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An NMR study of acid sites on chlorided alumina catalysts using trimethylphosphine as a probe

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Abstract

The MAS-NMR spectra of adsorbed trimethylphosphine (TMP) were used to determine the concentration of Brønsted and Lewis acid sites on pure and chlorinatedγ-Al2O3 samples. Chlorination with CHCl3,CCl4 or AlCl3 promoted the formation of Brønsted acid centers, which are characterized by the protonated adduct of TMP. This adduct has a31P chemical shift of ca. −3.8 ppm and a JP−H scalar coupling of 517 Hz. Additional resonances in the −44 to −54 ppm range are attributed to Lewis acid-base pairs. In some cases a partially resolved JP−Al coupling is observed, which confirms the assignment. Upon thermal treatment of a chlorinated sample at temperatures > 200°C, the concentration of Brønsted acid centers decreased; the concentration of one type of Lewis acid increased and another remained almost constant. In a parallel set of experiments the initial conversion ofn-hexane at 150°C and the yields of cracking and isomerization products were determined. Comparable functional relationships were observed between the loss of Brønsted acid sites and the decrease in yields of both cracking and isomerization products. These results suggest that Bransted acidity is responsible for the cracking and isomerization ofn-hexane over chlorided aluminas at 150°C.

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Sang, H., Chu, H.Y. & Lunsford, J.H. An NMR study of acid sites on chlorided alumina catalysts using trimethylphosphine as a probe. Catal Lett 26, 235–246 (1994). https://doi.org/10.1007/BF00810596

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  • DOI: https://doi.org/10.1007/BF00810596

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