W–O bond lengths. In the seventh W3+ site, W3+ is bonded to six O2- atoms to form WO6 octahedra that share corners with three WO4 trigonal pyramids, edges with two equivalent WO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of W–O bond distances ranging from 2.11–2.23 Å. In the eighth W3+ site, W3+ is bonded to four O2- atoms to form WO4 trigonal pyramids that share corners with six WO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 23–82°. There are a spread of W–O bond distances ranging from 2.01–2.51 Å. In the ninth W3+ site, W3+ is bonded to six O2- atoms to form distorted WO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with two equivalent WO4 trigonal pyramids, edges with three WO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of W–O bond distances ranging from 2.11–2.35 Å. In the tenth W3+ site, W3+ is bonded in a distorted trigonal planar geometry to three O2- atoms. There are two shorter (2.02 Å) and one longer (2.04 Å) W–O bond lengths. In the eleventh W3+ site, W3+ is bonded to six O2- atoms to form WO6 octahedra that share corners with three equivalent ZnO4 tetrahedra, corners with three equivalent WO4 trigonal pyramids, edges with two ZnO6 octahedra, and edges with four WO6 octahedra. There are a spread of W–O bond distances ranging from 2.11–2.20 Å. In the twelfth W3+ site, W3+ is bonded to four O2- atoms to form WO4 trigonal pyramids that share corners with three ZnO6 octahedra and corners with nine WO6 octahedra. The corner-sharing octahedra tilt angles range from 35–76°. There are a spread of W–O bond distances ranging from 2.02–2.32 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 WO6 octahedra. The corner-sharing octahedra tilt angles range from 51–63°. There are a spread of Zn–O bond distances ranging from 2.02–2.06 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with two equivalent WO4 tetrahedra, corners with three ZnO4 tetrahedra, a cornercorner with one WO4 trigonal pyramid, and edges with six WO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.11–2.23 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 WO6 octahedra. The corner-sharing octahedra tilt angles range from 49–59°. There are a spread of Zn–O bond distances ranging from 2.00–2.09 Å. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one WO4 tetrahedra, corners with two equivalent ZnO4 tetrahedra, corners with three WO4 trigonal pyramids, an edgeedge with one ZnO6 octahedra, and edges with five WO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.11–2.27 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with three WO4 trigonal pyramids, edges with two ZnO6 octahedra, and edges with four equivalent WO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.14 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with six WO4 trigonal pyramids, edges with two ZnO6 octahedra, and edges with four WO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.01–2.57 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 two equivalent WO4 trigonal pyramids, an edgeedge with one ZnO6 octahedra, and edges with five WO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.10–2.28 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share edges with two ZnO6 octahedra and edges with four WO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.06–2.20 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 W3+ and two Zn2+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent W3+ and two Zn2+ atoms. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three W3+ and one Zn2+ atom. In the fourth O2- site, O2- is bonded to four W3+ atoms to form a mixture of distorted corner and edge-sharing OW4 trigonal pyramids. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two W3+ and two Zn2+ atoms. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three W3+ and one Zn2+ atom. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three W3+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded to three W3+ and one Zn2+ atom to form distorted OZnW3 trigonal pyramids that share corners with two equivalent OZnW3 trigonal pyramids and an edgeedge with one OW4 trigonal pyramid. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three W3+ and one Zn2+ atom. In the tenth O2- site, O2- is bonded to two W3+ and two Zn2+ atoms to form distorted OZn2W2 trigonal pyramids that share a cornercorner with one OZnW3 tetrahedra, corners with six OZn2W2 trigonal pyramids, and an edgeedge with one OZn2W2 trigonal pyramid. In the eleventh O2- site, O2- is bonded in a 4-coordinate geometry to three W3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two W3+ and two Zn2+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent W3+ and one Zn2+ atom. In the fourteenth O2- site, O2- is bonded to three W3+ and one Zn2+ atom to form distorted corner-sharing OZnW3 trigonal pyramids. In the fifteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three W3+ and one Zn2+ atom. In the sixteenth O2- site, O2- is bonded to three W3+ and one Zn2+ atom to form distorted OZnW3 tetrahedra that share a cornercorner with one OZnW3 tetrahedra, corners with six OZn2W2 trigonal pyramids, and edges with three OZnW3 trigonal pyramids. In the seventeenth O2- site, O2- is bonded to two W3+ and two Zn2+ atoms to form distorted OZn2W2 trigonal pyramids that share corners with two OZnW3 tetrahedra, corners with six OZn2W2 trigonal pyramids, edges with two OZnW3 tetrahedra, and an edgeedge with one OZn2W2 trigonal pyramid. In the eighteenth O2- site, O2- is bonded to two W3+ and two Zn2+ atoms to form distorted OZn2W2 trigonal pyramids that share corners with two OZnW3 tetrahedra, corners with six OZn2W2 trigonal pyramids, an edgeedge with one OZnW3 tetrahedra, and edges with two OZnW3 trigonal pyramids. In the nineteenth O2- site, O2- is bonded to two equivalent W3+ and two Zn2+ atoms to form distorted OZn2W2 tetrahedra that share corners with four equivalent OZnW3 trigonal pyramids, an edgeedge with one OZnW3 tetrahedra, and edges with two equivalent OZn2W2 trigonal pyramids. In the twentieth O2- site, O2- is bonded to three W3+ and one Zn2+ atom to form distorted OZnW3 trigonal pyramids that share corners with four equivalent OZn2W2 trigonal pyramids, an edgeedge with one OZnW3 tetrahedra, and edges with two equivalent OZn2W2 trigonal pyramids. In the twenty-first O2- site, O2- is bonded to three W3+ and one Zn2+ atom to form distorted OZnW3 tetrahedra that share a cornercorner with one OZnW3 tetrahedra, corners with six OZn2W2 trigonal pyramids, an edgeedge with one OZn2W2 tetrahedra, and edges with two equivalent OZn2W2 trigonal pyramids. In the twenty-second O2- site, O2- is bonded in a 4-coordinate geometry to four W3+ atoms. In the twenty-third O2- site, O2- is bonded to three W3+ and one Zn2+ atom to form OZnW3 trigonal pyramids that share corners with three OZn2W2 tetrahedra, corners with five OZn2W2 trigonal pyramids, and an edgeedge with one OZnW3 trigonal pyramid. In the twenty-fourth O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent W3+ and one Zn2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Propane Dehydrogenation on Pt x Zn y Active Sites in Silicalite‐1

Abstract The improvement of Pt‐based catalysts for propane dehydrogenation (PDH) has progressed by recent investigations that have identified Zn as a promising promoter for Pt subnanometer catalysts. It is desirable to gain insights into the structure, stability, and activity of such active sites and the factors that influence them, such as Zn : Pt ratio, Pt coordination and nuclearity. Here, we employ density functional theory and microkinetic simulations to investigate the stability of Pt x Zn y ( x =1–3, y=0–3) active sites grafted on silanols of Silicalite‐1 and the PDH activity of Pt. We find that the coordination of a Pt atom to a nest of grafted Zn(II) atoms increases the stability of the Pt 1 Zn y sites, whose activity is similar for y=0–2 and drops dramatically for y>2. We further demonstrate, via linear scaling relations and microkinetic simulations, that the turnover frequency obeys a volcano law as a function of propylene binding strength. The Pt 2 Zn 1 and Pt 3 Zn 1 sites are stable and exhibit activity similar to Pt 1 Zn 2 , but only Pt 1 Zn 2 manifests reaction kinetics consistent with experimental data, strongly suggesting the active site composition in the synthesized catalyst samples. The methodology presented here suggests a general strategy for deducing active site information such as composition through simple kinetic experiments.

Liu, Yilang↗
DOE OSTI2024

Propane Dehydrogenation on Pt x Zn y Active Sites in Silicalite‐1

Abstract The improvement of Pt‐based catalysts for propane dehydrogenation (PDH) has progressed by recent investigations that have identified Zn as a promising promoter for Pt subnanometer catalysts. It is desirable to gain insights into the structure, stability, and activity of such active sites and the factors that influence them, such as Zn : Pt ratio, Pt coordination and nuclearity. Here, we employ density functional theory and microkinetic simulations to investigate the stability of Pt x Zn y ( x =1–3, y=0–3) active sites grafted on silanols of Silicalite‐1 and the PDH activity of Pt. We find that the coordination of a Pt atom to a nest of grafted Zn(II) atoms increases the stability of the Pt 1 Zn y sites, whose activity is similar for y=0–2 and drops dramatically for y>2. We further demonstrate, via linear scaling relations and microkinetic simulations, that the turnover frequency obeys a volcano law as a function of propylene binding strength. The Pt 2 Zn 1 and Pt 3 Zn 1 sites are stable and exhibit activity similar to Pt 1 Zn 2 , but only Pt 1 Zn 2 manifests reaction kinetics consistent with experimental data, strongly suggesting the active site composition in the synthesized catalyst samples. The methodology presented here suggests a general strategy for deducing active site information such as composition through simple kinetic experiments.

Liu, Yilang↗
DOE OSTI2026

Tetrahedral Zn 2+ doping LiNi 0.6 Mn 0.2 Co 0.2 O 2 improves discharge capacity retention by altering surface Ni valence during cycling and preventing oxygen evolution

5 mol-% Zn 2+ was added to the co-precipitation synthesis of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) to understand Zn's effect on the structural and electronic properties of NMC622. Zn is determined to successfully dope into the NMC crystal lattice as there is an increase in d-spacing along the [003], [104], and [110] directions and an increase in molar volume (100.75 cm 3 mol -1 for NMC622 and 101.00 cm 3 mol -1 for Zn-NMC). Through XPS, Zn is determined to dope on the tetrahedral 6c Wyckoff site in the NMC structure and TEM-EDS reveals that despite a slight ZnO impurity phase, 1.4 mol-% Zn successfully dopes into the crystal structure. Furthermore, cyclic voltammetry shows a suppressed anodic wave associated with oxygen evolution and EIS demonstrates that Zn-doped NMC decreases charge transfer resistance and increases Li diffusion by an order of magnitude. After the formation cycles, NMC has a higher 1 C accessible capacity, 141 mAh/g, over Zn-NMC (132 mAh/g), but after long term cycling Zn-NMC has a higher accessible capacity (117 mAh/g compared to 96 mAh/g for NMC) and increases discharge capacity retention by 18% leading to longer cycle life.

Electrochemistry↗
DOE OSTI2024

Impurity-enhanced core valence luminescence via Zn-doping in cesium magnesium chlorides

Scintillators with faster timing capabilities are currently in high demand for use in radiation detection systems in the fields of nuclear and medical physics. The limited number of suitable materials that meet the performance criteria of next generation detection systems presents an opportunity for discovery of new fast scintillator materials. In this work, the effects of doping several ultrafast core-valence luminescent (CVL) scintillators with divalent Zn is explored. Three compounds are investigated – CsMgCl 3 , Cs 2 MgCl 4 , and Cs 3 MgCl 5 – and single crystals of each doped with 5 mol% Zn are grown via the Bridgman method. Additionally, mixing across the full range of concentrations (from 0 % to 100 % Zn) is explored in the Cs 2 Mg 1-x Zn x Cl 4 and Cs 3 Mg 1-x Zn x Cl 5 systems. For low concentrations of Zn, light yields of all three compounds are enhanced (by up to ~60 %) compared to the pure crystals, achieving what we believe to be the brightest known CVL, CsMgCl 3 :Zn 5 % (3400 ± 170 ph/MeV light yield). More importantly, Zn doping does not affect the ultrafast timing properties, with each composition maintaining a single-component decay time around 1–3 ns. A sub-100 ps coincidence time resolution (CTR) is also achieved with CsMgCl 3 :Zn 5 %. The results of this work reveal a new avenue towards obtaining brighter CVL materials, which could open up possibilities for more advanced ultrafast scintillators to be discovered moving forward.

36 MATERIALS SCIENCE↗