Th-MOF showing six-fold imide-sealed pockets for middle-size-separation of propane from nature gas

Separation of propane from nature gas is of great importance to industry. However, in light of size-based separation, there still lacks effective method to directly separate propane from nature gas, due to the comparable physical properties for these light alkanes (C1-C4) and the middle size of propane. In this work, we found that a new Th-MOF could be an ideal solution for this issue. The Th-MOF takes UiO-66-type structure, but with the pocket sealed by six-fold imide groups; this not only precisely reduces the size of pocket to exactly match propane, but also enhances the host-guest interactions through multiple supramolecular interactions. As a result, highly selective adsorption of propane over methane, ethane, and butane was observed, implying unique middle-size separation. The actual separation was confirmed by breakthrough experiments, and it is found that both relatively smaller molecules (methane and ethane) and relatively bigger molecules (butane) break through the Th-MOF column within 10 min/g, whereas propane with middle size can maintain very long retention time up to 80 min/g, strongly suggesting middle-size separation and its superior application in direct separation of propane from nature gas. The separation mechanism, as unveiled by both theoretical calculation and comparative experiments, is due to the six-fold imide-sealed pockets that could effectively distinguish propane from other light alkanes through both size effect and host-guest interactions.