Crystallite aluminosilicates are inorganic microporous materials with well-defined pore-size and pore-structures, and have important industrial applications, including gas adsorption and separation, catalysis, etc. Crystallite aluminosilicates are commonly synthesized via hydrothermal processes, where the oligomerization of silicic acids is crucial. The mechanisms for the oligomerization of poly-silicic acids in neutral aqueous solution were systematically investigated by extensive first-principles-based calculations. We showed that oligomerization of poly-silicic acid molecules proceeds through the lateral attacking and simultaneously proton transfer from the approaching molecule for the formation of a 5-coordinated Si species as the transition state, resulting in the ejection of a water molecule from the formed poly-silicic acid. The barriers for this mechanism are in general more plausible than the conventional direct attacking of poly-silicic acid with reaction barriers in the range of 150-160 kJ/mol. The formation of linear or branched poly-silicic acids by intermolecular oligomerization is only slightly more plausible than the formation of cyclic poly-silicic acids via intramolecular oligomerization according to the reaction barriers (124.2-133.0 vs. 130.6-144.9 kJ/mol). The potential contributions of oligomer structures, such as the length of the linear oligomers, ring distortions and neighboring linear branches, etc., to the oligomerization were also investigated but found negligible. According to the small differences among the reaction barriers, we proposed that kinetic selectivity of the poly-silicic acids condensation would be weak in neutral aqueous solution and the formation of zeolite-like structures would be thermodynamics driven.
Keywords: first-principles; nucleation; oligomerization; ortho-silicic acid; zeolite.