Synthesis and post-synthetic silylation of MCM-68 (MSE)-type silicate

PETR 8

Yoshihiro Kubota, kubota@ynu.ac.jp1, Y. Koyama1, T. Ikeda2, and Takashi Tatsumi3. (1) Division of Materials Science & Chemical Engineering Graduate School of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, 240-8501, Japan, (2) Research Center for Compact Chemical Process, National Institute of Advanced Industrial Science and Technology, AIST Tohoku, AIST Tohoku, Sendai, 983-8551, Japan, (3) Div. of Catalytic Chemistry, Chemical Resources Lab, Tokyo Institute of Technology, Yokohama, 226-8503, Japan
The hydrothermal synthesis of MCM-68 (MSE topology) has been only possible so far by using N,N,N',N'-tetraethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidinium diiodide (diquat-diiodide) as an organic structure-directing agent (SDA). The gel composition window for the successful crystallization of the pure MCM-68 is very narrow and the Si/Al ratio of the product has been limited to 9-12. The use of so-called “steam-assisted crystallization (SAC) method” gives a highly crystalline MSE-analogue with currently unattainable chemical composition, i.e. purely siliceous composition, which is totally different from that of typical MCM-68. Unlike the starting gel for MCM-68 containing K+ and diquat-diiodide, the gel for YNU-2P has more ordinary, halogen-free composition containing Na+ as well as diquat-dihydroxide. Moreover, the crystallization period is much shorter for the SAC method than for the hydrothermal synthesis and the SAC product exhibits very high crystallinity. The as-synthesized SAC product is designated as YNU-2P. Upon calcination, the framework of YNU-2P collapsed to give amorphous. In order to avoid this collapse, post-synthetic silylation successfully provids the material with robustness and the framework remains after calcination. The SDA-free, pure-silia material is designated as YNU-2, which is the first example of highly crystalline, pure-silica version of the MSE-like molecular sieve.