Demetallation and reduction induced ultra-dispersed PtZn alloy confined in zeolite for propane dehydrogenation

doi:10.1016/S1872-2067(23)64548-6

Abstract

Abstract:

abstract: Developing efficient bimetallic Pt-based catalyst is highly desired for propane dehydrogenation (PDH) process. Typical co-impregnation method often results in inhomogeneous distributions of metal species on supports. Herein, we reported a facile method to support PtZn bimetal alloy nanoparticles onto Beta zeolite, mainly existing as highly dispersed Pt₁Zn₁ alloy species. Zn@Beta was first synthesized by hydrothermal method with the aid of ethylenediamine (EDA), leading to the introduction of Zn atoms into zeolite lattice. An impregnation process was subsequently employed to support Pt species. During this process, skeleton Zn atoms migrated out of the framework and were then reduced together with Pt in flowing H₂, leading to the formation of PtZn alloy with mainly Pt₁Zn₁ structures. Cs-corrected high-angle annular dark-field scanning transmission election microscope and X-ray absorption fine structure analyses revealed that this method was more conducive to the formation of PtZn alloy compared with the co-impregnation method. The obtained catalyst of 0.3Pt1Zn@Beta exhibited initial propane conversion of 36.8% and propylene selectivity of 99.3% combined with low deactivation rate (0.004 h^-1) over 24 h with propane WHSV of 4.7 h^-1 at 550 °C. The catalyst also exhibited good PDH performance in a long-term reaction (180 h) and robustness during regeneration reactions by simply flushing hydrogen.

Key words: Demetallation-reduction strategy, PtZn alloy, Beta zeolite, Propane dehydrogenation

Longkang Zhang, Yue Ma, Changcheng Liu, Zhipeng Wan, Chengwei Zhai, Xin Wang, Hao Xu, Yejun Guan, Peng Wu. Demetallation and reduction induced ultra-dispersed PtZn alloy confined in zeolite for propane dehydrogenation[J]. Chinese Journal of Catalysis, 2023, 55: 241-252.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64548-6

https://www.cjcatal.com/EN/Y2023/V55/I12/241

Figures/Tables 8

Scheme 1. Schematic illustration of the preparation process of PtZn@Beta catalyst.

Fig. 1. SEM (a) and HRTEM (b) images of 1Zn@Beta. (c) XRD patterns of Beta, 0.3Pt/Beta, 0.3Pt1Zn/Beta and 0.3Pt1Zn@Beta samples after reduction. HRTEM images and corresponding metal particles size distributions of 0.3Pt/Beta (d), 0.3Pt1Zn/Beta (e) and 0.3Pt1Zn@Beta (f) after reduction.

Fig. 2. (a,b) Cs-corrected HAADF-STEM image and corresponding line intensity profile of Pt1Zn1 alloy nanoparticle in 0.3Pt1Zn@Beta. Cs-corrected HAADF-STEM image of Pt1Zn1.7 alloy (c) and metallic Pt nanoparticle (d) in 0.3Pt1Zn@Beta. (e,f) Cs-corrected HAADF-STEM image and corresponding line intensity profile of Pt1Zn1 alloy nanoparticle in 0.3Pt1Zn/Beta. (g,h) Cs-corrected HAADF-STEM images of Pt nanoparticles and clusters in 0.3Pt1Zn/Beta. The scale bar is 1 nm. Pt is shown in red while Zn in blue.

Fig. 3. XPS and XAS results of the catalysts after reduction. (a) XPS spectra of Pt 4f of 0.3Pt/Beta, 0.3Pt1Zn/Beta and 0.3Pt1Zn@Beta. (b) XPS spectra of Zn 2p of 1Zn@Beta, 0.3Pt1Zn/Beta and 0.3Pt1Zn@Beta. (c) XANES spectra of 0.3Pt1Zn@Beta, 0.3Pt1Zn/Beta and Pt foil. (d) EXAFS at the Pt L3 edge and corresponding first scattering shell fitting results of 0.3Pt1Zn@Beta and 0.3Pt1Zn/Beta.

Fig. 4. (a) UV-vis spectra of 1Zn@Beta and 1Zn@Beta-HCl. XPS spectra of Zn 2p (b) and hydroxyl stretching region FTIR spectra (c) of 1Zn@Beta, 1Zn@Beta-HCl and 0.3Pt1Zn@Beta before reduction.

Fig. 5. (a) UV-vis spectra of 0.3Pt/Beta 0.3Pt1Zn/Beta and 0.3Pt1Zn@Beta. (b) XPS spectra of Pt 4f in 0.3Pt/Beta, 0.3Pt1Zn/Beta and 0.3Pt1Zn@Beta. (c) H2-TPR of 0.3Pt1Zn/Beta, 0.3Pt1Zn@Beta, 0.3Pt/Beta and 1Zn@Beta. All the samples were measured before reduction.

Fig. 6. (a) Initial C3H8 formation rate over 0.3PtxZn@Beta catalyst with different Zn contents. (b) Propane conversion and propylene selectivity over 0.3PtxZn@Beta with different Zn contents. (c) The deactivation rate constant kd (h?1) of 0.3PtxZn@Beta with different Zn contents. (d) Initial C3H8 formation rate and deactivation rate constant kd (h?1) of 1Zn@Beta, 0.3Pt1Zn@Beta, 0.3Pt1Zn/Beta and 0.3Pt1Zn/SiO2 in PDH reaction. The data of initial C3H6 formation rate in Fig. 6(a) and 6(d) were collected under kinetic regime. Reaction conditions: 550 °C, 20% of C3H8 balanced N2 with a total flow rate of 100 mL/min, propane conversions were maintained at 5%?10% by adjusting the catalyst dosage. The deactivation rate constant data in Fig.6(c) were collected from a continuous reaction of 24 h (Fig. 6(b)). Reactions conditions: 550 °C, WHSV(C3H8) = 4.7 h?1, P = 1 bar, 20% of C3H8 balanced N2 with a total flow rate of 20 mL/min.

Fig. 7. (a) Propane conversion and propylene selectivity over 0.3Pt1Zn@Beta under various WHSVs. Reaction conditions: 550 °C, 1 bar, 20% of C3H8 balanced with N2. (b) Propane conversion and propylene selectivity over 0.3Pt1Zn@Beta with the reaction temperature ranging from 520 to 600 °C. Reaction conditions: WHSV(C3H8) = 4.7 h?1, 1 bar, 20% of C3H8 balanced N2 with a total flow rate of 20 mL/min. (c) Propane conversion, propylene selectivity and C3H6 formation rate over 0.3Pt1Zn@Beta with time on stream. Reaction conditions: 550 °C, 1 bar, WHSV(C3H8) = 4.7 h?1, C3H8: H2 = 2: 1, with balance N2 for total flow rate of 20 mL/min. (d) Propane conversion and propylene selectivity over 0.3Pt1Zn@Beta catalyst for seven regeneration cycles. Reaction conditions: 550 °C, 1 bar, WHSV(C3H8) = 4.7 h?1, 20% of C3H8 balanced N2 with a total flow rate of 20 mL/min. Regeneration process: the atmosphere was switched to N2 (10 mL/min) for 10 min and then directly reduced at H2 atmosphere (20 mL/min) for 2 h at 550 °C.

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