用于SO_(2)高效脱除的富氮有机多孔聚合物合成与表征  

Synthesis and characterization of N-rich porous organic polymer for efficient SO_(2) capture

作　　者：张中辉 马和平 杨伯伦[1] ZHANG Zhonghui;MA Heping;YANG Bolun(School of Chemical Engineering and Technology,Xi¢an Jiaotong University,Xi¢an 710049,China)

机构地区：[1]西安交通大学化学工程与技术学院,陕西西安710049

出　　处：《高校化学工程学报》2023年第4期649-658,共10页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(22178280)。

摘　　要：为合成用于高效脱除烟道气SO_(2)的有机多孔聚合物席夫碱-1(SNW-1),提出使用环丁砜和二甲基砜混合溶剂,并通过调节其比例实现对SNW-1孔径大小与其吸附性能的调控。实验结果表明,溶剂配比调节不改变SNW-1的化学组成和连接结构,但影响吸附剂孔径大小,进而影响SO_(2)的吸附容量和选择性。所合成的4种SNW-1中,孔径小且比表面积大的SNW-1-3的SO_(2)吸附量最大,且SO_(2)/CO_(2)的选择性高达124.8~159.9,优于大多数有机多孔聚合物材料。此外,物理吸附的过程属性,使SNW-1具有稳定的重复使用性。密度泛函理论(DFT)计算表明,SO_(2)的吸附位点为SNW-1中的三嗪环N原子和亚氨基上的氢原子,而CO_(2)的吸附位点仅为亚氨基上的氢原子。N原子和S(SO_(2))原子之间的偶极-偶极相互作用以及O(SO_(2))和H(─NH─)之间氢键相互协同作用使得SO_(2)与SNW-1相互作用的结合能高于CO_(2)与SNW-1相互作用的结合能,进而使SO_(2)相对CO_(2)在SNW-1上呈现高的吸附选择性。A method of using sulfolane and dimethylsulfone as the mixed solvents with different ratios in the synthesis of porous organic polymer(POP),Schiff-base network-1(SNW-1)was proposed to modulate pore size and adsorption performance of SNW-1 for efficient SO_(2) removal from flue gas.The experimental results showed that solvent ratio did not change the chemical composition and bond structure of SNW-1,but affected its pore size,which in turn affected the adsorption capacity and selectivity of SO_(2).Among the four types of SNW-1 synthesized,SNW-1-3 with small pore size and large specific surface area shows the highest SO_(2) adsorption capacity,and the SO_(2)/CO_(2) selectivity is 124.8-159.9,which is superior to most POP materials.In addition,SNW-1 has stable reusability due to its physical adsorption process.Density functional theory(DFT)calculation reveals that SO_(2) binding sites are N atoms of triazine rings and hydrogen atoms of imino groups,while CO_(2) binding sites are only hydrogen atoms of imino groups.Moreover,the synergistic effect of dipole-dipole interaction between N atom and S(SO_(2))atom,and hydrogen bond interaction between O(SO_(2))and H(─NH─)makes the binding energy of SO_(2) interacting with SNW-1 higher than that of CO_(2),thus enhancing the adsorption selectivity for SO_(2) on SNW-1 relative to CO_(2).

关 键 词：有机多孔聚合物 吸附剂 二氧化硫 选择性 稳定性 

分 类 号：TQ465.92[化学工程—制药化工]