RESEARCH ARTICLE

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High-Density Nanopore Confined Vortical Dipoles and

Magnetic Domains on Hierarchical
Macro/Meso/Micro/Nano Porous Ultra-Light Graphited
Carbon for Adsorbing Electromagnetic Wave
Wenhuan Huang,* Xingxing Zhang, Jiamin Chen, Qiang Qiu, Yifan Kang, Ke Pei,
Shouwei Zuo, Jincang Zhang, and Renchao Che*

1. Introduction
Atomic-level structural editing is a promising way for facile synthesis and
accurately constructing dielectric/magnetic synergistic attenuated Optimizing dielectric/magnetic synergetic
attenuation ability with the balance of
hetero-units in electromagnetic wave absorbers (EWAs), but it is hard to
highly matched impedance is an effective
realize. Herein, utilizing the rapid explosive volume expansion of the approach for obtaining high electromag-
CoFe-bimetallic energetic metallic triazole framework (CoFe@E-MTF) during netic wave (EW) absorbing performance.[1]
the heat treatment, the effective absorption bandwidth and the maximum Recently, scientists have been dedicated
absorption intensity of a series of atomic CoFe-inserted hierarchical porous to constructing highly dispersed magnetic
units and chemical heterojunctions into
carbon (CoFe@HPC) EWAs can be modified under the diverse synthetic
highly porous dielectric materials, espe-
temperature. Under the filler loading of 15 wt%, the fully covered X and Ku cially carbon-based materials, which have
bands at 3 and 2.5 mm for CoFe@HPC800 and the superb minimum reflection promoted the blowout generation of a va-
loss (RLmin ) of −53.15 dB and specific reflection loss (SRL) of −101.24 dB riety of excellent EW absorbers (EWAs).[2]
mg−1 mm−1 for CoFe@HPC1000 are achieved. More importantly, the Among various magnetic metal-based
single-atomic chemical bonding among Co─Fe on the nanopores is captured organic compounds or complexes, crys-
talline metal-organic frameworks (MOFs)
by extended X-ray absorption fine structure, which reveals the formation
as precursors possess considerable merits
mechanism of nanopore-confined vortical dipoles and magnetic domains. of highly ordered and precise molecular
This work heralds the infinite possibilities of atomic editing EWA in the future. structures.[3] Their adjustable coordination
structures and stable physicochemical
properties contributed to the post-synthesis
of unique porous nanostructures, such as
W. Huang, X. Zhang, J. Chen, Q. Qiu, Y. Kang, S. Zuo hollow,[4] core–shell,[5] yolk-shell,[6] multi-layers,[4b,7] and hierar-
Key Laboratory of Chemical Additives for China National Light Industry chical pores,[8] which have shown great performance on mod-
College of Chemistry and Chemical Engineering ifying the dipolar and interfacial polarization and impedance
Shaanxi University of Science and Technology
matching.
Xi’an 710021, China
E-mail: [email protected] It is well-known that the complex post-synthesis ways have
K. Pei, R. Che been applied to MOF precursors for obtaining these spe-
Laboratory of Advanced Materials cial micro-nano structures such as multi-step hydrothermal
Shanghai Key Lab of Molecular Catalysis and Innovative Materials synthesis,[9] chemical etching,[3b,10] surfactant foaming,[11] and
Academy for Engineering & Technology electrochemical reactions.[12] The complex technical processes,
Fudan University
Shanghai 200438, P. R. China low metal utilization rates, and the resulting waste liquids have
E-mail: [email protected] greatly hindered the large-scale production and commercial ap-
J. Zhang, R. Che plications of these materials. Hence, developing simple and gen-
Zhejiang Laboratory tle methods to obtain highly porous EWAs, especially hierarchi-
Hangzhou 311100, P. R. China cal porous architectures with low density, has attracted the great
attention of scientists. For instance, polymer-bubbling,[13] su-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/advs.202303217
percritical CO2 foaming,[14] freeze-drying,[15] and alkane-blowing
agents,[16] have delivered a variety of excellent hierarchical porous
© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.
This is an open access article under the terms of the Creative Commons EWAs. However, such in situ assembly processes were unfavor-
Attribution License, which permits use, distribution and reproduction in able for the precise construction of highly dispersed magnetic
any medium, provided the original work is properly cited. metallic hetero-units into the structure owing to the aggregation
DOI: 10.1002/advs.202303217 of metals at high temperatures.

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Atomic-level structure editing from bottom to up may sat- CoFe@E-MTF as one equivalent volume, Figure S4, Supporting
isfy both the demands of facile synthesis and accurate build- Information) of ≈1.43, 80, 105.6, 125. For further study of the
ing dielectric/magnetic synergetic hetero-units in hierarchical porous morphology and structural evolution process, the SEM
porous architecture, which is very hard to realize. Herein, we de- and TEM images of CoFe@HPCx are presented in Figure 1b–
signed and synthesized a CoFe-bimetallic energetic metallic tri- m and Figures S5-S12, Supporting Information. The porous
azole framework (CoFe@E-MTF) from 1H-1,2,3-triazole under structures showed significant differences with the increase in
room-temperature reaction. Utilizing the rapid volume expan- temperature. The distribution of macro-pores (beyond 200 nm),
sion of the CoFe@E-MTF caused by the decomposition of high- macro/mesopores (beyond 20 nm), macro/meso/micro-pores
energetic N3 -bonds, we controlled the calcinated temperatures (beyond 2 nm), and macro/meso/micro/nano-pores (beyond
(≈400–1000 °C) and successfully captured four atomic CoFe- 1 nm) for CoFe@HPC400, CoFe@HPC600, CoFe@HPC800,
inserted hierarchical porous carbon (CoFe@HPCx, x = 400, 600, and CoFe@HPC1000 were observed. The ordered hierarchical
800, 1000 °C) in diverse states. In such a series of EWAs, the structures under high temperatures (800 and 1000 °C), espe-
atomic chemical bonding and existence status of Co and Fe in cially many sub-nano porous structures with clear boundaries for
materials were deeply analyzed by X-ray absorption near-edge CoFe@HPC1000 were observed in high-resolution TEM images
structure (XANES) and extended X-ray absorption fine structure (Figure S12, Supporting Information).
(EXAFS) spectra, revealing the structural evolution of Co and More importantly, the volume expansion and structural
Fe from the cluster to single atom state on the carbon matrix. stretching of carbon matrix for energetic precursor at high
The Lorentz transmission electron microscopy (LTEM) and holo- temperature were utilized for homogeneous planting sub-nano
gram imaging in situ monitor the formation and distribution of Co/Fe cluster or single atom in the minimum quantity. The
high-density nano-vortex dipoles and magnetic domains on a 3D EDS mapping images (Figures S9–S12, Supporting Informa-
conductive network, which is determined by the atomic Co─Fe tion) indicated the uniform dispersion of Co and Fe atoms in
coupling diploes. The polarization and magnetic exchange en- the CoFe@HPCx series. By incorporating hierarchical porous
hanced the EW attenuation ability with the modified impedance features and uniformly dispersed magnetic metals, this system
matching. As a result, under the filler loading of 15 wt%, the bi- achieves both lightweight property with high metal atom utiliza-
functional regulation of fully covered X and Ku bands at 3 and tion, as well as the highly efficient propagation 3D network for
2.5 mm for CoFe@HPC800 and the superb minimum reflection electromagnetic wave attenuation through multiple reflections
loss value (RLmin )of −53.15 dB and specific reflection loss ( SRL) and scattering.
of −101.24 dB mg−1 mm−1 for CoFe@HPC1000 were achieved.

2. Results and Discussion 2.2. Regulation of EW Absorbing Intensity and Bandwidth

2.1. Energetic Building Block Driven Macro/Meso/Micro/Nano The electromagnetic wave absorbing behaviors of the
Porous Evolution CoFe@HPCx series were evaluated by 3D RL, 2D RL contour
map, and effective absorption bandwidth (EAB) (RL < −10 dB)
To incorporate energetic functional organic fragments into the at the range of ≈2–18 GHz under a filler loading of 15 wt%. Poor
precursor, 1H-1,2,3-triazole ligand was employed as a building EW adsorptions for low-temperature calcinated samples were
block to assemble the crystalline CoFe@E-MTF. The morphol- observed, as shown in Figure 2, the RLmin of CoFe@HPC600
ogy of E-MTF and CoFe@E-MTF crystals were observed by scan- reaches only −13.14 dB with a narrow EAB of 0.56 GHz at the
ning electron microscope (SEM) and transmission electron mi- thickness of 2 mm, and the RLmin of CoFe@HPC400 could
croscope (TEM), displaying smooth octahedrons with an average not even reach −10 dB. The PXRD of the CoFe@HPCx series
diameter of ≈150 nm (Figures S1 and S2, Supporting Informa- indicated the characteristic peaks of 34.6°, 36.4°, 63°, and 67.9°
tion). The greatly matched simulated and experimental powder for (102), (020), (222), and (024) crystal planes of Fe3 C (PDF#
X-ray diffraction (PXRD) curves, and the uniform distribution of 03–0400) and 43° and 57.1° for (111) and (112) planes of Co2 C
corresponding Co, Fe, C, N, and O elements in energy disper- (PDF# 50–1371) in CoFe@HPC400 and CoFe@HPC600, imply-
sive spectroscopy (EDS) mapping indicated the highly-ordered ing the insufficient reduction of metals in the composites. The
arrangement of metals and N3 -bonds in crystalline structures of distinct peaks of 19.2°, 28.1°, and 28.6° in CoFe@HPC400 are
E-MTF and CoFe@E-MTF (Figure S3, Supporting Information). attributed to the maintained crystalline peaks of undecomposed
As thermal gravimetric analysis (TGA) shown in Figure 1a, the CoFe@E-MTF precursor. The enhanced broad peak of ≈22.4° for
fast breakage of energetic N3 -bonds at ≈420 °C, resulted in the CoFe@HPC800 and CoFe@HPC1000 can be indexed to (002)
high detonation velocity and pressure in the decomposition of planes of graphite carbon, indicating the increased degree of
CoFe@E-MTF. Such a rapid in situ volume expansion and mass graphitization at high temperatures. As a result, CoFe@HPC800
loss process generated a kind of foam-like hierarchical porous showed an intense RLmin of −46.40 dB and wide EABs of 4 (≈8–
carbon with ultra-low density above 420 °C. 12 GHz) and 7.5 GHz (≈10.5–18 GHz) at 3 and 2.5 mm, which
We captured four products under different calcination temper- fully covered X and Ku bands, respectively. The CoFe@HPC1000
atures of 400, 600, 800, and 1000 °C (Figure 1a), respectively, de- exhibited an excellent performance on EW absorbing intensity,
noted as CoFe@HPCx (x = 400, 600, 800, and 1000). The residual displaying the highest RLmin of −53.15 dB at 3.5 mm. It is worth
mass of ≈10%, 9%, and 8% for CoFe@HPC600, CoFe@HPC800, noting that, considering the low density (V/M) and only 15
and CoFe@HPC1000 were compared to their volume, present- wt% loading content for CoFe@HPCx fillers, the superior SRL
ing a high volume-mass ratio (V/M, the volume of 1 g pristine of −101.24 dB mg−1 mm−1 for CoFe@HPC1000 far exceeded

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Figure 1. The TGA curve of CoFe@E-MTF (ground layer in (a)) and the 3D illustration (upper layer in (a)), SEM (b–i), TEM (j–m), EDS mapping (n–q)
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images for CoFe@HPCx (x = 400, 600, 800, and 1000).
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Figure 2. The 3D RL values (a–d), 2D RL contour map (e–h), EAB (i–l), comparison of RL values (m), and EAB (n) in different thickness (m,n), summary
and comparison of RL and EAB (o) for CoFe@HPCx (x = 400, 600, 800, and 1000), comparison of CoFe@HPC800 and CoFe@HPC1000 with reported
EWAs in literature (p).

the reported EWAs in literature. The dual-regulation of EW fitted and analyzed by typical D1 (≈1340 cm−1 ) and G (≈1560
absorbing intensity and bandwidth on an ultralight hierarchical cm−1 ) peaks in Raman spectra (Figure 3e and Figure S14 and
porous carbon was achieved, showing promising commercial Table S1, Supporting Information). Compared with the ID1 /IG
applications. ratios for CoFe@HPC400 (1.10) and CoFe@HPC600 (1.11), the
lower ID1 /IG ratios (0.93 and 0.82) and the intense G peaks for
CoFe@HPC800 and CoFe@HPC1000 indicated the improved
2.3. Interfacial and Vortical Dipole in Graphitized Matrix graphitization degrees at the high temperature (Figure 3f), which
are in accordance with the PXRD results (Figure S13, Sup-
The CoFe@HPCx (x = 400, 600, 800, and 1000) is a series of porting Information). In Figure 3h and Figure S15a, Support-
dielectric-dominated EW absorbing materials. According to the ing Information, the highest of 𝜖′, 𝜖″, and tan 𝛿 𝜖 values for
relative complex permittivity equation of 𝜖 r = 𝜖′ – j𝜖″, the real part CoFe@HPC1000 implied the superior electrical conductivity and
(𝜖′) and the imaginary part (𝜖″) represent electric storage and dis- electron movements, contributing to the conversion from EW to
sipation capacity, respectively, which are highly related to the con- thermal energy.
ductivity and relaxation polarization. The sp2 hybrid carbon sites The relaxation polarization of CoFe@HPCx could be evaluated
and the distorted/defective carbon sites in CoFe@HPCx were by dipole and interfacial polarization, which can be illustrated

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Figure 3. The charge density maps (a–d), deconvolution peaks in Raman spectra (e), structural illustration images of graphitization degree (f), the local
observed interfacial dipole and vortical dipole (g), the real part and imaginary part of permittivity (h), the Cole–Cole plots (i), and the 3D attenuation
coefficient (j) for CoFe@HPCx (x = 400, 600, 800, and 1000).

by Debye’s theory (Equations (S8–S10), Supporting Information). bon confirmed the transformation of numerous nanocrystalline
The Cole–Cole semicircles (Figure 3i and Figure S16, Supporting graphite in CoFe@HPC1000. Hence, it can be concluded that car-
Information) among 𝜖′ and 𝜖″ can be used to explain the ability bon atoms in such a hierarchical porous architecture existed as
of polarization loss, displaying a sequence of CoFe@HPC1000 numerous tiny crystalline domains with sp2 hybridization, how-
> CoFe@HPC800 > CoFe@HPC600 > CoFe@HPC400. The ever, in a highly disordered and randomly stacked manner.[17]
highly distorted Cole–Cole curve of CoFe@HPC1000 indicated a The polarization wall/edges for the diverse scale of pores in
large number of disordered atoms or defects. Hence, combining the CoFe@HPCx matrixes was investigated by the HR-TEM and
both conductivity and polarization effects in the CoFe@HPCx hologram (Figure 3a–d), reflecting different scales of charge den-
series (Equation (S11), Supporting Information), the highest sity distribution maps. In the map, red represents the positive
attenuation constant (𝛼) for CoFe@HPC1000 in the sequence charge, blue represents the negative charge, and the lightness
of CoFe@HPC1000 (704.44) > CoFe@HPC800 (390.41) > color represents relative intensity (Figure S17, Supporting In-
CoFe@HPC600 (199.17) > CoFe@HPC400 (37.39) was demon- formation). The non-uniform large polarized charge regions in
strated. CoFe@HPC400 were detected (Figure 3a), which could be at-
The structural origins of this polarization in CoFe@HPCx tributed to the insufficient graphitization and porosity. The in-
were investigated by calculated R2 values (Equation (S13) and creased temperature induced the homogenous distribution of
Table S1, Supporting Information) in Raman spectra, which re- micro- and nano-pores in CoFe@HPC800 and CoFe@HPC1000,
flected the number of structural defects. The R2 value of 0.38 giving the high-density distribution of nanoscale charge dipoles
for CoFe@HPC1000 revealed its highest number of defects in (≈1–3 nm). A large number of dense nanoscale interfacial polar-
the carbon matrix, which can promote dipole polarization. The ization was generated in CoFe@HPC800 (Figure 3g, upper). The
highest peak area of the D3 band (AD3 of 80.4 in Table S1, Sup- intense dark red and blue charge dipoles in CoFe@HPC1000 re-
porting Information) which is attributed to the disordered car- vealed the local charge enrichment (Figure 3d), which confirms

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Figure 4. The magnetic moment distribution maps (a–d), the XPS spectra of Co 2p (e), Fe 2p (f), C 1s (g), and N 1s (h), the magnetic hysteresis loops
(i), the illustration images of vortex magnetic domains and spin texture (j), the real part and imaginary part of permeability (k), and the C0 value (l) for
CoFe@HPCx (x = 400, 600, 800, and 1000).

the highest degree of polarization. Moreover, to our surprise, The highly discrete Co and Fe metals in CoFe@HPC800 and
many unique vortical dipoles with a diameter of ≈1.2–1.5 nm CoFe@HPC1000 resulted in the enhanced low valent binding
were founded in CoFe@HPC1000 (Figure 3g, under), which have energy peaks at 780.6/795.9 eV for Co 2p and at 715.7/726 eV
never been detected before. The vortex dipoles are well matched for Fe 2p (Figure 4e,f). The growing intense peaks for C─C/C═C
with the diameter of ≈1–1.5 nm nanopores in TEM images of and C─N at 284.60 and 285.82 eV in C 1s spectra and graphitic
CoFe@HPC1000. Besides the defects and dipoles on the high N at 400.52 eV in N 1s spectra are attributed to the improved
porous matrix, the existing status of discrete distribution of Co graphitization degrees in CoFe@HPC800 and CoFe@HPC1000
and Fe metals may play important roles, which should be inves- (Figure 4g,h). Moreover, the higher pyridinic N and pyrrolic N
tigated in depth. peaks at 398.32 and 399.17 eV represented the more dipole po-
larization centers on the carbon matrix (Figure 4h).
The existing status of the Co and Fe metals influences the
2.4. Electron-Driven Co─Fe Coupling in Vortical Magnetic saturation magnetization of the material, which reflects the
Nano-Domains overall magnetic effects and associates with the permeability
(μr = μ′ − jμ″) and magnetic loss (tan 𝛿 μ = μ″/μ′). Gener-
Only about ≈0.67–1.18 wt% Co and Fe (Table S2, Supporting ally, the μ′, μ″, and tan 𝛿 μ values are running at low levels
Information) were highly dispersed into the carbon matrix in (Figure 4k and Figure S15b, Supporting Information), indicat-
the CoFe@HPCx series. The chemical valent states of all the ing the relatively small magnetic loss contributions. In addi-
elements in CoFe@HPCx are analyzed by XPS (Figure 4e–h). tion, the non-negligible eddy current loss of CoFe@HPCx can be

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Figure 5. The illustration of Co and Fe existing status and during the structural evolution process under calcination (a), the experimental XANES spectra
(b,c), the K-edge EXAFS spectra (d,e), the theoretically calculated TDOS curves (f), the PDOS curves (g,h), the LUMO and HOMO images (i), and the
orbital energy levels and band gaps for CoFe@HPCx (x = 400, 600, 800, and 1000).

evaluated by coefficient value (C0 = μ″(μ′)−2 f−1 ), which laid below highest demagnetizing energy and exchange energy, and its dy-
0.1 ns at the whole frequency range of ≈2–18 GHz (Figure 4l), namic magnetic domains corresponded to intense magnetic en-
indicating the suppressed eddy current effect. As Figure 4i ergy dissipations. In CoFe@HPC1000, the shifts and overlayers
shown, the calculated saturation magnetization (Ms ) values for of domain walls generated the vortex magnetic domains which
CoFe@HPCx (x = 400, 600, 800, and 1000) are 1.56 × 10−4 , can be schematically described as spin textures (Figure 4j) and
6.87 × 10−4 , 8.12 × 10−4 , and 21.3 × 10−4 emu g−1 , respectively. has never been reported in the porous EWAs as far as we know.[18]
The increased Ms from CoFe@HPC400 to CoFe@HPC600 and
CoFe@HPC800 is ascribed to the crystallization and reduction
of Co and Fe metals, which provide the ordered magnetic do- 2.5. Single-Atomic Evolution of Co and Fe during the Calcination
mains. In CoFe@HPC1000, the highly dispersed Co/Fe atoms
on discontinuous nanopores and their coupling interaction gave The generation of magnetic domains is directly related to the
the highest Ms value and the formation of high-density magnetic distribution form and electronic structure of Co and Fe met-
nano-domains. The coercivity (Hc ) values are highly related to als on the matrix, which was clarified by XANES and K-
the number of defects in this series, therefore, the lowest Hc of edge EXAFS spectroscopy. The XANES (Figure 5b) displays
47.06 Oe was observed. the lowest Co valence of CoFe@HPC1000 close to that of
The LTEM holography images displayed the multi-domain Co foil. The highest Co valence in CoFe@HPC400 is at-
structure of the CoFe@HPCx (Figure 4a–d). More complex do- tributed to the insufficient reduction of metals. The valent
main walls near the smaller pores were observed, manifesting state of Co in CoFe@HPC600 and CoFe@HPC800 lies between
the lowest local free energy under the porous shape confinement. CoFe@HPC400 and CoFe@HPC1000. In Figure 5c, the valence
As the heat treatment temperature increases, the magnetic do- of Fe in CoFe@HPCx gradually increases in slight degrees with
mains become more complex with the discontinuous distribu- the increase of their treatment temperature, indicating the charge
tion of magnetic moments. Hence, CoFe@HPC1000 showed the transfers between Fe and Co. The Fourier transform of K-edge

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Figure 6. The 2D contour maps |Zin /Z0 | (a–d), the illustration of multiple scatterings (e), the N2 adsorption–desorption isotherms (f), the pore size
distribution maps (g) for CoFe@HPCx (x = 400, 600, 800, and 1000), the scheme of EW absorbing mechanism (h).

EXAFS (Figure 5d,e and Table S3, Supporting Information) indi- CoFeN8 and B-CoFeN6 , indicating the half-metallic property and
cated that most of Co and Fe initially exist as clusters (Co─Co magnetic interaction among Co and Fe. The lowest unoccupied
bonds around ≈2.50–2.86) at low temperatures and gradually molecular orbital (LUMO) and highest occupied molecular or-
split into single atoms (Co─N bonds around ≈1.87–2.04) as tem- bital (HOMO) for the four models indicated the gradually en-
perature rise in CoFe@HPCx series (Figure 5a). The wavelet- riched orbitals around Fe atoms by reducing the Co─Fe distance
transformed images for the k2 -weighted EXAFS (Figures S24 (Figure 5i). Therefore, compared with the band gaps for CoN4
and S25, Supporting Information) clearly displayed the metal- (0.073 eV), FeN4 (0.070 eV), and D-CoFeN8 (0.061 eV), the lowest
lic clusters and single atoms in CoFe@HPCx on radial distance band gap of 0.045 eV is observed for D-CoFeN6 (Figure 5j) con-
maps. firmed its enhanced Co─Fe charge transfer, which is accordance
For revealing the internal structure diversities and their EW with the XANES results (Figure 5b,c).
attenuation mechanism, the density functional theory (DFT) the-
oretical calculations based on the isolated CoN4 , FeN4 , discrete
CoFeN8 (D-CoFeN8 ), and bonding CoFeN6 (B-CoFeN6 ) models 2.6. Synergy of Multi-Reflection with Nano-Confinement in
(Figure S26, Supporting Information) were conducted. As shown Hierarchical Architecture
in Figure 5f, the total density of states (TDOS) curves displayed
the stronger TDOS peaks lay closer to the Fermi level for D- To pursue a deeper insight into the EW absorbing behavior,
CoFeN8 and B-CoFeN6 than those for CoN4 and FeN4 , indicat- the EW reflection of the CoFe@HPCx series was evaluated by
ing the higher energy band overlaps in D-CoFeN8 and B-CoFeN6 . 2D impedance matching contour maps of |Zin /Z0 | (Figure 6a–
In addition, the partial density of states (PDOS) of the Co 3d d and Figure S18, Supporting Information). In Figure 6c,
and Fe 3d (Figure 5g,h) showed higher spin polarization in D- the well-matched |Zin /Z0 | close to 1 for CoFe@HPC800 at

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≈8–18 GHz is observed, meaning the incident wave permeates In the CoFe@HPCx series, the chemical bonding and existence
the absorber at the greatest degree with less reflection. It is the status of Co and Fe in materials was deeply analyzed by XANES
main reason for the wide EAB (fully covered X/Ku band) of and EXAFS spectra, revealing the structural evolution of Co and
CoFe@HPC800. The matched |Zin /Z0 | for CoFe@HPC1000 at Fe metal from the cluster to single atom state on the carbon
the frequency around 7.52 GHz delivered the strongest RLmin matrix. The LTEM and hologram imaging in situ monitor the
of −53.15 dB. In contrast, the big white areas in the maps of formation and distribution of high-density nano-vortex dipoles
CoFe@HPC400 and CoFe@HPC600 indicate the severely mis- and magnetic domains on a 3D conductive network, contribut-
matched impedance (Figure 6a–d), which should be attributed to ing to revealing the EW attenuation mechanism of Co─Fe cou-
the relatively lower porosities. Compared with the superior high pling dipoles. Under the filler loading of 15 wt%, the bifunctional
Brunauer–Emmett–Teller (BET) specific surface areas of 206.75 regulation of fully covered X and Ku bands at 3 and 2.5 mm
and 370.73 m2 g−1 for CoFe@HPC800 and CoFe@HPC1000 for CoFe@HPC800 and the superb RLmin of −53.15 dB and SRL
in the N2 adsorption–desorption isotherms and pore diame- of −101.24 dB mg−1 mm−1 for CoFe@HPC1000 were achieved.
ter distribution maps (Figure 6f,g), the low BET specific sur- This work highlights an atomic-level structure editing strategy
face areas of 29.56 and 51.04 m2 g−1 for CoFe@HPC400 and for assembling dielectric/magnetic synergetic ultra-light EWAs
CoFe@HPC600 are detected. As illustrated in Figure 6e, the with dual-function regulation.
increased porosity and diverse pore diameters distributed in
the whole macro/meso/micro/nano-porous range for the high-
temperature treated samples resulted in enhanced multiple in- Supporting Information
ternal EW scattering. Combined with the superior electric con- Supporting Information is available from the Wiley Online Library or from
ductivity, nano-vortex polarization, and magnetic exchange en- the author.
ergy, the dual-function regulation of EW absorbing intensity and
bandwidth is successfully realized in an ultralight molecular car-
bon sponge (Figure 6h).[19] Acknowledgements
W.H. and X.Z. contributed equally to this work. This work was fi-
3. Discussion nancially supported by the National Natural Science Foundation of
China (52231007, 51725101, 11727807, 22001156, and 22271178), the
The structural design strategies of CoFe@HPCx are concluded Ministry of Science and Technology of China (2021YFA1200600 and
in three aspects: i) Design and assemble an atypical hierar- 2018YFA0209100), International Cooperation Key Project of Science and
chical macro/meso/micro/nano-pores with high EW multiple Technology Department of Shaanxi, China (2022KWZ-06), the Youth Tal-
scatterings. Energetic triazole as a ligand was implanted into ent Promotion Project of Science and Technology Association of Univer-
sities of Shaanxi Province (20210602), Research project of Xi’an Science
the crystalline energetic MOF for driving rapid explosion and
and Technology Bureau (2022GXFW0011), Science and Technology New
volume expansion owing to the N═N─N bonds. ii) Construct- Star in Shaanxi Province (2023KJXX-045).
ing high-density of nanoscale interfacial/vortical polarization.
The rapid stretching of carbon substrate with the improved
heat-treated temperature during the calcination induced the Conflict of Interest
enhanced graphitization degree and increased number of dis-
The authors declare no conflict of interest.
orders/defects. iii) Building vortical magnetic nano-domains
with high-dynamic demagnetizing energy/exchange energy. Ad-
justable atomic Co─Fe coupling sites inserted on the walls of car-
Data Availability Statement
bon matrix nanopores in high dispersion manner resulting in
the formation of vortical magnetic domains. iv) The energy band The data that support the findings of this study are available from the cor-
overlaps promote the charge transfer of Co─Fe units with the en- responding author upon reasonable request.
hancement of the density of states. Capturing and monitoring
the nano-porous structural evolution and single-atom metallic
transformation by XANES, EXAFS, LTEM, and hologram imag- Keywords
ing contributed to explaining the formation of spin polarization electromagnetic wave absorber, electron holography, energetic metal-
and magnetic exchange through PDOS analysis in DFT theoret- organic framework, magnetic domain, vortical dipole
ical calculations.
Received: May 18, 2023
Revised: June 25, 2023
4. Conclusion Published online: August 1, 2023
In summary, we uniformly planted high-energetic N3 -bonds
into a CoFe-bimetallic energetic metallic triazole framework
(CoFe@E-MTF) precursor under a facile room-temperature reac-
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