The growth mechanism of silicalite-1 (MFI zeolite) is juxtaposed between classical models that postulate silica molecules as primary growth units and nonclassical pathways based on the aggregation of metastable silica nanoparticle precursors. Although experimental evidence gathered over the past two decades suggests that precursor attachment is the dominant pathway, direct validation of this hypothesis and the relative roles of molecular and precursor species has remained elusive. We present an in situ study of silicalite-1 crystallization at characteristic synthesis conditions. Using time-resolved atomic force microscopy images, we observed silica precursor attachment to crystal surfaces, followed by concomitant structural rearrangement and three-dimensional growth by accretion of silica molecules. We confirm that silicalite-1 growth occurs via the addition of both silica molecules and precursors, bridging classical and nonclassical mechanisms.

Tailoring the anisotropic growth rates of materials to achieve desired structural outcomes is a pervasive challenge in synthetic crystallization. Here we discuss a method to selectively control the growth of zeolite crystals, which are used extensively in a wide range of industrial applications. This facile method cooperatively tunes crystal properties, such as morphology and surface architecture, through the use of inexpensive, commercially available chemicals with specificity for binding to crystallographic surfaces and mediating anisotropic growth. We examined over 30 molecules as potential zeolite growth modifiers (ZGMs) of zeolite L (LTL type) crystallization. ZGM efficacy was quantified through a combination of macroscopic (bulk) and microscopic (surface) investigations that identified modifiers capable of dramatically altering the cylindrical morphology of LTL crystals. We demonstrate an ability to tailor properties critical to zeolite performance, such as external porous surface area, crystal shape, and pore length, which can enhance sorbate accessibility to LTL pores, tune the supramolecular organization of guest-host composites, and minimize the diffusion path length, respectively. We report that a synergistic combination of ZGMs and the judicious adjustment of synthesis parameters produce LTL crystals with unique surface features, and a range of length-to-diameter aspect ratios spanning 3 orders of magnitude. A systematic examination of different ZGM structures and molecular compositions (i.e., hydrophobicity and binding moieties) reveal interesting physicochemical properties governing their efficacy and specificity. Results of this study suggest this versatile strategy may prove applicable for a host of framework types to produce unrivaled materials that have eluded more conventional techniques.

Modified point of view: a bio-inspired approach was used to tailor silicalite-1 crystallization. Growth modifiers (ZGMs) with molecular recognition for binding to specific crystal faces produced drastic changes in zeolite crystal morphology. This facile approach offers an efficient method for tuning zeolite properties.

Here we summarize our recent findings in the area of zeolite synthesis, focusing on pathways to control crystallization in the absence of organics, tailoring crystal habit with growth modifiers, and pioneering techniques in zeolite surface science to elucidate the mechanisms of growth.

Modifizierte Sichtweise: Ein bioinspirierter Ansatz wurde zur maßgeschneiderten Kristallisation von Silicalit‐1 genutzt. Wachstumsmodifikatoren (ZGMs), die mittels molekularer Erkennung an spezifische Kristallflächen binden, erzeugten drastisch verschiedene Kristallmorphologien der Zeolithe. Der Ansatz bietet eine effiziente Methode für die gezielte Einstellung von Zeolitheigenschaften.