Acidity enhanced [Al]MCM-41 via ultrasonic irradiation for the Beckmann rearrangement of cyclohexanone oxime to ɛ-caprolactam

Zichun Wang, Huajuan Ling, Jeffrey Shi, Catherine Stampfl, Aibing Yu, Michael Hunger, Jun Huang*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)


Using solid acid catalysts to replace liquid acids in the liquid-phase Beckmann rearrangement of cyclohexanone oxime (CHO) into ɛ-caprolactam (CPL) is crucial for the environmentally friendly production of synthetic fibers, such as Nylon-6. In this work, we prepared aluminum-containing MCM-41 catalysts under ultrasonic irradiation with various Si/Al ratios for this purpose. Quantitative 1H MAS NMR investigations show that ultrasonic irradiation significantly promotes the formation of active Brønsted acid sites (BAS) on the [Al]MCM-41 catalysts up to 8 times higher than those prepared at the same conditions without ultrasonic irradiation, and up to 12 times higher BAS density than those reported in the literatures. The catalytic performance of [Al]MCM-41 catalysts can be strongly improved with increasing the BAS density, particularly to the ratio of BAS/(weakly acidic SiOH groups). Moreover, [Al]MCM-41 catalysts dehydrated at 393 K obtained two time higher CHO conversion and CPL yield than that dehydrated at 473 K. Hydrogen-bonded water molecules retained at low dehydration temperature may block surface SiOH groups and promote the reaction process. With higher BAS density resulting from ultrasonic irradiation, [Al]MCM-41 catalyst (Si/Al = 10) in this work obtained the highest CPL yield among all [Al]MCM-41 materials reported for liquid-phase Beckmann rearrangement up to now. Finally, the reusability of [Al]MCM-41 catalyst was tested and no significant activity loss can be observed after five reaction cycles.

Original languageEnglish
Pages (from-to)71-79
Number of pages9
JournalJournal of Catalysis
Publication statusPublished - Feb 2018
Externally publishedYes


  • MCM-41
  • Room-temperature synthesis by ultrasonic
  • irradiation
  • Solid-state NMR
  • Acid sites
  • Beckmann rearrangement


Dive into the research topics of 'Acidity enhanced [Al]MCM-41 via ultrasonic irradiation for the Beckmann rearrangement of cyclohexanone oxime to ɛ-caprolactam'. Together they form a unique fingerprint.

Cite this