Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal-Organic Framework with Mesoporous Silica for CO 2 Adsorption.

The HKUST-1@SBA-15 composites with hierarchical pore structure were constructed by in situ self-assembly of metal-organic framework (MOF) with mesoporous silica. The structure directing role of SBA-15 had an obvious impact on the growth of MOF crystals, which in turn affected the morphologies and structural properties of the composites. The pristine HKUST-1 and the composites with different content of SBA-15 were characterized by XRD, N ₂ adsorption-desorption, SEM, TEM, FT-IR, TG, XPS, and CO ₂ -TPD techniques. It was found that the composites were assembled by oriented growth of MOF nanocrystals on the surfaces of SBA-15 matrix. The interactions between surface silanol groups and metal centers induced structural changes and resulted in the increases in surface areas as well as micropore volumes of hybrid materials. Besides, the additional constraints from SBA-15 also restrained the expansion of HKUST-1, contributing to their smaller crystal sizes in the composites. The adsorption isotherms of CO ₂ on the materials were measured and applied to calculate the isosteric heats of adsorption. The HS-1 composite exhibited an increase of 15.9% in CO ₂ uptake capacity compared with that of HKUST-1. Moreover, its higher isosteric heats of CO ₂ adsorption indicated the stronger interactions between the surfaces and CO ₂ molecules. The adsorption rate of the composite was also improved due to the introduction of mesopores. Ten cycles of CO ₂ adsorption-desorption experiments implied that the HS-1 had excellent reversibility of CO ₂ adsorption. This study was intended to provide the possibility of assembling new composites with tailored properties based on MOF and mesoporous silica to satisfy the requirements of various applications.