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

Research output: Contribution to journalArticle

  • Stephanie Chapman
  • Alexander J. O'malley
  • Ivana Miletto
  • Marina Carravetta
  • Professor Paul Cox
  • Enrica Gianotti
  • Leonardo Marchese
  • Stewart F. Parker
  • Robert Raja
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
Issue number42
Early online date2 Jul 2019
Publication statusPublished - 25 Jul 2019


  • Probing Substrate–Framework Interactions

    Rights statement: This is the peer reviewed version of the following article: Stephanie Chapman Dr. Alexander J. O'Malley Dr. Ivana Miletto Dr. Marina Carravetta Dr. Paul Cox Prof. Enrica Gianotti Leonardo Marchese Dr. Stewart F. Parker Prof. Robert Raja, 'Integrated Theoretical and Empirical Studies for Probing Substrate–Framework Interactions in Hierarchical Catalysts'. Chemistry: A European Journal, 25(42), pp.9938-9947., which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

    Accepted author manuscript (Post-print), 1.38 MB, PDF document

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