Affiliation: State Key Laboratory of Materials- Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China.
Mesoporous solid superbases have high potentials for applications as environmentally friendly catalysts in diverse reactions. However, the generation of strong basicity on mesoporous silica is quite difficult because of the weak guest-host (precursor-silica) interaction and the poor alkali-resistant capacity of host. In this paper, a method was developed to generate strong basicity on mesoporous silica SBA-15 by precoating a metal oxide layer prior to modification by base precursor KNO3. The results show that the guest-host interaction is enhanced by the introduction of metal oxides including Al2O3, MgO, ZrO2, and CeO2, which can be quantitatively characterized by hydrophilicity and electronegativity of the surface of host. As a result, the decomposition of KNO3 can proceed at much lower temperatures as compared with KNO3 supported on pure SBA-15. The alkali-resistance of mesoporous silica can also be tailored by the introduction of metal oxides, while mesostructure and basicity of resultant materials are strongly dependent on the dispersion state of metal oxides. Al2O3 and MgO can form smooth layers on the surface of SBA-15, which prevents the host from corroding by resultant strongly basic species. However, ZrO2 and CeO2 tend to aggregate, and thus the reaction of basic species with siliceous frameworks is still inevitable. We demonstrate that in the presence of an Al2O3 interlayer, materials possessing both ordered mesostructure and superbasicity (H_ = 27.0) are successfully fabricated, which is impossible to realize on pure mesoporous silica. The present method may open a new way for the design and synthesis of functional materials with strong basicity.