Isolated Pt sites anchored by skeletal Fe in MFI zeolite nanosheets towards productive propane dehydrogenation

doi:10.1016/S1872-2067(26)65003-6

Abstract

Abstract:

The development of effective alkane dehydrogenation catalysts is essential to produce olefins from abundant shale gas. Commercial Pt-based propane dehydrogenation catalysts suffer from deactivation due to sintering and coke deposition, highlighting the need for substantial improvements in thermal stability and production efficiency. Herein, we present a facile one-pot strategy to create atomically dispersed bimetallic Pt-O-Fe motifs encapsulated within MFI zeolite nanosheet, serving as highly active and stable sites for propane dehydrogenation. Comprehensive characterization results reveal that the skeletal Fe (III) species in MFI zeolite act as anchoring sites, thereby stabilizing atomically dispersed Pt species through the unique linkages of ≡Si-O-Fe-O-Pt. The optimized 0.3Pt2Fe@NS catalyst, featuring high skeletal Fe content, low Pt loading, and ideal synergetic effect of Pt-Fe endowed by the suitable Pt-to-Fe ratio, achieves a propylene productivity of 48.0 mmol C₃H₆·g_cat^-1·h^-1 with >95% selectivity at 550 °C for 30 h without performance degradation. The 0.3Pt2Fe@NS catalyst also exhibits complete regenerability under harsh cycling conditions, establishing a new structure-performance paradigm for the design of industrial PDH catalysts.

Key words: Propane dehydrogenation, Isolated platinum, Skeletal iron, MFI zeolite nanosheets, Bimetallic sites

Xintong Lv, Zhengchang Wei, Xin Deng, Yuchao Chai, Guangjun Wu, Landong Li. Isolated Pt sites anchored by skeletal Fe in MFI zeolite nanosheets towards productive propane dehydrogenation[J]. Chinese Journal of Catalysis, 2026, 84: 61-73.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65003-6

https://www.cjcatal.com/EN/Y2026/V84/I5/61

Figures/Tables 4

Fig. 1. Electron microscopy analyses of 0.3Pt2Fe@NS catalyst with Fe loading of 1.85 wt% and Pt loading of 0.14 wt%. (a-c) Aberration-corrected HAADF-STEM images. (d,e) High-magnification iDPC-STEM images viewed along the orientation of [010] with detailed zoomed-in areas processed high dynamic images and line scan intensity profiles of atoms as distance: Fe and Pt atoms marked by yellow dash circle and red arrows. (f) Elemental mappings for Si, O, Fe, and Pt.

Fig. 2. Characterization of as-prepared PtFe bimetallic catalysts. (a) H2-TPR profiles. (b) Pyridine-adsorbed IR spectra at 350 °C. (c) In-situ DRIFT spectra of CO adsorption on fresh (solid line) and reduced (dashed line) samples. Fe K-edge XANES (d) and EXAFS (e) spectra of 0.3Pt2Fe@NS sample under different treatment (F, R, S represent fresh, reduced, and spent sample after 30 h of PDH reaction, respectively). (f) Full-range EXAFS WT 2D plots for Fe-foil, Fe2O3, and 0.3Pt2Fe@NS catalyst.

Fig. 3. (a,b) Catalytic performance of various PtFe bimetallic catalysts. Reaction conditions: 0.1 g of catalyst, atmospheric pressure, C3H8/N2 = 1/2, WHSV = 15 h-1, 550 °C. (c) Experimental Arrhenius relationship for PDH reaction. Catalytic performance of 0.3Pt2Fe@NS under various reaction conditions (ambient pressure, 550 °C) (d) and under various WHSVs (ambient pressure, 550 °C, pure C3H8 feeding) (e). (f) Recyclability of 0.3Pt2Fe@NS. Upon the completion of a cycle, the catalyst was calcinated in a 20% O2/N2 atmosphere with linear heating to 550 °C and holding for another 3 h. (g) Comparison of the catalytic performance with reported systems in literature: Productivity of C3H6 versus deactivation rate, numbers adjacent to symbols correspond to the row numbers in Table S3.

Fig. 4. Color-mapping spectra of in-situ C3H8-DRIFT spectra in the C-H stretching vibration region and the hydroxyl region on 0.3Pt2Fe@NS (a), 0.3Pt/2Fe@NS (b), and 0.3Pt2Fe/NS (c) catalysts. MS signals of C3H8, C3H6, CH4, and H2 (m/z = 41, 29, 16, and 2) in TPSR experiments for 0.3Pt2Fe@NS (d), 0.3Pt/2Fe@NS (e), and 0.3Pt2Fe/NS (f) catalysts. Pulse reactions for propane conversion (g) and C3H8-D2 exchange reactions (h) over 0.3Pt2Fe@NS (i), 0.3Pt/2Fe@NS (ii), and 0.3Pt2Fe/NS (iii) catalysts.

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