Description:
<jats:title>Abstract</jats:title><jats:p>M(IV)-incorporated zeolites have recently aroused wide interest due to outstanding catalytic effects while their active sites remain largely elusive. Here periodic density functional theory calculations are conducted finding that active sites are determined jointly by identity of M(IV) ions, topology of zeolites, type of framework species and choice of T sites. All M2(IV) active sites in BEA zeolites are penta-coordinated with chemisorption of one water while subsequent water molecules that form only H-bonds promote chemisorption of the first water, especially the second water possessing comparable or even higher adsorption strengths as the first water; Ti(IV) and Ge(IV) active sites at the intersection remain penta-coordinated and Sn(IV) and Zr(IV) active sites prefer to hexa-coordination although potentially expanded to hepta-coordination. Different from other zeolites, Ti(IV) active sites in FER zeolites are hexa-coordinated as Sn(IV) active sites, due to the promoting effect of the first water. Lewis acidic defects expand Ti(IV) active sites to hexa-coordination while inhibit the formation of hepta-coordinated Sn(IV) species. Two forms of Brϕnsted acidic defects exist for Sn(IV) sites instead of only one for Ti(IV) sites, and all M(IV) Brϕnsted acidic defects, regardless of different acidic forms and M(IV) ions, can chemisorb only one water.</jats:p>