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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$rightarrow$OH+H at the metal centers. After this dissociation, the OH groups coordinate to the metal centers, explaining the reduction in the MOFs 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.
We show that the water dissociation reaction H$_2$O$rightarrow$OH+H in the confined environment of MOF-74 channels can be precisely controlled by the addition of the noble gas He. Elucidating the entire reaction process with ab initio methods and inf
Using infrared spectroscopy combined with ab initio methods we study reactions of H$_2$O and CO inside the confined spaces of Zn-MOF-74 channels. Our results show that, once the water dissociation reaction H$_2$O$;rightarrow;$OH+H takes place at the
Recently, an aziridinium lead iodide perovskite was proposed as a possible solar cell absorber material. We investigated the stability of this material using a density-functional theory with an emphasis on the ring strain associated with the three-me
Molecular dynamics simulations combined with periodic electronic structure calculations are performed to decipher structural, thermodynamical and dynamical properties of the interfaced vs. confined water adsorbed in hexagonal 1D channels of the 2D la
Microporous organosilicas assembled from polysilsesquioxane (POSS) building blocks are promising materials that are yet to be explored in-depth. Here, we investigate the processing and molecular structure of bispropylurea bridged POSS (POSS-urea), sy