Capturing Ultrasmall EMT Zeolite from Template-Free Systems

Controlling Zeolite Nucleation Small zeolite crystals are of increasing interest as catalysts and for membrane separations because they allow the high selectivity of their cages to be exploited while minimizing the kinetic limitations caused by diffusion. Ng et al. (p. 70, published online 8 December) synthesized ultrasmall crystals (6 to 15 nanometers) of the EMT zeolite, which has a low framework density and good catalytic properties for hydrocarbon “cracking” (conversion of a large hydrocarbon to smaller ones). The synthesis of EMT has normally required expensive organic templates that limit its industrial use. Careful control of the synthesis conditions, such as ratios of reactants and short bursts of microwave heating, allowed small EMT crystals to nucleate and avoid formation of zeolites with closely related structures. Control of the early stages of nucleation favors the synthesis of large-pore zeolite crystals ~10 nanometers in size. Small differences between the lattice energies of different zeolites suggest that kinetic factors are of major importance in controlling zeolite nucleation. Thus, it is critical to control the nucleation kinetics in order to obtain a desired microporous material. Here, we demonstrate how careful investigation of the very early stages of zeolite crystallization in colloidal systems can provide access to important nanoscale zeolite phases while avoiding the use of expensive organic templates. We report the effective synthesis of ultrasmall (6- to 15-nanometer) crystals of the large-pore zeolite EMT from template-free colloidal precursors at low temperature (30°C) and very high yield.