Water Adsorption and Insertion in MOF-5

[Image: see text] The high surface areas and tunable properties of metal–organic frameworks (MOFs) make them attractive materials for applications in catalysis and the capture, storage, and separation of gases. Nevertheless, the limited stability of some MOFs under humid conditions remains a point of concern. Understanding the atomic-scale mechanisms associated with MOF hydrolysis will aid in the design of new compounds that are stable against water and other reactive species. Toward revealing these mechanisms, the present study employs van der Waals-augmented density functional theory, transition-state finding techniques, and thermodynamic integration to predict the thermodynamics and kinetics of water adsorption/insertion into the prototype compound, MOF-5. Adsorption and insertion energetics were evaluated as a function of water coverage, while accounting for the full periodicity of the MOF-5 crystal structure, that is, without resorting to cluster approximations or structural simplifications. The calculations suggest that the thermodynamics of MOF hydrolysis are coverage-dependent: water insertion into the framework becomes exothermic only after a sufficient number of H(2)O molecules are coadsorbed in close proximity on a Zn–O cluster. Above this coverage threshold, the adsorbed water clusters facilitate facile water insertion via breaking of Zn–O bonds: the calculated free-energy barrier for insertion is very low, 0.17 eV at 0 K and 0.04 eV at 300 K. Our calculations provide a highly realistic description of the mechanisms underlying the hydrolysis of MOFs under humid working conditions.