The flexible metal-organic framework MIL-53(Cr) has been demonstrated to be an efficient adsorbent for liquid phase adsorption and separation, while the effect of this attractive “breathing effect” on its performance remains uncertain. In this research, by increasing the amount of introduced water, MIL-53(Cr) first shrank into a narrow pore form through bound water and then reopened due to the introduction of free water. Using MIL-53(Cr) with diverse amounts of water as an adsorbent, the liquid-phase adsorption and separation of C8 aromatics, including o -xylene (OX), p -xylene (PX), m -xylene (MX) and ethylbenzene (EB), was manipulated by the pre-adsorbed water in MIL-53(Cr). Pre-adsorbing water in MIL-53(Cr) induced a preference reversal between MX and PX, where dry samples preferentially adsorbed MX, while high-water-addition samples preferred PX instead. In addition, the reopened MIL-53(Cr) with high water addition hardly adsorbed EB, thereby increasing the selectivity of xylene isomers to EB. A longer equilibrium time was observed on MIL-53(Cr) with high water addition, during which the adsorption preference shifted from OX to MX to PX. Further molecular simulation provided a microscopic explanation that water molecules in the pores tended to package around MX and EB, hindering their interaction with frameworks or other adsorbates.
Methane hydrate has been extensively studied as a potential medium for natural gas storage and transportation. Due to their high specific surface area, tunable porous structure, and surface chemistry, metal–organic frameworks are ideal materials to exhibit the catalytic effect for the formation process of gas hydrate. In this paper, hollow ZIF-8 nanoparticles are synthesized using the hard template method. The synthesized hollow ZIF-8 nanoparticles are used in the adsorption and methane hydrate formation process. The effect of pre-adsorbed water mass in hollow ZIF-8 nanoparticles on methane storage capacity and the hydrate formation rate is investigated. The storage capacity of methane on wet, hollow ZIF-8 is augmented with an increase in the mass ratio of pre-adsorbed water and dry, hollow ZIF-8 (RW), and the maximum adsorption capacity of methane on hollow ZIF-8 with aRWof 1.2 can reach 20.72 mmol/g at 275 K and 8.57 MPa. With the decrease inRW, the wet, hollow ZIF-8 exhibits a shortened induction time and an accelerated growth rate. The formation of methane hydrate on hollow ZIF-8 is further demonstrated with the enthalpy of the generation reaction. This work provides a promising alternative material for methane storage.
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