title: Defect creation by linker fragmentation in metal-organic frameworks and its effects on gas uptake properties.
abstract: We successfully demonstrate an approach based on linker fragmentation to create defects and tune the pore volumes and surface areas of two metal-organic frameworks, NU-125 and HKUST-1, both of which feature copper paddlewheel nodes. Depending on the linker fragment composition, the defect can be either a vacant site or a functional group that the original linker does not have. In the first case, we show that both surface area and pore volume increase, while in the second case they decrease. The effect of defects on the high-pressure gas uptake is also studied over a large temperature and pressure range for different gases. We found that despite an increase in pore volume and surface area in structures with vacant sites, the absolute adsorption for methane decreases for HKUST-1 and slightly increases for NU-125. However, the working capacity (deliverable amount between 65 and 5 bar) in both cases remains similar to parent frameworks due to lower uptakes at low pressures. In the case of NU-125, the effect of defects became more pronounced at lower temperatures, reflecting the greater surface areas and pore volumes of the altered forms.
authors.affiliation: Department of Chemistry, Northwestern University , 2145 Sheridan Road Evanston, Illinois 60208, United States.
authors.forename: Gokhan
authors.initials: G
authors.lastname: Barin
authors.forename: Vaiva
authors.initials: V
authors.lastname: Krungleviciute
authors.forename: Oleksii
authors.initials: O
authors.lastname: Gutov
authors.forename: Joseph T
authors.initials: JT
authors.lastname: Hupp
authors.forename: Taner
authors.initials: T
authors.lastname: Yildirim
authors.forename: Omar K
authors.initials: OK
authors.lastname: Farha