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


  • 1.

    Flytzani-Stephanopoulos, M. & Gates, B. C. Atomically dispersed supported metal catalysts. Annu. Rev. Chem. Biomol. Eng. 3, 545–574 (2012).

    CAS 
    PubMed 

    Google Scholar
     

  • 2.

    Liu, L. & Corma, A. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem. Rev. 118, 4981–5079 (2018).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar
     

  • 3.

    Thomas, J. M., Raja, R. & Lewis, D. W. Single-site heterogeneous catalysts. Angew. Chem. Int. Ed. 44, 6456–6482 (2005).

    CAS 

    Google Scholar
     

  • 4.

    Hansen, T. W. et al. Atomic-resolution in situ transmission electron microscopy of a promoter of a heterogeneous catalyst. Science 294, 1508–1510 (2001).

    CAS 
    PubMed 

    Google Scholar
     

  • 5.

    Hwang, S., Chen, X., Zhou, G. & Su, D. In situ transmission electron microscopy on energy-related catalysis. Adv. Energy Mater. https://doi.org/10.1002/aenm.201902105 (2019).

  • 6.

    Li, Z. et al. Well-defined materials for heterogeneous catalysis: from nanoparticles to isolated single-atom sites. Chem. Rev. 120, 623–682 (2019).

    PubMed 

    Google Scholar
     

  • 7.

    Pelletier, J. D. & Basset, J. M. Catalysis by design: well-defined single-site heterogeneous catalysts. Acc. Chem. Res. 49, 664–677 (2016).

    CAS 
    PubMed 

    Google Scholar
     

  • 8.

    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).

    CAS 

    Google Scholar
     

  • 9.

    Liu, L. et al. Evolution and stabilization of subnanometric metal species in confined space by in situ TEM. Nat. Commun. 9, 574 (2018).

    PubMed 
    PubMed Central 

    Google Scholar
     

  • 10.

    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).

    CAS 

    Google Scholar
     

  • 11.

    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).


    Google Scholar
     

  • 12.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 13.

    Juneau, M. et al. Characterization of metal–zeolite composite catalysts: determining the environment of the active phase. ChemCatChem https://doi.org/10.1002/cctc.201902039 (2019).

  • 14.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 15.

    Weckhuysen, B. M. Stable platinum in a zeolite channel. Nat. Mater. 18, 778–779 (2019).

    CAS 
    PubMed 

    Google Scholar
     

  • 16.

    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).

    CAS 

    Google Scholar
     

  • 17.

    Gates, B. C. Atomically dispersed supported metal catalysts: seeing is believing. Trends Chem. 1, 99–110 (2019).


    Google Scholar
     

  • 18.

    Yang, S. et al. Bridging dealumination and desilication for the synthesis of hierarchical MFI zeolites. Angew. Chem. Int. Ed. 56, 12553–12556 (2017).

    CAS 

    Google Scholar
     

  • 19.

    Lupulescu, A. I. & Rimer, J. D. In situ imaging of silicalite-1 surface growth reveals the mechanism of crystallization. Science 344, 729–732 (2014).

    CAS 
    PubMed 

    Google Scholar
     

  • 20.

    Anderson, M. W. et al. Modern microscopy methods for the structural study of porous materials. Chem. Commun. (8), 907–916 (2004).

  • 21.

    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).

    CAS 

    Google Scholar
     

  • 22.

    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).

    CAS 

    Google Scholar
     

  • 23.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 24.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 25.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 26.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 27.

    Diaz, I. & Mayoral, A. TEM studies of zeolites and ordered mesoporous materials. Micron 42, 512–527 (2011).

    CAS 
    PubMed 

    Google Scholar
     

  • 28.

    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).

    CAS 

    Google Scholar
     

  • 29.

    Mishra, R., Ishikawa, R., Lupini, A. R. & Pennycook, S. J. Single-atom dynamics in scanning transmission electron microscopy. MRS Bulletin 42, 644–652 (2017).

    CAS 

    Google Scholar
     

  • 30.

    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).

    CAS 

    Google Scholar
     

  • 31.

    Lazic, I., Bosch, E. G. T. & Lazar, S. Phase contrast STEM for thin samples: integrated differential phase contrast. Ultramicroscopy 160, 265–280 (2016).

    CAS 
    PubMed 

    Google Scholar
     

  • 32.

    Shen, B. et al. Atomic spatial and temporal imaging of local structures and light elements inside zeolite frameworks. Adv. Mater. e1906103 (2019).

  • 33.

    Egerton, R. F. & Watanabe, M. Characterization of single-atom catalysts by EELS and EDX spectroscopy. Ultramicroscopy 193, 111–117 (2018).

    CAS 
    PubMed 

    Google Scholar
     

  • 34.

    Bonilla, G. et al. Zeolite (MFI) crystal morphology control using organic structure-directing agents. Chem. Mater. 16, 5697–5705 (2004).

    CAS 

    Google Scholar
     

  • 35.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 36.

    Grand, J. et al. One-pot synthesis of silanol-free nanosized MFI zeolite. Nat. Mater. 16, 1010–1015 (2017).

    CAS 
    PubMed 

    Google Scholar
     

  • 37.

    Varela, M. et al. Materials characterization in the aberration-corrected scanning transmission electron microscope. Annu. Rev. Mater. Res. 35, 539–569 (2005).

    CAS 

    Google Scholar
     

  • 38.

    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).

    CAS 

    Google Scholar
     

  • 39.

    Erni, R. Aberration-Corrected Imaging in Transmission Electron Microscopy (Imperial College Press, 2010).

  • 40.

    Díaz, I., Kokkoli, E., Terasaki, O. & Tsapatsis, M. Surface structure of zeolite (MFI) crystals. Chem. Mater. 16, 5226–5232 (2004).


    Google Scholar
     

  • 41.

    Bernal, S. et al. The interpretation of HREM images of supported metal catalysts using image simulation: profile view images. Ultramicroscopy 72, 135–164 (1998).

    CAS 

    Google Scholar
     

  • 42.

    Kirkland, E. J. Advanced Computing in Electron Microscopy (Springer, 2010).

  • 43.

    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).

    CAS 

    Google Scholar
     

  • 44.

    Pei, Y. et al. Catalytic properties of intermetallic platinum–tin nanoparticles with non-stoichiometric compositions. J. Catal. 374, 136–142 (2019).

    CAS 

    Google Scholar
     

  • 45.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 46.

    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).


    Google Scholar
     

  • 47.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 48.

    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).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar
     

  • 49.

    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).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar
     

  • 50.

    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).


    Google Scholar
     

  • 51.

    Sun, Q. et al. Subnanometer bimetallic Pt–Zn clusters in zeolites for propane dehydrogenation. Angew. Chem. Int. Ed. https://doi.org/10.1002/anie.202003349 (2020).

  • 52.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 53.

    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).

    CAS 

    Google Scholar
     

  • 54.

    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).

    CAS 

    Google Scholar
     

  • 55.

    Drozdová, L. et al. Subnanometer platinum clusters in zeolite NaEMT via stoichiometric carbonyl clusters. Microporous Mesoporous Mater. 35–36, 511–519 (2000).


    Google Scholar
     

  • 56.

    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).

    CAS 

    Google Scholar
     

  • 57.

    Visser, T. et al. Promotion effects in the oxidation of CO over zeolite-supported Pt nanoparticles. J. Phys. Chem. B 109, 3822–3831 (2005).

    CAS 
    PubMed 

    Google Scholar
     

  • 58.

    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).

    CAS 

    Google Scholar
     

  • 59.

    Balakrishnan, K. A chemisorption and XPS study of bimetallic Pt-Sn/Al2O3 catalysts. J. Catal. 127, 287–306 (1991).

    CAS 

    Google Scholar
     

  • 60.

    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).

    CAS 

    Google Scholar
     

  • 61.

    Chen, Y. et al. Single-atom catalysts: synthetic strategies and electrochemical applications. Joule 2, 1242–1264 (2018).

    CAS 

    Google Scholar
     

  • 62.

    Wang, A., Li, J. & Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2, 65–81 (2018).

    CAS 

    Google Scholar
     

  • 63.

    Zhang, H., Liu, G., Shi, L. & Ye, J. Single-atom catalysts: emerging multifunctional materials in heterogeneous catalysis. Adv. Energy Mater. 8, 1701343 (2018).


    Google Scholar
     

  • 64.

    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).

    CAS 

    Google Scholar
     

  • 65.

    Liu, L. et al. Direct imaging of atomically dispersed molybdenum that enables location of aluminum in the framework of zeolite ZSM-5. Angew. Chem. Int. Ed. 59, 819–825 (2020).

    CAS 

    Google Scholar
     

  • 66.

    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).

    CAS 

    Google Scholar
     

  • 67.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 68.

    Zhou, Y. et al. Local structure evolvement in MOF single crystals unveiled by scanning transmission electron microscopy. Chem. Mater. 32, 4966–4972 (2020).

  • 69.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 70.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 71.

    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).

    PubMed 
    PubMed Central 

    Google Scholar
     

  • 72.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 73.

    Kliewer, C. E. in Zeolite Characterization and Catalysis (eds. Chester, A. W. & Derouane, E. G.) (Springer, 2009).

  • 74.

    Deng, D. et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotechnol. 11, 218–230 (2016).

    CAS 
    PubMed 

    Google Scholar
     

  • 75.

    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).

    CAS 

    Google Scholar
     

  • 76.

    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).

    CAS 

    Google Scholar
     

  • 77.

    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).

    CAS 

    Google Scholar
     

  • 78.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 79.

    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).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar
     

  • 80.

    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).

    CAS 
    PubMed 

    Google Scholar
     

  • 81.

    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).

    CAS 

    Google Scholar
     

  • 82.

    Li, Y. et al. Cryo-EM structures of atomic surfaces and host–guest chemistry in metal-organic frameworks. Matter 1, 428–438 (2019).


    Google Scholar
     

  • 83.

    Liu, L. & Corma, A. Evolution of isolated atoms and clusters in catalysis. Trends Chem. 2, 383–400 (2020).


    Google Scholar
     

  • 84.

    Barthel, J. Dr. Probe: a software for high-resolution STEM image simulation. Ultramicroscopy 193, 1–11 (2018).

    CAS 
    PubMed 

    Google Scholar
     

  • 85.

    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).

    PubMed 

    Google Scholar
     

  • 86.

    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).

    PubMed 

    Google Scholar
     



  • Source link

    Leave a Reply

    Your email address will not be published. Required fields are marked *