Research Article

pubs.acs.org/journal/ascecg

Composition Design and Structural Characterization of MOF-Derived

Composites with Controllable Electromagnetic Properties
Wei Liu,† Lei Liu,† Guangbin Ji,*,† Daoran Li,† Yanan Zhang,† Jianna Ma,† and Youwei Du‡
†
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, No. 29 Yudao Street, Nanjing
210016, P. R. China
‡
Laboratory of Solid State Microstructures, Nanjing University, No. 22 Hankou Road, Nanjing 210093, P. R. China
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Simply and effectively achieving the tunability of the

Downloaded via NATL INST OF TECH WARANGAL on March 28, 2023 at 18:44:58 (UTC).

composition and chemical state of each component remains a

challenge for modifying the electromagnetic performance of metal−
organic-framework-derived (MOF-derived) composites. In this work,
quaternary ZnO/Fe/Fe3C/carbon composites have been successfully
synthesized by thermal decomposition of FeIII-MOF-5. The
composition and chemical state of each component can be effectively
controlled by changing the heating temperature. In detail, with
increasing temperature, the Fe element would be transformed from
Fe3+ to Fe3C and Fe, which also leads to the graphitization and weight
loss of carbon. The effects on electromagnetic properties are also
investigated, and the ZFC-700 sample possesses optimized reflection-
loss (RL) performance with an RL value of −30.4 dB and a broad
effective frequency bandwidth of 4.96 GHz at a thin thickness of only
1.5 mm. Conduction loss, interfacial polarization, ferromagnetic resonance, and interference cancelation should be responsible
for ideal electromagnetic absorption. The porous quaternary composites not only convert incident electromagnetic energy to
heat rather than reflect it back which is in favor of solving electromagnetic pollution, but also reduce the consumption of the
metal source and poisonous raw materials for traditional microwave-absorbing materials.
KEYWORDS: MOF-derived composites, Metallic carbides, Composition design, Tunable electromagnetic properties,
Microwave absorption

■ INTRODUCTION
Recent years have witnessed expanded growth in electronic
devices, accompanied by serious electromagnetic (EM)
pollution, which not only threatens human health but also
hinders the normal operation of various kinds of commercial
and military equipment.1 Electromagnetic-shielding and micro-
wave-absorbing (MA) materials are both commonly used
against electromagnetic pollution. Although they can protect
organisms and devices, distinct targets and mechanisms lead to
varied environmental consequences. When an electromagnetic
wave is incident on a material, there would be three forms: the
reflectance (R), absorbance (A), and transmittance (T). The
relationship can be described as R + A + T = 1.2
Electromagnetic-shielding materials aim to obtain the smallest
T while microwave-absorbing materials try to obtain the
weakest R. The difference in target results in diverse
mechanisms, namely, shielding materials pay more attention
to R while absorbing materials emphasize A. From the
viewpoint of energy, incident electromagnetic energy can be
converted into thermal energy or other forms of energy in
absorbing materials while weak transformation occurs in
shielding materials. Thus, absorbing materials may be more
efficient in completely dealing with electromagnetic pollution.
For practical applications, a microwave absorber must meet
the requirements of having thin thickness, being lightweight,
and having a broad effective frequency bandwidth (fe) and
strong absorption intensity.3 However, traditional MA materials
are not able to achieve the balance between reflection-loss (RL)
performance and application conditions. Generally, MA
materials can be classified as dielectric- and magnetic-loss
materials according to the attenuation mechanism.4,5 On one
hand, dielectric-loss materials usually possess a strong
absorption intensity, while a broad fe is hard to reach and is
restricted by the material’s bad impedance matching and
limited loss mechanisms including conduction loss and a
polarization process.6 On the other hand, a strong absorption
intensity and broad fe can be obtained by magnetic-loss
materials. Nevertheless, the reported thickness is usually larger
than 3 mm, and the filling ratio is mostly larger than 80% which
is far from satisfactory. Thus, efforts have been devoted to the
synthesis of composites which may integrate the advantageous
properties of dielectric and magnetic components.7
Received: May 14, 2017
Revised: July 7, 2017
Published: July 20, 2017

© 2017 American Chemical Society 7961 DOI: 10.1021/acssuschemeng.7b01514

ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 1. PXRD pattern (a) and TEM image (b) of the as-synthesized FeIII-MOF-5.
Figure 2. PXRD pattern (a) and ICP results (b) of the as-synthesized composites.
Recently, metal−organic-framework-derived (MOF-derived)
composites have emerged as promising candidates for high-
performance MA composites.8−11 Generally, graphitic carbon
can be obtained by the catalysis of magnetic metal during the
decomposition process of MOFs which ensures a strong
dielectric-loss ability. Additionally, a magnetic metal or alloy
would bring excellent magnetic loss which would be propitious
for impedance matching and a broader fe.12−14 The existence of
metal oxides may improve the impedance matching by reducing
the electrical conductivity and inducing more interfaces which
may strengthen interfacial polarization. Our previous work
regarding ZnO/Co/carbon and CuO/carbon may enlighten
researchers designing novel microwave absorbers.15,16 We also
find that metal carbides can be introduced to ZnO/Co/carbon
composites which lead to an excellent MA performance.17
Although improvements have been made, several problems
still exist to be solved. First, our previous work pays more
attention to the optimization of impedance matching. TiO2,
CuO, ZnO, and amorphous carbon can be employed to
decrease the high complex permittivity of MOF-derived
materials to fulfill excellent impedance matching.15−18 How-
ever, the precondition of optimizing impedance matching is
that MA materials possess strong attenuation abilities. Hence,
more work is requested to enhance the attenuation abilities of
MOF-derived materials. Second, previous research about
improving the attenuation abilities of MOF-derived micro-
wave-absorbing materials is limited. One way is increasing the
conductivity of carbon through promoting pyrolysis temper-
ature.10,13 The other way is inducing components with strong
loss abilities, such as graphene, metal, etc.8,12 Unfortunately,
this research is in the early stages. The vital roles of
composition and structure in deciding the electromagnetic
7962
Research Article
properties remain equivocal. Meanwhile, the development of
facile yet effective techniques to obtain MOF-derived materials
with designed compositions and structures is urgent. Third,
energy consumption as well as poisonous substances should be
reduced in the synthesis route. Fortunately, FeIII-MOF-5 has
been found to be a promising precursor for high-performance
MA materials composed of ZnO, Fe, Fe3C, and carbon.
Interestingly, the chemical state of Zn, Fe, O, and C elements
can be effectively controlled by changing the calcination
temperature which involves a transformation from Fe3+ to
Fe3C and Fe. Effects on the electromagnetic properties are also
discussed which may provide useful hints for the fabrication of
novel MA materials against EM pollution.
■ EXPERIMENTAL SECTION
Preparation of Porous ZnO/Fe3C/C Composites. FeIII-MOF-5
was synthesized using a refluxing method based on the literature.19
Typically, 2.16 g of ferric acetylacetonate, 1.67 g of Zn(NO3)2·6H2O,
0.34 g of terephthalic acid, and 7.2 g of polyvinylpyrrolidone (PVP,
K29−K32) were added into mixtures of 180 mL of ethanol and 300
mL of dimethylformamide (DMF). After being completely dissolved
by stirring, the mixture was refluxed at 100 °C for 6 h. The products
were collected by centrifugation and washed with DMF and ethanol
three times and then vacuum-dried at 60 °C. After being ground, the
MOF powders were calcined in N2 with a ramping rate of 5 °C min−1
to 600, 650, 700, and 750 °C and kept for 2 h. The obtained
composites are denoted as ZFC-600, ZFC-650, ZFC-700, and ZFC-
750, respectively.
Characterizations. Powder X-ray diffraction (PXRD) patterns
were collected by a Bruker D8 Advance diffractometer with Cu Kα
irradiation and a scanning range 5−90°. Thermogravimetric (TG)
analyses of the MOF precursor were performed by a PerkinElmer
Diamond TG/DTA apparatus in N2 at a heating rate of 10 °C min−1.
Chemical states of each element were investigated by a PHI 5000
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 3. Raman spectra (a) of the as-prepared composites; XPS survey spectra (b) and Zn 2p (c), C 1s (d), O 1s (e), and Fe 2p (f) spectra for
ZFC-600, -650, -700, and -750.
VersaProbe device. Precise contents of Zn and Fe were provided by
inductively coupled plasma−atomic emission spectroscopy (ICP−
AES) in which the sample was treated by aqua regia. The bonding
state of carbon was further studied by Raman spectra using a Renishaw
in Via 2000 Raman microscope. SEM images were obtained from a
Hitachi S4800 device, and TEM and HRTEM images were gained
from a JEOL, JSM-2010 device. A micromeritics ASAP 2020 system
was employed at 77 K for examination of the porous structure of the
samples. Static magnetic properties were determined by a vibration
magnetometer (Lakeshore 7400). Complex permittivity and perme-
ability were measured by an Agilent PNA N5244A vector network
analyzer. The samples were made by mixing 40 wt % wax with samples
and then pressing this into a toroidal ring with a ϕout of 7.0 mm and a
ϕin of 3.04 mm.
■ RESULTS AND DISCUSSION
Figure 1a shows the PXRD pattern of the as-prepared FeIII-
MOF-5 and the simulated pattern of MOF-5. Prominent peaks
at 6.8°, 9.6°, 13.6°, 15.2°, and 22.3° of the sample are found to
match well with the simulated pattern. It may be inferred that
the inserted Fe3+ ions do not significantly change the crystal
7963
Research Article
structure of MOF-5.20 On the basis of previous research,
thermal treatment temperature plays a crucial role in not only
the composition but also the structure.14 Hollow FeIII-MOF-5
octahedra can be seen in Figure 1b which is consistent with
previous reports.19 The size of the octahedra is about 200 nm.
The composition of the samples is determined by PXRD and
ICP−AES. Figure 2a displays the PXRD patterns of ZFC-600,
-650, -700, and -750. The characteristic peaks at 31.8°, 34.4°,
36.2°, 47.5°, 56.6°, 62.9°, 68.0°, and 69.0° can be seen for all
three samples which should be indexed to the (100), (002),
(101), (102), (110), (103), (112), and (201) planes of
hexagonal ZnO, respectively.21 The diffraction peaks at 37.8°,
42.9°, 43.8°, 44.6°, 45.0°, 45.9°, 48.6°, and 49.1° matched well
with the (210), (211), (102), (220), (031), (112), (131), and
(221) planes of orthorhombic Fe3C, respectively.22 Interest-
ingly, ZFC-750 only possesses peaks of cubic Fe. It is generally
accepted that ZnO would be formed at less than 500 °C and
reduced to Zn metal by carbon around 800 °C during the MOF
decomposition process.23 Thus, it is anticipated that elemental
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 4. Deconvolution of ZFC-700 HR-XPS Zn 2p (a), Fe 2p (b), O 1s (c), and C 1s (d) data.
Zn exists in the form of ZnO in this case. It should be noted
that elemental Fe exists mainly in the form of Fe and Fe3C.
This may result from the shorter thermal treatment time and
the unique composition. The contents of each element are
given in Figure 2b. The contents of Zn of ZFC-600, -650, -700,
and -750 are 38.27%, 36.31%, 34.94%, and 3.35%, respectively.
It seems that, at higher temperature, Zn elements may be
vaporized or discharged from the composites which also lead to
the highest Fe content of 89.89% and the lowest C content of
5.94% for ZFC-750. It should be pointed out that the carbon
contents of the samples are all near 17% except for that of ZFC-
750 (5.94%).
Raman spectra are given to characterize the bonding state of
carbon. Two noticeable peaks at about 1335 and 1590 cm−1 can
be distinguished which are usually defined as the D band and
the G band, respectively. It has been well-documented that the
D band is related to defects or disorder in carbon materials and
that the G band is induced by the sp2-hybridized carbon.10 The
relatively high intensity of the G band for ZFC-600, -650, -700,
and -750 reveals that carbon is partially graphitized because of
the catalytic effect of the Fe species, while the obvious D band
may result from the defects and disorder among interfaces with
Fe, Zn species, and air. It is widely accepted that the intensity
ratio of ID/IG can be a criterion to represent the graphitization
degree. As shown in Figure 3a, the values of ID/IG are 0.872,
0820, 0.846, and 0.868 for ZFC-600, -650, -700, and -750,
respectively. On the basis of the above discussions, we may
infer that the number of graphitic walls developed by thermal
treatment at 750 °C is the smallest while ZFC-600, -650, and
-700 possess nearly the same graphitic walls. With increasing
temperature, the graphitization should be improved according
to previous research, while, in this case, the graphitization
degrees of ZFC-700 and -750 are lower than that of ZFC-650.
A possible reason would be the increased relative intensity of
7964
Research Article
the D band. Two aspects should be taken into consideration.
On one hand, increased temperature would favor the formation
of tiny crystalline domains.10 On the other hand, some defects
would be generated during the high-temperature carbothermal
reduction.10 In this case, some lattice carbon may capture
oxygen in ZnO which may lead to enhancement of the D band.
For further probing of the chemical state of as-prepared
composites, XPS is employed. The purity of the composites
and existence of Zn, Fe, O, and C elements are confirmed by
the XPS survey spectrum. Figure 3c shows the Zn 2p spectra of
three samples with two similar peaks at 1021.8 and 1044.8 eV,
which correspond to Zn 2p3/2 and Zn 2p1/2. C 1s spectra are
shown in Figure 3d with a single peak at around 284.8 eV
which may be ascribed to CO2, C, COH, OCO, and
Fe3C. A remarkable difference can be seen in the O 1s spectra.
The peak at 530.6 eV of ZFC-600 should be the O2− ions of
ZnO or Fe2O3. Other peaks at around 532.3 eV can be
distinguished which might be attributed to CO or CO.24
Remarkable differences also exist in the Fe 2p spectra. Peaks at
711.1 and 725.1 eV for ZFC-600 belong to Fe3+ 2p3/2 and Fe3+
2p1/2. Similarly, peaks at 710.9 and 724.9 eV for ZFC-650 as
well as peaks at 710.2 and 724.4 eV should be ascribed to Fe3+
ions which may come from the oxidation of Fe after exposure in
air with less carbon coating. Meanwhile, peaks at 707.3 and
719.8 eV for ZFC-600, peaks at 707.0 and 719.4 eV for ZFC-
650, peaks at 706.7 and 720.0 eV for ZFC-700, and peaks at
707.0 and 720.0 eV for ZFC-750 all reflect the binding energies
of Fe 2p3/2 and Fe 2p1/2, respectively. Noticeably, Fe3C,
namely, Fe+, should be observed clearly according to XRD
results. This is because XPS is a surface analysis technique
which focuses on the chemical state of elements less than
several tens of nanometers.
For a further understanding of the chemical state of each
element in ZFC-700, the HR-XPS data are analyzed in Figure 4.
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 5. TEM image (a) and HRTEM images (b, c) of ZFC-600. TEM image (d) and HRTEM images (e, f) of ZFC-650. TEM image (g),
HRTEM image (h), and electron diffraction pattern (i) of ZFC-700. TEM image (j), HRTEM image (k), and EDX result (l) of ZFC-750.
As for Zn, two peaks belonging to Zn2+ can be well-fitted with
HR-XPS spectra, indicating that ZnO is stable after thermal
treatment at 700 °C. The Fe 2p spectrum of ZFC-700 can be
deconvoluted into five peaks. Peaks at 711 and 724 eV belong
to Fe3+ ions, and peaks at 706.8 and 719.9 eV pertain to Fe,
while the characteristic peak at 708.1 eV of Fe+ in Fe3C can be
observed, too. We may infer that the Fe3+ in FeIII-MOF-5 may
be reduced gradually to Fe by carbon at a moderate
temperature (more than 600 °C) and further react with carbon
to form Fe3C. It is necessary to point out that our results seem
to contradict the previous report on Fe/C nanocubes derived
from prussian blue.10 This can be explained by the fact that the
existence of ZnO would affect the carbon content and chemical
environment of Fe to some extent; the relatively higher carbon
content in precursors probably favors the formation of Fe3C.
The O element in ZFC-700 shows a remarkable difference with
other samples, and the HR-XPS spectra can be deconvoluted
into three peaks including 530.6 eV for metal oxides, 532.3 eV
for CO, and 533.1 eV for CO. The O species may be
ZnO, Fe2O3, adsorbed CO2, H2O, surface OH, COOH, etc.
Additionally, the chemical state of carbon of all samples is
similar, and the C 1s HR-XPS spectrum of ZFC-700 can be
deconvoluted into four peaks: in detail, the peak at 284.3 eV
corresponds to graphitic carbon, the peak at 284.8 eV is a signal
of CO2, the peak at 285.4 eV should be assigned to COH,
and the peak at 289.1 eV may originate from OCO. This
7965
Research Article
is consistent with Raman data and proves the existence of
graphitic carbon in the composites.25
In conclusion, the as-prepared materials are composed of
ZnO, Fe, Fe3C, and partially graphitc carbon. In detail, ZnO is
quite stable under this circumstance with the slight chemical
state change of O which is caused by the reduction to Zn at
high temperature. As for Fe species, reduction from Fe3+ to Fe
and reaction with carbon to form Fe3C step by step should be
responsible for the varied chemical state. As for carbon, the
catalytic effect of Fe species substantially improves the
graphitization degree, and high temperature and the
carbothermal reduction may induce more defects which may
become polarization centers.
For identification of the structure of the composites, TEM
and HRTEM images are offered in Figure 5. After calcination in
N2 at 600 °C, the octahedral structure is basically collapsed, and
∼15 nm nanoparticles uniformly embedded in the carbon
matrix are obtained. In Figure 5b, the lattice fringes of 0.238 nm
can be clearly observed which can be assigned to the (121)
interplane spacing of Fe 3 C. Because of the catalytic
graphitization effect of Fe and Fe3C, few graphene layers can
be seen coating on nanoparticles. The lattice fringes belonging
to ZnO can also be found, and it is noteworthy that the coated
carbon is amorphous. When the temperature rises up to 650
°C, the nanoparticles would grow and partially aggregate with
each other. Fe nanoparticles can grow up to ∼100 nm, and a
part of ZnO would form a nanorod-like structure which is
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 6. Nitrogen adsorption−desorption isotherms (a) and pore size distribution (b) of the as-prepared composites.
Figure 7. M−H loops of ZFC-600 (a), ZFC-650 (b), ZFC-700 (c), and ZFC-750 (d) measured at room temperature.
confirmed by the HRTEM image in Figure 5e. Meanwhile,
ZnO nanoparticles can also be seen in Figure 5f. With increased
temperature to 700 °C, larger nanoparticles are obvious, as well
as more graphene layers. On the basis of Figure 5h, we may
speculate that large Fe nanoparticles catalyze the graphitization
of carbon and also supply more opportunities for the formation
of Fe3C. In addition, rings of Fe3C, ZnO, and Fe can all be seen
in Figure 5i, which further confirmed the composition of the as-
made samples. EDS mapping results of ZFC-700 are displayed
in Figure S3, indicating that ZnO disperses uniformly in the
carbon matrix and that Fe mainly exists in large particles. After
thermal treatment at 750 °C, Fe nanoparticles have grown to
more than 1 μm, and few ZnO and carbon species can be
found. The morphology evolution can also be described by
SEM images in Figure S2. ZFC-600 possesses a similar shape
with FeIII-MOF-5, while massive nanorods can be observed for
ZFC-650 which is consistent with the TEM study. As for ZFC-
700, nanoparticles grow to large particles and become larger for
ZFC-750. In a word, ordered structure is unstable at a higher
7966
Research Article
temperature: Nanoparticles would grow and aggregate with
each other. A change of chemical state of Fe, Zn, O, and C may
also lead to disordered structure.
In addition, the porous structures should not be neglected.
N2 sorption isotherms and pore distributions of all samples are
given. Typical type-IV isotherms can be found which indicate a
mesoporous character (see Figure 6a). The BET surface areas
are 69.71, 64.55, 48.28, and 8.41 m2 g−1 for ZFC-600, -650,
-700, and -750, respectively. This is consistent with SEM and
TEM studies in which ZFC-750 is mainly composed of large
nanoparticles while a porous structure can be observed in other
samples. Meanwhile, the surface area is less than that from a
previous report which should originate from a higher
calcination temperature.19 The average pore size is about 12
nm which further proves the mesoporous structures of the
sample. It is interesting that pores of nearly 2.0 and 2.5 nm are
obvious in ZFC-600, -650, and -700, which may be inherited
from the porous structures of MOFs. When the MOF structure
is destroyed at about 750 °C, only broad peaks of about 2.2 nm
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 8. Real parts (a) and imaginary parts (b) of complex permittivity of all samples. Real parts (c) and imaginary parts (d) of complex
permeability of all samples.
can be seen which may be the pores in unreacted carbon in
ZFC-750 (see Figure 6b).
Moreover, for an evaluation of the magnetic properties of the
samples, hysteresis loops are exhibited in Figure 7. Typical
ferromagnetic behavior can be seen for all the samples with Ms
values of 33.0, 50.3, 58.9, and 103.5 emu g−1 for ZFC-600, -650,
-700, and -750, respectively. They are all smaller than the
literature value of 140 emu g−1 for Fe3C, which should be the
reason for the existence of nonmagnetic ZnO and carbon,26
while, for the Hc value, a “V”-shaped trend can be found with
increasing temperature in which 231, 88, and 136 Oe belong to
ZFC-600, -650, and -700, respectively. Meanwhile, ZFC-750
possesses the smallest Hc value of 54.9 Oe. This may be related
to the varied size and distinct chemical state of Fe species in
each sample.12
Caused by a diverse structure and distinct composition, the
electromagnetic properties of the as-prepared materials are
unique. In particular, complex permittivities (εr) and complex
permeabilities (μr) are supplied. From Figure 8a and 8b, one
can see that the real permittivity (ε′) values of ZFC-600
decrease from 9.06 at 2 GHz to 7.56 at 18 GHz while the
imaginary permittivity (ε″) values fluctuate around 1.7. The
dielectric properties of ZFC-650 are very similar to those of
ZFC-600. The ε′ values decline from 10.16 to 8.38 in the
measuring range, and the ε″ values hover around 1.5. An
obvious change can be noticed for ZFC-700 in which the ε′
values drop from 14.94 to 10.58, and the ε″ values rise and
drop between 4.12 and 3.30. Generally, ε′ represents the
storage capability, and ε″ stands for the loss ability of dielectric
energy.27 However, ZFC-750 possesses a complex permittivity
that is too high and can be ignored in later discussions. It can
be deduced that the loss abilities enhance with increasing
temperature as well as the storage capabilities. On the basis of
7967
Research Article
previous research, the relation between ε″ and electrical
conductivity can be expressed as
σAC = ε0ε″2πf (1)
where the terms are as follows: σAC is the electrical
conductivity, ε0 is the dielectric constant of free space, ε″ is
the imaginary permittivity, and f is the microwave frequency.12
As we can see, the ε″ values of ZFC-600, -650, and -700 show
fluctuation within a narrow range. Thus, we may speculate that
the improvement of electrical conductivity should be
responsible for the rise of ε″ values. On one hand, the varied
content of each component should be stressed. In detail, the
decreased content of semiconductive ZnO and the increased
content of more conductive Fe species are all conducive to
electrical conductivity. When it comes to complex permeability,
a similar trend can be observed (see Figure 8c and 8d). The real
permeability (μ′) values of ZFC-600 decreased from 1.20 to
1.02, and the imaginary permeability (μ″) values go down from
0.17 to 0.03 in the measuring frequency range. It should be
noted that the permeabilities of ZFC-650 and -700 are quite
different from that of ZFC-600. The μ′ values of ZFC-650 and
-700 fall from 1.30 to 1.07 and from 1.33 to 1.09, respectively.
The μ″ values of ZFC-650 reach the highest point at 10.5 GHz
(0.25) and the lowest point at 18 GHz (0.10). With regard to
ZFC-700, μ″ values of 0.23 at 10 GHz and 0.10 at 10 GHz are
the highest and lowest, respectively. This may indicate that
ZFC-650 and ZFC-700 possess stronger storage and loss
abilities of magnetic energy. The Globus equation is as follows:
μ ∝ (Ms 2D/K1)1/2 (2)
where, for a higher complex permeability, a higher Ms, a larger
grain size (D), and a smaller magnetocrystalline anisotropy
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 9. 3D representation of RL values of ZFC-600 (a), ZFC-650 (b), and ZFC-700 (c). RL curves of as-made composites at 1.5 mm (d).
constant (K1) are required.12 In this case, larger Ms values for
ZFC-650 and -700 and a larger grain size may contribute to the
larger permeability.
For comparison of the dielectric-loss abilities, dielectric-loss
tangents (tan δε = ε″/ε′) are calculated in Figure S4a. The
shape of the curves resembles each other, and ZFC-700
possesses the highest value which means it possesses the
strongest dielectric-loss abilities. For comparison of the
magnetic-loss abilities, magnetic-loss tangents (tan δμ = μ″/
μ′) are shown in Figure S4b. The values of ZFC-600 directly
decrease from 0.15 to 0.03 within several peaks, while ZFC-650
and ZFC-700 possess almost the same curves with values going
up from about 0.13 at 2 GHz to 0.20 at 10 GHz and dropping
to 0.09 at 18 GHz. We should point out that ZFC-700
possesses the strongest magnetic-loss capability.
Considering the strong attenuation ability of the as-prepared
materials, the reflection-loss performance can be expected.
According to the transmission line theory, the reflection-loss
(RL) values can be gained by experimentally obtaining
electromagnetic parameters based on the following formulas:28
⎛ μ ⎞1/2
Z in = Z0⎜ r ⎟ tanh[j(2πfd /c)(με
r r
)1/2 ]
⎝ εr ⎠ (3)
RL = 20 log|(Z in − Z0)/(Z in + Z0)| (4)
Here, the terms are as follows: Zin is the input impedance of the
absorber, Z0 is the impedance of free space, d is the thickness of
the absorber, and c is the velocity of an electromagnetic wave in
free space. In general, strong absorption intensity (RL ≤ −10
dB), broad effective frequency bandwidth ( fe), and thin
thickness are demanded for high-performance microwave
absorbers. Figure 9a−c presents the calculated results at
different thicknesses from 1 to 5 mm. As for ZFC-600, poor
7968
Research Article
performance can be seen. The minimum RL value can reach
−15.54 dB at 4.65 mm, and the maximum fe is about 2.88 GHz
at 4.8 mm. Obviously, ZFC-600 cannot meet the requirement
for practical applications even at a high frequency which is
related to its relatively low complex permittivity and
permeability. With increasing temperature, better RL perform-
ance can be gained because of strengthened attenuation
abilities. The minimum RL value is up to −18.69 dB at 2.35
mm with fe from 9 to 11.96 GHz. Moreover, an fe value of 3.52
GHz can be obtained at both 2.10 and 2.15 mm with a
minimum RL value of approximately −17 dB. However, it is
still far from practical use. When the attenuation ability is
strongest (ZFC-700), excellent microwave absorption behavior
can be attained. It is worth pointing out that the −50.5 dB can
be reached at 7.44 GHz with a thickness of 2.6 mm, and a
broad fe of 4.96 GHz could be obtained at only 1.5 mm. In
summary, ZFC-700 shows obvious superiority in RL perform-
ance which is able to fulfill the requirements of having thin
thickness, being lightweight, and having a broad effective
frequency bandwidth and strong absorption intensity. Specif-
ically, fe values of 4.48, 4.96, 4.76, 4.28, and 3.72 GHz could be
realized at 1.4, 1.5, 1.6, 1.8, and 2.0 mm for ZFC-700,
respectively. In addition, we can find that the RL peaks shift to
a lower frequency with increasing thickness which can be
explained by the quarter-wavelength matching model:
tm = nc /(4fm (|εr||μr |)1/2 ) (5)
Here, the terms are as follows: tm is the thickness of the
absorber, f m is the peak frequency, and n is constant (n = 1, 3,
5, ...). Thus, it is easy to understand that when tm is larger, f m is
lower. The fact also proves that interference cancelation
contributes to the attenuation of incident microwaves.29 Figure
9d further shows the RL curves of ZFC-600, -650, and -700 at
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
Figure 10. Attenuation constants (a) and comparison of impedance matching at 1.5 mm (b) of ZFC-600, -650, and -700.
Figure 11. Cole−Cole plot (a) and C0 values (b) of ZFC-700.
1.5 mm. We can clearly see that, with increasing temperature,
RL peaks shift to a lower frequency, and RL values become
more negative. This is decided by the increasing complex
permittivity and permeability which are benefits for better RL
performance at thin thicknesses.
For a comprehensive understanding of the attenuation
properties of the samples, attenuation constants are provided
on the basis of the following equation:
2 πf
α= (μ″ε″ − μ′ε′) + (μ″ε″ − μ′ε′)2 + (μ′ε″ + μ″ε′)2
c high-frequency range which should be ascribed to the strong
(6)
Obviously, with increasing temperature, the attenuation
constants improve. ZFC-700 possesses the largest α values
from 39.19 to 267.11 in the entire microwave frequency range.
Another point is that α values gradually increase with rising
frequency, which illustrates that the as-prepared composites
show a stronger attenuation ability in the high-frequency
range.16
Although attenuation ability is important for a microwave
absorber, the impedance matching cannot be ignored, either. If
the characteristic impedance of the microwave absorber is not
close to the impedance of air, the incident wave would mostly
reflect at the interface.9 Thus, excellent impedance matching is
necessary for developing high-performance microwave-absorb-
ing materials. |Zin/Z0| values can be employed for determination
of the condition of impedance matching, and when it is 1,
which means that the input impedance equals the impedance of
air, perfect impedance matching is achieved. When the
thickness is 1.5 mm, |Zin/Z0| values of 0.8−1.2 cover the
frequency range 11.8−15.72 GHz, and in this frequency range,
7969
Research Article
the RL values of ZFC-700 are more negative than −10 dB,
indicating that better impedance matching is in favor of more
satisfying microwave absorption performance. However, for
ZFC-600 and ZFC-650, the values are not close to 1, and
impedance matching is even worse at a high-frequency range
above 15 GHz. Thus, promising RL performance requirements
cannot be fulfilled by ZFC-600 or ZFC-650. Comparisons of
attenuation constants and impedance matching are shown in
Figure 10a and Figure 10b, respectively.
It is interesting that ZFC-650 possesses weak absorption at a
attenuation at a high frequency. The fact also illustrates that
attenuation and impedance matching are both critical points for
designing a microwave absorber while attenuation ability should
receive more attention. Hence, the attenuation mechanisms are
further discussed. It is generally accepted that conduction loss
and interfacial polarization loss contributed most in the
microwave frequency range for dielectric absorbers. On the
basis of Debye theory, the relations between ε′ and ε″ can be
roughly written as
⎛ εs + ε∞ ⎞2 2 ⎛ εs − ε∞ ⎞2
⎜ε′ − ⎟ + (ε ″ ) = ⎜ ⎟
⎝ 2 ⎠ ⎝ 2 ⎠ (7)
Herein, εs and ε∞ are the static permittivity and the relative
permittivity at infinite frequency. Thus, the curve of ε′ to ε″
corresponds to a single semicircle which indicates 1 Debye
relaxation process.30 The Cole−Cole plot of ZFC-700 is given
in Figure 11a, and we can easily divide it into two segments.
One is a straight line in the ε′ range 14−15 which is related to
conduction loss. In this case, it mainly comes from graphitic
carbon and Fe species.
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering Research Article

Table 1. Microwave Absorption Performance of Similar Materials

sample filling ratio (wt %) optimal thickness (mm) RLmin (dB) fe (GHz) ref
ZnO/SiC/wax 30 2.5 −31.31 6.60 32
C/ZnO/wax 40 1.75 −52 2.5 33
Fe−Fe3C/C/wax 25 1.5 −17.9 4.0 34
RGO/ZnO/wax 15 2.4 −54.2 6.7 35
ZnO/Fe/wax 60 1.5 −40 4.0 36
C/Fe3C/wax 10 3.6 −62.6 6.5 37
ZnO/C@/Co@C/wax 50 1.9 −28.8 4.2 15
ZnO/Co3ZnC/Co/C/wax 50 1.9 −32.4 5.24 17
ZFC-700/wax 60 1.5 −30.4 4.96 this work

The other curve is multiple semicircles in the ε′ range 10−
14. It reveals that multiple relaxation processes exist in the
composites upon irradiation by microwaves. As we know,
interfacial polarization usually occurs between components with
a distinct electrical conductivity.31 Therefore, interfacial polar-
ization may occur in interfaces among ZnO/C, Fe3C/C, ZnO/
Fe3C, C/air, Fe/C, Fe/Fe3C, and so on. Moreover, it should be
noted that the porous structure of the composites might
facilitate the scattering of incident waves and also be conducive
to the increase of dipole amount which further strengthens the
interfacial polarization. Meanwhile, we could not neglect
magnetic loss. In most cases, the ferromagnetic resonance
and eddy current effect are the main magnetic-loss mechanisms
in the microwave frequency range. C0 is always used to confirm
dB and a broad fe of 4.96 GHz can be reached at a thin
thickness of only 1.5 mm which makes ZFC-700 an excellent
MA material. Conduction loss, interfacial polarization,
ferromagnetic resonance, and interference cancelation should
be responsible for the satisfying RL performance.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.7b01514.
SEM images of as-prepared products, and PXRD pattern,
electromagnetic parameters, and RL curves of ZFC-750
(PDF)

■
that eddy current loss dominates the magnetic loss on the basis
of the following equation.
AUTHOR INFORMATION
C0 = μ″(μ′)−2 f −1 (8) Corresponding Author
*E-mail: gbji@nuaa.edu.cn. Phone: +86-25-52112902.
As we can see in Figure 11b, C0 values are not constant in the
entire frequency range which means that eddy current is not ORCID
the main loss mechanism and that ferromagnetic resonance of Lei Liu: 0000-0001-5816-8699
Fe3C should be the dominating magnetic-loss mechanism. Guangbin Ji: 0000-0002-5150-3949
In summary, the influence of carbon focuses on the Author Contributions
following: supplying a highly conductive matrix which ensures The paper was written through contributions of all authors. All
a high ε″ value and strong conduction loss, and isolating Zn authors approved the final version of the paper.
and Fe species which guarantees many more interfaces and Notes
enhanced interfacial polarization. Fe and Fe3C offer mainly The authors declare no competing financial interest.

conduction loss and ferromagnetic resonance. ZnO is in favor
of strong interfacial polarization. In addition, recent progress in
similar microwave materials is summarized in Table 1.
Compared with samples from similar work, ZFC-700 shows
outstanding performance at a thin thickness and may be more
appealing. Nevertheless, a breakthrough is demanded in
decreasing the filling ratio and further broadening the effective
■
ACKNOWLEDGMENTS
Financial support from the National Nature Science Founda-
tion of China (11575085), Qing Lan Project, Six Talent Peaks
project in Jiangsu Province (XCL-035), and the Priority
Academic Program Development of Jiangsu Higher Education
Institutions is gratefully acknowledged.

■
frequency bandwidth.

■ CONCLUSIONS
Novel microwave-absorbing composites of ZnO/Fe/Fe3C/
carbon have been successfully synthesized by thermal
decomposition of FeIII-MOF-5. The composition and chemical
state of each component can be effectively controlled by
changing the calcination temperature. ZnO is relatively stable
while physical and chemical properties of Fe and C elements
are tunable. With increasing temperature, the Fe element would
be transformed from Fe3+ to Fe3C and Fe during the
carbonization process. This process also leads to the
graphitization and weight loss of carbon. The effects on
electromagnetic properties are also investigated, and ZFC-700
possesses the strongest attenuation ability with better
impedance matching at a thin thickness. RL values of −30.4
REFERENCES
(1) Zhao, B.; Guo, X.; Zhao, W.; Deng, J.; Fan, B.; Shao, G.; Bai, Z.;
Zhang, R. Facile synthesis of yolk-shell Ni@void@SnO2(Ni3Sn2)
ternary composites via galvanic replacement/Kirkendall effect and
their enhanced microwave absorption properties. Nano Res. 2017, 10
(1), 331−343.
(2) Zhang, L.; Liu, M.; Roy, S.; Chu, E. K.; See, K. Y.; Hu, X.
Phthalonitrile-based carbon foam with high specific mechanical
strength and superior electromagnetic interference shielding perform-
ance. ACS Appl. Mater. Interfaces 2016, 8 (11), 7422−7430.
(3) Ding, Y.; Zhang, L.; Liao, Q.; Zhang, G.; Liu, S.; Zhang, Y.
Electromagnetic wave absorption in reduced graphene oxide function-
alized with Fe3O4/Fe nanorings. Nano Res. 2016, 9 (7), 2018−2025.
(4) Liu, P.; Huang, Y.; Yan, J.; Zhao, Y. Magnetic graphene@PANI@
porous TiO2 ternary composites for high-performance electromagnetic
wave absorption. J. Mater. Chem. C 2016, 4 (26), 6362−6370.

7970 DOI: 10.1021/acssuschemeng.7b01514

ACS Sustainable Chem. Eng. 2017, 5, 7961−7971
ACS Sustainable Chemistry & Engineering
(5) Liu, Y.; Li, Y.; Jiang, K.; Tong, G.; Lv, T.; Wu, W. Controllable
synthesis of elliptical Fe3O4@C and Fe3O4/Fe@C nanorings for
plasmon resonance-enhanced microwave absorption. J. Mater. Chem. C
2016, 4 (30), 7316−7323.
(6) Fang, J.; Liu, T.; Chen, Z.; Wang, Y.; Wei, W.; Yue, X.; Jiang, Z. A
wormhole-like porous carbon/magnetic particles composite as an
efficient broadband electromagnetic wave absorber. Nanoscale 2016, 8
(16), 8899−8909.
(7) Zhang, N.; Huang, Y.; Zong, M.; Ding, X.; Li, S.; Wang, M.
Synthesis of ZnS quantum dots and CoFe2O4 nanoparticles co-loaded
with graphene nanosheets as an efficient broad band EM wave
absorber. Chem. Eng. J. 2017, 308, 214−221.
(8) Zhang, X.; Ji, G.; Liu, W.; Quan, B.; Liang, X.; Shang, C.; Cheng,
Y.; Du, Y. Thermal conversion of an Fe3O4@metal-organic framework:
a new method for an efficient Fe-Co/nanoporous carbon microwave
absorbing material. Nanoscale 2015, 7 (30), 12932−12942.
(9) Qiang, R.; Du, Y.; Chen, D.; Ma, W.; Wang, Y.; Xu, P.; Ma, J.;
Zhao, H.; Han, X. Electromagnetic functionalized Co/C composites
by in situ, pyrolysis of metal-organic frameworks (ZIF-67). J. Alloys
Compd. 2016, 681, 384−393.
(10) Qiang, R.; Du, Y.; Zhao, H.; Wang, Y.; Tian, C.; Li, Z.; Han, X.;
Xu, P. Metal organic framework-derived Fe/C Nanocubes toward
efficient microwave absorption. J. Mater. Chem. A 2015, 3 (25),
13426−13434.
(11) Zeng, X.; Yang, B.; Zhu, L.; Yang, H.; Yu, R. Structure evolution
of Prussian blue analogues to CoFe@C core−shell nanocomposites
with good microwave absorbing performances. RSC Adv. 2016, 6
(107), 105644−105652.
(12) Yang, Z.; Lv, H.; Wu, R. Rational construction of graphene
oxide with MOF-derived porous NiFe@C nanocubes for high-
performance microwave attenuation. Nano Res. 2016, 9 (12), 3671−
3682.
(13) Lu, Y.; Wang, Y.; Li, H.; Lin, Y.; Jiang, Z.; Xie, Z.; Kuang, Q.;
Zheng, L. MOF-Derived porous Co/C nanocomposites with excellent
electromagnetic wave absorption properties. ACS Appl. Mater.
Interfaces 2015, 7 (24), 13604−13611.
(14) Liu, W.; Shao, Q.; Ji, G.; Liang, X.; Cheng, Y.; Quan, B.; Du, Y.
Metal-organic-frameworks derived porous carbon-wrapped Ni compo-
sites with optimized impedance matching as excellent lightweight
electromagnetic wave absorber. Chem. Eng. J. 2017, 313, 734−744.
(15) Liang, X.; Quan, B.; Ji, G.; Liu, W.; Cheng, Y.; Zhang, B.; Du, Y.
Novel nanoporous carbon derived from metal-organic frameworks
with tunable electromagnetic wave absorption capabilities. Inorg. Chem.
Front. 2016, 3, 1516−1526.
(16) Ma, J.; Zhang, X.; Liu, W.; Ji, G. Direct synthesis of MOF-
derived nanoporous CuO/carbon composites for high impedance
matching and advanced microwave absorption. J. Mater. Chem. C
2016, 4 (48), 11419−11426.
(17) Liu, W.; Pan, J.; Ji, G.; Liang, X.; Cheng, Y.; Quan, B.; Du, Y.
Switching the electromagnetic properties of multicomponent porous
carbon materials derived from bimetallic metal-organic frameworks:
effect of composition. Dalton Trans. 2017, 46, 3700−3709.
(18) Zhang, X. M.; Ji, G. B.; Liu, W.; Zhang, X. X.; Gao, Q. W.; Li, Y.;
Du, Y. W. A novel Co/TiO2 nanocomposite derived from a metal−
organic framework: synthesis and efficient microwave absorption. J.
Mater. Chem. C 2016, 4 (9), 1860−1870.
(19) Zou, F.; Hu, X.; Li, Z.; Qie, L.; Hu, C.; Zeng, R.; Jiang, Y.;
Huang, Y. MOF-Derived Porous ZnO/ZnFe2O4/C octahedra with
hollow interiors for high-rate lithium-ion batteries. Adv. Mater. 2014,
26 (38), 6622−6628.
(20) Zhang, Z.; Chen, Y.; Xu, X.; Zhang, J.; Xiang, G.; He, W.; Wang,
X. Well-defined metal−organic framework hollow nanocages. Angew.
Chem., Int. Ed. 2014, 53 (2), 429−433.
(21) Liu, J.; Zeng, M.; Yu, R. Surfactant-free synthesis of octahedral
ZnO/ZnFe2O4 heterostructure with ultrahigh and selective adsorption
capacity of malachite green. Sci. Rep. 2016, 6, 25074.
(22) Zhu, J.; Xiao, M.; Liu, C.; Ge, J.; St-Pierre, J.; Xing, W. Growth
mechanism and active site probing of Fe3C@N-doped carbon
nanotubes/C catalysts: guidance for building highly efficient oxygen
7971
Research Article
reduction electrocatalysts. J. Mater. Chem. A 2015, 3 (43), 21451−
21459.
(23) Mahmood, A.; Guo, W.; Tabassum, H.; Zou, R. Metal-organic
framework-based nanomaterials for electrocatalysis. Adv. Energy Mater.
2016, 6 (17), 1600423.
(24) Chen, M.; Wang, Z.; Han, D.; Gu, F.; Guo, G. Porous ZnO
polygonal nanoflakes: synthesis, use in high-sensitivity NO2 gas sensor,
and proposed mechanism of gas sensing. J. Phys. Chem. C 2011, 115
(26), 12763−12773.
(25) Zeng, T.; Yu, M.; Zhang, H.; He, Z.; Chen, J.; Song, S. Fe/
Fe3C@N-doped porous carbon hybrids derived from nano-scale
MOFs: robust and enhanced heterogeneous catalyst for peroxymono-
sulfate activation. Catal. Sci. Technol. 2017, 7, 396−404.
(26) Schnepp, Z.; Wimbush, S. C.; Antonietti, M.; Giordano, C.
Synthesis of highly magnetic iron carbide nanoparticles via a
biopolymer route. Chem. Mater. 2010, 22 (2010), 5340−5344.
(27) Ding, D.; Wang, Y.; Li, X.; Qiang, R.; Xu, P.; Chu, W.; Han, X.;
Du, Y. Rational design of core-shell Co@C microspheres for high-
performance microwave absorption. Carbon 2017, 111, 722−732.
(28) Lv, H.; Zhang, H.; Ji, G.; Xu, J. Z. Interface strategy to achieve
tunable high frequency attenuation. ACS Appl. Mater. Interfaces 2016,
8 (10), 6529−6538.
(29) Qiao, L.; Wang, T.; Mei, Z. L.; Li, X. L.; Sui, W. B.; Tang, L. Y.;
Li, F. S. Analyzing bandwidth on the microwave absorber by the
interface reflection model. Chin. Phys. Lett. 2016, 33 (2), 027502.
(30) Wang, Y.; Chen, D.; Yin, X.; Xu, P.; Wu, F.; He, M. Hybrid of
MoS2 and reduced graphene oxide: a lightweight and broadband
electromagnetic wave absorber. ACS Appl. Mater. Interfaces 2015, 7
(47), 26226−26234.
(31) Li, G.; Xie, T.; Yang, S.; Jin, J.; Jiang, J. Microwave absorption
enhancement of porous carbon fibers compared with carbon
nanofibers. J. Phys. Chem. C 2012, 116 (16), 9196−9201.
(32) Sun, M.; Lv, X.; Xie, A.; Jiang, W.; Wu, F. Growing 3D ZnO
nano-crystals on 1D SiC nanowires: enhancement of dielectric
properties and excellent electromagnetic absorption performance. J.
Mater. Chem. C 2016, 4 (38), 8897−8902.
(33) Han, M.; Yin, X.; Ren, S.; Duan, W.; Zhang, L.; Cheng, L. Core/
shell structured C/ZnO nanoparticles composites for effective
electromagnetic wave absorption. RSC Adv. 2016, 6 (8), 6467−6474.
(34) Li, W.; Qi, H.; Niu, X.; Guo, F.; Chen, X.; Wang, L.; Lv, B. Fe−
Fe3C/C microspheres as a lightweight microwave absorbent. RSC Adv.
2016, 6 (30), 24820−24826.
(35) Feng, W.; Wang, Y.; Chen, J.; Wang, L.; Guo, L.; Ouyang, J.; Jia,
D.; Zhou, Y. Reduced graphene oxide decorated with in-situ growing
ZnO nanocrystals: facile synthesis and enhanced microwave
absorption properties. Carbon 2016, 108, 52−60.
(36) Guo, Y.; Liu, S.; Zhang, Z.; Dong, S.; Wang, H. Fabrication of
ZnO/Fe rod-like core-shell structure as high-performance microwave
absorber. J. Alloys Compd. 2017, 694, 549−555.
(37) Sun, C.; Guo, Y.; Xu, X.; Du, Q.; Duan, H.; Chen, Y.; Li, H.;
Liu, H. In situ preparation of carbon/Fe3C composite nanofibers with
excellent electromagnetic wave absorption properties. Composites, Part
A 2017, 92, 33−41.
DOI: 10.1021/acssuschemeng.7b01514
ACS Sustainable Chem. Eng. 2017, 5, 7961−7971