Dipole Polarization and Synchronous Magnetic Modulation Induced by FeN₄ Moiety on Ti₃C₂T_x for Superior Electromagnetic Wave Absorption Performance

Abstract

Polarization-dependent loss is important to the highly electromagnetic wave absorption (EWA) performance. Recently, metal–N_x moieties have been discovered to trigger polarization loss, but the physical origin and other possible related loss mechanisms still need to be deeply explored. In this article, we reveal that the FeN₄ moiety from iron phthalocyanine (FePc) can coordinate with Ti₃C₂T_x through Ti–OH groups, inducing dipole polarization and synchronous magnetic modulation in Fe/TiO₂/Ti₃C₂T_x composites. Interestingly, using the enhanced electric dipole moment and increased number of unpaired electrons in Fe atoms, the dipole polarization loss and possible magnetic response can be rapidly confirmed and evaluated. As a result, the minimum reflection loss (RL_min) of Fe/TiO₂/Ti₃C₂T_x composites reaches −67.12 dB at 6.72 GHz with a thickness of 3.32 mm. This study elaborates the EWA mechanism based on the atomic scale, and provides a new idea to design efficient EWA materials.

Keywords

dipole polarization / electromagnetic wave / FeN₄ moiety / magnetic property / Ti₃C₂T_x MXene

References

[1] H. Lv, Z. Yang, H. Pan, and R. Wu, “Electromagnetic Absorption Materials: Current Progress and New Frontiers,” Progress in Materials Science 127 (2022): 100946.

[2] F. Hu, P. Ding, F. Wu, et al., “Novel Cable-Like Tin@Carbon Whiskers Derived From the Ti₂SnC MAX Phase for Ultra-Wideband Electromagnetic Wave Absorption,” Carbon Energy 6, no. 12 (2024): e638.

[3] X. Liu, L. Wu, J. Liu, et al., “Dynamically Frequency-Tunable and Environmentally Stable Microwave Absorbers,” Carbon Energy 6, no. 10 (2024): e589.

[4] C. Gong, J. Ding, C. Wang, et al., “Defect-Induced Dipole Polarization Engineering of Electromagnetic Wave Absorbers: Insights and Perspectives,” Composites, Part B: Engineering 252 (2023): 110479.

[5] Z. Su, S. Yi, W. Zhang, et al., “Ultrafine Vacancy-Rich Nb₂O₅ Semiconductors Confined in Carbon Nanosheets Boost Dielectric Polarization for High-Attenuation Microwave Absorption,” Nano-Micro Letters 15 (2023): 183.

[6] J. Yu, J. Yu, T. Ying, X. Liu, X. Zhang, and D. Han, “Zeolitic Imidazolate Framework Derived Fe-N/C for Efficient Microwave Absorbers,” Journal of Alloys and Compounds 838 (2020): 155629.

[7] K.-M. Zhao, S. Liu, Y.-Y. Li, et al., “Insight Into the Mechanism of Axial Ligands Regulating the Catalytic Activity of Fe-N₄ Sites for Oxygen Reduction Reaction,” Advanced Energy Materials 12, no. 11 (2022): 2103588.

[8] W. Zhang, C. Shu, J. Zhan, S. Zhang, L. Zhang, and F. Yu, “Deep Electronic State Regulation Through Unidirectional Cascade Electron Transfer Induced by Dual Junction Boosting Electrocatalysis Performance,” Advanced Science 10, no. 31 (2023): 2304063.

[9] Y. Dai, B. Liu, Z. Zhang, et al., “Tailoring the d-Orbital Splitting Manner of Single Atomic Sites for Enhanced Oxygen Reduction,” Advanced Materials 35, no. 14 (2023): 2210757.

[10] Y. Lee, J. H. Ahn, H. Jang, et al., “Very Strong Interaction Between FeN₄ and Titanium Carbide for Durable 4-Electron Oxygen Reduction Reaction Suppressing Catalyst Deactivation by Peroxide,” Journal of Materials Chemistry A 10, no. 45 (2022): 24041-24050.

[11] Z. Li, Z. Zhuang, F. Lv, et al., “The Marriage of the FeN₄ Moiety and MXene Boosts Oxygen Reduction Catalysis: Fe 3d Electron Delocalization Matters,” Advanced Materials 30, no. 43 (2018): 1803220.

[12] T. Gao, R. Zhao, Y. Li, et al., “Sub-Nanometer Fe Clusters Confined in Carbon Nanocages for Boosting Dielectric Polarization and Broadband Electromagnetic Wave Absorption,” Advanced Functional Materials 32, no. 31 (2022): 2204370.

[13] Z. Du, L. Li, G. Shen, et al, “Proton-Conducting Hydrogel Electrolytes With Tight Contact to Binder-Free MXene Electrodes for High-Performance Thermally Chargeable Supercapacitor,” Carbon Energy 6, no. 11 (2024): e562.

[14] M. Li, W. Zhu, X. Li, et al., “Ti₃C₂T_x/MoS₂ Self-Rolling Rod-Based Foam Boosts Interfacial Polarization for Electromagnetic Wave Absorption,” Advanced Science 9, no. 16 (2022): 2201118.

[15] C. Peng, T. Zhou, P. Wei, et al., “Regulation of the Rutile/Anatase TiO₂ Phase Junction In-Situ Grown on -OH Terminated Ti₃C₂T_x (MXene) Towards Remarkably Enhanced Photocatalytic Hydrogen Evolution,” Chemical Engineering Journal 439 (2022): 135685.

[16] H. Liang, G. Chen, D. Liu, et al., “Exploring the Ni 3d Orbital Unpaired Electrons Induced Polarization Loss Based on Ni Single-Atoms Model Absorber,” Advanced Functional Materials 33, no. 7 (2023): 2212604.

[17] A. Sarycheva, M. Shanmugasundaram, A. Krayev, and Y. Gogotsi, “Tip-Enhanced Raman Scattering Imaging of Single-to Few-Layer Ti₃C₂T_x MXene,” ACS Nano 16, no. 4 (2022): 6858-6865.

[18] B. Ji, S. Fan, X. Ma, et al., “Electromagnetic Shielding Behavior of Heat-Treated Ti₃C₂T_x MXene Accompanied by Structural and Phase Changes,” Carbon 165 (2020): 150-162.

[19] H.-W. Cho, K.-L. Liao, J.-S. Yang, and J.-J. Wu, “Revelation of Rutile Phase by Raman Scattering for Enhanced Photoelectrochemical Performance of Hydrothermally-Grown Anatase TiO₂ Film,” Applied Surface Science 440 (2018): 125-132.

[20] N. Liu, Q. Li, H. Wan, et al., “High-Temperature Stability in Air of Ti₃C₂T_x MXene-Based Composite With Extracted Bentonite,” Nature Communications 13 (2022): 5551.

[21] J. Wei, D. Xia, Y. Wei, X. Zhu, J. Li, and L. Gan, “Probing the Oxygen Reduction Reaction Intermediates and Dynamic Active Site Structures of Molecular and Pyrolyzed Fe-N-C Electrocatalysts by In Situ Raman Spectroscopy,” ACS Catalysis 12, no. 13 (2022): 7811-7820.

[22] N. Li, B. Wen, X. Li, S. Yang, G. Yang, and S. Ding, “Phase Structure-Induced Amplification of Interfacial Polarization Loss for Excellent Electromagnetic Wave Absorption,” Chemical Engineering Journal 488 (2024): 150420.

[23] S. Doo, A. Chae, D. Kim, et al., “Mechanism and Kinetics of Oxidation Reaction of Aqueous Ti₃C₂T_x Suspensions at Different pHs and Temperatures,” ACS Applied Materials & Interfaces 13, no. 19 (2021): 22855-22865.

[24] Z. Zhang, M. Dou, J. Ji, and F. Wang, “Phthalocyanine Tethered Iron Phthalocyanine on Graphitized Carbon Black as Superior Electrocatalyst for Oxygen Reduction Reaction,” Nano Energy 34 (2017): 338-343.

[25] X. Zhang, C. Liu, J. Li, R. Chu, Y. Lyu, and Z. Lan, “Dual Source-Powered Multifunctional Pt/FePc@Mn-MOF Spindle-Like Janus Nanomotors for Active CT Imaging-Guided Synergistic Photothermal/Chemodynamic Therapy,” Journal of Colloid and Interface Science 657 (2024): 799-810.

[26] S. Xu, Y. Ding, J. Du, et al., “Immobilization of Iron Phthalocyanine on Pyridine-Functionalized Carbon Nanotubes for Efficient Nitrogen Reduction Reaction,” ACS Catalysis 12, no. 9 (2022): 5502-5509.

[27] M. Krämer, B. Favelukis, A. A. El-Zoka, et al., “Near-Atomic-Scale Perspective on the Oxidation of Ti₃C₂T_x MXenes: Insights From Atom Probe Tomography,” Advanced Materials 36, no. 3 (2024): 2305183.

[28] C. Zhou, X. Wang, H. Luo, et al., “Rapid and Direct Growth of Bipyramid TiO₂ From Ti₃C₂T_x MXene to Prepare Ni/TiO₂/C Heterogeneous Composites for High-Performance Microwave Absorption,” Chemical Engineering Journal 383 (2020): 123095.

[29] C. Jin, D. Sun, Z. Sun, et al., “Interfacial Engineering of Ni-Phytate and Ti₃C₂T_x MXene-Sensitized TiO₂ Toward Enhanced Sterilization Efficacy under 808 nm NIR Light Irradiation,” Applied Catalysis, B: Environmental 330 (2023): 122613.

[30] X. Xu, B. Sun, Z. Liang, H. Cui, and J. Tian, “High-Performance Electrocatalytic Conversion of N₂ to NH₃ Using Oxygen-Vacancy-Rich TiO₂ In Situ Grown on Ti₃C₂T_x MXene,” ACS Applied Materials & Interfaces 12, no. 23 (2020): 26060-26067.

[31] W. Cheng, P. Yuan, Z. Lv, et al., “Boosting Defective Carbon by Anchoring Well-Defined Atomically Dispersed Metal-N₄ Sites for ORR, OER, and Zn-Air Batteries,” Applied Catalysis, B: Environmental 260 (2020): 118198.

[32] H. Jiang, L. Cai, F. Pan, et al., “Ordered Heterostructured Aerogel With Broadband Electromagnetic Wave Absorption Based on Mesoscopic Magnetic Superposition Enhancement,” Advanced Science 10, no. 21 (2023): 2301599.

[33] Y. Wu, X. Song, W. Xu, et al., “NIR-Activated Multimodal Photothermal/Chemodynamic/Magnetic Resonance Imaging Nanoplatform for Anticancer Therapy by Fe(II) Ions Doped MXenes (Fe-Ti₃C₂),” Small 17, no. 33 (2021): 2101705.

[34] X. Zeng, C. Zhao, T. Nie, Z. Y. Shen, R. Yu, and G. D. Stucky, “Construction of 0D/1D/2D MXene Nanoribbons-NiCo@NC Hierarchical Network and Their Coupling Effect on Electromagnetic Wave Absorption,” Materials Today Physics 28 (2022): 100888.

[35] M. Ding, D. Zhao, R. Wei, et al., “Multifunctional Elastomeric Composites Based on 3D Graphene Porous Materials,” Exploration 4, no. 2 (2024): 20230057.

[36] P. Liu, Y. Zhang, J. Yan, Y. Huang, L. Xia, and Z. Guang, “Synthesis of Lightweight N-Doped Graphene Foams With Open Reticular Structure for High-Efficiency Electromagnetic Wave Absorption,” Chemical Engineering Journal 368 (2019): 285-298.

[37] Z. Liu, W. Gao, L. Liu, et al., “Work Function Mediated Interface Charge Kinetics for Boosting Photocatalytic Water Sterilization,” Journal of Hazardous Materials 442 (2023): 130036.

[38] S. Zhou, L. Jiang, H. Wang, et al., “Oxygen Vacancies Modified TiO₂/O-Terminated Ti₃C₂ Composites: Unravelling the Dual Effects Between Oxygen Vacancy and High-Work-Function Titanium Carbide,” Advanced Functional Materials 33, no. 41 (2023): 2307702.

[39] J.-P. Chen, Y.-F. Du, Z.-F. Wang, et al., “Anchoring of SiC Whiskers on the Hollow Carbon Microspheres Inducing Interfacial Polarization to Promote Electromagnetic Wave Attenuation Capability,” Carbon 175 (2021): 11-19.

[40] H. Liu, X. Li, X. Zhao, et al., “Large Annular Dipoles Bounded Between Single-Atom Co and Co Cluster for Clarifying Electromagnetic Wave Absorbing Mechanism,” Advanced Functional Materials 33, no. 40 (2023): 2304442.

[41] J. Liu, H. Liang, B. Wei, J. Yun, L. Zhang, and H. Wu, “Matryoshka Doll” Heterostructures Induce Electromagnetic Parameters Fluctuation to Tailor Electromagnetic Wave Absorption,” Small Structures 4, no. 7 (2023): 2200379.

[42] L. Chen, Y. Li, B. Zhao, et al., “Multiprincipal Element M₂FeC (M = Ti, V, Nb, Ta, Zr) MAX Phases With Synergistic Effect of Dielectric and Magnetic Loss,” Advanced Science 10, no. 10 (2023): 2206877.

[43] M. Qiao, J. Wang, D. Wei, et al., “Influence of Crystalline Phase Evolution of Shells on Microwave Absorption Performance of Core-Shell Fe₃O₄@TiO₂ Nanochains,” Materials Today Nano 18 (2022): 100203.

[44] X. Huang, J. Wei, Y. Zhang, et al., “Ultralight Magnetic and Dielectric Aerogels Achieved by Metal-Organic Framework Initiated Gelation of Graphene Oxide for Enhanced Microwave Absorption,” Nano-Micro Letters 14 (2022): 107.

[45] G. Shao, R. Xu, Y. Chen, et al., “Miniaturized Hard Carbon Nanofiber Aerogels: From Multiscale Electromagnetic Response Manipulation to Integrated Multifunctional Absorbers,” Advanced Functional Materials 34, no. 48 (2024): 2408252.

[46] Z. Ma, K. Yang, D. Li, et al., “The Electron Migration Polarization Boosting Electromagnetic Wave Absorption Based on Ce Atoms Modulated Yolk@Shell Fe_xN@NGC,” Advanced Materials 36 (2024): 2314233.

[47] K. Wakabayashi, T. Yoshii, and H. Nishihara, “Quantitative Study on Catalysis of Unpaired Electrons in Carbon Edge Sites,” Carbon 210 (2023): 118069.

[48] X. Huang, J. Guan, Y. Feng, et al., “Mn and O Defect Modulation in Birnessite Creates Multiplicate Polyhedra to Improve Dielectric and Magnetic Losses,” Cell Reports Physical Science 6, no. 1 (2025): 102350.

[49] X. Huang, G. Yu, B. Quan, et al., “Harnessing Pseudo-Jahn-Teller Disordering of Monoclinic Birnessite for Excited Interfacial Polarization and Local Magnetic Domains,” Small Methods 7, no. 9 (2023): 2300045.

[50] S. Wang, X. Zhang, S. Hao, et al., “Nitrogen-Doped Magnetic-Dielectric-Carbon Aerogel for High-Efficiency Electromagnetic Wave Absorption,” Nano-Micro Letters 16 (2024): 16.

RIGHTS & PERMISSIONS

2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.