Materials Letters 283 (2021) 128749

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Materials Letters
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Efficient photocatalytic degradation of crystal violet under natural

sunlight using Fe3O4/ZnO nanoparticles embedded carboxylate-rich
carbon
Van Thuan Le a,b, Van Dat Doan c, Thi Thanh Nhi Le a,b, My Uyen Dao a,b, Thu-Thao Thi Vo d,
Ha Huu Do e, Dinh Quoc Viet f, Vy Anh Tran g,⇑
a
Center for Advanced Chemistry, Institute of Research and Development, Duy Tan University, 03 Quang Trung, Da Nang 550000, Viet Nam
b
The Faculty of Environmental and Chemical Engineering, Duy Tan University, 03 Quang Trung, Da Nang 550000, Viet Nam
c
Faculty of Chemical Engineering, Industrial University of Ho Chi Minh City, 12 Nguyen Van Bao, Ho Chi Minh 700000, Viet Nam
d
Department of Food Science and Biotechnology, Gachon University, 1342 Seongnamdaero, Sujeong-gu, Seongnam-si 13120, Republic of Korea
e
School of Chemical Engineering and Materials Science, Institute of Interdisciplinary Convergence Research, Chung- Ang University, 84 Heukseok-ro,
Dongjak-gu, Seoul 06974, Republic of Korea
f
Faculty of Natural Sciences, Quy Nhon University, Viet Nam
g
NTT Hi-Tech Institute, Nguyen Tat Thanh University, 298-300A Nguyen Tat Thanh, Ward 13, District 4, Ho Chi Minh City, Viet Nam

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

Article history: A novel photocatalyst of Fe3O4/ZnO nanoparticles embedded carboxylate-rich carbon (Fe3O4/ZnO/CRC)
Received 22 August 2020 was developed, and its photocatalytic activity was evaluated for the degradation of crystal violet (CV)
Received in revised form 18 September under natural sunlight. The CV (100 mL, 10 ppm) could be entirely degraded by Fe3O4/ZnO/CRC
2020
(75 mg) within 60 min. The O2 reactive species had the main contribution to CV degradation. The pre-
Accepted 25 September 2020
Available online 30 September 2020
pared photocatalyst displayed high stability after five cycles. Fe3O4/ZnO/CRC can be used as an effective
sunlight-driven photocatalyst for dyes removal due to its simple preparation, high photocatalytic activity,
easy separation, and good reusability.
Keywords:
Carboxylate-rich carbon
Ó 2020 Elsevier B.V. All rights reserved.
Crystal violet
Sunlight
Fe3O4/ZnO

1. Introduction high loadings, results in decreasing the photocatalytic efficiency.

Water pollution by dyes is a growing worldwide problem,
which can negatively impact aquatic life, animals, and humans
[1]. Heterogeneous photocatalysis using metal oxide semiconduc-
tors has been considered the most effective technology for convert-
ing harmful organic pollutants into nontoxic substances [2,3].
Among the available semiconductors, ZnO nanoparticles have
found a broader application in photocatalysis due to its high pho-
tosensitivity, nontoxic nature, good stability, low-cost, and simple
preparation [4]. However, some challenges with the use of ZnO
nanoparticles have been recognized, including (i) it can only
impart catalytic activity in the ultraviolet region because of its
wide bandgap (3.2 eV), (ii) the difficulty in separating and recycling
the ZnO powder from treated solution due to its small size, and (iii)
the high aggregation propensity of ZnO nanoparticles, especially at
⇑ Corresponding author at: NTT Hi-Tech Institute, Nguyen Tat Thanh University,
298-300A Nguyen Tat Thanh, Ward 13, District 4, Ho Chi Minh City, Viet Nam.
E-mail address: tranhvy@gmail.com (V.A. Tran).
An effective way to solve these problems was to combine magnetic
semiconductors with ZnO to form a nanocomposite loaded on cat-
alyst supports [5].
In this study, we developed a novel photocatalyst of Fe3O4/ZnO
nanoparticles embedded carboxylate-rich carbon (Fe3O4/ZnO/CRC),
which was synthesized by a one-step low-temperature carboniza-
tion process from the mixture of FeCl3, ZnCl2, and sodium glu-
conate. The integration of the narrow bandgap Fe3O4
semiconductor with ZnO resulted in increased sensitivity to visible
light and the improved separation of the photoinduced charge car-
riers, enhancing photocatalytic activity [5]. Moreover, the presence
of Fe3O4 nanoparticles with strong magnetic properties made the
photocatalyst easy to be recovered by a magnetic field. Meanwhile,
the abundant carboxyl groups in the amorphous carbon generated
from sodium gluconate acted a critical role not only in homoge-
neous distribution and immobilization of Fe3O4/ZnO nanoparticles
but also in improving their dispersion in water. Besides, these
functional groups could coordinate with metal ions to form

https://doi.org/10.1016/j.matlet.2020.128749
0167-577X/Ó 2020 Elsevier B.V. All rights reserved.
V.T. Le et al.
ligand-to-metal charge transfer complexes, which enhanced visi-
ble light absorption ability, increasing the visible-light-driven pho-
tocatalytic activities [6]. The as-prepared material was
characterized through different techniques and evaluated for its
photocatalytic activity toward crystal violet (CV) under natural
sunlight.
2. Experimental
The detailed information on catalyst preparation, material char-
acterization, and photocatalytic experiments were presented in
Supplementary Material.
3. Results and discussion
The Fourier-transform infrared (FTIR) spectra of the prepared
samples are presented in Fig. 1a. The presence of FeAO and ZnAO
bonds in the samples was identified by the bands around 565 and
540 cm 1, respectively. The functional groups characteristic for
CRC such as CAO, CAC, C@O, CAH, and OAH were observed in sam-
ples. The small peaks at 1044 and 1564 cm 1 indicated the CAO
stretching vibration and the CAC stretching in the aromatic ring,
respectively. The peaks at 1690 and 1385 cm 1 assigned to the
C@O stretching vibrations confirmed an abundance of carboxylate
groups in the carbon shell. The peaks at 2920 and 2855 cm 1 were
attributed to the HACAH stretching vibrations. The presence of
OAH in the synthesized composites proved by the broadening
band at 3394 cm 1 [7].
Fig. 1b displays the X-Ray diffraction (XRD) patterns of Fe3O4/
CRC, ZnO/CRC, and Fe3O4/ZnO/CRC. The XRD pattern of Fe3O4/CRC
showed peaks at 24.20° (1 1 1), 30.34° (2 2 0), 33.14 (1 0 0), 35.62°
(3 1 1), 40.98° (1 1 3), 43.28° (4 0 0), 49.48° (0 2 4), 53.98° (4 2 2),
57.48° (5 1 1), 62.92° (4 4 0), 71.94° (6 2 0), and 75.54° (5 3 3), corre-
sponding to the cubic phase of Fe3O4 (JCPDS 19–0629). In the case
Fig. 1. FTIR spectra (a), XRD pattern (b), UV–vis DRS spectra (c), magnetization curves (d) of the synthesized photocatalysts.
2
Materials Letters 283 (2021) 128749
of ZnO/CRC, the diffraction peaks at 31.68°, 34.38°, 36.14°, 47.42°,
56.42°, 62.84°, 67.86°, 68.96°, and 76.90°, corresponding to (1 0 0),
(0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (1 1 2), (2 0 1), and (2 0 2) planes
of ZnO with wurtzite structure (JCPDS No. 36-1451). Most promi-
nent peaks of Fe3O4/CRC and ZnO/CRC were found in the XRD pat-
tern of Fe3O4/ZnO/CRC. No characteristic peaks of carbon were
detected in Fe3O4/CRC and Fe3O4/ZnO/CRC because CRC is amor-
phous carbon, and there was an overlap of strong peaks of Fe3O4
[8]. Moreover, numerous iron and zinc atoms can be hidden in
the grain boundary segregation layers, which could not be
observed by the XRD technique [9].
The light absorption properties of the photocatalysts were fur-
ther investigated by UV–Vis diffuse reflectance (DRS) spectra. As
illustrated in Fig. 1c, ZnO/CRC exhibited a large optical absorption
band, while this value of Fe3O4/CRC indicated lower a little bit.
Compared with both of Fe3O4/CRC and ZnO/CRC, Fe3O4/ZnO/CRC
presented the enhanced absorption intensity in the UV and visible
light region around 400–500 nm. It is supposed that the visible
light absorption of Fe3O4/ZnO/CRC was mainly attributed to the
formation of carboxylate–Fe3O4/ZnO complexes [6].
Hysteresis loops of Fe3O4/CRC and Fe3O4/ZnO/CRC are shown in
Fig. 1d. Both samples revealed a superparamagnetic behavior that
was desirable for environmental applications. Fe3O4/CRC possessed
a saturation magnetization of 30.5 emu/g. This value was reduced
to 21.6 emu/g for Fe3O4/ZnO/CRC. The decrease in the magnetiza-
tion was due to the presence of nonmagnetic mixing ZnO nanopar-
ticles. It can be seen (insert in Fig. 1d) that the Fe3O4/ZnO/CRC
could be easily separated from the solution using an external mag-
netic field.
The element valence in Fe3O4/ZnO/CRC was characterized by
X-ray photoelectron spectroscopy (XPS) (Fig. 2a–c). A survey
spectrum containing Fe2p, Zn2p, and C1s proved the presence of
these elements in Fe3O4/ZnO/CRC. The Fe2p region was deconvo-
luted into six peaks, as shown in Fig. 2a. The two peaks at binding
energies of 724.28 and 710.88 eV could be attributed to 2p1/2 and
V.T. Le et al. Materials Letters 283 (2021) 128749

Fig. 2. XPS of deconvoluted spectrum of Fe2p (a), Zn2p (b), and C1s (c), SEM image (d), TEM image (e) and EDX spectra of Fe3O4/ZnO/CRC.

2p3/2 of Fe2+ species. The two spectral bands are located at 726.28 formation of the Fe3O4 in Fe3O4/ZnO/CRC [10]. As seen in Fig. 2b,
and 713.08 eV, corresponding to 2p1/2 and 2p3/2 of Fe3+ species, the Zn2p core-level XPS spectrum showed two peaks at 1045.18
respectively. The remaining two weak peaks at 719.68 and and 1021.98 eV, which were assigned to Zn2p1/2 and Zn2p3/2 of
732.48 eV were satellite peaks, indicating the purity and successful tetrahedral Zn2+, respectively, confirming that the oxidation state

Fig. 3. (a) Degradation of CV under sunlight over different synthesized photocatalysts, (b) kinetic plots of ln(Ct/Co) versus reaction time t, (e) effects of radical scavengers,
and (f) reusability of Fe3O4/ZnO/CRC for CV degradation. Reaction conditions: pH of 7, catalyst dosage of 0.75 g/L, and CV concentration of 10 mg/L, the concentration of
scavengers of 1 mM.

3
V.T. Le et al.
of Zn is +2 in Fe3O4/ZnO/CRC. In the case of C1s, the binding energy
at 284.78 eV of C–C bonds. Besides, the binding energies at 286.38
and 288.58 eV could be attributed to CAOAC and CAO@C groups of
CRC, respectively [11].
From scanning electron microscopy (SEM) image of Fe3O4/ZnO/
CRC (Fig. 2d), we could observe cluster-like nanoparticles of uni-
form size and shape. The transmission electron microscopy
(TEM) image (Fig. 2e) indicated that the average particle size of
cubic Fe3O4 was 30–40 nm. Meanwhile, the ZnO nanoparticles
were nearly spherical with a size of around 10 nm, and seemingly
encapsulated the Fe3O4 nanoparticles. In the prepared composite,
ZnO and Fe3O4 nanoparticles appeared in the matrix and were cov-
ered by amorphous carbon from CRC. Besides, the energy-
dispersive X-ray spectroscopy (EDX) study verified the existence
of Fe, Zn, O, and C elements in Fe3O4/ZnO/CRC (Fig. 2f).
Fig. 3a shows the removal of CV by the prepared samples in the
dark and under natural sunlight. The photolysis without catalysts
was negligible, and the dark adsorption removed about 15–20%
of CV. After 90 min of sunlight irradiation, the CV conversion was
29.3, 42.6, and 94.5% on CRC, Fe3O4/CRC, and ZnO/CRC, respec-
tively. Meanwhile, Fe3O4/ZnO/CRC reached complete degradation
of CV within just 60 min. More significantly, the comparison
Table S1 presented in supplementary data revealed that the
Fe3O4/ZnO/CRC composite not only possessed a higher photocat-
alytic activity than three control samples but also exhibited higher
than others reported in the literature. The excellent photocatalytic
effectiveness of Fe3O4/ZnO/CRC may be mainly attributed to the
synergistic effects created by combining the three components of
the photocatalyst, leading to the enhancement of electron-hole
pair separation and the intensification of visible light absorption
ability. The degradation rate constants (k), calculated by the
Langmuir-Hinshelwood equation ( ln(Ct/Co) = kt), increased in
the follow order: CRC (0.006 min 1) > Fe3O4/CRC (0.014 min 1)
> ZnO/CRC (0.032 min 1) > Fe3O4/ZnO/CRC (0.067 min 1) (Fig. 3b).
The main radical species that promoted the photocatalytic pro-
cess were determined through the trapping experiments. Herein,
p- benzoquinone (p-BQ), isopropyl alcohol (IPA), ammonium oxa-
late (AO), and K2S2O8 were used for quenching O2, OH, h+, and
e , respectively. As reflected in Fig. 3c, the degradation efficiency
of CV slightly decreased after the introduction of IPA, K2S2O8, and
AO. In contrast, the removal of CV inhibited significantly with the
presence of p-BQ. This result suggested O2 was the dominant reac-
tive species for degrading CV. Besides, the reusability study
showed that the photocatalytic activity of Fe3O4/ZnO/CRC was vir-
tually unchanged in the first three runs and remained around
95.4% after the 5th use (Fig. 3d), demonstrating the highly reusable
nature of the prepared material.
4. Conclusions
In summary, Fe3O4/ZnO/CRC composite was successfully syn-
thesized, characterized, and applied for CV degradation under nat-
ural sunlight. The prepared photocatalyst showed high
Materials Letters 283 (2021) 128749
photocatalytic activity with the rate degradation constant of
0.067 min 1. The O2 was found to be the main reactive species.
Furthermore, Fe3O4/ZnO/CRC exhibited good reusability. The over-
all results indicated that Fe3O4/ZnO/CRC could be a suitable candi-
date for natural sunlight driven photocatalytic application.
CRediT authorship contribution statement
Van Thuan Le: Conceptualization, Writing - original draft,
Investigation. Van Dat Doan: Software, Data curation. Thi Thanh
Nhi Le: Resources, Investigation. My Uyen Dao: Resources, Investi-
gation. Thu-Thao Thi Vo: Investigation, Conceptualization. Ha Huu
Do: Visualization, Investigation. Dinh Quoc Viet: Conceptualiza-
tion, Investigation. Vy Anh Tran: Writing - review & editing,
Supervision.
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
This research is funded by Vietnam National Foundation for
Science and Technology Development (NAFOSTED) under grant
number 104.05-2019.03.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matlet.2020.128749.
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