Nanospace Engineering of Metal–Organic Frameworks through Dynamic Spacer Installation of Multifunctionalities for Efficient Separation of Ethane from Ethane/Ethylene Mixtures

• Published in: Angewandte Chemie International Edition Vol. 60; no. 17; pp. 9680 - 9685
• Main Authors: Chen, Cheng‐Xia, Wei, Zhang‐Wen, Pham, Tony, Lan, Pui Ching, Zhang, Lei, Forrest, Katherine A., Chen, Sha, Al‐Enizi, Abdullah M., Nafady, Ayman, Su, Cheng‐Yong, Ma, Shengqian
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 19.04.2021
• Edition: International ed. in English
• Subjects: C2H6/C2H4 separation; carboxylic acids; Dicarboxylic acids; Ethane; Ethylene; Installation; materials chemistry; Metal-organic frameworks; nanostructures; Pore size; Porosity; Selectivity; Separation; materials chemistry; C2H6/C2H4 separation; nanostructures; carboxylic acids; metal-organic frameworks
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202100114

Herein, a dynamic spacer installation (DSI) strategy has been implemented to construct a series of multifunctional metal—organic frameworks (MOFs), LIFM‐61/31/62/63, with optimized pore space and pore environment for ethane/ethylene separation. In this respect, a series of linear dicarboxylic acids were deliberately installed in the prototype MOF, LIFM‐28, leading to a dramatically increased pore volume (from 0.41 to 0.82 cm3 g−1) and reduced pore size (from 11.1×11.1 Å2 to 5.6×5.6 Å2). The increased pore volume endows the multifunctional MOFs with much higher ethane adsorption capacity, especially for LIFM‐63 (4.8 mmol g−1), representing nearly three times as much ethane as the prototypical counterpart (1.7 mmol g−1) at 273 K and 1 bar. Meanwhile, the reduced pore size imparts enhanced ethane/ethylene selectivity of the multifunctional MOFs. Theoretical calculations and dynamic breakthrough experiments confirm that the DSI is a promising approach for the rational design of multifunctional MOFs for this challenging task. A dynamic spacer installation (DSI) strategy has been developed to realize a series of multifunctional metal—organic frameworks (MOFs) with optimized pore space and pore environment for ethane/ethylene separation. The installation of functional spacers into the proto‐LIFM‐28 not only improves the pore volume, but also reduces the pore size, leading to enhanced C2H6/C2H4 separation performance.