具有宽频与可控微波吸收性能的石墨烯空心微球的自组装
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摘要
用简单高效的两步法制备了一种包覆有四氧化三铁的还原石墨烯空心微球(Air@r GO€Fe_3O_4)。两步法包括油包水乳化技术和高温煅烧技术。Air@r GO€Fe_3O_4空心微球的介电损耗和磁损耗优异,使其具有良好的微波吸收性能。空心微球在石蜡中的添加量为33.3%、厚度为2.8 mm的微球在10 GHz处有最小反射率,为-52 d B,反射率小于-10 d B的频率范围为7.5~14.7 GHz。调节各成分的配比和样品厚度可控制空心微球的吸波性能。随着四氧化三铁含量的提高,微球的最小反射率的峰值位置向高频移动。Air@r GO€Fe_3O_4空心微球有吸收频率范围宽、吸收强度大以及吸波性能可调控等优点,使其成为具有潜在应用价值的高性能吸波材料。
Fe_3O_4 nanoparticles coated hollow microspheres of reduced graphene oxide(Air@r GO€Fe_3O_4) were synthesized via a simple and efficient two-step method consisting of water-in-oil(W/O)emulsion technique and subsequent annealing process. The Air@r GO €Fe_3O_4 hollow microspheres showed good electromagnetic properties because of the coexistence of magnetic loss and dielectric loss to microwave. The microwave absorbing bandwidth(reflection loss<-10 d B) for Air@r GO€Fe_3O_4 of thickness in 2.8 mm(with 33.3 mass% paraffin) locates in the range of 7.5~14.7 GHz, while a minimum reflection loss-52 d B at 10.0 GHz. More interestingly, the microwave absorbing properties of the hollow microspheres can be easily controlled by tuning the ratio of the two components in the composites and the thickness of samples, and as the Fe_3O_4 content increase, the minimum reflection loss valve of Air@r GO€Fe_3O_4 microspheres move to higher frequency range. These Air@r GO€Fe_3O_4 hollow microspheres are great potential candidate as microwave absorbents due to their excellent properties such as wide absorbing frequency, strong absorption, low density and controllable absorbing properties.
Fe_3O_4 nanoparticles coated hollow microspheres of reduced graphene oxide(Air@r GO€Fe_3O_4) were synthesized via a simple and efficient two-step method consisting of water-in-oil(W/O)emulsion technique and subsequent annealing process. The Air@r GO €Fe_3O_4 hollow microspheres showed good electromagnetic properties because of the coexistence of magnetic loss and dielectric loss to microwave. The microwave absorbing bandwidth(reflection loss<-10 d B) for Air@r GO€Fe_3O_4 of thickness in 2.8 mm(with 33.3 mass% paraffin) locates in the range of 7.5~14.7 GHz, while a minimum reflection loss-52 d B at 10.0 GHz. More interestingly, the microwave absorbing properties of the hollow microspheres can be easily controlled by tuning the ratio of the two components in the composites and the thickness of samples, and as the Fe_3O_4 content increase, the minimum reflection loss valve of Air@r GO€Fe_3O_4 microspheres move to higher frequency range. These Air@r GO€Fe_3O_4 hollow microspheres are great potential candidate as microwave absorbents due to their excellent properties such as wide absorbing frequency, strong absorption, low density and controllable absorbing properties.
引文
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[2]Wang H,Ma N,Yan Z,et al.Cobalt/polypyrrole nanocomposites with controllable electromagnetic properties[J].Nanoscale,2015,7(16):7189
[3]Wang L,Zhu J,Yang H,et al.Fabrication of hierarchical graphene@Fe3O4@Si O2@polyaniline quaternary composite and its improved electrochemical performance[J].J.Alloys Compd.,2015,634:232
[4]Qi X,Hu Q,Xu J,et al.The synthesis and excellent electromagnetic radiation absorption properties of core/shell-structured Co/carbon nanotube-graphene nanocomposites[J].Rsc Adv.,2016,6(14):11382
[5]Ye W,Fu.J,Wang Q,et al.Electromagnetic wave absorption properties of Ni Co P alloy nanoparticles decorated on reduced graphene oxide nanosheets[J].J.Magn.Magn.Mater.,2015,395:147
[6]Ji R,Cao C,Chen Z,et al.Solvothermal synthesis of CoxFe3-xO4spheres and their microwave absorption properties[J].J.Mater.Chem.C.,2014,2(29):5944
[7]Jian X,Wu B,We Y,et al.Facile synthesis of Fe3O4/GCs composites and their enhanced microwave absorption properties[J].Acs Appl.Mater.Inter.,2016,8(9):6101
[8]Liu P,Huang Y.Synthesis of reduced graphene oxide-conducting polymers-Co3O4composites and their excellent microwave absorption properties[J].Rsc Adv.,2013,3(41):19033
[9]Pan Y F,Wang G S,Yue Y H.Fabrication of Fe3O4@Si O2@RGOnanocomposites and their excellent absorption properties with low filler content[J].Rsc Adv.,2015,5(88):71718
[10]Cao M S,Song W L,Hou Z L,et al.The effects of temperature and frequency on the dielectric properties,electromagnetic interference shielding and microwave-absorption of short carbon fiber/silica composites[J].Carbon.,2010,48(3):788
[11]Wen B,Cao M S,Liu M M,et al.Reduced Graphene Oxides:Light-Weight and high-efficiency electromagnetic interference shielding at elevated temperatures[J].Adv.Mater.,2014;26:3484
[12]Cao W Q,Wang X X,Yuan J,et al.Temperature dependent microwave absorption of ultrathin graphene composites[J].J.Mater.Chem.C,2015,3(38):10017
[13]Wang L,Huang Y,Li C,et al.Hierarchical graphene@Fe3O4nanocluster@carbon@Mn O2nanosheet array composites:synthesis and microwave absorption performance[J].Phys.Chem.Chem.Phys.,2015,17(8):5878
[14]Chen P,Zeng Q,Yu Q,et al.Method for preparing graphene hollow microsphere loaded with magnetic nano particle[P].China patent,ZL 201510925343.3,2017(陈平,曾强,于祺等.一种负载磁性纳米粒子的石墨烯空心微球的制备方法[P].中国发明专利,ZL 201510925343.3,2017)
[15]He H,Gao C.Supraparamagnetic,Conductive,and Processable multifunctional graphene nanosheets coated with high-density Fe3O4nanoparticles[J].Acs Appl.Mater.Inter.,2010,2(11):3201
[16]Zeng.Q,Xiong.X.H,Chen.P,et al Air@r GO€Fe3O4microspheres with spongy shells:self-assembly and microwave absorption performance[J].Journal of Materials Chemistry C.2016;4(44):10518
[17]Fang R,Guang Z,Peng R,et al.Cyanate ester resin filled with graphene nanosheets and Co Fe2O4-reduced graphene oxide nanohybrids as a microwave absorber[J].Appl.Surf.Sci.,2015,351:40
[18]Wang L,Huang Y,Li C,et al.Hierarchical composites of polyaniline nanorod arrays covalently-grafted on the surfaces of graphene@Fe3O4@C with high microwave absorption performance[J].Compos.Sci.Technol.,2015,108:1
[19]Duan Y,Liu Z,Jing H,et al.Novel microwave dielectric response of Ni/Co-doped manganese dioxides and their microwave absorbing properties[J].J.Mater.Chem.,2012,22(35):18291
[20]Min Z,Fei L,Li T Y,et al.Loss mechanism and microwave absorption properties of hierarchical Ni Co2O4nanomaterial[J].J.Phys.D:Appl.Phys.,2015,48(21):215305
[21]Pan G,Zhu J,Ma S,et al.Enhancing the electromagnetic performance of co through the phase-controlled synthesis of hexagonal and cubic co nanocrystals grown on graphene[J].Acs Appl.Mater.Inter.,2013,5(23):12716
[22]Wan Y,Xiao J,Li C,et al.Microwave absorption properties of Fe Co-coated carbon fibers with varying morphologies[J].J.Magn.Magn.Mater.,2016,399:252
[23]Wang Z,Bi H,Wang P,et al.Magnetic and microwave absorption properties of self-assemblies composed of core-shell cobalt-cobalt oxide nanocrystals[J].Phys.Chem.Chem.Phys.,2015,17(5):3796
[24]Zhang S,Jiao Q,Zhao Y,et al.Preparation of rugby-shaped Co Fe2O4particles and their microwave absorbing properties[J].J.Mater.Chem.A,2014,2(42):18033
[25]Wang Z,Wu L,Zhou J,et al.Enhanced microwave absorption of Fe3O4nanocrystals after heterogeneously growing with Zn Onanoshell[J].Rsc Adv.,2013,3(10):3309
[26]Zhao B,Zhao W,Shao G,et al.Corrosive synthesis and enhanced electromagnetic absorption properties of hollow porous Ni/Sn O2hybrids[J].Dalton Trans.,2015,44(36):15984
[27]Zhou M,Zhang X,We J,et al.Morphology-controlled synthesis and novel microwave absorption properties of hollow urchinlikeα-Mn O2nanostructures[J].J.Phys.Chem.C,2011,115(5):1398
[28]Zong M,Huang Y,Zhang N,et al.Influence of(RGO)/(ferrite)ratios and graphene reduction degree on microwave absorption properties of graphene composites[J].J.Alloys Compd.,2015,644:491
[29]Liu G,Jiang W,Wang Y,et al.One-pot synthesis of Ag@Fe3O4/reduced graphene oxide composite with excellent electromagnetic absorption properties[J].Ceram.Int.Part B,2015,41(3):4982
[30]Huang Y,Wang L,Sun X.Sandwich-structured graphene@Fe3O4@carbon nanocomposites with enhanced electromagnetic absorption properties[J].Mater.Lett.,2015,144:26
[31]Huang X,Zhang J,Lai M,et al.Preparation and microwave absorption mechanisms of the Ni Zn ferrite nanofibers[J].J.Alloys Compd.,2015,627:367
[32]Kong L,Yin X,Ye F,et al.Electromagnetic wave absorption properties of Zn O-based materials modified with Zn Al2O4nanograins[J].J.Phys.Chem.C,2013,117(5):2135
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