MOFs-derived flower-like cobalt@carbon multiscale hierarchical composites with effective microwave absorption in the low frequency range

Abstract

The wave-absorbing materials are kinds of special electromagnetic functional materials and have been widely used in electromagnetic pollution control and military fields. In-situ integrated hierarchical structure construction is thought as a promising route to improve the microwave absorption performance of the materials. In the present work, layer-structured Co-metal-organic frameworks (Co-MOFs) precursors were grown in-situ on the surface of carbon fibers with the hydrothermal method. After annealed at 500°C under Ar atmosphere, a novel multiscale hierarchical composite (Co@C/CF) was obtained with the support of carbon fibers, keeping the flower-like structure. Scanning electron microscope, transmission electron microscope, X-ray diffraction, Raman, and X-ray photoelectron spectroscopy were performed to analyze the microstructure and composition of the hierarchical structure, and the microwave absorption performance of the Co@C/CF composites were investigated. The results showed that the growth of the flower-like structure on the surface of carbon fiber was closely related to the metal-to-ligand ratio. The optimized Co@C/CF flower-like composites achieved the best reflection loss of −55.7 dB in the low frequency band of 6–8 GHz at the thickness of 2.8 mm, with the corresponding effective absorption bandwidth (EAB) of 2.1 GHz. The EAB of 3.24 GHz was achieved in the high frequency range of 12–16 GHz when the thickness was 1.5 mm. The excellent microwave absorption performance was ascribed to the introduction of magnetic components and the construction of the unique structure. The flower-like structure not only balanced the impedance of the fibers themselves, but also extended the propagation path of the microwave and then increased the multiple reflection losses. This work provides a convenient method for the design and development of wave-absorbing composites with in-situ integrated structure.

Keywords

carbon fiber / metal-organic framework / hierarchical structure / flower-like composite / microwave absorption

References

[1] BiYX, MaML, LiuYY, et al.. Microwave absorption enhancement of 2-dimensional CoZn/C@MoS₂@PPy composites derived from metal-organic framework. J. Colloid Interface Sci., 2021, 600: 209

[2] H.Y. Zhang, H. Ji, G.L. Dai, et al., Nanoarchitectonics of integrated impedance gradient MXene/PPy/polyester composite fabric for enhanced microwave absorption performances, Composites Part A, 163(2022), art. No. 107163.

[3] M. Zhang, J.H. Zhang, H. Lin, et al., Designable synthesis of reduced graphene oxide modified using CoFe₂O₄ nanospheres with tunable enhanced microwave absorption performances between the whole X and Ku bands, Composites Part B, 190(2020), art. No. 107902.

[4] ChengZ, CaoYS, WangRF, et al.. Hierarchical surface engineering of carbon fiber for enhanced composites interfacial properties and microwave absorption performance. Carbon, 2021, 185: 669

[5] X.X. Zhao, Y. Huang, X.D. Liu, M. Yu, M. Zong, and T.H. Li, Magnetic nanorods/carbon fibers heterostructures coated with flower-like MoS₂ layers for superior microwave absorption, Carbon, 213(2023), art. No. 118265.

[6] WangSP, LiuZY, LiuQC, et al.. Promoting the microwave absorption performance of hierarchical CF@NiO/Ni composites via phase and morphology evolution. Int. J. Miner. Metall. Mater., 2023, 30(3): 494

[7] T. Zhu, W. Shen, X.Y. Wang, Y.F. Song, and W. Wang, Paramagnetic CoS₂@MoS₂ core–shell composites coated by reduced graphene oxide as broadband and tunable high-performance microwave absorbers, Chem. Eng. J., 378(2019), art. No. 122159.

[8] W.H. Zhou, X. Xiong, and Y.L. He, In-situ growing CoFe₂O₄ nanoparticles on porous fibrous carbon derived from silkworm cocoons as high-performance microwave absorber, Diam. Relat. Mater., 132(2023), art. No. 109636.

[9] QiuJ, QiuTT. Fabrication and microwave absorption properties of magnetite nanoparticle–carbon nanotube–hollow carbon fiber composites. Carbon, 2015, 81: 20

[10] GaoZG, YangK, ZhaoZH, et al.. Design principles in MOF-derived electromagnetic wave absorption materials: Review and perspective. Int. J. Miner. Metall. Mater., 2023, 30(3): 405

[11] SongSW, ZhangAT, ChenL, et al.. A novel multi-cavity structured MOF derivative/porous graphene hybrid for high performance microwave absorption. Carbon, 2021, 176: 279

[12] YangLQ, WangY, LuZ, ChengRR, WangN, LiYF. Construction of multi-dimensional NiCo/C/CNT/rGO aerogel by MOF derivative for efficient microwave absorption. Carbon, 2023, 205: 411

[13] YangK, CuiYH, WanLY, ZhangQY, ZhangBL. MOF-derived magnetic–dielectric balanced Co@ZnO@N-doped carbon composite materials for strong microwave absorption. Carbon, 2022, 190: 366

[14] ZhouYY, BaiZY, YangXY, et al.. In-situ. Int. J. Miner. Metall. Mater., 2023, 30(3): 515

[15] ChenJB, ZhengJ, WangF, HuangQQ, JiGB. Carbon fibers embedded with Fe^III-MOF-5-derived composites for enhanced microwave absorption. Carbon, 2021, 174: 509

[16] ZhangX, YanF, ZhangS, et al.. Hollow N-doped carbon polyhedron containing CoNi alloy nanoparticles embedded within few-layer N-doped graphene as high-performance electromagnetic wave absorbing material. ACS Appl. Mater. Interfaces, 2018, 10(29): 24920

[17] YanJ, HuangY, YanYH, DingL, LiuPB. High-performance electromagnetic wave absorbers based on two kinds of nickel-based MOF-derived Ni@C microspheres. ACS Appl. Mater. Interfaces, 2019, 11(43): 40781

[18] LiuPB, ZhuCY, GaoS, GuanC, HuangY, HeWJ. N-doped porous carbon nanoplates embedded with CoS₂ vertically anchored on carbon cloths for flexible and ultrahigh microwave absorption. Carbon, 2020, 163: 348

[19] P.B. Liu, S. Gao, G.Z. Zhang, Y. Huang, W.B. You, and R.C. Che, Hollow engineering to Co@N-doped carbon nanocages via synergistic protecting-etching strategy for ultrahigh microwave absorption, Adv. Funct. Mater., 31(2021), No. 27, art. No. 2102812.

[20] XiangZ, ZhangX, ShiYY, et al.. Efficient microwave absorption of MOFs derived laminated porous Ni@C nanocomposites with waterproof and infrared shielding versatility. Carbon, 2021, 185: 477

[21] ZhaoYZ, WangW, WangJN, et al.. Constructing multiple heterogeneous interfaces in the composite of bimetallic MOF-derivatives and rGO for excellent microwave absorption performance. Carbon, 2021, 173: 1059

[22] QiuY, YangHB, MaL, et al.. In situ. J. Colloid Interface Sci., 2021, 581: 783

[23] ChengRR, WangY, DiXC, et al.. Construction of MOF-derived plum-like NiCo@C composite with enhanced multi-polarization for high-efficiency microwave absorption. J. Colloid Interface Sci., 2022, 609: 224

[24] F.Y. Li, H. Xia, and Q.Q. Ni, Co, Ni-coordinated ZIF derived nitrogen doped carbon network with encapsulated alloy for microwave absorption, Diam. Relat. Mater., 120(2021), art. No. 108669.

[25] ZhuXY, QiuHF, ChenP, ChenGZ, MinWX. Graphitic carbon nitride (g-C₃N₄) in situ polymerization to synthesize MOF-Co@CNTs as efficient electromagnetic microwave absorption materials. Carbon, 2021, 176: 530

[26] WangL, DuZ, BaiXY, LinY. Constructing macroporous C/Co composites with tunable interfacial polarization toward ultra-broadband microwave absorption. J. Colloid Interface Sci., 2021, 591: 76

[27] Q. Wu, B.L. Wang, Y.G. Fu, Z.F. Zhang, P.F. Yan, and T. Liu, MOF-derived Co/CoO particles prepared by low temperature reduction for microwave absorption, Chem. Eng. J., 410(2021), art. No. 128378.

[28] ZhouQ, ShiTT, XueB, et al.. Gradient carbonyl-iron/carbon-fiber reinforced composite metamaterial for ultra-broadband electromagnetic wave absorption by multi-scale integrated design. Int. J. Miner. Metall. Mater., 2023, 30(6): 1198

[29] J.Y. Li, W. Tian, Y.F. Liu, B.S. Wu, X. Jian, and L.J. Deng, Achieving enhanced microwave absorption performance based on metal/covalent organic frameworks-derived heterostructures, Composites Part B, 245(2022), art. No. 110199.

[30] WeiJW, ShaoGF, HuangXG. Freeze-cast Ni-MOF nanobelts/chitosan-derived magnetic carbon aerogels for broadband electromagnetic wave absorption. ACS Appl. Mater. Interfaces, 2024, 16(16): 20969

[31] RenLG, WangYQ, ZhangX, HeQC, WuGL. Efficient microwave absorption achieved through in situ construction of core–shell CoFe₂O₄@mesoporous carbon hollow spheres. Int. J. Miner. Metall. Mater., 2023, 30(3): 504

[32] LiuPB, ZhangYQ, YanJ, HuangY, XiaL, GuangZX. Synthesis of lightweight N-doped graphene foams with open reticular structure for high-efficiency electromagnetic wave absorption. Chem. Eng. J., 2019, 368: 285

[33] TianCH, DuYC, XuP, et al.. Constructing uniform core–shell PPy@PANI composites with tunable shell thickness toward enhancement in microwave absorption. ACS Appl. Mater. Interfaces, 2015, 7(36): 20090

[34] C.Q. Ge, L.Y. Wang, G. Liu, et al., Willow catkins-derived Co/C nanoparticles anchored on porous carbon fibers with lightweight and enhanced microwave absorption performances, Mater. Lett., 331(2023), art. No. 133529.

[35] LyuLF, ZhengSN, WangFL, LiuY, LiuJR. High-performance microwave absorption of MOF-derived Co₃O₄@N-doped carbon anchored on carbon foam. J. Colloid Interface Sci., 2021, 602: 197

[36] JiaoZB, HuyanWJ, YaoJR, YaoZJ, ZhouJT, LiuPJ. Heterogeneous ZnO@CF structures and their excellent microwave absorbing properties with thin thickness and low filling. J. Mater. Sci. Technol., 2022, 113: 166

[37] LiuY, ChenZ, XieWH, SongSK, ZhangY, DongLJ. In-situ growth and graphitization synthesis of porous Fe₃O₄/carbon fiber composites derived from biomass as lightweight microwave absorber. ACS Sustainable Chem. Eng., 2019, 7(5): 5318

[38] R. Sadeghi, A. Sharifi, M. Orlowska, and I. Huynen, Investigation of microwave absorption performance of CoFe₂O₄/NiFe₂O₄/carbon fiber composite coated with polypyrrole in X-band frequency, Micromachines, 11(2020), No. 9, art. No. 809.

[39] HuJH, JiaoZG, HanXK, et al.. Facile synthesis of FeNi nanoparticle-loaded carbon nanocomposite fibers for enhanced microwave absorption performance. J. Mater. Sci. Technol., 2024, 175: 141

[40] ZhangXC, QiS, ZhaoY, WangLR, FuJ, YuM. Synthesis and microwave absorption properties of Fe@carbon fibers. RSC Adv., 2020, 10(54): 32561

[41] ZhouXD, HanH, WangYC, ZhangC, LvHL, LouZC. Silicon-coated fibrous network of carbon nanotube/iron towards stable and wideband electromagnetic wave absorption. J. Mater. Sci. Technol., 2022, 121: 199

[42] WenGS, ZhaoXC, LiuY, ZhangH, WangC. Facile synthesis of RGO/Co@Fe@Cu hollow nanospheres with efficient broadband electromagnetic wave absorption. Chem. Eng. J., 2019, 372: 1

[43] ZhouY, WangHP, WangD, et al.. Insight to the enhanced microwave absorption of porous N-doped carbon driven by ZIF-8: Competition between graphitization and porosity. Int. J. Miner. Metall. Mater., 2023, 30(3): 474

[44] XuZJ, HeM, ZhouYM, et al.. Spider web-like carbonized bacterial cellulose/MoSe₂ nanocomposite with enhanced microwave attenuation performance and tunable absorption bands. Nano Res., 2021, 14(3): 738

[45] WenB, YangHB, LinY, et al.. Synthesis of core–shell Co@S-doped carbon@ mesoporous N-doped carbon nanosheets with a hierarchically porous structure for strong electromagnetic wave absorption. J. Mater. Chem. A, 2021, 9(6): 3567

[46] F. Zhang, Z.R. Jia, Z. Wang, et al., Tailoring nanoparticles composites derived from metal-organic framework as electromagnetic wave absorber, Mater. Today Phys., 20(2021), art. No. 100475.

[47] ZhouPP, WangM, SongZ, GuanYK, WangLX, ZhangQT. Coral-like carbon-based composite derived from layered structure Co-MOF-71 with outstanding impedance matching and tunable microwave absorption performance. J. Mater. Sci. Technol., 2022, 108: 10

[48] GouGJ, MengFB, WangHG, JiangM, WeiW, ZhouZW. Wheat straw-derived magnetic carbon foams: In situ preparation and tunable high-performance microwave absorption. Nano Res., 2019, 12(6): 1423

[49] GaoS, ZhangGZ, WangY, HanXP, HuangY, LiuPB. MOFs derived magnetic porous carbon microspheres constructed by core–shell Ni@C with high-performance microwave absorption. J. Mater. Sci. Technol., 2021, 88: 56

[50] XuXQ, RanFT, FanZM, et al.. Microstructural engineering of flexible and broadband microwave absorption films with hierarchical superstructures derived from bimetallic metal-organic framework. Carbon, 2021, 178: 320

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