Sulfonic acid-functionalized MIL-101(Cr): An efficient catalyst for esterification of oleic acid and vapor-phase dehydration of butanol

• Acidic metal-organic framework (MOF) was synthesized in one step.
• Acidic MOF can be used for not only liquid but also vapor-phase catalyses.
• Esterification reaction can be accelerated under microwave irradiation.
• Butanol dehydration was very stable over the acidic MOF.

A highly porous and acidic metal-organic framework (MOF), MIL-101(Cr)-SO3H, was hydrothermally synthesized in one step using sulfonic acid-functionalized ligands. The prepared catalysts were systematically characterized with X-ray diffraction, FTIR, nitrogen adsorption, and thermogravimetric analysis. MIL-101(Cr)-SO3H was successfully used in the liquid-phase reaction (esterification of oleic acid), and also applied for the first time in the vapor-phase (2-butanol dehydration) reaction. The esterification is catalyzed in the heterogeneous mode, as confirmed by a negligible increase in the esterification yield after the filtration of the catalyst. The esterification was performed under both microwave (MW) and conventional heating (CE), and a beneficial effect of the MW reaction for rapid reactions was observed. The vapor-phase dehydration of 2-butanol to olefins (BTO) over MIL-101(Cr)-SO3H was very stable in conversion, which is different from the results obtained using the SAPO-34 molecular sieve, which has been widely used in the dehydration of simple alcohols. The obtained results demonstrated the versatile applicability of the sulfonic acid-functionalized MOFs both in the liquid- and vapor-phase reactions.

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