花状二维铜基卟啉气凝胶制备与气体吸附与分离性能研究  

Synthesis of two-dimensional flower-like Cu-TCPP aerogel for gas adsorption and separation

作　　者：张琦[1,2] 梁贺 范宇莹[1,2] 刘锐平 简美鹏 胡承志[2] 肖亚楠 ZHANG Qi;LIANG He;FAN Yuying;LIU Ruiping;JIAN Meipeng;HU Chengzhi;XIAO Yanan(School of Environment,Northeast Normal University,Changchun 130117;State Key Laboratory of Environmental Aquatic Chemistry,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences,Beijing 100085;Department of Chemical Engineering,Monash University,Australia,VIC 3800;Center for Water and Ecology,State Key Joint Laboratory of Environment Simulation and Pollution Control,School of Environment,Tsinghua University,Beijing 100084;Tongliao City Water Supply Co.,Ltd.,Inner Mongolia,Tongliao 028000)

机构地区：[1]东北师范大学环境工程系,长春130117 [2]中国科学院生态环境研究中心,中国科学院饮用水科学与技术重点实验室,北京100085 [3]蒙纳士大学化学工程系,澳大利亚维多利亚州3800 [4]清华大学环境学院,清华大学水质与水生态研究中心,北京100084 [5]通辽市自来水有限责任公司,内蒙古,通辽028000

出　　处：《环境科学学报》2020年第8期2977-2985,共9页Acta Scientiae Circumstantiae

基　　金：港澳及海外青年学者合作研究基金(No.51729801);国家自然科学基金项目(No.5181001028,51438011)。

摘　　要：本研究针对混合气体选择性分离和二氧化碳捕获等问题,在小分子聚乙烯吡咯烷酮(PVP)和三氟乙酸的作用下控制纵向生长,通过金属铜离子与卟啉配体的自组装形成花状二维金属有机框架材料(2D Flower-like Cu-TCPP),进一步冷冻干燥获得低密度纯2D Flower-like Cu-TCPP气凝胶.元素含量分析显示,2D Flower-like Cu-TCPP可以充分暴露金属活性位点,克服传统三维纳米材料内部位点难以被利用的缺点;比表面积(BET)分析显示,2D Flower-like Cu-TCPP比表面积为321.92 m^2·g^-1,主要孔道尺寸分布在1.8 nm左右.由于充分暴露出金属活性位点Cu-O-Cu,对CO2、N2和CH4表现出优异的吸附分离性能.根据Langmuir吸附等温线拟合得到,CO2、CH4和N2的最大吸附量分别为7.357、 2.852、 2.002 mmol·g^-1.CO2/N2、CO2/CH4和CH4/N2的最大分离系数分别为9.86、2.52和4.00.2D Flower-like Cu-TCPP在碳捕获、混合气体选择性分离中具有较好的应用前景.This study focuses on the carbon dioxide capture and selective separation of mixture gases by using a flowered two-dimensional metal-organic framework, i.e., 2D Flower-like Cu-TCPP. By the self-assembling of Cu and porphyrin ligand with the surfactant assistant, the pure 2D Flower-like Cu-TCPP was obtained and the corresponding aerogel was also prepared via a freeze drying process. 2D Flower-like Cu-TCPP exhibits the richer active sites, owning to the highly exposed surface, in contrast to 3D metal-organic framework. The as-synthesized Flower-like Cu-TCPP aerogel exhibits the high BET surface area of 321.92 m^2·g^-1, and the main pore size distribution of Flower-like Cu-TCPP is around 1.8 nm. Based on the experimental results, 2D Flower-like Cu-TCPP shows the favorable adsorption performance towards CO2,CH4, and N2 with the maximum adsorption capacity of 7.357, 2.852, 2.002 mmol·g^-1,respectively. Accordingly, the separation factors of CO2/N2,CO2/CH4,and CH4/N2 were determined to be 9.86, 2.52 and 4.00. 2D Flower-like Cu-TCPP is potentially valuable for the CO2 capturing and the selective separation of different gases mixture.

关 键 词：二维花状Cu-TCPP 气凝胶 小分子气体 吸附 分离系数 

分 类 号：X701[环境科学与工程—环境工程]