Two-Step to One-Step Nucleation of a Zeolite through a Metastable Gyroid Mesophase

The importance of nonclassical nucleation pathways in the formation of complex crystals has become apparent in recent years. Nonclassical pathways were unraveled for, among others, the crystallization of proteins, colloids, and clathrates. In those cases, the formation of a metastable fluid with density close to the crystal decreases the crystallization barrier. Recent simulations indicate that mesophases can facilitate the nucleation of zeolites. Here, we use molecular simulations to investigate the role of a gyroid mesophase on the crystallization of a model zeolite from liquid. The nucleation pathway is always nonclassical. At warmer temperatures, the mechanism proceeds in two well-defined steps: nucleation of a metastable gyroid followed by its crystallization into a zeolite. At colder temperatures, the second barrier becomes negligible, and the crystallization occurs in one step. This second scenario is also nonclassical, as the critical nucleus for the crystallization has the structure of the gyroid and seamlessly transforms into a zeolite as it grows past its critical size. To our knowledge, this is the first report of a nonclassical mechanism of crystallization mediated by a mesophase.