INTRODUCTION

Bismuth oxide (Bi2O3) is known for its optical and electrical properties such as dielectric
permittivity, refractive index, large energy band gap, photoconductivity and photoluminescence
[1]. Due to these properties, Bi2O3 play a vital role in the various fields such as optoelectronics,
gas sensors and optical coatings. Bi2O3 has five polymorphs i.e. α- Bi2O3 (monoclinic), β- Bi2O3
(tetragonal), γ- Bi2O3 (BCC), δ- Bi2O3 (Cubic), and ε- Bi2O3(triclinic) [2]. Among these phase, α-
Bi2O3 and δ- Bi2O3 are the stable phases, while rest other phases are metastable. Furthermore, δ-
Bi2O3 exists in the form of face centered cubic crystal structure [3]. The δ- Bi 2O3 is known for its
high conductivity among all other phases, which make it best material in solid oxide fuel cell.
Although its application as oxide ion conductor is limited, because it is only stable in the narrow
temperature range.
Methyl orange, with molecular structure shown in Fig. 1, is a dye that is believed to be
mutagenic [Ref]. It slightly dissolves in water. Its color changes with pH, from yellow (at pH
higher than 4.4) to red (at lower pH values), and therefore it is used as an indicator [Ref]. Methyl
orange is also used as a dye in textile industry [Ref]. It is an example of the widely spread azo
dies [Ref], which are resistant to complete biodegradation [36]. For these reasons, methyl orange
is commonly used as a model dye to study in environmental cleanup, and this work is no
exception.

2.5

2.0
Absorbance

1.5

1.0

0.5

0.0
200 300 400 500 600
Wavelength (nm)

Molecular Structure and UV-Vis absorption spectrum

of methyl orange
2. EXPERIMENTAL SECTION
2.1 Reagents and Chemicals.
Picolonic acids, ammonium bismuth citrate, oleic acid, dimethyl amine, Methyl orange,
concentrated nitric acid were purchased from Sigma Aldrich. The chemical reagents have not
been further purified and ultrapure water is employed to prepare various solutions. .
2.2 Syntheses.
(A) Synthesis of bismuth piconilate (RA-1)
The synthesis of bismuth picnolate [Bi(2-O2C-C5H4N)3]n (RA 1) was carried out by previously
reported method [Ref]. Picolonic acid (0.074 g, 0.6 mmol) and ammonium bismuth citrate
(0.187g, o.1 mmol) were dissolved separately in distilled water (15 mL) each to obtain clear
solution. The solution of ammonium bismuth citrate was added drop wise into the solution of
picolonic acid with stirring at room temperature for 30 minutes. The crystalline compound were
filtered, washed three times with distilled water to remove unreacted precursors and dried.
(Yield: 62%), M.p.: ˃ 320 oC. Mol. formula: [Bi(2-O2C-C5H4N)3]n. Mol. wt = 1875. IR (4000-
400cm-1): 3075 ν(CH), 1651 ν(OCO)asym, 1332 ν(OCO)sym. 472 ν(Bi-O) EI-MS, m/z (%):
(B) Synthesis of nanoparticals of bismuth oxide
To synthesize nanoparticals of bismuth oxide (Bi2O3) RA-2 from the complex (RA-1), the hot
injection method was used. In this method 200 mg of bismuth picnolate (RA-1) was dispersed in
5 mL of diethyl amine and injected it into 10 mL oleic acid. The temperature of the oleic acid
was 80 °C prior to the addition of the solution. The temperature was increased up to 180 °C. The
reaction mixture was refluxed for 90 minutes and a brown solution was formed. The reaction
mixture was cooled to room temperature and 20 mL methanol was added for precipitation. The
mixture was centrifuge and a light yellow precipitate was obtained. Then, the obtained
precipitate was washed repeatedly with deionized water and then filtered. The precipitate was
dried in hot air oven at 100 °C for 1 h.
2.3 Characterizations

The melting points of the synthesized compounds were determined using M-560 (BUCHI)
electrothermal melting point apparatus. FT-IR spectra were recorded cm -1 on a incollet IS-10
(Thermo Scientific) spectrophotometer in the range of 4000-400. KBr and solid substrate were
used for mid and far IR spectroscopy respectively. Elemental analysis was done using LECO
Ultimate Analyzer 628 Series apparatus. The electron impact mass spectra (EI-MS) were
recorded on MAT 312 mass spectrometer connected to a MASPEEC system (msw/A091).
PXRD…. Thermal stability was tested by Shimadzu DTG-60/DTG-60A. Field emission
scanning electron microscopy (FE-SEM) was performed using a Philips XL30 FEG SEM.
Energy dispersive X-ray (EDX) spectroscopy was performed using a DX4 detector. All samples
were carbon coated using the Edwards coating system E306A prior to SEM analysis.
2.4 Photocatalytic Test

2.1. XRD Study

The XRD analysis of control and treated Bi2O3 was accomplished on Phillips, Holland PW 1710
X-ray diffractometer system. The X-ray of wavelength 1.54056×10-10 m was used. From the
XRD diffractogram, the peak intensity counts, d value (A), full width half maximum (FWHM)
(θ°), relative intensity (%) values were obtained. The PowderX software was used to compute
the lattice parameter and unit cell volume of the control and treated Bi2O3 samples. The
crystallite size (D) was calculated by using Scherrer equation as following:

D = kλ/(bCosθ)
Here, b is full width half maximum (FWHM) of XRD peaks,
k=0.94, and λ =1.54056 A.
The percentage change in crystallite size was calculated using following formula:
% change in crystallite size = [(Dt-Dc)/Dc] ×100
Where, Dc and Dt are crystallite size of control and treated powder samples respectively.
2.2. Thermal Analysis
The thermal analysis of Bi2O3 powder was done using. TGA-DTG. For that, Mettler Toledo
simultaneous TGA-DTG instrument was used. The samples were heated from room temperature
to 900oC with a heating rate of 10oC/min under nitrogen atmosphere.

Results and discussion

Functional group analysis (FT-IR)
FTIR analysis has been recorded for the synthesized complex (RA-1) in the range of 400-4000
cm-1 and the result is shown in Fig .In the FTIR spectrum of bismuth piconilate complex 3075
ν(CH), 1651 ν(OCO)asym, 1332 ν(OCO)sym. 472 ν(Bi-O) α-Bi2O3, the peak at 540 cm-1 is
assigned to the Bi-O-Bi stretching vibration and the peak around 620 cm-1can be attributed to
the Bi-O stretching vibration of non-bonding oxygen of the distorted Bi-O
Thermogravimetric analysis (TGA/DSC)

Thermogravimetric analysis was used to determine the decomposition temperature of the

synthesized complexes bismuth picnolate (RA-1). Figure 2 (a) represents the TGA and DSC
curves of complex RA1 within the temperature range of 40-600 °C. TGA of the complex RA-1
showed close to single step decomposition. The major weight loss was occurred in the
temperature range of 150-450 °C with an approximate weight loss of 75%. This weight loss
corresponds to the decomposition of the organic moiety in the complex and giving residue of
Bi2O3. The decomposition start point is 290 °C and end point is 470 °C.

FIGURE TGA

3.1. XRD Study

The XRD is a quantitative and non-destructive technique, which have been widely used to study
the crystal structure parameters of a compound. Figure 1 shows the XRD diffractogram of
control and treated Bi2O3 samples. It can be observed that the control sample showed the
crystalline peaks at Bragg angle (2θ) 27.08°, 27.68°, 32.70°, 32.93°, 34.70°,
37.24°, 46.03°, and 52.08°. However, the treated sample showed the peaks at Bragg’s angle
27.17°, 27.79°, 32.82°,
33.03°, 34.84°, 37.39°, 46.09°, and 52.17°. It indicated that the XRD peaks were shifted toward
higher angles in the treated sample as compared to control, after biofield energy
treatment. It is reported that the reduction in lattice parameter and unit cell volume lead to
shifting of the XRD peaks toward higher angles [17]. The XRD data of the control and treated
samples were analyzed using PowderX software. The crystal structure parameters such as lattice
parameter, unit cell volume, density, and molecular weight were computed and
presented in Table 1. The data showed that the lattice parameter of treated sample was decreased
from 5.6596 A to 5.6487A. Kumar et al. reported that the XRD peaks can shift to the higher side
if larger radii atoms are replaced by smaller radii atoms [18]. Nevertheless the unit cell volume
of treated Bi2O3 powder was decreased by 0.58% as compared to control. Thus, the decrease in
lattice parameter and unit cell volume were supported by shifting of XRD peaks toward higher
angles. Hence, based on shifting of XRD peaks and reduction in the lattice parameter, it is
assumed that the biofield treatment might induce compressive stress in treated Bi2O3 powder
and this might be responsible for the internal strain in treated Bi2O3. Ekhelikar et al. reported
that the lattice parameter of Bi2O3 unit cell was reduced from 5.560 A to 5.540 A when the
doping composition of Y2O3 was increased from 10 to 20% in Bi2O3 and increased the stability
of δ- Bi2O3 [19]. Thus, it is

A. Bismith oxide (Bi2O3) nanoparticals

Hot injection method was used to synthesize Bismith oxide (Bi2O3) nanoparticles. The
PXRD spectra of Bi2O3 is presented in Figure. The Bi2O3 nanoparticles formed by using
complex RA-1 by hot injection method belongs to the monoclinic crystalline phase having
space group P21/c number 14. The diffracted peaks are small in intensity, but broad
indicating the small size of crystallites. The peaks at 2 θ° = 25.14, 27.36, 33.62, 34.09, 37.79,
42.09, 45.92, 52.88, 56.03 and 62.40 can be indexed to (021), (121), (122), (202), (113),
(123), (223), (322), (323) and (104) plans, matched well with ICDD: 00-027-0053.

The SEM images of the (Bi2O3) produced by hot injection method from complex RA-1
are shown in Figure 3.41 (a). It can be observed that the formation of nano sheets having
diameter 41 nm ± 6 was appeared.
Figure : PXRD spectra of Bi2O3 nanoparticles formed using complex RA-1
Figure 3.41: SEM images of Bi2O3 nanoparticles using complex RA-1 (a) 5 µm (b) 2 µm (c) 1
µm

Effect of Methyl orange Concentration on photocatalytic process

In the useful wastewaters, the contaminants concentration may vary tremendously and deception
a threat to photocatalytic activity. As presented in Figure 7a, a set of initial concentrations of
methyl orange azo dye from 5 to 20 mg L -1 were selected to investigate the influence of
pollutant concentrations on photocatalytic activity. Results illustrate that the photodegradation
efficiency decreases (from 100% to 75%) accordingly when MO concentrations increase from 5
to 20 mg L-1. The first one reason for this phenomenon is that higher the concentrations of
methyl orange azo dye prevent photon from entering dye solution due to the increase of the
pathway length and reducing the number of photons on the catalyst surface[Ref]. For another,
there are some intermediates producing in the photocatalytic process and these intermediates
competed with methyl orange for limited reactive sites [Ref ]. The competition between
intermediates and azo dye will soar with the increase of dye concentrations because more and
more intermediates produce in high the concentration of MO. Therefore, in order to achieve
better photodegradation efficiency, a dilution process should be needed to conduct to cut down
the high contaminant concentrations in the practical application. And 5 mg L -1 of mehyl orange
azo dye is chosen as the optimal initial concentration in whole experiment.

Effect of pH on Photocatalytic process

Degradation efficiency of methyl orange dye for Bi 2O3 with different initial pH value of
dye solution is exhibited in Figure . It is found that the photocatalytic activity was highly pH
dependent and degradation efficiency decreases when initial pH increases, showing the highest
degradation for the lowest pH values as and the efficiency has a dramatically reduced when
initial pH increases from 3 to 11 depicted in Figure .which indicates that neutral or alkaline
environment exhibits negative influence on photocatalytic process. The other reason for this
phenomenon may be due to special structure of the MO molecule in acid and basic environment
(insets of fig.). As the degradation of the dye solution at neutral pH and basic pH was very low
so it is decided that we evaluate the photocatalytic activity of the nanoparticles under acidic
condition (pH=3). The synthesized Bi2O3 has performed good photocatalytic efficiency and
achieved more than 85% of discolorationof the dye after 35min as it can be seen in the change of
the absorption spectrum of the dye (Fig)

HCl is an important influential factor to the synthesis processes of BiOCl samples.

Adding HCl not only provides Cl− required for reaction but also decreases the pH value of the
reaction solution to control the hydrolysis rate. When the HCl concentration is lower, it may
quickly form precipitates that have influence on particle-size distribution; when the HCl
concentration is higher, it goes against to produce BiOCl.

To study the influence of pH values on the photocatalytic activity of Bi 2O3, the MO

degradation rates under different acidic and basic media were tested, and the results are shown
in Fig. showed the best photocatalytic activity for MO and the degradation efficiency could reach
99.5% after 2.5 h reaction. Thus, the optimum HCl concentration in preparing the BiOCl catalyst
is 1.5 mol/L.
Effect of Temperature on Photocatalytic process

To investigate the influence of temperature on the photocatalytic activity of the prepared

Bi2O3 catalyst under xenon light irradiation is shown in Fig. The experimental conditions are
C0=5mg/L, V=50 mL, m(Bi2O3)=1.0 mg/L, and pH 8. It can be seen that the photocatalytic
activities of Bi2O3 on the MO solution decrease with the increase of heat treatment temperature
and that Bi2O3 catalyst with the temperatures of 80 and 300°C exhibit the best and the worst
photocatalytic activities, respectively. Elevating temperature promotes the crystallite growth but
deteriorates its photocatalytic performance, because the temperature can influence the
morphology and compositions of Bi2O3 catalyst. The photocatalyst with high activity requires at a
low temperature of 80°C.

Photocatalytic activities of Bi2O3 nanoparticles prepared at

different temperatures.
The Stability of Catalyst

Photostability of as-prepared catalyst is a crucial parameter to assess its practical appl ication.
The cycling experiment for RhB degradation by BFWO-7 was preformed to evaluate its
stability. The result reveals after five recycling runs for RhB removal, the photocatalytic
performance of BFWO-7 does not display any palpable reduction for RhB removal (Figure 8).
It confirms that the BFWO -7 heterojunction is not easily photocorroded during the reaction
process, which further suggests that the BFWO-7 is considerable stable. Based on above results,
BFWO-7 will be an effective photocatalyst in env ironment remediation.
Cycling experiments for MO degradation by
Bi2O3