TY - JOUR
T1 - Morphology-Dependent Phase Selectivity of Cobalt Sulfide during Nanoparticle Cation Exchange Reactions
AU - Butterfield, Auston G.
AU - McCormick, Connor R.
AU - Veglak, Joseph M.
AU - Schaak, Raymond E.
N1 - Funding Information:
This work was supported by the U.S. National Science Foundation under Grant DMR-1904122. TEM and XRD data were acquired at the Materials Characterization Lab of the Penn State Materials Research Institute.
Publisher Copyright:
©
PY - 2021/6/2
Y1 - 2021/6/2
N2 - Achieving phase selectivity during nanoparticle synthesis is important because crystal structure and composition influence reactivity, growth, and properties. Cation exchange provides a pathway for targeting desired phases by modifying composition while maintaining crystal structure. However, our understanding of how to selectively target different phases in the same system is limited. Here, we demonstrate morphology-dependent phase selectivity for wurtzite (wz) CoS, which is hcp, vs pentlandite Co9S8, which is ccp, during Co2+ exchange of roxbyite Cu1.8S plates, spheres, and rods. The plates form wz-CoS, the spheres form both wz-CoS and Co9S8, and the rods form Co9S8. The plates, spheres, and rods have nearly identical widths but increase in length in the direction that the close-packed planes stack, which influences the ability of the anions to shift from hcp to ccp during cation exchange. This morphology-dependent behavior, which correlates with the number of stacked close-packed planes, relies on an anion sublattice rearrangement that is concomitant with cation exchange, thereby providing a unique pathway by which crystal structure can be controlled and phase selectivity can be achieved during nanocrystal cation exchange.
AB - Achieving phase selectivity during nanoparticle synthesis is important because crystal structure and composition influence reactivity, growth, and properties. Cation exchange provides a pathway for targeting desired phases by modifying composition while maintaining crystal structure. However, our understanding of how to selectively target different phases in the same system is limited. Here, we demonstrate morphology-dependent phase selectivity for wurtzite (wz) CoS, which is hcp, vs pentlandite Co9S8, which is ccp, during Co2+ exchange of roxbyite Cu1.8S plates, spheres, and rods. The plates form wz-CoS, the spheres form both wz-CoS and Co9S8, and the rods form Co9S8. The plates, spheres, and rods have nearly identical widths but increase in length in the direction that the close-packed planes stack, which influences the ability of the anions to shift from hcp to ccp during cation exchange. This morphology-dependent behavior, which correlates with the number of stacked close-packed planes, relies on an anion sublattice rearrangement that is concomitant with cation exchange, thereby providing a unique pathway by which crystal structure can be controlled and phase selectivity can be achieved during nanocrystal cation exchange.
UR - http://www.scopus.com/inward/record.url?scp=85107711518&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85107711518&partnerID=8YFLogxK
U2 - 10.1021/jacs.1c03478
DO - 10.1021/jacs.1c03478
M3 - Article
C2 - 34019412
AN - SCOPUS:85107711518
SN - 0002-7863
VL - 143
SP - 7915
EP - 7919
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 21
ER -