Rapid synthesis of CNTs@MIL-101(Cr) using multi-walled carbon nanotubes (MWCNTs) as crystal growth accelerator

In this work, hybrid material CNTs@MIL-101(Cr) was synthesized in 2 h using multi-walled carbon nanotubes (MWCNTs) as the crystal growth accelerator with hydrothermal method. The characteristic differences between the crystals of CNTs@MIL-101(Cr) and MIL-101 were investigated by N2 adsorption-desorption isotherms, X-ray diffraction (XRD), scanning electron microscope (SEM) and thermogravimetric analyzer (TGA). The results showed that MWCNTs embedding in the hybrid material provide more mesoporous volumes than that of MIL-101. Moreover, the fast synthesized crystals of CNTs@MIL-101(Cr) still preserve the octahedral shape like MIL-101 and have a larger size ranging from 1.5 to 2.0 μm which were approximately three times larger than that of MIL-101. In the proposed mechanism, the roles of MWCNTs played in the crystallization were discussed where MWCNTs can be seen as coaxial cylindrical tubes composed of multi-layer graphenes and the place where nucleation and crystal growth processes occur at the tubes' out surface. Then, a crystal seeding layer bonding with the MWCNTs may be easily formed which accelerates the growth rate of MIL-101 crystals. Thus, larger crystals of CNTs@MIL-101(Cr) were formed due to the faster crystal growth rate of MIL-101.