基于多氮唑配体制备金属有机框架用于乙炔吸附分离  

Synthesis of metal organic frameworks based on multiazole ligands for adsorption and separation of acetylene

作　　者：王恺华 陈杨[1,2] 王毅 陈久弘 李晋平 李立博[1,2] Kaihua Wang;Yang Chen;Yi Wang;Jiuhong Chen;Jinping Li;Libo Li(College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,China;Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization,Taiyuan 030024,China)

机构地区：[1]太原理工大学化学工程与技术学院,太原030024 [2]气体能源高效清洁利用山西省重点实验室,太原030024

出　　处：《科学通报》2024年第16期2278-2287,共10页Chinese Science Bulletin

基　　金：国家自然科学基金(22278287);山西省基础研究计划(202203021224005);山西省回国留学人员科研资助项目(2021-053)资助。

摘　　要：电石法制备的乙炔(C_(2)H_(2))中会混入氮气、氧气和二氧化碳等杂质组分,为获得高纯度乙炔,相应的纯化分离研究十分必要.金属有机框架(metal organic framework,MOF)材料是一种具有超高孔隙率和易于功能化的多孔材料.基于特殊的孔腔特点,该类材料在气体吸附分离领域展现出优异的性能.本研究以一水合乙酸铜和5-(4-吡啶基)-1H-四唑为原料,制备了一种新的MOF材料——Cu(Hptz),命名为TYUT-15.该材料基于特殊的方形孔腔结构和多氮吸附位点触发了孔中乙炔分子间的偶极矩协同吸附,在主客体的共同作用下极大地提高了乙炔的吸附容量.采用单晶X射线衍射、同步热重分析、单组分气体吸附及混合气体穿透测试等对样品的结构及气体吸附分离性能进行了表征.分离实验表明,该材料可以从C_(2)H_(2)/CO_(2)/N_(2)/O_(2)四组分混合气体中直接捕集C_(2)H_(2).Acetylene(C_(2)H_(2))production using the calcium carbide method produces several impurities,such as nitrogen,oxygen,and carbon dioxide.To obtain high-purity acetylene,research regarding the corresponding purification and separation is vital.Metal organic framework(MOF)materials have ultrahigh porosity and easy functionalization.Based on the specific characteristics of their pores,these materials typically possess large surface areas,abundant functional sites,and flexible and tunable pore structures.Thus,these materials demonstrate excellent performance in gas adsorption and separation.This study is based on MOF material construction using multiple nitrogen-containing imidazole ligands.A novel MOF material(Cu(Hptz)),named TYUT-15,was successfully synthesized using copper acetate monohydrate and 5-(4-pyridyl)-1H-tetrazole as raw materials.TYUT-15 has a basic structural unit comprising five-coordinated copper atoms linked to three different ligand units and two bridging oxygen atoms.Moreover,these units form a one-dimensional square channel structure with pore openings of approximately 6.0A×6.0A and have a BET(Brunauer,Emmett and Teller)specific surface area of approximately 416 m^(2)/g.Considering the unique square-shaped pore structures and multiple nitrogen adsorption sites,TYUT-15 triggers the dipole moment synergistic adsorption among acetylene molecules in the pores,and it improves the adsorption capacity of acetylene under the joint action of host and guest.Single-crystal X-ray diffraction,thermogravimetric analysis,single-component gas adsorption,and a breakthrough test were performed to characterize the sample structure and gas adsorption/separation performance.The results indicate that TYUT-15 is structurally stable and possesses numerous microporous structures.The single-component gas adsorption test reveals that this material has a high C_(2)H_(2)adsorption capacity.The desorption isotherm of C_(2)H_(2)exhibits certain hysteresis compared to the desorption isotherms of other gases,indicating a stronger

关 键 词：乙炔 二氧化碳 金属有机框架 混合气体分离 

分 类 号：O641.4[理学—物理化学] TQ028.15[理学—化学]