Chemical Engineering Journal 383 (2020) 123095

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Chemical Engineering Journal

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Rapid and direct growth of bipyramid TiO2 from Ti3C2Tx MXene to prepare T
Ni/TiO2/C heterogeneous composites for high-performance microwave
absorption
⁎,1
Congli Zhoua,1, Xiaoxia Wanga, , Heng Luob, Lianwen Dengb, Shuang Weic, Yiwei Zhenga,
⁎
Qiang Jiaa, Jingquan Liua,
a
College of Materials Science and Engineering, Institute for Graphene Applied Technology Innovation, Qingdao University, Qingdao 266071, China
b
Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, Central South University, Changsha 410083, China
c
School of Material Science and Engineering, Ocean University of China, Qingdao 266071, China

H I GH L IG H T S

• This work proposed a new method for the synthesis of TiO /C from Ti C T .
2 3 2 x

• Different morphologies of TiO were obtained by adjusting the composition of the suspension.
2

• The minimum reflection loss (RL) of −39.91 dB was obtained at 16.93 GHz with a thickness of only 1.4 mm.

A R T I C LE I N FO A B S T R A C T

Keywords: The layered structure with large specific area and moderate conductivity endow MXene with desired properties
MXene for microwave absorption. To date, oxidation of two dimensional (2D) Ti3C2Tx to obtain composites including
Ni/TiO2/C TiO2 and C usually proceed under complex process, which impedes their further development. Herein, Ni/TiO2/
Rapid synthesis C heterogeneous composites were synthesized in one pot reaction within a short time (10 min) by microwave
Microwave absorption
irradiation of an aqueous mixture of nickel chloride and hexadecyltrimethylammonium bromide (CTAB) func-
tionalized Ti3C2Tx MXene. This simple one-pot microwave-assisted method is beneficial to obtain uniform TiO2
nanoparticles with different morphologies (bipyramid and irregular) embedded in C layers, and the expanded
interlayer originated from the intercalation of TiO2 and Ni nanoparticles. In addition, the growth mechanism and
different morphologies of TiO2 from Ti3C2Tx MXene are discussed. The elaborately designed laminar Ni/TiO2/C
composites can be used as light and high efficient microwave absorption materials due to the synergistic effect of
dielectric loss, magnetic loss and unique 2D heterogeneous nanostructure. The minimum reflection loss (RL) of
−39.91 dB was obtained at 16.93 GHz with a thickness of only 1.4 mm. In addition, the dissipating heat ability
of Ni/TiO2/C composites coated on lab-gown cloth was investigated via thermal infrared images. This work
provides a simple and effective strategy for preparing other MXene-based heterogeneous composites.

1. Introduction hollow spheres composed of MXene monolayers [6,7], and flower-like

MXenes, a class of two-dimensional (2D) transitional metal car-
bides, nitrides and carbonitrides, have attracted great attention because
of their unique 2D structures, large specific surface area, and high
electrical conductivity [1–3]. Recent years, in order to explore new
applications of MXenes, composites with different structures have been
designed and developed, such as intercalated layered structures [4,5],
MXene-based composites [8,9], etc. These designed special structures
have profound influences on MXenes’ properties and applications. Be-
sides their nanostructures, another important factor impacting proper-
ties and applications of MXenes is its oxidation degree. It has been
known that MXenes like Ti3C2Tx, are unstable and easily to be oxidized
when exposed in air atmosphere, which greatly decreased their con-
ductivity and limited their applications in the fields of supercapacitors,

⁎
Corresponding authors.
E-mail addresses: wxx@qdu.edu.cn (X. Wang), jliu@qdu.edu.cn (J. Liu).
1
Congli Zhou and Xiaoxia Wang contributed equally to this work.

https://doi.org/10.1016/j.cej.2019.123095
Received 22 May 2019; Received in revised form 16 September 2019; Accepted 6 October 2019
Available online 08 October 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
C. Zhou, et al.
electrocatalysts, lithium-ion batteries, etc. [10–13]. However, when the
demand for conductivity is not very high, the oxidation of MXenes into
their corresponding transitional metal oxides can be a facile method to
obtain MXene-based 2D composites with desired structure and con-
ductivity. When transitional metal carbides are converted into their
corresponding oxides, the remaining carbon atoms having dangling
bonds will recombine to form amorphous carbon structure [14,15].
Based on the lamellar structure of MXenes, the corresponding oxides
can seed and root on the MXene nanosheets, and the interlayer spacing
of MXenes can be effectively increased due to the grain growth im-
planted in the lamellar structure. Thus, through oxidation process,
precursor MXenes can be converted into the corresponding 2D transi-
tional metal oxides (TMO-MX). At the same time, a variety of compo-
nents can be obtained, including TMO-MX, carbon layers and unreacted
MXenes with large inter-lamellar spacing [16].
However, to date, the preparation of this kind of TMO-MX usually
requires complicated steps, resulting in poor controllability and time
and energy consuming. Now, the most frequently applied oxidation
methods for MXenes are calcination and hydrothermal synthesis
[17–20]. For calcinations synthesis, it is energy-intensive and compli-
cated due to the requirement of high temperature and CO2 atmosphere.
For hydrothermal synthesis, it is also time-consuming, and the
morphologies of oxides are uncontrollable. In addition, contacting with
air or immersing into H2O2 could also trigger oxidation of MXenes at
ambient temperature [21,22], but this oxidation usually occurs on the
surface of MXenes and leads to the incomplete oxidation.
Microwave assisted heating method is becoming more and more
popular in the last few decades. Comparing with the traditional heating
method, its heating time is short and the product yield is high. In mi-
crowave-assisted synthesis, microwave energy can be directly coupled
into the molecules in the reaction system to achieve efficient internal
heating. And the method uniformly heats all the substances in the
closed vessel [23]. Therefore, microwave-assisted method is an ideal
way to obtain TMO-MX due to the advantages of simplicity, con-
venience, good controllability, uniformity and high yield. However,
according to our knowledge, no study about the preparation of TMO-
MX by this method has been reported as yet.
MXenes have attracted more attention in the microwave absorption
(MA) field due to their multilayer microstructure and excellent di-
electric property [24]. Nevertheless, oxidation to TMO-MX enriches the
ways for MXenes to dissipate microwave energy, such as dipole polar-
ization and related relaxation, and increased interfacial polarization
[25]. For instance, Ti3C2Tx could be converted into TiO2 and carbon
layers, and the newly formed TiO2 TMO-MX can synergize with the
carbon layer to compensate shortage of decreased conduction loss
compared with pure Ti3C2Tx MXene [26], and optimize the absorbers’
impedance matching performance [27–29]. In addition, the MA per-
formance can be further improved by the increased chance of multiple
reflection and scattering caused by the increased layer spacing of
MXenes. Nevertheless, the wide use MXenes in the field of MA is se-
verely hindered by its lack of magnetism [30]. The generation of ne-
gatively charged functional groups on the MXenes nanosheets can
endow MXenes with the capability to electrostatically adsorb metal ions
to afford MXene based metal composites by in-situ reduction. Here,
magnetic Ni nanoparticles are adopted to enhance the magnetic prop-
erties of TMO-MX-based composites and further modulate the im-
pedance matching. Among them, Ni nanoparticles can be replaced with
other magnetic materials, like Co or Fe3O4, etc.
Herein, in this work, microwave-assisted synthesis was used to
prepare Ni/TiO2/C heterogeneous ternary composites for the first time.
The morphologies, microstructure features, dielectric properties, and
MA performance were systematically investigated. For Ni/TiO2/C
composites, the minimum RL value of −39.91 dB was obtained at
16.93 GHz with a thickness of only 1.4 mm. In addition, the funda-
mental MA mechanism was illustrated in detail. The result indicates
that the Ni/TiO2/C heterogeneous ternary composites are ideal
2
Chemical Engineering Journal 383 (2020) 123095
candidates for MA applications. The microwave-assisted synthesis
provides a new means for the rapid and direct growth of TiO2 from
Ti3C2Tx MXene, and can also be generated to the preparation of a
variety of other MXene oxides.
2. Experimental section
2.1. Materials
Titanium aluminum carbide (Ti3AlC2, ≥98 wt% purity, 200 mesh)
was purchased from Beijing Forsman Scientific Co., Ltd. Hydrofluoric
acid (HF, ≥49 wt%) was purchased from Macklin Biochemical Co., Ltd
(Shanghai, China). Hydrazine hydrate aqueous solution (N2H4·H2O,
≥85 wt%), hexadecyltrimethylammonium bromide (CTAB) and so-
dium hydroxide (NaOH) were purchased from Sinopharm Chemical
Reagent Co., Ltd (Shanghai, China). Nickel (Ⅱ) chloride hexahydrate
(NiCl2·6H2O) was obtained from Jutai Special Reagent Co., Ltd
(Shanghai, China). Deionized water was obtained from laboratory ul-
trapure water machine of Qingdao Flom Technology Co., Ltd. All re-
agents were of analytical grade and used without further purification.
2.2. Synthesis of Ni/TiO2/C heterogeneous composites
Ti3AlC2 powder was immersed into HF acid with magnetic stirring
for 65 h [31], and then the precipitate was repetitively centrifuged and
washed by deionized water until the pH value reached neutral, and the
obtained black precipitate Ti3C2Tx MXene was freeze-dried for 24 h.
Then, 0.5 g of Ti3C2Tx and 0.08 g of NiCl2·6H2O were dispersed in
40 mL water, the resulting mixture was sonicated for 1 h. After that,
0.25 g of CTAB was added to the solution, followed by sonication for
2 h. Then, a solution containing 500 μL hydrazine hydrate, 10 mL
deionized water and 0.053 g NaOH were added dropwise to the above
solution. After that, the resulting mixture was placed in a microwave
digestion apparatus and heated at 160 °C for 10 min (400 PSI). The
obtained precipitate was centrifuged and washed with deionized water
until there was no foam in the suspension and freeze-dried for 24 h.
For comparison, pure Ti3C2Tx (denoted as p-Ti3C2Tx) was treated
with microwave irradiation using the same experiment condition, but
without the addition of CTAB, NiCl2·6H2O, N2H4·H2O, and NaOH. In the
same way, CTAB treated Ti3C2Tx (denoted as TiO2/C) was prepared
using the similar method without the addition of NiCl2·6H2O,
N2H4·H2O, and NaOH. Composite of Ti3C2Tx and Ni nanoparticles
(denoted as Ni/Ti3C2Tx) was prepared using the same method, just
without the addition of CTAB.
2.3. Characterization and measurement
X-ray diffraction (XRD) patterns were recorded on a Rigaku Ultima
IV diffractometer (Cu Kα radiation, λ = 1.5406 Å), with angle ranges
from 5 to 90° and scan rate of 5°/min. Raman spectroscopy was carried
out on a Lab RAMHR confocal Raman system with 532 nm diode laser
excitation. The morphology and corresponding elemental mapping
images of all the samples were obtained on a field-emission scanning
electron microscope (FE-SEM, JEOL JSM-7800F). In addition, trans-
mission electron microscope (TEM, JEOL JEM-2100F) was also im-
plemented to characterize microstructure. Lakeshore 7307 vibration
sample magnetometer was applied to measure the magnetic properties.
ESCALAB 250Xi electron spectrometer was used to record XPS spectra.
Microwave digestion system was supported by SINEO (TANK BASIC).
Thermal infrared images were photographed by FLUKE Ti S20 infrared
camera. The basic electromagnetic parameters were tested by a vector
network analyzer (Agilent N5234A) in the frequency range of
2.0–18.0 GHz. The mass ratio of samples to wax was 3:2, and their
mixture was moulded into coaxial cylinder with outer diameter of
7.00 mm and inner diameter of 3.04 mm.
C. Zhou, et al. Chemical Engineering Journal 383 (2020) 123095

Fig. 1. Schematic diagram for stepwise preparation of Ni/TiO2/C.

3. Results and discussion
The stepwise preparation of Ni/TiO2/C is schematically illustrated
in Fig. 1. Firstly, Ti3C2Tx was obtained by removing Al layers from
Ti3AlC2 by HF etching. Then the Ni/TiO2/C composites was prepared
by ultrasonic treatment of the Ti3C2Tx suspension and further micro-
wave digestion. With the action of microwave and reducing agent
(N2H4·H2O), nickel ions were converted into ultrasmall Ni nanoparticles
to afford Ni/TiO2/C composites finally.
The morphology was first characterized by scanning electron mi-
croscopy (SEM). As shown in Fig. 2a, Ti3C2Tx exhibited flat surface and
layered structure after etching by HF. After microwave digestion in
deionized water, p-Ti3C2Tx was slightly oxidized and formed oxidized
particles on the surface (Fig. 2b), and this is because titanium atoms
exposed on the Ti3C2Tx surface are thermodynamically unstable, and
could be easily oxidized into TiO2 [2,32]. As shown in Fig. 2c, there
were nanoparticles appeared on the surface of Ni/Ti3C2Tx after micro-
wave digestion. For further increasing layer spacing, CTAB should be
introduced into the interlayer of Ti3C2Tx [33]. As shown in Fig. 2d,
abundant large-sized irregular TiO2 particles (about 100 nm) could be
observed between the layers of Ti3C2Tx, and magnified images of the
irregular TiO2 particles could be observed in Fig. S1. However, when
NiCl2·6H2O, N2H4·H2O, and CTAB were all added in the aqueous solu-
tion and treated with microwave irradiation, the bipyramid TiO2

Fig. 2. SEM images of (a) Ti3C2Tx, (b) p-Ti3C2Tx, (c) Ni/Ti3C2Tx, (d) TiO2/C, (e) Ni/TiO2/C, (f, g) SEM images of Ni/TiO2/C at higher magnification and its
corresponding elemental mapping images.

3
C. Zhou, et al.
nanoparticles were clearly observed (Fig. 2e, f, and g). Crystal size
along the longer axis direction (c-axis) was about 180 nm, and about
100 nm in the a-axis direction. It was worth noting that the generated
TiO2 nanoparticles not only located on the surface of the Ti3C2Tx, but
also embedded in the nanosheets of Ti3C2Tx. Due to the growth of TiO2,
the layer spacing was further increased, which was conducive to the
insertion of more Ni ions into the layers. The rich interfaces generated
among TiO2, C layers, unreacted Ti3C2Tx layers, Ni nanoparticles and
air, are beneficial for dissipating microwave [34]. As shown in Fig. 2g,
Ni, Ti, O, C elements were uniformly distributed in the composites of
Ni/TiO2/C.
In this work, the addition of CTAB was a key factor for the gen-
eration of TiO2 from Ti3C2Tx. Both p-Ti3C2Tx and Ni/Ti3C2Tx formed a
few TiO2 particles on the surface without adding CTAB. While TiO2/C
and Ni/TiO2/C correspondingly formed a large amount of irregular
(Fig. 2d) and bipyramid (Fig. 2e) TiO2 in the layers and on the surfaces
with adding CTAB. As a surfactant, CTAB has an amphiphilic molecular
structure with a hydrophobic and hydrophilic group, and the hydro-
carbon chain of cetyltrimethylammonium cation exists at the interfaces
between water and air [35]. By contrast, the hydrophilic polar heads
stretch into water. During the continuous agitation process, surfactant
CTAB reduces water’s surface tension, increases gas-liquid interface
area of system, and improves the entering of oxygen. When the entire
system is transferred to a reaction vessel for digestion, the sufficient
oxygen is beneficial to the conversion of Ti3C2Tx to TiO2. In the pre-
sence of CTAB, cetyltrimethylammonium cations bond with Ti(OH)62−
anions around Ti3C2Tx MXene through electrostatic adsorption, then
they further contribute to the conversion of Ti3C2Tx into TiO2 [35–37].
To further explore the formation mechanism of different mor-
phology of TiO2 (Fig. 2d and e), three comparative experiments were
carried out to investigate the effect of each reactant. CTAB was all used
in the following experiments to achieve high production of TiO2. For
comparison, the addition amount of NaOH or N2H4·H2O and reaction
conditions in the following experiments is as same as those for the
synthesis of Ni/TiO2/C. In the first control group, CTAB, NaOH, and
Ti3C2Tx were added, and the product was denoted as N-TiO2/C for
studying the influence of NaOH on TiO2 morphology. Similarly, in
second control group, CTAB, N2H4·H2O, and Ti3C2Tx were added for
studying the impact of N2H4·H2O, and the product was denoted as H-
TiO2/C. As for the third control group, a mixture of CTAB, NaOH,
N2H4·H2O, and Ti3C2Tx were all added, and its corresponding final
product was denoted as N–H-TiO2/C. As shown in Figs. S2–S4, the
generated TiO2 in H-TiO2/C and N–H-TiO2/C exhibited the same bi-
pyramid structure as Ni/TiO2/C, while the generated TiO2 in N-TiO2/C
showed the irregular morphology. It was assumed that N2H4·H2O
played an important role in the production of bipyramid structure TiO2.
As we known, facet energy of anatase TiO2 (0 0 1), (1 0 0), and (1 0 1) is
0.90, 0.53, and 0.44 J/cm2, respectively [38,39]. This might be caused
by the easy adsorption of N2H4·H2O molecules on (0 0 1) facets of TiO2
due to its high surface energy [40]. This kind of combination restrains
the growth along the direction of (0 0 1). However, the TiO2 growth
along the direction of (1 0 1) is still slower than that along the direction
of (0 0 1) [41] since the natural anatase TiO2 exposes more (1 0 1) facet
of low surface energy to reduce surface energy. Therefore, it can be
concluded that TiO2 could be generated easily from Ti3C2Tx by adding
of CTAB under microwave digestion, and the bipyramid TiO2 could be
generated by adjusting surface chemistry through the addition of
N2H4·H2O.
The morphology and structure information of Ni/TiO2/C were fur-
ther studied by transmission electron microscopy (TEM) and the results
were shown in Fig. 3. Bipyramid TiO2 nanoparticles grew in the carbon
slices (Fig. 3a). Ni nanoparticles on the surface of Ti3C2Tx were also
observed (Fig. 3b). As shown in HRTEM images, the interplanar spacing
of 0.35 nm and 0.20 nm were related to the (1 0 1) plane of anatase
TiO2 and (1 1 1) plane of Ni nanoparticles, respectively. The layer dis-
tance of the laminar structure of Ti3C2Tx was 1.51 nm (Fig. 3c), which is
4
Chemical Engineering Journal 383 (2020) 123095
larger than the general Ti3C2Tx layer spacing, further demonstrating the
intercalation of TiO2. Selected area electron diffraction (SAED) pattern
of Ni/TiO2/C is shown in Fig. 2d and the dot-like diffraction pattern
indicates that the single crystal TiO2 owns fine crystallinity [21].
X-ray diffraction (XRD) were carried out to determine the phase
composition of as prepared samples. As shown in Fig. 4a the p-Ti3C2Tx
and Ni/Ti3C2Tx still remained the pattern of Ti3C2Tx, and the (0 0 2)
peak of p-Ti3C2Tx appeared at around 8.98°. For Ni/Ti3C2Tx, the (0 0 2)
peak downshifted to 6.90°, which demonstrated that layer space was
increased due to insertion of Ni nanoparticles. In the pattern of TiO2/C,
(0 0 2) peak of Ti3C2Tx was retained, however, the peak at around 9.01°
was weak. For Ni/TiO2/C, the (0 0 2) peak of Ti3C2Tx was further
downshifted to 6.80°, that was, comparing to Ni/Ti3C2Tx, the presence
of TiO2 increased the layer spacing of Ti3C2Tx. The retained (0 0 2) peak
in the pattern of Ni/TiO2/C demonstrated that Ti3C2Tx was not com-
pletely converted into TiO2, so the Ni/TiO2/C composites should in-
clude TiO2, amorphous carbon, Ti3C2Tx MXene, and Ni. The peaks of
TiO2/C and Ni/TiO2/C at 25.3° and 48.0° were correspondingly as-
cribed to (1 0 1) and (2 0 0) facets of anatase TiO2 (JCPDS No.
21–1272). As for the XRD patterns of N-TiO2/C, H-TiO2/C, and N–H-
TiO2/C (Fig. S5), the characteristic peaks were also well indexed with
anatase TiO2 (JCPDS No. 21–1272), and the main peaks around 25.3°,
37.8°, 48.0°, 53.9° and 55.1° were ascribed to (1 0 1), (0 0 4), (2 0 0),
(1 0 5) and (2 1 1) facets.
Raman spectra of p-Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C, and Ni/TiO2/C
were shown in Fig. 4b. The peaks at around 151 cm−1, 401 cm−1 and
628 cm−1 were ascribed to anatase TiO2 [16,42], which could be as-
signed as Eg, B1g, and Eg modes of the anatase TiO2, respectively [43].
Among them, the peak of Eg mode caused by the external vibration of
the anatase TiO2 was easily observed, which indicated the different
degrees of oxidation in all four samples. The higher peak intensities for
TiO2/C and Ni/TiO2/C indicated the stronger oxidation degree or
higher content of TiO2 after the addition of CTAB. In addition, the D
band of Ni/TiO2/C in Fig. S6 indicated the presence of amorphous
carbon.
The surface chemical states of Ni/TiO2/C composite was identified
by the high-resolution XPS measurement. XPS spectrum of Ni 2p was
shown in Fig. 4c, and the signal could be deconvolted into five peaks
located at 883.5, 877.6, 865.8, 859.9, and 851.1 eV, respectively. Ni
2p1/2 (883.5 and 877.6 eV) and 2p3/2 (865.8 and 859.9 eV) were as-
signed to Ni2+, which could be attributed to the oxidation of nickel
surface [44]. While the peak at 851.1 eV was related to zero-valent state
originating from Ni nanoparticles, which further demonstrated the ex-
istence of Ni nanoparticles [45]. As shown in Fig. 4d, the Ti 2p signals
could be deconvoluted into eight peaks centered at 465.1, 463.8, 460.9,
459.4, 458.5, 457.7, 455.8, and 454.8 eV, which should correspond to
Ti-O (465.1 and 459.4 eV), Ti3+ (463.8 and 457.7 eV), Ti2+ (460.9 and
455.8 eV), and the retained Ti-C bond (458.5 and 454.8 eV) species,
respectively. The detected Ti-O peak verified the existence of TiO2
[14,46]. Peaks of O 1 s in Fig. 4e centered at 532.2 and 530.5 eV were
attributed to the oxidation of titanium to Ti-OH and O-Ti [47]. Peaks of
C 1 s in Fig. 4f centered at 286.5 and 285.2 and 281.4 eV indicated the
presence of C–O, C–C, and C–Ti bonds [46].
As for the microwave absorption properties, the electromagnetic
parameters of real (ε′) and imaginary parts (ε″) of the dielectric per-
mittivity, the real (μ′) and imaginary parts (μ″) of the magnetic per-
meability were tested by vector analyzer. According to the theory of
transmission lines, the reflection loss (RL) can be calculated by the
following equations:
Zin = Z0 μr / εr tanh[j (2πfd/ c )] μr εr (1)
RL (dB ) = 20log |(Zin − Z0)/(Zin + Z0)| (2)
where εr is the relative complex permittivity (εr = ε′ − jε″), μr is the
relative complex permeability (μr = μ′ − jμ″), Zin is the normalized
input impedance, j is the imaginary part, f is the given microwave
C. Zhou, et al.
Fig. 3. (a, b) TEM images of Ni/TiO2/C, (c, d) HRTEM images of Ni/TiO2/C, and inset shows SAED pattern of Ni/TiO2/C.
frequency, d is the thickness of the specimens, and c is the velocity of
microwave in the free space. Generally speaking, the effective RL value
should be lower than −10 dB (corresponded more than 90% incident
microwave absorption), and the bandwidth of the absorption should be
as wide as possible at a small thickness.
The calculated reflection loss (RL) values of p-Ti3C2Tx, Ni/Ti3C2Tx,
TiO2/C, and Ni/TiO2/C in 2.0–18.0 GHz at different thickness from 1.0
to 5.0 mm were shown as three dimensional (3D) plots in Fig. 5. The
minimum RL values were derived to be −12.74, −34.76, −21.31, and
−39.91 dB at 6.90, 14.78, 13.97, and 16.93 GHz for p-Ti3C2Tx, Ni/
Ti3C2Tx, TiO2/C, and Ni/TiO2/C with thickness of only 2.3, 1.3, 1.8 and
1.4 mm, respectively. Comparing to p-Ti3C2Tx and TiO2/C, Ni/Ti3C2Tx
and Ni/TiO2/C exhibited better microwave absorption performance
which should be due to the introduction of Ni nanoparticles. For Ni/
TiO2/C, Ni and TiO2 together contributed a greater RLmin of −39.91 dB,
which was three times larger than that of p-Ti3C2Tx.
To figure out the microwave absorption mechanism of Ni/TiO2/C
composites, the electromagnetic (EM) parameters were measured and
shown in Fig. 6. The real parts of permittivity (ε′) and permeability (μ′)
represent the strength of saving electromagnetic energy. As for the
imaginary parts of permittivity (ε″) and permeability (μ″), they express
the depletion ability of electromagnetic energy [48]. These parameters
link intimately to the internal structure and composition of the com-
posites. Permittivity curves versus 2.0–18.0 GHz were given in Fig. 6a,
b. It could be seen that p-Ti3C2Tx owned the highest ε′ and ε″ values,
which demonstrated that p-Ti3C2Tx had good dielectric property. The ε′
and ε″ values decreased in order of Ni/Ti3C2Tx, Ni/TiO2/C and TiO2/C
5
Chemical Engineering Journal 383 (2020) 123095
in the frequency range of 2.0–12.0 GHz, which means that the dielectric
values decreased as the TiO2 content increased. The ε′ values of p-
Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C and Ni/TiO2/C varied in the range of
27.2–13.5, 20.5–18.8, 8.4–6.3, and 12.4–9.1, respectively. The ε″ va-
lues of p-Ti3C2Tx, Ni/Ti3C2Tx, C-TiO2/C and Ni/TiO2/C varied in the
range of 13.6–8.3, 6.7–9.1, 0.4–6.3, and 2.0–8.3, respectively.
As shown in Fig. 6c and 6d, Ni/Ti3C2Tx and Ni/TiO2/C had the
higher μ′ and μ″ values compared with p-Ti3C2Tx and TiO2/C in the
most frequency range due to the introduction of magnetic Ni nano-
particles. The resonance peaks in μ″ plot located at around 4.48 GHz,
9.32 GHz, and 14.69 GHz for Ni/TiO2/C were obviously observed,
which could be attributed to the natural and exchange resonance [49].
The magnetic properties of p-Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C, and Ni/
TiO2/C were tested at room temperature. As shown in Fig. S7, the
hysteresis loops showed weak saturation magnetization (Ms) of p-
Ti3C2Tx and TiO2/C. With the introduction of Ni nanoparticles, slightly
improvement in magnetism was observed for both Ni/Ti3C2Tx and Ni/
TiO2/C, and their Ms values were derived to be 0.020 emu/g and
0.015 emu/g, respectively, which were consistent with the high μ′ and
μ″ values of Ni/Ti3C2Tx and Ni/TiO2/C above. Ni/Ti3C2Tx and Ni/TiO2/
C gained the modulated permeability, promoting impedance matching,
and improving magnetic loss, and then resulting in the enhanced mi-
crowave absorption performance.
As shown in Fig. 7a, Ni/TiO2/C showed the minimum RL value of
−39.91 dB at thickness of 1.4 mm, while the minimum RL values of p-
Ti3C2Tx, Ni/Ti3C2Tx, and TiO2/C at this thickness were −7.13 dB,
−24.34 dB, and −7.62 dB, respectively. The effective absorption
C. Zhou, et al.
Fig. 4. (a) XRD patterns and (b) Raman spectra of p-Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C, Ni/TiO2/C, XPS spectra for (c) Ni 2p, (d) Ti 2p, (e) O 1 s, (f) C 1 s of Ni/TiO2/C
composites, respectively.
bandwidth (corresponded to −10 dB) of Ni/TiO2/C ranged from
14.60 GHz to 15.58 GHz and from 16.12 GHz to 17.28 GHz, which
covered 2.14 GHz totally. When the thickness of absorber was 1.5 mm
(Fig. S8) the effective absorption bandwidth (corresponded to −10 dB)
of Ni/TiO2/C was expanded to 3.04 GHz, which ranged from 14.24 GHz
to 17.28 GHz. It is worth noting that, with the introduction of Ni na-
noparticles, Ni-TiO2/C and Ni-Ti3C2Tx composites showed higher MA
performance than those of TiO2/C and p-Ti3C2Tx.
In order to further explore absorption mechanism of Ni/TiO2/C
composites, tangent dielectric loss (tan δε = ε″/ε′) versus frequency was
6
Chemical Engineering Journal 383 (2020) 123095
plotted in Fig. 7b. The p-Ti3C2Tx exhibited the highest tan δε value,
showing the best conductivity and highest dielectric loss among them.
In the frequency of 2.0–14.0 GHz, the tan δε values decreased in the
order of p-Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C, Ni/TiO2/C. Ti3C2Tx had good
conductivity and high dielectric loss [50,51], so both p-Ti3C2Tx and Ni/
Ti3C2Tx showed the higher tan δε. In addition, the high dielectric
properties of samples with magnetic metal Ni might also result from the
high conductivity of metal Ni. A significant increase of tan δε in the
14.0–18.0 GHz was observed, which may be induced by the presence of
hydrogenated TiO2 [52].
C. Zhou, et al. Chemical Engineering Journal 383 (2020) 123095

Fig. 5. The reflection loss of (a) p-Ti3C2Tx, (b) Ni/Ti3C2Tx, (c) TiO2/C, and (d) Ni/TiO2/C versus frequency of 2.0–18.0 GHz at different thickness.

Fig. 6. Microwave electromagnetic parameters of p-Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C, and Ni/TiO2/C: (a) real and (b) imaginary parts of permittivity, (c) real and (d)
imaginary parts of permeability.

7
C. Zhou, et al.
Fig. 7. (a) The calculated theoretical reflection loss for p-Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C and Ni/TiO2/C versus frequency in the range of 2–18 GHz at a thickness of
1.4 mm. (b) Tangent dielectric loss (tan δε), (c) tangent magnetic loss (tan δμ), and (d) impedance matching versus frequency for p-Ti3C2Tx, Ni/Ti3C2Tx, TiO2/C and
Ni/TiO2/C.
In Fig. 7c, both Ni/Ti3C2Tx and Ni/TiO2/C with magnetic particles
exhibited higher tan δμ, while p-Ti3C2Tx tan δμ value was the lowest.
This was consistent with intrinsic low magnetic loss of p-Ti3C2Tx, which
further confirmed that the addition of magnetic particles to increase
magnetic loss was necessary.
Generally speaking, Debye model can explain the relaxation process
in dielectric loss, and the description of Cole-Cole semicircle can be
deduced from the equation below:
εs + ε∞ 2 ε − ε∞ 2
⎛ε′ − ⎞ + (ε″)2 = ⎛ s ⎞
⎝ 2 ⎠ ⎝ 2 ⎠
The curves ε″ versus ε′ for samples were shown in Fig. S9. Each
semicircle in curve stood for a Debye relaxation process. For p-Ti3C2Tx
and Ni/Ti3C2Tx, the apparent semicircles indicated double Debye re-
laxation losses, among which one was from the small particles of the
Ti3C2Tx surfaces, and the other was from the relaxation caused by the
interfaces between wax and samples. For the other two samples, there
were three semicircles in both TiO2/C and Ni/TiO2/C, demonstrating
the multiple relaxation losses. The extra semicircle could be attributed
to polarization relaxation, which derived from the oxygen atom po-
larization center. The observed distorted semicircles in all samples in-
dicated other forms of polarization relaxation also existed [53]. Ni/
TiO2/C exhibited superior MA properties than TiO2/C because the in-
troduced magnetic Ni nanoparticles could greatly improve the MA
ability.
As for magnetic loss, it mainly originates from natural resonance,
exchange resonance and eddy current in the tested range of
2.0–18.0 GHz [54–57]. Natural resonances occurs at frequency of
Chemical Engineering Journal 383 (2020) 123095
2–10 GHz and exchange resonance appears in the frequency of
10–18 GHz. Eddy current can be interpreted as C0 = μ″(μ′)−2f−1. If C0
maintains a constant as the frequency increases, magnetic loss is mainly
provided by the eddy current loss; if C0 changes, there is resonance loss
besides the eddy current loss [55]. As shown in Fig. S10, C0 for TiO2/C
remained constants in the range of 4–14 GHz, indicating that eddy
current loss was the main source of magnetic loss. The C0 fluctuation of
p-Ti3C2Tx around 12 GHz in Fig. S10 was consistent with its fluctuation
of μ″ as shown in Fig. 6d, which can be assigned to the exchange re-
sonance at high frequency. While For Ni/Ti3C2Tx and Ni/TiO2/C, the
(4) existing resonance loss would contribute to the magnetic loss.
Impedance matching stands for the capability to capture micro-
wave, which can be evaluated by the value of |Zin/Z0|. When |Zin/Z0|
value closes to 1, the better impedance matching property can be ob-
tained [58]. As for impedance matching, |Zin/Z0| of Ni/TiO2/C values
reached the highest and close to 1, indicating the samples with TiO2
showed the better impedance matching than that without TiO2
(Fig. 7d). The expanded layer spacing (facilitating the entry of micro-
wave) and the increased magnetic properties contributed to the en-
hanced RL value.
Attenuation constants (α) relates to EM attenuation capability (Fig.
S11), which can be calculated by the following equation
α = ( 2 π f/c) × (μ″ε″ − μ′ε′) + (μ″ε″ − μ′ε′)2 + (μ′ε″ + μ″ε′)2 (3)
Obviously, p-Ti3C2Tx showed the higher α values than other three
samples, originating from the higher conductivity of Ti3C2Tx. However,
high conductivity could easily lead to high reflection of incident elec-
tromagnetic wave, and then result in poor MA performance. After
8
C. Zhou, et al.
Fig. 8. Schematic illustration of microwave absorption mechanisms for Ni/TiO2/C.
Fig. 9. Thermal infrared images of lab-gown cloth with (upper row) and without (bottom row) Ni/TiO2/C composites. (a, e) Illuminated for 30 s, (b, f) illuminated for
5 min, (c. g) remove the light for 1 min, and (d, h) remove the light for 3 min.
introduction of the Ni nanoparticles, the as-formed Ni/TiO2/C exhibited
good impedance matching characteristic as a result of the expanded
layer space and the magnetism of Ni nanoparticles (Fig. 7d). Therefore,
though the attenuation constant of Ni/TiO2/C was lower than that of p-
Ti3C2Tx, Ni/TiO2/C exhibited superior RL to p-Ti3C2Tx due to its good
impedance matching characteristic.
Generally, MA performance depends on the impedance matching
and attenuation characteristics, which connect closely with absorbers’
microstructure, morphologies, constituent, magnetic and dielectric
properties [59]. In this work (Fig. 8), MA mechanism of Ni/TiO2/C can
be interpreted as follows: Firstly, multiple reflection and scattering
benefit to the attenuation of electromagnetic wave. Secondly, Ni na-
noparticles can enhance the magnetic loss and improve the impedance
matching performance of Ni/TiO2/C. The capacitor-like structure of Ni/
TiO2/C is also good for electromagnetic wave attenuation [60]. Thirdly,
The generation of TiO2 accompanying the formation of amorphous
carbon will contribute to the dielectric loss and interfacial loss. Ad-
ditionally, the migration of charge carriers between the layers could
generate the microcurrent [7], which also contributed to conductive
loss.
In order to cope with complex environments, other properties of
microwave absorbing materials should be explored [49,61–63]. In this
9
Chemical Engineering Journal 383 (2020) 123095
work, the dissipating heat ability of Ni/TiO2/C composites was in-
vestigated by dispersing its powder in ethanol and then coated on lab-
gown cloth (3 cm × 3 cm, mass loading of 5 mg cm−2), which was
usually used in our daily life. Under solar simulator at an optical density
of 2.1 kW m−2, the clothes with or without Ni/TiO2/C composites were
illuminated for different times and recorded temperature changes via
thermal infrared images.
As shown in Fig. 9a, under illumination for 30 s, the temperature of
cloth with Ni/TiO2/C coating was increased from room temperature
22.0 °C to 98.5 °C (a net increase of 76.5 °C). After illumination for
5 min, the temperature was further increased to 114 °C (a net increase
of 15.5 °C) (Fig. 9b). While for bare cloth without Ni/TiO2/C coating,
under the same illumination condition, the temperatures of 42 °C
(Fig. 9e) and 52 °C (Fig. 9f) were monitored, the corresponding net
temperature increase were only by 20 °C and 10 °C, respectively. After
removing illumination for 1 min, the temperature of cloth with Ni/
TiO2/C coating dropped to 34 °C (Fig. 9c) (a net drop of 80 °C). After
3 min of removal, the temperature was further dropped to 27 °C (a net
drop of 7 °C). For the bare cloth, the temperatures dropped to 30 °C
(Fig. 9g) (a net drop of 22 °C) and 27 °C (Fig. 9h) (a net drop of 3 °C),
respectively. Herein, Ni/TiO2/C coating gives the cloth fast heating and
cooling rate. Though the heat dissipation mechanism in absorber is still
C. Zhou, et al.
not clear, the ability of this novel coating to quickly dissipate heat
provides possibility for its broad applications in many areas besides
absorption.
4. Conclusion
In this work, uniform Ni/TiO2/C heterogeneous composites were
synthesized from Ti3C2Tx MXene through microwave mediated reaction
in a short time, through which large amount of TiO2 with bipyramid
morphology could be generated from hydrazine hydrate and CTAB
modified Ti3C2Tx. The as prepared Ni/TiO2/C composites exhibited
high performance of microwave absorption with a reflection loss of
−39.91 dB at thickness of only 1.4 mm, and the absorption mechanism
was also investigated. We also studied the heat dissipation capability of
Ni/TiO2/C coating when it was coated on a lab gown, which exhibited
fast heating and heat dissipation rate. Though its heat dissipation me-
chanism is not clear at present, this exploration has reference value for
researching MA materials with heating dissipation capability. This new
method for preparing Ni/TiO2/C composites based on Ti3C2Tx can be
generated to preparation of other TMO-MX materials.
Acknowledgments
This work was supported by Qingdao Innovation Leading Talent
Program and Taishan Scholars Program.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.123095.
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