Computer simulation of the self-assembly of crystal structures of zeolites Ca64(Sr,K,Ba)48(Cu12(O,Cl))4[Si192Al192O786](H2O) n (tschoertnerite, TSC, V = 31 614 Å3) and Ca2K2[Al6Si6O24](H2O)10 (willhendersonite, cha, V = 804 Å3) from template nanocluster precursors K48 and K12

Abstract

The self-assembly of zeolites Ca64(Sr,K,Ba)48(Cu12(O,Cl))4[Si192Al192 O786](H2O) n (tschoertnerite, TSC-type framework, V = 31614 A3) and Ca2K2[Al6Si6O24] (H2O)10 (willhendersonite, CHA-type framework, V = 804 A3), which form paragenetic associations, has been simulated using computational methods (TOPOS program package). A new method for analyzing zeolites of any complexity has been used, which is based on the complete expansion of the three-dimensional structural graph (3D factor graph) in tiles and the selection of nonintersecting tiles forming a packing. The code of self-assembly of 3D structures from complementary linked nanocluster precursors is reconstructed: primary chain → microlayer → microframework. A supracluster precursor K48 with the symmetry $\bar 4$ 3m, formed of four K12 clusters corresponding to the t-hpr tile, is established for TSC. The K48 cluster contains Ca template cations, which stabilize its local region in the stages of K12 → K24 → K48 self-assembly. Bifurcations of evolution paths (structural branching points) during the self-assembly of TSC and CHA microframeworks are established in the stage of formation of the K24 supracluster from invariant templated K12 clusters. The models under consideration explain the 100% localization of B = Ca cations, which play the role of templates, and the 50% occupation of the positions of K, Sr, and Ba spacer cations (in TSC) and K spacer cations (in CHA).