Synthesis strategies and design principles for nanosized and hierarchical zeolites

The preparation of zeolites has long been viewed as an empirical practice in which the impact of numerous synthesis parameters on complex pathways of crystallization remains unresolved. Efforts to achieve predictive control in zeolite crystal engineering are often motivated by the benefits of producing materials with nanosized dimensions for improved mass transport properties. In the past decade there has been substantial progress in the synthesis of zeolites and zeotypes with nanosized and hierarchical structures that have been shown to outperform conventional analogues in various applications. The ability to synthesize state-of-the-art nanoporous materials has socioeconomic advantages in processes that are critical to addressing twenty-first-century problems. Here we summarize synthetic methods used to prepare different classes of zeolitic materials and we highlight the diversity of nucleation and growth mechanisms, approaches to control these pathways through experimental design, and the advantages of infusing computational and big data analyses to transition zeolite synthesis away from trial-and-error methodologies. Crystal engineering of nanosized and hierarchical zeolites may improve the mass transport properties of materials at the nanoscale in various applications. In this Review, synthetic methods used to prepare different classes of zeolitic materials are summarized, with a focus on nucleation and growth mechanisms. Experimental and computational advances, as well as future challenges in the field, are discussed.