Computational Exploration of the Water Concentration Dependence of the Proton Transport in the Porous UiO–66(Zr)–(CO₂H)₂ Metal–Organic Framework

The UiO–66(Zr)–(CO 2 H) 2 metal–organic framework (MOF) has been recently revealed as a promising proton conducting material under humidification. Here, aMS-EVB3 molecular dynamics simulations are performed to reveal at the molecular level the structure, thermodynamics, and dynamics of the hydrated proton in three-dimensional (3D)-cages MOF as a function of the water loading. It is found that the most stable proton solvation structure corresponds to a H 7 O 3 + cation and that a transition between this complex and a Zundel cation likely governs the proton transport in this MOF occurring via a Grotthuss-type mechanism. It is further shown that the formation of a H 2 O hydrogen-bonded bridge that connects the cages occurs only at high water concentration and this creates a path allowing the excess proton to jump from one cage to another. This leads to a faster self-diffusivity of proton at high water concentration, thereby supporting the increase of the proton conductivity with the water loading as experimentally evidenced.