The role of surface complexes in ketenes formation from fatty acids via pyrolysis over silica: from platform molecules to waste biomass

Azizova, Liana R., Kulik, Tetiana V., Palianytsia, Borys B., Ilchenko, Mykola M., Telbiz, German M., Balu, Alina M., Tarnavskiy, Sergiy, Luque, Rafael, Roldan, Alberto ORCID: https://orcid.org/0000-0003-0353-9004 and Kartel, Mykola T. 2023. The role of surface complexes in ketenes formation from fatty acids via pyrolysis over silica: from platform molecules to waste biomass. Journal of the American Chemical Society 145 (49) , pp. 26592-26610. 10.1021/jacs.3c06966

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Abstract

Fatty acids (FA) are the main constituents of lipids and oil crop waste, considered to be a promising 2G biomass that can be converted into ketenes via catalytic pyrolysis. Ketenes are appraised as promising synthons for the pharmaceutical, polymer, and chemical industries. Progress in the thermal conversion of short- and long-chain fatty acids into ketenes requires a deep understanding of their interaction mechanisms with the nanoscale oxide catalysts. In this work, the interactions of fatty acids with silica are investigated using a wide range of experimental and computational techniques (TPD MS, DFT, FTIR, in situ IR, equilibrium adsorption, and thermogravimetry). The adsorption isotherms of linear and branched fatty acids C1–C6 on the silica surface from aqueous solution have been obtained. The relative quantities of different types of surface complexes, as well as kinetic parameters of their decomposition, were calculated. The formation of surface complexes with a coordination bond between the carbonyl oxygens and silicon atoms in the surface-active center, which becomes pentacoordinate, was confirmed by DFT calculations, in good agreement with the IR feature at ∼1680 cm 1. Interestingly, ketenes release relate to these complexes’ decomposition as confirmed by the thermal evolution of the absorption band (1680 cm–1) synchronously with the TPD peak of the ketene molecular ion. The established regularities of the ketenezation are also observed for the silica-induced pyrolysis of glyceryl trimyristate and real waste, rapeseed meals.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Dentistry Chemistry
Publisher:	American Chemical Society
ISSN:	0002-7863
Date of First Compliant Deposit:	8 November 2023
Date of Acceptance:	6 November 2023
Last Modified:	20 Dec 2023 14:37
URI:	https://orca.cardiff.ac.uk/id/eprint/163728

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