Interchain-expanded extra-large-pore zeolites

• 成果类型: Article
• 署名作者: Gao, Zihao Rei; Yu, Huajian; Chen, Fei-Jian; Mayoral, Alvaro; Niu, Zijian; Niu, Ziwen; Li, Xintong; Deng, Hua; Marquez-Alvarez, Carlos; He, Hong; Xu, Shutao; Zhou, Yida; Xu, Jun; Xu, Hao; Fan, Wei; Balestra, Salvador R. G.; Ma, Chao; Hao, Jiazheng; Li, Jian; Wu, Peng; Yu, Jihong; Camblor, Miguel A.
• 署名单位: Consejo Superior de Investigaciones Cientificas (CSIC); CSIC - Instituto de Ciencia de Materiales de Madrid (ICMM); Jilin University; Consejo Superior de Investigaciones Cientificas (CSIC); East China Normal University; Chinese Academy of Sciences; Institute of Urban Environment, CAS; Consejo Superior de Investigaciones Cientificas (CSIC); CSIC - Instituto de Catalisis y Petroleoquimica (ICP); Chinese Academy of Sciences; Chinese Academy of Sciences; Dalian Institute of Chemical Physics, CAS; Chinese Academy of Sciences; Innovation Academy for Precision Measurement Science & Technology, CAS; University of Massachusetts System; University of Massachusetts Amherst; Universidad Pablo de Olavide; Nanjing University; Chinese Academy of Sciences; Institute of High Energy Physics, CAS; Chinese Academy of Sciences; Institute of High Energy Physics, CAS; Johns Hopkins University; Johns Hopkins University
• 刊物名称: Nature
• ISSN/ISSBN: 0028-5829
• DOI: 10.1038/s41586-024-07194-6
• 发表日期: 2024-04-04
• 关键词: mechanism; mww

摘要

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 recently1-3, they proved elusive. In analogy to the interlayer expansion of layered zeolite precursors4,5, 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-CH3 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. 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.