Abstract
The phase transition process of the MnO2 phase with increases in Co2+ doping can be described by the Ouroboros symbol. The undoped sample is pure δ-MnO2 with nanosheets structures. Then a small amount of Co2+ ions changes the final products and generates α-MnO2 nanofibres in the δ-MnO2 matrix. The products become pure α-MnO2 with an appropriate amount of Co added. However, when the Co amount continues to increase, the amount of α-MnO2 decreases in the products and turns back to form pure δ-MnO2 in the end. Analysing the electromagnetic absorption performance, the relationship between the properties and the proportion of δ-MnO2/α-MnO2 in the powders adjusted by Co2+ doping has been explored, and the composites of δ-/α-MnO2 show better absorption ability than the single-phase samples. As a result, the optimal reflection loss (RL) is −54.8 dB, and the effective absorption bandwidth can cover the Ku band at a thickness of 2.2 mm and the X band at a thickness of 3.1 mm with 50 wt.% filler loading ratios. This research might shed new light on the improvement of novel microwave absorption materials.
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Yuan, Y. F.; Nie, A. M.; Odegard, G. M.; Xu, R.; Zhou, D. H.; Santhanagopalan, S.; He, K.; Asayesh-Ardakani, H.; Meng, D. D.; Klie, R. F. et al. Asynchronous crystal cell expansion during lithiation of K+-Stabilized α-MnO2. Nano Lett.2015, 15, 2998–3007.
Li, Y. Q.; Shi, X. M.; Lang, X. Y.; Wen, Z.; Li, J. C.; Jiang, Q. Remarkable improvements in volumetric energy and power of 3D MnO2 microsupercapacitors by tuning crystallographic structures. Adv. Funct. Mater.2016, 26, 1830–1839.
Liu, P. B.; Zhu, Y. D.; Gao, X. G.; Huang, Y.; Wang, Y.; Qin, S. Y.; Zhang, Y. Q. Rational construction of bowl-like MnO2 nanosheets with excellent electrochemical performance for supercapacitor electrodes. Chem. Eng. J.2018, 350, 79–88.
Ren, H.; Zhao, J.; Yang, L.; Liang, Q. H.; Madhavi, S.; Yan, Q. Y. Inverse opal manganese dioxide constructed by few-layered ultrathin nanosheets as high-performance cathodes for aqueous zinc-ion batteries. Nano Res.2019, 12, 1347–1353.
Wang, Y.; Han, B. Q.; Chen, N.; Deng, D. Y.; Guan, H. T.; Wang, Y. D. Enhanced microwave absorption properties of MnO2 hollow microspheres consisted of MnO2 nanoribbons synthesized by a facile hydrothermal method. J. Alloys Compd.2016, 676, 224–230.
Zhou, M.; Zhang, X.; Wei, J. M.; Zhao, S. L.; Wang, L.; Feng, B. X. Morphology-controlled synthesis and novel microwave absorption properties of hollow urchinlike α-MnO2 nanostructures. J. Phys. Chem. C2011, 115, 1398–1402.
Xing, X. B.; Lv, G. C.; Xu, W.; Liao, L. B.; Jiang, W. T.; Li, Z. H.; Wang, G. S. Controllable adjustment of the crystal symmetry of K-MnO2 and its influence on the frequency of microwave absorption. RSC Adv.2016, 6, 58844–58853.
Sikam, P.; Moontragoon, P.; Sararat, C.; Karaphun, A.; Swatsitang, E.; Pinitsoontorn, S.; Thongbai, P. DFT calculation and experimental study on structural, optical and magnetic properties of Co-doped SrTiO3. Appl. Surf. Sci.2018, 446, 92–113.
Kang, J. L.; Hirata, A.; Kang, L. J.; Zhang, X. M.; Hou, Y.; Chen, L. Y.; Li, C.; Fujita, T.; Akagi, K.; Chen, M. W. Enhanced supercapacitor performance of MnO2 by atomic doping. Angew. Chem., Int. Ed.2013, 52, 1664–1667.
Ye, Z. G.; Li, T.; Ma, G.; Dong, Y. H.; Zhou, X. L. Metal-ion (Fe, V, Co, and Ni)-Doped MnO2 ultrathin nanosheets supported on carbon fiber paper for the oxygen evolution reaction. Adv. Funct. Mater.2017, 27, 1704083.
Sun, Q.; Liu, C.; Alves, M. E.; Ata-Ul-Karim, S. T.; Zhou, D. M.; He, J. Z.; Cui, P. X.; Wang, Y. J. The oxidation and sorption mechanism of Sb on δ-MnO2. Chem. Eng. J.2018, 342, 429–437.
Guan, H. T.; Wang, Y.; Dong, C. J.; Chen, G.; Xiao, X. C.; Wang, Y. D. A novel microwave absorption material of Ni doped cryptomelane type manganese oxides. Ceram. Int.2015, 47, 5688–5695.
Agrawal, S.; Parveen, A.; Azam, A. Microwave assisted synthesis of Co doped NiO nanoparticles and its fluorescence properties. J. Lumin.2017, 184, 250–255.
Staniland, S.; Williams, W.; Telling, N.; Van Der Laan, G.; Harrison, A.; Ward, B. Controlled cobalt doping of magnetosomes in vivo. Nat. Nanotechnol.2008, 3, 158–162.
Huang, X. G; Zhang, M. J.; Qin, Y. S.; Chen, Y. Y. Bead-like Co-doped ZnO with improved microwave absorption properties. Ceram. Int.2019, 45, 7789–7796.
Ahamed, I.; Pathak, R.; Skomski, R.; Kashyap, A. Magnetocrystalline anisotropy of ε-Fe2O3. AIP Adv.2018, 8, 055815.
Tang, C. L.; Wei, X.; Jiang, Y. M.; Wu, X. Y.; Han, L. N.; Wang, K. X.; Chen, J. S. Cobalt-doped MnO2 hierarchical yolk-shell spheres with improved supercapacitive performance. J. Phys. Chem. C2015, 119, 8465–8471.
Liu, P. J.; Yao, Z. J.; Zhou, J. T.; Yang, Z. H.; Kong, L. B. Small magnetic Co-doped NiZn ferrite/graphene nanocomposites and their dual-region microwave absorption performance. J. Mater. Chem. C2016, 4, 9738–9749.
Yan, L. J.; Niu, L. Y.; Shen, C.; Zhang, Z. K.; Lin, J. H.; Shen, F. Y.; Gong, Y. Y.; Li, C.; Liu, X. J.; Xu, S. Q. Modulating the electronic structure and pseudocapacitance of 5-MnO2 through transitional metal M (M = Fe, Co and Ni) doping. Electrochim. Acta2019, 306, 529–540.
Lv, G. C.; Xing, X. B.; Wu, L. M.; Jiang, W. T.; Li, Z. H.; Liao, L. B. Tunable high-performance microwave absorption for manganese dioxides by one-step Co doping modification. Sci. Rep.2016, 6, 37400.
Zhao, P. F.; Liang, C. Y.; Gong, X. W.; Gao, R.; Liu, J. W.; Wang, M.; Che, R. C. Microwave absorption enhancement, magnetic coupling and ab initio electronic structure of monodispersed (Mn1−xCox)3O4 nanoparticles. Nanoscale2013, 5, 8022–8028.
Duan, Y. P.; Liu, Z.; Jing, H.; Zhang, Y. H.; Li, S. Q. Novel microwave dielectric response of Ni/Co-doped manganese dioxides and their microwave absorbing properties. J. Mater. Chem.2012, 22, 18291–18299.
Wang, J. W.; Chen, Y.; Chen, B. Z. Effects of transition-metal ions on the morphology and electrochemical properties of δ-MnO2 for supercapacitors. Met. Mater. Int.2014, 20, 989–996.
Xie, Y. J.; Yu, Y. Y.; Gong, X. Q.; Guo, Y.; Guo, Y. L.; Wang, Y. Q.; Lu, G. Z. Effect of the crystal plane figure on the catalytic performance of MnO2 for the total oxidation of propane. CrystEngComm2015, 17, 3005–3014.
Wang, C.; Liu, Y.; Feng, X.; Zhou, C. Y.; Liu, Y. L.; Yu, X.; Zhao, G. J. Phase regulation strategy of perovskite nanocrystals from 1D orthomorphic NH4PbI3 to 3D cubic (NH4)0.5Cs0.5pb(I0.5Br0.5)3 phase enhances photoluminescence. Angew. Chem., Int. Ed.2019, 58, 11642–11646.
Sun, G. B.; Dong, B. X.; Cao, M. H.; Wei, B. Q.; Hu, C. W. Hierarchical dendrite-like magnetic materials of Fe3O4, γ-Fe2O3, and Fe with high performance of microwave absorption. Chem. Mater.2011, 23, 1587–1593.
Devaraj, S.; Munichandraiah, N. Effect of crystallographic structure of MnO2 on its electrochemical capacitance properties. J. Phys. Chem. C2008, 112, 4406–4417.
Yuan, Y. F.; Wood, S. M.; He, K.; Yao, W. T.; Tompsett, D.; Lu, J.; Nie, A. M.; Islam, M. S.; Shahbazian-Yassar, R. Atomistic insights into the oriented attachment of tunnel-based oxide nanostructures. ACS Nano2016, 10, 539–548.
Li, Y. L.; Wang, J. J.; Zhang, Y.; Banis, M. N.; Liu, J.; Geng, D. S.; Li, R. Y.; Sun, X. L. Facile controlled synthesis and growth mechanisms of flower-like and tubular MnO2 nanostructures by microwave-assisted hydrothermal method. J. Colloid Interface Sci.2012, 369, 123–128.
Collier, A. P.; Hetherington, C. J. D.; Hounslow, M. J. Alignment mechanisms between particles in crystalline aggregates. J. Cryst. Growth2000, 208, 513–519.
Li, J.; Hietala, S.; Tian, X. L. BaTiO3 supercages: Unusual oriented nanoparticle aggregation and continuous ordering transition in morphology. ACS Nano2015, 9, 496–502.
Yec, C. C.; Zeng, H. C. Synthesis of complex nanomaterials via Ostwald ripening. J. Mater. Chem. A2014, 2, 4843–4851.
Li, X.; Wang, L.; You, W. B.; Xing, L. S.; Yu, X. F.; Li, Y. S.; Che, R. C. Morphology-controlled synthesis and excellent microwave absorption performance of ZnCo2O4 nanostructures via a self-assembly process of flake units. Nanoscale2019, 11, 2694–2702.
Peng, R. C.; Wu, N.; Zheng, Y.; Huang, Y. B.; Luo, Y. B.; Yu, P.; Zhuang, L. Large-scale synthesis of metal-ion-doped manganese dioxide for enhanced electrochemical performance. ACS Appl. Mater. Interfaces2016, 8, 8474–8480.
Song, L. L.; Duan, Y. P.; Zhang, Y. H.; Wang, T.M. Promoting defect formation and microwave loss properties in δ-MnO2 via Co doping: A first-principles study. Comput. Mater. Sci.2017, 138, 288–294.
Zhang, Y. L.; Wang, X. X.; Cao, M. S. Confinedly implanted NiFe2O4-rGO: Cluster tailoring and highly tunable electromagnetic properties for selective-frequency microwave absorption. Nano Res.2018, 11, 1426–1436.
Wang, L.; Li, X.; Li, Q. Q.; Zhao, Y. H.; Che, R. C. Enhanced polarization from hollow cube-like ZnSnO3 wrapped by multiwalled carbon nanotubes: As a lightweight and high-performance microwave absorber. ACS Appl. Mater. Interfaces2018, 10, 22602–22610.
Singh, S. K.; Akhtar, M. J.; Kar, K. K. Hierarchical carbon nanotube-coated carbon fiber: Ultra lightweight, thin, and highly efficient microwave absorber. ACS Appl. Mater. Interfaces2018, 10, 24816–24828.
Zhang, M. M.; Jiang, Z. Y.; Lv, X. Y.; Zhang, X. F.; Zhang, Y. H.; Zhang, J. W.; Zhang, L.; Gong, C. H. Microwave absorption performance of reduced graphene oxide with negative imaginary permeability. J. Phys. D: Appl. Phys.2020, 53, 02LT01.
Wang, H. G.; Meng, F. B.; Huang, F.; Jing, C. F.; Li, Y.; Wei, W.; Zhou, Z. W. Interface modulating CNTs@PANi hybrids by controlled unzipping of the walls of CNTs to achieve tunable high-performance microwave absorption. ACS Appl. Mater. Interfaces2019, 11, 12142–12153.
Gu, J. W.; Lv, Z. Y.; Wu, Y. L.; Guo, Y. Q.; Tian, L. D.; Qiu, H.; Li, W. Z.; Zhang, Q. Y. Dielectric thermally conductive boron nitride/polyimide composites with outstanding thermal stabilities via in-situ polymerization-electrospinning-hot press method. Compos. Part A: Appl. Sci. Manuf.2017, 94, 209–216.
Wei, Y.; Zhang, L.; Gong, C. H.; Liu, S. C.; Zhang, M. M.; Shi, Y. P.; Zhang, J. W. Fabrication of TiN/carbon nanofibers by electrospinning and their electromagnetic wave absorption properties. J. Alloys Compd.2018, 735, 1488–1493.
Sun, X.; He, J. P.; Li, G. X.; Tang, J.; Wang, T.; Guo, Y. X.; Xue, H. R. Laminated magnetic graphene with enhanced electromagnetic wave absorption properties. J. Mater. Chem. C2013, 1, 765–777.
Terao, T. Hopping electron model with geometrical frustration: Kinetic Monte Carlo simulations. Eur. Phys. J. B2016, 89, 209.
Gu, J. W.; Xu, S.; Zhuang, Q.; Tang, Y. S.; Kong, J. Hyperbranched polyborosilazane and boron nitride modified cyanate ester composite with low dielectric loss and desirable thermal conductivity. IEEE Trans. Dielect. Electr. In.2017, 24, 784–790.
Duan, Y. L.; Xiao, Z. H.; Yan, X. Y.; Gao, Z. F.; Tang, Y. S.; Hou, L. Q.; Li, Q.; Ning, G. Q.; Li, Y. F. Enhanced electromagnetic microwave absorption property of peapod-like MnO@carbon nanowires. ACS Appl. Mater. Interfaces2018, 10, 40078–40087.
Wang, Y.; Guan, H. T.; Du, S. F.; Wang, Y. D. A facile hydrothermal synthesis of MnO2 nanorod—reduced graphene oxide nanocomposites possessing excellent microwave absorption properties. RSC Adv.2015, 5, 88979–88988.
Huang, L.; Li, J. J.; Li, Y. B.; He, X. D.; Yuan, Y. Fibrous composites with double-continuous conductive network for strong low-frequency microwave absorption. Ind. Eng. Chem. Res.2019, 58, 11927–11938.
Wang, Z. J.; Wu, L. N.; Zhou, J. G.; Cai, W.; Shen, B. Z.; Jiang, Z. H. Magnetite nanocrystals on multiwalled carbon nanotubes as a synergistic microwave absorber. J. Phys. Chem. C2013, 117, 5446–5452.
Zhang, X. F.; Guo, J. J.; Guan, P. F.; Qin, G. W.; Pennycook, S. J. Gigahertz dielectric polarization of substitutional single niobium atoms in defective graphitic layers. Phys. Rev. Lett.2015, 115, 147601.
Su, T. T.; Zhao, B.; Han, F. Q.; Fan, B. B.; Zhang, R. The effect of hydrothermal temperature on the crystallographic phase of MnO2 and their microwave absorption properties. J. Mater. Sci.: Mater. Electron.2019, 30, 475–484.
Su, T. T.; Zhao, B.; Fan, B. B.; Li, H. X.; Zhang, R. Enhanced microwave absorption properties of novel hierarchical core-shell δ/α MnO2 composites. J. Solid State Chem.2019, 273, 192–198.
Qiao, M. T.; Lei, X. F.; Ma, Y.; Tian, L. D.; Su, K. H.; Zhang, Q. Y. Dependency of tunable microwave absorption performance on morphology-controlled hierarchical shells for core-shell Fe3O4@MnO2 composite microspheres. Chem. Eng. J.2016, 304, 552–562.
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The authors acknowledge the Support by Program for the National Natural Science Foundation of China (Nos. 51577021 and U1704253), and the Fundamental Research Funds for the Central Universities (No. DUT17GF107).
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Transformation between nanosheets and nanowires structure in MnO2 upon providing Co2+ ions and applications for microwave absorption
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Song, L., Duan, Y., Liu, J. et al. Transformation between nanosheets and nanowires structure in MnO2 upon providing Co2+ ions and applications for microwave absorption. Nano Res. 13, 95–104 (2020). https://doi.org/10.1007/s12274-019-2578-2
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DOI: https://doi.org/10.1007/s12274-019-2578-2