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Journal of Taibah University for Science 9 (2015) 508–512

Short Communication

Synthesis, characterization and photocatalytic activity of ␣-Bi2O3

nanoparticles
Hicham Oudghiri-Hassani a,c , Souad Rakass a , Fahd T. Al Wadaani a ,
Khalaf J. Al-ghamdi a , Ahmed Omer a , Mouslim Messali a , Mostafa Abboudi a,b,∗
a Taibah University, College of Science, Chemistry Department, Almadinah 30002, Saudi Arabia
b Université Abdelmalek Essadi, Faculté des Sciences et Techniques de Tanger, Département de Génie Chimique, B.P. 416 Tangier, Morocco
c Cégep de Drummondville, 960 rue Saint-Georges, Drummondville J2C 6A2, Québec, Canada

Available online 7 March 2015

Abstract
Monoclinic bismuth oxide ␣-Bi2 O3 nanoparticles were synthesized starting from a mixture of oxalate complexes of bismuth
Bi(C2 O4 )OH and Bi2 (C2 O4 )3 ·xH2 O obtained by a direct solid-state reaction between a nitrate salt of bismuth and oxalic acid.
The starting oxalate mixture precursors were studied by thermal gravimetric analysis (TGA) and characterized by Fourier trans-
form infrared spectroscopy (FTIR). After heat treatment of the oxalate precursors, the obtained oxide ␣-Bi2 O3 was characterized
by X-ray diffraction (XRD) and transmission electron microscopy (TEM). These ␣-Bi2 O3 nanoparticles show low efficiency in
photodegradation under UV light irradiation of the dye rhodamine B.
© 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: ␣-Bi2 O3 ; Photocatalysis; Nanoparticles

1. Introduction (2–3.96 eV), a high refractive index and photolu-

Bismuth-based semiconductors are receiving
increased attention as photocatalysts that degrade
organic pollutants under UV–vis light [1–8]. In par-
ticular, bismuth oxide (Bi2 O3 ) [9–11] has a variety
of desirable properties, including a high band gap
∗ Corresponding author at: Taibah University, College of Science,
Chemistry Department, Almadinah 30002, Saudi Arabia.
Tel.: +966 541123908; fax: +212 39393953.
E-mail address: abboudi14@hotmail.com (M. Abboudi).
Peer review under responsibility of Taibah University.
minescence, and this oxide is implicated in a range
of fields such as solid oxide fuel cells, gas sensors,
high temperature superconductor materials, functional
ceramics and catalysis [2,3]. As a consequence of the
high band gap of bismuth oxide, this material produces
electron–hole pairs when subjected to a beam of photons
with equal or greater energy, generating free radicals
that undergo secondary reactions [5]. Bismuth oxide
exhibits well-known polymorphism with five modifi-
cations: ␣, ␤, ␥, ␦, and ␻-Bi2 O3 . Monoclinic ␣-Bi2 O3
and cubic ␦-Bi2 O3 are low- and high-temperature stable
forms, respectively [12,3].
A growing number of methods are available for
the preparation of Bi2 O3 , including precipitation, flame
spray pyrolysis, sol–gel methods [2], atomization, mag-
netron sputtering deposition [5] and low-temperature

http://dx.doi.org/10.1016/j.jtusci.2015.01.009
1658-3655 © 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 H. Oudghiri-Hassani et al. / Journal of Taibah University for Science 9 (2015) 508–512
electrodeposition [3]. Recently, Chen et al. prepared
mesh-like bismuth oxide single crystalline nanoflakes
(monoclinic ␣-Bi2 O3 and tetragonal ␤-Bi2 O3 ) via a bis-
muth oxalate precursor and tested the photocatalytic
activity of these nanoflakes using the photodegrada-
tion of rhodamine B under visible light irradiation. The
study showed that the photocatalytic activity of bismuth
oxide was related to its crystalline phase and morphol-
ogy [13]. Other studies have shown that bismuth oxide
films annealed at 550 ◦ C (containing a higher propor-
tion of the tetragonal phase) have high photocatalytic
activity in the photodegradation of rhodamine B [4]. In
addition, degradation experiments using rhodamine 6G
and bismuth oxide nanowires produced by magnetron
sputtering deposition report a direct relationship between
nanowire density and photocatalytic activity [5].
In this work, we report a photodegradation study
of rhodamine B in aqueous solution using a ␣-
Bi2 O3 catalyst prepared via a solid-state reaction of
Bi(NO3 )3 ·5H2 O and oxalic acid. The catalysts are
characterized by a combination of thermogravimetric
analysis (TGA), X-ray diffraction (XRD), IR spec-
troscopy and transmission electron microscopy (TEM).
2. Experimental
2.1. Reagents
Bismuth (III) nitrate hexahydrate [Bi(NO3 )3 ·6H2 O]
and oxalic acid dihydrate [H2 C2 O4 ·2H2 O] were pur-
chased from Sigma–Aldrich and used as received.
2.2. Materials characterization
The thermal gravimetric analysis study (TGA) was
conducted on a SDT Q 600 analyser. Fourier transform
infrared (FTIR) spectroscopy analysis was conducted
on a Shimadzu 8400S instrument using standard KBr
pellets. Powder X-ray diffraction (XRD) patterns to
determine the phase purity and the structure of the end
product were performed on an XRD P-6000-Shimadzu
X-ray diffractometer (40 kV/20 mA) in a conventional
θ–2θ reflection geometry and using Cu K␣ radiation
´ The Scherrer equation was used to esti-
(λ = 1.5406 Å).
mate the particles size from the XRD pattern of the as
prepared nanoparticles:
kλ
DXRD =
β cos θ
where DXRD is the average particle diameter, λ is the
used wavelength of Cu k␣, k is equal to 0.9, β is the full-
width at half-maximum (FWHM) of the diffraction peak
509
and θ is the diffraction angle. For transmission electron
microscopy (TEM), a JEOL 1400 microscope was used
to study the morphology and particle size of the prepared
bismuth oxide.
2.3. Photocatalytic experiments
The photocatalytic experiments were carried out in a
quartz cell cooled with cycled water. In a typical pho-
tocatalytic experiment, 0.1 g of Bi2 O3 was added to
250 ml of an aqueous solution of rhodamine B (rhodB) in
the concentration 10 mg/L. The solution was maintained
under magnetic stirring in darkness for one hour to reach
rhodB adsorption–desorption equilibrium. The solution
with the suspended nano-photocatalyst was irradiated by
UV light from a 450 W Ace-Hanovia medium-pressure
quartz mercury vapour arc lamp with a wavelength peak
centred at 366 nm, and periodically, 3 ml of the solution
was taken with a syringe equipped with a micro filter and
analyzed in a Varian Cary 100 UV-visible spectropho-
tometer at a wavelength of 554 nm, corresponding to the
highest absorbance by rhodB.
2.4. Synthesis of materials
In a typical procedure, a mixture of bismuth nitrate
and oxalic acid in the molar ratio 1:3 was well mixed
and ground in an agate mortar and pestle. Then, the mix-
ture was placed in a large ceramic crucible and heated
on a hot plate at 160 ◦ C. An oxido-reduction reaction
occurred in which the nitrate anions were reduced to
nitrogen monoxide (NO), which reacted with oxygen
to form nitrogen dioxide (NO2 ) and produced its char-
acteristic brown-red colour [14–16]. At the end of this
reaction, we obtained an oxalate precursor. This pre-
cursor is then heated in the range of 280–500 ◦ C in a
tubular furnace open from both sides where the precursor
is decomposed thermally to form the final oxide.
3. Results and discussion
The obtained precursor was characterized by infrared
spectroscopy FTIR. Fig. 1 shows the obtained infrared
spectra. The coordinated oxalate group has absorption
bands at 1589, 1454, 1385, and 794 cm−1 , confirming
the presence of a chelating oxalate group in the com-
plex as previously studied by Rivenet et al. [17]. These
bands are assigned to C O stretching, C O stretching,
C C stretching and O C O in plane bending vibrations
[18,19]. A band at 1628 cm−1 corresponding to δ(H2 O)
is also observed, and this bland is clarified by deconvo-
lution of the large peak at 1589 cm−1 [20]. A broad band
510 H. Oudghiri-Hassani et al. / Journal of Taibah University for Science 9 (2015) 508–512

120

100

1304
1454
1385
Transmittance (%)

3459

794
80

60
1628

40
1589

20
36003200 1800 1600 1400 1200 1000 800 600
-1
Wavenumber (cm )

Fig. 1. Infrared spectrum of the complex precursor.

100

95
Temperature difference ( C)
Mass loss weight (%)

90

85
Fig. 3. XRD patterns of (a) the as-prepared bismuth oxide ␣-Bi2 O3
80 at 500 ◦ C and (b) the as-prepared bismuth oxide ␣-Bi2 O3 at different
temperatures.
75
o

70 heating at 160 ◦ C on the hot plate. Thus, the unique

65
source of the impurity should be the formation of differ-
0 50 100 150 200 250 300 350 400 450 500 550 600 ent complexes. Conversely, the thermal decomposition
of bismuth oxalate Bi2 (C2 O4 )3 ·xH2 O did not show any
o
Temperature ( C)
final small weight loss at 300 ◦ C that is characteris-
Fig. 2. Thermal gravimetric curves of the as-prepared precursors.
tic of an existing hydroxyl bismuth [17]. This result
permits us to confirm the existence of the mixture of
at 3459 cm−1 , attributed to O H vibration, is observed Bi2 (C2 O4 )3 ·xH2 O and Bi(C2 O4 )OH.
indicating the presence of the water molecule and the The XRD pattern of the obtained oxide after decom-
hydroxyl group. This result is confirmed by the thermal position at 500 ◦ C is shown in Fig. 3a. All of the peaks are
analysis study, which reproduces the results obtained by assigned and indexed in accordance with the J.C.P.D.S.
Rivenet et al. [17], where the bismuth oxalate hydrox- file #41-1449. The observed oxide is of the ␣-Bi2 O3
ide (Bi(C2 O4 )OH) is obtained. The hydroxyl OH group variety, which crystallizes in the monoclinic system
appears at a lower wave number because this group is with the linear parameters a = 5.8499(3), b = 8.1698(4),
bonded to two bismuth atoms in the molecular structure, and c = 7.5123(3). The angular parameters are α = 90◦ ,
which explains the observed shift. In Fig. 2, the ther- β = 112.988(4)◦ and γ = 90◦ . This result is in agreement
mal gravimetric curve shows a weight loss of 34% (the with the work of Rivenet et al. [17], which discusses how
theoretical loss is 25%). A small mass loss is observed the different allotropic varieties are obtained depend-
at 300 ◦ C (2.5%), as is observed for bismuth hydroxy ing on the temperature range used for the synthesis of
oxalate. The 9% difference between the theoretical and bismuth oxide Bi2 O3 . To detect the phase transition,
the observed of mass loss values is due to the exis- several decompositions of the precursor were conducted
tence of hydrated bismuth oxalates Bi2 (C2 O4 )3 ·xH2 O at different temperatures. The comparison of the XRD
formed at the same time as an impurity. Neither hydra- patterns obtained for these different compounds did not
tion water nor an excess of oxalic acid can cause this show any differences, as the same pattern is observed for
difference because hydration water would have evapo- different temperatures ranging from 280 to 500 ◦ C, as is
rated and oxalic acid would have sublimed during prior shown in Fig. 3b.
 H. Oudghiri-Hassani et al. / Journal of Taibah University for Science 9 (2015) 508–512 511

Fig. 4. TEM micrographs of the as-prepared bismuth oxide at (a) 380 ◦ C and (b) 400 ◦ C.

6.0 absence of the photocatalyst, the degradation reaction

5.5 takes 16 min. In the presence of the ␣-Bi2 O3 photo-
5.0 catalyst prepared at 500 ◦ C, the pollutant is completely
4.5 degraded after 12 min. From these curves, assuming that
4.0 we have a first-order reaction, the rate constants of the
3.5
-Ln(C/C0)

reactions with and without the photocatalyst were 0.73

3.0
and 0.39 min−1 , respectively.
2.5
2.0
1.5 4. Conclusion
Without Catalyst
1.0 With Bi2O3
0.5 Nanoparticles of the ␣ variety of bismuth oxide Bi2 O3
0.0 were successfully prepared, characterized and tested in
0 1 2 3 4 5 6 7 8 9 10 11
the photodegradation of rhodamine B. The synthesis
Time (min)
of this oxide is via a precursor, a mixture of oxalate
Fig. 5. Plot of ln(C/C0 ) versus the reaction time for the photodegrada- complexes Bi(C2 O4 )OH and Bi2 (C2 O4 )3 ·xH2 O. The ␣-
tion of rhodamine B. The variation of the absorbance is shown in the Bi2 O3 crystallization in the monoclinic structure begins
inset. at 280 ◦ C. The size of the obtained particles was in the
range of 150 nm, as confirmed from the Debye Scher-
Crystallite size estimation was obtained using the
rer equation and observed with transmission electron
Debye-Scherrer formula applied to the separated peak
microscopy. These particles are efficient in the degra-
(0 0 2), and this technique yields values varying from
dation of a standard pollutant, rhodamine B, under UV
120 to 170 nm with the temperature of the heat treat-
radiation. An interesting topic for future work is to mod-
ment ranging from 280 to 500 ◦ C. A comparable value is
ify the Bi2 O3 oxide by the inclusion of elements to
observed in the TEM micrographs for samples prepared
enhance its efficiency in the photodegradation of pol-
at 380 and 400 ◦ C shown in Fig. 4a and b, respectively,
lutants.
which is approximately 140 nm.
However, these micrographs show an agglomerated
powder where smaller, very agglomerated nanocrystal- Acknowledgement
lites are forming approximately 140-nm particles. Fig. 5
depicts the photocatalytic performance results. The con- This work was supported financially by the Research
centration of RhodB vs time is decreasing, indicating Deanship of Taibah University under the grant no
the photocatalytic activity of the photocatalyst. In the (433/795).
512 H. Oudghiri-Hassani et al. / Journal of Taibah University for Science 9 (2015) 508–512
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