Illuminating the Black Box: A Perspective on Zeolite Crystallization in Inorganic Media

[Image: see text] Since the discovery of synthetic zeolites in the 1940s and their implementation in major industrial processes involving adsorption, catalytic conversion, and ion exchange, material scientists have targeted the rational design of zeolites: controlling synthesis to crystallize zeolites with predetermined properties. Decades later, the fundamentals of zeolite synthesis remain largely obscured in a black box, rendering rational design elusive. A major prerequisite to rational zeolite design is to fully understand, and control, the elementary processes governing zeolite nucleation, growth, and stability. The molecular-level investigation of these processes has been severely hindered by the complex multiphasic media in which aluminosilicate zeolites are typically synthesized. This Account documents our recent progress in crystallizing zeolites from synthesis media based on hydrated silicate ionic liquids (HSIL), a synthesis approach facilitating the evaluation of the individual impacts of synthesis parameters such as cation type, water content, and alkalinity on zeolite nucleation, growth, and phase selection. HSIL-based synthesis allows straightforward elucidation of the relationship between the characteristics of the synthesis medium and the properties and structure of the crystalline product. This assists in deriving new insights in zeolite crystallization in an inorganic aluminosilicate system, thus improving the conceptual understanding of nucleation and growth in the context of inorganic zeolite synthesis in general. This Account describes in detail what hydrated silicate ionic liquids are, how they form, and how they assist in improving our understanding of zeolite genesis on a molecular level. It describes the development of ternary phase diagrams for inorganic aluminosilicate zeolites via a systematic screening of synthesis compositions. By evaluating obtained crystal structure properties such as framework composition, topology, and extraframework cation distributions, critical questions are dealt with: Which synthesis variables govern the aluminum content of crystallizing zeolites? How does the aluminum content in the framework determine the expression of different topologies? The crucial role of the alkali cation, taking center stage in all aspects of crystallization, phase selection, and, by extension, transformation is also discussed. New criteria and models for phase selection are proposed, assisting in overcoming the need for excessive trial and error in the development of future synthesis protocols. Recent progress in the development of a toolbox enabling liquid-state characterization of these precursor media has been outlined, setting the stage for the routine monitoring of zeolite crystallization in real time. Current endeavors on and future needs for the in situ investigation of zeolite crystallization are highlighted. Finally, experimentally accessible parameters providing opportunities for modeling zeolite nucleation and growth are identified. Overall, this work provides a perspective toward future developments, identifying research areas ripe for investigation and discovery.