Jh. Lunsford et al., AN NMR-STUDY OF ACID SITES ON SULFATED-ZIRCONIA CATALYSTS USING TRIMETHYLPHOSPHINE AS A PROBE, Catalysis letters, 27(3-4), 1994, pp. 305-314
Concentrations of Bronsted and Lewis acid sites on sulfated-zirconia c
atalysts were determined using the P-31 MAS NMR spectra of adsorbed tr
imethylphospine. A sample that had been calcined and exposed to air fo
r a long period exhibited only Bronsted acidity; however, treatment of
the sample at progressively higher temperatures resulted in the devel
opment of at least three types of Lewis acidity, along with a decrease
in the concentration of Bronsted acid sites. In a related study the a
ctivity of these catalysts for the alkylation of isobutane with 2-bute
ne was determined. The aged catalyst was inactive, but activation of t
he material at 100-degrees-C resulted in the most active catalyst. The
rmal treatment at higher temperatures resulted in a loss in activity w
hich paralleled the decrease in the Bronsted acid sites. These results
are consistent with a model in which strong Bronsted acidity is a res
ult of the interaction between bisulfate groups and adjacent Lewis aci
d sites.