Surface hydroxyl groups on metal oxides play significant roles in catalyst synthesis and catalytic reactions. Despite the importance of surface hydroxyls in broader material applications, quantitative measurements of surface acid-base properties are not regularly reported. Here, we describe direct methods to quantify fundamental properties of surface hydroxyls on several titania- and alumina-based supports. Comparing commercially available anatase, rutile, P25, and P90 titania, thermogravimetric analysis (TGA) indicated that the total surface hydroxyl density varied by a factor of 2, and each surface hydroxyl is associated with approximately one weakly adsorbed water molecule. Proton-exchange site densities, determined at 25 °C with slurry acid-base titrations, led to several conclusions: (i) the intrinsic acidity/basicity of surface hydroxyls were similar regardless of the titania source; (ii) differences in the surface isoelectric point (IEP) were primarily attributable to differences in the surface concentration of acid and base sites; (iii) rutile has a higher surface concentration of basic hydroxyls, leading to a higher IEP; and (iv) P25 and P90 titania have slightly higher surface concentrationsof acidic hydroxyls relative to anatase or rutile. Temperature effects on surface acid-base properties are rarely reported yet are significant: from 5 to 65 °C, IEP values change by roughly one pH unit. The IEP changes were associated with large changes to the intrinsic acid-base equilibrium constants over this temperature range, rather than changes in the composition or concentration of the surface sites.
Keywords: acid−base titration; isoelectric point; metal oxides; surface hydroxyls; thermogravimetric analysis.