NMR and Theoretical Study of Acidity Probes on Sulfated Zirconia Catalysts

Abstract

The measurement of the type and number of acid sites on sulfated zirconia catalysts using the 31P NMR spectrum of adsorbed P(CH3)3 has been vexed by spectral assignment controversies. Using a combination of NMR experiments and theoretical methods, including chemical shift calculations at the GIAO-MP2 level, we show that a previously observed 31P resonance at +27 ppm is due to P(CH3)4+, formed in a reaction that consumes a Bronsted site. The coproduct of this reaction, PH(CH3)2, is protonated on the surface to yield a 31P resonance in the region expected for P(CH3)3 on a Lewis site. Further complications result from a signal due to OP(CH3)3, formed by oxidizing sites on the surface, complexed to unidentified acid sites. As an alternative, we show that carefully designed 15N experiments using the less reactive and less basic probe pyridine-15N provide more easily interpreted measurements of Bronsted and Lewis sites on sulfated zirconias of diverse composition, preparation, and treatment. Quantitative studie...