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5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Defective Sn-Zn perovskites through bio-directed routes for modulating CO 2 RR

Sn and Zn oxides can catalyze electrochemical CO 2 reduction reactions (CO 2 RR) to produce useful chemicals. Herein, we report on perovskite-type tin-zinc oxides (TZO) synthesized by a biomineralization approach under benign aqueous conditions. The resulting TZO catalysts are disordered and possess a high quantity of defects, which serve as highly reactive active sites in CO 2 RR. Selectively toward formate or CO is tunable toward the relative amounts of Sn and Zn and their associated O defects. In-situ X-ray absorption spectroscopy measurements reveal electronic and structural transformations consistent with oxygen vacancy formation at Sn-O-Zn bridges as a function of cathodic potential that strongly correlates to CO2RR selectivity. Further, Density functional theory (DFT) calculations demonstrate that introducing an oxygen vacancy in TZO influences drastically influences formate/CO selectivity, consistent with our in-situ XAS findings and catalytic performance. Overall, these findings demonstrate the potential of biomineralization to fabricate perovskite-type metal oxides for energy conversion reactions.

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

Materials Data on ZnSn3 by Materials Project

ZnSn3 is beta Cu3Ti-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Zn is bonded to twelve equivalent Sn atoms to form ZnSn12 cuboctahedra that share corners with six equivalent ZnSn12 cuboctahedra, corners with twelve equivalent SnZn4Sn8 cuboctahedra, edges with eighteen equivalent SnZn4Sn8 cuboctahedra, faces with eight equivalent ZnSn12 cuboctahedra, and faces with twelve equivalent SnZn4Sn8 cuboctahedra. There are six shorter (3.29 Å) and six longer (3.31 Å) Zn–Sn bond lengths. Sn is bonded to four equivalent Zn and eight equivalent Sn atoms to form distorted SnZn4Sn8 cuboctahedra that share corners with four equivalent ZnSn12 cuboctahedra, corners with fourteen equivalent SnZn4Sn8 cuboctahedra, edges with six equivalent ZnSn12 cuboctahedra, edges with twelve equivalent SnZn4Sn8 cuboctahedra, faces with four equivalent ZnSn12 cuboctahedra, and faces with sixteen equivalent SnZn4Sn8 cuboctahedra. There are a spread of Sn–Sn bond distances ranging from 3.24–3.34 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn3Sn by Materials Project

Zn3Sn is beta Cu3Ti-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Zn sites. In the first Zn site, Zn is bonded to eight Zn and four equivalent Sn atoms to form ZnZn8Sn4 cuboctahedra that share corners with twelve equivalent ZnZn8Sn4 cuboctahedra, edges with eight equivalent SnZn12 cuboctahedra, edges with sixteen ZnZn8Sn4 cuboctahedra, faces with four equivalent SnZn12 cuboctahedra, and faces with fourteen ZnZn8Sn4 cuboctahedra. There are four shorter (2.93 Å) and four longer (3.01 Å) Zn–Zn bond lengths. All Zn–Sn bond lengths are 3.01 Å. In the second Zn site, Zn is bonded to eight equivalent Zn and four equivalent Sn atoms to form distorted ZnZn8Sn4 cuboctahedra that share corners with four equivalent ZnZn8Sn4 cuboctahedra, corners with eight equivalent SnZn12 cuboctahedra, edges with twenty-four ZnZn8Sn4 cuboctahedra, faces with six equivalent SnZn12 cuboctahedra, and faces with twelve ZnZn8Sn4 cuboctahedra. All Zn–Sn bond lengths are 2.93 Å. Sn is bonded to twelve Zn atoms to form SnZn12 cuboctahedra that share corners with four equivalent SnZn12 cuboctahedra, corners with eight equivalent ZnZn8Sn4 cuboctahedra, edges with eight equivalent SnZn12 cuboctahedra, edges with sixteen equivalent ZnZn8Sn4 cuboctahedra, faces with four equivalent SnZn12 cuboctahedra, and faces with fourteen ZnZn8Sn4 cuboctahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on ZnSn3 by Materials Project

ZnSn3 is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Zn is bonded in a body-centered cubic geometry to eight equivalent Sn atoms. All Zn–Sn bond lengths are 3.20 Å. There are two inequivalent Sn sites. In the first Sn site, Sn is bonded in a body-centered cubic geometry to four equivalent Zn and four equivalent Sn atoms. All Sn–Sn bond lengths are 3.20 Å. In the second Sn site, Sn is bonded in a body-centered cubic geometry to eight equivalent Sn atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on ZnSn3 by Materials Project

ZnSn3 crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Zn is bonded in a square co-planar geometry to twelve Sn atoms. There are four shorter (3.13 Å) and eight longer (3.42 Å) Zn–Sn bond lengths. There are two inequivalent Sn sites. In the first Sn site, Sn is bonded to four equivalent Zn and eight Sn atoms to form a mixture of distorted face, edge, and corner-sharing SnZn4Sn8 cuboctahedra. There are four shorter (3.13 Å) and four longer (3.42 Å) Sn–Sn bond lengths. In the second Sn site, Sn is bonded in a square co-planar geometry to four equivalent Zn and eight equivalent Sn atoms.

36 MATERIALS SCIENCE↗