A Strategy for Hydroxide Exclusion in Nanocrystalline Solid-State Metathesis Products

We demonstrate a simple strategy to either prevent or enhance hydroxide incorporation in nanocrystalline solid-state metathesis reaction products prepared in ambient environments. As an example, we show that ZnCO(3) (smithsonite) or Zn(5)(CO(3))(2)(OH)(6) (hydrozincite) forms extremely rapidly, in less than two minutes, to form crystalline domains of 11 ± 2 nm and 6 ± 2 nm, respectively. The phase selectivity between these nanocrystalline products is dominated by the alkalinity of the hydrated precursor salts, which may in turn affect the availability of carbon dioxide during the reaction. Thus, unlike traditional aqueous precipitation reactions, our solid-state method offers a way to produce hydroxide-free, nanocrystalline products without active pH control.