UiO-67-type Metal–Organic Frameworks with Enhanced Water Stability and Methane Adsorption Capacity

The
structure and properties of two new UiO-67-type metal–organic
frameworks, along with their linker synthesis and powder and single
crystal synthesis, are presented. The new MOFs, UiO-67-Me and UiO-67-BN,
are based on 3,3′-dimethylbiphenyl and 1,1′-binaphthyl
linker scaffolds, and show a much higher stability to water than the
thoroughly investigated UiO-67, which is based on the biphenyl scaffold.
On the basis of structure models obtained from single crystal X-ray
diffraction, it is seen that these linkers are partly shielding the
Zr cluster. The new materials have higher density than UiO-67, but
show a higher volumetric adsorption capacity for methane. UiO-67-BN
exhibits excellent reversible water sorption properties, and enhanced
stability to aqueous solutions over a wide pH range; it is to the
best of our knowledge the most stable Zr-MOF that is isostructural
to UiO-67 in aqueous solutions.