TY - JOUR
T1 - Structure-Selective Cation Exchange in the Synthesis of Zincblende MnS and CoS Nanocrystals
AU - Fenton, Julie L.
AU - Schaak, Raymond E.
N1 - Funding Information:
This work was supported by the U.S. National Science Foundation under grant DMR-1607135. TEM imaging was performed in the Penn State Microscopy and Cytometry facility. HR-TEM imaging, S/TEM imaging, and EDS mapping were performed at the Materials Characterization Lab of the Penn State Materials Research Institute. The authors thank Dr. James M. Hodges and Robert W. Lord for helpful discussions and initial experimental support.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/6/1
Y1 - 2017/6/1
N2 - The ability to selectively form one crystal structure among several options in a polymorphic system is an important goal in solid-state synthesis. Nanocrystal cation exchange, which proceeds rapidly under mild conditions, can retain key structural features and yield otherwise inaccessible phases, but the extent to which crystal structure can be retained and therefore selectively targeted during such reactions has been limited. Here, we show that nanocrystals of digenite Cu2−xS transform to zincblende MnS and CoS upon cation exchange. Zincblende MnS and CoS, which are metastable in bulk, retain both the tetrahedral cation coordination and cubic close packed anion sublattice of digenite Cu2−xS. Comparison with wurtzite MnS and CoS, which have been accessed previously through analogous cation exchange of roxbyite Cu2−xS, demonstrates the selective formation of the related zincblende vs. wurtzite polymorphs by cation exchange of structurally distinct templates.
AB - The ability to selectively form one crystal structure among several options in a polymorphic system is an important goal in solid-state synthesis. Nanocrystal cation exchange, which proceeds rapidly under mild conditions, can retain key structural features and yield otherwise inaccessible phases, but the extent to which crystal structure can be retained and therefore selectively targeted during such reactions has been limited. Here, we show that nanocrystals of digenite Cu2−xS transform to zincblende MnS and CoS upon cation exchange. Zincblende MnS and CoS, which are metastable in bulk, retain both the tetrahedral cation coordination and cubic close packed anion sublattice of digenite Cu2−xS. Comparison with wurtzite MnS and CoS, which have been accessed previously through analogous cation exchange of roxbyite Cu2−xS, demonstrates the selective formation of the related zincblende vs. wurtzite polymorphs by cation exchange of structurally distinct templates.
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U2 - 10.1002/anie.201701087
DO - 10.1002/anie.201701087
M3 - Article
C2 - 28464360
AN - SCOPUS:85018987252
SN - 1433-7851
VL - 56
SP - 6464
EP - 6467
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 23
ER -