Unsaturated cobalt single-atoms stabilized by silanol nests of zeolites for efficient propane dehydrogenation

doi:10.1016/S1872-2067(25)64660-2

Abstract

Abstract:

Propane dehydrogenation (PDH) has emerged as a key on-purpose technology for the production of propylene, but it often depends on toxic chromium and expensive platinum catalysts, highlighting the need for environmentally friendly and cost-effective alternatives. In this study, we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co₁O₃H_x structure by regulating silanol nests in purely siliceous Beta zeolites. Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity. Additionally, the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles. Notably, the optimized Co_0.3%/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_C3H6 g_cat^-1 h^-1, with an exceptional propylene selectivity of 99.1% at 550 °C. Moreover, the Co_0.3%/deAl-meso-Beta catalyst demonstrated excellent stability, with negligible deactivation after 5 consecutive regeneration cycles. This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites, providing valuable insights for the design of high-activity, high-stability, and low-cost PDH catalysts.

Key words: Propane dehydrogenation, Unsaturated cobalt, Single-atoms, Silanol nest, Zeolite

Liwen Guo, Dao Shi, Tianjun Zhang, Yanhang Ma, Guodong Qi, Jun Xu, Qiming Sun. Unsaturated cobalt single-atoms stabilized by silanol nests of zeolites for efficient propane dehydrogenation[J]. Chinese Journal of Catalysis, 2025, 72: 323-333.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64660-2

https://www.cjcatal.com/EN/Y2025/V72/I5/323

Figures/Tables 4

Fig. 1. (a) Schematic illustration of creating silanol nests by dealumination and single-sites Co trapped by silanol nests. (b) FT-IR spectra of pyridine adsorption on meso-Beta and deAl-meso-Beta. ATR-IR spectra (c) and FT-IR spectra (d) of hydroxyl group on the meso-Beta and deAl-meso-Beta. STEM image (e), aberration-corrected HAADF-STEM image (f) and EDX elemental mapping images (g) of Co0.3%/deAl-meso-Beta.

Fig. 2. Catalytic performance of Co0.3%/deAl-meso-Beta, Co0.3%/deAl-con-Beta, and Co0.3%/Si-Beta catalysts in propane dehydrogenation. Conversion of propane (a) and selectivity of propylene (b) over various catalysts. Reaction conditions: 0.33 g of catalyst, C3H8: N2 = 12.5: 37.5 mL min-1, WHSV = 4.5 h-1, 550 °C. Propane conversion and propylene selectivity over Co0.3%/deAl-meso-Beta at various temperature (525-600 °C) under 4.5 h-1 (c) and at 550 °C under various WHSVs (1.5-9.0 h-1) (d). (e) Arrhenius plots of various reaction temperatures of Co0.3%/deAl-meso-Beta and Co0.3%/deAl-con-Beta. (f) The comparison of the net propylene formation rate over Co0.3%/deAl-meso-Beta and previously reported state-of-the-art Co-based catalysts (see Table S4 for details). (g) Regeneration test of Co0.3%/deAl-meso-Beta. Regeneration condition: calcination in air at 600 °C for 1 h.

Fig. 3. (a) FT-IR spectra of hydroxyl group on the deAl-meso-Beta and Co0.3%/deAl-meso-Beta (I3500 and I3740 is the signal intensity at 3500 and 3740 cm-1). XANES spectra (b) and the Fourier transforms of k2-weighted Co K-edge EXAFS experimental data and fitting curves (dashed line) (c) for Co0.3%/deAl-meso-Beta, Co0.3%/Si-Beta and standards. (d) CO-TPSR curves of Co0.3%/deAl-meso-Beta.

Fig. 4. ATR-IR spectra (a) and FT-IR spectra (b) of deAl-meso-Beta before and after recrystallization. (c) Catalytic performance of recrystallization catalysts. 1H MAS NMR (d) and 1H-29Si CP MAS NMR (e) spectra of deAl-meso-Beta and Cox%/deAl-meso-Beta (x = 0.1-0.3). (f) Propane conversion of various Cox%/deAl-meso-Beta.

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