English

Rational Design of a Core-Shell Rh@Zeolite Catalyst for Selective Diene Hydrogenation

• Zhang Jian ^1, ,
• Wang Liang ^{2, ,} ,
• Wu Zhiyi ^1, ,
• Wang Chengtao ^3, ,
• Su Zerui ^1, ,
• Xiao Feng-Shou ^1,2,3,

• 1.

  Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China

• 2.

  Key Lab of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China

• 3.

  Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310028, P. R. China

Corresponding author: Wang Liang, liangwang@zju.edu.cn

• Received Date: 02 December 2019
  Accepted Date: 06 January 2020
  Revised Date: 31 December 2019
  Available Online: 15 September 2020
• Fund Project:

  The project was supported by the National Key Research and Development Program of China (2018YFB0604801), the National Natural Science Foundation of China (21822203, 91645105, 91634201), the Natural Science Foundation of Zhejiang Province, China (LR18B030002), the Beijing Advanced Innovation Center for Soft Matter Science, Engineering of the Beijing University of Chemical Technology, China (21530009067), and the Fundamental Research Funds for the Central Universities, China (2019XZZX004-02)

Abstract: Selective hydrogenation of dienes and alkynes to monoenes is an important topic of research in the fields of pharmacology and organic synthesis. Catalyst design plays a key role in this process, where a general principle involves controlling the steric diene adsorption by modifying the surface of the metal nanoparticles. For example, upon introducing Bi species into Rh nanoparticles, the resulting RhBi/SiO₂ showed 90% selectivity to 2-hexene, with 95% conversion of 1, 4-hexadiene under ambient conditions, because of the suppressed adsorption of the internal C＝C bond. However, the catalyst activity decreased remarkably; that is, the activity of the unmodified Rh/SiO₂ was about 27 times higher than that of RhBi/SiO₂. Controlled steric adsorption of the diene molecules could also be achieved by the constructing porous channels around the metal nanoparticles. For example, metal-organic framework (ZIF-8) or mesoporous silica (MCM-41) encapsulated noble metals showed high selectivity for the hydrogenation of terminal C＝C bonds. However, these catalysts had poor durability under the thermal/hydrothermal reaction/regeneration conditions. In contrast, zeolites have superior durability under harsh reaction conditions, but they are rarely used in semi-hydrogenation reactions. We recently found that metal nanoparticles fixed within zeolite crystals (e.g., ZSM-5 and Beta) efficiently catalyze the selective hydrogenation of molecules bearing multiple reducible groups. Thus inspired, we developed a catalyst by fixing Rh nanoparticles within zeolite crystals via an inter-zeolite transformation method. The Rh@CHA catalyst was synthesized by introducing Rh species into the parent Y zeolite (Rh@Y) and transformation of the Y zeolite to chabazite (CHA zeolite) under hydrothermal conditions. X-ray diffraction patterns, N₂ sorption isotherms, scanning/transmission electron microscopy images, and model reactions (hydrogenation of probe molecules) confirmed the successful fixation of the Rh nanoparticles inside the CHA zeolite crystals. As expected, the Rh@CHA catalyst was highly selective for the hydrogenation of dienes. For example, Rh@CHA showed a 2-hexene selectivity of 86.7%, with 91.2% conversion of 1, 4-hexadiene. In contrast, the generally supported Rh nanoparticle catalyst (Rh/CHA) showed a low 2-hexene selectivity of 37.2% under identical reaction conditions. Considering that Rh@CHA and Rh/CHA comprise the same CHA zeolite crystals and have similar Rh nanoparticle sizes, the remarkably high selectivity of Rh@CHA is assigned to the steric adsorption of dienes on the Rh surface controlled by the micropores of the CHA zeolite. This work demonstrates that a zeolite-fixed metal core-shell structure is a powerful tool for developing efficient catalysts to be used in diene hydrogenation.

Key words:
• Heterogeneous catalysis
•  /  Diene hydrogenation
•  /  Rh nanoparticle
•  /  CHA zeolite
•  /  Core-shell structure
•  /  Inter-zeolite transformation

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