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Interchain-expanded extra-large-pore zeolites


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 recently1,2,3, 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.

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Fig. 1: Preparation and structure of ZEO-4A, ZEO-4B and ZEO-5.
Fig. 2: Characterization of ZEO-4 and ZEO-5.
Fig. 3: Generation of extra-large pores by σ-expansion.

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Data availability

The datasets generated and/or analysed during the current study have been deposited in DIGITAL.CSIC ( Crystallographic parameters for the structures of ZEO-4A, ZEO-4B and ZEO-5 refined against synchrotron powder X-ray diffraction data (SPXRD) and continuous rotation electron diffraction (cRED) data are archived at the Cambridge Crystallographic Data Center ( under reference numbers 2249198 and 2249199 (ZEO-4A and ZEO-4B, SPXRD), 22491032249106 (ZEO-5A, ZEO-5B, ZEO-4A and ZEO-4B, cRED) and 2288122 (ZEO-5, combining cRED, SPXRD and neutron powder diffraction). Source data are provided with this paper.


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Financial support from the Spanish Ministry of Science Innovation (PID2019-105479RB-I00 and TED2021-131223B-I00 Projects, MCIN/AEI/10.13039/501100011033 and grants RYC2018-024561-I and FJC2018-035697-I); the National Natural Science Foundation of China (grants 22371121, 22288101, 21920102005, 21835002, 22271115 and 52270111); the National Key Research and Development Program of China (grants 2022YFA1503600, 2021YFA1501202 and 2021YFA1501401); the 111 Project (grant B17020); the Fundamental Research Funds for the Central Universities of China (grant 020514380306); and the Consejería de Universidades, Investigación e Innovación, Junta de Andalucía (grant POSTDOC_21_00069) is gratefully acknowledged. Continuous rotation electron diffraction data were collected at the Electron Microscopy Center, Department of Materials and Environmental Chemistry at Stockholm University with the support of the Knut and Alice Wallenberg Foundation (grant 2012-0112) through the 3DEM-NATUR Project. We acknowledge the use of instrumentation provided by the National Facility ELECMI (Integrated Infrastructure for Electron Microscopy of Materials) ICTS (Instalación Científico Técnica Singular) node Laboratorio de Microscopías Avanzadas at the University of Zaragoza. Additional funding from the European Union’s Horizon 2020 Research and Innovation Program (grant 823717-ESTEEM3) and the Regional Government of Aragon (grant DGA E13_20R) is also acknowledged. H.Y. is grateful to the China Scholarship Council for a PhD grant. Synchrotron powder X-ray diffraction data experiments were performed at the MSPD (Materials Science Powder Diffraction) beamline bl04 at the ALBA Spanish Synchrotron with the collaboration of the ALBA staff. We thank C3UPO (Centro de Cálculo Científico de la Universidad Pablo de Olavide) for providing high-performance computing facilities and L.-H. He for help with the powder neutron diffractions data collection performed at the general purpose powder diffractometer of China Spallation Neutron Source, Dongguan, China (Project General Purpose Powder Diffractometer, P1823060200002).

Author information

Authors and Affiliations



M.A.C. conceived the project. J.L., P.W., J.Y. and M.A.C. supervised this work. Z.R.G., H.Y., F.-J.C. and Zijian Niu performed the synthesis. C.M. and J.L. solved the structures, and J.H. and J.L. performed Rietveld refinement. A.M. performed the Cs-corrected STEM analysis. Z.R.G. analysed the topology. S.R.G.B. performed and analysed all computer calculations. Z.R.G., H.Y., F.-J.C., Zijian Niu, Ziwen Niu, H.D., C.M.-Á., H.X., W.F. and M.A.C. carried out the physicochemical characterization. S.X., Y.Z. and J.X. performed two-dimensional and dynamic nuclear polarization magic-angle spinning nuclear magnetic resonance spectroscopy. H.D. and H.H. worked on the volatile organic compounds adsorption. Ziwen Niu, X.L., H.X. and P.W. performed the catalytic tests. M.A.C. wrote the initial draft of the manuscript. J.L., P.W., J.Y. and M.A.C. organized the work and the draft. All the authors discussed the results and revised the manuscript.

Corresponding authors

Correspondence to Jian Li, Peng Wu, Jihong Yu or Miguel A. Camblor.

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Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature thanks Alex Yip and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.

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Extended data figures and tables

Extended Data Fig. 1 Field emission scanning electron microscopy.

FESEM images of ZEO-4A (a), ZEO-4B (b), ZEO-5A (c), and ZEO-5B (d), showing the same morphology of ZEO-22.

Source Data

Extended Data Fig. 2 Zeolite porosity.

The pores in fully connected framework ZEO-5 (a-b) and interrupted structure ZEO-4A (c-d) and ZEO-4B (e-f), the 20-ring pore (a, c, e) approximately along [001] and the 16-ring pore (b, d, f) approximately along [110].

Extended Data Fig. 3 Rietveld structure refinement.

Rietveld refinement plots of (a) ZEO-4A and (b) ZEO-4B against SPXRD (λ = 0.61928 Å).

Source Data

Extended Data Fig. 4 29Si MAS NMR spectroscopy.

29Si MAS NMR spectra of ZEO-5 (from bottom): Experimental, DFT-simulated and individual components (see SM). The DFT study confirms that the very low field signal at −98 ppm corresponds to the Si sites in the central 4-ring of the t4r unit (Si12 and Si13).

Extended Data Fig. 5 Cs-corrected STEM analysis of the pore systems.

Along [110] (a-c) for a) ZEO-4A b) ZEO-4B and c) ZEO-5 with the units involved in the structural transformation circumscribed by yellow dashed ellipses. Condensation of ZEO-4A and ZEO-4B into ZEO-5 brings about an expansion of the interchain distance, as shown by the yellow solid lines and in full agreement with the refined structures. In d) the 20 R pore of ZEO-5 is observed along the [001] projection. A t4r unit is marked by a green dashed ellipse. The micrographs simulated using the Rietveld refined data are shown in the insets and corroborate the structural models.

Extended Data Fig. 6 Thermal and hydrothermal stability tests for ZEO-5.

PXRD patterns of ZEO-4A (a), and ZEO-5 upon calcination at 600 °C (b), 800 °C (c), and 1000 °C (d) with one-hour plateau, and ZEO-5 steamed at 760 °C for 3 h under 10% H2O (e).

Source Data

Extended Data Fig. 7 Catalytic oxidation of propylene.

Dependence of PO yield (A) and specific PO yield per Ti site (B) on reaction time over Ti-ZEO-5 (a) and Ti-HMS (b) catalysts in the propylene epoxidation reaction. Reaction conditions: catalyst, 0.01 g; cumene hydroperoxide (CHP), 10 mmol; propylene, 100 mmol; cumene solvent, 10 mL; temp., 373 K; reaction pressure, 2.4 MPa.

Source Data

Extended Data Fig. 8 Framework density – Energy plot.

The lattice energy versus density of the zeolite-like materials (black dots) was minimized using the Sanders-Leslie-Catlow (SLC) interatomic potential, according to Deem et al.21 The red line appears in the original publication as “the linear fit of energy versus density for the known zeolite structures.” We have included our data points for updated porous crystalline silica polymorphs from the IZA database (red points), dense silica polymorphs (green points), and ZEO-1, ZEO-3, and ZEO-5 materials (large blue points) calculated using the same methodology. Reprinted (adapted) with permission from ref. 21, copyright 2009 American Chemical Society.

Source Data

Extended Data Table 1 A comparison of cyclooctene oxidation between Ti-ZEO-5 and Ti-Beta[a]
Extended Data Table 2 A comparison of propylene oxidation with cumene hydroperoxide between Ti-ZEO-5 and other titanosilicates[a]

Supplementary information

Supplementary Information

This file contains Supplementary Figs. 1–25, Tables S1–S27 and references.

Peer Review File

Supplementary Data (Source Data Supplementary Fig. 8)

Ar adsorption/desorption isotherms of ZEO-4 and ZEO-5 at 87 K.

Supplementary Data (Source Data Supplementary Fig. 9)

Toluene adsorption on largely porous zeolites.

Supplementary Data (Source Data Supplementary Fig. 10)

1H, 13C and 31P liquid NMR spectra of as-synthesized OSDACl and the OSDA recovered from the filtrated solution of ZEO-4A and ZEO-4B after IChEZ treatments.

Supplementary Data (Source Data Supplementary Fig. 11)

FTIR of ZEO-4 and ZEO-5, A and B.

Supplementary Data (Source Data Supplementary Fig. 12)

13C and 31P MAS NMR spectra of ZEO-4A and ZEO-4B after the IChEZ reaction.

Supplementary Data (Source Data Supplementary Fig. 13)

1H MAS NMR of ZEO-4.

Supplementary Data (Source Data Supplementary Fig. 14)

29Si–1H CP MAS NMR of ZEO-4A.

Supplementary Data (Source Data Supplementary Fig. 15)

29Si–1H CP MAS NMR of ZEO-4B.

Supplementary Data (Source Data Supplementary Fig. 16)

1H–29Si HETCOR MAS NMR spectra of ZEO-4A at short (500 μs) and long (5000 μs) contacting time.

Supplementary Data (Source Data Supplementary Fig. 17)

1H–29Si HETCOR MAS NMR spectra of ZEO-4B at long contact time (6 ms).

Supplementary Data (Source Data Supplementary Fig. 18)


Supplementary Data (Source Data Supplementary Fig. 19)

1H DQ-SQ MAS NMR spectra of ZEO-5A.

Supplementary Data (Source Data Supplementary Fig. 20)

29Si MAS NMR of ZEO-5A.

Supplementary Data (Source Data Supplementary Fig. 21)

29Si–1H MAS NMR of ZEO-5A.

Supplementary Data (Source Data Supplementary Fig. 22)

1H–29Si HETCOR MAS NMR spectra of ZEO-5A at short (1,500 μs) and long (5,000 μs) contacting time.

Supplementary Data (Source Data Supplementary Fig. 23)

EPR spectra of ZEO-5.

Supplementary Data (Source Data Supplementary Fig. 24)

Cycloctane adsorption.

Supplementary Data (Source Data Supplementary Fig. 25)

PXRD of catalysts.

Source data

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Gao, Z.R., Yu, H., Chen, FJ. et al. Interchain-expanded extra-large-pore zeolites. Nature 628, 99–103 (2024).

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