金属有机骨架化合物MIL-101负载纳米Ni的制备及储氢性能
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摘要
采用2-甲基咪唑代替HF酸以溶剂热法成功制备了纯度较高的金属有机骨架化合物MIL-101,利用过量浸渍法结合液相还原法成功负载了Ni,制备出Ni/MIL-101复合材料。通过XRD、SEM、TEM、BET、TG对所得MIL-101、Ni/MIL-101复合材料的结构、形貌、比表面积孔径及热稳定性进行表征,对MIL-101、Ni/MIL-101复合材料的氢扩散系数、吸氢形成焓进行测定计算,考查其储氢能力。结果表明,该方法成功制备了Ni/MIL-101复合材料,该产物是一种两类孔结构的金属骨架化合物,Ni的负载可降低Ni/MIL-101复合材料的吸氢形成焓,Ni/MIL-101复合材料的氢扩散系数达到7.6373×10-7 cm/s,提高了MIL-101的储氢能力。
The high purity metal organic frameworks MIL-101 was prepared by the solvent hot method using2-methyl imidazole instead of HF acid in this experiment.Ni/MIL101 composite was prepared from the successful load of Ni by the method of excessive impregnation and liquid phase reduction.The product structure,morphology,specific surface area and pore size and thermal stability were characterized via XRD,SEM,BET,TG,FIRT.The hydrogen diffusion coefficient and hydrogen absorption enthalpy of MIL-101 and Ni/MIL-101 composite were measured to investigate the hydrogen storage capacity.The results show that Ni/MIL-101 composite is successfully prepared by this method.The product is a metal skeleton compound with two kinds of pore structure,and the load of Ni can reduce the hydrogen absorption enthalpy of Ni/MIL-101 composite,and the hydrogen diffusion coefficient of Ni/MIL-101 composite reaches 7.6373×10-7 cm/s,which improves the hydrogen storage capacity of MIL-101.
The high purity metal organic frameworks MIL-101 was prepared by the solvent hot method using2-methyl imidazole instead of HF acid in this experiment.Ni/MIL101 composite was prepared from the successful load of Ni by the method of excessive impregnation and liquid phase reduction.The product structure,morphology,specific surface area and pore size and thermal stability were characterized via XRD,SEM,BET,TG,FIRT.The hydrogen diffusion coefficient and hydrogen absorption enthalpy of MIL-101 and Ni/MIL-101 composite were measured to investigate the hydrogen storage capacity.The results show that Ni/MIL-101 composite is successfully prepared by this method.The product is a metal skeleton compound with two kinds of pore structure,and the load of Ni can reduce the hydrogen absorption enthalpy of Ni/MIL-101 composite,and the hydrogen diffusion coefficient of Ni/MIL-101 composite reaches 7.6373×10-7 cm/s,which improves the hydrogen storage capacity of MIL-101.
引文
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[3]陈恒,程少云,苑兴洲,等.咪唑衍生物辅助合成金属有机骨架MIL-101及CO2吸附性能[J].化工进展,2014,33(7):1808-1815.CHEN H,CHENG S Y,YUAN X Z,et al.Synthesis and CO2adsorption property of metal-organic framework MIL-101by an imidazole-assistant route[J].Chemical Industry and Engineering Progress,2014,33(7):1808-1815(in Chinese).
[4]王涛.金属有机骨架负载TiO2复合催化剂的制备及性能研究[D].上海:华东理工大学,2015.WANG T.Preparation and property research of composite catalyst-metal-organic frameworks loading with TiO2[D].Shanghai:East China University of Science and Technology,2015(in Chinese).
[5]黄思思,夏启斌,朱宝璋,等.微波辐射合成MIL-101多孔材料及其对苯的吸附热[J].功能材料,2010,41(6):961-963.HUANG S S,XIA Q B,ZHU B Z,et al.Microwave synthesis of MIL-101and its adsorption heat of benzene[J].Function Materials,2010,41(6):961-963(in Chinese).
[6]高志强.MOFs负载钯材料的制备及其Ullmann反应性能研究[D].广州:华南理工大学,2013.GAO Z Q.Ullmann reaction catalyzed by palladium supported on metal-organic frameworks[D].Guangzhou:South China University of Technology,2013(in Chinese).
[7]刘宏利.MIL-101负载金属纳米催化剂的制备及其绿色催化研究[D].广州:华南理工大学,2013.LIU H L.Synthesis of metal nanocatalysts supported on MIL-101and their applications in green synthesis[D].Guangzhou:South China University of Technology,2013(in Chinese).
[8]陈玉贞.基于金属-有机骨架纳米复合材料的设计合成与催化性能研究[D].合肥:中国科学技术大学,2016.CHEN Y Z.Design,synthesis and catalytic applications of metal-organic frameworks-based nanocomposites[D].Hefei:University of Science and Technology of China,2016(in Chinese).
[9]王天琦,肖国勇,鲁云华,等.镧系金属有机骨架/聚酰亚胺复合材料的制备及其性能[J].复合材料学报,2018,35(11),DOI:10.13801/j.cnki.fhclxb.20180126.002.WANG T Q,XIAO G Y,LU Y H,et al.Preparation and properties of lanthanide metal-organic frameworks/polyimide composites[J].Acta Materiae Compositae Sinica,2018,35(11),DOI:10.13801/j.cnki.fhclxb.20180126.002(in Chinese).
[10]张春梅.MIL-101系列材料的合成及性能研究[D].哈尔滨:哈尔滨工业大学,2014.ZHANG C M.Synthesis and performance study of MIL-101materials[D].Harbin:Harbin Institute of Technology,2014(in Chinese).
[11]刘菲,苏云星,王仲明,等.菲克定律在氢扩散系数研究中的应用[J].广西大学学报(自然科学版),2010,35(5):841-846.LIU F,SU Y X,WANG Z M,et al.Appication of Fick's law in measurement of hydrogen diffusion coefficient by electrochemical method[J].Journal of Guangxi University(Natural Science Edition),2010,35(5):841-846(in Chinese).
[12]刁红敏,任素贞.沸石咪唑酯骨架结构材料合成及性能研究进展[J].化工进展,2010,29(9):1655-1658.DIAO H M,REN S Z.Progress in synthesis and property of zeolitic imidazolate frameworks[J].Chemical Industry and Engineering Progress,2010,29(9):1655-1658(in Chinese).
[13]LIU F,XU Z J,WANG Z M,et al.Structures and mechanical properties of Nb-Mo-Co(Ru)solid solutions for hydrogen permeation[J].Journal of Alloys and Compounds,2018,756:26-32.
[14]刘颖雅,张箭,曾巨澜,等.负载镍的金属有机骨架化合物在温和条件下的储氢性能[J].催化学报,2008,29(7):655-659.LIU Y Y,ZHANG J,ZENG J L,et al.Hydrogen storage capacity of nickel supported on a metal-organic framework compound under mild conditions[J].Chinese Journal of Catalysis,2008,29(7):655-659(in Chinese).
[15]BROOM D P.Hydrogen storage materials:The characterization of their storage properties[M].London:Springer,2011.