English

Acid Properties of SAPO-34 Molecular Sieves with Different Si Contents Templated by Various Organic Structure-Directing Agents

• Lei Wang ^{1, 2, †,} ,
• Tantan Sun ^{1, 3, †,} ,
• Nana Yan ^{1, 3,} ,
• Xiaona Liu ^{1, 3,} ,
• Chao Ma ^{1, 3, 4,} ,
• Shutao Xu ^1, ,
• Peng Guo ^{1, ,} ,
• Peng Tian ^1, ,
• Zhongmin Liu ^{1, ,}

• 1.

  National Engineering Laboratory for Methanol to Olefins, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

• 2.

  College of Chemistry, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, China

• 3.

  University of Chinese Academy of Sciences, Beijing 100049, China

• 4.

  Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian 116024, Liaoning Province, China

• ^†These authors contributed equally to this work.

Corresponding author: Peng Guo, pguo@dicp.ac.cn Zhongmin Liu, zml@dicp.ac.cn

• Received Date: 19 March 2020
  Accepted Date: 18 May 2020
  Revised Date: 17 May 2020
  Available Online: 15 April 2022
• Fund Project:

Abstract: The acid properties of SAPO-34 molecular sieves (MSs), including the strength and density of Brönsted acids, have attracted enormous attention in past decades because of the excellent performance of SAPO-34 in industrial processes such as the methanol-to-olefins (MTO) process and the selective catalytic reduction of NO_x with NH₃ (NH₃-SCR). Currently, pure-phase SAPO-34 MSs with different Si contents can be easily obtained by utilizing multifarious organic structure-directing agents (OSDAs). However, the resulting SAPO-34 MSs have different acid properties, which may affect their catalytic performance. Hence, correlating the acid properties with the OSDAs and Si contents is of significance to synthesize SAPO-34 MSs with the desired properties. Herein, the acid properties of four series of SAPO-34 MSs with varying Si contents synthesized using tetraethylammonium hydroxide (TEAOH), diisopropylamine (DIPA), n-butylamine (nBA), and morpholine (MOR) as the OSDAs were probed in detail by thermogravimetry (TG), Rietveld refinement, and solid-state nuclear magnetic resonance (ss-NMR) analyses. The strength and acid density were systematically investigated by exploring the host-guest interactions between the probed molecule CD₃CN and the framework using ¹H magic angle spinning (MAS) NMR spectroscopy, and the local environments of Si were studied by ²⁹Si MAS NMR spectroscopy. The results of TG and Rietveld refinement showed that the SAPO-34 MSs templated by TEAOH and DIPA have only one OSDA per cha (one of the composite building units) cage in the longitudinal configuration, while those templated by nBA and MOR possess two OSDAs occluded in the cha cage in an up-and-down arrangement. Interestingly, the acid strength of SAPO-34 templated by TEAOH increased with increasing Si content, while the acid density remained almost unchanged. In contrast, the acid density of SAPO-34 templated by DIPA decreased evidently with an increase in the Si content, while the acid strength showed only a small variation. Among the other two samples, SAPO-34 templated by MOR has the most amounts of acid densities compared to SAPO-34 templated by nBA, while the strength is not superior. Thus, we conclude that the acid density is associated with the number of OSDAs in each cha cage and their protonation ability, while the difference in acid strength is attributed to the number of Si atoms at the edges of the Si islands. The findings of this study will provide insight into the acid properties of related crystalline porous materials.

Key words:
• SAPO-34
•  /  OSDA
•  /  Acid property
•  /  ss-NMR
•  /  Rietveld refinement
•  /  Si distribution
•  /  Porous materials

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