Abstract
The shale gas revolution has shifted propylene production from naphtha cracking to on-purpose production with propane dehydrogenation (PDH) as the dominant technology1,2,3,4,5,6,7,8,9. Because PDH is endothermic and requires high temperatures that favour sintering and coking, the challenge is to develop active and stable catalysts1,2,3 that are sufficiently stable10,11. Zeolite-supported Pt–Sn catalysts have been developed to balance activity, selectivity and stability12,13 and more recent work documented a PDH catalyst based on zeolite-anchored single rhodium atoms with exceptional performance and stability14. Here we show for silicalite-1 (S-1) that migration of encapsulated Pt–Sn2 clusters and hence agglomeration and anchoring within the zeolite versus agglomeration on the external surface can be controlled by adjusting the length of the S-1 crystals’ b-axis. We find that, when this axis is longer than 2.00 μm, migration of Pt–Sn2 monomers during PDH results in intracrystalline formation of (Pt–Sn2)2 dimers that are securely locked in the channels of S-1 and capable of converting pure propane feed to propylene at 550 °C for more than 6 months with 98.3% selectivity at 91% equilibrium conversion. This performance exceeds that of other Pt-based PDH catalysts and approaches that of the Rh-based catalyst. Although synthesis requirements and cost are at present prohibitive for industrial use, we anticipate that our approach to controlling the migration and lockup of metals in zeolites may enable the development of other noble-metal catalysts that offer extended service lifetimes in industrial applications15,16,17.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (22178062, 22221005, 22478076, U23A20113, 22288101, 22293021 and 22208337), the National Key R&D Program of China (2021YFA1500302), Industrial Joint Fund of Qingyuan Innovation Laboratory (00422001), 111 Project (D17005) and Foundation of State Key Laboratory of Coal Conversion (J21-22-620). We thank A. Lu and G. Hao from Dalian University of Technology for helpful discussion and diffusion measurement. We thank D. Zhao and D. E. Doronkin from Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany, for operando XAS measurements. We thank the staff from the BL06B1, BL14W1, BL17U1 and BL20U beamlines of the National Facility at Shanghai Synchrotron Radiation Facility for their assistance in the collection of spectroscopy data. We thank Z. Jia and W. Liu from Dalian Institute of Chemical Physics, Chinese Academy of Sciences and S. Liu from Thermo Fisher Scientific for HAADF-STEM characterization. We thank J. Zhang from Inner Mongolia University for his help in the data analysis of SR-XRD. We thank Q. Qiao and Z. Xu from Dalian Institute of Chemical Physics, Chinese Academy of Sciences, for the structural illumination imaging. We thank B. Peng from SINOPEC Research Institute of Petroleum Processing (RIPP) for the discussion of the kinetic study. We thank DESY (Hamburg, Germany), a member of the Helmholtz Association (HGF), for the provision of experimental facilities. We thank E. Welter for assistance in using beamline P65. M.G. took his new position at Xiamen University during the revision of this manuscript and we thank Xiamen University for providing the necessary resources to support this study.
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H.Z. and X.B. initiated and led the project and wrote the manuscript. M.G. and M.Y. performed the migration–agglomeration model and theoretical calculations, along with diffusion and fluorescence imaging experiments. Z.L. performed theoretical calculations. Y.W. and B.M. performed XAS and analysed the data. P.F. and J.-M.B. analysed the data and helped write the manuscript. Z.X., Y.Y., Z.B. and P.Y. prepared catalysts with different methods (one-pot hydrothermal crystallization and traditional impregnation), characterized the catalysts with various techniques (ICP-AES, SEM, HAADF-STEM, FIB/SEM, CO-FTIR, IGA and so on) and tested the catalysts’ performance (activity, selectivity and stability).
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Extended data figures and tables
Extended Data Fig. 1 Crystalline phase and morphology of 0.25%Pt–Sn@S-1 catalysts.
a–c, Powder XRD pattern, SEM image and morphology parameters of 0.25%Pt–Sn@S-1(0.10 μm). d–f, Powder XRD pattern, SEM image and morphology parameters of 0.25%Pt–Sn@S-1(0.15 μm). g–i, Powder XRD pattern, SEM image and morphology parameters of 0.25%Pt–Sn@S-1(0.50 μm). j–l, Powder XRD pattern, SEM image and morphology parameters of 0.25%Pt–Sn@S-1(2.00 μm). m–o, Powder XRD pattern, SEM image and morphology parameters of 0.25%Pt–Sn@S-1(3.00 μm). p–r, Powder XRD pattern, SEM image and morphology parameters of 0.25%Pt–Sn@S-1(4.00 μm).
Extended Data Fig. 2 Diffusion-rate measurements of propane or propylene in 0.25%Pt–Sn@S-1.
a–c, The uptake curves of propane in 0.25%Pt–Sn@S-1(0.10 μm), 0.25%Pt–Sn@S-1(0.50 μm) and 0.25%Pt–Sn@S-1(4.00 μm) at 25, 40, 55 and 70 °C (0 → 20 mbar), respectively (details of this figure are summarized in Supplementary Table 14). d–f, The uptake curves of propylene at 25, 40, 55 and 70 °C (0 → 20 mbar) in 0.25%Pt–Sn@S-1(0.10 μm), 0.25%Pt–Sn@S-1(0.50 μm) and 0.25%Pt–Sn@S-1(4.00 μm), respectively (details of this figure are summarized in Supplementary Table 14). g, The inverse of diffusion time constant of propane in 0.25%Pt–Sn@S-1(0.10 μm), 0.25%Pt–Sn@S-1(0.50 μm) and 0.25%Pt–Sn@S-1(4.00 μm), respectively. The error bar is the error of fitting between experimental data and the theoretical model. h, The inverse of diffusion time constant propylene in 0.25%Pt–Sn@S-1(0.10 μm), 0.25%Pt–Sn@S-1(0.50 μm) and 0.25%Pt–Sn@S-1(4.00 μm), respectively. The error bar is the error of fitting between experimental data and theoretical model. i, The uptake curves of propane in 0.25%Pt–Sn@S-1(4.00 μm) with different loading qualities. Notes: it should be emphasized that the effect of external diffusion was eliminated by changing the quality of samples shown in panel i. The details of uptake curves fitting are listed in Supplementary Tables 15 and 16. It can be noticed that the coefficient of determination of fitting R2 by the dual resistance model (DRM) for all uptake curves measured in this work is above 0.95, which confirms the feasibility and acceptable fitting error of the DRM in fitting uptake curves (panels a–f). In theory, the DRM takes the intracrystalline diffusion and surface barriers as two dominated mass-transport mechanisms in the samples based on the assumption of uniform crystal-size distribution. In practice, the fitting errors between the DRM and experiments can be affected by the non-uniform size distribution of samples42 and the adsorption-dependent diffusion rate of guest molecules in different samples43.
Extended Data Fig. 3 Catalytic performance of 0.25%Pt–Sn@S-1(4.00 μm).
a, Propane conversion and propylene selectivity over 0.25%Pt–Sn@S-1(4.00 μm) at different WHSVs (2.90, 5.30, 21.2, 36.8, 1,060 and 3,680 h−1). Catalytic test conditions: atmospheric pressure, 100% C3H8 and T = 600 °C. b, The calculated intrinsic activity (turnover frequency, TOF) over 0.25%Pt–Sn@S-1(4.00 μm) at different reaction temperatures. Catalytic test conditions: atmospheric pressure, 100% C3H8, WHSV = 3,680 h−1 and T = 550–600 °C. c, PDH over 0.37%Pt–Sn@S-1(4.00 μm) with different C3H8 concentrations (25%, 75% and 100%) and WHSVs at 550 °C. d, PDH over 0.37%Pt–Sn@S-1(4.00 μm) with different C3H8 concentrations (25%, 75% and 100%) and WHSVs at 600 °C. e, Comparison of the specific activity of 0.37%(Pt–Sn2)2@S-1 with that of previously reported Pt-based PDH catalysts with pure propane as feed. f, Comparison of the specific activity of 0.37%(Pt–Sn2)2@S-1 with that of previously reported Pt-based PDH catalysts with diluted propane as feed (detailed data are summarized in Extended Data Fig. 3c,d and Supplementary Table 1). g, Propane conversion versus propylene selectivity over 0.25%Pt–Sn@S-1(4.00 μm) catalyst at different WHSVs (3.80, 5.30, 13.2, 36.8 and 1,060 h−1). Catalytic test conditions: atmospheric pressure, 100% C3H8 and T = 550 °C. h, Conversion–selectivity plots for 0.25%(Pt–Sn2)2@S-1 and different PDH catalysts in ref. 11 (red dots are from Extended Data Fig. 3g). i, Propane conversion and propylene selectivity over 0.25%Pt–Sn@S-1(4.00 μm) and industrial analogue Pt–Sn/Al2O3. Catalytic test conditions: atmospheric pressure, C3H8/H2 = 2:1, WHSV = 5.9 h−1 and T = 600 °C.
Extended Data Fig. 4 PDH performance over 0.25%Pt–Sn@S-1 catalysts.
a, Propane conversion and propylene selectivity over 0.25%Pt–Sn@S-1(4.00 μm) and 0.25%Pt–Sn@S-1(0.10 μm) after pretreatments at different temperatures. b, Propane conversion and propylene selectivity over 0.25%Pt–Sn@S-1(4.00 μm) and 0.25%Pt–Sn@S-1(0.10 μm) in several reaction sequences of 600–650–550 °C, respectively. c, Propane conversion and propylene selectivity over 0.25%Pt–Sn@S-1(4.00 μm) in the presence of H2S. The mixture of H2S (25 ppm) and propane was used as reactant. d, Propane conversion and propylene selectivity over 0.25%Pt–Sn@S-1(4.00 μm) in the presence of H2O. The mixture of H2O (37.8 vol%) and propane was used as reactant. Catalytic test conditions: atmospheric pressure, WHSV = 5.3 h−1 and T = 600 °C. e,f, Specimen morphology of spent 0.25%(Pt–Sn2)2@S-1(4.00 μm) after PDH for APT analysis (e) and 3D atom distribution map of Si, O, Sn and Pt within 0.25%(Pt–Sn2)2@S-1(4.00 μm) after PDH (f). Bounding box dimensions: 30 × 40 × 110 nm3.
Extended Data Fig. 5 Operando XAS analysis results.
a, Pt L3-edge XANES spectra of 0.25%Pt–Sn@S-1(4.00 μm) at different reaction times in PDH at 600 °C. The quantitative χ(R) space Pt L3-edge spectrum fitted curves of 0.25%Pt–Sn@S-1(4.00 μm)-600-H2 (b), 0.25%Pt–Sn@S-1(4.00 μm)-PDH-1 h (c), 0.25%Pt–Sn@S-1(4.00 μm)-PDH-3 h (d), 0.25%Pt–Sn@S-1(4.00 μm)-PDH-5 h (e), 0.25%Pt–Sn@S-1(4.00 μm)-PDH-7 h (f) and 0.25%Pt–Sn@S-1(4.00 μm)-PDH-10 h (g). Notes: for the EXAFS spectra fitting, the amplitude reduction factor \({S}_{0}^{2}=0.80\) was obtained through fitting the Pt foil. The Pt L3-edge EXAFS spectra were obtained by subtracting the pre-edge appropriate background and post-edge normalizing. The k2-weighted EXAFS functions were Fourier transformed (FT) in the k range 3–10 Å−1 and multiplied by a hanging window with a sill size of 1 Å−1, obtaining the high-quality data ranges (R = 1.2–3.4 Å) in radical space.
Extended Data Fig. 6 Operando XAS analysis results.
a, Sn K-edge XANES spectra of 0.25%Pt–Sn@S-1(4.00 μm) at different reaction times in PDH at 600 °C. b, The radial distance space χ(R) spectra of 0.25%Pt–Sn@S-1(4.00 μm) at different reaction times in PDH at 600 °C. The quantitative χ(R) space Sn K-edge spectrum fitted curves of 0.25%Pt–Sn@S-1(4.00 μm)-600-H2 (c), 0.25%Pt–Sn@S-1(4.00 μm)-PDH-3 h (d) and 0.25%Pt–Sn@S-1(4.00 μm)-PDH-10 h (e). Notes: for the EXAFS spectra fitting, the amplitude reduction factor \({S}_{0}^{2}=0.70\) was obtained through fitting the SnO2. The Sn K-edge EXAFS spectra were obtained by subtracting the pre-edge appropriate background and post-edge normalizing. The k2-weighted EXAFS functions were Fourier transformed (FT) in the k range 3–10 Å−1 and multiplied by a hanging window with a sill size of 1 Å−1, obtaining the high-quality data ranges (R = 1.0–3.0 Å) in radical space.
Extended Data Fig. 7 Atomic-level characterization of 0.25%Pt–Sn@S-1(4.00 μm) and 0.25%Pt–Sn@S-1(0.10 μm) catalysts.
a, SR-XRD pattern and 2D XRD image of 0.25%Pt–Sn@S-1(4.00 μm). b, SR-XRD pattern and 2D XRD image of 0.25%Pt–Sn@S-1(4.00 μm)spent. c, Viewed along the [010] direction of the MFI framework. d, The values of dmax and dmin in the ten-membered ring. e, Profile analysis of the ten-membered ring in S-1 from the [010] projection. f, Profile analysis of the ten-membered ring from the [010] projection in 0.25%Pt–Sn@S-1(4.00 μm)spent. g–i, Simulated structures for empty MFI framework and MFI framework loaded with (Pt–Sn2)2 dimers and corresponding values of dmax/dmin. j, STEM images of 0.25%Pt–Sn@S-1(4.00 μm) after thermal treatment at 800 °C. k, Profile analysis of the ten-membered ring from the [010] projection in 0.25%Pt–Sn@S-1(4.00 μm) after thermal treatment at 800 °C.
Extended Data Fig. 8 The adsorption energies of (Pt–Sn2)x clusters within the MFI framework.
Optimized structure and adsorption energy of one Pt–Sn2 cluster located at intersection site (a), zigzag (b) and straight channels (c), one (Pt–Sn2)2 cluster located at intersection site (d), intersection site with the formation of Pt–Si and Pt–O bonds (e), zigzag (f) and straight channels (g), one (Pt–Sn2)3 (h) and one (Pt–Sn2)4 (i) cluster located at intersection site in the channels of S-1.
Extended Data Fig. 9 Dynamic evolution of agglomeration–migration for Pt–Sn2 monomers and (Pt–Sn2)2 dimers within the MFI framework.
Dynamic evolution of intracrystalline content of Pt–Sn2 monomers with mobility and agglomeration properties within S-1 with Lb of 0.1 (a), 0.15 (b), 0.5 (c), 1.0 (d), 2.0 (e), 3.5 (f) and 4.0 μm (g) obtained from agglomeration–migration modelling. Dynamic evolution of formed intracrystalline content of formed (Pt–Sn2)2 dimers within S-1 with Lb of 0.1 (h), 0.15 (i), 0.5 (j), 1.0 (k), 2.0 (l), 3.5 (m) and 4.0 μm (n) obtained from agglomeration–migration modelling. Notes: as time τ increases, the intracrystalline content of Pt–Sn2 monomers (or (Pt–Sn2)2 dimers) decreases (or increases) owning to the mobility and agglomeration of Pt–Sn2 monomers. For S-1 with short Lb, the short intracrystalline residence time of Pt–Sn2 monomers facilitates the agglomeration of Pt–Sn2 monomers at the external surface of S-1. For S-1 with a long Lb, the intracrystalline residence time of Pt–Sn2 monomers substantially increases, which promotes the agglomeration of Pt–Sn2 monomers in the channels of S-1. The intracrystalline content of (Pt–Sn2)2 dimers in S-1 with short Lb are much lower than those in S-1 with long Lb.
Extended Data Fig. 10 Periodic DFT computations for the PDH steps over Pt–Sn2 monomers and (Pt–Sn2)2 dimers confined within the MFI framework.
Geometries of initial (IS), transitional (TS) and final (FS) states for the dehydrogenation of propane (a), propyl isomer (b), propylene (c) and H2 (d) formation over Pt–Sn2 monomers within S-1. Geometries of IS, TS and FS for the dehydrogenation of propane (e), propyl isomer (f), propylene (g) and H2 (h) formation over (Pt–Sn2)2 dimers within S-1. Geometries of IS, TS and FS for the dehydrogenation of propane (i), propyl isomer (j), propylene (k) and H2 (l) formation over (Pt–Sn2)2 dimers with the formation of Pt–Si and Pt–O bonds with framework (named (Pt–Sn2)2*). m, Energy profiles for dehydrogenation of propane to propylene and coke precursor and H2 formation on Pt–Sn2 monomers, (Pt–Sn2)2 and (Pt–Sn2)2* dimers in the channels of S-1. All of the intermediates marked with ≠ indicate that they are transition-state intermediates adsorbed on the surfaces of clusters. Projected density of states (PDOS) analysis for C3H8 adsorbed at Pt–Sn2 monomer (n) and (Pt–Sn2)2 dimer (o) confined in the channels of S-1 and (Pt–Sn2)2 dimer with the formation of Pt–Si and Pt–O bonds with framework (p). Blue and red lines represent the spin-up and spin-down electrons of sum PDOS (s-orbitals < −10 eV and p-orbitals > −10 eV) for adsorbed propane at corresponding Pt sites, respectively. Yellow and orange lines represent the spin-up and spin-down electrons of d-orbitals PDOS of corresponding Pt sites, respectively. Notes: the geometries of TSs for the dehydrogenation steps over Pt–Sn2 monomers are schematically represented in panels a–c. From the data, some general trends are observed. (1) In the activated complex, the propane and monovalent group (1-propyl) prefer to be bound to the atop site and the divalent group (propylene) is bonded to the bridge site. The H atom that is detached from the C3 intermediates is relaxed to the atop or bridge site. (2) On the alloyed surfaces, the geometries of TSs are close to FSs on the potential-energy surface.
Extended Data Fig. 11 Coking-resistant properties of 0.25%Pt–Sn@S-1.
a, Thermogravimetric analysis of spent 0.25%Pt–Sn@S-1 catalysts after 96 h in PDH. Catalytic test conditions: atmospheric pressure, 100% C3H8, WHSV = 5.3 h−1 and T = 600 °C. b, SEM images of spent 0.25%Pt–Sn@S-1(4.00 μm) after 96 h in PDH. c, Spatiotemporal distribution obtained by SIM of aromatic hydrocarbons in a single crystal of spent 0.25%Pt–Sn@S-1(4.00 μm) at different reaction times. d, STEM images of the spent 0.25%Pt–Sn@S-1(4.00 μm) after 96 h in PDH. e, Coking-resistant mechanism of the MFI framework and the scheme of molecular size of aromatic hydrocarbons. Notes: all of the samples were exposed to air during measurement of SIM. The dimensions of coke precursors were measured by Materials Studio and presented by van der Waals radius.
Supplementary information
Supplementary Information
This file contains ‘Materials and methods’, ‘Characterizations’, ‘Catalytic reactions’, ‘Mass transfer effects’, ‘Criterion on internal diffusion limitations’, ‘Molecular dynamics simulations’, ‘Periodic density functional theory (DFT) computations’, Supplementary Figs. 1–37, Supplementary Tables 1–21 and Supplementary References.
Supplementary Code file
Main code for dual resistance model fitting procedure.
Supplementary Video 1
Migration of Pt in Pt–Sn@S-1(0.10 μm). Migration–agglomeration of Pt–Sn2 clusters in S-1 with Lb of 0.10 μm for the formation of Pt–Sn particles at S-1 surface.
Supplementary Video 2
Migration of Pt in Pt–Sn@S-1(4.00 μm). Migration–agglomeration of Pt–Sn2 clusters in S-1 with Lb of 4.00 μm for the formation of (Pt–Sn2)2 dimers locked in S-1 channels.
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Xu, Z., Gao, M., Wei, Y. et al. Pt migration–lockup in zeolite for stable propane dehydrogenation catalyst. Nature 643, 691–698 (2025). https://doi.org/10.1038/s41586-025-09168-8
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DOI: https://doi.org/10.1038/s41586-025-09168-8
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