锆基金属有机骨架材料用于氨吸附性能的研究  

Research on Zr-based metal-organic frameworks for NH_(3) adsorption

作　　者：王毅 熊启钊 陈杨[1,2] 杨江峰 李立博 李晋平[1,2,3] WANG Yi;XIONG Qizhao;CHEN Yang;YANG Jiangfeng;LI Libo;LI Jinping(College of Chemistry and Chemical Engineering,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization,Taiyuan 030024,Shanxi,China;Key Laboratory of Coal Science and Technology,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China)

机构地区：[1]太原理工大学化学化工学院,山西太原030024 [2]气体能源高效清洁利用山西省重点实验室,山西太原030024 [3]太原理工大学煤科学与技术重点实验室,山西太原030024

出　　处：《化工学报》2022年第4期1772-1780,共9页CIESC Journal

基　　金：国家自然科学基金项目(22090062,21908155);山西省回国留学人员科研资助项目(2021-053)。

摘　　要：近年来,金属有机骨架材料(MOF)在气体吸附和储存领域得到了迅速发展,但由于结构的不稳定性,其在强腐蚀性气体氨(NH_(3))的吸附方面并不令人满意。考虑到NH_(3)是唯一的无碳排放的氢能源载体,开发高效的储氨技术来载氢是有效的降低二氧化碳排放的手段。利用MOF材料具有的高比表面积和结构多样的特性,在NH_(3)的吸附和储存方面具有广阔的应用前景。而NH_(3)具有孤对电子,会攻击金属与配体之间形成的配位键,使MOF材料的结构遭到破坏。锆基金属有机骨架材料是公认结构稳定性较好的MOF材料,但其是否能胜任干燥NH_(3)及含水条件下的稳定性仍未深入考察,由此需探究该系列材料在NH_(3)吸附领域的适用性。在此,通过实验和计算模拟研究锆基系列的金属有机骨架UiO-66、NU-1000、MOF-801和MOF-808的结构特征、稳定性和NH_(3)吸附性能。结果表明,UiO-66、NU-1000和MOF-808在纯NH_(3)环境下的稳定性较好,并且显示出高吸附量且可循环的氨吸附性能(13.04、6.38、9.65 mmol/g)。受限于水和氨对结构的协同破坏作用,NU-1000和MOF-801的结构均不能维持,而UiO-66和MOF-808的结构非常稳定,无论在干燥NH_(3)环境及含水NH_(3)环境下均能胜任而应用于NH_(3)吸附和储存。Metal-organic framework(MOF)has been developed rapidly in the fields of gas adsorption and storage in recent years,but they are unsatisfactory in the adsorption of strong corrosive gas ammonia(NH_(3))due to structural instability.Considering NH_(3) is the only carbon-free chemical energy carrier,developing efficient ammonia storage technology to carry hydrogen is an effective technology to reduce carbon dioxide emissions.MOFs exhibit great prospects for adsorption and storage of NH_(3) due to their high surface area and structural diversity advantages.NH_(3) has a lone pair of electrons,which will attack the coordination bond formed between the metal ion and the ligand,resulting in the structural destruction of MOFs.Herein,the structural characteristics,stability,and NH_(3) adsorption properties of Zr-based metal-organic frameworks,including UiO-66,NU-1000,MOF-801,and MOF-808,were investigated by experiments and computational simulations.The results showed that UiO-66 has excellent structural stability in NH_(3) adsorption with a high uptake of 13.04,6.38 and 9.65 mmol/g.However,Due to the limited stability and low adsorption capacity,NU-1000 and MOF-801 are not suitable for ammonia adsorption under the humid environment.Conversely,the structure of UiO-66 and MOF-808 is very stable,which can be used in NH_(3) adsorption and storage applications both in dry and humid NH_(3) environments.

关 键 词：金属有机骨架材料 锆基系列 氨吸附 稳定性 循环性 

分 类 号：TQ536.9[化学工程—煤化学工程]