Understanding and controlling water stability of MOF-74

Metal organic framework (MOF) materials in general, and MOF-74 in particular, have promising properties for many technologically important processes. However, their instability under humid conditions severely restricts practical use. We show that this instability and the accompanying reduction of the CO 2 uptake capacity of MOF-74 under humid conditions originate in the water dissociation reaction H 2 O → OH + H at the metal centers. After this dissociation, the OH groups coordinate to the metal centers, explaining the reduction in the MOF's CO 2 uptake capacity. This reduction thus strongly depends on the catalytic activity of MOF-74 towards the water dissociation reaction. We further show that-while the water molecules themselves only have a negligible effect on the crystal structure of MOF-74-the OH and H products of the dissociation reaction significantly weaken the MOF framework and lead to the observed crystal structure breakdown. With this knowledge, we propose a way to suppress this particular reaction by modifying the MOF-74 structure to increase the water dissociation energy barrier and thus control the stability of the system under humid conditions. The H 2 O → OH + H reaction poisons the metal centers and starts the degradation of the crystal structure of MOF-74.