Shi Lijuan , Deyun Sun , Hongxue Xu , Zunaira Maqsood , Chen Shangqing , Qun Yi
2025 Green Chemical Engineering DOI: 10.1016/j.gce.2025.02.002
Abstract
Core-shell metal organic frameworks (MOFs) have emerged as a promising platform for efficient separation and sensing, benefiting from the sieving effect of the shell and the large storage capacity of the core. However, conventional core-shell MOFs often encounter challenges with compromised pore integrity, which predominantly restricts their design to microporous cores. In this study, a straightforward strategy to construct functional shells on mesoporous MOFs is proposed. By leveraging dynamic imine chemistry, small-molecule amines are assembled into supramolecular polymers and anchored onto the surface of mesoporous MOFs through metal coordination. This approach preserves the mesoporous structure of the core while introducing hydrogen-bonding channels in the shell, facilitating the selective capture and storage of polar gases. The resulting core-shell MOF demonstrates exceptional CO2/N2 selectivity of up to 10,943 and a high CO2 adsorption capacity, enabling the direct production of high-purity CO2 (99.7 vol.%) from humid flue gas in a single breakthrough experiment. Furthermore, this strategy exhibits excellent stability and versatility across various mesoporous MOFs, underscoring its potential for practical industrial gas separation applications.
核殼金屬有機框架（MOFs）因其外殼的篩分效應和核的大存儲容量，已成為高效分離和傳感的有前景平台。然而，傳統的核殼MOFs通常面臨孔隙完整性受損的挑戰，這主要限制了其設計以微孔核為主。在本研究中，提出了一種在介孔MOFs上構建功能外殼的直接策略。通過利用動态亞胺化學，小分子胺被組裝成超分子聚合物，并通過金屬配位錨定到介孔MOFs的表面。這種方法在保留介孔核結構的同時，在外殼中引入了氫鍵通道，從而促進了極性氣體的選擇性捕獲和存儲。所得的核殼MOF表現出高達10,943的優異CO2/N2選擇性以及高CO2吸附能力，能夠在單一穿透實驗中直接從潮濕煙道氣中生産高純度CO2（99.7 vol.%）。此外，該策略在各種介孔MOFs中展現出卓越的穩定性和通用性，突顯了其在實際工業氣體分離應用中的潛力。
