Novel Magnetically-Recoverable Solid Acid Catalysts with a Hydrophobic Layer in Protecting the Active Sites from Water Poisoning

Three novel magnetically-recoverable solid acid catalysts (hydrophobic catalysts Fe3O4@SiO2-Me&PrSO3H, Fe3O4@SiO2-Oc&PrSO3H and hydrophilic catalyst Fe3O4@SiO2-PrSO3H) were synthesized by introducing organic propylsulfonic acid and alkyl groups to Fe3O4@SiO2nanocomposites. We characterized these catalysts by FT-IR, EDS, XRD, VSM and SEM, and found that they had excellent core-shell structure and magnetic responsiveness. We also explored the impact of surface hydrophobicity on activity and stability of catalysts in ethyl acetate (EAC) synthesis reaction. The results indicated that: for reactivity and reusability, Fe3O4@SiO2-Oc&PrSO3H > Fe3O4@SiO2-Me&PrSO3H > Fe3O4@SiO2-PrSO3H. This was because octyl and methyl groups could build a hydrophobic layer on the surfaces of Fe3O4@SiO2-Oc&PrSO3H and Fe3O4@SiO2-Me&PrSO3H, and this could effectively prevent water molecules from poisoning active sites; the hydrophobicity of octyl was stronger than methyl. Fe3O4@SiO2-Oc&PrSO3H also showed higher catalytic activity in the external aqueous reaction system, which indicated that it had good water toleration. Moreover, we could easily separate Fe3O4@SiO2-Oc&PrSO3H from the reaction mixture with an external magnetic field, in the meanwhile, its reactivity could still remain above 80% after reusing 6 times.