Defect-Engineered MOF-808-SO4 as Efficient Solid Acid Catalysts for Esterification of n-Butyl Acetate.

In order to address corrosion and pollution problems of liquid acids and limitations of traditional solid acids, sulfated MOF-808-SO4 catalysts were developed by creating unsaturated sites in MOF-808 for sulfate grafting with ligand defect engineering. Characterization verified framework integrity, successful sulfate coordination, and maintenance of high surface areas and tunable porosity. Temperature-programmed desorption of ammonia (NH3-TPD) establishes a clear consistent trend between defect density and the concentration as well as the strength of acid sites, indicating that a higher degree of ligand deficiency promotes the formation of more abundant and stronger acid centers. For esterification of acetic acid with n-butanol, the catalyst prepared by replacing 40 mol% of BTC with BDC achieved ≥99% conversion of acetic acid under mild conditions of 2.0 wt% catalyst loading and 1:2 alcohol/acid molar ratio at 120 °C for 6 h, outperforming conventional solid acids. This performance stems from high-density strong Brønsted acid sites strongly coordinated at defects and an open pore structure facilitating diffusion. The catalyst was easily recovered by ethanol washing and maintained stable activity over five cycles without loss of catalytic capability. This work suggests defect engineering as an effective strategy for tuning acidity and catalytic performance in MOF-based solid acids for green esterification.