Lu Zhiyong, Bai Junfeng, Hang Cheng, Meng Fei, Liu Wenlong, Pan Yi, You Xiaozeng
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210093, P.R. China.
College of Mechanics and Materials, Hohai University, Nanjing, 210098, P.R. China.
Chemistry. 2016 Apr 25;22(18):6277-85. doi: 10.1002/chem.201504907. Epub 2016 Mar 31.
A new stepwise ligand-elongation strategy by amide spacers is utilized to prepare isoreticularly high-porous metal-organic frameworks (MOFs), namely, quasi-mesoporous [Cu2 (PDBAD)(H2 O)]n (H4 PDBAD=5,5'-((4,4'-((pyridine-3,5-dicarbonyl)bis(azanediyl))bis(benzoyl))bis(azanediyl))diisophthalic acid; NJU-Bai22: NJU-Bai for Nanjing University Bai's group), and mesoporous [Cu2 (PABAD)(H2 O)]n (H4 PABAD=5,5'-((4,4'-((4,4'-((pyridine-3,5-dicarbonyl)bis(azanediyl))bis(benzoyl))bis (azanediyl))bis(benzoyl))bis(azanediyl))diisophthalic acid; NJU-Bai23). Compared with the prototypical MOF of [Cu2 (PDAD)(H2 O)]n (H4 PDAD=5,5'-(pyridine-3,5-dicarbonyl)bis(azanediyl)diisophthalic acid; NJU-Bai21, also termed as PCN-124), both MOFs exhibit almost the same CO2 adsorption enthalpy and CO2 selectivity values, and better capacity for CO2 storage under high pressure; these results make them promising candidate materials for CO2 capture and sequestration. Interestingly, this new method, in comparison with traditional strategies of using phenyl or triple-bond spacers, is easier and cheaper, resulting in a better ability to retain high CO2 affinity and selectivity in MOFs with large pores and high CO2 storage capacity. Additionally, it may lead to the high thermal stability of the MOFs and also their tolerance to water, which is related to the balance between the density of functional groups and pore sizes. Therefore, this strategy could provide new opportunities to explore more functionalized mesoporous MOFs with high performance.
通过酰胺间隔基采用一种新的逐步配体延长策略来制备等规高孔隙率金属有机框架（MOF），即准介孔的[Cu2 (PDBAD)(H2 O)]n（H4 PDBAD = 5,5'-((4,4'-((吡啶-3,5-二羰基)双(氮杂二亚基))双(苯甲酰基))双(氮杂二亚基))二间苯二甲酸；NJU-Bai22：NJU-Bai代表南京大学的白课题组）和介孔的[Cu2 (PABAD)(H2 O)]n（H4 PABAD = 5,5'-((4,4'-((4,4'-((吡啶-3,5-二羰基)双(氮杂二亚基))双(苯甲酰基))双(氮杂二亚基))双(苯甲酰基))双(氮杂二亚基))二间苯二甲酸；NJU-Bai23）。与原型MOF [Cu2 (PDAD)(H2 O)]n（H4 PDAD = 5,5'-(吡啶-3,5-二羰基)双(氮杂二亚基)二间苯二甲酸；NJU-Bai21，也称为PCN-124）相比，这两种MOF表现出几乎相同的CO2吸附焓和CO2选择性值，并且在高压下具有更好的CO2储存能力；这些结果使它们成为用于CO2捕获和封存的有前途的候选材料。有趣的是，与使用苯基或三键间隔基的传统策略相比，这种新方法更简便、成本更低，从而在具有大孔和高CO2储存容量的MOF中具有更好的保持高CO2亲和力和选择性的能力。此外，它可能导致MOF具有高热稳定性以及对水的耐受性，这与官能团密度和孔径之间的平衡有关。因此，该策略可为探索更多具有高性能的功能化介孔MOF提供新的机会。
