Interchain-expanded extra-large-pore zeolites.

Gao, Zihao Rei; Yu, Huajian; Chen, Fei-Jian; Mayoral, Alvaro; Niu, Zijian; Niu, Ziwen; Li, Xintong; Deng, Hua et al. · Nature · 2024

basic_science · Level V

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Abstract

Stable aluminosilicate zeolites with extra-large pores that are open through rings of more than 12 tetrahedra could be used to process molecules larger than those currently manageable in zeolite materials. However, until very recently<sup>1-3</sup>, they proved elusive. In analogy to the interlayer expansion of layered zeolite precursors<sup>4,5</sup>, we report a strategy that yields thermally and hydrothermally stable silicates by expansion of a one-dimensional silicate chain with an intercalated silylating agent that separates and connects the chains. As a result, zeolites with extra-large pores delimited by 20, 16 and 16 Si tetrahedra along the three crystallographic directions are obtained. The as-made interchain-expanded zeolite contains dangling Si-CH<sub>3</sub> groups that, by calcination, connect to each other, resulting in a true, fully connected (except possible defects) three-dimensional zeolite framework with a very low density. Additionally, it features triple four-ring units not seen before in any type of zeolite. The silicate expansion-condensation approach we report may be amenable to further extra-large-pore zeolite formation. Ti can be introduced in this zeolite, leading to a catalyst that is active in liquid-phase alkene oxidations involving bulky molecules, which shows promise in the industrially relevant clean production of propylene oxide using cumene hydroperoxide as an oxidant.