Piperazine as a versatile organic structure-directing agent for zeolite synthesis: effect of SiO2/Al2O3 ratio on phase selectivity

  • Luyi Bai
  • Zhiping Xiong
  • Ensheng ZhanEmail author
  • Shuang LiEmail author
  • Wenjie Shen
Chemical routes to materials


The synthesis of aluminosilicate zeolites by using piperazine as the organic structure-directing agent was studied. Under optimized conditions, zeolites ZSM-4 (MAZ), mordenite (MOR), ZSM-35 (FER), ZSM-5 (MFI) and ZSM-12 (MTW) were obtained in pure phase. The effect of SiO2/Al2O3 ratio in the initial gel on zeolite phase selectivity was systematically investigated. The SiO2/Al2O3 ratio ranges for the formation of each zeolite had been established. At low SiO2/Al2O3 ratios, ZSM-4 (SiO2/Al2O3 = 9) and mordenite (SiO2/Al2O3 = 12.8) could be obtained, while ZSM-35 (14.3 ≤ SiO2/Al2O3 ≤ 29.3), ZSM-5 (SiO2/Al2O3 = 58.7) and ZSM-12 (SiO2/Al2O3 = 117.2) gradually evolved as the SiO2/Al2O3 ratio increased. Piperazine was considered to have a charge-compensatory role when the amine group was protonated; its overall effectiveness depended on the zeolite structure. Piperazine fitted best with the FER structure, and the obtained FER zeolite had a hierarchical house of card texture which was assembled by the primary plate-shaped crystals. The ZSM-4, mordenite and ZSM-35 zeolites (in acidic form) were tested for the dimethyl ether carbonylation reaction; the essential role of 12-member ring (12MR) pore in mordenite for molecule transportation to the 8MR pore was proved by comparing to ZSM-4 that lacks interconnectivity between 12MR and 8MR pores.



This work was supported by the Natural Science Foundation of China (Grant No. 21773229 and 21878244).

Compliance with ethical standards

Conflict of interest

The authors declare no conflict of interest.


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Authors and Affiliations

  1. 1.School of Chemical EngineeringNorthwest UniversityXi’anChina
  2. 2.State Key Laboratory of Catalysis, Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalianChina
  3. 3.University of Chinese Academy of SciencesBeijingChina

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