Role of Hydrogen Bonding on Transport of Coadsorbed Gases in Metal-Organic Frameworks Materials

Coadsorption of multicomponerits in metal-organic framework (MOP) Materials can lead to a number of cooperative effects, such as modification of adsorption sites or during transport. In this work, :we explore the incorporation of NH3 and H2O into MOFs preloaded with small molecules such as CO, CO2, and SO2. We find that NH3 (or H2O) first displaces a certain amount of preadsorbed molecules in the otter portion of IMF crystallites, and then substantially hinders diffusion. Combining in situ spectroscopy with first-principles calculations, we show that hydrogen bonding between NH3 (or H2O) is responsible for an increase of a factor of 7 and 8 in diffusion barrier of CO and CO2 through the MOF channels. Understanding such cooperative effects is important for designing new strategies to. enhance adsorption in nanoporous materials.