Tuning Zeolite Precursor Interactions by Switching the Valence of Polyamine Modifiers

Nonclassical mechanisms of crystal growth often involve the formation of amorphous precursors that play a direct role in what is generally referred to as crystallization by particle attachment (or CPA). One of the most studied CPA systems in the literature is zeolite MFI, which is a microporous crystal with siliceous (silicalite-1) and aluminosilicate (ZSM-5) isostructures. The self-assembly, microstructural evolution, and mechanistic role of nanoparticle precursors (1-6 nm) during silicalite-1 crystallization have been the subjects of prior investigation by combined experimental and modeling techniques. Here we investigate for the first time the effects of zeolite growth modifiers (ZGMs) on MFI precursors. ZGMs are organic molecules that alter the anisotropic rate(s) of crystal growth as a means of tailoring crystal size and/or habit. We show that most ZGMs have little effect on precursor assembly and evolution during the prenucleation stages of silicalite-1 and ZSM-5 synthesis; however, studies at varying alkalinity reveal that pH can be used as a "switch" to tune ZGM speciation and concurrently the colloidal stability of precursors. This has been proven effective for various polyamine compounds, such as spermine, that exhibit divalent (positive) charge near negatively charged nanoparticle surfaces. Our finding is consistent with colloidal models that predict a higher concentration of divalent modifiers within the diffuse double layer surrounding the surfaces of (alumino)silicate precursors. Multivalent polyamines seemingly promote precursor-precursor aggregation at elevated temperature, which is consistent with a proposed hypothesis that modifiers with two or more sufficiently spaced cationic functional moieties are capable of bridging neighboring precursor surfaces, thus overcoming an electrostatic repulsive force that contributes to their colloidal stability. Given the importance of precursor-precursor and precursor-crystal interactions in zeolite nucleation and growth, respectively, our observations provide additional insight into the role of organics in zeolite crystallization.