孔道修饰MOF-808混合基质膜制备及其CO2分离性能
作者:张萌萌,郭翔宇,黄宏亮,仲崇立
单位: 天津工业大学省部共建分离膜与膜过程国家重点实验室,化学与化工学院,天津 300387
关键词: 金属-有机骨架材料;混合基质膜;CO2分离;后合成修饰
分类号: TQ 028.8
出版年,卷(期):页码: 2021,41(3):1-8

摘要:
 利用MOF-808结构中含有易于被取代的甲酸这一特性,选用一种结构中含有丰富含氮基团的羧酸分子,L-组氨酸,对微波法合成的MOF-808纳米颗粒进行了后合成改性修饰,在其孔道中引入了对CO2具有较高亲和力的含氮官能团。进一步采用孔道修饰后的MOF-808(MOF-808-His)与6FDA-DAM复合制备了一种新型混合基质膜,结合气体分离性能测试与膜的微观结构表征系统地分析了孔道修饰对MOF-808/6FDA-DAM混合基质膜CO2分离性能的影响。结果表明,MOF-808孔道内含氮官能团的引入能够明显改善其对CO2的选择性吸附能力,进而提高混合基质膜的CO2/CH4分离性能。当MOF-808-His质量分数为10%时,混合基质膜的CO2渗透通量为764 Barrer,CO2/CH4分离因子为32.4,比纯6FDA-DAM膜分别提高了104%和35%,超过了CO2/CH4分离的Robeson上限。
 The formic acid molecules coordinated to Zr-O clusters in MOF-808 can be easily substituted through post-synthetic modification, providing an efficient way for the engineering of its pore environment. Here, L-histidine (His), a carboxylic acid molecule with rich nitrogen-containing groups, was selected to modify the MOF-808 nanoparticles synthesized through microwave method in this work. CO2 adsorption isotherms indicate that introducing His with nitrogen-containing functional groups into the pore channels of MOF-808 can improve its CO2 affinity and CO2/CH4 separation. Furthermore, a new type of mixed matrix membranes (MMMs) was prepared through the combination of MOF-808-His and 6FDA-DAM. The effect of pore modification on CO2 separation performance of MOF-808/6FDA-DAM MMMs was systematically analyzed by gas separation performance tests and membrane microstructure characterization. The results show that the introduction of His in MOF-808 can significantly improve its selective adsorption capacity towards CO2, and thus improve the CO2/CH4 separation performance of the MMMs. When 10 wt% MOF-808-His nanoparticles were incorporated, the CO2 permeability of the membrane was 764 Barrer, and the CO2/CH4 separation factor was 32.4, which was 104% and 35% respectively higher than that of the pure 6FDA-DAM membrane, exceeding the Robeson upper bound for CO2/CH4 separation.

基金项目:
国家自然科学基金项目(21878229, 22008179);天津市科技计划项目(19PTSYJC00020)

作者简介:
第一作者:张萌萌(1994—),女,河北邢台人,硕士研究生,主要研究方向为MOF基复合膜的制备

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