Lv Hong-Juan, Zhang Jian-Wei, Jiang Yu-Cheng, Li Shu-Ni, Hu Man-Cheng, Zhai Quan-Guo
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an, Shaanxi 710062, People's Republic of China.
Henan Engineering Center of New Energy Battery Materials, Henan D&A Engineering Center of Advanced Battery Materials, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000, People's Republic of China.
Inorg Chem. 2022 Feb 28;61(8):3553-3562. doi: 10.1021/acs.inorgchem.1c03562. Epub 2022 Feb 11.
High storage capacity, high separation selectivity, and high structure stability are essential for an idea gas adsorbent. However, it is not easy to achieve all three at the same time, even for the promising metal-organic framework (MOF) adsorbents. We demonstrate herein that robust [ScO]-organic frameworks could be regulated by a micropore combination strategy for high-performance acetylene adsorption. Under the same solvent system with formic acid as a modulator, similar tritopic ligands extend [ScO(COO)] trigonal-prismatic clusters to generate SNNU-5-Sc and SNNU-150-Sc adsorbents. Notably, the two Sc-MOFs can keep their architectures over 24 h in water at different pH values (2-12) or at 90 °C. Modulated by the linker symmetry, the final stacking metal-organic polyhedral cages produce open window sizes of about 10 Å for SNNU-5-Sc and 5 Å + 7 Å for SNNU-150-Sc. Due to such micropore combinations, SNNU-5-Sc exhibits a top-level CH uptake of 211.2 cm g (1 atm and 273 K) and SNNU-150-Sc shows high CH/CH, CH/CH, and CH/CO selectivities of 80.65, 4.03, and 8.19, respectively, under ambient conditions. Dynamic breakthrough curves obtained on a fixed-bed column and grand canonical Monte Carlo (GCMC) simulations further support their prominent acetylene storage and purification performance. High framework stability, storage capacity, and separation selectivity make SNNU-5-Sc and SNNU-150-Sc ideal acetylene adsorbents in practical applications.
对于理想的气体吸附剂而言，高存储容量、高分离选择性和高结构稳定性至关重要。然而，即使对于前景广阔的金属有机框架（MOF）吸附剂来说，同时实现这三点也并非易事。我们在此证明，稳健的[ScO]有机框架可通过微孔组合策略进行调控，以实现高性能乙炔吸附。在以甲酸为调节剂的相同溶剂体系下，类似的三齿配体扩展[ScO(COO)]三角棱柱簇，生成SNNU-5-Sc和SNNU-150-Sc吸附剂。值得注意的是，这两种Sc-MOFs在不同pH值（2-12）的水中或90°C下可保持其结构超过24小时。受连接体对称性的调节，最终堆叠的金属有机多面体笼为SNNU-5-Sc产生约10 Å的开放窗口尺寸，为SNNU-150-Sc产生5 Å + 7 Å的开放窗口尺寸。由于这种微孔组合，SNNU-5-Sc在1 atm和273 K下表现出211.2 cm³ g⁻¹的顶级CH₄吸附量，SNNU-150-Sc在环境条件下分别表现出80.65、4.03和8.19的高CH₄/C₂H₄、CH₄/C₂H₂和CH₄/CO₂选择性。在固定床柱上获得的动态突破曲线和巨正则蒙特卡罗（GCMC）模拟进一步支持了它们卓越的乙炔存储和净化性能。高框架稳定性、存储容量和分离选择性使SNNU-5-Sc和SNNU-150-Sc成为实际应用中理想的乙炔吸附剂。
