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

Abstract 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 SO 2 , the resultant F‐Ce‐MOF‐SC‐x@yPA delivers exceptional performance in terms of the high‐temperature reversible adsorption and separation of SO 2 , including a remarkable capacity for SO 2 , spectacular selectivity for SO 2 /CO 2 /N 2 , 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 SO 2 adsorbents.