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.