Insights into the crystal growth mechanisms of zeolites from combined experimental imaging and theoretical studies.

Detailed investigations into surface mediated crystal growth at zeolite external surfaces are presented. High resolution TEM is able to directly resolve surface and bulk crystallographic features and the unusual surface structural features are interpreted from simulation work. The growth of the double 4 ring is found to be a crucial and rate-determining step in the surface mediated, post-nucleation crystal growth mechanism of zeolite Beta C. Growth of 4 rings is found to be more favourable on fast growing rather than slow growing faces, explaining the relative growth rate of crystal faces in this materials. Similarly, the terminating structures of zeolite Y/Faujasite can be partly explained by considering the condensation of 6 ring and double 6 ring species at the crystal surface. Whilst 4-ring and double 4 rings are known solution species, 6 rings and double 6 rings are not, and hence it is speculated that post-nucleation crystal growth may involve competition between primary building unit and secondary building unit mediated crystal growth mechanisms.