金属有机骨架(MOFs)材料具有比表面积大、可提供活性位点多等特点,采用溶胶-凝胶水热法合成了MOFs材料(MIL-100),掺杂金属元素后制备了用于超级电容器的改性MIL-100材料。通过X射线衍射仪、X射线光电子能谱仪、循环伏安法、计时电位法等对改性材料的结构、化学组成、碳和金属键之间的配位过程以及电化学性能进行表征和分析,通过亚甲基蓝吸附实验评价了改性材料的吸附性能。结果表明:改性材料吸附率提升了28.43%,掺杂V元素后改性材料比表面积增加292.5%,孔容提高了约2倍;掺杂摩尔分数50%的氧化石墨烯后,改性材料比电容提高了165%,达到417.08F/g,说明改性MIL-100具有良好的吸附性和导电性能。正是由于配位过程中几何结构的多样性使得改性MIL-100具有优异的吸附性能和导电性能,可作为超级电容器的电极材料。
Metal organic frameworks (MOFs) materials have the characteristics of large specific surface area and can provide abundant active sites.MOFs materials (MIL-100) were synthesized by sol-gel hydrothermal method,and modified MIL-100 materials for supercapacitors were prepared after doping metal elements.The structure,chemical composition,coordination process between carbon and metal bonds,and electrochemical properties of the modified materials were characterized and analyzed using X-ray diffractometer,X-ray photoelectron spectroscopy,cyclic voltammetry,chronopotentiometry,etc.The adsorption performance of the modified materials was evaluated through methylene blue adsorption experiments.The results showed that the adsorption rate of the modified material increased by 28.43%,and after doping with V element,the specific surface area of the modified material was increased to 292.5% of the original one,and the pore volume increased by about two times.After doping graphene oxide with 50% molar fraction,the specific capacitance of the modified material increased by 165%,reaching 417.08F/g,indicating that the modified MIL-100 had good adsorption and conductivity properties.It was precisely because of the diversity of geometric structures during the coordination process that the modified MIL-100 exhibited excellent adsorption and conductivity properties,making it a suitable electrode material for supercapacitors.
[1] 周健,谢林华,豆义波,等.MOFs基材料在超级电容器中的应用[J].化工进展,2016,35(9):2830-2838.
[2] 邢锦娟,孙平平,史发年.Co-MOFs材料在超级电容器方面的应用进展[J].材料科学与工程学报,2022,40(1):160-170.
[3] 王晓亮,张多,石雪梅,等.Co金属有机骨架模板制备NiCo水滑石/泡沫镍复合材料及电容性能[J].无机化学学报,2023,39(4):607-616.
[4] 庞欢.MOFs及MOFs复合材料在超级电容器中的应用[J].四川师范大学学报(自然科学版),2022,45(1):1-12;149.
[5] Yaghi O M,Li H.Hydrothermal synthesis of a metal-organic framework containing large rectangular channels[J].Journal of the American Chemical Society,1995,117(41):10401-10402.
[6] Lee D Y,Yoon S J,Shrestha N K,et al.Unusual energy sto-rage and charge retention in Co-based metal-organic-frameworks[J].Microporous and Mesoporous Materials,2012,153:163-165.
[7] Tan Y,Zhang W,Gao Y,et al.Facile synthesis and supercapacitive properties of Zr-metal organic frameworks (UiO-66)[J].RSC Advances,2015,5(23):17601-17605.
[8] Yang J,Zheng C,Xiong P,et al.Zn-doped Ni-MOF material with a high supercapacitive performance[J].Journal of Materials Chemistry A,2014,2(44):19005-19010.
[9] 靳彦岭,耿家慧,任鹏刚,等.MOF及其衍生物复合MXene在储能领域的研究进展[J].化工新型材料,2023,51(9):85-90.
[10] 高春,张松涛,庞欢.金属-有机骨架/石墨烯基复合材料在电化学领域的应用[J].化学试剂,2022,44(10):1482-1490.
[11] Liu W,Wang K,Li C,et al.Boosting solid-state flexible supercapacitors by employing tailored hierarchical carbon electrodes and a high-voltage organic gel electrolyte[J].Journal of Materials Chemistry A,2018,6(48):24979-24987.
[12] Li L,Chen R,Gong Y,et al.Assembling laminated films via the synchronous reduction of graphene oxide and formation of copper-based metal organic frameworks[J].Journal of Materials Chemistry A,2019,7(1):107-111.
[13] Azadfalah M,Sedghi A,Hosseini H.Synthesis of nano-flower metal-organic framework/graphene composites as a high-performance electrode material for supercapacitors[J].Journal of Electronic Materials,2019,48(11):7011-7024.
[14] Li D,Müller M B,Gilje S,et al.Processable aqueous dispersions of graphene nanosheets[J].Nature Nanotechnology,2008,3(2):101-105.
[15] Yang X,He Y S,Jiang G,et al.High voltage supercapacitors using hydrated graphene film in a neutral aqueous electrolyte[J].Electrochemistry Communications,2011,13(11):1166-1169.
[16] 刘洋,艾常春,胡意,等.碳包覆金属氧化物作为超级电容器电极材料的研究进展[J].化工进展,2013,32(8):1849-1854.
[17] 黄均艳,王小丽,黄美英,等.乙酸锌活化制备柚子皮衍生活性碳及其电化学和吸附性能研究[J].硅酸盐通报,2020,39(7):2335-2342.
[18] 张义东.基于金属有机骨架的超级电容器电极材料的制备与性能研究[D].南京:东南大学,2017.
[19] 顾波,秦志宏,杨小芹,等.基于MOFs超级电容器电极材料研究进展[J].功能材料,2021,52(9):9043-9050.
[20] 姚江峰,相文峰,孙睿,等.Ni-Al层状双金属氢氧化物制备及其超级电容特性[J].微纳电子技术,2019,56(4):274-278.
[21] Cao J,He P,Brent J R,et al.Supercapacitor electrodes from the in situ reaction between two-dimensional sheets of black phosphorus and graphene oxide[J].ACS Applied Materials & Interfaces,2018,10(12):10330-10338.
[22] 陈南,庞宁,童新,等.石墨烯量子点修饰的石墨毡电极的电容性能[J].微纳电子技术,2020,57(2):119-124.
[23] 赵泽铭,吴昌桐,王浅云,等.钒酸镍/生物质碳复合材料的制备及其作为超级电容器性能的研究[J].化工新型材料,2023,51(S2):214-219.
[24] Chen Y,Long X,Zou S,et al.Carbon nanotubes@Ni3V2O8@NiCo2S4 nanosheets on Ni foam as a cathode for high-performance aqueous supercapacitors[J].Journal of Energy Sto-rage,2021,44:103496.
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