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Changes in the crystal system of an ionic nanocrystal during a cation exchange reaction are unusual yet remain to be systematically investigated. In this study, chemical synthesis and computational modeling demonstrated that the height of hexagonal-prism roxbyite (Cu1.8S) nanocrystals with a distorted hexagonal close-packed sulfide anion (S2-) sublattice determines the final crystal phase of the cation-exchanged products with Co2+ wurtzite cobalt sulfide (CoS) with hexagonal close-packed S2- and/or cobalt pentlandite (Co9S8) with cubic close-packed S2-. Thermodynamic instability of exposed planes drives reconstruction of anion frameworks under mild reaction conditions. Other incoming cations (Mn2+, Zn2+, and Ni2+) modulate crystal structure transformation during cation exchange reactions by various means, such as volume, thermodynamic stability, and coordination environment.
Li et al. (Thu,) studied this question.
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