Interchain-expanded extra-large-pore zeolites

Zihao Rei Gao; Huajian Yu; Fei-Jian Chen; Alvaro Mayoral; Zijian Niu; Ziwen Niu; Xintong Li; Hua Deng; Carlos Márquez-Álvarez; Hong He; Shutao Xu; Yida Zhou; Jun Xu; Hao Xu; Wei Fan; Salvador R G Balestra; Chao Ma; Jiazheng Hao; Jian Li; Peng Wu; Jihong Yu; Miguel A Camblor

doi:10.1038/s41586-024-07194-6

Interchain-expanded extra-large-pore zeolites

Nature. 2024 Apr;628(8006):99-103. doi: 10.1038/s41586-024-07194-6. Epub 2024 Mar 27.

Authors

Zihao Rei Gao^#^{1

2}, Huajian Yu^#¹, Fei-Jian Chen^#³, Alvaro Mayoral⁴, Zijian Niu³, Ziwen Niu⁵, Xintong Li⁵, Hua Deng⁶, Carlos Márquez-Álvarez⁷, Hong He^{6

8}, Shutao Xu⁹, Yida Zhou⁹, Jun Xu¹⁰, Hao Xu⁵, Wei Fan¹¹, Salvador R G Balestra^{1

12}, Chao Ma¹³, Jiazheng Hao^{14

15}, Jian Li¹⁶, Peng Wu¹⁷, Jihong Yu¹⁸, Miguel A Camblor¹⁹

Affiliations

¹ Instituto de Ciencia de Materiales de Madrid (ICMM), CSIC, Madrid, Spain.
² Department of Chemical and Biomolecular Engineering and Institute for NanoBioTechnology, Johns Hopkins University, Baltimore, MD, USA.
³ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, International Center of Future Science, Jilin University, Changchun, China.
⁴ Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-Universidad de Zaragoza, Zaragoza, Spain.
⁵ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China.
⁶ Center for Excellence in Regional Atmospheric Environment, Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, China.
⁷ Instituto de Catálisis y Petroleoquímica (ICP), CSIC, Madrid, Spain.
⁸ State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, China.
⁹ National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
¹⁰ National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, China.
¹¹ Department of Chemical Engineering, University of Massachusetts, Amherst, MA, USA.
¹² Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Seville, Spain.
¹³ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
¹⁴ Spallation Neutron Source Science Center, Dongguan, China.
¹⁵ Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China.
¹⁶ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China. jian.li@nju.edu.cn.
¹⁷ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China. pwu@chem.ecnu.edu.cn.
¹⁸ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, International Center of Future Science, Jilin University, Changchun, China. jihong@jlu.edu.cn.
¹⁹ Instituto de Ciencia de Materiales de Madrid (ICMM), CSIC, Madrid, Spain. macamblor@icmm.csic.es.

^# Contributed equally.

PMID: 38538794
DOI: 10.1038/s41586-024-07194-6

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^1-3, they proved elusive. In analogy to the interlayer expansion of layered zeolite precursors^4,5, 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.