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Finned zeolite catalysts

Abstract

There is growing evidence for the advantages of synthesizing nanosized zeolites with markedly reduced internal diffusion limitations for enhanced performances in catalysis and adsorption. Producing zeolite crystals with sizes less than 100 nm, however, is non-trivial, often requires the use of complex organics and typically results in a small product yield. Here we present an alternative, facile approach to enhance the mass-transport properties of zeolites by the epitaxial growth of fin-like protrusions on seed crystals. We validate this generalizable methodology on two common zeolites and confirm that fins are in crystallographic registry with the underlying seeds, and that secondary growth does not impede access to the micropores. Molecular modelling and time-resolved titration experiments of finned zeolites probe internal diffusion and reveal substantial improvements in mass transport, consistent with catalytic tests of a model reaction, which show that these structures behave as pseudo-nanocrystals with sizes commensurate to that of the fin. This approach could be extended to the rational synthesis of other zeolite and aluminosilicate materials.

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Fig. 1: One-pot preparation of finned ZSM-11.
Fig. 2: Seed-assisted preparation of finned ZSM-11 and ZSM-5.
Fig. 3: Superior performance of finned zeolite catalysts.
Fig. 4: Enhanced mass-transport properties of finned zeolites.

Data availability

The data represented in Table 1 and Figs. 1, 3 and 4 of the manuscript, Supplementary Figs. 2, 511, 13, 1518 and 20, and Supplementary Tables 1, 3, 5 and 7 are provided as Source data with this paper. Additional data related to the paper may be requested from the authors.

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Acknowledgements

J.D.R. acknowledges support primarily from the US Department of Energy, Office of Science, Office of Basic Energy Sciences (award DE-SC0014468). J.D.R. and J.C.P. acknowledge funding from the Welch Foundation (award nos. E-1794 and E-1882, respectively). X.Z. received funding from the Swedish Research Council (award no. 2017-0432) and the Knut and Alice Wallenberg Foundation (award no. 2012.0112). P.J.D. and M.T. received funding from the Catalysis Center for Energy Innovation, a US Department of Energy—Energy Frontier Research Center under Grant DE-SC0001004. B.M.W. acknowledges financial support from a European Research Council (ERC) Advanced Grant (no. 321140) and the Netherlands Organization for Scientific Research (NWO) Gravitation Program (Netherlands Center for Multiscale Catalytic Energy Conversion, MCEC) funded by the Ministry of Education, Culture and Science of the government of the Netherlands. J.C.P. received additional funding from the National Science Foundation (award CBET-1629398). We thank P. Kumar for assistance with XRD analysis.

Author information

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Authors

Contributions

J.D.R. and Y.S. conceived the project and designed the experiments. H.D., T.Y., C.L., D.F., A.A. and T.T.L. were primarily responsible for the data collection and analysis. X.Z. and B.M.W. were responsible for TEM and operando UV–vis measurements, respectively. P.J.D. and M.T. were responsible for the TMPyr titration measurements. J.C.P. conducted the computational studies. J.D.R. was responsible for the zeolite synthesis, characterization and catalytic testing. J.D.R. and H.D. wrote the manuscript and prepared the figures with help from the other co-authors. All the authors contributed to the scientific discussions and preparation of the manuscript and Supplementary Information materials.

Corresponding author

Correspondence to Jeffrey D. Rimer.

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Competing interests

J.D.R., Y.S. and H.D. filed a provisional patent based on the concepts developed in this manuscript.

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Supplementary information

Supplementary Information

Supplementary Methods, Notes 1–3, Tables 1–7, Figs. 1–21, Videos 1–5 captions and references 40–59.

Supplementary Video 1

Sequence of z stacks from electron tomography of the finned MEL-F1 sample prepared by a one-pot synthesis, corresponding to Fig. 1c.

Supplementary Video 2

Sequence of z stacks from electron tomography of the MEL-finned sample prepared by seeded growth, corresponding to snapshots in Fig. 2i.

Supplementary Video 3

Sequence of z stacks from electron tomography of the MFI-finned sample prepared by seeded growth, corresponding to snapshots in Fig. 2j.

Supplementary Video 4

An SMD trajectory of TMPyr cage hopping in a straight channel of MEL (silicalite-2), viewed along the [001] direction.

Supplementary Video 5

An SMD trajectory of TMPyr cage hopping in the straight channel of MFI (silicalite-1), viewed along the [100] direction.

Source data

Source Data Fig. 1

MTH conversion and selectivity as a function of TOS for one-pot ZSM-11 catalysts.

Source Data Fig. 3

MTH conversion and selectivity as a function of TOS for seeded ZSM-11 catalysts; MTH conversion and selectivity as a function of TOS for seeded ZSM-5 catalysts; Selectivity comparisons for seeded ZSM-11 and ZSM-5 catalysts; Ethene/2MBu ratio for seeded ZSM-11 and ZSM-5 catalysts; Operando UV-vis diffuse reflectance spectroscopy for ZSM-11 and ZSM-5 catalysts; Time-on-stream methanol conversion over as-received and finned commercial H-ZSM-5 during the MTH reaction.

Source Data Fig. 4

Log probability density distribution of benzene diffusion path length r for a finned zeolite and a seed crystal; Time-resolved titration of Brønsted acid sites for H-ZSM-11 seed and finned samples; Differential plot of titrated Brønsted acid sites in Zeolyst ZSM-5 seed/finned samples and self-pillared pentasil (SPP) zeolite.

Source Data Fig. S2

Nitrogen adsorption/desorption isotherm for the finned ZSM-11 sample prepared by a one-pot synthesis.

Source Data Fig. S5

Powder X-ray diffraction patterns of as-synthesized ZSM-11 samples.

Source Data Fig. S6

Powder X-ray diffraction patterns of as-synthesized ZSM-5 samples.

Source Data Fig. S7

Nitrogen adsorption/desorption isotherms for seed and finned samples of ZSM-11 and ZSM-5 catalysts.

Source Data Fig. S8

Calculated percent increase in specific surface area for finned zeolites compared to their original seeds as a function of seed crystal size, β.

Source Data Fig. S9

Solid state 27Al NMR analysis for seed and finned samples of zeolite ZSM-11 and ZSM-5 catalysts.

Source Data Fig. S10

Product selectivities and methanol conversion as a function of TOS for seed and finned ZSM-11 and ZSM-5 catalysts.

Source Data Fig. S11

Operando UV-vis diffuse reflectance spectroscopy data within 3 min TOS for seed and finned ZSM-11 and ZSM-5 catalysts.

Source Data Fig. S13

Product selectivities and methanol conversion as a function of TOS for Zeolyst and finned Zeolyst ZSM-5 catalysts.

Source Data Fig. S15

Raw FTIR spectra of a catalyst as a function of time highlighting peaks of interest.

Source Data Fig. S16

Parity plot between loss of Brønsted acid sites and increased 2,4,6-trimethylpyridinium ions.

Source Data Fig. S17

Time-resolved titration of Brønsted acid sites for ZSM-5 seed/finned samples and Zeolyst/finned Zeolyst samples.

Source Data Fig. S18

Differential plot of titrated Brønsted acid sites in ZSM-11 seed/finned samples and H-ZSM-5 seed/finned samples.

Source Data Fig. S20

Uptake data of MEL-Seed, MFI-Seed, MEL-Finned, and MFI-Finned samples from Brønsted acid site titrations by 2,4,6-trimethylpyridine for two separate runs.

Source Data Table 1

Diffusion time constants from TMPyr titrations of ZSM-11, ZSM-5, and SPP zeolite catalysts.

Source Data Table S1

Characterization of conventional and finned ZSM-11 samples prepared by a one-pot synthesis.

Source Data Table S3

Characterization of seed and finned ZSM-11 and ZSM-5 samples prepared by seeded synthesis.

Source Data Table S5

Characterization of commercial and finned H-ZSM-5 catalysts.

Source Data Table S7

Kinetic Monte Carlo simulation results for benzene transport in silicalite-1 for seed and finned crystals with linear dimensions of α ≈ 50 nm and β ≈ 500 nm.

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Dai, H., Shen, Y., Yang, T. et al. Finned zeolite catalysts. Nat. Mater. 19, 1074–1080 (2020). https://doi.org/10.1038/s41563-020-0753-1

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