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Tutorial: structural characterization of isolated metal atoms and subnanometric metal clusters in zeolites

Abstract

The encapsulation of subnanometric metal entities (isolated metal atoms and metal clusters with a few atoms) in porous materials such as zeolites can be an effective strategy for the stabilization of those metal species and therefore can be further used for a variety of catalytic reactions. However, owing to the complexity of zeolite structures and their low stability under the electron beam, it is challenging to obtain atomic-level structural information of the subnanometric metal species encapsulated in zeolite crystallites. In this protocol, we show the application of a scanning transmission electron microscopy (STEM) technique that records simultaneously the high-angle annular dark-field (HAADF) images and integrated differential phase-contrast (iDPC) images for structural characterization of subnanometric Pt and Sn species within MFI zeolite. The approach relies on the use of a computational model to simulate results obtained under different conditions where the metals are present in different positions within the zeolite. This imaging technique allows to obtain simultaneously the spatial information of heavy elements (Pt and Sn in this work) and the zeolite framework structure, enabling direct determination of the location of the subnanometric metal species. Moreover, we also present the combination of other spectroscopy techniques as complementary tools for the STEM–iDPC imaging technique to obtain global understanding and insights on the spatial distributions of subnanometric metal species in zeolite structure. These structural insights can provide guidelines for the rational design of uniform metal–zeolite materials for catalytic applications.

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Fig. 1: One-pot synthesis of Pt–zeolite materials.
Fig. 2: XRD patterns of the Pt–MFI zeolites with different chemical compositions.
Fig. 3: FESEM images of Pt–zeolite materials.
Fig. 4: HAADF–STEM images of K-free Pt@MFI-Air sample after calcination in air.
Fig. 5: HAADF–STEM images of K-Pt@MFI-Air sample after calcination in air.
Fig. 6: HAADF–STEM images of K-free Pt@MFI sample after calcination in air at 600 °C and then further reduction by H2 at 600 °C.
Fig. 7: HAADF–STEM images of K-Pt@MFI sample after calcination in air at 600 °C and then further reduction by H2 at 600 °C.
Fig. 8: STEM image of Pt–zeolite samples after reduction by H2 at 600 °C.
Fig. 9
Fig. 10: Stability test of the K-PtSn@MFI sample under the beam.
Fig. 11: Influence of defocus value on the imaging of isolated Pt atoms.
Fig. 12: Influence of defocus value on the imaging of isolated Sn atoms.
Fig. 13: Image simulation of isolated Pt and Sn atoms in MFI zeolite.
Fig. 14: Image simulation of Pt and Sn species in MFI zeolite.
Fig. 15: Image simulation of Pt and Sn species in MFI zeolite.
Fig. 16: Image simulation of Pt clusters comprising interaction with Sn species in MFI zeolite.
Fig. 17: Characterization of K-Pt@MFI-Air sample by STEM–iDPC imaging technique.
Fig. 18: Identification of the location of subnanometric Pt clusters within the MFI structure.
Fig. 19: Correlation between the simulated image and experimental STEM–iDPC images.
Fig. 20: Chemical analysis on the K-PtSn@MFI sample by EDS.
Fig. 21: K-means clustering analysis on the simulated images.
Fig. 22: Distinguishing subnanometric Pt and Sn species by K-means clustering analysis.
Fig. 23: PtSn clusters in experimental HAADF–STEM images.
Fig. 24: Characterization of the Pt–zeolite materials after calcination in air by XAS.
Fig. 25: Characterization of Pt–zeolite materials by XAS.
Fig. 26: Comparison of the Sn-edge XAS results of K-PtSn@MFI-Air sample with Sn-Beta.
Fig. 27: CO-IR spectra of K-PtSn@MFI and K-Pt@MFI samples.

Data availability

Data supporting this publication are available from the corresponding author upon reasonable request.

Code availability

The code and scripts used in this work are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the European Union through the European Research Council (grant ERC-AdG-2014-671093, SynCatMatch) and the Spanish government through the ‘Severo Ochoa Program’ (SEV-2016-0683). The authors also thank the Microscopy Service of UPV for the TEM and STEM measurements. The XAS measurements were carried out in CLAESS beamline of ALBA synchrotron. HR STEM measurements were performed at the DME-UCA node of the ELECMI Singular Infrastructure at Cadiz University, with financial support from FEDER/MINECO (MAT2017-87579-R and MAT2016-81118-P). The authors thank C. W. Lopes and P. Concepcion for their help with the analysis of spectroscopic results. The financial support from ExxonMobil on this project is also gratefully acknowledged.

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A.C. conceived the project and directed the study. L.L. carried out the synthesis and characterizations of the Pt–zeolite materials. M.L.-H. and J.J.C. carried out the HR STEM measurements, image analysis and simulations, with assistance from L.L. All authors discussed the results and contributed to the formation of the manuscript.

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Correspondence to Avelino Corma.

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Liu, L., Lopez-Haro, M., Calvino, J.J. et al. Tutorial: structural characterization of isolated metal atoms and subnanometric metal clusters in zeolites. Nat Protoc 16, 1871–1906 (2021). https://doi.org/10.1038/s41596-020-0366-9

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