Multiscale Co‐Assembly to Meso‐Macroporous Foamed Single‐Crystal Metal–Organic Frameworks for the Supported Capture of Sulfur Dioxide

• Published in: Advanced functional materials 2024-05, Vol.34 (19), p.n/a
• Main Authors: Kan, Xun, Zhang, Guanqing, Ma, Jun, Liu, Fengqing, Tang, Yu, Liu, Fujian, Yi, Xianfeng, Liu, Yuefeng, Zheng, Anmin, Jiang, Lilong, Xiao, Feng‐Shou, Dai, Sheng
• Format: Article
• Language: English
• Subjects: Adsorption; Amines; Assembly; Carbon dioxide; Copolymers; foam nanostructure; macromolecule immobilization; Metal clusters; Metal-organic frameworks; metal–organic framework; multiscale assembly; Nanochannels; separation; Single crystals; SO2 adsorption; Sulfur dioxide; Trimethylbenzene
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202312044

The introduction of enlarged and interconnected nanochannels into metal–organic frameworks (MOFs) overcome their micropore size restriction, enhances mass transportation, and improves the accessibility of anchored metal clusters. Herein, foamed Ce‐MOF single crystals (F‐Ce‐MOF‐SC‐x) designed from a multiscale co‐assembly is reported in the presence of a copolymer template and 1,3,5‐trimethylbenzene as a structural regulator. The resultant F‐Ce‐MOF‐SC‐x possessed well‐defined microporous tandem‐ordered meso‐macroporous foams with superior connectivity and versatile Ce‐defective unsaturated sites (Ce‐DUS). F‐Ce‐MOF‐SC‐x is applied as a stable carrier for anchoring polytertiary amines (PA) via coordination interactions with Ce‐DUS. Owing to the superior ability of PA to recognize SO2, the resultant F‐Ce‐MOF‐SC‐x@yPA delivers exceptional performance in terms of the high‐temperature reversible adsorption and separation of SO2, including a remarkable capacity for SO2, spectacular selectivity for SO2/CO2/N2, an ultrafast adsorption equilibrium rate, and stability for 50 cycles. These characteristics are outstanding among those of MOFs and superior to those of many reported SO2 adsorbents. Isolated and intricate micropores in MOFs offer high mass‐transfer resistance, inaccessibility of metal active sites, and coking of the inner pores. A multiscale assembly is developed to design open and interconnected meso‐macroporous foams in Ce‐MOF single crystals to overcome these drawbacks of MOFs. The prepared F‐Ce‐MOF‐SC‐x is applied as a stable carrier for encapsulating functional macromolecules and delivered extraordinary performance for the high‐temperature reversible adsorption and separation of SO2.