微波制备MIL-101(Cr)多孔材料及其储氢性能  

Microwave Preparation of MIL-101(Cr)Porous Materials and Their Hydrogen Storage Properties

作　　者：孙彦丽 石恒杰 王瑞琪 李娴 吴建波[2] 白红存[2] 张慧 SUN Yanli;SHI Hengjie;WANG Ruiqi;LI Xian;WU Jianbo;BAI Hongcun;ZHANG Hui(Institute of Systems Engineering,AMS,PLA,Beijing 102300,China;State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering,College of Chemistry and Chemical Engineering,Ningxia University,Yinchuan 750021,China)

机构地区：[1]军事科学院系统工程研究院,北京102300 [2]宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室,宁夏银川750021

出　　处：《石油学报(石油加工)》2025年第2期507-517,共11页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：基础加强计划技术领域基金项目(2021-JCJQ-JJ-0434-02);国家自然科学基金项目(U21A20325,52367023);中央引导地方发展专项(2022FRD05035);宁夏自然科学基金优秀青年项目(2023AAC05026)资助。

摘　　要：以Cr^(3+)为金属离子、对苯二甲酸(H_(2)BDC)为配体,采用微波水热技术合成MIL-101(Cr)材料,探索传统加热方式及微波法对MIL-101(Cr)结构的影响。基于微波水热法,考察晶化温度、时间、氢氟酸调节剂对MIL-101(Cr)结构、形态的调控,研究了MIL-101(Cr)材料对氢气的吸附情况,并采用XRD、SEM和N_(2)吸附-脱附等手段对其结构进行表征。结果表明,当Cr^(3+)/H_(2)BDC/氢氟酸摩尔比为1/1/0.2、晶化温度483 K和时间1.0 h时,制备的MIL-101(Cr)材料结晶度最优,并呈现出规整的八面体形状,其比表面积高达3536 m^(2)/g。在温度77 K、压力0~5 MPa的条件下,MIL-101(Cr)材料的氢气吸附量达到5.79%(质量分数)。此外,对MW-5储氢的吸附动力学过程进行探究,通过LDF模型计算得到其晶内扩散系数为9.62×10^(-17)m^(2)/s,说明氢分子在MW-5材料中有较快的扩散率。MIL-101(Cr)was successfully synthesized by microwave hydrothermal technology using Cr^(3+)as metal ion and terephthalic acid(H_(2)BDC)as ligand,aiming to explore the effect of traditional heating methods and microwave methods on the structure of MIL-101(Cr).Based on the microwave hydrothermal method,the effects of crystallization temperature and time,as well as hydrogen fluoride regulators on the structure and morphology of MIL-101(Cr)were investigated.Moreover,the adsorption of hydrogen by MIL-101(Cr)material was studied,and the structure was characterized by XRD,SEM,and N_(2)adsorption-desorption experiments.The results show that when the molar ratio of Cr^(3+)/H_(2)BDC/hydrofluoric acid is 1/1/0.2,the prepared MIL-101(Cr)material crystallized at 483 K for 1.0 h has the best crystallinity and exhibits a regular octahedral shape,with a specific surface area of up to 3536 m^(2)/g.Under the conditions of temperature 77 K and pressure 0—5 MPa,the hydrogen adsorption capacity of MIL-101(Cr)can reach 5.79%(mass fraction).In addition,the adsorption kinetics of hydrogen storage in MW-5 were explored,and its intragranular diffusion coefficient of 9.62×10^(-17)m^(2)/s was calculated by LDF model,indicating that hydrogen molecules have a faster diffusion rate in MW-5 materials.

关 键 词：微波合成 金属有机框架 MIL-101(Cr)材料 储氢 吸附动力学 

分 类 号：TQ028[化学工程]