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Advances in Synthesis，Modification，and Application of Cu-SSZ-39 Molecular Sieves AITranslate

Yafeng Yan1; Lina Han1; Zhanggen Huang2; Weiren Bao3; Liping Chang3; Jiancheng Wang3,4
1.College of Materials Science and Engineering，Taiyuan University of Technology，Taiyuan 030024，China
2.State Key Laboratory of Coal Conversion Institute of Coal Chemistry，Chinese Academy of Science，Taiyuan 030001，China
3.Key Laboratory of Coal Science and Technology，Ministry of Education，Taiyuan University of Technology，Taiyuan 030024，China
4.Shanxi Key Laboratory of Compound Air Pollutions Identification and Control，College of Environmental Science and Engineering，Taiyuan University of Technology，Taiyuan 030600，China
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Abstract AITranslate

Cu-SSZ-39 zeolite catalyst has become a research hotspot due to its unique AEI topology and excellent high-temperature hydrothermal stability. This article systematically explored their synthesis, modification, and catalytic applications, with a focus on summarizing the pathways for constructing Cu-SSZ-39 catalysts using different silicon-aluminum sources. The catalytic performance was enhanced through bimetallic synergistic modification and oxide composite modification, and their effectiveness in selective catalytic reduction (SCR) of nitrogen oxides (NOx) and other catalytic reactions was evaluated. Specifically, in terms of synthesis, SSZ-39 zeolite was initially synthesized using FAU-type zeolite as the primary silicon-aluminum source, resulting in highly crystalline products. Additionally, a solvent-free method was developed, utilizing ultra-stable Y zeolite (USY) zeolite and colloidal silica as silicon-aluminum sources to prepare lamellar SSZ-39 zeolite, significantly improving the acidity and hydrothermal stability of the product. Compared to traditional hydrothermal synthesis, this method offered higher SiO2 utilization and scalability. To reduce preparation costs, synthesis routes using ZSM-5 and Beta zeolites as precursors were explored. The transformation mechanism involved the aggregation of single four-membered and six-membered rings from ZSM-5/Beta zeolites into AEI framework and the resulting SSZ-39 zeolite exhibited comparable crystallinity and catalytic activity to FAU-derived products. Furthermore, silica sol was directly used as the silicon source in alkaline media with N, N-diethyl-2, 6-dimethylpiperidinium (DEDMP) as the template, although this method suffered from low yield and limited Si/Al ratio control. Cu-SSZ-39 catalysts could be prepared through ion exchange and one-pot methods. In the ion exchange process, copper ions (Cu2+) were introduced into SSZ-39 framework by replacing Na+ or H+. The one-pot method combined FAU zeolite with copper-tetraethylenepentamine (Cu-TEPA) complexes, enabling simultaneous zeolite crystallization and copper incorporation. This approach simplified the synthesis process and produces catalysts with higher copper dispersion and SCR activity. In terms of modification strategies for Cu-SSZ-39 catalysts, approaches included bimetallic synergistic modification and metal oxide composite modification. Ce, Mn, and Y were introduced via ion exchange to enhance catalytic performance. Ce-Cu-SSZ-39 catalyst exhibited excellent low-temperature SCR activity (90% NOx conversion at 180℃), attributed to the addition of Ce, which inhibited the aggregation of copper oxides and induced more Cu2+ into ion exchange sites. Yttrium modification (Y-Cu-SSZ-39)suppressed dealumination and stabilized Cu2+ active sites, maintaining 75% NOx conversion even after hydrothermal aging at 900℃. Metal oxide composites, such as Ce-MnOx and CeZrOx, were combined with Cu-SSZ-39 to broaden the active temperature window. Ce-MnOx/Cu-SSZ-39 achieved 90% NOx conversion within the range of 180~600℃, remaining stable even after aging at 850℃, owing to the Ce-Mn synergistic effect and structural stability. CeZrOx/Cu-SSZ-39 extended the operating window to 190~550℃ and retained 80% NH3-SCR activity after hydrothermal aging at 750℃. In terms of the application of Cu-SSZ-39 catalysts, the focus was on their progress in ammonia selective catalytic reduction (NH3-SCR) for NOx removal. Cu-SSZ-39 catalysts achieved ≥90% NOx conversion within the temperature range of 250~500℃. After hydrothermal aging (750~900℃), the catalysts maintained ≥90% activity in the range of 250~450℃. Copper loading and its location significantly influenced the catalytic activity, with Cu2+ located in double six-membered rings (D6R) identified as the active sites. Excessive copper loading (>4%) led to the aggregation of CuOx and a decline in activity. After high-temperature hydrothermal aging, Cu2+ near the double six-membered rings could transform into CuxOy, promoting the formation of key nitrate intermediates during NH3-SCR reaction, thereby maintaining high low-temperature catalytic activity. Despite the progress made, challenges remained in reducing template costs, controlling silicon-to-aluminum ratios, and ensuring long-term stability. Future research should focus on multi-metal co-modification, catalytic mechanism studies, and expansion into photocatalysis and biomass conversion. Cu-SSZ-39 catalysts held significant potential in environmental catalysis and green chemistry, with their tunable properties and robust performance under demanding conditions laying the foundation for broad applications. Additionally, this study provided valuable insights for further exploration and development of small-pore zeolites in the field of catalysis.

KeyWords AITranslate

Cu-SSZ-39 catalyst bimetallic synergistic modification composite catalyst ammonia selective catalytic reduction （NH3-SCR） high-temperature hydrothermal stability

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY25030001

Chinese Library Classification Number:O613.72

Citation Information:

Cu-SSZ-39 zeolite catalyst has become a research hotspot due to its unique AEI topology and excellent high-temperature hydrothermal stability. This article systematically explored their synthesis, modification, and catalytic applications, with a focus on summarizing the pathways for constructing Cu-SSZ-39 catalysts using different silicon-aluminum sources. The catalytic performance was enhanced through bimetallic synergistic modification and oxide composite modification, and their effectiveness in selective catalytic reduction (SCR) of nitrogen oxides (NOx) and other catalytic reactions was evaluated. Specifically, in terms of synthesis, SSZ-39 zeolite was initially synthesized using FAU-type zeolite as the primary silicon-aluminum source, resulting in highly crystalline products. Additionally, a solvent-free method was developed, utilizing ultra-stable Y zeolite (USY) zeolite and colloidal silica as silicon-aluminum sources to prepare lamellar SSZ-39 zeolite, significantly improving the acidity and hydrothermal stability of the product. Compared to traditional hydrothermal synthesis, this method offered higher SiO2 utilization and scalability. To reduce preparation costs, synthesis routes using ZSM-5 and Beta zeolites as precursors were explored. The transformation mechanism involved the aggregation of single four-membered and six-membered rings from ZSM-5/Beta zeolites into AEI framework and the resulting SSZ-39 zeolite exhibited comparable crystallinity and catalytic activity to FAU-derived products. Furthermore, silica sol was directly used as the silicon source in alkaline media with N, N-diethyl-2, 6-dimethylpiperidinium (DEDMP) as the template, although this method suffered from low yield and limited Si/Al ratio control. Cu-SSZ-39 catalysts could be prepared through ion exchange and one-pot methods. In the ion exchange process, copper ions (Cu2+) were introduced into SSZ-39 framework by replacing Na+ or H+. The one-pot method combined FAU zeolite with copper-tetraethylenepentamine (Cu-TEPA) complexes, enabling simultaneous zeolite crystallization and copper incorporation. This approach simplified the synthesis process and produces catalysts with higher copper dispersion and SCR activity. In terms of modification strategies for Cu-SSZ-39 catalysts, approaches included bimetallic synergistic modification and metal oxide composite modification. Ce, Mn, and Y were introduced via ion exchange to enhance catalytic performance. Ce-Cu-SSZ-39 catalyst exhibited excellent low-temperature SCR activity (90% NOx conversion at 180℃), attributed to the addition of Ce, which inhibited the aggregation of copper oxides and induced more Cu2+ into ion exchange sites. Yttrium modification (Y-Cu-SSZ-39)suppressed dealumination and stabilized Cu2+ active sites, maintaining 75% NOx conversion even after hydrothermal aging at 900℃. Metal oxide composites, such as Ce-MnOx and CeZrOx, were combined with Cu-SSZ-39 to broaden the active temperature window. Ce-MnOx/Cu-SSZ-39 achieved 90% NOx conversion within the range of 180~600℃, remaining stable even after aging at 850℃, owing to the Ce-Mn synergistic effect and structural stability. CeZrOx/Cu-SSZ-39 extended the operating window to 190~550℃ and retained 80% NH3-SCR activity after hydrothermal aging at 750℃. In terms of the application of Cu-SSZ-39 catalysts, the focus was on their progress in ammonia selective catalytic reduction (NH3-SCR) for NOx removal. Cu-SSZ-39 catalysts achieved ≥90% NOx conversion within the temperature range of 250~500℃. After hydrothermal aging (750~900℃), the catalysts maintained ≥90% activity in the range of 250~450℃. Copper loading and its location significantly influenced the catalytic activity, with Cu2+ located in double six-membered rings (D6R) identified as the active sites. Excessive copper loading (>4%) led to the aggregation of CuOx and a decline in activity. After high-temperature hydrothermal aging, Cu2+ near the double six-membered rings could transform into CuxOy, promoting the formation of key nitrate intermediates during NH3-SCR reaction, thereby maintaining high low-temperature catalytic activity. Despite the progress made, challenges remained in reducing template costs, controlling silicon-to-aluminum ratios, and ensuring long-term stability. Future research should focus on multi-metal co-modification, catalytic mechanism studies, and expansion into photocatalysis and biomass conversion. Cu-SSZ-39 catalysts held significant potential in environmental catalysis and green chemistry, with their tunable properties and robust performance under demanding conditions laying the foundation for broad applications. Additionally, this study provided valuable insights for further exploration and development of small-pore zeolites in the field of catalysis.

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GB/T 7714-2015 [1] Yafeng Yan, Lina Han, Zhanggen Huang, et al. Advances in Synthesis，Modification，and Application of Cu-SSZ-39 Molecular Sieves[J]. Chinese Journal of Rare Metals, 2025, 49(12): 1871-1884. DOI:10.13373/j.cnki.cjrm.XY25030001.
MLA [1] Yafeng Yan, et al., "Advances in Synthesis，Modification，and Application of Cu-SSZ-39 Molecular Sieves." Chinese Journal of Rare Metals, vol. 49, no. 12, 2025, pp. 1871-1884, https://doi.org/10.13373/j.cnki.cjrm.XY25030001.
APA [1] Yafeng Yan, Lina Han, Zhanggen Huang, Weiren Bao, Liping Chang, & Jiancheng Wang. (2025). Advances in Synthesis，Modification，and Application of Cu-SSZ-39 Molecular Sieves. Chinese Journal of Rare Metals, 49(12), 1871-1884. https://doi.org/10.13373/j.cnki.cjrm.XY25030001
IEEE [1] Yafeng Yan, Lina Han, Zhanggen Huang, Weiren Bao, Liping Chang, and Jiancheng Wang, "Advances in Synthesis，Modification，and Application of Cu-SSZ-39 Molecular Sieves," Chinese Journal of Rare Metals, vol. 49, no. 12, pp. 1871-1884, 2025, doi: 10.13373/j.cnki.cjrm.XY25030001. keywords: {Cu-SSZ-39 catalyst;bimetallic synergistic modification;composite catalyst;ammonia selective catalytic reduction （NH-SCR）;high-temperature hydrothermal stability}