Synthesis of Extra-Large-Pore Zeolite ECNU-9 with Intersecting 14*12-Ring Channels.

Highly crystalline and (hydro)thermally stable zeolites with extra-large pores [≥14-ring (14-R)] are desirable as catalysts. A novel zeolite, ECNU-9, with an intersecting 14*12-R channel system was rationally designed and synthesized by a building block strategy, in which the interlayer expansion of a two-dimensional silicate structure was realized by combining organic amine assisted layer-stacking reorganization and subsequent silylation with a square-shaped single 4-ring (S4R) silane, 1,3,5,7-tetramethylcyclotetrasiloxane (TMCS). The PLS-3 precursor was disassembled into building blocks and then intercalated with flexible and removable organic amine pillars to offer enough interlayer spacing for accommodating TMCS molecules. The additionally introduced building blocks interconnected the neighboring layers to construct new 14-R and 12-R pores. ECNU-9 possesses a well-ordered structure with a novel topology. The corresponding Ti-ECNU-9, with tetrahedral Ti ions in the framework, showed superior catalytic performance in the selective epoxidation of bulky alkenes.