The influence of solvent on the acidity and activity of supported sulfonic acid catalysts

The acid strengths and catalytic activities of sulfonic acids supported on polystyrene resins and ordered mesoporous HMS and SBA-15 silicas are compared. Acid strengths are measured by acid - base titration calorimetry in terms of the molar enthalpies of neutralisation with either NaOH or n-butylamine in water, acetonitrile and cyclohexane. Catalytic activities ( turnover numbers) are reported in model reactions in water, 1,2-dichlorobenzene and anisole, and compared with acid strengths. In water, sulfonated resins are both stronger acids and more active catalysts than sulfonated silicas. Catalytic activities in water correlate well with these measured acid strengths. In acetonitrile the order of acid strengths is reversed and the sulfonated silicas are the stronger acids. Catalytic measurements in 1,2-dichlorobenzene, a similar dipolar aprotic solvent, show the same reversed order of activities. In the non-polar solvent cyclohexane ( where only macroporous sulfonated resins show measurable acidity) the sulfonated silicas are again the stronger acids but by a larger margin. Catalytic activities in anisole, which is also only very weakly solvating towards sulfonic acid groups, show a similar trend. The results illustrate the role of the solvent in controlling the acid strength of solid acid catalysts, and the importance of taking this into account when designing acid catalysts for liquid phase processes.