Stable Silica‐Based Zeolites with Three‐Dimensional Systems of Extra‐Large Pores

Zeolites are microporous crystalline materials that find a very wide range of applications, which, however, are limited by the size and dimensionality of their pores. Stable silica zeolites with a three‐dimensional (3D) system of extra‐large pores (ELP, i.e., pores with minimum windows along the diffusion path consisting of more than 12 SiO4/2 tetrahedra, 12R) are in demand for processing larger molecules than zeolites can currently handle. However, they have challenged worldwide synthetic capabilities for more than eight decades. In this review we first present a brief history of the discovery of ELP zeolites. Next, we show that earlier successes of zeolites with 3D ELP were not actually zeolites, but rather interrupted structures with, in addition, a composition that severely detracted from their stability. Finally, we present three new fully connected stable silica‐based 3D ELP zeolites ZEO‐1, ZEO‐3 and ZEO‐5, discuss their preparation methods and stability as well as the clear advantage of their increased porosity in catalysis and adsorption processes involving large molecules. We will discuss peculiar characteristics of their preparation and present two new reaction types giving rise to zeolites (1D‐to‐3D topotactic condensation and interchain expansion), highlighting how new synthesis methods can provide materials that would otherwise be unfeasible.