Template-directed fabrication of MIL-101(Cr)/mesoporous silica composite: Layer-packed structure and enhanced performance for CO2 capture

Abstract

A novel hybrid material constituted of MIL-101(Cr) and mesoporous silica was successfully assembled through an in-situ hydrothermal method. The MCM−41 with well-ordered mesopores acted as the structure-directing agent, which regulated the growth of MIL-101(Cr) crystals along a certain direction and restricted the expansion of framework. Meanwhile, the hydroxyl groups existed in MCM−41 preferentially coordinated with the Cr3+ centers in MOF, followed by the layer-packed arrangement of MIL-101(Cr) nanocrystals on the surface of matrix. The structural characterizations further revealed that the introduction of MCM−41 could increase the micropore volume and specific surface area. The MIL-101(Cr)@MCM−41 exhibited higher CO2 uptake capacity and adsorption rate compared with the original MIL-101(Cr) at 298 K and 1 bar. Via ideal adsorbed solution theory (IAST), it could be further predicted that the composite was more inclined to adsorb CO2 than N2. The calculated isosteric heats of CO2 adsorption and desorption activation energy demonstrated that the interaction between CO2 molecules and the composite was also enhanced. The as-prepared MIL-101(Cr)@MCM−41 showed good reusability and could be easily regenerated without any reduction in its CO2 adsorption capacity. Hence, this study opened up a new pathway for designing hierarchical porous structured MOF-based materials with advanced gas separation performance.