Regulating Nonclassical Pathways of Silicalite-1 Crystallization through Controlled Evolution of Amorphous Precursors

Differentiating mechanisms of zeolite crystallization is challenging owing to the vast number of species in growth solutions. The presence of amorphous colloidal particles is ubiquitous in many zeolite syntheses, and has led to extensive efforts to understand the driving force(s) for their self-assembly and putative roles in processes of nucleation and growth. In this study, we use a combination of in situ scanning probe microscopy, particle dissolution measurements, and colloidal stability assays to elucidate the degree to which silica nanoparticles evolve in their structure during the early stages of silicalite-1 synthesis. We show how changes in precursor structure are mediated by the presence of organics, and demonstrate how these changes lead to significant differences in precursor-crystal interactions that alter preferred modes of crystal growth. Our findings provide guidelines for selectively controlling silicalite-1 growth by particle attachment or monomer addition, thus allowing for the manipulation of anisotropic rates of crystallization. In doing so, we also address a longstanding question regarding what factors are at our disposal to switch from a nonclassical to classical mechanism.