Carbon Dioxide Capture Enhanced by Pre‐Adsorption of Water and Methanol in UiO‐66

Abstract The rapidly rising level of carbon dioxide in the atmosphere resulting from human activity is one of the greatest environmental problems facing our civilization today. Most technologies are not yet sufficiently developed to move existing infrastructure to cleaner alternatives. Therefore, techniques for capturing carbon dioxide from emission sources may play a key role at the moment. The structure of the UiO‐66 material not only meets the requirement of high stability in contact with water vapor but through the water pre‐adsorbed in the pores, the selectivity of carbon dioxide adsorption is increased. We successfully applied the recently developed methodology for water adsorption modelling. It allowed to elucidate the influence of water on CO 2 adsorption and study the mechanism of this effect. We showed that water is adsorbed in octahedral cage and stands for promotor for CO 2 adsorption in less favorable space than tetrahedral cages. Water plays a role of a mediator of adsorption, what is a general idea of improving affinity of adsorbate. On the basis of pre‐adsorption of methanol as another polar solvent, we have shown that the adsorption sites play a key role here, and not, as previously thought, only the interaction between the solvent and quadrupole carbon dioxide. Overall, we explained the mechanism of increased CO 2 adsorption in the presence of water and methanol, as polar solvents, in the UiO‐66 pores for a potential post‐combustion carbon dioxide capture application.