Electrochimica Acta 299 (2019) 357e365

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Synthesis of oxygen deficient bismuth oxide photocatalyst for

improved photoelectrochemical applications
Paramita Hajra a, Sanjib Shyamal a, Harahari Mandal a, Debasis Sariket a, Arjun Maity b, c,
Sukumar Kundu d, Chinmoy Bhattacharya a, *
a
Department of Chemistry, Indian Institute of Engineering Science & Technology, Shibpur, Howrah 711103, West Bengal, India
b
DST/CSIR Innovation Centre, National Centre for Nanostructured Materials, Pretoria 0001, South Africa
c
University of Johannesburg, Department of Applied Chemistry, South Africa
d
Department of Metallurgy & Materials Engineering, Indian Institute of Engineering Science & Technology, Shibpur, Howrah 711103, West Bengal, India

a r t i c l e i n f o a b s t r a c t

Article history: The present paper reports the effect of nitrogen modification on photoelectrochemical (PEC) water
Received 24 November 2017 oxidation behavior of Bi2O3 semiconductor thin film. The semiconductor particles were synthesized via
Received in revised form hydrothermal route using Bi(NO3)3 as a Bi3þ ion precursor and urea as the nitrogen source followed by
23 April 2018
drop-cast the particles and annealing the film at 600  C. The synthesized Bi2O3 exhibited band gap en-
Accepted 2 January 2019
ergy of 3.01 eV, calculated from the UVevisibleabsorption spectrum which decreases to 2.75 eV through
Available online 4 January 2019
N-modification. Water oxidation behavior of the material has been tested through linear sweep vol-
tammetry under periodic illumination. Highest photo-current of 180 mAcm2 has been measured for
Keywords:
Hydrothermal synthesis
water oxidation reaction at 0.95 V vs. Ag/AgCl, under illumination of 35 mWcm2. N-incorporation can
N-modification enhance the photocurrent up to 50% whereas the visible responsiveness of the material improves
Bismuth oxide photocatalyst significantly as confirmed from electrochemical action spectra and UVevisible absorption spectra. The
Oxygen vacancies photocatalytic activity of the semiconductor particles was confirmed through decoloration of
PEC water oxidation Rhodamine-B dye, by spectrophotometric measurements.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Development of photocatalysts with visible-light sensitivity is
an attractive research at present for solar assisted water splitting to
form H2 and O2 as a reality but a significant cost reduction in the
construction of an efficient photoelectrochemical cell (PEC) is
critical. However, the primary limitation of using the effective solar
spectrum (i.e. visible light, which is a major fraction) driven pho-
tocatalysts is the wide-band gaps of the earth-abundant metal
oxide semiconductors, like, ZnO, TiO2 etc. [1,2]. In order to improve
their photo-induced properties different sensitizers (like dyes) is
being applied to make these materials for the best use of visible
light absorption. Among the compounds, Bi2O3 has attracted sig-
nificant interest due to its unique crystal structures with various
probable modifications and band gaps in the desired range [3,4].
Bi2O3 mainly has four polymorphs, including the monoclinic (a),
* Corresponding author.
E-mail addresses: cbhattacharya.besus@gmail.com, chinmoy@chem.iiests.ac.in
(C. Bhattacharya).
tetragonal (b), body centered cubic (g), and face centered (d) pha-
ses. Among these, narrow band gaps of 2.8 and 2.48 eV for a-Bi2O3
and b-Bi2O3, respectively, have been reported in most experimental
studies out of which b-Bi2O3 has been well known to exhibit su-
perior photocatalytic activity under visible light illumination [5e7].
Doping of a semiconductor is one of the effective strategies to
extend its optical absorption ranges such that the materials become
suitable for visible light-driven photocatalytic processes. There are
some literature reports on the doping of different elements on
Bi2O3 semiconductors for their applications in photo-
electrochemical processes. It has been observed that Fe-doped
Bi2O3 nano-catalyst is quite effective on photodegradation of syn-
thetic dyes and waste water treatment of textile industries [8].
Theoretical calculations on the effect of N/In co-doping of b-Bi2O3
suggested narrowing the band gap with favorable structure for PEC
H2 production from water [9]. Visible-light active Fe, Sm and Ta-
doped Bi2O3 photocatalysts were synthesized hydrothermally and
the influence of the dopants for the overall photocatalytic activity
for methylene blue dye and phenol degradation under solar irra-
diation were evaluated [10]. Effect of doping with Nb depends upon
its amount, heat treatment temperatures, heating period, cooling

https://doi.org/10.1016/j.electacta.2019.01.009
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
358 P. Hajra et al. / Electrochimica Acta 299 (2019) 357e365
rates, mechanical regrinding etc. which controls the crystallo-
graphic and electrical conductivity properties of the body centered
cubic Bi2O3 type solid electrolyte system [11]. On the other hand,
anion doping has been the subject of many theoretical and exper-
imental studies. Among these, doping with N- like heteroatom has
often been reported for significant improvement of the visible ac-
tivity of the material.
Nitrogen, the natural candidate having the comparable atomic
size to oxygen displays similar chemical, structural and electronic
property and having same electronegativity, coordination numbers
and thus makes it as general choice to develop N-doped metal
oxides that absorbs visible light by forming a new energy state in
which the N2p is above the O2p in the band-diagram [12e21]. In
comparison to the different metal ions, nitrogen may be considered
among possible anion for visible-light sensitization in TiO2 as re-
ported in literature with significant photocatalytic activities under
visible light illumination [22e25]. Similarly, N doped ZnO [26e28]
was also quite common for applications in electron field emission
and PEC water splitting. Among the Bi2O3 modifications, Wang et al.
have demonstrated the thermal stability of N-doped a- and b-Bi2O3
with enhanced visible-light driven photocatalytic performance
considering the doping effect on the electronic and optical prop-
erties of these semiconductors [3]. In some other studies, N-
modified bismuth oxides have been synthesized with enhanced
visible-light absorption due to favorably positioned band edges for
solar water splitting [29e31]. In these studies, it was demonstrated
that the enhanced visible light absorption is due to the presence of
nitrogen that reduces the effective band gap and suppresses
electronhole recombination processes that lead to improvement
of photocatalytic activity. In N-doped metal oxides, defects like
oxygen vacancies are formed, which can spontaneously compen-
sate the charge imbalance.
This paper describes the hydrothermal synthesis of Bi2O3 and its
N-modified samples through selective addition of urea in the
preparation bath. The semiconductor particles were used to form
thin film on FTO coated glass substrates for applications in PEC
water oxidation under suitable illumination (35 mWcm2). Highest
photocurrent of 180 mAcm2 was recorded using pure Bi2O3 for
water oxidation process increases to 280 mAcm2 through N-
modification. This is the first reported photocurrent for water
oxidation using N-modified Bi2O3 without applying any codopant,
sensitizer or electrocatalysts. Physicochemical, optical and elec-
trochemical characterizations were performed to correlate their
photocatalytic properties with semiconductor behavior.
2. Experimental section
2.1. Materials
Bismuth nitrate, ethanol were purchased from Sigma-Aldrich,
NaH2PO4, Na2HPO4, Na2SO4, Na2SO3, ethylene glycol (EG), urea
were purchased from E-merck (AR quality) and used as received
condition. The Rhodamine B dye sample (Eastman, AR grade) was
used for the photocatalytic study. Milli-Q grade water was used in
all the experiments to prepare the solutions. 2.0  1.5 cm2 FTO-
coated glass slides (Xinyan Tech. Ltd., Hong Kong) were thor-
oughly cleaned by sonication in successive solutions of soap water
and ethanol and finally rinsed with Milli-Q water.
2.2. Synthesis of Bi2O3 and N-Bi2O3 particles
The Bi2O3 nanoparticles were synthesized via hydrothermal
route using bismuth nitrate precursor in aqueous solution. For N-
Bi2O3, urea was used as nitrogen source in the hydrothermal bath
using a teflon lined SS304 autoclave. After 20 hrs reaction at 160  C,
the products were separated by filtration, washed several times
with ethanol and finally dried.
2.3. Preparation of the Bi2O3 and N-Bi2O3 semiconductor thin film
electrode
Hydrothermally synthesized Bi2O3 and N-Bi2O3 particles were
suspended (10 mM) in EG and 400 ml of the solution was drop-cast
on FTO coated glass substrate (1.5 cm  2.0 cm). Thin films were
heated at 120  C, followed by annealing in air at 600  C temperature
for 10 hrs with ramping rate of 1  C per minute and 4 hrs soaking.
2.4. Photoelectrochemical measurements of Bi2O3Semiconductor
❖ Linear sweep voltammetry:
The Bi2O3 or N- Bi2O3 thin films were used as working electrode
with a 0.27 cm2 geometric area exposed to the electrolyte solution
under light irradiation. The experiments were carried out in a
conventional three electrode borosilicate glass cell using an Ag/
AgCl reference electrode, Pt-foil counter electrode and the semi-
conductor working electrode. The photoelectrochemical measure-
ment was carried out either in 0.1 M Na2SO4 for water oxidation or
in 0.1 M Na2SO4 with 0.1 M Na2SO3 solution for SO2 3 (sacrificial)
oxidation reaction using Autolab 302 PG stat (Metrohm). During
the reaction, the pH of the solution was maintained at 7 using
Na2HPO4 and NaH2PO4 buffer solution. Photoelectrochemical
measurements were carried out using Xe-lamp source with the
power of the incident beam fixed at 35 mWcm2, measured
through an optical power meter (Newport).
❖ Chronoamperometry:
Stability of the semiconductors undergoing water oxidation
reaction was determined through chronoamperometry using the
similar cell configuration under constant illumination of
35 mWcm2 at an applied potential of 0.8 V. PEC action spectrum
was determined through chronoamperometry using similar
experimental set up under periodic illumination through a mono-
chromator (Oriel). Incident photon or absorbed photon to current
conversion efficiencies (IPCE or APCE) were calculated from the
optical power (using Newport Power meter) of the monochromatic
incident beam and absorbance of the semiconductor, respectively.
2.5. Electrochemical impedance spectroscopy
Electrochemical impedance spectroscopic measurements were
performed using the similar experimental setup, as mentioned
above, using 0.1 M Na2SO4 in pH 7 buffer (PBS) solution employing
Autolab 302 PG-stat with frequency response analyzer (FRA).
Nyquist plot, variation of impedance with frequency under
UVevisible illumination was obtained within the frequency range
of 100 kHz to 20 mHz at an applied potential of 0.8 V. Mott-
Schottky plot, i.e., change in space charge capacitance with
applied potential were measured within the potential range of 0.4
to 1.0 V at a fixed frequency of 1 kHz, to ascertain the
semiconductor-redox electrolyte interfacial charge transfer
mechanism.
2.6. Photocatalytic dye decoloration study
Rhodamine-B was chosen as a model dye molecule to measure
the efficiency of the material towards photochemical decoloration
reaction. 20 mg of the semiconductor particle and 50 mg of
Rhodamine-B dyes was added to 50 ml 0.2 M Na2HPO4-NaH2PO4
 P. Hajra et al. / Electrochimica Acta 299 (2019) 357e365 359

buffer solution (pH 7), and homogeneous mixture was obtained

through ultrasonication for 30 min. The mixture was subjected to
irradiation using the same Xe-lamp source under constant stirring
conditions. Kinetics of the dye decomposition reaction was moni-
tored by taking 2.5 ml of the mixture at a certain interval and after
removing the suspended particles through a centrifuge; the
absorbance of the solution was measured through the UVevisible
spectrometer.

2.7. Physicochemical characterization

❖ UVevisible Absorption Spectroscopy:

Optical measurements were carried out for the pure and N-

modified Bi2O3 films using a model V-630 UVevisible spectro-
photometer (Jasco, Japan) within the wavelength range of
350e700 nm, and the band gap energy was calculated from the
edge of the absorption spectra.

❖ Surface characterization through X-ray diffraction and Scanning Fig. 1. (a) Comparative UVevisible absorption spectra of Bi2O3 and N-modified Bi2O3
Electron Microscopy: thin film and (b, inset Tauc plot) for calculation of the optical band gap of the
semiconductors.

The crystalline behavior of the Bi2O3 semiconductor was iden-

tified through the powder X-ray diffraction (XRD) measurement
(Rigaku Miniflex II) operated with a CuKa source (l ¼ 1.54 Å), and
the data were recorded with a scan rate of 2 min1 within the
range of 2q of 20 e80 . The surface morphology of the Bi2O3 par-
ticles was observed through scanning electron microscopy (SEM)
using JEOL S4800 FESEM. Energy dispersive X-ray analysis (EDS)
spectra were characterized using an Oxford EDX detector and Aztec
software.

3. Result and discussion

Fig. 2. SEM images of Bi2O3 (a, a‫ )׳‬and N-Bi2O3 (b, b‫ )׳‬powder at lower to higher
magnification annealed at 600  C.
3.1. Physicochemical characterizations of the semiconductor thin
films

Thin film semiconductor electrodes were prepared over the F-
doped SnO2 (FTO) coated glass substrate using the hydrothermally
synthesized Bi2O3 and N-Bi2O3 particles suspended in ethylene
glycol. UVevisible absorption spectra of the thin films were used to
ascertain the nature of bands within the semiconductors and to
calculate its band gap energy. Fig. 1a shows the UVevisible ab-
sorption spectra of Bi2O3 and N-modified Bi2O3 thin films semi-
conductor. The optical band gap energy of 3.01 eV for pure Bi2O3
and 2.75 eV for N-Bi2O3 were determined from the edge of the
absorption spectra. The N-modified samples exhibit a red shift i.e.
towards visible region of the spectra indicating band-to-band
transition through absorption of lower energy photons compared
to pure Bi2O3. Incorporation of N to the semiconductor matrix leads
to significant disorder in the atomic arrangement and O defect sites
along with formation of a new inter-band state (N2p band is above
than O2p band) in the bandgap region and are responsible for
decrease in the band gap energy. Fig. 1b represents the Tauc plot, as
derived from the absorption spectra and used to obtain the
bandgap energy and to predict the band-to-band transition pattern.
The sharp nature of the plot indicates the ‘direct band gap’ nature
for both of the semiconductors.
The surface morphology of the Bi2O3 powder samples were
observed through scanning electron microscopy (SEM). Fig. 2 (a, a‫)׳‬
represent the micrographs of pure Bi2O3 at different magnifications
(10 k and 40 k respectively). Agglomerated nature of the particles
was confirmed from the images, as the inter-particle boundaries
are almost invisible. On the other hand, micrographs of N-modified
sample, as presented in Fig. 2 (b, b‫)׳‬, in same magnifications, as
mentioned above, indicate reduction in degree of agglomeration to
some extent, than that for pure material, with formation of porous
surface. This may lead to increase in effective surface area of the N-
modified sample which in turn influences the improved photo-
catalytic property of the material.
The chemical composition of the semiconductor matrix was
determined through elemental analyses of the pure and N-modi-
fied Bi2O3 samples using energy dispersive X-ray analysis (EDS).
From the analysis it is evident that for both of the materials, the
relative content of cationic (Bi) part is higher than the corre-
sponding anionic proportion which acts as donor sites and trans-
lates to the n-type conductivity in the SC film as demonstrated
through electrochemical impedance studies, discussed later [32].
However, among these two, for the N-modified sample, there is
even more oxygen deficiencies, i.e., availability of O per Bi atom is
only 82%, as compared to that for pure sample (92%), suggesting
increase in relative trend of donor density (carrier concentration)
for the N-modified semiconductor. Although there was no detect-
able amount of nitrogen present in the N-modified sample, distinct
difference in the surface morphology and crystalline pattern as
compared to the pure sample, supports the above results.
Crystallinity of the semiconductors has been analyzed through
XRD measurements. Fig. 3 (i) represents the comparative XRD
pattern of the pure and N-modified Bi2O3 thin films prepared over
FTO coated glass substrates. For pure Bi2O3, maximum number of
peaks appear corresponding to monoclinic Bi2O3 (a-phase) along
with some oxygen deficient bismuth oxides (Bi2O2.33, Bi2O2.5 and
Bi2O2.7) and the different peaks were indexed with the
360 P. Hajra et al. / Electrochimica Acta 299 (2019) 357e365
Fig. 3. (i) XRD plot of Bi2O3 and N-Bi2O3 thin film annealed at 600  C [(A) (hkl)-Monoclinic Bi2O3 (761730), (a) (hkl)-Tetragonal Bi2O3 (781793), (b) (hkl)-Hexagonal BiO (270054), (c)
(hkl)-Tetragonal Bi2O2.33 (270051), (d) (hkl)-Tetragonal Bi2O2.5 (741999), (e) (hkl)-Tetragonal Bi2O2.7 (750993)], (ii) Shifting and broadening of the ‘strongest’ peak.
corresponding (hkl) values comparing with the standard JCPDS
data files (no.76e1730: Monoclinic-Bi2O3, 74e1999: Tetragonal-
Bi2O2.5, 27e0051: Tetragonal-Bi2O2.33, 75e0993: Tetragonal-
Bi2O2.7). In contrast, for N-modified sample, the majority of the
peaks arises due to oxygen deficient phases, as stated above, along
with a few more peaks from another oxygen deficient hexagonal
BiO crystallite (JCPDS no.27e0054). Further, the peaks corre-
sponding to stoichiometric Bi2O3, which were predominating in
pure semiconductor, are suppressed significantly through N-
modification. Variation of highest intense peak at 2q ~27.55 for
pure Bi2O3 corresponding to (hkl) value (120) for monoclinic Bi2O3,
has been presented in Fig. 3(ii). However, for N-modified sample,
the intensity of this particular peak depressed and the new maxima
appear at higher 2q value of 28.1 corresponding to (hkl) value of
(101) for hexagonal BiO crystallite. The appearance of new peaks in
significant proportions corresponding to the oxygen deficient bis-
muth oxides is thus justified through N modification of the metal
oxide. The peaks were found to perfectly matching with the oxygen
deficient bismuth oxides as: at peak position of 2q corresponding to
23.6 (101- Tetragonal Bi2O2.33), 25.13 (210 - Tetragonal Bi2O2.5),
28.1 (101- Hexagonal BiO), 29.6 (107- Tetragonal Bi2O2.33), 40.02
(311 - Tetragonal Bi2O2.5), 42.18 (320 - Tetragonal Bi2O2.5), 44.02
(006- Tetragonal Bi2O2.7), 45.92 (1012 - Tetragonal Bi2O2.33), 56.29
(006- Hexagonal BiO), 61.08 (2111- Tetragonal Bi2O2.33), 75.1 (211-
Hexagonal BiO), 79.7 (312- Tetragonal Bi2O2.5). More oxygen
deficient phases in case of N-modified samples suggest higher
donor density (n-type carrier concentrations) and better photo-
catalytic behavior for this material than that for the pure semi-
conductor, as discussed later.
The crystallize size D (in Å), of the individual peaks were
analyzed using the Scherrer equation:
D ¼ ð0:9lÞ=ðb cos qÞ (1)
where ‘l’ is wavelength of X-ray, q is the diffraction angle (in de-
gree), b is the line broadening, calculated as full width at half
maxima (FWHM); q is the Bragg's angle. The value of d, the inter-
planar spacing between the atoms, was calculated using Bragg's
equation
nl ¼ 2d sin q (2)
The XRD results further confirm that the pure Bi2O3 is composed
of crystallites with an average diameter of 65 ± 5 nm. However,
through N-modification, the width of the diffraction peaks was
found to increase significantly (b value increases) indicating a
reduced crystallite size to 27 ± 5 nm, which contribute towards its
better photocatalytic performance.
3.2. Photoelectrochemical characterizations of semiconductor
electrodes
PEC behaviors of pure and N-modified Bi2O3 semiconductors
were evaluated under periodic chopped UVevisible illumination of
35 mWcm2. Fig. 4 represents the linear sweep voltammograms
(LSVs) of the thin film semiconductor electrodes for (a) water
oxidation in 0.1 M Na2SO4 solution (pH 7 phosphate buffer) within
the potential range of 0.2e1.0 V and (b) the sacrificial oxidation in
0.1 M Na2SO3-0.1 M Na2SO4 solution within the potential range
of 0.4e0.6 V, at a scan rate of 10 mVs1. Highest photocurrent of
180 mAcm2 was observed for water oxidation (H2O / O2) at an
 P. Hajra et al. / Electrochimica Acta 299 (2019) 357e365 361

Fig. 5. Comparative Mott-Schottky plots of Bi2O3 and N-Bi2O3 film.

.  
1 C 2sc ¼ ð2=eεε0 ND Þ E  Efb  KT=e (3)

where Csc is the space-charge capacitance (in F cm2), e is the

electronic charge in C; ε is the dielectric constant of the semi-
conductor (taken as 32 for Bi2O3) [33]; ε0 is the permittivity of free
space; ND is the carrier density in cm3; E is the applied potential in
V; Efb is the flat band potential; k is the Boltzmann constant; and T
is the temperature in K. Positive slope of the plots confirm n-type
semiconductivity of the materials. From the slope, the carrier
concentration (ND) is calculated as 0.94  1017 cm3, for pure ma-
terial which increased to 1.20  1017 cm3 for N-modified material.
Since the modified semiconductor is more oxygen deficient than
Fig. 4. Comparative LSV plots of pure and N-Bi2O3 electrode in (a) 0.1 M SO2
4 solution
(PBS buffer) (b) 0.1 M SO2- 2-
4 -SO3 under UVevisible light illumination.
the pure one, as evident from EDS and XRD analyses, availability of
free electrons (which acts as the charge carrier for n-type material)
increases to balance the positive charges of the excess cations.
applied potential 0.95 V vs Ag/AgCl using pure Bi2O3 film which Relatively higher carrier concentration of N-modified Bi2O3 may
increased to almost 1.5 folds (280 mAcm2) for N-modified semi- lead to reduce the ohmic resistivity of the semiconductor matrix
conductor. To the best of our knowledge this is first reported and thereby improving the photoelectrochemical oxidation of
photocurrent for water oxidation using N-modified Bi2O3 without
employing any sensitizer, co-dopants or electrocatalysts. Fig. 4b,
LSV plots for sacrificial (SO2
3 ) oxidation, indicates the successful
modification of Bi2O3 with N as the photocurrent increased to 410
mAcm2 at 0.4 V vs Ag/AgCl compared to 200 mAcm2 for pure
semiconductor. The significant enhancement of photocurrent for
the N-modified sample may be ascertained by the fact that an in-
crease in photon absorption on semiconductor surface, particularly
in the visible region, leads to efficient electronehole separation,
which promotes facile charge transfer kinetics at the semi-
conductor surface. Moreover, decrease in the crystallite size with
more porous surface morphology of the N-modified film as well as
increase in carrier concentration, as evident from more oxygen
deficient phases, lead to increase in effective surface area of the
photocatalyst to perform enhanced charge transfer reaction ki-
netics over its surface.

3.3. EIS analysis of the semiconductor electrode-electrolyte

interface

Mott-Schottky (M-S) plot (Fig. 5), the linear variation of 1/C2

(space charge capacitance) with respect to the applied potential can
be expressed using the relation shown in equation (3). Fig. 6. Band-diagram for water oxidation (vs Ag/AgCl reference electrode).
362 P. Hajra et al. / Electrochimica Acta 299 (2019) 357e365
water and SO2 3 , discussed earlier. The flat band potential of the
semiconductors were calculated from the intercept on the potential
axis of the Mott-Schottky plot, and was found to be of the order
of 0.35 ± 0.05 V vs. Ag/AgCl.
The energy band diagram for the Bi2O3 and N-Bi2O3 semi-
conductors has been presented in Fig. 6 where the position of the
conduction band (CB) fixed near to the flat band position
(~ 0.35 V) and the corresponding valence band (VB), considering
their individual band gap energies. The redox potential of the
photo-generated holes for N-Bi2O3 is high enough to drive the
water oxidation reaction (H2O / O2, E0 þ0.59 V vs. Ag/AgCl at pH
7), and the material exhibits superior PEC oxidation behavior.
The frequency dispersive impedance data were collected under
UVevisible illumination and the Nyquist plot showing the variation
of real and imaginary part of the impedance has been presented in
Fig. 7a. The Nyquist plots were analyzed based on the equivalent
circuit model (Fig. 7b) which includes a solution resistance (Rs),
charge-transfer resistance (Rct) and the double-layer capacitance
(Cct) associated with the charge transfer process. In the Nyquist
Fig. 7. (a) Nyquist plots of Bi2O3 and N-Bi2O3 film in presence of UVevisible light illumination, (b) equivalent circuit model, (c) Variation of different equivalent circuit parameters.
plot, the high-frequency limit, Rs, indicates the ohmic resistance,
whereas the low-frequency limit is a characteristic of the sum of
the Rs and the charge transfer resistance (Rct). Variation of equiv-
alent circuit parameters as obtained from the respective Nyquist
plots have been presented in Fig. 7c. The ohmic resistance (Rs) for
the samples varies, to some extent, as the smaller value of Rs was
observed for N-modified Bi2O3, indicating better electronic con-
ductivity in the material compared to pure oxide. From the Nyquist
plot, it is also evident that N-Bi2O3 exhibited a semicircle with
much smaller diameter indicating lower Rct value (almost 1/3rd)
than pure material. The N-modified semiconductor thus expected
to behave as better photo-anode due to their higher efficacy in the
conduction of charge carriers within the bulk of the matrix as well
as their transfer across the electrode e electrolyte interface. From
the figure (Fig. 7c) it is further evident that the double layer
capacitance associated with the charge transfer process increases
to two-fold for N-modified sample which may be explained due to
certain changes in surface morphology with the formation of more
oxygen-deficient phases than the pure sample.
 P. Hajra et al. / Electrochimica Acta 299 (2019) 357e365
3.4. Stability measurement and calculation of IPCE and APCE for
photoelectrochemical water oxidation
Continuous photocurrent was measured for 10 min in 0.1 M
Na2SO4 (pH7 PBS) when the electrodes were held at a potential of
0.8 V under the fixed illumination of 35 mWcm2. Fig. 8 represents
the chronoamperometric plots of the pure and N-modified Bi2O3
films, which indicate fairly stable behavior of both the materials for
photoelectrochemical water oxidation.
Electrochemical action spectra were obtained under periodic
chopped monochromatic illumination. Fig. 9 represents the PEC
action spectrum for the semiconductors in 0.1 M Na2SO4 in pres-
ence of PBS measured at 0.8 V vs Ag/AgCl with gradually change in
monochromatic light wavelength from 320 to 550 nm. The onset of
photocurrent for pure semiconductor appears as 525 nm which is
shifted to 550 nm for N-modified sample corresponding to their
‘true’ or ‘photoelectrochemical band gap’ as 2.36, 2.25 eV, respec-
tively, indicating lowering of band gap energy to some extent due
to N-modifications and results in improved PEC activity towards
water oxidation.
The incident photon to current conversion efficiency (IPCE) was
derived with determination of power of the incident
Fig. 8. Chronoamperometric stability (I - t) plot of the pure and N-modified Bi2O3
photoanode at an applied potential of 0.8 V in 0.1 M Na2SO4 (pH 7 PBS) under
UVevisible irradiation.
Fig. 9. Photoelectrochemical action spectra of pure and N-Bi2O3 film for water
oxidation under monochromatic illumination.
363
monochromatic beam at each of the wavelength using the
equation,
 . 
IPCEð%Þ ¼ ð1240=lÞ  lph pin  100 (4)
where, l is the wavelength of the incident light in nm, IPh is the
photocurrent in A cm2 and Pin is the power of the incident
monochromatic light in W cm2. The absorbed photon to current
conversion efficiency (APCE) was further calculated by considering
the absorbance (Al) of the material at that particular wavelength
using the following equation.
 
APCEð%Þ ¼ IPCE=1  10Al  100 (5)
Fig. 10 represents % of conversion efficiency in terms of IPCE and
APCE, for the different materials, and it was observed that N-
modified bismuth oxide exhibit higher orders than the corre-
sponding values of pure Bi2O3. Highest value of IPCE of ~18% and
corresponding APCE of ~47% was recorded for pure bismuth oxide
which increases to 35% and 59%, respectively, for N-modified ma-
terial for water oxidation reaction.
3.5. Photocatalytic decoloration of organic dyes
Fig. 11 (a, b) compare the gradual decrease of absorbance i.e.
decoloration of Rhodamin-B (RhB) dye in presence of pure and N-
modified bismuth oxide particles, respectively, under UVevis illu-
mination. Within first one hour of exposure to light, the N-modified
samples was found to change the color of the solution to 50% as
compared to only 40% for the pure semiconductor. Fig. 11c repre-
sents the kinetic expression, i.e. the variation of lnC0/C versus t
(min) and linearity of the plot confirms the pseudo-first order na-
ture of the photocatalytic degradation of RhB dye. The observed
photocatalytic reaction rate constant (kobs) as calculated from the
slope of the linear plot (pseudo first order kinetics), and the co-
efficients of the linear regression (R square), has been tabulated
within the graph. Appearance of R-square terms ~1 further con-
firms pseudo 1st order kinetics for the process [34]. The observed
rate constant (kobs) for the pure semiconductor was found to be
9.4  103 min1 which improves to some extent to 10.2  103
min1 for N-modified sample. Increase in the overall performance
of the N-modified photocatalysts may be attributed to the
Fig. 10. Variation of % conversion efficiency (IPCE & APCE) of different semiconductors.
364 P. Hajra et al. / Electrochimica Acta 299 (2019) 357e365
Fig. 11. Rhodamine-B (RhB) dye decoloration kinetics plots using (a) pure and (b) N-modified Bi2O3 semiconductors (c) pseudo-first order kinetics of dye decoloration using
different photocatalyst.
synergistic role of several factors: (i) surface morphology of the
sample changes significantly, leading to more porous structure and
thus surface area increases. (ii) Relative content of the O decreases
leading to the formation of more oxygen vacancies in the lattice.
(iii) XRD analysis results indicate the increase in the O-deficient
Bi2O3 crystallites with significant suppression of stoichiometric
monoclinic Bi2O3 phases (say, (120) forms). (iv) The O-vacancies
causes more charge carriers in the crystal and thus donor density
increases and charge transfer resistance decreases significantly. (v)
Previous literature reports also suggest that these non-
stoichiometric crystallites are known to absorb in the visible re-
gion resulting in increase in photocatalytic behavior. (vi) XRD
analysis further indicates that crystallite size decreases leading to
increase in effective surface area and better electrical connectivity
within the crystallites as represented by lower ohmic resistance.
4. Conclusion
The pure and nitrogen-modified bismuth oxide films were
synthesized through hydrothermal method and were tested as the
potential photocatalysts. Pure semiconductor film exhibits highest
photocurrent for PEC water oxidation as 180 mAcm2 whereas that
for the N-modified film appears as 280 mAcm2. N-modification can
decreases the bandgap energy from 3.01 to 2.75 eV i.e the material
absorbs significant portion of visible light. N-modification can lead
to increase in donor density with decrease in the charge transfer
resistance. XRD analysis confirms that through N-modification the
crystal size decreases from 65 nm to 27 nm with formation of more
oxygen deficient metal oxides. The photocatalytic degradation of
Rhodamin-B dye on the semiconductors confirms improvement in
performance through N-modification.
Acknowledgments
The present work was financially supported by SERB-DST, Govt.
of India (File no. SB/S1/PC-042/2013). Financial assistance from the
DST, Govt. of West Bengal, (File no. 902(Sanc.)/ST/P/S & T/4G e 1/
2013) to the Department of Chemistry, IIEST, Shibpur are gratefully
acknowledged.
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