Platinum clusters stabilized by zincosilicate zeolite for efficient propane dehydrogenation

doi:10.1016/S1872-2067(24)60258-5

Chinese Journal of Catalysis ›› 2025, Vol. 71: 208-219.DOI: 10.1016/S1872-2067(24)60258-5

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Platinum clusters stabilized by zincosilicate zeolite for efficient propane dehydrogenation

Hao Liu^a^,^b^,¹, Ying Zhang^a^,¹, Liyang Liu^a^,¹, Tianxiang Chen^d^,^*(), Xingcong Zhang^a, Peng Hu^a, Chao Xiong^a, Jie Zhou^a, Hao Zhang^a, Lihui Dong^b, Tsz Woon Benedict Lo^d, Bing Nan^c^,^*(), Xiaohui He^a^,^f^,^*(), Hongbing Ji^a^,^e^,^*()

^aKey Laboratory of Bioinorganicand Synthetic Chemistry of Ministry of Education, Fine Chemical Industry Research Institute, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou 510275, Guangdong, China
^bGuangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^cShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Shanghai 200120, China
^dState Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hunghom, Hong Kong, China
^eState Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Institute of Green Petroleum Processing and Light Hydrocarbon Conversion, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^fGuangdong Technology Research Center for Synthesis and Separation of Thermosensitive Chemicals, Guangzhou 510006, Guangdong, China

Received:2024-10-29 Accepted:2025-01-25 Online:2025-04-18 Published:2025-04-13
Contact: * E-mail: jihb@mail.sysu.edu.cn (H. Ji), hexiaohui@mail.sysu.edu.cn (X. He),nanb@sari.ac.cn (B. Nan), Selwin-tianxiang.chen@connect.polyu.hk (T. Chen).
About author:
¹Contributed equally to this work.
Supported by:
National Key Research and Development Program Nanotechnology Specific Project(2020YFA0210902);Guangdong Natural Science Funds for Distinguished Young Scholar(2022B1515020035);National Natural Science Foundation of China(22422815);National Natural Science Foundation of China(22078371);National Natural Science Foundation of China(U22A20428);National Natural Science Foundation of China(21938001);special fund for Science and Technology Innovation Teams of Shanxi Province(202304051001007);The authors thank the Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, and the Chemistry and Chemical Engineering Guangdong Laboratory(1922010)

Abstract

Abstract:

Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods, which exhibit unique properties such as suppressing structure-sensitive side reactions. However, this method is limited by the use of different metal precursor salts corresponding to different ligands. An alternative approach, the ion exchange (IE) method, can overcome this limitation to some extent. Nevertheless, there is still an urgent need to address the stabilization of metals (especially precious metals) by using IE method. Here, we reported a Pt cluster catalyst prepared mainly by anchoring Pt atoms via O located near the framework Zn in zincosilicate zeolites and riveted by zeolite surface rings after reduction (reduced Pt/Zn-3-IE). The catalyst can achieve an initial propane conversion of 26% in a pure propane atmosphere at 550 °C and shows little deactivation even after 7.5 d of operation. Moreover, the alteration of catalyst by the introduction of framework Zn was also highlighted and interpreted.

Key words: Zincosilicate zeolite, Acid-site identification, Rivet effect, Pt clusters, Propane dehydrogenation

Hao Liu, Ying Zhang, Liyang Liu, Tianxiang Chen, Xingcong Zhang, Peng Hu, Chao Xiong, Jie Zhou, Hao Zhang, Lihui Dong, Tsz Woon Benedict Lo, Bing Nan, Xiaohui He, Hongbing Ji. Platinum clusters stabilized by zincosilicate zeolite for efficient propane dehydrogenation[J]. Chinese Journal of Catalysis, 2025, 71: 208-219.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60258-5

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Figures/Tables 6

Fig. 1. (a) Schematic representation of the synthesis of a Zn-based zeolite and Pt loading (taking Pt/Zn-3-IE as an example). Characterization of the Pt/Zn-3-IE sample (after H2 reduction-550 °C): (b-e) AC-HAADF-STEM imaging at high magnification; (f) elemental mappings of (e) for Pt and Zn; (g) intensity profile along the line of (e) after moderate smoothing.

Fig. 2. (a,b) Pt LIII-edge XANES and EXAFS spectra of Pt/Zn-3-IE-H2 and Pt/Zn-3-IWI-H2. (c,d) Zn K-edge XANES and EXAFS spectra of Zn-3-H2, Pt/Zn-3-IE-H2 and Pt/Zn-3-IWI-H2. (e,f) Wavelet transform (WT) plots of Pt/Zn-3-IE-H2 and Pt/Zn-3-IWI-H2.

Fig. 3. (a-c) In situ XPS spectra of Pt 4f and Zn 2p of the Pt/Zn-3-IWI and the Pt/Zn-3-IE under 20 vol% H2/Ar at 550 °C for 1 h reduction. (d) In situ CO-DRIFTS of various samples (H2 reduction temperature-550 °C).

Fig. 4. Characterizations of synthesized catalysts. (a) FT-IR spectra. (b) UV-vis spectra. (c) DRIFTS spectra of -OH groups. (d) 1H MAS NMR spectra. (e) FT-IR spectra of Zn-3 and Pt/Zn-3-IE after CD3CN adsorption and desorption at different temperatures. (f) Attribution of CD3CN adsorption peaks and changes after Pt loading. (g) FT-IR spectra of Zn-3 and Pt/Zn-3-IE after pyridine adsorption and desorption at different temperatures. Numbers of acid sites (h) and NH3-TPD curves (i).

Fig. 5. (a) Propane conversion and propylene selectivity over various catalysts. Reaction condition: C3H8/N2 = 25/75, WHSV = 6 h-1, 600 °C (reaction temperature). (b) Propane conversion and propylene selectivity over various catalysts. Reaction condition: C3H8/N2 = 25/75, WHSV = 6 or 60 h-1, 550/600 °C (reduction temperature) -550/600 °C (reaction temperature). (c) PDH performance of Pt/Zn-3-IE under various WHSV conditions at 550 °C. (d) PDH performance of Pt/Zn-3-IE at different temperatures and reaction atmospheres, pure C3H8, WHSV = 17 h-1 (unless otherwise specified). (e) Propane conversion and propylene selectivity over Pt/Zn-3-IE after several regeneration cycles; upon completion of a cycle, the catalyst was calcinated in the air with linear heating to 350 °C for 1 h and holding for 4 h. (f) Productivity of C3H6 versus deactivation rate for the catalysts in this study compared with those reported in the literature (see Table S6, the catalysts included here are only the best-performing ones from the articles considered).

Fig. 6. AC-HAADF-STEM imaging of the Pt distribution in spent Pt/Zn-3-IE and elemental mapping for Si, O, Na, Zn, and Pt. Reaction conditions: (a1,a2) pure C3H8, WHSV = 17 h-1, 550 °C, 7.5 d; (b1,b2) after several regeneration cycles).

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Platinum clusters stabilized by zincosilicate zeolite for efficient propane dehydrogenation

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