Materials Letters 277 (2020) 128396

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Materials Letters
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Featured Letter

Microwave-induced catalytic degradation of methyl violet by a Ni-TiO2/

ACFs composite catalyst
Qinglei Sun a,⇑, Mei Tang b, Yekuan Duan c, Yun Li c, Yang Peng d,⇑
a
School of Mechanical Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b
Pfizer (Wuhan) Research and Development Co., Ltd., Wuhan 430075, China
c
Jiangsu Changzhou Technician College, Changzhou 213032, China
d
School of Aerospace Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

a r t i c l e i n f o a b s t r a c t

Article history: A hierarchically porous and magnetic Ni-TiO2/ACFs (activated carbon fibers) composite catalyst was pre-
Received 12 June 2020 pared by loading Ni-TiO2 nanoparticles on ACFs to realize microwave-induced catalytic degradation for
Received in revised form 14 July 2020 methyl violet (MV). The effect of synthesis conditions and compositions on Ni-TiO2/ACFs were investi-
Accepted 22 July 2020
gated and characterized by XRD, BET, SEM and FT-IR. Results indicated that Ni-TiO2/ACFs exhibited higher
Available online 26 July 2020
catalytic activity than ACFs and TiO2/ACFs. After calcining at 900 °C for 2 h, Ni-TiO2/ACFs with respective
weight ratio of 2:8 achieved 96.13% degradation ratio of MV after 3 min microwave.
Keywords:
Ó 2020 Elsevier B.V. All rights reserved.
Porous materials
Carbon materials
Ni-TiO2/ACFs
Microwave-induced
Degradation
Catalytic

1. Introduction
Methyl violet (MV) as a group of triarylmethane compound
used in textile printing and dyeing industries generally contains
aromatic rings, –NH2, etc., which are difficult to be decomposed
through traditional biological and chemical treatments, thus
threatening natural environment severely [1]. Researchers
employed adsorption, photocatalysis, etc. methods to degrade
MV, however, the degradation is incomplete and the products
may cause second pollution [2,3]. One of the most promising tech-
nologies is to utilize microwave-induced catalytic method [4].
Water treatment through microwave (MW) irradiation method is
currently getting wider scientific recognition owing to its low acti-
vation energy, and high reaction rate. Furthermore, it can further
reduce the activation system, and make the chemicals bonds of dif-
ferent molecules weakened [5]. Zhang et al. [6] discovered the
combination of MW and activated carbon fibers (ACFs) showed a
satisfying degradation effect in organic pollutants. The mechanism
was based on absorption and degradation of organic pollutants on
short lived ‘‘hot spots” that were formed on ACFs and disappeared
immediately under MW.
To effectively utilize the energy from the ‘‘hot spots”, Zhang
et al. [7] loaded TiO2 on ACFs and applied the composite in sodium
dodecyl benzene sulfonate degradation under MW, which exhib-
ited excellent degradation effect. TiO2 played a significant role in
absorbing more energy from the ‘‘hot spots’’ on ACFs surface, thus
producing more electron-hole pairs to attack organic pollutants in
wastewater.
Generally, the use of Ni as a catalyst has been reported as the
effective method to improve the efficiency of various reactions
[8], and the charge separation efficiency of TiO2 can be further
improved by doping magnetic Ni nanoparticles [9]. In current
study, we synthesize a hierarchical and porous Ni-TiO2/ACFs com-
posite with excellent catalytic activity for MV under MW.
2. Experimental
The details of sample preparation, abbreviations of samples,
characterization and MW degradation were specified in Supple-
mentary Information.
3. Results and discussion

⇑ Corresponding authors. The crystal structures of NT20/A80 under different calcined

E-mail addresses: Sunqinglei704@hotmail.com (Q. Sun), ypeng@hust.edu.cn temperatures are characterized by XRD (Fig. 1a). A series of
(Y. Peng).

https://doi.org/10.1016/j.matlet.2020.128396
0167-577X/Ó 2020 Elsevier B.V. All rights reserved.
2 Q. Sun et al. / Materials Letters 277 (2020) 128396

Fig. 1. (a) XRD patterns of NT20/A80-800, NT20/A80-900 and NT20/A80-1000, (b) N2 adsorption–desorption isotherms, and (c) corresponding PSD of NT0/A100-900, NT10/
A90-900 and NT20/A80-900, respectively, SEM images of (d-e) NT0/A100-900 and (f-h) NT20/A80-900.

lysts with hierarchically porous structure containing both inter-

diffraction peaks marked in solid circles are indexed to the anatase
TiO2 (PDF#21–1272), and those peaks with hollow circle come
from Ni (PDF#04–850). Beyond these, the small peaks marked in
squares could be attributed to the amorphous carbon. With
increasing the calcined temperature, all diffraction peaks belong-
ing to TiO2 and Ni become sharper and stronger, implying the
increase in crystallinity and grain size, while the peaks belonging
to carbon decrease, especially for the peak located at 26.59°, indi-
cating the transformation of crystal phase to amorphous carbon.
Typical N2 adsorption–desorption isotherms and corresponding
pore size distributions (PSD) of NT0/A100-900, NT10/A90-900 and
NT20/A80-900 are presented in Fig. 1b-c. The isotherms of ACFs
belonging to type I hysteresis loop are attributed to microporous
materials, and isotherms of NT10/A90-900 and NT20/A80-900
belonging to IV hysteresis loop are attributed to mesoporous mate-
rial. The corresponding PSD exhibit that mesopore and macropore
materials increase with Ni-TiO2 loading, which complies with the
preceding results. More loading Ni-TiO2 blocks some micropores
of the ACFs, thus increasing the mesopore and macropore. Cata-
connected mesopore and macropore structures often exhibited
increased catalytic activity through combination of high surface
area and accessible mass transport pathway of macropores tunnel
[10].
Cotton fibers demonstrate 20 mm in diameter with hollow
structures (Fig. S1). The synthesized ACFs retain the fibrous mor-
phology with networks composed of coalescing and interwoven
fibers in 10–18 mm diameter range, relatively smaller than that
of cotton fibers due to carbon gasification (Fig. 1d-e). And the inset
in Fig. 1e shows the surface of ACFs without loading is smooth. An
enlarged image shows uniform dispersal of a large number of
nanoparticles on ACFs surface, and no significant changes in the
morphology compared with ACFs (Fig. 1 f-h). EDS result (inset of
Fig. 1h) reveals that these particles are composed of Ti, Ni, O and
C elements.
Almost complete degradation of MV is achieved after 3 min MW
irradiation by using NT20/A80-900, while the MV degradation ratio
is only about 30% using ACFs, and that for T20/A80-900 is 70%
(Fig. 2a), showing that the simultaneous combination of MW and
 Q. Sun et al. / Materials Letters 277 (2020) 128396
Fig. 2. Different factors influencing MV degradation under MW: (a) different Ni-TiO2 loading weights, (b) different calcined temperatures, (c) different NT20/A80-900 dosages
and (d) Kinetic fitting of MW-induced degradation of MV using 10 mg NT20/A80-900.
Ni-TiO2 effectively degrades MV. Although Ni metal has higher
reflectivity to MW, according to Bo et al. [11] research, MW could
penetrate metallic particle when its size was lower than the depth
of 1.3 lm. The SEM in Fig. 1h clearly shows the average grain size
of Ni is much smaller than the reported datum. The penetration of
Ni nanoparticles creates elevated temperature, and thus further
favoring the MV degradation. The degradation rate also increases
with increasing Ni-TiO2 content, as a magnetic metal with higher
Snoek’s limit and large saturation magnetization [12], Ni addition
can decrease the complex permeability of the composite, thus
leading to higher loss of magnetic hysteresis, which in turn results
in elevated temperature field.
The degradation ratio increases with increasing calcined tem-
perature from 800 to 900 °C, and then drops partly at 1000 °C
(Fig. 2b). Combined the XRD analysis, the loading Ni-TiO2 nanopar-
ticles on NT20/A80-800 have paracrystals, which decrease catalytic
activity; while those on NT20/A80-1000 have larger grain size,
which may cover the activated sites of ACFs and obstruct MW
penetration.
3
The degradation ratio increases rapidly with increasing NT20/
A80-900 dosage, while at higher dosage (above 10 mg), the speed
becomes slowly (Fig. 2c). Under 3 min MW, the degradation ratio
reaches 96.13% using 10 mg NT20/A80-900, while that for 20 mg
only enhances about 1%. Considering efficiency and economy,
10 mg NT20/A80-900 catalyst is adopted throughout the remain-
ing experiments.
To establish the kinetic of degradation, the data of -ln(C/C0) for
pseudo-first-order reaction versus MW radiation time (t) is calcu-
lated and checked for 10 mg NT20/A80-900, expressing using the
equation below:
C

ln ¼
kt þ A ð1Þ
C0
The relationship between -ln(C/C0) and t in Fig. 2d is approxi-
mately linear, and so the rate constant k for the degradation of
MV could be calculated from the slope, the degradation process fits
4 Q. Sun et al. / Materials Letters 277 (2020) 128396

Fig. 3. (a) The degradation ratio of MV degraded by NT20/A80-900 under MW before and after reuse (seven cycles), (b) FT-IR spectra of MV degraded by NT20/A80-900 after
different MW time, (c-d) SEM images of NT20/A80-900 after the cyclic degradation of MV under MW.

observed, suggesting the destruction of aromatic ring in MV mole-

well to the pseudo-first-order rate equation (R = 0.96693), which
confirms ‘‘catalysis” rather than ‘‘adsorption” of ACFs leads to the
degradation of MV [13].
The used NT20/A80-900 sample is recovered by magnet,
washed out and then reused in next seven experiments. After
seven consecutive cycles, the catalytic activity maintains high
value of 57% (Fig. 3a). ACFs can be destroyed synchronously partly
due to the strong oxidation condition under MW irritation [14],
resulting in the catalytic activity of reused sample declines consid-
erably. Higher removal ratio of 57% is still kept (much larger than
ACFs). Further SEM of NT20/A80-900 after cyclic degradation
(Fig. 3c-d) confirm that Oxygenium weight substantial increases,
and Ni/Ti elements change slightly, the nanoparticles maintain
uniform distribution on ACFs. The higher catalytic activity is
assigned to the formation of dispersed Ni-TiO2 particles on carbon
support. MW facilitates high temperature reduction of Ni oxida-
tions, which stabilize Ni nanoparticles on ACFs surface.
In FT-IR spectrum of original MV (Fig. 3b), the sharp band at
1630 cm
1 supports alkene (C = C) stretching band [15]. The
intense band at 1160 cm
1 signifies the presence of aromatic C-N
stretching vibrations [16]. For MV after different MW radiation
times, the decrease of alkene (C = C) at 1630 cm
1 can be clearly
cule. The band at 1160 cm
1 disappears and transforms to the
broad band at 1120 cm
1, indicating the formation of C-O-C
stretching [16]. Other bands at 3430, 2930, 2850 and 1380 cm
1
correspond to non-polluting small molecules of O–H, C–H asym-
metric stretching and –CH2 scissoring bend, respectively. These
confirm that the benzene ring and connective C-N are gradually
split, and then decompose to small inorganic species, which are
innocuous to the environment.
4. Conclusion
This paper reports the synthesis of a novel Ni-TiO2/ACFs com-
posite catalyst for MW-induced degrading MV from water. It is
examined how the Ni-TiO2 loading weights, calcined temperatures
and catalyst dosages influence the degradation efficiency. Ni plays
a crucial role in improvement of the efficiency, and the best cat-
alytic activity is obtained by magnetic NT20/A80-900, which might
be applied for triphenylmethane pollutions removal from water.
 Q. Sun et al. / Materials Letters 277 (2020) 128396
CRediT authorship contribution statement
Qinglei Sun: Conceptualization, Investigation, Supervision,
Methodology, Software, Writing - original draft, Writing - review
& editing. Mei Tang: Data curation, Investigation. Yekuan Duan:
Software, Validation. Yun Li: Writing - review & editing. Yang
Peng: Supervision, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
The research was financially supported by National Natural
Science Foundation of China (No. 51578327).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matlet.2020.128396.
5
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