Pore surface fluorination and PDMS deposition within commercially viable metal-organic framework for efficient C_(2)H_(2)/CO_(2) separation  

可商业化的金属有机框架的孔表面氟化和PDMS复合用于高湿度下C_(2)H_(2)/CO_(2)高效分离

作　　者：Hongyan Liu Xiaokang Wang Fei Gao Yutong Wang Meng Sun Deyu Xie Wenmiao Chen Zixi Kang Rongming Wang Weidong Fan Daofeng Sun 刘红岩;王小康;高飞;王雨桐;孙萌;谢德禹;陈文淼;康子曦;王荣明;范卫东;孙道峰(State Key Laboratory of Heavy Oil Processing,School of Materials Science and Engineering,China University of Petroleum(East China),Qingdao 266580,China)

机构地区：[1]State Key Laboratory of Heavy Oil Processing,School of Materials Science and Engineering,China University of Petroleum(East China),Qingdao 266580,China

出　　处：《Science China Materials》2024年第11期3692-3699,共8页中国科学（材料科学）（英文版）

基　　金：supported by the Key Basic Research Projects of Natural Science Foundation of Shandong Province(ZR2023ZD40);the Key Research and Development Projects of Shandong Province(2023CXGC010315);the National Natural Science Foundation of China(22275210 and 22201305);the Outstanding Youth Science Fund Projects of Shandong Province(2022HWYQ-070);Taishan Scholar Foundation(tsqnz20221123)。

摘　　要：A Removing CO_(2)impurities from C_(2)H_(2)/CO_(2)mixtures is an essential process for producing high-purity C_(2)H_(2)under high humidity.High-stability and low-cost metalorganic frameworks(MOFs)have great potential in C_(2)H_(2)/CO_(2)industrial separation.However,due to the complementary adsorption of H_(2)O and CO_(2),water vapor has a negative impact on the implementation of C_(2)H_(2)purification.Herein,we propose a synergistic strategy of pore surface functionalization and polydimethylsiloxane(PDMS)deposition to avoid the influence of water vapor while improving C_(2)H_(2)/CO_(2)separation performance.A commercially available metal-organic framework(ALP-MOF-1)was used as a template to functionalize its pore surface with CH3,Br,and F.The optimized material ALP-MOF-1(F)exhibits the highest C_(2)H_(2)uptake(117.78 cm3/g at 298 K and 106 Pa)and C_(2)H_(2)/CO_(2)uptake ratio(3.1)among ALP-MOF systems.Computational simulations show that the well-matched pore space and the significant electronegativity and polarizability of the fluorine groups on the pore surface jointly enhance the framework-C_(2)H_(2)interaction.Furthermore,the deposition of PDMS on ALP-MOF-1 and ALP-MOF-1(F)significantly improves their C_(2)H_(2)/CO_(2)separation stability under 80%humidity conditions.从C_(2)H_(2)/CO_(2)混合物中去除CO_(2)杂质是在高湿度下生产高纯度C_(2)H_(2)的重要过程.高稳定性和低成本的金属有机框架(MOFs)在C_(2)H_(2)/CO_(2)工业分离中具有巨大的应用潜力.然而,由于H_(2)O和CO_(2)的竞争吸附,水蒸气会影响C_(2)H_(2)的吸附.因此,我们提出了一种孔表面功能化和聚二甲基硅氧烷(PDMS)沉积的协同策略,以避免水蒸气的影响,同时提高C_(2)H_(2)/CO_(2)分离性能.用可商业化的金属有机骨架(ALP-MOF-1)作为模板,用CH_(3)、Br和F对其孔表面进行官能化,最佳材料ALPMOF-1(F)在298 K和10~6 Pa下表现出最高的C_(2)H_(2)吸附量(117.78 cm~3/g)和3.1 C_(2)H_(2)/CO_(2)吸附比.模拟计算表明,ALP-MOF-1(F)孔空间与C_(2)H_(2)匹配良好,并且氟基团显著的电负性和极化率增强了骨架与C_(2)H_(2)的相互作用.此外,PDMS在ALP-MOF-1上的沉积(ALP-MOF-1(F))显著提高了其在80%湿度条件下的C_(2)H_(2)/CO_(2)分离稳定性.

关 键 词：metal-organic framework C_(2)H_(2)/CO_(2) separation fluorination strategy PDMS coating 

分 类 号：TQ221.242[化学工程—有机化工] O647.3[理学—物理化学]