International Journal of Trend in Scientific Research and Development (IJTSRD)

Volume 7 Issue 3, May-June 2023 Available Online: www.ijtsrd.com e-ISSN: 2456 – 6470

Sonocatalytic Performance of Fe3O4 Cluster

Microspheres/Gratiphic Carbon Composite for
Efficient Degradation of Organic Dyes
Xuan Sang Nguyen
Environmental Engineering Institute, Viet Nam Maritime University, Haiphong, Vietnam

ABSTRACT How to cite this paper: Xuan Sang

Fe3O4/g-C3N4 composite was synthesized using hydrothermal simple Nguyen "Sonocatalytic Performance of
and facile techniques. The sonocatalytic activity of the magnetic Fe3O4 Cluster Microspheres/Gratiphic
Fe3O4/g-C3N4 composite was studied through the H2O2-assisted Carbon Composite for Efficient
system for degradation of water soluble organic pollutants such as Degradation of Organic Dyes" Published
in International
methylene blue (MB), rhodamine B (RhB) and methyl orange (MO).
Journal of Trend in
X-ray diffraction (XRD) and scanning electron microscopy (SEM) Scientific Research
equipped were employed for the characterizing the structure and and Development
morphology of the so-synthesized nanohybrid. The integration of (ijtsrd), ISSN: 2456-
H2O2 and catalyst dosage enhaced the sonocatalytic degradation of 6470, Volume-7 |
dyes. Furthermore, the magnetic property of the sample leaded to Issue-3, June 2023, IJTSRD57418
easier separation of the microhybrid, made it recyclable with a pp.605-610, URL:
negligible decline in the dye degradation even after four consecutive www.ijtsrd.com/papers/ijtsrd57418.pdf
recycles.
Copyright © 2023 by author (s) and
KEYWORDS: Cluster sphere Fe3O4; sonocatalytic; composite; dye International Journal of Trend in
degradation Scientific Research and Development
Journal. This is an
Open Access article
distributed under the
terms of the Creative Commons
Attribution License (CC BY 4.0)
(http://creativecommons.org/licenses/by/4.0)

1. INTRODUCTION
Recently, the development of many industries are a promising external field-enhanced catalytic
widely using organic dyes that are among new technology that can significantly promote the
chemicals. Large amount of production and extensive efficiency of both downhill and uphill reactions[5, 6] .
applications of organic dyes make a lot of toxic Sonocatalyst has widely used as an advanced
industrial wastewaters polluted biological oxidation process (AOP) for water and wastewater
degradation. However, using conventional treatment treatment because of its high efficiency and simple
methods could not effectively degrade and mineralize operation [7]. However, application by only
of organic dyes [1, 2]. Due to generating physical and ultrasonic show a low rate for degradation organic
chemical effects, such as promoting the mass transfer contaminants using a lot of energy and time for an
and active radical formation, sonication can be incomplete removal process, unless using
employed for process intensification in numerous sonocatalysts which are active under ultrasonic
fields, including catalysis. Ultrasound, that is, sound irradiation resulting in accelerate •OH forming [8].
waves of frequency above 20 kHz, can benefit Various catalysts such as CuS, TiO2, ZnTiO3, Er
catalysis in multiple ways, from enhacing the doped ZnO have exposed high sonocatalytic activities
synthesis of photocatalysts with tailored [9, 10]. However, there is a need for developing new
physicochemical properties to improving reaction magnetic composite sonocatalysts with high catalytic
efficiency via synergisms between ultrasound and activity. Photocatalytic and sonocatalytic processes
light irradiation in sonophotocatalysis [3, 4]. In recent show the same creating electron–hole pairs on the
years, the application of ultrasound has considered as surface of catalyst [11].

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Gratiphic carbon (g-C3N4) is considered to be the 2.2. Characterization
most stable allotrope among various carbon nitrides X-ray diffraction (XRD analysis was carried out an
under ambient conditions. The proposed structure of X-ray powder diffractometer with Cu Kα radiation at
g-C3N4 is two-dimensional frameworks of tri-s- 40 kV and 40 mA. The morphology and internal
triazine connected via tertiary amines, which makes it structure of the prepared samples were further
possess high stable thermal (up to 600 °C in air) and checked by transmission electron microscopy
chemical stability (against acid, base, and organic (FESEM), using a JEM 2100F electron microscope
solvents) [12]. Because of their unique size- and operated at a voltage of 200 kV. UV–vis reflectance
morphology-dependent physical and chemical spectra of the powder catalysts were recorded by a
properties, Fe3O4 nanoparticle have paid more Perkin Elmer spectrometer Lambda 35 using an
attention by world-wide researcher for their potential RSAPE-20 reflectance spectroscopy accessory
applications as magnetic storage, biosensors, (Labsphere Inc., NorthSutton, NH). The PL spectra of
communication materials, magnetic resonance products were measured by a transient fluorescence
imaging [13]. The controlled synthesis processes of spectrometer (Shimadzu RF-5301PC).
Fe3O4 NPs to deliver a desired structure, composition,
2.3. The sonocatalytic degradation
and shape control made them be used in various
The sonocatalytic degradation experiments were
promising applications.
carried out by measuring the decoloration of dyes
In recent years, loading the catalysts with magnetic solution. RhB, MB, MO were used as the model
materials has been used as a new approach for pollutant to evaluate the sonodegradation activity of
enhancing catalytic activity, magnetic and the Fe3O4/gC3N4 composites. In a typical process, 0.1
antiphotocorrosion characteristics for effective g of Fe3O4/gC3N4 composite was added into 50 mL of
recovery and reuse [14, 15]. In the present study, the dye (10mg/L) aqueous solution with countinuous
application the magnetic Fe3O4 cluster spheres/g- stirring. Then 0.1ml of the H2O2 aqueous solution
C3N4 applied as a new sonocatalyst for an efficient (30%) was added to the reaction solution. The mixed
H2O2-assisted sonodegradation of three organic dyes solution was then placed inside an a EYG-3003 bath
in aqueous solutions were reported. This sonocatalyst with the frequency fixed at 40 kHz and temperature
composite was synthesized via simple hydrothermal range controlled from 25 to 28 ◦C. About 5ml of the
method. Methylene blue (MB), methyl orange (MO) suspension were collected after a defined time and
and rhodamine B (RhB) were employed as organic centrifuged to remove the catalyst for UV-vis
dye models for evaluating sonocatalytic activity of spectrum measurement.
pure Fe3O4 cluster spheres, g-C3N4 and Fe3O4 cluster
3. Result and Discussion
spheres/g-C3N4.
3.1. XRD analysis
2. Experimental Fig.1 shows X-ray diffaction pattens of g-C3N4,
2.1. Synthesis of composites Fe3O4 and Fe3O4 clusters/gC3N4 20% wt. The patterns
Pure g-C3N4 powder was prepared using melamine as showed the sharp and intense peaks indicating the
a precursor at 550 0C for 4h in a muffle furnace. The photocatalysts were well crystallized. As shown in the
obtained products were washed several times with de- Fig. 1, all the diffraction peaks and position of pure
ionized water then grounded for further use. The Fe3O4 and Fe3O4 clusters/gC3N4 composite can be
Fe3O4/g-C3N4 composite was prepared by simple indexed to the cubic Fe3O4 (JCPDS 86-1354). The
hydrothermal method. In a typical procedure, a strong and sharp diffraction peaks signify exbihite the
certain amount of g-C3N4 (0.5g) and Fe(NO3)3·9H2O high crystallinity of Fe3O4 cluster microspheres [16].
(2.04 g ) were dissolved in 60ml of deionized water The two characteristic peaks of g-C3N4 at 13.28 and
under magnetic stirring. The solution was put into a 27.33 can be indexed to (100) and (002) diffraction
Teflon-lined autoclave, followed by adding with 10 planes (JCPDS 87-1526). Compared to pure g-C3N4,
mL of sodium alginate solution (10 g/L), and 10 ml it can be seen clearly most peaks for Fe3O4/g-C3N4
KOH (2M). After 30 min ultrasonic treatment, the indexing to the structure of Fe3O4. The character of g-
mixture was transfered into a Teflon liner of 100mL C3N4 could not be exposed in the XRD pattern of
capability. The autoclave was sealed and heated at Fe3O4/g-C3N4 composite sample could be attributed
180℃ for 12h and cooled to room temperature by the low adding content and well dispersion of g-
naturally. The resulting precipitant was recovered by C3N4 powders. However, g-C3N4 can still be found in
filtration, followed by washing with distilled water the composites due of the appearance of the peak at
three times, and drying at 80℃ for 10h. 26.50. The results suggests the composites were
formed between g-C3N4 and Fe3O4 cluster spheres.

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Fig. 1. XRD pattern of g-C3N4, Fe3O4 and Fe3O4/gC3N4

3.2. SEM analysis
The surface properties of pure cluster sphere Fe3O4 and Fe3O4 clusrter spheres/g-C3N4 composite catalyst was
observed using SEM method. The obtained results are shown in Fig. 2. As depicted in Fig. 2a, the as-prepared
product is composed of a large quantity of well-dispersed microspherical particles. These particles have uniform
size and shape, most of which are spheres of 300-500 nm. In addition, the SEM image of spherical particles
reveal that these Fe3O4 particles are colloidal nanocrystal clusters with a hierarchical architecture, and were built
up from many single crystallites of approximately 30-40 nm in size. The average crystallite size observed from
the SEM image, which are consistent with the calculation result from the XRD pattern. In particular, it can be
seen products are composed of nanocrystal pieces by the ordered assembly. As depicted in Fig. 2b, the
characteristic lamellar layered and planar structure can be obtained for the pure g-C3N4 . From Fig. 2c, it is seen
that when Fe3O4 clusters were modified with the g-C3N4, the surface of the samples became less rough. It can be
attributed to covering the surface of Fe3O4 by g-C3N4 particles. The accommodation of g-C3N4 on the surface of
Fe3O4 lead to the formation of a tight heterostructure. In this case, two phases of g-C3N4 and Fe3O4 are clearly
seen and close contact to form an intimate interface [17-19]. It is found that cavitations created in sonochemical
technique play an important role in the preparation of heterostructure materials. This can promote the formation
of the stable hybrid structure between g-C3N4 and Fe3O4 composite [20].

Fig. 2. SEM image of Fe3O4 cluster spheres (a); g-C3N4 (b), and Fe3O4/g-C3N4 composites (c)

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3.3. Sonocatalytic degradation of dye
The sonocatalytic activity of the Fe3O4/g-C3N4 catalysts were evaluated through the degradation of RhB, MB,
MO in the presence of H2O2 with ultrasonic irradiation. The results of sonocatalytic activities of the samples
prepared at different conditions are shown in Fig. 3. No dye degradation can be observed without catalytic. The
sonocatalytic activity of the cluster Fe3O4/g-C3N4 composite are further examinated by comparison with that of
pure two-component. Compared with sonolysis/H2O2, the higher degradation of dyes were achieved via
sonocatalytic process. The degradation efficiency of sonolysis/H2O2, sonocatalysis using g-C3N4/H2O2,
Fe3O4/H2O2, Fe3O4/g-C3N4/H2O2 systems was 3%, 64%, 22 % and 96.5% within reaction time of 150 min for
RhB, respectively. Cluster Fe3O4/g-C3N4 composite show much more efficient than pure cluster sphere Fe3O4
and pure g-C3N4 (Fig. 3a). The sonocatalytic processes for MB and MO degradation show the same results as
depicted in Fig. 3b and Fig. 3c.

Fig. 3. The dye sono-degradation with different catalysts: (a) RhB degradation; (b) MB degradation;
(c) MO degradation
The excellent sonocatalytic activity of cluster sphere Fe3O4/g-C3N4 composite can be ascribed to their high
crystalline, morphology and hibrid structure. The chemical effect of sonolysis eventuates in a phenomena known
as the acoustic cavitation that involves generation, growth and collapse of the microbubbles that are created as a
result of ultrasound crossing through the aquatic medium [21]. The final outcome of this process is the
fabrication hot spots that exposes high pressure and temperature on the catalyst surface. These hot spots result in
the appropriate conditions to active and dissociate H2O molecules. As the result, the strong oxidizing agents and
the •OH reactive radicals are formed continuously [22]. The accelerating impact of the heterogeneous catalyst
could be explained by the synergy effect between the ultrasonic irradiation and the catalyst. Therefore, these
composites with a hybrid structure would result in an electric field at the interface, then improving the
sonocatalytic activity.

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To investigate the stability of the Fe3O4/g-C3N4 composites, the recycle tests were conducted in the oxidation
process under ultrasonic irradiation. The results reveal that the as-obtained composite was easily collected by an
internal magnet and dyes removal effective has no significant change during the 4th successive cycles, indicating
the high stability of the composite (Fig. 5). The chracteristic plays a very important role in application for water
treatment at industry scale. The high sonocatalytic activity, the stability and the easily separation suggest that the
Fe3O4/g-C3N4 can be promising candidates for the dyes removal application.

Fig. 5. The stability of the Bi/g-C3N4 composites after 4 recycles

4. Conclusion [2] E. Bartfai, K. Nemeth, B.E. Mrabate, M.
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