Integrated theoretical and empirical studies for probing substrate–framework interactions in hierarchical catalysts

Stephanie Chapman, Alexander J. O'malley, Ivana Miletto, Marina Carravetta, Paul Cox, Enrica Gianotti, Leonardo Marchese, Stewart F. Parker, Robert Raja

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Abstract

Soft templating with siliceous surfactant is an established protocol for the synthesis of hierarchically porous silicoaluminophosphates (HP SAPOs) with improved mass transport properties. Motivated by the enhanced performance of HP SAPOs in the Beckmann rearrangement of cyclohexanone oxime to the nylon 6 precursor ϵ‐caprolactam, an integrated theoretical and empirical study was carried out to investigate the catalytic potential of the siliceous mesopore network. Inelastic neutron scattering (INS) studies, in particular, provided unique insight into the substrate‐framework interactions in HP (Si)AlPOs and allowed reactive species to be studied independent of the catalyst matrix. The spectroscopic (INS, FTIR spectroscopy, MAS NMR spectroscopy) and computational analyses revealed that in the organosilane‐templated SAPO, the interconnectivity of micro‐ and mesopores permits cooperativity between their respective silanol and Brønsted acid sites that facilitates the protonation of cyclohexanone oxime in a physical mixture at ambient temperature.
Original languageEnglish
Pages (from-to)9938-9947
JournalChemistry
Volume25
Issue number42
Early online date2 Jul 2019
DOIs
Publication statusPublished - 25 Jul 2019

Keywords

  • RCUK
  • EPSRC
  • EP/K014706/1
  • EP/K014668/1
  • EP/K014854/1
  • EP/K014714/1
  • EP/M013219/1
  • STFC

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