Assembly of Zeolitic Crystals From a Model of Mesogenic Patchy Nanoparticles

Porous zeolitic crystals made of nanoparticles could have interesting applications in membranes and photonics. However, there is not yet a synthetic pathway to realize these complex architectures using nanoparticles. The challenge arises from the difficulty to control independently the different length scales intrinsic to the ordering of zeolitic crystals: the short-range tiling of the typically tetravalent sites that form the crystal, and the medium- and long-range order and connectivity of the pores. Here we propose a strategy to nucleate and grow zeolitic crystals from a binary mixture of nanoparticles in which one component favors tetravalent coordination and the two types of particles interact through frustrated attraction that promotes the formation of mesophases. We use molecular simulations to demonstrate that this approach produces zeolitic crystals in which the ordering of the pores is controlled by the structure of the mesophase, while the tiling of the network-former particles is controlled by the strength of orientational interactions of the model patchy particles. We investigate the formation of two gyroidal zeolitic crystals and the transformations between them to elucidate the role of the mesophases in the crystallization, polymorph selection, and crystal-to-crystal transformations between zeolitic crystals. This study provides a novel and distinct avenue to assemble porous zeolitic crystals from mesogenic patchy nanoparticles.