Simple Shape-Selective Control of Germanium Pyroxene Crystals

Molecular recognition at interfaces is essential approach for growth of crystals with selectively exposed facets. In general, this process is guided by impurities or solvents that favor the development of surfaces with particular reticular density. However, the specific agents that direct the crystal habit of one system often remain irrelevant for another, and thus, the control of crystal surface of many materials is still poorly known. Here we show selective resizing of prismatic crystal facets of germanium clinopyroxene (NaFeGe2O6) only by a simple switch between nitrate (Fe3+), chloride (Fe3+), and sulfate (Fe2+) sources of iron. The observed effect is explained by the combination of different rates of ion transport to the crystal surface and binding affinity of the hydrolyzed derivatives of the iron precursors that cap the crystal surface during the crystallization. Furthermore, this work reveals the first mild hydrothermal synthesis of germanium clinopyroxene.