Chemistry at the Entrances of Zeolite L Nanochannels

Hybrid composites based on Zeolite L (ZL) are disclosing novel frontiers in nano- and bio-technology areas of topic interest. Site-specific modification with stopper molecules (stopcocks) enables to plug zeolite L nanochannel entrances and connect them to molecules or materials in hierarchically organized functional architectures. Herein, atomistic-level structural data on bare and modified ZL channel entrances, relevant for further progress in applications, are obtained from first-principles modeling. Calculations show that stopper molecules preferably bind to Al-sites of the channel entrances and evidence different degrees of plugging according to the shape, size and functional groups of the stopcock. First-principles molecular dynamics simulations reveal that hydrogen bonds with water molecules are of key relevance for stabilizing the functionalized ZL at room temperature conditions.