Mesoporous Metal-Organic Framework MIL-101 at High Pressure

Abstract

The chromium terephthalate MIL-101 is a mesoporous metal-organic framework (MOF) with unprecedented adsorption capacities due to the presence of giant pores. The application of an external pressure can effectively modify the open structure of MOFs and its interaction with guest molecules. In this work, we study MIL-101 under pressure by synchrotron X-ray diffraction and infrared (IR) spectroscopy with several pressure transmitting media (PTM). Our experimental results clearly show that when a solid medium as NaCl is employed, an irreversible amorphization of the empty structure occurs at about 0.4 GPa. Using a fluid PTM, as Nujol or high-viscosity silicone oil, results in a slight lattice expansion and a strong modification of the peak frequency and shape of the MOF hydroxyl vibration below 0.1 GPa. Moreover, the framework stability is enhanced under pressure with the amorphization onset shifted to about 7 GPa. This coherent set of results points out the insertion of the fluid inside the MIL-101 pores. Above 7 GPa, concomitantly to the nucleation of the amorphous phase, we observe a peculiar medium-dependent lattice expansion. The behavior of the OH stretching vibrations under pressure is profoundly affected by the presence of the guest fluid, showing that OH bonds are sensitive vibrational probes of the host-guest interactions. The present study demonstrates that even a polydimethylsiloxane silicone oil, although highly viscous, can be effectively inserted into the MIL-101 pores at a pressure below 0.2 GPa. High pressure can thus promote the incorporation of large polymers in mesoporous MOFs.