Chemically and hydrolytically stable metal–organic
frameworks
(MOFs) have shown great potential for many water-adsorption-related
applications. However, MOFs with large pores that show high water-uptake
capacity and high hydrolytic and mechanical cycle stability are rare.
Through a deliberate adjustment of the linker of a typical zirconium-based
MOF (Zr-MOF) (NU-1000), a new isomer of NU-1000 with blocked c-pores, but large mesopores was successfully
synthesized. This new isomer, ISO-NU-1000, exhibits excellent
water stability, one of the highest water vapor uptake capacities,
and excellent cycle stability, making it a promising candidate for
water-vapor-sorption-based applications such as water-adsorption-driven
heat transfer. We find that the high water-cycling stability of ISO-NU-1000 is traceable to its blocking c-pore that hinders the hydrolysis of node-coordinating formate in
the c-pore area and thereby prevents the introduction
of node aqua and terminal hydroxo ligands. With the absence of these
ligands and their ability to hydrogen-bond to channel-located water
molecules, the strength of guest (water)/host (MOF) interactions is
diminished and the absolute magnitude of the capillary force exerted
by water during its evacuation from MOF channels is attenuated. The
attenuation leaves the MOF capable of resisting pore collapse, capacity
loss, and crystallinity loss during repetitive evaporative removal
(and re-introduction) of water from pores.
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