Nonclassical crystallization of zinc carbonate hydroxide hydrate nanofilm mediated by calcium ions

To satisfy the demand of zinc oxide (ZnO) with advanced muti-functional properties, significant efforts have been made in synthesizing ZnO with various structure and morphology. In particular, hydrothermal method has attracted considerable attentions, in which Zn4CO3(OH)6·H2O (ZCHH) is commonly found as a metastable precursor. However, the formation and crystallization mechanisms of ZCHH are still lacking and urgently needed. In the present study, the crystallization pathway of ZCHH was systematically investigated, and the results demonstrate that the amorphous zinc carbonate (AZC) was an even more unstable precursor. AZC nanoparticles typically aggregated to form one-dimensional (1D) ZCHH nanorods, however, two-dimensional (2D) ZCHH nanofilms were obtained in the presence of a certain concentration of calcium ion. The results suggest that calcium ions could promote the partial dissolution of AZC and facilitate the aggregation of AZC nanoparticles to form crystalline nanofilm. Moreover, 2D ZnO nanofilms could be obtained by heat treatment of the ZCHH nanofilms. The calcium ion mediated nonclassical crystallization pathway provides inspiration for fabrication of ZnO with controlled morphology and offers new opportunities for inorganic regulated material synthesis.