Abstract
Mild acid functionalization method is used to synthesize sulfonic acid functionalized metal-organic framework (MOF), particularly, S-MIL-101, and is evaluated as a heterogeneous catalyst for esterification of acetic acid with n-butanol. BrÖnsted acidic S-MIL-101 is developed by post-synthetic functionalization of the MOF, NH2-MIL-101(Al). The incorporation of propylsulfonic acid groups was carried out by nucleophilic ring-open reaction between amino groups in NH2-MIL-101 and 1,3- propanesultone. The mild functionalization method successfully introduces BrÖnsted acidity to the NH2-MIL-101(Al), without any significant structural degradation as confirmed by structural characterizations. As a BrÖnsted acidic heterogeneous catalyst, S-MIL-101 exhibits 66% acetic acid conversion at a low esterification temperature of 70 °C and is successfully reused for 3 reaction cycles without any considerable leaching. The performance of S-MIL-101 is comparable to commercial Amberlyst-15 and Nafion NR-50. various structural characterizations and kinetic studies were performed and the excellent performance of S-MIL-101 as a solid acid catalyst is attributed to the high surface area and favorable influence of the BrÖnsted acidic sulfonic groups.
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