Structural and Morphological Properties of Boron Doped V2O5 Thin Films: Highly Efficient Photocatalytic Degradation of Methyl Blue

Article abstract of DOI:10.1134/S1070427219020216

Boron doped vanadium thin films were fabricated on the micro-slide glass substrates by spray pyrolysis technique at substrate temperature of 400°C. Initially, 0.1 M vanadium(III) chloride (VCl₃) solution was prepared in ethanol: water mixture (1: 4) solvent. To prepare the boron doped vanadium oxide films as the concentrations of 2, 5, 7, 10, 20%, the suitable amount of H₃BO₃ was added in 0.1 M VCl₃ solution for each of the samples. X-Ray diffraction experiment with the produced films showed that tetragonal β-V₂O₅ phases formed. The synthesized boron-doped V₂O₅ thin films having the large surface area demonstrated the efficient catalytic properties in the photocatalytic degradation of methyl blue in water samples under Xenon light. The photocatalytic reaction efficiency was measured by recording the decrease of absorbance at 590 nm in UV-Vis absorption spectra. The methyl blue dye was degradated in approximately 30 min. The photocatalytic experiment results of the produced thin films showed that boron doping amount positively effects the degradation efficiency and reaction time.

Full text of DOI:10.1134/S1070427219020216

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2019, Vol. 92, No. 2, pp. 304−309. © Pleiades Publishing, Ltd., 2019.
VARIOUS TECHNOLOGICAL
PROCESSES
Structural and Morphological Properties of Boron Doped
V O Thin Films: Highly Efficient Photocatalytic
2
5
Degradation of Methyl Blue
a,
b
c
d,e
c
Süleyman Kerli *, Ümit Alver , Hasan Eskalen , Serhan Uruş , and Ali Kemal Soğuksu
a
Energy System Engineering Department, Kahramanmaras İstiklal University, Kahramanmaras, Turkey
*
e-mail: suleymankerli@yahoo.com
b
Department of Metallurgical and Materials Engineering, Karadeniz Technical University, Trabzon, Turkey
Department of Physics, Faculty of Science and Letter, Kahramanmaras Sutcu Imam, Turkey
Chemistry Department, Faculty of Science and Letters, Kahramanmaras¸ Sutcu Imam University, Turkey
c
d
e
Research and Development Centre for University Industry Public Relations (ÜSKİM),
Kahramanmaraş Sütçü İmam University, 46100 Kahramanmaraş, Turkey
Received January 30, 2019; revised February 6, 2019; accepted February 6, 2019
Abstract—Boron doped vanadium thin films were fabricated on the micro-slide glass substrates by spray pyrolysis
technique at substrate temperature of 400°C. Initially, 0.1 M vanadium(III) chloride (VCl ) solution was prepared
3
in ethanol : water mixture (1 : 4) solvent. To prepare the boron doped vanadium oxide films as the concentrations
of 2, 5, 7, 10, 20%, the suitable amount of H BO was added in 0.1 M VCl solution for each of the samples.
3
3
3
X-Ray diffraction experiment with the produced films showed that tetragonal β-V O phases formed. The syn-
2
5
thesized boron-doped V O thin films having the large surface area demonstrated the efficient catalytic properties
2
5
in the photocatalytic degradation of methyl blue in water samples under Xenon light. The photocatalytic reaction
efficiency was measured by recording the decrease of absorbance at 590 nm in UV-Vis absorption spectra. The
methyl blue dye was degradated in approximately 30 min. The photocatalytic experiment results of the produced
thin films showed that boron doping amount positively effects the degradation efficiency and reaction time.
Keywords: V O , spraying pyrolysis, boron, photocatalytic materials, methyl blue
2
5
DOI: 10.1134/S1070427219020216
INTRODUCTION
dealing with wastewater pollutions [5, 6]. Among the
available photocatalytic materials, TiO nanoparticles
2
Dyes bring color to our world and save us from the
monotony of black and white, but some of them have
polluted fresh water resources and cause waste waters
pollutions. Moreover, it has been proven that some of
dyes substances also cause cancer. Dyes are needed in
medicine, textile, food and many other sectors and at
the present time, the amount of use of these substances
is increasing rapidly. For these reasons, the pollution
caused by dye substances is tried to be eliminated by
different methods [1–4]. Although there are various
different physical, chemical and biological treatment
methods exist, photocatalytic treatment is known as one
of the most simple and promising green technology for
have been examined deeply due to its high efficiency,
low cost, non-toxicity and high stability [7–12]. However,
its low quantum efficiency and wide band gap limit its
application in visible light region [13–15]. So, various
different materials, other than TiO2 nanoparticles, were
used as photocatalytic materials. Zinc oxide (ZnO) [16–
1
9], cadmium sulphide (CdS) [20, 21], tungsten oxide/
tungsten-trioxide (WO-WO /WO ) [22-24] were some
2
3
other examples [25].
Vanadium pentoxide (V O ) is an ntype semiconductor
2
5
and it is an important transition metal oxide, an application
of which is ranging from lithium-ion battery to sensors
mainly because of its high-energy density, low cost, and
3
04

STRUCTURAL AND MORPHOLOGICAL PROPERTIES OF BORON DOPED V O THIN FILMS
305
2
5
easy synthesis [26–28]. They have also been used in
photocatalyst due to their narrow band gap ranging from
10, 20% using appropriate amounts of boric acid (H BO )
3 3
for boron source. The spray nozzle-substrate distance was
2
.2 to 2.8 eV [29]. However photo and electrochemical
adjusted to 35 cm. The volumetric spray flow rate was set
–
1
corrosion of V O limits its usability in photocatalyst
to be about 0.25 mL s . Firstly, vanadium (III) chloride
solution was sprayed onto the cleaned glass set at 400°C
in order to coat with the boron doped–V O thin films on
2
5
[30]. Because of this reason V O generally doped with
2 5
different elements or coupled with another material
to limit its corrosion and enhance its some important
properties. In literature, the degradation of phenol
and its derivatives by using V O was evaluated [31].
2
5
the glass surface using airbrush method.After then, these
films were annealed at 550°C for 2 h.
2
5
Photocatalytic degradation of methyl blue us-
Photocatalytic activity for degrading rhodamine B of
hollow V O microsphere had studied by Fei et al. [32].
ing boron doped V O thin films. Melthy Blue
2
5
(C H N Na O S ) was used as a dye in the photocata-
2
5
37 27
3
2
9 3
Moreover V O [33], TiO –V O [34], graphene–V O
lytic degradation trials in water samples. 300 W Xenon
lamp at a distance 20 cm from sample was used as a light
source in the photocatalytic degradation tests. The deg-
radation efficiencies of the boron doped vanadium thin
films on the glass were analysed by using UV-Vis spec-
troscopy during the determined period of time. Firstly,
control sample was scanned in the range of 200–800 nm
with an 1 nm interval. Maximum absorption for methyl
blue (MB) in water was evaluated as 590 nm. The scans of
the water samples containing adsorbed dye were recorded
between 400–800 nm, absorbance values were collected
at 590 nm for each samples. Methyl blue dye solutions
2
5
2
2
5
2
5
[
35], SnO–V O [29], CsV O [36], Co–V O [37]
2 5 3 8 2 5
and PANI–V O [38] systems were investigated. The
2
5
photocatalytic activity of pure V O was increased with
2
5
addition to different metal oxide M O –V O (M: Ti, Zn,
x
y
2
5
Zr, Bi) has reported [39].
In the present study, V O thin films obtained by using
2
5
simple spray pyrolysis technique. The effect of boron
doping concentration on structural and morphological
properties of V O thin films are studied. Photocatalytic
2
5
activities of the systematically produced boron doped
vanadium pentoxide thin films are also examined deeply.
–
1
[
5 ppm (mg L )] were prepared for each degradation
tests. The thin film immersed into 10 mL prepared MB
solution. The 2 mL samples were taken and measured
in the ranging from 400–800 nm at every 5 min starting
from 0 min to 40 min. Degradation efficiency (DE) were
calculated using the equation:
EXPERIMENTAL
General. FTIR spectra were obtained using KBr
pellets with Perkin-Elmer Spectrum 400 system in
−
1
the range 4000–400 cm . X-ray diffraction (XRD)
patterns were recorded on the PANalytical XPert Pro.
X-ray diffraction (XRD) with CuK radiation was
α
employed to investigate the structural evolution and
the phase identification. The morphology of the powder
particles was characterized by SEM with a using
Zeiss EVO 10LS scanning electron microscope at an
acceleration voltage of 10 kV after the specimen was
coated with a vacuum, attached with Bruker Quantax
EDS. Photoluminescence spectra were measured using
Perkin Elmer equipment. The photocatalytic degradation
efficiencies were measured using a Shimadzu UV-1800
ultraviolet-visible spectrophotometer. Luzchem’s 300W
Xenon photoreactor was used as a light source in the
photocatalytic experiments.
where C represents the initial concentration, C represents
concentration at the sampling time.
0
t
RESULTS AND DISCUSSION
Characterization. The surface morphology of the thin
film used as a photocatalytic source is very important. The
total surface area of a photocatalyst greatly affects the
degradation mechanism in the reaction. SEM images of
the pure and boron doped vanadium(V) oxide thin films
are given in Fig. 1. It has also been observed that the
synthesized films have a very dense structure and also
adhere homogeneously on to the glass surface.
Obtaining boron doped V O thin films on glass.
2
5
Appropriate amount of VCl was dissolved in 40 mL
When the microstructure is examined, it can be seen
that the surface of the thin films have the rod structures.
This morphological structure of the thin films increases
the total effective surface area. SEM images of the the
3
distilled water and 10 mL ethanol mixture in order to
obtain 0.1 M vanadium(III) chloride solution. The boron
concentration in the thin films were adjusted as 2, 5, 7,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 92 No. 2 2019

306
SÜLEYMAN KERLI et al.
on glass substrates in a 0.1 M solution without additives
and with 2, 5, 7, 10, 20%. For undoped and boron doped
vanadium oxide thin films, a dominant peak (200)* was
observed. XRD pattern indicate that the structures of the
obtained films have tetragonal structures with the β-V O5
2
phase (JPDS-45 1074). This result is consistent with the
literature [40, 41]. As seen from the figure, other peaks
were negligibly small. With the effect of boron doping, it
is seen that the intensity of the (200)* peak is also slightly
reduced. It is thought to cause deterioration in the structure
of the vanadium oxide by boron doping. Furthermore, no
peaks of boron or its compounds were observed.
1
μm
2
μm
Photocatalytic degradation of methyl blue. The
time and amount-dependent photocatalytic degradation
of methyl blue were investigated under the xenon light at
room temperature. The glass samples having the different
percentages of boron doped-V O thin films were added
1
μm
2
μm
2
5
–
1
in methyl blue samples in water (5 mg L ) and stirred
for 40 min. The samples were collected at 5, 10, 15, 20,
3
0, and 40 min for each trial and scanned in UV-Vis
spectrophotometer in the range of 400–800 nm. The
degradations of methyl blue in the water samples were
determined by recording the decrease in absorbance at
2
μm
2 μm
5
90 nm in UV–Vis absorption spectra.
Fig. 1. SEM images of pure and boron-doped vanadium(V)
oxide thin films.
UV-Vis absorbance spectra shows the degradation
of methyl blue in the range of 400–800 nm (Fig. 4).
The time-dependent degradation percentages are
given in Fig. 5. The possible photocatalytic reaction
mechanism is schematized in Fig. 6. According to the
probable mechanism of the heterogeneous photocatalytic
degradation of methyl blue under the xenon light
irradiation in solar simulator we can suppose that, firstly,
boron doped V O thin films fabricated by the sprayed
2
5
pyrolsis of vanadium(III) chloride (VCl ) solution are
3
shown in Fig. 2. The thickness of the films was measured
as approximately 1 μm.
Figure 3 shows the X-ray diffraction patterns of boron
doped vanadium(V) oxide thin films deposited at 400°C
Fig. 2. (Color online) Cross-sectional thicknesses of
thin films.
Fig. 3. (Color online) XRD images of undoped and boron
doped vanadium oxide thin films.
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STRUCTURAL AND MORPHOLOGICAL PROPERTIES OF BORON DOPED V O THIN FILMS
307
2
5
,
nm
, nm
,
nm
, nm
Fig. 4. (Color online) Visible spectra of photocatalytic degradation of methyl blue. (a) Undoped, (b) 2% , (c) 10% , (d) 20%
boron-doped V O thin films.
2
5
the electrons in the valence band in the thin film can be
excited to the conduction band and the positive holes
left in the valance band on the surface of the material.
Photo-generated electrons in conduction band react with
•2−
acceptors and a radical anion O formed. In addition, the
boron doped V O structure gets an electron for positive
2
5
•
holes from water and produced OH radicals. During
this step, methyl blue having negative sulfonate groups
electrostatically attracts to the positively charged the
surface of the thin film. Finally, the dye is oxidated by the
radical moieties to carbon dioxide and water [42, 43]. It
can be said that 20% of boron doped V O thin film is the
2
5
best catalyst in the photocatalytic degradation of methyl
blue amount compared with the all others. In other words,
as the sample boron content increases, photocatalytic
activity also increases.
Fig. 5. (Color online) The photocatalytic degradation
of MB in the presence of boron-doped V O thin films.
2
5
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SÜLEYMAN KERLI et al.
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CO +
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