AbstractSO42−/TiO2‐H3Ti5NbOl4 solid acid catalyst was prepared via high‐temperature calcination, proton exchange, pillaring, and impregnation processes. The structures and anchoring model can be confirmed by XRD, SEM, and FT‐IR. The acidic properties and specific surface area were characterized by NH3‐TPD and N2 adsorption‐desorption isotherms. The thermal stability was measured by TG‐DTG. The catalytic performances were evaluated via the esterification reaction of acetic acid and n‐butanol. The results show that SO42−/TiO2‐H3Ti5NbOl4 has stronger acid strength and higher acid content than H3Ti5NbOl4 and TiO2‐H3Ti5NbOl4. The esterification rate of ST‐HTN can be reached at 73.82%. The optimal esterification scheme is as follows: the catalyst dosage is 5 wt%, the molar ratio of alcohol to acid is 1.8:1, the reaction temperature is 127 °C, and reaction time is 5.5 h. Based on the structure‐activity relationship, the esterification properties of the selected catalysts were rationalized, which provided a useful perspective for the development and application of a new generation of esterification catalysts.
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