Composites Part A 139 (2020) 106107

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Composites Part A
journal homepage: www.elsevier.com/locate/compositesa

The composition design of MOF-derived Co-Fe bimetallic autocatalysis T

carbon nanotubes with controllable electromagnetic properties
Jing Yana,b, Ying Huanga, , Yonghui Yanc, Xiaoxiao Zhaoa, Panbo Liua
⁎

a
MOE Key Laboratory of Material Physics and Chemistry under Extrodinary Conditions, Ministry of Education, School of Chemistry and Chemical Engineering,
Northwestern Polytechnical University, Xi'an 710072, PR China
b
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, Singapore 117575, Singapore
c
Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710072, China

ARTICLE INFO ABSTRACT

Keywords: MOF-derived magnetic carbon nanotubes microwave absorbers have been prepared by some researchers, but
Composition design how to control the length and quantity of MOF-derived carbon nanotubes is still a big challenge. In this work, the
MOF-derived carbon nanotubes number and length of carbon nanotubes were regulated by introducing Fe atoms into the bimetallic Zn-Co MOFs
Interfacial polarization and optimizing the composition proportion of Zn2+ and Co2+ in the precursor. When the molar ratio of Zn2+
Microwave absorption performance
and Co2+ was 1:1, the carbon nanotubes was most; When changed to 6:1, the obtained absorbers possess not
only strong absorption capability but also wide absorption bandwidth only under 15 wt% filling loading. The
excellent performance ascribed to the strong interfacial polarization and impedance matching. The dielectric loss
mainly resulted from the conductive network formed by a suitable number of long carbon tubes. We believe that
this research will provide a necessary reference for future MOFs-derived magnetic carbon nanotubes microwave
absorbers.

1. Introduction framework structure with periodic network structure formed by self-

The growing demand for civil and military uses has spurred the
development of new electromagnetic wave absorbing materials. The
combination of dielectric loss materials [1–6] and magnetic loss ma-
terials [7,8] is a promising approach to improve the electromagnetic
wave absorbing performance. However, how to uniformly and effec-
tively combine the magnetic loss material and the dielectric material is
an important problem that needs to be solved currently. As an im-
portant dielectric loss material, carbon materials include ordinary
carbon [9], one-dimensional carbon nanotubes (CNTs) [10–12], two-
dimensional graphene [13–17], etc. Among them, CNTs are usually
considered to be a good candidate because of the wide absorption fre-
quency bandwidth, controllability, good compatibility, lightweight,
and thin thickness. Due to the one-dimensional structure of carbon
nanotubes, the uniform and stable combination of carbon nanotubes
and other magnetic materials to form a composite material is also an
urgent problem to be solved.
Some scholars have studied the forces between dielectric materials
and magnetic loss materials, including covalent bonds [18,19] and non-
covalent bonds [20,21]. In this case, the metal-organic frameworks
(MOFs) material have been found as the times require. MOFs is a
assembly of transition metal ions or clusters and organic ligands by
coordination bonds. Due to the special structure, this material itself is a
good precursor for the preparation of magnetic carbon materials
[22–26].
At present, it is common to generate magnetic carbon materials by
inert gas pyrolysis of MOFs materials [27–29]. As the important kind of
MOFs, zeolitic imidazolate frameworks (ZIFs) such as ZIF-67 and ZIF-8,
composed of Co or Zn metal and rich carbon and nitrogen, have
emerged as promising precursors as electromagnetic wave absorbing
material [30–31]. We know that the transition metal Co or Fe can be
used as a catalyst under certain conditions [10]. Under the hydrogen
atmosphere, the pyrolysis of MOFs materials can generate a part of
carbon nanotubes by using its metal atom [32]. Our previous work has
prepared magnetic carbon nanotubes by pyrolysis of ZIF-67 under hy-
drogen [33]. However, the carbon nanotubes produced by mono-
metallic MOF's own metal-ligand atoms are small unless externally in-
troduced carbon nanotubes [34]. Furthermore, the sample-paraffin
need to fill in a higher proportion of the previous sample, this will
undoubtedly limit their practical application. Normally, there have
been many reports of single metal MOF-derived porous carbon absor-
bers, but rarely studies focus on the hetero bimetallic MOFs (BMOFs)-

⁎
Corresponding author.
E-mail address: yingh@nwpu.edu.cn (Y. Huang).

https://doi.org/10.1016/j.compositesa.2020.106107
Received 30 January 2020; Received in revised form 17 June 2020; Accepted 31 August 2020
Available online 06 September 2020
1359-835X/ © 2020 Elsevier Ltd. All rights reserved.
J. Yan, et al.
Fig. 1. Schematic illustration for the formation process of ZnxCoyFe. (For in-
terpretation of the references to colour in this figure legend, the reader is re-
ferred to the web version of this article.)
derived porous carbon nanocomposites as the absorbers. It is worth
mentioning that compared with monometallic MOFs, the BMOFs ex-
hibit diversely structural topologies originating from the metal centers
and ligand structures, and adjustable electromagnetic parameters
[35–40].
Herein, we consider generating a large number of carbon nanotubes
by introducing the other atoms such as Fe atoms into BMOFs of Zn and
Co. By preparing the BMOFs ZnCo precursors, and then externally
added Fe3+ and pyrolysis under H2 and N2 to obtain Co-Fe alloy em-
bedded carbon and myriad carbon nanotubes, as shown in Fig. 1.
During the pyrolysis process (up to 800 °C), the volatile Zn metal center
evaporates to form a special N-doped porous carbon that has large
surface area and porosity. The resulting cavity was used as a host for
encapsulating Fe ions to form Co-Fe alloys and long carbon nanotubes.
When compositionally optimized, the composites of Co-Fe alloy and
carbon nanotubes with excellent electromagnetic absorbing perfor-
mance have been found and the corresponding mechanism have been
analyzed. We believe that this strategy about introducing iron atoms
and modulating binary MOF metal atomic ratio offers a novel thought
for the optimization of MOFs-derived magnetic carbon nanotubes ab-
sorbing materials, and it is significantly crucial for the development of
new absorbing materials.
2. Experimental section
2.1. Preparation of BMOFs ZnxCoy
The Co(NO3)2·6H2O and Zn(NO3)2·6H2O with different molar ratios
were dissolved in a mixed solution of 40 mL of ethanol and 40 mL of
methanol (the total molar ratio of zinc to cobalt was 6 mmol) to form A
solution. At the same time, 2-Methylimidazole (1.97 g) and 1-
Methylimidazole (0.97 mL) were also dissolved in 40 mL of methanol
and 40 mL of ethanol with stirring to form B solution. Then, solution B
was poured into solution A under the magnetic stirring. The mixture
was allowed to stand at room temperature for 48 h. The formed pre-
cipitate was collected by centrifugation, washed with isopropyl alcohol
and dried in an oven at 60 °C.
2.2. Bmofs ZnxCoyFe derived carbon materials
0.3 g of BOMF ZnxCoy dissolved in 20 mL hexane by sonicating for
1 h. Then 2 mL of iron acetylacetonate solution (2 mg/mL) was added
to the above mixture (added dropwise under magnetic stirring). Then
continue ultrasound for 1 h and stir for 12 h at room temperature. The
particles were centrifuged and dried overnight. Finally, after complete
pyrolysis in the mixture of H2 and N2 (VN2: VH2 = 95%:5%) at 300 °C
for 1.5 h and further 800 °C for 2 h with the heating rate of 5 °C/min.
For convenience, we named the derivative as ZnxCoyFe directly ac-
cording to the molar ratio of zinc to cobalt in BMOF. All the obtained
2
Composites Part A 139 (2020) 106107
Table 1
The naming of the samples.
Name Molar ratio of Co Molar ratio of Zn Total moles
ZnCo6Fe 6/7 1/7 6
ZnCoFe 1/2 1/2 6
Zn4CoFe 1/5 4/5 6
Zn6CoFe 1/7 6/7 6
Zn11CoFe 1/12 11/12 6
samples were named as shown in Table 1.
3. Results and discussion
The crystallographic structure of the samples which were fabricated
by the steps above was characterized by XRD. The XRD patterns of five
intermediate BMOFs precursors were consisted with the combination of
ZIF-67 and ZIF-8 [41], demonstrating the successful preparation of the
BMOFs, as shown in Fig. S1. Fig. 2a shows the XRD patterns of the
ZnxCoyFe. It is clear that wide diffraction peaks around 25° (marked as:
♣) was matched well with the (0 0 2) peaks of carbon, indicating the
high degree of graphitization. The XRD peaks located at 44° and 51°
were attributed to the (1 1 1) and (2 0 0) peaks of metallic Co0.9Fe0.1
(PDF:#04-004-9067) with a face-centered cubic structure. The higher
the molar ratio of Co, the more obvious the peaks will be. Besides, we
did not find the peaks of Zn in the XRD spectrum because the zinc
element would escape under high-temperature conditions [41,42].
Raman spectra is utilized to detect the graphitization degree of carbon
component in the ZnxCoyFe, as illustrated in Fig. 2b. The five samples
exhibited typical G band at 1580 cm−1 and D band at 1350 cm−1. The
ID/IG represent the intensity of D band and G band. The ID/IG was
measured to be 0.635 for ZnCo6Fe, but the ID/IG of other ZnxCoFe equal
to 1, which indicated that the defects and structural distortion of
samples with more Zn content higher than that of ZnCo6Fe. Moreover,
the N2 adsorption-desorption isotherms were employed to examine the
surface area and pore size distribution of the samples. The curves of the
three samples were consistent with the typical IV-type isotherms, which
indicated the mesoporous existed in all the samples. From Fig. 2c, it can
be seen that the Zn6CoFe has a high specific surface area (653.92) than
ZnCoFe (418.42) and ZnCo6Fe (266.12). This phenomenon can be at-
tributed to the Zn components’ evaporate lead to a highly porous tex-
ture throughout the whole dodecahedrons at a high-temperature [40].
The large specific surface area facilitates sufficient contact between
carbon nanotubes and Co-Fe alloys. In addition, the curves in Fig. 2d
were the calculation results of the DFT method. As is shown in Fig. 2d,
the holes of all three samples diapered between 2 and 10 nm, which
validated that all samples are mesoporous materials.
To deeply observe the effect of the ratio of Zn2+ and Co2+ on the
morphology of the samples, the morphology of the samples were pre-
sented by FESEM. As shown in Fig. 3a, the binary MOF Zn6Co pre-
cursors with regular dodecahedron have a diameter of 500 nm. The
Fig. 3b, c, d, e, f were the SEM figure of ZnCo6Fe, ZnCoFe, Zn4CoFe,
Zn6CoFe and Zn11CoFe, respectively. It can be seen from Fig. 3b that
ZnCo6Fe retains almost the original morphology of the ZnxCoy pre-
cursor and grows many fine carbon nanotubes on the surface. As the
zinc content increases, the carbon nanotubes on the surface became
very long and wrap around the surface of the ZnxCoy derivative body to
form a large conductive network. It can be seen that the carbon na-
notubes on the surface are the longest and most when the molar ratio of
zinc to cobalt is 1:1, the length of long carbon nanotubes ranges from
500 nm to 3 µm. But the carbon nanotubes on the surface gradually
decrease after the proportion of zinc continues to increase. In the ab-
sence of Fe3+, the BMOF with a Zn2+/Co2+ ratio of 1: 1 was also been
pyrolyzed for comparison, named as ZnCo. The morphology of ZnCo
was shown in Fig. S2. Obviously, the derived short carbon nanotubes
were tightly attached to the surface of ZnCo. Compared with ZnCoFe,
J. Yan, et al.
Fig. 2. XRD patterns (a), Raman spectrum (b), N2 adsorption-desorption isotherms (c) and pore size distribution (d) of ZnxCoyFe samples. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
there is a big gap between the carbon nanotubes on the surface of the
two, which is a good indication that the introduction of iron facilitated
the growth of carbon nanotubes in derivatives. Take Zn6CoFe as an
example, the element mappings (Fig. 3g) demonstrated that the C, N, O,
Co and Fe elements were uniformly mixed and each component was
observed over the surface of the sample. Besides, the corresponding
mass fraction is 83.75 wt%, 13.43 wt%, 1.62 wt%, 1.08 wt%, and
0.12 wt%, respectively. The mass ratio of Co and Fe in accordance with
the XRD results.
The TEM can be more clearly observed in the changes of the sam-
ples’ internal, as shown in Fig. 4. From Fig. 4g, it can be seen that the
Zn6Co precursor exhibited a uniform element distribution and the
atomic fraction for C, N, O, Co and Zn elements were 43.83 wt%,
26.15 wt%, 4.28 wt%, and 25.7 wt%, respectively. Obviously, the ratio
of zinc to cobalt was almost near 6 to 1. Furthermore, the ZnCo and
ZnCo6 precursor’s elements were also analyzed in Fig. S3 and Fig. S4
(supporting information). All elemental composition of these three
samples corresponded to their respective proportions, which proved the
good control and successful synthesis of precursor ratio. From Fig. 4a, it
can be seen that Zn6Co precursor had a rhombic dodecahedral shape. As
shown in Fig. 4b, ZnCo6Fe had many obvious black particles and very
short carbon nanotubes around the particles. When increasing the
proportion of zinc ions, the amount of black particles became smaller,
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Composites Part A 139 (2020) 106107
and it can be inferred that the black particles were Co-Fe particles.
Compare to the edge of ZnCo6Fe, ZnCoFe had many very long carbon
nanotubes at the edge. As the proportion of zinc ions continues to in-
crease, the number of carbon nanotubes would decrease. Until
Zn11CoFe, we can see that there are few black particles and carbon
nanotubes on the surface. In addition, the HRTEM images showed the
lattice information of ZnCo6Fe in Fig. S5. It was estimated that the
spacing of the lattice fringes was 0.2 nm, which was corresponded to
the (1 1 1) crystal planes of Co0.9Fe0.1.
In addition, the XPS was applied to the further investigation ele-
mental state of Zn6CoFe in Fig. 5. It can be determined from Fig. 5a that
Zn6CoFe contained five elements of C, O, N, Co, and Fe. The individual
peaks of each element were also been analyzed. The C1s spectrum in
Fig. 5b showed peaks at 284.6 eV, 285.1 eV, 286.2 eV and 287.9 eV,
which can be attributed to the CeC, CeN, C]O and CeOeC bonds,
respectively. In the N 1s spectrum (Fig. 5c), pyridinic N, pyrrolic N and
graphitic N at binding energies of 398.4 eV, 399.4 eV and 401 eV were
included, respectively. There were two peaks in Fig. 5d, located at
780.5 eV and 797 eV, corresponding to the Co 2p3/2 and Co 2p1/2.
Fig. 5e shows a high-resolution spectrum of Fe 2p where the peaks are
at the binding energies of 710.9 eV and 723.3 eV, which can be at-
tributed to Fe 2p3/2 and Fe 2p1/2, respectively. The curve near the fixed
value in Fig. 5f proved the disappearance of Zn element after high
J. Yan, et al.
Fig. 3. SEM images of Zn6Co precursor (a), ZnCo6Fe (b), ZnCoFe (c), Zn4CoFe (d), Zn6CoFe (e) and Zn11CoFe (f). Element mapping and EDS image (g) of Zn6CoFe.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
temperature pyrolysis. It should to be aware that nitrogen doping in the
sample can significantly improve dipole polarization, interfacial po-
larization, and impedance matching, thereby improving microwave
absorption performance [37].
The electromagnetic parameters were performed to investigate the
electromagnetic energy conversion principle, the electromagnetic of the
five composites were measured. Fig. 6 shows the complex permittivity
(εr = ε′-jε″), the complex permeability (μr = μ′-jμ″), the dielectric
tangent loss (tan δε = ε″/ε′) and the magnetic tangent loss
(tanδμ = μ″/μ′) of ZnCo6Fe, ZnCoFe, Zn4CoFe, Zn6CoFe and Zn11CoFe
at the frequency of 2–18 GHz, respectively. In general, the real and
imaginary parts of the parameters stands for the storage and loss ca-
pacities of EM energy. As shown in Fig. 6, all parameter curves showed
the same trend, which proved the similarity of the sample. From Fig. 6a,
the ɛ′ values of Zn6CoFe was bigger than that of the other four samples,
almost decline from 8.43 to 5.48. While the ε″ values of Zn6CoFe rise
from 1.6 to 4.03. Meanwhile, the ε″ values of ZnCo6Fe, ZnCoFe,
Zn4CoFe and Zn11CoFe fluctuate in the range of 0.4–0.88, 0.8–4.46,
1.75–3.37 and 1.24–2.21, respectively (Fig. 6b). It’s worth noting that
ε″ should decrease with the increase of frequency according to the re-
laxation dispersion. We see that the ε″ values of the five samples in-
crease with increasing frequency, which proves the existence of re-
sonance dispersion in the sample [43]. The μ' values of five samples
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Composites Part A 139 (2020) 106107
showed a decreasing trend, while the μ″ values showed an increasing
trend at 2–18 GHz (Fig. 6c–d). In order to better analysis the ability of
EM wave attenuation, the curves of tan δε and tan δμ were shown in
Fig. 6e–f, respectively. We can observe that the variation of tan δε and
tan δμ values for all samples exhibit a similar trend with the ɛ″ and μ″.
In high frequency, the size of the tan δε and tan δμ value were sorted in
order of ZnCoFe, Zn4CoFe, Zn6CoFe, and Zn11CoFe. Overall, the value
of tan δε is larger than the value of tanδμ, which proved that dielectric
loss accounts for the main position of loss.
The quality of electromagnetic absorbing wave performance ulti-
mately needs to be judged by reflection loss (RL). The RL can be cal-
culated by electromagnetic parameters, the specific expression is as
follows [44,45]:
Zin
Z= = |µr / r | tanh [j (2 fd/c ) µr r ]
Z0 (1)
Zin Z0
RL (dB ) = 20log10
Zin + Z0 (2)
where d refers to the thickness of MAMs, and c and f are the theoretical
velocity, and frequency of incident EM waves, respectively. Fig. 7 ex-
hibited the RL values for ZnCo6Fe, ZnCoFe, Zn4CoFe, Zn6CoFe and
Zn11CoFe with different thicknesses and the corresponding three-
J. Yan, et al. Composites Part A 139 (2020) 106107

Fig. 4. TEM images of Zn6Co precursor (a), ZnCo6Fe (b), ZnCoFe (c), Zn4CoFe (d), Zn6CoFe (e) and Zn11CoFe (f). Element mapping and EDS image (g) of Zn6Co
precursor. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

dimensional RL diagrams. At present, the threshold for an effective
response bandwidth is usually set at −10.0 dB, because it corresponds
to an absorption efficiency of 90%. From Fig. 7a, the RL value of
ZnCo6Fe was much higher than −10 dB, demonstrating that there was
no absorbing performance. For ZnCoFe (Fig. 7b), the minimum value of
RL was −32.7 dB at 10.4 GHz with the thickness of 2.7 mm, and ef-
fective response bandwidth was 4.94 GHz. For Zn4CoFe (Fig. 7c), the
minimum value of RL was −47 dB at 9.28 GHz with the thickness of
3.2 mm, and the corresponding response bandwidth was 5.57 GHz. For
Zn6CoFe (Fig. 7d), the minimum value of RL was −66 dB at 9.43 GHz
and 2.8 mm in thickness, and response bandwidth was 4.79 GHz. As
displayed in Fig. 7e, the minimum RL value of Zn11CoFe was −41 dB
and the effective absorption bandwidth was 4.6 GHz with the thickness
of 2.1 mm. It is should be noted that both the minimum RL value and
the effective absorption bandwidth of ZnCoFe, Zn4CoFe, Zn6CoFe, and
Zn11CoFe were significantly enhanced compared with ZnCo6Fe due to

5
J. Yan, et al. Composites Part A 139 (2020) 106107

Fig. 5. Survey spectrum (a), C 1s spectrum (b), N 1s spectrum (c), Co 2p spectrum (d), Fe 2p spectrum (e) and Zn 2p spectrum (f) of Zn6CoFe. (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)

the enhanced specific surface area and dipolar/interfacial polarization
caused by conductive network formed by long carbon nanotubes. As the
zinc ion content increases, the electromagnetic absorbing performance
of ZnxCoFe became better, but not the higher, the better. When X = 6,
the composite showed the excellent electromagnetic absorbing
performance. The appropriate amount of zinc ions in precursor and
long carbon nanotubes would both affect the electromagnetic absorbing
properties of the material. When X = 11, there was only a small amount
of carbon nanotubes on the surface of the sample, that is why the
performance begins to decline. Furthermore, a comparison about EAW

Fig. 6. Permittivity real part ε′ (a), permittivity imaginary part ε″ (b), permeability real part μ′ (c), permeability imaginary part μ″ (d), dielectric loss tangent tan δε
(e) and magnetic loss tangent tanδμ (f) of ZnCo6Fe, ZnCoFe, Zn4CoFe, Zn6CoFe and Zn11CoFe. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

6
J. Yan, et al. Composites Part A 139 (2020) 106107

Fig. 7. The calculated 2D/3D reflection loss ZnCo6Fe (a1, a2), ZnCoFe (b1, b2), Zn4CoFe (c1, c2), Zn6CoFe (d1, d2) and Zn11CoFe (e1, e2). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

Table 2 that the rational regulation on chemical composition and microstructre

Comparison of microwave absorption performance of ZnxCoyFe that we pre- is quite helpful for the enhancement of microwave absorption.
pared. It is obvious that the maximum RL values shift toward low frequency
Material Ratio Thickness Effective bandwidth RLmin (dB) with the thickness increase from 1.5 to 4 mm, which can be expressed
by the interference effect according to the following equation:
ZnCo6Fe 15% 3 mm 0 GHz −6.7
ZnCoFe 15% 2.7 mm 4.94 GHz −32.7 tm =nc/(4fm |µr || r | ) (3)
Zn4CoFe 15% 3.2 mm 5.57 GHz −47
Zn6CoFe 15% 2.8 mm 4.79 GHz −66 where tm refers to the matching thickness and fm represents the
Zn11CoFe 15% 2.1 mm 4.6 GHz −41 matching frequency. If the tm at the corresponding fm values meet the
equation (3), the incident and reflected microwave are out of phase by
180°, then the interference effect will occur, leading to the dissipation
absorbing performance of samples that we prepared is listed in Table 2.
of microwave. As can be seen in Fig. 8, it is obvious that the matching
The Zn6CoFe manifests its advantages in microwave absorption per-
thickness dexp corresponding the optimal reflection loss of four samples
formance as compared with other ZnxCoyFe composites, which suggests
both were matched well with the simulated thicknesses dfit, suggesting

7
J. Yan, et al.
Fig. 8. Dependence of matching thickness (tm) on frequency (fm) under λ/4 and
normalized input impedance of ZnCoFe (red line), Zn4CoFe (pink line), Zn6CoFe
(black line) and Zn11CoFe (green line). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article.)
that the microwave absorption performance of these samples obeys the
quarter-wavelength matching model.
The attenuation factor (α) and impedance match are the two most
important factors determining the absorbing properties. The impedance
matching ratio (Z) can be calculated from the Eqs. (4) and (5):
Z1
Z=
Z2
µr
Z1 = × Z0
r (5)
where Z0 and Z1 stand for the impedance matching of vacuum and
absorber, respectively. Generally, the impedance matching reflect the
interface characteristics of electromagnetic wave absorber. If the
modulus value is close to 1, the impedance of air is equal to that of the
absorber, which means that most of the incident microwave at the
surface of the absorber will easily penetrate into the interior. As shown
in Fig. 8, the thickness-dependent relative input impedance varied with
increasing the frequency. Compared with ZnCo6Fe, ZnCoFe, and
Zn11CoFe, the Z value of Zn6CoFe was around 1 in the X band
(8–12 GHz) in the thickness of 2.8 mm, suggesting a good impedance
matching in the X band. Although Zn6CoFe is not the closest to 1 re-
lative to Zn4CoFe. The final absorption performance also depends on
the attenuation constant of the material.
Literature review indicates that attenuation constant (α) may be
utilized to describe the integrated loss capability (dieletric loss and
magnetic loss) of electromagnetic absorption wave material according
to the following equation [46]:
2 f '
= × (µ'' I µ' ') + (µ'' '' µ' ')2 + (µ' ''+ µ'' ')2
c (6)
In general, the attenuation ability of materials is resulted from the
synergistic effect of magnetic loss and dielectric loss. From Fig. 9a, it
was seen that α value increased with the increasing frequency. The high
attenuation constant values of Zn6CoFe can reach 400, implying that
the sample can strongly attenuate or dissipate microwaves. When the
Composites Part A 139 (2020) 106107
thickness was 2.8 mm and the optimum reflection loss was −66 dB, the
attenuation constant was 145. The high α value indicated the best EM
wave attenuation ability, which was attributed to the synergistic effect
of carbon nanotubes and Co-Fe particles. For the optimal RL corre-
sponding frequency band, the value of Zn6CoFe is greater than
Zn4CoFe, that is why the electromagnetic absorption performance of
Zn6CoFe is better than Zn4CoFe.
As for dielectric loss and magnetic loss, the Cole-Cole semicircle
curves and eddy current data can reflect the mechanism in detail, re-
spectively. Usually, the dissipation of EM wave energy is the result of
the interaction of dielectric loss and magnetic loss [47–50]. The di-
electric loss mechanism of absorber usually explained by Debye re-
laxation. The ε′, ε″ value are described as the Eqs. (7) and (8):
' s
= +
1 + (2 f)2 2
(7)
'' '' '' 2 f
= p + c =( s ) +
1 + (2 f) 2 2 f 0 (8)
Combining the Eqs. (7) and (8), the relationship between ε′ and ε″
can be expressed as the Eq. (9):
' s + s
( )2 + ( '') = ( )2
2 2 (9)
The plots of ɛ′ versus ɛ″ should be a single semicircle, which defined
as Cole-Cole semicircle. Fig. 9b described the Cole-Cole semicircle
curves of five samples. It is obvious that all samples exhibited more
distinguishable semicircles in 2–18 GHz, indicating that Debye-relaxa-
tion processes have occurred. However, some distorted semicircles can
be observed, suggesting that other polarization processes contribute to
the dielectric loss, such as Maxwell-Wagner relaxation. It is well known
that the multi-relaxation process may be ascribed to the special struc-
ture of the material. The presence of a large number of long carbon
nanotubes will generate more interfaces, resulting in more interface
polarization. In addition, the potential space charge polarization was
resulted from the interface between the Co-Fe nanoparticles and carbon
in derivative. Generally, the magnetic loss of the absorbing material can
(4) be judged by the value of current coefficient (C0) [51–52]. According to
the principle of skin effect, it can be expressed according to the fol-
lowing equation: (10):
C0 = µ'' (µ') 2 f 1 = 2 µ0 d2 (10)
If the C0 value maintains a constant with the increase of frequency,
the eddy current effect is in a dominant position of the magnetic loss,
and when the value of C0 has variety, it is mainly caused by resonance.
From Fig. 9c, the C0 values of five samples changed in the all frequency
range, suggesting that the magnetic loss was caused by natural re-
sonance.
The possible fundamental microwave absorbing mechanism of the
ZnxCoFe composites was illustrated in Fig. 10. Firstly, the high im-
pedance matching between the carbon nanotubes and Co-Fe nano-
particles allows more incident EM wave being absorbed the inner of
material. Secondly, the doped N heteroatoms and defects in the carbon
can act as polarized centers to produce enhanced interfacial polariza-
tion and dipolar polarization under an alternative electromagnetic
field, which enhances the EMW attenuation capacity. Finally and im-
portantly, the good EM wave attenuation ability of Zn6CoFe was at-
tributed to the multiple scattering and synergistic effect between the
suitable number of long carbon tubes and large specific surface area
lead by evaporate of Zn2+ at high temperature.
4. Conclusions
In summary, we have designed a strategy to regulate the length and
quantity of MOFs-derived magnetic carbon nanotubes. By introducing
an iron atom into the BMOF ZnCo and adjusting the molar ratio of Zn2+
8
J. Yan, et al.
Fig. 9. The attenuation constant, typical Cole-Cole plots and C0 curve of ZnCo6Fe, ZnCoFe, Zn4CoFe, Zn6CoFe and Zn11CoFe. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 10. Schematic illustration of the possible microwave absorption me-
chanism of ZnxCoFe. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
to Co2+ in the precursor, an EMW absorber of BMOF-derived Co-Fe
alloys embedded in a carbon and carbon nanotubes composite with
excellent electromagnetic absorbing properties was been obtained. The
minimum reflection loss of Zn6CoFe can reach −66 dB and the corre-
sponding absorption bandwidth exceeding < −10 dB reaches 4.79 GHz
only with a filler loading of 15 wt%. The outstanding microwave ab-
sorption performance due to the unique structure that containing sui-
table number of long carbon tubes, large specific surface area, enhanced
dipolar/interfacial polarizations and promoted impedance matching.
This work may pave us a unique strategy for the rational design and
construction of MOF-derived magnetic carbon nanotubes in the devel-
opment of high-efficiency microwave absorption material.
CRediT authorship contribution statement
Jing Yan: Data curation, Writing - original draft, Conceptualization.
Ying Huang: Methodology, Supervision. Yonghui Yan: Software, Data
curation. Xiaoxiao Zhao: Software, Formal analysis. Panbo Liu:
Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The work was supported by the National Natural Science
Foundation of China (No. 51672222), Joint Fund Project-Enterprise-
Shaanxi Coal Joint Fund Project (2019JLM-32), Innovation Foundation
for Doctor Dissertation of Northwestern Polytechnical University
(CX202054) and the Graduate innovation team of Northwestern
9
Composites Part A 139 (2020) 106107
Polytechnical University. The authors thank the Analysis And Testing
Center of Northwestern Polytechnical University for their technical
assistance in SEM (Verios G4).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.compositesa.2020.106107.
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