Abstract
Shape-selective solution-phase nanocrystal growth is facilitated by capping agents, or structure-directing agents (SDAs), which guide shape evolution. It is often stated that these chemical additives impart shape selectivity by promoting nanocrystals with a majority of facets to which they bind most strongly. However, little is known on the mechanisms through which they impart shape selectivity. In this Feature Article, we highlight our recent studies aimed at understanding the thermodynamic and kinetic influences of SDAs using theory and computational tools. We review our studies of the poly(vinylpyrrolidone) (PVP)-mediated synthesis of {100}-faceted Ag nanocubes in ethylene glycol solution, which has been studied experimentally. Our studies of the interfacial free energy of Ag–PVP solution interfaces show that while solution-phase PVP does bind more strongly to Ag(100) than to Ag(111), this selectivity is not sufficient to thermodynamically change the Wulff shape of a PVP-covered Ag nanocrystal in solut...
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