Issue

Vol. 16 (2024)

Multifunctional Film Assembled from N-Doped Carbon Nanofiber with Co–N4–O Single Atoms for Highly Efficient Electromagnetic Energy Attenuation

https://doi.org/10.1007/s40820-024-01440-2
Jia Xu
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Bei Li
Key Laboratory of In‑Fiber Integrated Optics, College of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Zheng Ma
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Xiao Zhang
Key Laboratory of In‑Fiber Integrated Optics, College of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Chunling Zhu
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Feng Yan
Key Laboratory of In‑Fiber Integrated Optics, College of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Piaoping Yang
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China
Yujin Chen
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, People’s Republic of China

Corresponding Author: Yujin Chen

chenyujin@hrbeu.edu.cn

Nano-Micro Letters, Vol. 16 (2024), Article Number: 240

Abstract

Single-atom materials have demonstrated attractive physicochemical characteristics. However, understanding the relationships between the coordination environment of single atoms and their properties at the atomic level remains a considerable challenge. Herein, a facile water-assisted carbonization approach is developed to fabricate well-defined asymmetrically coordinated Co–N4–O sites on biomass-derived carbon nanofiber (Co–N4–O/NCF) for electromagnetic wave (EMW) absorption. In such nanofiber, one atomically dispersed Co site is coordinated with four N atoms in the graphene basal plane and one oxygen atom in the axial direction. In-depth experimental and theoretical studies reveal that the axial Co–O coordination breaks the charge distribution symmetry in the planar porphyrin-like Co–N4 structure, leading to significantly enhanced dielectric polarization loss relevant to the planar Co–N4 sites. Importantly, the film based on Co–N4–O/NCF exhibits light weight, flexibility, excellent mechanical properties, great thermal insulating feature, and excellent EMW absorption with a reflection loss of − 45.82 dB along with an effective absorption bandwidth of 4.8 GHz. The findings of this work offer insight into the relationships between the single-atom coordination environment and the dielectric performance, and the proposed strategy can be extended toward the engineering of asymmetrically coordinated single atoms for various applications.


Highlights:
1 Asymmetrically coordinated Co–N4–O sites on N-doped carbon nanofiber were prepared.
2 Co–O coordination along the axial direction led to enhanced dielectric polarization loss.
3 Multifunctional films were developed for practical application in harsh environments.

Keywords

Co single atoms Asymmetric coordination structure Axial oxygen coordination Electromagnetic wave absorption Multifunctional film
Xu, Jia, Bei Li, Zheng Ma, Xiao Zhang, Chunling Zhu, Feng Yan, Piaoping Yang, and Yujin Chen. 2024. “Multifunctional Film Assembled from N-Doped Carbon Nanofiber With Co–N4–O Single Atoms for Highly Efficient Electromagnetic Energy Attenuation”. Nano-Micro Letters 16 (July):240. https://doi.org/10.1007/s40820-024-01440-2.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. F. Shahzad, M. Alhabeb, C.B. Hatter, B. Anasori, S. Man Hong et al., Electromagnetic interference shielding with 2D transition metal carbides (MXenes). Science 353, 1137–1140 (2016). https://doi.org/10.1126/science.aag2421
  2. A. Iqbal, F. Shahzad, K. Hantanasirisakul, M.K. Kim, J. Kwon et al., Anomalous absorption of electromagnetic waves by 2D transition metal carbonitride Ti3CNTx (MXene). Science 369, 446–450 (2020). https://doi.org/10.1126/science.aba7977
  3. Y. Li, X. Chen, Q. Wei, W. Liu, Y. Zhang et al., Oxygen-sulfur Co-substitutional Fe@C nanocapsules for improving microwave absorption properties. Sci. Bull. 65, 623–630 (2020). https://doi.org/10.1016/j.scib.2020.01.009
  4. M. Cheng, M. Ying, R. Zhao, L. Ji, H. Li et al., Transparent and flexible electromagnetic interference shielding materials by constructing sandwich AgNW@MXene/wood composites. ACS Nano 16, 16996–17007 (2022). https://doi.org/10.1021/acsnano.2c07111
  5. X. Zuo, H. Zhang, C. Zhou, Y. Zhao, H. Huang et al., Hierarchical and porous structures of carbon nanotubes-anchored MOF derivatives bridged by carbon nanocoils as lightweight and broadband microwave absorbers. Small 19, e2301992 (2023). https://doi.org/10.1002/smll.202301992
  6. Y. Zhao, H. Qi, X. Dong, Y. Yang, W. Zhai, Customizable resilient multifunctional graphene aerogels via blend-spinning assisted freeze casting. ACS Nano 17, 15615–15628 (2023). https://doi.org/10.1021/acsnano.3c02491
  7. S. Yu, W. Guo, Z. Zhou, Y. Li, J. Qiu, Rough-endoplasmic-reticulum-like hierarchical composite structures for efficient mechanical-electromagnetic wave-energy attenuation. Adv. Funct. Mater. 34, 2312835 (2024). https://doi.org/10.1002/adfm.202312835
  8. Y. Li, Y. Liao, L. Ji, C. Hu, Z. Zhang et al., Quinary high-entropy-alloy@graphite nanocapsules with tunable interfacial impedance matching for optimizing microwave absorption. Small 18, e2107265 (2022). https://doi.org/10.1002/smll.202107265
  9. P. Zhu, X. Xiong, D. Wang, Y. Li, Advances and regulation strategies of the active moiety in dual-atom site catalysts for efficient electrocatalysis. Adv. Energy Mater. 13, 2300884 (2023). https://doi.org/10.1002/aenm.202300884
  10. M. Duan, C. Huang, G. Zhang, H. Shi, P. Zhang et al., Spin-state conversion by asymmetrical orbital hybridization in Ni-doped Co3O4 to boost singlet oxygen generation for microbial disinfection. Angew. Chem. Int. Ed. 63, e202318924 (2024). https://doi.org/10.1002/anie.202318924
  11. P. Yang, J. Li, D.G. Vlachos, S. Caratzoulas, Tuning active site flexibility by defect engineering of graphene ribbon edge-hosted Fe-N3 sites. Angew. Chem. Int. Ed. 63, e202311174 (2024). https://doi.org/10.1002/anie.202311174
  12. X. Wan, X. Liu, Y. Li, R. Yu, L. Zheng et al., Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells. Nat. Catal. 2, 259–268 (2019). https://doi.org/10.1038/s41929-019-0237-3
  13. J. Xi, H.S. Jung, Y. Xu, F. Xiao, J.W. Bae et al., Synthesis strategies, catalytic applications, and performance regulation of single-atom catalysts. Adv. Funct. Mater. 31, 2008318 (2021). https://doi.org/10.1002/adfm.202008318
  14. J. Xu, M. Liu, X. Zhang, B. Li, X. Zhang et al., Atomically dispersed cobalt anchored on N-doped graphene aerogels for efficient electromagnetic wave absorption with an ultralow filler ratio. Appl. Phys. Rev. 9, 011402 (2022). https://doi.org/10.1063/5.0067791
  15. Y. Shi, Z. Ma, X. Zhang, F. Yan, Y. Zhao et al., Flexible film constructed by asymmetrically-coordinated La1N4Cl1 moieties on interconnected nitrogen-doped graphene nanocages for high-efficiency electromagnetic wave absorption. Adv. Funct. Mater. 34, 2313483 (2024). https://doi.org/10.1002/adfm.202313483
  16. X. Zhang, B. Li, J. Xu, X. Zhang, Y. Shi et al., Metal ions confined in periodic pores of MOFs to embed single-metal atoms within hierarchically porous carbon nanoflowers for high-performance electromagnetic wave absorption. Adv. Funct. Mater. 33, 2210456 (2023). https://doi.org/10.1002/adfm.202210456
  17. H. Liu, X. Li, X. Zhao, M. Zhang, X. Liu et al., Large annular dipoles bounded between single-atom Co and Co cluster for clarifying electromagnetic wave absorbing mechanism. Adv. Funct. Mater. 33, 2304442 (2023). https://doi.org/10.1002/adfm.202304442
  18. H. Yuan, B. Li, C. Zhu, Y. Xie, Y. Jiang et al., Dielectric behavior of single iron atoms dispersed on nitrogen-doped nanocarbon. Appl. Phys. Lett. 116, 153101 (2020). https://doi.org/10.1063/1.5143154
  19. T. Gao, R. Zhao, Y. Li, Z. Zhu, C. Hu et al., Sub-nanometer Fe clusters confined in carbon nanocages for boosting dielectric polarization and broadband electromagnetic wave absorption. Adv. Funct. Mater. 32, 2204370 (2022). https://doi.org/10.1002/adfm.202204370
  20. P. Cui, Q. Yang, C. Liu, Y. Wang, G. Fang et al., An N, S-anchored single-atom catalyst derived from domestic waste for environmental remediation. ACS ES&T Engg. 1, 1460–1469 (2021). https://doi.org/10.1021/acsestengg.1c00255
  21. Y. Jia, Z. Xue, J. Yang, Q. Liu, J. Xian et al., Tailoring the electronic structure of an atomically dispersed zinc electrocatalyst: coordination environment regulation for high selectivity oxygen reduction. Angew. Chem. Int. Ed. 61, e202110838 (2022). https://doi.org/10.1002/anie.202110838
  22. L. Shen, D. Ye, H. Zhao, J. Zhang, Perspectives for single-atom nanozymes: advanced synthesis, functional mechanisms, and biomedical applications. Anal. Chem. 93, 1221–1231 (2021). https://doi.org/10.1021/acs.analchem.0c04084
  23. S. Zhang, X. Ao, J. Huang, B. Wei, Y. Zhai et al., Isolated single-atom Ni–N5 catalytic site in hollow porous carbon capsules for efficient lithium–sulfur batteries. Nano Lett. 21, 9691–9698 (2021). https://doi.org/10.1021/acs.nanolett.1c03499
  24. X. Zhang, P. Zhai, Y. Zhang, Y. Wu, C. Wang et al., Engineering single-atomic Ni-N4-O sites on semiconductor photoanodes for high-performance photoelectrochemical water splitting. J. Am. Chem. Soc. 143, 20657–20669 (2021). https://doi.org/10.1021/jacs.1c07391
  25. M. Huang, B. Deng, X. Zhao, Z. Zhang, F. Li et al., Template-sacrificing synthesis of well-defined asymmetrically coordinated single-atom catalysts for highly efficient CO2 electrocatalytic reduction. ACS Nano 16, 2110–2119 (2022). https://doi.org/10.1021/acsnano.1c07746
  26. H. Jin, P. Li, P. Cui, J. Shi, W. Zhou et al., Unprecedentedly high activity and selectivity for hydrogenation of nitroarenes with single atomic Co1-N3P1 sites. Nat. Commun. 13, 723 (2022). https://doi.org/10.1038/s41467-022-28367-9
  27. B. Chang, Z. Cao, Y. Ren, C. Chen, L. Cavallo et al., Electronic perturbation of isolated Fe coordination structure for enhanced nitrogen fixation. ACS Nano 18, 288–298 (2024). https://doi.org/10.1021/acsnano.3c06212
  28. G. Zhang, F. Tang, X. Wang, L. Wang, Y.-N. Liu, Atomically dispersed Co–S–N active sites anchored on hierarchically porous carbon for efficient catalytic hydrogenation of nitro compounds. ACS Catal. 12, 5786–5794 (2022). https://doi.org/10.1021/acscatal.2c01113
  29. J. Shi, Y. Wei, D. Zhou, L. Zhang, X. Yang et al., Introducing Co–O moiety to Co–N–C single-atom catalyst for ethylbenzene dehydrogenation. ACS Catal. 12, 7760–7772 (2022). https://doi.org/10.1021/acscatal.2c01873
  30. C. Tang, L. Chen, H. Li, L. Li, Y. Jiao et al., Tailoring acidic oxygen reduction selectivity on single-atom catalysts via modification of first and second coordination spheres. J. Am. Chem. Soc. 143, 7819–7827 (2021). https://doi.org/10.1021/jacs.1c03135
  31. L. Zhang, N. Jin, Y. Yang, X.-Y. Miao, H. Wang et al., Advances on axial coordination design of single-atom catalysts for energy electrocatalysis: a review. Nano-Micro Lett. 15, 228 (2023). https://doi.org/10.1007/s40820-023-01196-1
  32. C. Chen, Z. Chen, J. Zhong, X. Song, D. Chen et al., Regulating electronic structure of CoN4 with axial Co—S for promoting oxygen reduction and Zn-air battery performance. Nano Res. 16, 4211–4218 (2023). https://doi.org/10.1007/s12274-022-5164-y
  33. N. Yu, H. Chen, J. Kuang, K. Bao, W. Yan et al., Efficient oxygen electrocatalysts with highly-exposed Co-N4 active sites on N-doped graphene-like hierarchically porous carbon nanosheets enhancing the performance of rechargeable Zn-air batteries. Nano Res. 15, 7209–7219 (2022). https://doi.org/10.1007/s12274-022-4382-7
  34. Y. Hou, M. Qiu, M.G. Kim, P. Liu, G. Nam et al., Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets for efficient water oxidation. Nat. Commun. 10, 1392 (2019). https://doi.org/10.1038/s41467-019-09394-5
  35. J. Wan, Z. Zhao, H. Shang, B. Peng, W. Chen et al., In situ phosphatizing of triphenylphosphine encapsulated within metal-organic frameworks to design atomic Co1-P1N3 interfacial structure for promoting catalytic performance. J. Am. Chem. Soc. 142, 8431–8439 (2020). https://doi.org/10.1021/jacs.0c02229
  36. B. Wang, Y. Ren, Y. Zhu, S. Chen, S. Chang et al., Construction of Co3O4/ZnO heterojunctions in hollow N-doped carbon nanocages as microreactors for lithium-sulfur full batteries. Adv. Sci. 10, e2300860 (2023). https://doi.org/10.1002/advs.202300860
  37. X. Sun, Y. Li, Y. Huang, Y. Cheng, S. Wang et al., Achieving super broadband electromagnetic absorption by optimizing impedance match of rGO sponge metamaterials. Adv. Funct. Mater. 32, 2107508 (2021). https://doi.org/10.1002/adfm.202107508
  38. X. Ren, J. Zhao, X. Li, J. Shao, B. Pan et al., In-situ spectroscopic probe of the intrinsic structure feature of single-atom center in electrochemical CO/CO2 reduction to methanol. Nat. Commun. 14, 3401 (2023). https://doi.org/10.1038/s41467-023-39153-6
  39. J. Gao, Y. Wang, H. Wu, X. Liu, L. Wang et al., Construction of a sp3/sp2 carbon interface in 3D N-Doped nanocarbons for the oxygen reduction reaction. Angew. Chem. Int. Ed. 58, 15089–15097 (2019). https://doi.org/10.1002/anie.201907915
  40. C. Tang, B.-Q. Li, Q. Zhang, L. Zhu, H.-F. Wang et al., CaO-templated growth of hierarchical porous graphene for high-power lithium–sulfur battery applications. Adv. Funct. Mater. 26, 577–585 (2016). https://doi.org/10.1002/adfm.201503726
  41. N. Ramaswamy, U. Tylus, Q. Jia, S. Mukerjee, Activity descriptor identification for oxygen reduction on nonprecious electrocatalysts: linking surface science to coordination chemistry. J. Am. Chem. Soc. 135, 15443–15449 (2013). https://doi.org/10.1021/ja405149m
  42. A. Zitolo, V. Goellner, V. Armel, M.-T. Sougrati, T. Mineva et al., Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 14, 937–942 (2015). https://doi.org/10.1038/nmat4367
  43. Y. Chen, S. Ji, Y. Wang, J. Dong, W. Chen et al., Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew. Chem. Int. Ed. 56, 6937–6941 (2017). https://doi.org/10.1002/anie.201702473
  44. H. Gong, Z. Wei, Z. Gong, J. Liu, G. Ye et al., Low-coordinated Co-N-C on oxygenated graphene for efficient electrocatalytic H2O2 production. Adv. Funct. Mater. 32, 2106886 (2021). https://doi.org/10.1002/adfm.202106886
  45. X. Wang, Y. Pan, H. Ning, H. Wang, D. Guo et al., Hierarchically micro- and meso-porous Fe-N4O-doped carbon as robust electrocatalyst for CO2 reduction. Appl. Catal. B Environ. 266, 118630 (2020). https://doi.org/10.1016/j.apcatb.2020.118630
  46. M. Cao, X. Wang, W. Cao, X. Fang, B. Wen et al., Thermally driven transport and relaxation switching self-powered electromagnetic energy conversion. Small 14, e1800987 (2018). https://doi.org/10.1002/smll.201800987
  47. H. Zhang, J. Cheng, H. Wang, Z. Huang, Q. Zheng et al., Initiating VB-group laminated NbS2 electromagnetic wave absorber toward superior absorption bandwidth as large as 6.48GHz through phase engineering modulation. Adv. Funct. Mater. 32, 2108194 (2022). https://doi.org/10.1002/adfm.202108194
  48. M. Ning, P. Jiang, W. Ding, X. Zhu, G. Tan et al., Phase manipulating toward molybdenum disulfide for optimizing electromagnetic wave absorbing in gigahertz. Adv. Funct. Mater. 31, 2011229 (2021). https://doi.org/10.1002/adfm.202011229
  49. Z. Wu, K. Pei, L. Xing, X. Yu, W. You et al., Enhanced microwave absorption performance from magnetic coupling of magnetic nanops suspended within hierarchically tubular composite. Adv. Funct. Mater. 29, 1901448 (2019). https://doi.org/10.1002/adfm.201901448
  50. J. Qiao, X. Zhang, C. Liu, L. Lyu, Y. Yang et al., Non-magnetic bimetallic MOF-derived porous carbon-wrapped TiO2/ZrTiO4 composites for efficient electromagnetic wave absorption. Nano-Micro Lett. 13, 75 (2021). https://doi.org/10.1007/s40820-021-00606-6
  51. Z. Gao, D. Lan, L. Zhang, H. Wu, Simultaneous manipulation of interfacial and defects polarization toward Zn/Co phase and ion hybrids for electromagnetic wave absorption. Adv. Funct. Mater. 31, 2106677 (2021). https://doi.org/10.1002/adfm.202106677
  52. T. Zhu, W. Shen, X. Wang, Y.-F. Song, 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, 122159 (2019). https://doi.org/10.1016/j.cej.2019.122159
  53. C. Xu, L. Wang, X. Li, X. Qian, Z. Wu et al., Hierarchical magnetic network constructed by CoFe nanops suspended within “tubes on rods” matrix toward enhanced microwave absorption. Nano-Micro Lett. 13, 47 (2021). https://doi.org/10.1007/s40820-020-00572-5
  54. Y. Song, F. Yin, C. Zhang, W. Guo, L. Han et al., Three-dimensional ordered mesoporous carbon spheres modified with ultrafine zinc oxide nanops for enhanced microwave absorption properties. Nano-Micro Lett. 13, 76 (2021). https://doi.org/10.1007/s40820-021-00601-x
  55. Z. Zhou, Q. Zhu, Y. Liu, Y. Zhang, Z. Jia et al., Construction of self-assembly based tunable absorber: lightweight, hydrophobic and self-cleaning properties. Nano-Micro Lett. 15, 137 (2023). https://doi.org/10.1007/s40820-023-01108-3
  56. L. Wang, M. Huang, X. Qian, L. Liu, W. You et al., Confined magnetic-dielectric balance boosted electromagnetic wave absorption. Small 17, e2100970 (2021). https://doi.org/10.1002/smll.202100970
  57. X. Qian, Y. Zhang, Z. Wu, R. Zhang, X. Li et al., Multi-path electron transfer in 1D double-shelled Sn@Mo2C/C tubes with enhanced dielectric loss for boosting microwave absorption performance. Small 17, e2100283 (2021). https://doi.org/10.1002/smll.202100283
  58. X. Liang, Z. Man, B. Quan, J. Zheng, W. Gu et al., Environment-stable CoxNiy encapsulation in stacked porous carbon nanosheets for enhanced microwave absorption. Nano-Micro Lett. 12, 102 (2020). https://doi.org/10.1007/s40820-020-00432-2
  59. F. Pan, Z. Liu, B. Deng, Y. Dong, X. Zhu et al., Lotus leaf-derived gradient hierarchical porous C/MoS2 morphology genetic composites with wideband and tunable electromagnetic absorption performance. Nano-Micro Lett. 13, 43 (2021). https://doi.org/10.1007/s40820-020-00568-1
  60. H. Liang, G. Chen, D. Liu, Z. Li, S. Hui et al., Exploring the Ni 3d orbital unpaired electrons induced polarization loss based on Ni single-atoms model absorber. Adv. Funct. Mater. 33, 2212604 (2023). https://doi.org/10.1002/adfm.202212604
  61. F. Pan, M. Ning, Z. Li, D. Batalu, H. Guo et al., Sequential architecture induced strange dielectric-magnetic behaviors in ferromagnetic microwave absorber. Adv. Funct. Mater. 33, 2300374 (2023). https://doi.org/10.1002/adfm.202300374
  62. H. Jiang, L. Cai, F. Pan, Y. Shi, J. Cheng et al., Ordered heterostructured aerogel with broadband electromagnetic wave absorption based on mesoscopic magnetic superposition enhancement. Adv. Sci. 10, e2301599 (2023). https://doi.org/10.1002/advs.202301599
  63. F. Pan, K. Pei, G.-Y. Chen, H. Guo, H. Jiang et al., Integrated electromagnetic device with on-off heterointerface for intelligent switching between wave-absorption and wave-transmission. Adv. Funct. Mater. 33, 6599 (2023). https://doi.org/10.1002/adfm.202306599
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 2440 Download : 1802

Most read articles by the same author(s)