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

Lichen Liu, Miguel Lopez-Haro, Jose J. Calvino, Avelino Corma

Published: 2020-09-03 DOI: 10.1038/s41596-020-0366-9

subnanometric metal clusters

zeolites

STEM-iDPC imaging

catalytic reactions

structural characterization

AI 解读

Efficient and safe single-cell cloning of human pluripotent stem cells using the CEPT cocktail

Profiling native pulmonary basement membrane stiffness using atomic force microscopy

Genetic circuit design automation with Cello 2.0

Synthesis of siRNA nanoparticles to silence plaque-destabilizing gene in atherosclerotic lesional macrophages

Scalable dual-omics profiling with single-nucleus chromatin accessibility and mRNA expression sequencing 2 (SNARE-seq2)

A practical guide to scanning light-field microscopy with digital adaptive optics

Effective high-throughput isolation of fully human antibodies targeting infectious pathogens

Improved sampling and DNA extraction procedures for microbiome analysis in food-processing environments

MOF-derived nanoporous carbons with diverse tunable nanoarchitectures

Tutorial: a statistical genetics guide to identifying HLA alleles driving complex disease

查看全部

Sections

Figures

References

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 f
Introduction
Generation and stabilization of isolated Pt atoms and subnanometric Pt clusters in MFI zeolite
Materials
- Reagents
- Equipment
Procedure
Timing
Troubleshooting
Preliminary characterization of the Pt-zeolite materials
Structural characterization of the Pt–nobreakzeolite materials by HR STEM
Complementary characterization with other techniques
Extension of the STEM–nobreakiDPC technique
Limitations of the current technique and outlooks
References
ACKNOWLEDGMENTS

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

Gates, B. C. Atomically dispersed supported metal catalysts: seeing is believing. Trends Chem. 1, 99–110 (2019).
Yang, S. et al. Bridging dealumination and desilication for the synthesis of hierarchical MFI zeolites. Angew. Chem. Int. Ed. 56, 12553–12556 (2017).
Lupulescu, A. I. & Rimer, J. D. In situ imaging of silicalite-1 surface growth reveals the mechanism of crystallization. Science 344, 729–732 (2014).
Anderson, M. W. et al. Modern microscopy methods for the structural study of porous materials. Chem. Commun. (8), 907–916 (2004).
Flytzani-Stephanopoulos, M. & Gates, B. C. Atomically dispersed supported metal catalysts. Annu. Rev. Chem. Biomol. Eng. 3, 545–574 (2012).
Liu, L. & Corma, A. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem. Rev. 118, 4981–5079 (2018).
Thomas, J. M., Raja, R. & Lewis, D. W. Single-site heterogeneous catalysts. Angew. Chem. Int. Ed. 44, 6456–6482 (2005).
Hansen, T. W. et al. Atomic-resolution in situ transmission electron microscopy of a promoter of a heterogeneous catalyst. Science 294, 1508–1510 (2001).
Hwang, S., Chen, X., Zhou, G. & Su, D. In situ transmission electron microscopy on energy-related catalysis. Adv. Energy Mater. http://doi.org/10.1002/aenm.201902105 (2019).
Li, Z. et al. Well-defined materials for heterogeneous catalysis: from nanoparticles to isolated single-atom sites. Chem. Rev. 120, 623–682 (2019).
Pelletier, J. D. & Basset, J. M. Catalysis by design: well-defined single-site heterogeneous catalysts. Acc. Chem. Res. 49, 664–677 (2016).
Kulkarni, A., Lobo-Lapidus, R. J. & Gates, B. C. Metal clusters on supports: synthesis, structure, reactivity, and catalytic properties. Chem. Commun. 46, 5997–6015 (2010).
Liu, L. et al. Evolution and stabilization of subnanometric metal species in confined space by in situ TEM. Nat. Commun. 9, 574 (2018).
Gates, B. C., Flytzani-Stephanopoulos, M., Dixon, D. A. & Katz, A. Atomically dispersed supported metal catalysts: perspectives and suggestions for future research. Catal. Sci. Technol. 7, 4259–4275 (2017).
Li, H., Wang, M., Luo, L. & Zeng, J. Static regulation and dynamic evolution of single-atom catalysts in thermal catalytic reactions. Adv. Sci 6, 1801471 (2019).
Liu, L. et al. Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis. Nat. Mater. 18, 866–873 (2019).
Juneau, M. et al. Characterization of metal–zeolite composite catalysts: determining the environment of the active phase. ChemCatChem http://doi.org/10.1002/cctc.201902039 (2019).
Shamzhy, M., Opanasenko, M., Concepcion, P. & Martinez, A. New trends in tailoring active sites in zeolite-based catalysts. Chem. Soc. Rev. 48, 1095–1149 (2019).
Weckhuysen, B. M. Stable platinum in a zeolite channel. Nat. Mater. 18, 778–779 (2019).
Gai, P. L. & Calvino, J. J. Electron microscopy in the catalysis of alkane oxidation, environmental control, and alternative energy sources. Annu. Rev. Mater. Res. 35, 465–504 (2005).
Mayoral, A., Carey, T., Anderson, P. A., Lubk, A. & Diaz, I. Atomic resolution analysis of silver ion-exchanged zeolite A. Angew. Chem. Int. Ed. 50, 11230–11233 (2011).
Lu, J., Aydin, C., Browning, N. D. & Gates, B. C. Imaging isolated gold atom catalytic sites in zeolite NaY. Angew. Chem. Int. Ed. 51, 5842–5846 (2012).
Ortalan, V., Uzun, A., Gates, B. C. & Browning, N. D. Direct imaging of single metal atoms and clusters in the pores of dealuminated HY zeolite. Nat. Nanotechnol. 5, 506–510 (2010).
Yang, M. et al. Catalytically active Au-O(OH)x-species stabilized by alkali ions on zeolites and mesoporous oxides. Science 346, 1498–1501 (2014).
Liu, L. et al. Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nat. Mater. 16, 132–138 (2017).
Slater, B., Ohsuna, T., Liu, Z. & Terasaki, O. Insights into the crystal growth mechanisms of zeolites from combined experimental imaging and theoretical studies. Faraday Discussions 136, 125–141 (2007).
Diaz, I. & Mayoral, A. TEM studies of zeolites and ordered mesoporous materials. Micron 42, 512–527 (2011).
Wan, W., Su, J., Zou, X. D. & Willhammar, T. Transmission electron microscopy as an important tool for characterization of zeolite structures. Inorg. Chem. Frontiers 5, 2836–2855 (2018).
Mishra, R., Ishikawa, R., Lupini, A. R. & Pennycook, S. J. Single-atom dynamics in scanning transmission electron microscopy. MRS Bulletin 42, 644–652 (2017).
DeLaRiva, A. T., Hansen, T. W., Challa, S. R. & Datye, A. K. In situ transmission electron microscopy of catalyst sintering. J. Catal. 308, 291–305 (2013).
Lazic, I., Bosch, E. G. T. & Lazar, S. Phase contrast STEM for thin samples: integrated differential phase contrast. Ultramicroscopy 160, 265–280 (2016).
Shen, B. et al. Atomic spatial and temporal imaging of local structures and light elements inside zeolite frameworks. Adv. Mater. e1906103 (2019).
Egerton, R. F. & Watanabe, M. Characterization of single-atom catalysts by EELS and EDX spectroscopy. Ultramicroscopy 193, 111–117 (2018).
Bonilla, G. et al. Zeolite (MFI) crystal morphology control using organic structure-directing agents. Chem. Mater. 16, 5697–5705 (2004).
Karwacki, L. et al. Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers. Nat. Mater. 8, 959–965 (2009).
Grand, J. et al. One-pot synthesis of silanol-free nanosized MFI zeolite. Nat. Mater. 16, 1010–1015 (2017).
Varela, M. et al. Materials characterization in the aberration-corrected scanning transmission electron microscope. Annu. Rev. Mater. Res. 35, 539–569 (2005).
Mitchell, DavidR. G. & Mitchell, J. B. Nancarrow probe current determination in analytical TEM/STEM and its application to the characterization of large area EDS detectors. Microscopy Res. Technique 78, 886–893 (2015).
Erni, R. Aberration-Corrected Imaging in Transmission Electron Microscopy (Imperial College Press, 2010).
Díaz, I., Kokkoli, E., Terasaki, O. & Tsapatsis, M. Surface structure of zeolite (MFI) crystals. Chem. Mater. 16, 5226–5232 (2004).
Bernal, S. et al. The interpretation of HREM images of supported metal catalysts using image simulation: profile view images. Ultramicroscopy 72, 135–164 (1998).
Kirkland, E. J. Advanced Computing in Electron Microscopy (Springer, 2010).
Corma, A., Fornes, V., Pergher, S. B., Maesen, T. L. M. & Buglass, J. G. Delaminated zeolite precursors as selective acidic catalysts. Nature 396, 353–356 (1998).
Pei, Y. et al. Catalytic properties of intermetallic platinum–tin nanoparticles with non-stoichiometric compositions. J. Catal. 374, 136–142 (2019).
Moliner, M. et al. Reversible transformation of Pt nanoparticles into single atoms inside high-silica chabazite zeolite. J. Am. Chem. Soc. 138, 15743–15750 (2016).
de Graaf, J., van Dillen, A. J., de Jong, K. P. & Koningsberger, D. C. Preparation of highly dispersed Pt particles in zeolite Y with a narrow particle size distribution: characterization by hydrogen chemisorption, TEM, EXAFS spectroscopy, and particle modeling. J. Catal. 203, 307–321 (2001).
Bare, S. R. et al. Uniform catalytic site in Sn-beta-zeolite determined using X-ray absorption fine structure. J. Am. Chem. Soc. 127, 12924–12932 (2005).
Hammond, C. et al. Identification of active and spectator Sn sites in Sn-beta following solid-state stannation, and consequences for Lewis acid catalysis. ChemCatChem 7, 3322–3331 (2015).
Liu, L. et al. Determination of the evolution of heterogeneous single metal atoms and nanoclusters under reaction conditions: which are the working catalytic sites? ACS Catal. 9, 10626–10639 (2019).
Derevyannikova, E. A. et al. Structural insight into strong Pt–CeO2 interaction: from single Pt atoms to PtOx clusters. J. Phys. Chem. C 123, 1320–1334 (2018).
Sun, Q. et al. Subnanometer bimetallic Pt–Zn clusters in zeolites for propane dehydrogenation. Angew. Chem. Int. Ed. http://doi.org/10.1002/anie.202003349 (2020).
Concepcion, P. et al. The promotional effect of Sn-beta zeolites on platinum for the selective hydrogenation of alpha,beta-unsaturated aldehydes. Phys. Chem. Chem. Phys. 15, 12048–12055 (2013).
Heiz, U., Sanchez, A., Abbet, S. & Schneider, W. D. Catalytic oxidation of carbon monoxide on monodispersed platinum clusters: each atom counts. J. Am. Chem. Soc. 121, 3214–3217 (1999).
Serykh, A. I. et al. Stable subnanometre Pt clusters in zeolite NaX via stoichiometric carbonyl complexes: probing of negative charge by DRIFT spectroscopy of adsorbed CO and H2. Phys. Chem. Chem. Phys. 2, 5647–5652 (2000).
Drozdová, L. et al. Subnanometer platinum clusters in zeolite NaEMT via stoichiometric carbonyl clusters. Microporous Mesoporous Mater. 35–36, 511–519 (2000).
Mishra, D. K., Dabbawala, A. A. & Hwang, J.-S. Ruthenium nanoparticles supported on zeolite Y as an efficient catalyst for selective hydrogenation of xylose to xylitol. J. Mol. Catal. A: Chem. 376, 63–70 (2013).
Visser, T. et al. Promotion effects in the oxidation of CO over zeolite-supported Pt nanoparticles. J. Phys. Chem. B 109, 3822–3831 (2005).
Rivallan, M. et al. Platinum sintering on H-ZSM-5 followed by chemometrics of CO adsorption and 2D pressure-jump IR spectroscopy of adsorbed species. Angew. Chem. Int. Ed. 49, 785–789 (2010).
Balakrishnan, K. A chemisorption and XPS study of bimetallic Pt-Sn/Al2O3 catalysts. J. Catal. 127, 287–306 (1991).
Panja, C. & Koel, B. E. Probing the influence of alloyed Sn on Pt(100) surface chemistry by CO chemisorption. Israel J. Chem 38, 365–374 (1998).
Chen, Y. et al. Single-atom catalysts: synthetic strategies and electrochemical applications. Joule 2, 1242–1264 (2018).
Wang, A., Li, J. & Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2, 65–81 (2018).
Zhang, H., Liu, G., Shi, L. & Ye, J. Single-atom catalysts: emerging multifunctional materials in heterogeneous catalysis. Adv. Energy Mater. 8, 1701343 (2018).
Wiktor, C., Meledina, M., Turner, S., Lebedev, O. I. & Fischer, R. A. Transmission electron microscopy on metal–organic frameworks – a review. J. Mater. Chem. A 5, 14969–14989 (2017).
Liu, L. et al. Direct imaging of atomically dispersed molybdenum that enables of aluminum in the framework of zeolite ZSM-5. Angew. Chem. Int. Ed. 59, 819–825 (2020).
Zuo, Q. et al. Ultrathin metal–organic framework nanosheets with ultrahigh loading of single Pt atoms for efficient visible-light-driven photocatalytic H2 evolution. Angew. Chem. Int. Ed. 58, 10198–10203 (2019).
Liu, L. et al. Imaging defects and their evolution in a metal-organic framework at sub-unit-cell resolution. Nat. Chem. 11, 622–628 (2019).
Zhou, Y. et al. Local structure evolvement in MOF single crystals unveiled by scanning transmission electron microscopy. Chem. Mater. 32, 4966–4972 (2020).
Borisevich, A. Y., Lupini, A. R. & Pennycook, S. J. Depth sectioning with the aberration-corrected scanning transmission electron microscope. Proc. Natl Acad. Sci. USA 103, 3044–3048 (2006).
Zecevic, J., van der Eerden, A. M., Friedrich, H., de Jongh, P. E. & de Jong, K. P. Heterogeneities of the nanostructure of platinum/zeolite y catalysts revealed by electron tomography. ACS Nano 7, 3698–3705 (2013).
Schmidt, J. E., Oord, R., Guo, W., Poplawsky, J. D. & Weckhuysen, B. M. Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts. Nat. Commun. 8, 1666 (2017).
Chen, Z. et al. Direct synthesis of core-shell MFI zeolites with spatially tapered trimodal mesopores via controlled orthogonal self-assembly. Nanoscale 11, 16667–16676 (2019).
Kliewer, C. E. in Zeolite Characterization and Catalysis (eds. Chester, A. W. & Derouane, E. G.) (Springer, 2009).
Deng, D. et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotechnol. 11, 218–230 (2016).
Li, Z. et al. Reactive metal–support interactions at moderate temperature in two-dimensional niobium-carbide-supported platinum catalysts. Nat. Catal. 1, 349–355 (2018).
Goldsmith, B. R., Peters, B., Johnson, J. K., Gates, B. C. & Scott, S. L. Beyond ordered materials: understanding catalytic sites on amorphous solids. ACS Catal. 7, 7543–7557 (2017).
van Deelen, T. W., Hernández Mejía, C. & de Jong, K. P. Control of metal–support interactions in heterogeneous catalysts to enhance activity and selectivity. Nat. Catal. 2, 955–970 (2019).
Hodnik, N., Dehm, G. & Mayrhofer, K. J. Importance and challenges of electrochemical in situ liquid cell electron microscopy for energy conversion research. Acc. Chem. Res. 49, 2015–2022 (2016).
Boyes, E. D., LaGrow, A. P., Ward, M. R., Mitchell, R. W. & Gai, P. L. Single atom dynamics in chemical reactions. Acc. Chem. Res. 53, 390–399 (2020).
Nakamura, E. Atomic-resolution transmission electron microscopic movies for study of organic molecules, assemblies, and reactions: the first 10 years of development. Acc. Chem. Res. 50, 1281–1292 (2017).
Li, T. et al. Cryo-TEM and electron tomography reveal leaching-induced pore formation in ZSM-5 zeolite. J. Mater. Chem. A 7, 1442–1446 (2019).
Li, Y. et al. Cryo-EM structures of atomic surfaces and host–guest chemistry in metal-organic frameworks. Matter 1, 428–438 (2019).
Liu, L. & Corma, A. Evolution of isolated atoms and clusters in catalysis. Trends Chem. 2, 383–400 (2020).
Barthel, J. Dr. Probe: a software for high-resolution STEM image simulation. Ultramicroscopy 193, 1–11 (2018).
De Wael, A., De Backer, A., Jones, L., Nellist, P. D. & Van Aert, S. Hybrid statistics-simulations based method for atom-counting from ADF STEM images. Ultramicroscopy 177, 69–77 (2017).
Hwang, J., Zhang, J. Y., D’Alfonso, A. J., Allen, L. J. & Stemmer, S. Three-dimensional imaging of individual dopant atoms in SrTiO3. Phys. Rev. Lett. 111, 266101 (2013).

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

Supplementary information

Reporting Summary

推荐阅读