First Principles Studies on Boron Sites in Zeolites.

A systematic computational investigation on protonated and nonprotonated boron-containing zeolites (boralites), performed by using different periodic density functional theory approximations, is presented. Both minimum energy structures and finite temperature behavior of model boron sodalites were analyzed. All of the adopted computational schemes agree in predicting an acid site composed of a silanol Si−OH group loosely linked to a planar BO3 structure in the protonated system and a BO4 tetrahedral site in the sodium-containing zeolite. Calculated structural and vibrational properties are in line with experimental data. Comparisons of the protonated boralite site with Al and Ga zeolitic acid sites are discussed as well. Results indicate that this class of mild acid catalysts is characterized by significant framework flexibility and pronounced thermal effects due to the loosely bound acid site.