Gas-flow activation of MOFs: unlocking efficient catalysis through dynamic bonding.

Metal-organic frameworks (MOFs), characterized by dynamic metal-ligand coordination bonding, have pivotal roles in catalysis, gas storage, and separation processes, owing to their open metal sites (OMSs). These sites, however, are frequently occupied by Lewis-base solvent molecules, necessitating activation to expose the OMSs for practical applications. Traditional thermal activation methods involve harsh conditions, risking structural integrity. This study presents a novel 'gas-flow activation' technique using inert gases like nitrogen and argon to eliminate these coordinating solvent molecules at low temperatures, thereby maintaining the structural integrity of MOFs. We specifically explored this method with HKUST-1, demonstrating that gas-flow activation at mild temperatures is not only feasible but also superior in efficiency compared to the conventional thermal methods. This approach highlights the potential for safer, more efficient activation processes in MOF applications, making it a valuable addition to the repertoire of MOF activation techniques. This activation function of inert gas flow allows HKUST-1 as a catalyst for the hydrogenation of acetophenone even at room temperature. In addition, it is demonstrated that this 'gas-flow activation' is broadly applicable in other MOFs such as MOF-14 and UTSA-76. Furthermore, the findings reveal that dynamic coordination bonding, the repeating transient dissociation-association of solvent molecules at OMSs, are key mechanisms in facilitating this activation, pointing towards new directions for designing activation strategies that prevent structural damage.