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Tandem catalysis with double-shelled hollow spheres

Nature Materials volume 21, pages 572–579 (2022)Cite this article

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Abstract

Metal–zeolite composites with metal (oxide) and acid sites are promising catalysts for integrating multiple reactions in tandem to produce a wide variety of wanted products without separating or purifying the intermediates. However, the conventional design of such materials often leads to uncontrolled and non-ideal spatial distributions of the metal inside/on the zeolites, limiting their catalytic performance. Here we demonstrate a simple strategy for synthesizing double-shelled, contiguous metal oxide@zeolite hollow spheres (denoted as MO@ZEO DSHSs) with controllable structural parameters and chemical compositions. This involves the self-assembly of zeolite nanocrystals onto the surface of metal ion-containing carbon spheres followed by calcination and zeolite growth steps. The step-by-step formation mechanism of the material is revealed using mainly in situ Raman spectroscopy and X-ray diffraction and ex situ electron microscopy. We demonstrate that it is due to this structure that an Fe2O3@H-ZSM-5 DSHSs-showcase catalyst exhibits superior performance compared with various conventionally structured Fe2O3-H-ZSM-5 catalysts in gasoline production by the Fischer–Tropsch synthesis. This work is expected to advance the rational synthesis and research of hierarchically hollow, core–shell, multifunctional catalyst materials.

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Fig. 1: Synthesis of MO@ZEO DSHSs.
Fig. 2: Phase variation during synthesis of Fe2O3@S-1 DSHSs.
Fig. 3: Monitoring of the transformation from an Fe3+-CS@S-1 colloid to a hollow Fe2O3 sphere@S-1 colloid during calcination in air.
Fig. 4: Manipulation of structural parameters and chemical compositions in MO@ZEO DSHSs.
Fig. 5: Catalytic performances of different catalyst materials in syngas conversion.

Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

B.M.W. acknowledges financial support from the Netherlands Organization for Scientific Research (NWO) in the frame of a Gravitation Program MCEC (Netherlands Center for Multiscale Catalytic Energy Conversion, www.mcec-researchcenter.nl). X.X. (Utrecht University) acknowledges financial support from the EU H2020-MSCA-ITN-2015 project ‘MULTIMAT’ (project no. 676045). K.C. and Y.W. acknowledge financial support from the National Natural Science Foundation of China (grant nos. 91945301, 22121001 and 22072120). J.X. thanks D. Wezendonk (Utrecht University) for his help with the in situ XRD measurements.

Author information

Author notes

  1. Jiadong Xiao

    Present address: Research Initiative for Supra-Materials, Interdisciplinary Cluster for Cutting Edge Research, Shinshu University, Nagano-shi, Japan

  2. Xiaobin Xie

    Present address: Electron Microscopy for Materials Science (EMAT), University of Antwerp, Antwerp, Belgium

  3. Yuanshuai Liu

    Present address: Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, China

  4. Donglong Fu

    Present address: Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA

  5. These authors contributed equally: Jiadong Xiao, Kang Cheng.

Authors and Affiliations

  1. Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, the Netherlands

    Jiadong Xiao, Shiyou Xing, Yuanshuai Liu, Thomas Hartman, Donglong Fu, Koen Bossers & Bert M. Weckhuysen

  2. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Kang Cheng, Mengheng Wang & Ye Wang

  3. Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, the Netherlands

    Xiaobin Xie, Marijn A. van Huis & Alfons van Blaaderen

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Contributions

J.X., B.M.W., K.C. and Y.W. conceived and designed the experiments. B.M.W. and Y.W. supervised the project. J.X. synthesized and characterized the materials, analysed the data and wrote the initial manuscript. K.C. and M.W. performed the catalytic reactions, analysed the resulting data and drafted the catalytic reaction part. X.X. and M.A.v.H. performed the (S)TEM-related measurements. Y.L. and T.H. performed the ex situ IR and in situ Raman measurements, respectively. S.X. performed a part of the SEM measurements and the ex situ Raman measurements. D.F. and K.B. contributed to the exploration of the zeolite secondary growth conditions. A.v.B. helped with the mechanistic understanding of the self-assembly process. J.X., B.M.W., K.C. and Y.W. revised the paper with contributions from all the other co-authors.

Corresponding authors

Correspondence to Ye Wang or Bert M. Weckhuysen.

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Nature Materials thanks Michael Claeys and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–39, Tables 1–7 and refs. 1–17.

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Source Data Fig. 3

Source data for Fig. 3a–c,f,g.

Source Data Fig. 4

Source data for Fig. 4d,e–h,l,m–s.

Source Data Fig. 5

Source data for Fig. 5a–d.

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Xiao, J., Cheng, K., Xie, X. et al. Tandem catalysis with double-shelled hollow spheres. Nat. Mater. 21, 572–579 (2022). https://doi.org/10.1038/s41563-021-01183-0

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