以油酸表面处理后的纳米四氧化三铁为添加剂,制备了聚苯胺/四氧化三铁复合物。将该复合物在氮气气氛下于500℃炭化、800～1300℃进行石墨化处理,得到介孔炭材料。使用扫描电子显微镜、透射电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪和等温吸脱附仪等对介孔炭材料进行表征,探讨了石墨化温度对材料形貌和结构的影响规律。研究表明:石墨化温度从800℃到1000℃,复合物转变为不规则颗粒状的多孔炭,具有不规则局部石墨化的碳层结构;石墨化温度为1200℃时,材料中存在碳化铁(Fe3C),出现大量开口的球状物,大小约600nm,壁为石墨化的碳层,壁厚约为50nm;石墨化温度为1300℃时,则得到空心炭球,直径1～2μm,球壁厚约为20nm。另外,通过改变石墨化温度可以调控介孔炭材料的孔结构和比表面积,平均孔径为5.9～19.9nm,比表面积为62.6～677.8m2/g。循环伏安法测试表明,经过800℃石墨化处理的介孔炭材料比容量最高,以0.5mol/L硫酸为电解液,扫描速率为5mV/s时,介孔炭材料比容量为161F/g。
Mesoporous carbon has extensive application in many fields,such as second-batteries,supercapacitors,fuel cells,etc.It is the hottest project to obtain mesoporous carbon with certain morphology or components in order to meet particular needs for a long time.The composite of polyaniline and ferroferric oxide was manufactured through polymerization of aniline in suspension of ferroferric oxide with its surface modified by oleic acid.A series of mesoporous carbon was obtained after the composite being carbonized at 500℃,graphitized at the temperature from 800℃ to 1300℃ under nitrogen atmosphere in a tube oven.SEM,TEM,XRD,FT-IR and isothermal desorption apparatus were adopted to characterize as-prepared carbon.Effect of graphitic temperature on morphology and components of the carbon was explored in detail.The research results shown that graphitic temperature of the composite was the key factor to structure and properties of as-obtained carbon.For example,it shown particles possessing irregular shapes,which was with partly graphitic carbon layers,when graphitic temperature was from 800℃ to 1000℃.Some spheres with open mouths,liked bows,were found in samples when the composite being treated at 1200℃.Diameter of the bows was about 600nm.The wall of bows was conformed by graphitic carbon layers,with about 50nm in thickness.Fe3C component was also found in these samples.However,when the graphitic temperature was at 1300℃,only some hollow spheres were found in as-obtained carbon.Diameter of these hollow spheres was about from 1μm to 2μm.Wall of the hollow spheres was about 20nm in thickness,which was formed by highly graphitic carbon-layers.By changing graphitic temperature of the composite,BJH adsorption average pore diameter and BET specific surface area of the mesoporous carbon can be easily adjusted in the range from 5.9nm to 19.9nm,and from 62.6m2/g to 677.8m2/g,respectively.Among all these as-prepared mesoporous carbon,the sample from being graphitized at 800℃ had the best electrochemical performance,whose specific capacitance was 161F/g in 0.5mol/L sulfuric acid aqueous solution,at the scan rate of 5mV/s,tested by cyclic voltammetry technics.
[1] 刘红缨,王双宝,朱英,等.水热法制备聚苯胺及其铁氧化物纳米复合材料[J].高等学校化学学报,2013,34(5):1303-1308.
[2] 张龙,后洁琼,秋虎,等.膨胀石墨/聚苯胺/Fe3O4复合材料的制备及吸波性能[J].高等学校化学学报,2017,38(12):2352-2360.
[3] 陈仲欣,卢红斌.石墨烯-聚苯胺杂化超级电容器电极材料[J].高等学校化学学报,2013,34(9):2020-2033.
[4] Wang X L,Fan X Y,Li G,et al.Composites of MnO2 nanocrystals and partially graphitized hierarchically porous carbon spheres with improved rate capability for high-performance supercapacitors[J].Carbon,2015,93:258-265.
[5] Liu S K,Hong X B,Li Y J,et al.Encapsulating sulfur into highly graphitized hollow carbon spheres as high performance cathode for lithium-sulfur batteries[J].RSC Advances,2016,6(100):98035-98041.
[6] Song M Y,Yang D S,Singh K P,et al.Nitrogen-doped hollow carbon spheres with highly graphitized mesoporous shell:role of Fe for oxygen evolution reaction[J].Applied Catalysis B:Environmental,2016,191:202-208.
[7] Li X F,Chi M F,Mahurin S M,et al.Graphitized hollow carbon spheres and yolk-structured carbon spheres fabricated by metal-catalyst-free chemical vapor deposition[J].Carbon,2016,101:57-61.
[8] 吴娟,吴雪艳,魏霄,等.聚苯胺/介孔碳纳米线复合电极材料的制备和性能[J].高等学校化学学报,2012,33(7):1540-1544.
[9] 张龙,万晓娜,段文静,等.Fe3O4@聚吡咯@聚苯胺核壳结构的制备及吸波性能[J].高等学校化学学报,2018,39(1):185-192.
[10] 高磊,廖奕,张小华,等.聚苯胺纳米刺/掺氮空心炭球复合材料的制备及电容性能[J].高等学校化学学报,2013,34(12):2845-2849.
[11] Yuan D S,Zhou T X,Zhou S L,et al.Nitrogen-enriched carbon nanowires from the direct carbonization of polyaniline nanowires and its electrochemical properties[J].Electrochemistry Communications,2011,13(3):242-246.
[12] Rozlívková Z,Trchová M,Eenerová M,et al.The carbonization of granular polyaniline to produce nitrogen-containing carbon[J].Synthetic Metals,2011,161(11/12):1122-1129.
[13] Morávková Z,Trchová M,Exnerová M,et al.The carbonization of thin polyaniline films[J].Thin Solid Films,2012,520(19):6088-6094.
[14] Peng H,Ma G F,Sun K J,et al.A novel fabrication of nitrogen-containing carbon nanospheres with high rate capability as electrode materials for supercapacitors[J].RSC Advances,2015,5(16):12034-12042.
[15] Wang G,Sun Y H,Li D B,et al.Controlled synthesis of N-doped carbon nanospheres with tailored mesopores through self-assembly of colloidal silica[J].Angewandte Chemie-International Edition,2015,54(50):15191-15196.
[16] Hassan M,Wu D D,Song X D,et al.Polyaniline-derived metal-free hollow nitrogen-doped carbon microspheres as an efficient electrocatalyst for supercapacitors and oxygen reduction[J].Journal of Electroanalytical Chemistry,2018,829:157-167.
[17] Han J P,Xu G Y,Ding B,et al.Porous nitrogen-doped hollow carbon spheres derived from polyaniline for high performance supercapacitors[J].Journal of Materials Chemistry A,2014,2(15):5352-5357.
[18] Tian J Y,Zhang H Y,Li Z H.Synthesis of double-layer nitrogen-doped microporous hollow carbon@MoS2/MoO2 nanospheres for supercapacitors[J].ACS Applied Materials & Interfaces,2018,10(35):29511-29520.
[19] Tan Y M,Xu C F,Chen G X,et al.Synthesis of ultrathin nitrogen-doped graphitic carbon nanocages as advanced electrode materials for supercapacitor[J].ACS Applied Materials & Interfaces,2013,5(6):2241-2248.
[20] Long C L,Wei T,Yan J,et al.Supercapacitors based on graphene-supported iron nanosheets as negative electrode materials[J].ACS Nano,2013,7(12):11325-11332.
[21] Zhu Y,Li J M,Wan M X,et al.Electromagnetic functional urchin-like hollow carbon spheres carbonized by polyaniline micro/nanostructures containing FeCl3 as a precursor[J].European Journal of Inorganic Chemistry,2009(19):2860-2864.
[22] Sheng H Y,Wei M,D'Aloiaa,et al.Heteroatom polymer-derived 3D high-surface-area and mesoporous graphene sheet-like carbon for supercapacitors[J].ACS Applied Materials & Interfaces,2016,8(44):30212-30224.
[23] Kim D K,Zhang Y,Voit W,et al.Synthesis and characterization of surfactant-coated superparamagnetic monodispersed iron oxide nanoparticles[J].Journal of Magnetism and Magnetic Materials,2001,225(1/2):30-36.
[24] 曾桓兴,周文运.单分子层油酸包覆Fe3O4的研究[J].应用科学学报,1989,7(1):75-79.
[25] 张晴晴,张庆武,王文华,等.对苯二胺低聚物改性氧化石墨烯及其在超级电容器中的应用研究[J].矿业科学学报,2019,4(6):558-563.
[26] Zhang Q Q,Zhang Q W,Lu H,et al.A comparative study of electrochemical capacitance of graphene oxide affected by oligomers of p-phenylenediamine and hydrazine hydrate in solvothermal condition[J].Journal of Wuhan University of Technology Materials Science,2020,35(2):253-262.
