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Heteroatoms-doped carbon nanocages with enhanced dipolar and defective polarization toward light-weight microwave absorbers

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Abstract

Light-weight and exceptional microwave absorption are two vital characteristics for microwave absorbers in practical applications, but still face challenges. Herein, we employ a sacrificial template strategy to fabricate heteroatoms-doped carbon nanocages (CNs) via chemical vapor deposition, in which heteroatoms are simultaneously doped into the carbon frameworks by bubbling flowing source liquid. Compared with CNs, doped heteroatoms, accompanied with the inevitably defective arrangements in the lattice, not only decrease the electrical conductivity and balance the impedance characteristics, but also introduce structural-chemical defects and trigger dominant dipolar/defect polarization. As a result, both the minimum reflection loss (RL,min) and effective absorption bandwidth (EAB) greatly increase at an ultralow filler loading of 5 wt.% owing to internal hollow void and high specific surface area. The RL,min values reach −53.6, −43.2, and −50.1 dB for N-CNs, S-CNs, and N,S-CNs with the corresponding EAB of 4.9, 2.5, and 3.1 GHz, respectively. Furthermore, this work provides an effective strategy for the construction of heteroatoms-doped hollow carbon frameworks in large-scale production and the obtained doped carbon nanocages can be used as light-weight and high-performance microwave absorbers.

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References

  1. Ma, L. L.; Xiang, X. L.; Shao, L.; Zhang, Y. L.; Gu, J. W. Multifunctional wearable silver nanowire decorated leather nanocomposites for joule heating, electromagnetic interference shielding and piezoresistive sensing. Angew. Chem., Int. Ed. 2022, 61, e202200705.

    CAS  Google Scholar 

  2. Zhu, R. Q.; Li, Z. Y.; Deng, G.; Yu, Y. H.; Shui, J. L.; Yu, R. H.; Pan, C. F.; Liu, X. F. Anisotropic magnetic liquid metal film for wearable wireless electromagnetic sensing and smart electromagnetic interference shielding. Nano Energy 2022, 92, 106700.

    Article  CAS  Google Scholar 

  3. Zhang, Y. L.; Kong, J.; Gu, J. W. New generation electromagnetic materials: Harvesting instead of dissipation solo. Sci. Bull., in press, https://doi.org/10.1016/j.scib.2022.06.017.

  4. Li, W. C.; Cai, H. W.; Kang, Y.; Ying, Y.; Yu, J.; Zheng, J. W.; Qiao, L.; Jiang, Y.; Che, S. L. High permeability and low loss bioinspired soft magnetic composites with nacre-like structure for high frequency applications. Acta Mater. 2019, 167, 267–274.

    Article  CAS  Google Scholar 

  5. Kang, Y.; Li, W. C.; Ma, T.; Huang, X. C.; Mo, Y. P.; Chu, Z. Y.; Zhang, Z. J.; Feng, G. T. Microwave-constructed honeycomb architectures of h-BN/rGO nano-hybrids for efficient microwave conversion. Compos. Sci. Technol. 2019, 174, 184–193.

    Article  CAS  Google Scholar 

  6. Niu, H. H.; Tu, X. Y.; Zhang, S.; Li, Y. Y.; Wang, H. L.; Shao, G.; Zhang, R.; Li, H. X.; Zhao, B.; Fan, B. B. Engineered core-shell SiO2@Ti3C2Tx composites: Towards ultra-thin electromagnetic wave absorption materials. Chem. Eng. J. 2022, 446, 137260.

    Article  CAS  Google Scholar 

  7. Wu, Z. C.; Cheng, H. W.; Jin, C.; Yang, B. T.; Xu, C. Y.; Pei, K.; Zhang, H. B.; Yang, Z. Q.; Che, R. C. Dimensional design and core-shell engineering of nanomaterials for electromagnetic wave absorption. Adv. Mater. 2022, 34, 2107538.

    Article  CAS  Google Scholar 

  8. Zhang, X. J.; Zhu, J. Q.; Yin, P. G.; Guo, A. P.; Huang, A. P.; Guo, L.; Wang, G. S. Tunable high-performance microwave absorption of Co1−xS hollow spheres constructed by nanosheets within ultralow filler loading. Adv. Funct. Mater. 2018, 28, 1800761.

    Article  Google Scholar 

  9. Zhang, Y.; Huang, Y.; Chen, H. H.; Huang, Z. Y.; Yang, Y.; Xiao, P. S.; Zhou, Y.; Chen, Y. S. Composition and structure control of ultralight graphene foam for high-performance microwave absorption. Carbon 2016, 105, 438–447.

    Article  CAS  Google Scholar 

  10. Ye, F.; Song, Q.; Zhang, Z. C.; Li, W.; Zhang, S. Y.; Yin, X. W.; Zhou, Y. Z.; Tao, H. W.; Liu, Y. S.; Cheng, L. F. et al. Direct growth of edge-rich graphene with tunable dielectric properties in porous Si3N4 ceramic for broadband high-performance microwave absorption. Adv. Funct. Mater. 2018, 28, 1707205.

    Article  Google Scholar 

  11. Li, C.; Li, Z. H.; Qi, X. S.; Gong, X.; Chen, Y. L.; Peng, Q.; Deng, C. Y.; Jing, T.; Zhong, W. A generalizable strategy for constructing ultralight three-dimensional hierarchical network heterostructure as high-efficient microwave absorber. J. Colloid Interf. Sci. 2022, 605, 13–22.

    Article  CAS  Google Scholar 

  12. Liu, P. B.; Gao, S.; Wang, Y.; Huang, Y.; He, W. J.; Huang, W. H.; Luo, J. H. Carbon nanocages with N-doped carbon inner shell and Co/N-doped carbon outer shell as electromagnetic wave absorption materials. Chem. Eng. J. 2020, 381, 122653.

    Article  CAS  Google Scholar 

  13. Zhao, H. H.; Xu, X. Z.; Wang, Y. H.; Fan, D. G.; Liu, D. W.; Lin, K. F.; Xu, P.; Han, X. J.; Du, Y. C. Heterogeneous interface induced the formation of hierarchically hollow carbon microcubes against electromagnetic pollution. Small 2020, 16, 2003407.

    Article  CAS  Google Scholar 

  14. Li, T.; Zhi, D. D.; Chen, Y.; Li, B.; Zhou, Z. W.; Meng, F. B. Multiaxial electrospun generation of hollow graphene aerogel spheres for broadband high-performance microwave absorption. Nano Res. 2020, 13, 477–484.

    Article  CAS  Google Scholar 

  15. Wu, Z. C.; Pei, K.; Xing, L. S.; Yu, X. F.; You, W. B.; Che, R. C. Enhanced microwave absorption performance from magnetic coupling of magnetic nanoparticles suspended within hierarchically tubular composite. Adv. Funct. Mater. 2019, 29, 1901448.

    Article  Google Scholar 

  16. Gu, W. H.; Sheng, J. Q.; Huang, Q. Q.; Wang, G. H.; Chen, J. B.; Ji, G. B. Environmentally friendly and multifunctional shaddock peel-based carbon aerogel for thermal-insulation and microwave absorption. Nano-Micro Lett. 2021, 13, 102.

    Article  CAS  Google Scholar 

  17. Zhao, H. Q.; Cheng, Y.; Liu, W.; Yang, L. J.; Zhang, B. S.; Wang, L. P.; Ji, G. B.; Xu, Z. J. Biomass-derived porous carbon-based nanostructures for microwave absorption. Nano-Micro Lett. 2019, 11, 24.

    Article  CAS  Google Scholar 

  18. Liu, Z. C.; Pan, F.; Deng, B. W.; Xiang, Z.; Lu, W. Self-assembled MoS2/3D worm-like expanded graphite hybrids for high-efficiency microwave absorption. Carbon 2021, 174, 59–69.

    Article  CAS  Google Scholar 

  19. Zhang, X.; Cheng, J.; Xiang, Z.; Cai, L.; Lu, W. A hierarchical Co@mesoporous C/macroporous C sheet composite derived from bimetallic MOF and oroxylum indicum for enhanced microwave absorption. Carbon 2022, 187, 477–487.

    Article  CAS  Google Scholar 

  20. Luo, J. H.; Dai, Z. Y.; Feng, M. N.; Chen, X. W.; Sun, C. H.; Xu, Y. Hierarchically porous carbon derived from natural porphyra for excellent electromagnetic wave absorption. J. Mater. Sci. Technol. 2022, 129, 206–214.

    Article  Google Scholar 

  21. Li, C.; Qi, X. S.; Gong, X.; Peng, Q.; Chen, Y. L.; Xie, R.; Zhong, W. Magnetic-dielectric synergy and interfacial engineering to design yolk—shell structured CoNi@void@C and CoNi@void@C@MoS2 nanocomposites with tunable and strong wideband microwave absorption. Nano Res. 2022, 15, 6761–6771.

    Article  CAS  Google Scholar 

  22. Zhang, J. J.; Qi, X. S.; Gong, X.; Peng, Q.; Chen, Y. L.; Xie, R.; Zhong, W. Microstructure optimization of core@shell structured MSe2/FeSe2@MoSe2 (M = Co, Ni) flower-like multicomponent nanocomposites towards high-efficiency microwave absorption. J. Mater. Sci. Technol. 2022, 128, 59–70.

    Article  Google Scholar 

  23. Liu, P. B.; Gao, S.; Zhang, G. Z.; Huang, Y.; You, W. B.; Che, R. C. Hollow engineering to Co@N-doped carbon nanocages via synergistic protecting-etching strategy for ultrahigh microwave absorption. Adv. Funct. Mater. 2021, 31, 2102812.

    Article  CAS  Google Scholar 

  24. Liu, D. W.; Du, Y. C.; Xu, P.; Wang, F. Y.; Wang, Y. H.; Cui, L. R.; Zhao, H. H.; Han, X. J. Rationally designed hierarchical N-doped carbon nanotubes wrapping waxberry-like Ni@C microspheres for efficient microwave absorption. J. Mater. Chem. A 2021, 9, 5086–5096.

    Article  CAS  Google Scholar 

  25. Liu, P. B.; Zhang, Y. Q.; Yan, J.; Huang, Y.; Xia, L.; Guang, Z. X. Synthesis of lightweight N-doped graphene foams with open reticular structure for high-efficiency electromagnetic wave absorption. Chem. Eng. J. 2019, 368, 285–298.

    Article  CAS  Google Scholar 

  26. Sun, Y. W.; Wang, H. L.; Wei, W. R.; Zheng, Y. L.; Tao, L.; Wang, Y. X.; Huang, M. H.; Shi, J.; Shi, Z. C.; Mitlin, D. Sulfur-rich graphene nanoboxes with ultra-high potassiation capacity at fast charge: Storage mechanisms and device performance. ACS Nano 2021, 15, 1652–1665.

    Article  CAS  Google Scholar 

  27. Luo, J. H.; Feng, M. N.; Dai, Z. Y.; Jiang, C. Y.; Yao, W.; Zhai, N. X. MoS2 wrapped MOF-derived N-doped carbon nanocomposite with wideband electromagnetic wave absorption. Nano Res. 2022, 15, 5781–5789.

    Article  CAS  Google Scholar 

  28. Liu, P. B.; Wang, Y.; Zhang, G. Z.; Huang, Y.; Zhang, R. X.; Liu, X. H.; Zhang, X. F.; Che, R. C. Hierarchical engineering of double-shelled nanotubes toward hetero-interfaces induced polarization and microscale magnetic interaction. Adv. Funct. Mater., in press, https://doi.org/10.1002/adfm.202202588.

  29. Xu, H. X.; Zhang, G. Z.; Wang, Y.; Ning, M. Q.; Ouyang, B.; Zhao, Y.; Huang, Y.; Liu, P. B. Size-dependent oxidation-induced phase engineering for MOFs derivatives via spatial confinement strategy toward enhanced microwave absorption. Nano-Micro Lett. 2022, 14, 102.

    Article  Google Scholar 

  30. Wu, T. J.; Jing, M. J.; Yang, L.; Zou, G. Q.; Hou, H. S.; Zhang, Y.; Zhang, Y.; Cao, X. Y.; Ji, X. B. Controllable chain-length for covalent sulfur-carbon materials enabling stable and high-capacity sodium storage. Adv. Energy Mater. 2019, 9, 1803478.

    Article  Google Scholar 

  31. Wang, J. J.; Yu, S. L.; Wu, Q. Q.; Li, Y.; Li, F. Y.; Zhou, X.; Chen, Y. H.; Li, B. Z.; Liu, P. B. Heterogeneous junctions of magnetic Ni core@binary dielectric shells toward high-efficiency microwave attenuation. J. Mater. Sci. Technol. 2022, 115, 71–80.

    Article  Google Scholar 

  32. Yu, Y. H.; Yi, P.; Xu, W. B.; Sun, X.; Deng, G.; Liu, X. F.; Shui, J. L.; Yu, R. H. Environmentally tough and stretchable MXene organohydrogel with exceptionally enhanced electromagnetic interference shielding performances. Nano-Micro Lett. 2022, 14, 77.

    Article  CAS  Google Scholar 

  33. Li, Y.; Liu, X. F.; Nie, X. Y.; Yang, W. W.; Wang, Y. D.; Yu, R. H.; Shui, J. L. Multifunctional organic-inorganic hybrid aerogel for self-cleaning, heat-insulating, and highly efficient microwave absorbing material. Adv. Funct. Mater. 2019, 99, 1807624.

    Article  Google Scholar 

  34. Han, Y. X.; Ruan, K. P.; Gu, J. W. Janus (BNNS/ANF)-(AgNWs/ANF) thermal conductivity composite films with superior electromagnetic interference shielding and Joule heating performances. Nano Res. 2022, 15, 4747–4755.

    Article  CAS  Google Scholar 

  35. Zhang, Y. L.; Ruan, K. P.; Gu, J. W. Flexible sandwich-structured electromagnetic interference shielding nanocomposite films with excellent thermal conductivities. Small 2021, 17, 2101951.

    Article  CAS  Google Scholar 

  36. Cao, M. S.; Han, C.; Wang, X. X.; Zhang, M.; Zhang, Y. L.; Shu, J. C.; Yang, H. J.; Fang, X. Y.; Yuan, J. Graphene nanohybrids: Excellent electromagnetic properties for the absorbing and shielding of electromagnetic waves. J. Mater. Chem. C 2018, 6, 4586–4602.

    Article  CAS  Google Scholar 

  37. Wang, L.; Ma, Z. L.; Zhang, Y. L.; Chen, L. X.; Cao, D. P.; Gu, J. W. Polymer-based EMI shielding composites with 3D conductive networks: A mini-review. SusMat 2021, 1, 413–431.

    Article  CAS  Google Scholar 

  38. Huang, W. H.; Gao, W. M.; Zuo, S. W.; Zhang, L. X.; Pei, K.; Liu, P. B.; Che, R. C.; Zhang, H. B. Hollow MoC/NC sphere for electromagnetic wave attenuation: Direct observation of interfacial polarization on nanoscale hetero-interfaces. J. Mater. Chem. A 2022, 10, 1290–1298.

    Article  CAS  Google Scholar 

  39. Liu, Q. H.; Cao, Q.; Bi, H.; Liang, C. Y.; Yuan, K. P.; She, W.; Yang, Y. J.; Che, R. C. CoNi@SiO2@TiO2 and CoNi@Air@TiO2 microspheres with strong wideband microwave absorption. Adv. Mater. 2016, 28, 486–490.

    Article  CAS  Google Scholar 

  40. Li, W. J.; Li, W. C.; Ying, Y.; Yu, J.; Zheng, J. W.; Qiao, L.; Li, J.; Che, S. L. Multifunctional flower-like core-shell Fe/Fe4N@SiO2 composites for broadband and high-efficiency ultrathin electromagnetic wave absorber. J. Mater. Sci. Technol. 2023, 132, 90–99.

    Article  Google Scholar 

  41. Song, L. M.; Chen, Y. Q.; Gao, Q. C.; Li, Z.; Zhang, X. Y.; Wang, H. L.; Guan, L.; Yu, Z. J.; Zhang, R.; Fan, B. B. Low weight, low thermal conductivity, and highly efficient electromagnetic wave absorption of three-dimensional graphene/SiC-nanosheets aerogel. Compos. Part A 2022, 158, 106980.

    Article  CAS  Google Scholar 

  42. Song, P.; Ma, Z. L.; Qiu, H.; Ru, Y. F.; Gu, J. W. High-efficiency electromagnetic interference shielding of rGO@FeNi/epoxy composites with regular honeycomb structures. Nano-Micro Lett. 2022, 14, 51.

    Article  CAS  Google Scholar 

  43. Du, H.; Zhang, Q. P.; Zhao, B.; Marken, F.; Gao, Q. C.; Lu, H. X.; Guan, L.; Wang, H. L.; Shao, G.; Xu, H. L. et al. Novel hierarchical structure of MoS2/TiO2/Ti3C2Tx composites for dramatically enhanced electromagnetic absorbing properties. J. Add. Ceram. 2021, 10, 1042–1051.

    Article  CAS  Google Scholar 

  44. Hu, F. Y.; Wang, X. H.; Bao, S.; Song, L. M.; Zhang, S.; Niu, H. H.; Fan, B. B.; Zhang, R.; Li, H. X. Tailoring electromagnetic responses of delaminated Mo2TiC2Tx MXene through the decoration of Ni particles of different morphologies. Chem. Eng. J. 2022, 440, 135855.

    Article  CAS  Google Scholar 

  45. Li, W. C.; Xu, L. Y.; Zhang, X.; Gong, Y.; Ying, Y.; Yu, J.; Zheng, J. W.; Qiao, L.; Che, S. L. Investigating the effect of honeycomb structure composite on microwave absorption properties. Compos. Commun. 2020, 19, 182–188.

    Article  Google Scholar 

  46. Kuang, B. Y.; Song, W. L.; Ning, M. Q.; Li, J. B.; Zhao, Z. J.; Guo, D. Y.; Cao, M. S.; Jin, H. B. Chemical reduction dependent dielectric properties and dielectric loss mechanism of reduced graphene oxide. Carbon 2018, 127, 209–217.

    Article  CAS  Google Scholar 

  47. Sun, L.; Shi, S. C.; He, B. L.; Wang, H. L.; Liu, S.; Huang, M. H.; Shi, J.; Dastan, D.; Wang, H. Asymmetric trilayer all-polymer dielectric composites with simultaneous high efficiency and high energy density: A novel design targeting advanced energy storage capacitors. Add. Funct. Mater. 2021, 31, 2100280.

    Article  CAS  Google Scholar 

  48. Sun, S. B.; Shi, Z. C.; Sun, L.; Liang, L.; Dastan, D.; He, B. L.; Wang, H. L.; Huang, M. H.; Fan, R. H. Achieving concurrent high energy density and efficiency in all-polymer layered paraelectric/ferroelectric composites via introducing a moderate layer. ACS Appl. Mater. Interfaces 2021, 13, 27522–27532.

    Article  CAS  Google Scholar 

  49. Sun, L.; Shi, Z. C.; Liang, L.; Dong, J. F.; Pan, Z. Z.; Wang, H. L.; Gao, Z.; Qin, Y.; Fan, R. H.; Wang, H. Concurrently achieving high discharged energy density and efficiency in composites by introducing ultralow loadings of core-shell structured graphene@TiO2 nanoboxes. ACS Appl. Mater. Interfaces 2022, 14, 29292–29301.

    Article  CAS  Google Scholar 

  50. Ma, T. B.; Ma, H.; Ruan, K. P.; Shi, X. T.; Qiu, H.; Gao, S. Y.; Gu, J. W. Thermally conductive poly(lactic acid) composites with superior electromagnetic shielding performances via 3D printing technology. Chin. J. Polym. Sci. 2022, 40, 248–255.

    Article  CAS  Google Scholar 

  51. Wang, H. Y.; Sun, X. B.; Yang, S. H.; Zhao, P. Y.; Zhang, X. J.; Wang, G. S.; Huang, Y. 3D ultralight hollow NiCo compound@MXene composites for tunable and high-efficient microwave absorption. Nano-Micro Lett. 2021, 13, 206.

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the Natural Science Foundation of Shaanxi Province (No. 2022JM-260), the Natural Science Foundation of Shandong Province (No. ZR2020ME038), and the Fundamental Research Funds of the Central Universities (No. G2022KY05109).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an, 710129, China

    Hanxiao Xu, Guozheng Zhang, Yi Wang, Yiruo Wang, Ying Huang & Panbo Liu

  2. School of Materials Science and Engineering, Ocean University of China, Qingdao, 266100, China

    Huanlei Wang

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  1. Hanxiao Xu
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  2. Guozheng Zhang
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  3. Yi Wang
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  4. Yiruo Wang
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  7. Panbo Liu
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Correspondence to Huanlei Wang or Panbo Liu.

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Xu, H., Zhang, G., Wang, Y. et al. Heteroatoms-doped carbon nanocages with enhanced dipolar and defective polarization toward light-weight microwave absorbers. Nano Res. 15, 8705–8713 (2022). https://doi.org/10.1007/s12274-022-4820-6

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