通过有机配体中四嗪基团的原位水解提高金属有机框架的CO_2吸附性能（英文）

Enhanced CO_2 Sorption Performance of Metal-Organic Frameworks by in-Situ Hydrolysis of Tetrazine Moiety in the Ligand

在保持原有"层-柱"MOF,[Zn_4(bpta)_2(dipytz)2(H_2O)_2]·4DMF·H_2O(1)(H4bpta=2,2′,6,6′-联苯四羧酸,dipytz=3,6-二(4-吡啶基)-1,2,4,5-四嗪)主体结构不变的情况下,通过dipytz配体中四嗪环的原位水解反应将极性的二芳酰基联氨基团引入框架,成功构筑出配合物[Zn_4(bpta)_2(dipytzhydr)_2(H_2O)_2]·solvent(2)(dipytzhydr=1,2-二异烟酰基肼)。对配合物2的系统表征和气体吸附性质研究结果证实了功能化目标的实现:配合物2相比于配合物1展现出更高的二氧化碳吸附热(由28.8 k J·mol-1升高至30.3 k J·mol-1)和CO_2/CH_4吸附选择性。以上结果表明基于配体中四嗪基团的原位水解后修饰能够有效提高相关MOFs材料的CO_2吸附性能。

The polar acyl hydrazine groups were introduced into a ＂pillar-layer＂ MOF, [Zn4（bpta）2（dipytz）2（H2O）2]·4 DMF·H2O（1）（H4 bpta=1,1′-biphenyl-2,2′,6,6′-tetracarboxylic acid and dipytz=di-3,6-（4-pyridyl）-1,2,4,5-tetrazine）,through the in-situ hydrolysis modification of the dipytz pillar ligand, and [Zn4（bpta）2（dipytzhydr）2（H2O）2]·solvent（2）（dipytzhydr=1,2-diisonicotinoylhydrazine） was obtained. The results of gas sorption measurement show that complex2 has an enhanced CO2-framework affinity（initial CO2 adsorption enthalpies increase from 28.8 to 30.3 k J·mol-1）and higher CO2/CH4 selectivity compared with that of complex 1. The present work indicates that in-situ hydrolysis modification is highly potential for the enhancement of CO2 adsorption performance of tetrazine functionalized MOFs.