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Germanium-enriched double-four-membered-ring units inducing zeolite-confined subnanometric Pt clusters for efficient propane dehydrogenation

Nature Catalysis volume 6, pages 506–518 (2023)Cite this article

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Abstract

It is a great challenge to regulate the precise placement of confined metal species and assemble specific structures at the atomic level. Here we report the design and synthesis of a durable supported-metal-cluster catalyst, Pt@Ge-UTL, that features subnanometric Pt clusters encapsulated inside the extra-large pores of a stabilized UTL-type germanosilicate. Integrated differential phase contrast scanning transmission electron microscopy, in situ X-ray absorption fine structure, 19F magic-angle-spinning NMR, full-range synchrotron pair distribution function G(r) analysis and density functional theory calculations revealed that Pt clusters with an average of four atoms are firmly segregated within 14-membered-ring channels. This is achieved by selectively and directionally anchoring Pt, via Pt–O–Ge bonding, to the UTL zeolite’s unique secondary building units that feature a double-four-membered-ring (d4r) configuration and a Ge-enriched composition. The host–guest bimetallic structure (Pt4-Ge2-d4r@UTL) promotes propane dehydrogenation with high activity, high propylene selectivity and long-term stability. This research demonstrates the use of germanosilicates in the designed synthesis of high-performance propane dehydrogenation catalysts.

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Fig. 1: Dispersity of Pt species in a series of UTL zeolites with different Si/Ge ratios.
Fig. 2: Catalytic performance for the PDH reaction.
Fig. 3: Location of subnanometric Pt species within the channels of UTL topology.
Fig. 4: Characterization of the chemical states and coordination environments of Pt and Ge.
Fig. 5: Positions of Ge atoms in the support and Pt-confined catalyst.
Fig. 6: Calculation results for constructing the theoretical structure.
Fig. 7: Validation of the Pt4-Ge2-d4r@UTL structure model.
Fig. 8: Calculation results for the theoretical PDH process.

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All the data needed to support the plots and evaluate the conclusions of this study are present within the Article and the Supplementary Information or are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant numbers 21872052, 21972044, 22172050 and 22105028), the National Key R&D Program of China (2021YFA1501401), ‘Grassland Talents’ of Inner Mongolia Autonomous Region, Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region (NJYT23030), ‘Steed plan High level Talents’ of Inner Mongolia University, and Fundamental Research Funds for the Central Universities (grant number 2022CDJXY-003). We gratefully acknowledge the BL17B beamline of the National Facility for Protein Science (NFPS), Shanghai Synchrotron Radiation Facility (SSRF) Shanghai, China for providing the beam time.

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Authors and Affiliations

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China

    Yue Ma, Longkang Zhang, Yuhong Zhao, Hao Xu, Yejun Guan, Jingang Jiang & Peng Wu

  2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing, China

    Shaojia Song & Weiyu Song

  3. Research Institute of Petroleum Processing, Sinopec, Beijing, China

    Changcheng Liu & Xin Wang

  4. Multi-Scale Porous Materials Center, Institute of Advanced Interdisciplinary Studies & School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, China

    Lingmei Liu

  5. Institute of Eco-Chongming, Shanghai, China

    Hao Xu, Yejun Guan & Peng Wu

  6. Advanced Membranes and Porous Materials Center (AMPMC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, Kingdom of Saudi Arabia

    Yu Han

  7. Electron Microscopy Center, South China University of Technology, Guangzhou, China

    Yu Han

  8. Science Center of Energy Material and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, China

    Jiangwei Zhang

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  1. Yue Ma
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Contributions

P.W. conceived the project and directed the study. Y.M. carried out the synthesis, structural characterizations and catalytic measurements and wrote the manuscript. H.X. and Y.G. contributed to the experimental design and data interpretation. J.J. carried out the 19F MAS NMR measurements. L.Z. carried out the infrared CO-adsorption experiments. C.L., Y.Z. and X.W. assisted in the preparation method of the catalyst. L.L. and Y.H. carried out the Cs-corrected HAADF-STEM and iDPC-STEM measurements and images. J.Z. contributed to the collection and analysis of XAFS and PDF data in the BL17b beamline of the National Facility for Protein Science (NFPS), Shanghai Synchrotron Radiation Facility (SSRF). S.S. and W.S. carried out the theoretical calculations. All the authors discussed the results and contributed to the preparation of the manuscript.

Corresponding authors

Correspondence to Hao Xu, Yejun Guan, Weiyu Song, Yu Han, Jiangwei Zhang or Peng Wu.

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Ma, Y., Song, S., Liu, C. et al. Germanium-enriched double-four-membered-ring units inducing zeolite-confined subnanometric Pt clusters for efficient propane dehydrogenation. Nat Catal 6, 506–518 (2023). https://doi.org/10.1038/s41929-023-00968-7

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