Functionalization of Diamine-Appended MOF-Based Adsorbents by Ring Opening of Epoxide: Long-Term Stability and CO₂Recyclability under Humid Conditions

Although diamine-appended metal-organic framework (MOF) adsorbents exhibit excellent CO₂adsorption performance, a continuous decrease in long-term capacity during repeated wet cycles remains a formidable challenge for practical applications. Herein, we present the fabrication of diamine-appended Mg₂(dobpdc)-alumina beads (een-MOF/Al-Si-Cx; een = N-ethylethylenediamine; x = number of carbon atoms attached to epoxide) coated with hydrophobic silanes and alkyl epoxides. The reaction of epoxides with diamines in the portal of the pore afforded sufficient hydrophobicity, hindered the penetration of water vapor into the pores, and rendered the modified diamines less volatile. een-MOF/Al-Si-C17-200 (een-MOF/Al-Si-C17-y; y = 50, 100, and 200, denoting wt % of C17 with respect to the bead, respectively), with substantial hydrophobicity, showed a significant uptake of 2.82 mmol g^-1at 40 °C and 15% CO₂, relevant to flue gas concentration, and a reduced water adsorption. The modified beads maintained a high CO₂capacity for over 100 temperature-swing adsorption cycles in the presence of 5% H₂O and retained CO₂separation performance in breakthrough tests under humid conditions. This result demonstrates that the epoxide coating provides a facile and effective method for developing promising adsorbents with high CO₂adsorption capacity and long-term durability, which is a required property for postcombustion applications.