1H and 2H NMR studies of benzene confined in porous solids: melting point depression and pore size distribution

Abstract

The pore size distributions of four controlled pore glasses and three silica gels with nominal diameters in the range 4–24 nm were determined by measuring the 1H and 2H NMR signals from the non-frozen fraction of confined benzene and perdeuterated benzene as a function of temperature, in steps of ca. 0.1–1 K. The liquid and solid components of the adsorbate were distinguished, on the basis of the spin–spin relaxation time T 2, by employing a spin-echo sequence. The experimental intensity curves of the liquid component are well represented by a sum of two error functions. The mean melting point depression of benzene and perdeuterated benzene confined in the four controlled pore glasses, with pore radius R, follows the simplified Gibbs–Thompson equation Δ T= k p/ R with a k p value of 44 K nm. As expected, the k p value mainly determines the position of the pore size distribution curve, i.e., the mean pore radius, while the transition width determines the shape of the pore size distribution curve. The excellent agreement between the results from the 1H and 2H measurements shows that the effect of the background absorption from protons in physisorbed water and silanol groups is negligible under the experimental conditions used. The overall pore size distributions determined by NMR are in reasonable agreement with the results specified by the manufacturer, or measured by us using the N 2 sorption technique. The NMR method, which is complementary to the conventional gas sorption method, is particularly appropriate for studying pore sizes in the mesoporous range.