Comparison of TiO2 nanoparticles and Fe3O4@TiO2
core-shell nanostructures and their photocatalytic
activity
Cesar de Jesus Alarcon-Hernandez, Alba Arenas-Hernandez, Abel Garzon-Roman, and Carlos Zuñiga-Islas
Electronics Department
Instituto Nacional de Astrofísica, Óptica y Electrónica
Puebla, México
cesar.alarcon@inaoep.mx, alba.arenas@inaoep.mx, abelgr@inaoep.mx , czuniga@inaoep.mx
Abstract— The catalytic activity is very important in the
applications of gas sensors and pollutants degradation because it
can increase the reactivity of sensing films and rate the
degradation process. This paper, we report TiO2 and Fe3O4
nanoparticles (NP’s) prepared by hydrothermal and
coprecipitation methods, respectively, as well as, Fe3O4@TiO2
core-shell nanostructures fabricated by the hydrothermal method.
The morphological and structural characterization were studied
by Scanning Electron Microscopy (SEM), and X-ray diffraction
(XRD). TiO2 nanoparticles (NP's-TiO2) and Fe3O4 core-shell
nanostructures were used as catalysts to degrade methylene blue
(MB). The results showed that Fe3O4@TiO2 core-shell
nanostructures have good catalytic performance because in this
catalyst have a grainy texture, which increase the active sites due
to surface area.
Keywords—TiO2, Fe3O4, nanoparticles, core-shell, methylene
blue, degradation.
1. INTRODUCTION
Nowadays, nanoscience and nanotechnology have emerged
to revolutionize electronics, medicine, and chemistry. The
implementation of nanotechnology in different metal oxide
nanomaterials, for instance, TiO2, ZnO, SnO2, CuO, and Fe3O4,
has been used to improve their properties for energy
applications, pollutant photodegradation, and chemical and gas
sensors [1, 2]. TiO2 is the most widely used due to its non-toxic
nature, chemical stability, high photo-active, biocompatibility,
low cost, and environmentally friendly [3, 4]. In addition, TiO2
has a large number of applications, such as water treatment and
purification, gas and chemical sensors, solar cells, and
degradation [5-7]. However, a restriction is that the TiO2 energy
range is large (~ 3.2 eV), which means that TiO2 is active only
in the UV light range [8]. To improve the catalytic capacity and
expand the fields of application, the modification of TiO2 with
magnetic metals is often adopted to allow the separation and
recovery of the TiO2 nanoparticles (NP’s-TiO2) as well as
change the absorption in the visible spectrum [9, 10]. As a
typical magnetic material, magnetite (Fe3O4) has high surface
redox activity and strong electron transport capability and can
also be used to solve the problem of TiO2 photocatalyst recovery
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[11]. Globally, water contamination sources are one of the most
serious problems to safe life development. [12,13]. Dyes
synthetics such as MB are widely used in industries, and these
are the more common pollutants in wastewater [14]. Also, they
are toxic and carcinogenic [15]. Research to counteract these
problems has boomed, as quick and simple methods must be
developed, so photocatalysis has become a promising way to
solve pollution problems [16,17].
In this work, TiO2 and Fe3O4 nanoparticles were
synthesized by hydrothermal and co-precipitation methods,
respectively. Additionally, Fe3O4@TiO2 core-shell
nanostructures were prepared by a hydrothermal method. The
morphological and structural characteristics by Scanning
Electron Microscopy (SEM) and X-ray diffraction (XRD) are
presented. According to the results, the NP's-TiO2 and Fe3O4
core-shell nanostructures have a similar degradation. However,
at the end of 180 min, the Fe3O4@TiO2 were the ones that
degraded more due to their granular texture that increased the
active surface area.
2. EXPERIMENTAL SECTION
2.1 Synthesis of TiO2 nanoparticles (NP’s TiO2)
First, 10 ml of methanol, 83µL of titanium butoxide, and 1
mL of hydrochloric acid (HCl) are mixed with magnetic stirring
for 10 min. Second, the solution is transferred inside the
autoclave, and this heated at 180 °C for 4 h using a muffle. Then,
the autoclave is cooled at room temperature. Subsequently, the
NP’s-TiO2 solution were centrifuged at 3000 rpm. Finally, the
NP’s were thermal treatment at 400 °C for 3 hrs.
2.2 Synthesis of Fe3O4 nanoparticles (NP’s Fe3O4)
The synthesis of the magnetic nanoparticles was carried out
using the coprecipitation technique. Polyvinylpyrrolidone
(PVP) and sodium citrate were used as a stabilizer and reducing
agent, respectively. Ferrous chloride and ferric chloride were
mixed in deionized water (1:2 molar ratio) with magnetic
stirring. Subsequently, the NaOH (3 g), PVP (1 g), and sodium
citrate (250 mg) were mixed under magnetic stirring to reach 60
°C. Then, ferrous chloride and ferric chloride were emptied
dropwise slowly with constant stirring. The change in color of change the size and morphology of Fe3O4@TiO2
the solution to black indicates the presence of NP’s Fe3O4. The nanostructures [22].
resulted solid was washed with methanol and deionized water
three times. Finally, NP’s Fe3O4 were annealed at 100 ° C for 3
h using a muffle. 3.2 Structural Characterization
X-ray diffraction (XRD) was used to verify the crystal
2.3 Synthesis of nanostructures Fe3O4@TiO2 core-shell
structure of NP’s-TiO2 and NP-Fe3O4, and analyze the effect of
5 mg of NP's-Fe3O4 and 10 ml of methanol were mixed and Fe3O4@TiO2core-shell nanostructures. The results are
emptied into the teflon cell. The solution was homogeneous presented in Fig. 2.
dispesed using a sonicator for 20 min. Next, the teflon cell is Fig. 2 (a) displays the diffraction peaks were located at 2θ=
placed inside the autoclave at 180 °C for 4 hrs. The autoclave 25.41°, 38.01°, 48.20°, 54.13°, 55.11°, 62.86°, 68.96°, 70.60°,
was allowed to cool down to room temperature and after, the and 75.27° corresponding to the planes (101), (004), (200),
solution was centrifuge. Finally, the nanostructures powder was (105), (211), (204), (115), (220) and (215), respectively.
annealed at 400 °C for 3 hrs. According to XRD results, the tetragonal structure of the
2.4 Characterization anatase phase of TiO2 was confirmed [23]. Also, the
diffractogram Fig. 2 (b) illustrates a sequence of diffraction
In order to investigate the morphology and size of TiO2
peaks at 2θ = 30.35°, 32.17°, 35.94°, 37.62°, 43.45°, 53.95°,
nanoparticles and Fe3O4@TiO2 core-shell nanostructures
57.62°, 63.14°, 71.64°, 74.60°, and 75.55° attributed to plans
synthesized by the hydrothermal method; a morphological
(220), (300), (311), (222), (400), (422), (511), (440), (620),
analysis using field emission scanning electron microscopy
(533), and (622), respectively, which confirmed the cubic
(FE-SEM) SCIOS DualBeam model was performed. The phase
spinel structure for NP-Fe3O4 [24, 25]. Fig. 2 (c) shows the
structure of TiO2, Fe3O4 nanoparticles, and nanostructures
pattern of Fe3O4@TiO2 core-shell. A a decreases intensity the
Fe3O4@TiO2 core-shell were obtained using a Panalytical-
anatase and magnetite phases were observed which confirms
Empyrean diffractometer with Cu Kα radiation (λ = 0.15418
the formation of core-shell nanostructures.
nm), in the 2θ range from 10° to 70° at a scan speed of 0.017°.
The photocatalytic activities of the materials were examined by
the degradation of MB under UV light irradiation using a 26W
reptile UVB100 lamp (model PT2187). MB was dissolved in
100 ml of DI water to obtain a concentration of 13 ppm. Then
100 mg of NP’s-TiO2 and Fe3O4@TiO2 were dissolved. Next,
suspensions were shaken on a sonicator for 10 min. Before
starting the UV light irradiation, the samples were left in the
dark for 15 min. Approximately 3 ml of the mixture was taken
at regular intervals. Absorbance was measured using a Horiba
Jobin Yvon spectrophotometer in a range of 400-800 nm with
a step of 1 nm
3. RESULTS AND DISCUSSION
3.1 Morphological Characterization
Fig. 1 shows the FE-SEM micrographs of different
nanostructures. Fig. 1a shows the NP’s-TiO2 obtained by
solvothermal method. A homogeneous quasi-spherical shape
and good dispersion of NP's-TiO2 with around 8 nm of particle
size were observed. On the other hand, Fig. 1 (b) and (c)
illustrate the morphology of the Fe3O4@TiO2 core-shell
particles with diameters of 382 ± 80 nm and rough shape were
evident, with agglomerates in each one (see Fig. 1b). The
formation of agglomerates may associate with the synthesis
process due to the rapid boiling of the titanium species and the
solvents [18-20]. From Fig. 1 (c) it can be seen a grainy texture
of the nanostructure shell, which can be ascribable to the
breaking of the NP's-TiO2 coating due to the drying and
calcination processes (400 °C). According to Xin et al., [21]
morphological irregularities are related to the concentration of
NP's-Fe3O4 because a greater or lesser concentration of Fig. 1. FE-SEM micrographs of a) NP's-TiO2, b)
particles in the core affects the texture of the shell. In this way, nanostructures Fe3O4 core-shell and c) their magnification view.
the amount of precursor, solvent, and concentration of core
 changes in the concentration of MB (Ct/C0) as a function of
time. The Fe3O4@TiO2 nanostructures showed a gradual
photocatalytic degradation than NP's-TiO2. Nevertheless, NP's-
TiO2 obtained the highest rate of degradation at 45 min. In
addition, based on the L-H model (Ec. 2), a photocatalytic
efficiency linear and constant was observed by Fe3O4@TiO2
nanostructures, especially between 60 and 120 min. On the
other hand, the velocity constant of the NP's-TiO2 and
Fe3O4@TiO2 nanostructures were k=0.00402 and 0.0043 min -
1
, respectively. The result indicated that Fe3O4@TiO2
nanostructures have a high catalytic performance ascribed to
the fact that the sample has a grainy texture, which increases
catalytic active sites due to specific surface area.

Fig. 2 Diffractograms of, (a) NP’s TiO2, (b) NP’s Fe3O4 and (c)
nanostructures Fe3O4@TiO2 core-shell.

3.3 Photocatalytic activity

To study the catalytic activity of all nanostructures, the MB
degradations are shown in fig. 3.
Fig. 3 (a) and (b) display the UV–vis spectra of the
suspension of MB in interaction with NP's-TiO2 and
Fe3O4@TiO2, respectively. Typically, a cationic MB has a
strong band centered at 665 nm and another small absorption
band at the shoulder around 617 nm. Also, these illustrate a
gradual decrease of the adsorption peak intensity with an
increase in the degradation time. The percentage of degradation
(% D) is calculated from the following equation [27].
𝐴0 −𝐴𝑡
%𝐷 = ∗ 100 ()
𝐴0

Where A0 is the initial absorbance and At is the absorbance

at a specific time. Fig 3 (c) illustrates the %D of the samples
obtained an MB degradation performance for NP's-TiO2 of 53%
and for Fe3O4@TiO2 55% at 180 min. The Langmuir–
Hinshelwood standard Model (L-H) equation was used to study
the kinetics of the heterogeneously catalyzed photodegradation
reaction. The formula of this model pseudo-first-order is
expressed as follows [28]:
𝐶
ln⁡( 0 ) = 𝑘𝛼 𝑡 ()
𝐶𝑡
Fig. 3 MB absorbance in (a) NP’s-TiO2 and (b) core-shell Fe3O4@TiO2, (c)
degradation percentage vs time of NP’s-TiO2 and Fe3O4@TiO2 core-shell,
Where the initial concentration is C0, Ct is the (d) linear relationship of ln(C0/Ct) of MB degradation.
concentration at a specific time, and the velocity constant of the
pseudo-first-order model is Kα (min−1). Fig. 3 (d) shows the
 4. CONCLUSIONS
In conclusion, NP's-TiO2 and Fe3O4@TiO2 core-shell
nanostructures with diameters of 8 nm and 382 ± 80 nm,
respectively, were synthesized by the hydrothermal method. In
addition, NP's-TiO2 shows homogeneous quasi-spherical shapes
and good dispersion, while Fe3O4@TiO2 core-shell particles
have rough shapes, agglomerates, and irregularities texture of
the nanostructure shell. The XRD results obtained on NP's-TiO2
and NP's Fe3O4 corroborate the crystalline anatase and spinel
phases, respectively. For Fe3O4@TiO2 core shell nanostructures,
a decreases intensity the anatase and magnetite phases were
observed, which confirms the formation of core-shell
nanostructures. The best catalyst Fe3O4@TiO2 core shell
because this achieves a degradation of 55% during 180 min. The
high catalytic performance of Fe3O4@TiO2 nanostructures is
due to the grainy texture, which increase the effective active
sites to improve the charge carrier transport.
REFERENCES
[1] Krishna, K. G., Parne, S., Pothukanuri, N., Kathirvelu, V., Gandi, S., &
Joshi, D. (2022). Nanostructured metal oxide semiconductor-based gas
sensors: A comprehensive review. Sensors and Actuators A: Physical.
[2] Liu, D., Liang, H., Xu, T., Bai, J., & Li, C. (2022). Construction of ternary
hollow TiO2-ZnS@ ZnO heterostructure with enhanced visible-light
photoactivity. Journal of Molecular Structure, 1248, 131493
[3] S. Tek, E. Mutlugun, I.M. Soganci, N.K. Perkgoz, D. Yucel, G. Celiker,
H. V Demir Comparative study of optically activated nanocomposites
with photocatalytic TiO2 and ZnO nanoparticles for massive
environmental decontamination J. Nanophotonics, 1 (2007),
10.1117/1.2828851.
[4] A. Hernández-Ramírez, I. Medina-Ramírez Photocatalytic
semiconductors A. Hernández-Ramírez, I. Medina-Ramírez (Eds.),
Photocatalytic Semicond, Springer International Publishing, Cham
(2015), pp. 1-289, 10.1007/978-3-319-10999-2
[5] Kumar, A., Kumar, M., Kumar, R., Singh, R., Prasad, B., & Kumar, D.
(2019). Numerical model for the chemical adsorption of oxygen and
reducing gas molecules in presence of humidity on the surface of
semiconductor metal oxide for gas sensors applications. Materials Science
in Semiconductor Processing, 90, 236-244.
[6] J. Molina, C. Zuniga, E. Gutierrez, (2014). “Carrier Photogeneration in
Metal-Semiconductor Structures Using Thin Films of Rutile-Phase TiO2
Nanoparticles”. International Journal on Advances in Systems and
Measurements, vol 7 no 1 & 2.
[7] Comini, E. (2020). Metal oxides nanowires chemical/gas sensors: Recent
advances. Materials Today Advances, 7, 100099.
[8] Li, Y., Wang, W., Wang, F., Di, L., Yang, S., Zhu, S., ... & Yu, F. (2019).
Enhanced photocatalytic degradation of organic dyes via defect-rich TiO2
prepared by dielectric barrier discharge plasma. Nanomaterials, 9(5),
720.
[9] Długokęcka, M., Łuczak, J., Polkowska, Ż., Zaleska-Medynska, A., 2017.
The effect of microemulsion composition on the morphology of Pd
nanoparticles deposited at the surface of TiO2 and photoactivity of Pd-
TiO2. Appl. Surf. Sci. 405, 220-230.
[10] H.S. Li, Y. P. Zhang, S. Y. Wang, Q. Wu, C. H. Liu, Study on nano-
magnets supported TiO2 photocatalysts prepared by a sol–gel process in
reverse microemulsion combining with solvent-thermal technique, J.
Hazard. Mater. 169 (2009) 1045 – 1053.
[11] de Jesús Ruíz-Baltazar, Á., Reyes-López, S. Y., de Lourdes Mondragón-
Sánchez, M., Robles-Cortés, A. I., & Pérez, R. (2019). Eco-friendly
synthesis of Fe3O4 nanoparticles: evaluation of their catalytic activity in
methylene blue degradation by kinetic adsorption models. Results in
Physics, 12, 989-995.
[12] C.M. Teh, A.R. Mohamed Roles of titanium dioxide and ion-doped
titanium dioxide on photocatalytic degradation of organic pollutants
(phenolic compounds and dyes) in aqueous solutions: a review J. Alloy.
Comp., 509 (2011), pp. 1648-1660, 10.1016/j.jallcom.2010.10.181J.
Clerk Maxwell, A Treatise on Electricity and Magnetism, 3rd ed., vol. 2.
Oxford: Clarendon, 1892, pp.68–73.
[13] L.M. Schell, M. V Gallo, M. Denham, J. Ravenscroft Effects of pollution
on human growth and development: an introduction J. Physiol.
Anthropol., 25 (2006), pp. 103-112, 10.2114/jpa2.25.103.
[14] S. Anandan, Y. Ikuma, K. NiwaAn overview of semi-conductor
photocatalysis: modification of TiO2 nanomaterials Solid State Phenom.,
162 (2010), pp. 239-260, 10.4028/www.scientific.net/SSP.162.239.
[15] Boughrara, L., Zaoui, F., Sebba, F. Z., Bounaceur, B., & Kada, S. O.
(2022). New alginic acid derivatives ester for methylene blue dye
adsorption: kinetic, isotherm, thermodynamic, and mechanism study.
International Journal of Biological Macromolecules, 205, 651-663.
[16] Zulfiqar, M., Sufian, S., Bahadar, A., Lashari, N., Rabat, N. E., & Mansor,
N. (2021). Surface-fluorination of TiO2 photocatalysts for remediation of
water pollution: A review. Journal of Cleaner Production, 317, 128354.
[17] Liu, D., Liang, H., Xu, T., Bai, J., & Li, C. (2022). Construction of ternary
hollow TiO2-ZnS@ ZnO heterostructure with enhanced visible-light
photoactivity. Journal of Molecular Structure, 1248, 131493
[18] Rafienia, M., Bigham, A., & Hassanzadeh-Tabrizi, S. A. (2018).
Solvothermal synthesis of magnetic spinel ferrites. Journal of Medical
Signals and Sensors, 8(2), 108.
[19] Shen, M., Yu, Y., Fan, G., Chen, G., Tang, W., & Jia, W. (2014). The
synthesis and characterization of monodispersed chitosan-coated Fe3O4
nanoparticles via a facile one-step solvothermal process for adsorption of
bovine serum albumin. Nanoscale research letters, 9(1), 1-8.
[20] Przybylska, D., & Grzyb, T. (2020). Synthesis and up-conversion of
core/shell SrF2: Yb3+, Er3+@ SrF2: Yb3+, Nd3+ nanoparticles under
808, 975, and 1532 nm excitation wavelengths. Journal of Alloys and
Compounds, 831, 154797.
[21] T. Xin, M. Ma, H. Zhang, J. Gu, S. Wang, M. Liu, Q. Zhang, A Facile
Approach for the Synthesis of Magnetic Separable Fe3O4@TiO2, Core-
Shell Nanocomposites as Highly Recyclable Photocatalysts, Applied
Surface Science (2013), http://dx.doi.org/10.1016/j.apsusc.2013.09.108
[22] Liu, C., & Shaw, L. (2015). Nanoparticulate materials and core/shell
structures derived from wet chemistry methods. Encyclopedia of
Nanotechnology. Dordrecht: Springer Netherlands, 1-21.
[23] Dubey, R.S. (2018). Temperature-dependent phase transformation of
TiO2 nanoparticles synthesized by sol-gel method. Materials Letters,
215(), 312–317. doi:10.1016/j.matlet.2017.12.120
[24] Niu, H., Zhang, D., Zhang, S., Zhang, X., Meng, Z., & Cai, Y. (2011).
Humic acid coated Fe3O4 magnetic nanoparticles as highly efficient
Fenton-like catalyst for complete mineralization of sulfathiazole. Journal
of Hazardous Materials, 190(1-3), 559-565.
[25] Popat, Y., Orlandi, M., Patel, N., Edla, R., Bazzanella, N., Gupta, S., ... &
Miotello, A. (2019). Pulsed laser deposition of CoFe2O4/CoO
hierarchical-type nanostructured heterojuction forming a Z-scheme for
efficient spatial separation of photoinduced electron-hole pairs and highly
active surface area. Applied Surface Science, 489, 584-594.
[26] Sheikhmohammadi, A., Asgari, E., Nourmoradi, H., Fazli, M. M., &
Yeganeh, M. (2021). Ultrasound-assisted decomposition of
metronidazole by synthesized TiO2/Fe3O4 nanocatalyst: Influencing
factors and mechanisms. Journal of Environmental Chemical
Engineering, 9(5), 105844.
[27] Arenas-Hernandez, A., Zuñiga Islas, C., Moreno, M., Calleja Arriaga, W.,
Mendoza-Cervantes, J. C., Carlos, N., ... & Heredia Jiménez, A. (2022).
Study of oxygen vacancies in TiO2 nanostructures and their relationship
with photocatalytic activity. Applied Sciences, 12(7), 3690.
[28] ] S. Kumar, K.Æ. NavjeetPhotocatalytic degradation of two commercial
reactive dyes in aqueous phase using nanophotocatalysts Nanoscale Res
Lett. (2009), pp. 709-716, 10.1007/s11671-009-9300-3.
[29] Chen, Y., Yuan, T., Wang, F., Hu, J., & Tu, W. (2016). Magnetically
separable Fe3O4@ TiO2 nanospheres: preparation and photocatalytic
activity. Journal of Materials Science: Materials in Electronics.