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

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

Research output: Contribution to journalArticle

Abstract

Soft-templating with siliceous surfactant is an established protocol for the synthesis of hierarchically-porous silicoaluminophosphates (HP SAPOs) with improvedmass transport properties.Motivated by the enhanced performance of HP SAPOs in the Beckmann rearrangementof cyclohexanone oxime to the nylon-6 precursor, ε-caprolactam, we have undertakenan integrated theoretical and empirical studyto investigate thecatalytic potential of thesiliceous mesopore network.Neutron scattering studies, in particular, have provided unique insight into the substrate-framework interactions in HP (Si)AlPOs, allowing reactive species to be studied independent of the catalyst matrix.The spectroscopic (INS, FTIR, MAS NMR) and computational analyses reveal that inthe organosilane-templated SAPO, the interconnectivity of micro-and meso-pores permits a cooperativity between their respective silanol and Brønsted acid sitesthat facilitates the protonation of cyclohexanone oxime in a physical mixture, at ambient temperature.
Original languageEnglish
Pages (from-to)9938-9947
Number of pages10
JournalChemistry - A European Journal
Volume25
Issue number42
Early online date29 Apr 2019
DOIs
Publication statusPublished - 25 Jul 2019

Cite this

Integrated theoretical and empirical studies for probing substrate-framework interactions in hierarchical catalysts. / Chapman, Stephanie; O'Malley, Alexander; Miletto, Ivana; Carravetta, Marina; Cox, Paul; Gianotti, Enrica; Marchese, Leonardo; Parker, Stewart F. ; Raja, Robert.

In: Chemistry - A European Journal, Vol. 25, No. 42, 25.07.2019, p. 9938-9947.

Research output: Contribution to journalArticle

Chapman, S, O'Malley, A, Miletto, I, Carravetta, M, Cox, P, Gianotti, E, Marchese, L, Parker, SF & Raja, R 2019, 'Integrated theoretical and empirical studies for probing substrate-framework interactions in hierarchical catalysts', Chemistry - A European Journal, vol. 25, no. 42, pp. 9938-9947. https://doi.org/10.1002/chem.201901188
Chapman, Stephanie ; O'Malley, Alexander ; Miletto, Ivana ; Carravetta, Marina ; Cox, Paul ; Gianotti, Enrica ; Marchese, Leonardo ; Parker, Stewart F. ; Raja, Robert. / Integrated theoretical and empirical studies for probing substrate-framework interactions in hierarchical catalysts. In: Chemistry - A European Journal. 2019 ; Vol. 25, No. 42. pp. 9938-9947.
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