Abstract
Organic structure-directing agents (OSDAs) are commonly avoided in commercial zeolite synthesis because of the economic and environmental disadvantages associated with the synthesis and removal of organics occluded within zeolite micropores. Zeolite crystallization in OSDA-free media is the route by which microporous clays form in nature, and it is also the preferred method of producing zeolites in bulk for a wide range of applications. There are many synthesis parameters that influence zeolite crystallization, among which include the molar fractions of reagents (silica, alumina, and hydroxide ions), water content, temperature, synthesis aging and heating time, the selection of extraframework cations, the choice of silica and alumina sources, and the use of crystal seeds. In this review, we discuss zeolite framework types that form in OSDA-free solutions at these different synthesis conditions in an effort to highlight structure-property relationships while simultaneously emphasizing the areas where further studies are needed to optimize and/or discover new materials. Interestingly, fewer than 15% of the total reported zeolite structures have been prepared in the absence of OSDAs. For many of these structures, fundamental mechanisms governing their formation are not well understood. In addition, OSDA-free syntheses tend to be more susceptible to the formation of crystal polymorphs (or impurities) that can be generated through a series of structural transformations during the course of zeolite growth. Here we examine the driving forces for phase transitions and explore methods to control phase selection and polymorphism. In order to better facilitate comparisons among zeolite synthesis parameters, we have reinstituted the approach of using kinetic phase diagrams to identify conditions of phase stability.
About the authors

Matthew Dowd Oleksiak received his BS degree in Chemical Engineering from the University of Delaware. He is currently pursuing his PhD in Chemical Engineering at the University of Houston. His research interests include rational approaches in zeolite synthesis and catalysis.

Jeffrey Daniel Rimer received dual BS degrees in Chemistry from Allegheny College in 1999 and Chemical Engineering from Washington University in St. Louis in 2001. He received his PhD in Chemical Engineering from the University of Delaware in 2006 and began his position at the University of Houston in 2009, where he now serves as the Ernest J. and Barbara M. Henley Assistant Professor of Chemical Engineering. His research interests in the area of crystal engineering include studies of zeolite and biogenic crystal formation with applications that span catalysis to drug design.
We wish to thank the National Science Foundation (CAREER 1151098), the Norman-Hackerman Advanced Research Program (Award 003652-0024-2011), the American Chemical Society Petroleum Research Fund (Award 52422-DNI5), and the Welch Foundation (Award E-1794) for funding. We are grateful to M. Maldonado for assistance preparing ternary diagrams.
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