Journal of Molecular Structure 1235 (2021) 130205

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstr

Visible-Light-Harvesting Hedgehog like Copper Bismuth Oxide:

Optical, Structural and Electrochemical Properties
Arumukham Manjceevan a,∗, Naajla sulaimalebbe b, Thamilchelvi Somapala b
a
Department of Chemistry, Faculty of Science, University of Jaffna, Sri Lanka
b
Department of Chemical Sciences, Faculty of Applied Sciences, South Eastern University of Sri Lanka

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

Article history: Synthesize of materials with desired properties such as harvest wide range of solar spectrum includ-
Received 31 December 2020 ing visible light and better charge transport properties preferred due to its many potential applications
Revised 14 February 2021
such as water hydrogen splitting, photocatalytic dye degradation and photovoltaic application etc. In this
Accepted 23 February 2021
present study the CuBi2 O4 material successfully synthesized by solution based synthesize method, fol-
Available online 1 March 2021
lowed by dried at 150°C and sintered at various temperature such as 300°C, 400°C and 500°C and the
Keywords: variation of its’ optical, structural and electrochemical properties were analyzed. The sample sintered at
CuBi2 O4 500°C exists in pure form and there are no identified incomplete phases of CuO and Bi2 O3 . However,
optical properties the sample sintered at higher temperature shows higher charge transfer resistance between electrode-
structural properties electrolyte interface. CuBi2 O4 sintered at lower temperature shows better charge transfer characteristic
electrochemical impedance due to formation of small size of crystal and existence of different incomplete phases of CuBi2 O4 such
as CuO and Bi2 O3 etc. However, the sample sintered at high temperature showed better characteristic
properties for visible light-driven photocatalyst such as enhanced in crystallinity, low dislocation density,
and enhanced absorption in visible region of the spectrum. Therefore, the higher sintered temperature is
more suitable to synthesize the visible light-driven CuBi2 O4 photocatalyst.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction Solar energy harvesting ability mainly depends on bandgap of

Synthesize of semiconductor materials with ability to harvest a
wide range of solar spectrum is an interesting research as it gives
a great support to future development of renewable energy utiliz-
ing devices. Solar irradiation is far largest renewable energy source
in which the energy strikes the earth surface in an hour has suffi-
cient energy for utilization of the world population per year. Solar
irradiation average energy flux per year is 1,700 to 2,400 kW m2
year−1 [1]. However, solar energy utilization is still low and world
energy consumption mainly depends on fossil fuel [2]. The world
energy demand is not stable and it is increasing every year. Usage
of renewable energy instead for fossil fuel leads to free from en-
vironmental damage and harmful emissions like CO2 , CO, NO2 and
SO2 etc [2]. Semiconductor materials with the ability to harvest
a wide range of solar spectrum have many potential applications
such as solar cells [3], solar thermal process [4], photocatalytic ac-
tivities [5] etc. Although the usage of solar renewable energy is still
limited due to the lower efficiencies of the solar light harvesting
devices.
∗
Corresponding author.
E-mail address: manjceevan@univ.jfn.ac.lk (A. Manjceevan).
materials. Higher bandgap materials need higher energy radiation
to excite the electron from valence band to conduction band. The
wide bandgaps of ZnO, TiO2 , SnO2 absorb the light mainly in the
ultraviolet (uv) region of the solar spectrum [6, 7]. These semi-
conductors used in many potential applications including photo-
voltaic applications [8-10], photocatalyst for hydrogen generation
[11-15] and photocatalytic degradation [16-19] etc. Although, to
harvest a wide range of solar spectrum including visible light, fab-
rication of materials with different properties become a great in-
terest among scientists. CuBi2 O4 is one of the narrow bandgap ma-
terials used to harvest visible region of the solar spectrum [20].
The bandgap of that material is around 1.5-1.8 eV and varies based
on the synthesized conditions. The CuBi2 O4 materials synthesized
by different methods such as solution processing methods [20], hy-
drothermal methods [21], rapid thermal process [22], inkjet print-
ing method [23], electrospinning [24] et. The properties of a semi-
conductor may be modified by manipulating its structure, mor-
phology, tuning the bandgap, increasing surface area, charge trans-
port properties [25, 26] and so on. CuBi2 O4 material is a narrow
bandgap material and can be used in various applications such as
dye degradation, photocatalytic water splitting and antibacterial ef-
fect against Escherichia coli etc [27]. CuBi2 O4 with different mor-

https://doi.org/10.1016/j.molstruc.2021.130205
0022-2860/© 2021 Elsevier B.V. All rights reserved.
A. Manjceevan, N. sulaimalebbe and T. Somapala
phologies such as hedgehog and dumbbell shapes were synthe-
sized at room temperature and the photochemical performances of
hedgehog like morphology of materials showed more desired pho-
tochemical performances than dumbbell shape of CuBi2 O4 and it
shows strong absorption in 20 0-90 0 nm region of the spectrum
[20]. Although, the CuBi2 O4 material used as photocathode for wa-
ter splitting applications [28, 29] and as photocatalyst for degra-
dation of pollutants [30], the CuBi2 O4 material alone shows poor
photocatalytic performances due to higher charge recombination
[31]. Therefore, there are several researches performed to improve
the efficiency of CuBi2 O4 material by formation of heterojunctions
such as CuBi2 O4 /Bi3 ClO4 [32], CuBi2 O4 /CuO [33], CuBi2 O4 /Bi2 WO6
[30, 34], CuBi2 O4 /Amorphous-BiFeO3 [35], CuBi2 O4 /TiO2 [36], α -
Bi2 O3 /CuBi2 O4 [24, 37], CuBi2 O4 /BiOBr [38], ZnO/CuBi2 O4 [39],
CuBi2 O4 /Bi2 MoO6 [40], CuBi2 O4 /WO3 [41], CuBi2 O4 /MnO2 [42] and
BiFeO3 /CuBi2 O4 /BaTiO3 [43] etc. Concentration of metal precursor
used to synthesize the CuBi2 O4 and Cu2+ /Bi3+ molar ratio influ-
enced the structure and crystal orientation of CuBi2 O4 [44]. The
CuBi2 O4 materials synthesized with surface oxygen vacancies re-
duce the recombination of excited electrons in narrow bandgap
CuBi2 O4 and facilitates the effective photocatalytic process [31]. In
this present study we synthesized CuBi2 O4 by solution processing
method by using Cupric acetate, bismuth nitrate precursor solu-
tions and the synthesized CuBi2 O4 sintered at different temper-
ature. The sintering temperature of nanomaterial may bring the
changes in structure and properties of materials [45, 46]. In this
study the optical, structural and electrochemical properties of syn-
thesized CuBi2 O4 due to annealing effect were analyzed and pre-
sented in this paper.
2. Experimental details
2.1. Materials
Analytical grade chemicals purchased and used as re-
ceived without further purification. Cupric acetate monohydrate
((CH3 COO)2 Cu.H2 O) (purity>99%), bismuth nitrate pentahydrate
(Bi(NO3 )3 .5H2 O) (purity >99%) purchased from Fluka chemica and
sodium hydroxide (NaOH) (purity 97 %. ACS reagent) were used to
prepare CuBi2 O4 nanoparticles. Distilled water and small amount
of nitric acid (HNO3 ) (purity 70 %, ACS reagent) were used as
solvents.
2.2. Synthesize of CuBi2 O4
Bismuth nitrate pentahydrate (1 mmol) was dissolved in con-
centrated nitric acid (2 ml) and distilled water (60 ml) was added
to it. The solution was stirred for 2 hours for complete dissolution.
Copper precursor solution was prepared by dissolving cupric ac-
etate monohydrate (0.5 mmol) in distilled water (30 ml). Copper
precursor solution was added in to the bismuth solution and ad-
ditionally distilled water (90 ml) was added and stirred well. The
resulting solution was slowly heated to 80 °C. Then 1 M NaOH so-
lution was added to the precursor solution until the pH of the so-
lution reached 10. The solution maintained at 80 °C for another
two hours. Precipitate was allowed to settle and supernatant solu-
tion was removed. Then precipitate was dispersed again in distilled
water and cleaning process was repeated three times and dried in
an oven at 150°C for about 2.5 hours. After that the powder sin-
tered at different temperatures such as 300 °C, 400 °C and 500 °C
in a muffle furnace (Figure 1).
2.3. Instrumental analysis and specification
The synthesized sample at different sintering temperature were
characterized by using XRD, FTIR, TEM, SEM, uv-visible absorbance,
2
Journal of Molecular Structure 1235 (2021) 130205
electrochemical impedance spectroscopic techniques (EIS). XRD
analysis was performed by using Bruker D8 Advanced Eco Powder
X-ray Diffraction system with Cu Kα radiation source (λ=1.5418
A0 ). Scanning electron microscope images were obtained by using
Hitachi SU6600. Transition electron microscopy (TEM) images were
obtained by using JEOL JEM-2100. The absorbance spectra and
diffuse reflectance spectra obtained by using Shimadzu 2450 uv-
visible spectrometer in which the BaSO4 used as background. FT-
IR spectrum obtained by using Nicolet iS50 FT-IR instrument. XPS
analysis were performed by using thermo scientificTM ESCALAB
Xi+ photoelectron spectrometer and electrochemical impedance
spectroscopic analysis(EIS) was performed by using Zahner Zan-
nium universal electro-chemical work station equipped with a fre-
quency response analyzer (Thalas)in the 10 mV amplitude signal
and in 0.1 Hz to 1 MHz frequency range. The electrode for EIS was
prepared by dispersed the sample in ethanol and added one drop
of acetic acid and ground it as paste and coated on top of FTO glass
by drop casting method and dried at 150°C.
3. Results and Discussions
The powdered sample was synthesized at 150°C without fur-
ther sintered, sintered at 30 0°C,40 0°C and 50 0°C under the normal
atmospheric condition. The structural, optical and electrochemical
properties of such powdered samples prepared at various sintered
temperature were analyzed.
3.1. Structural Properties
The Figure 2 shows the XRD pattern of samples prepared at
various temperature. The structural properties of copper bismuth
oxide sintered at different temperature were analyzed by using
X-ray powder diffraction methods. The sample sintered at 500 ͦ
C shows high intensity peaks at the 2ϴ values (in degree) 27.94,
30.64, 33.23, 37.30, 46.64, 52.89, 55.58 and those peaks match
with standard diffraction pattern of tetragonal CuBi2 O4 (a = 8.4875
Aͦ c = 5.7901 Aͦ, Space group: P4/ncc, JCPDS number: 79-1810).
The most preferred orientation of the crystal is (211), (411) shows
higher intensity and (200), (310), (213), (332) peaks has less inten-
sity. The XRD peaks of CuBi2 O4 at low temperature shows broad
peak and the peak intensities and sharpness increase with increas-
ing temperature due to enhance in size of the crystal and crys-
tallinity [47]. Further, at low temperature the high intense peaks
of Bi2 O3 and CuO observed at 27.50° (JCPDS number:76-1730) and
35.29° (JCPDS number:44-0706) respectively. However, those peaks
were disappeared in XRD of sample sintered at 500°C. At very low
temperature due to formation of small size CuBi2 O4 crystal shows
broad XRD peaks and very difficult to distinguish the impurity
peaks with noise. The peak positions slightly shift through small
2Ɵ angle due to the change in crystal size and lattice strain [48].
To ensure the observed behavior of XRD peaks the crystal sizes
and dislocation densities of CuBi2 O4 sintered at various temper-
ature were calculated. Crystal sizes calculated by using Sherrer
equation (equation 1). The average crystal sizes of CuBi2 O4 calcu-
lated by using Sherrer equation shown in Table 1.
k×λ
D= (1)
β × Cosθ
Where β , k, D, λ and θ are full width at half maximum, dimen-
sionless shape factor, average crystal size, wavelength of x-ray and
x-ray diffraction angle of high intensity peak. The dislocation den-
sity of sintered samples of CuBi2 O4 defined as length of dislocation
lines per unit volume and calculated by using equation 2 [49].
1
δ= (2)
D2
Where, δ indicates dislocation density.
A. Manjceevan, N. sulaimalebbe and T. Somapala Journal of Molecular Structure 1235 (2021) 130205

Figure 1. Diagram of the methodology used to synthesize the CuBi2 O4 .

Table 1 come sharp with increasing temperature and its due to formation
Particle size and dislocation density of samples of CuBi2 O4 sintered at various tem-
of crystal nature of structure. Further, the crystalline sample shows
perature.
low dislocation densities.
Sample sintered Average Crystal Dislocation
temperature (°C) Sherrer method crystal size size (nm) density m−2 3.2. Morphological Characterization
211 411
SEM and magnified SEM images of CuBi2 O4 hedgehog like mi-
150 14.88 21.66 18.27 3.00 × 1015
300 27.28 30.85 29.07 1.18 × 1015 crosphere sintered at 300 ͦ C shown in Figure 3(a) and (b). The
400 40.92 43.27 42.10 5.64 × 1014 structure consists of rectangular shape rod like morphology with
500 45.48 45.54 45.51 4.83 × 1014 cross section average 48.2 nm length and 36.6 nm width. The rod
like morphology seem to arise from one stem and it gave the ap-
pearance of Hedgehog like morphology. The hedgehog morphology
exists in around 1.8 to 2 μm size. However, at 300 ͦ C different
Lattice strain not considered while calculating the average crys- incomplete phases of crystal exist and it was confirmed by XRD
tal size of CuBi2 O4 at various temperature. The crystal structure analysis. TEM image shows in Figure 4 clearly shows the rod like
increases with increasing temperature. The sample synthesized at morphology of the structure with 39.4 nm width.
room temperature shows smaller average size of crystal. Small av-
erage crystal size of materials shows high surface area and leads 3.3. Optical properties of CuBi2 O4
to better catalytic activities. The sample synthesized at low tem-
perature shows broad indistinguishable peaks corresponds to the uv-visible absorbance and diffuse reflection technique used to
polycrystalline nature of materials. Although, the XRD peaks be- study the optical properties of CuBi2 O4 material sintered at differ-

3
A. Manjceevan, N. sulaimalebbe and T. Somapala Journal of Molecular Structure 1235 (2021) 130205

Figure 2. XRD pattern of CuBi2 O4 (a) as synthesized at 150°C without further sin-
tered, sintered at 300°C, 400°C and 500°C.

Figure 4. TEM image of CuBi2 O4 sintered at 300 ͦ C.

ent temperature. The uv-visible spectra of CuBi2 O4 material shows
the CuBi2 O4 material absorbs a wide range of spectrum including
uv, visible and near IR region (shown in Figure 5). The onset of ab-
sorbance peak of samples sintered at 150 ˚C, 300 ˚C, 400 ˚C and
1
500 ˚C arise from around 900 nm, 878 nm, 872.5 nm, and 871 nm. (F (Rα ).hν ) /n = B(hν − Eg ) (5)
There optical bandgap energy calculated by using Tauc plot derived
from diffuse reflectance spectra (shows in Figure 5(b) and (c)). The CuBi2 O4 materials shows indirect bandgap and the bandgap en-
Tauc equation shows the correlation between bandgap energy (Eg ) ergy of such sample obtained from the Figure 5(c). The bandgap
and absorption coefficient (α ) as shown in equation 3 [50]. energy of sample sintered at 150 ˚C, 300 ˚C, 400 ˚C and 500 ˚C
1 are 1.35 eV, 1.40 eV, 1.55 eV and 1.65 eV respectively. However,
(α hν ) /n = B(hν − Eg ) (3) the bandgap energies of samples synthesized at 150 ˚C, 300 ˚C are
less than the reported values due to presence of higher amount
Where n take values ½ and 2 for direct and indirect bandgap
of impurities [20, 51]. The sample as synthesized at 150°C without
of materials respectively. Planck’s constant and photon frequency
further sintering shows the absorbance edge closer to 900 nm due
are denoted by h and ν respectively. The diffuse reflectance spec-
to presence of CuBi2 O4 and incomplete products of CuO [51]. The
tra could be converted as absorbance spectra using Kubelka-Munk
optical bandgap of CuO nanoparticle is 1.2 eV [52]. In higher tem-
function F (R∞ ) [50].
perature due to the absence of CuO phase shows the higher optical
K (1 − R∞ )2 bandgap energy and it is match with the previous reported values
F ( R∞ ) = = (4)
S 2R∞ [29, 51].
Maximum absorbance of sintered materials varies with sinter-
Where K, S and R are absorbance coefficient, scattering coeffi-
ing temperature. The samples sintered at 30 0 °C, 40 0 °C and 50 0
cient and diffuse reflectance respectively. R∞ is given by the ratio
°C shows enhanced absorbance in visible region than the sample
between Rsample and Rstandard of infinite thick specimen. Substitu-
sintered at lower temperature. The absorbance of material sintered
tion of Kubelka-Munk function instead for absorbance coefficient
at 500 ˚C shows slightly higher absorbance in visible region due
(α ) in tauc equation given by equation 5. The bandgap energy cal-
1 to the higher absorbance coefficient of crystalline CuBi2 O4 . The ab-
culated by extrapolation of linear part of plot (F (Rα ).hν ) /n Vs hν . sorbance onset peak moves slightly towards high energy with in-

Figure 3. (a) SEM (b) magnified SEM images of CuBi2 O4 sintered at 300 ͦ C.

4
A. Manjceevan, N. sulaimalebbe and T. Somapala
Figure 5. (a) uv-visible absorbance spectra (b) Diffuse reflectance spectra (c) Tauc plots of CuBi2 O4 microsphere as synthesized without further sintering, with sintered at
30 0 ˚C, 40 0 ˚C and 50 0 ˚C. The absorbance and diffuse reflectance spectra measured by using powder sample which was placed on BaSO4 powder and the diffuse reflectance
setup used to measure the absorbance.
Figure 6. FTIR spectra measured by ATR mode of CuBi2 O4 samples as prepared at
150°C without further sintering, at 300°C, 400°C and 500°C.
creasing sintering temperatures due to variation in optical bandgap
energy.
3.4. FTIR spectra
FTIR spectra of prepared different CuBi2 O4 samples were ob-
served in Figure 6. A broad peak at 3450 cm−1 is attributed to
O-H bond stretching. Also, a peak which is located at 1650 cm−1
refers to bending vibration of surface adsorbed H2 O [39, 53]. The
sharp peaks at 536 cm−1 and 1398 cm−1 due to stretching vibra-
tion of Cu-O bonds [54, 55] and Bi-O bond respectively [53, 56].
Those peaks are characteristic peaks of CuBi2 O4 [57].
5
Journal of Molecular Structure 1235 (2021) 130205
3.5. XPS analysis
The XPS analysis was performed to sample sintered at 300°C
to confirm the existence of chemical composition into the sample
(shown in Figure 7). Sample sintered at 300°C consist of Cu, Bi,
C and O which were found in the surface. The Bi 4f7/2 and 4f5/2
peaks found in 158.3 eV and 163.6 eV. It indicates the existence
of bismuth in +3 oxidation state. The Copper 2p3/2 peak observed
at 933.4 eV and its shake-up satellite line at 942.4 eV [58]. De-
convoluted peak at 933.4 eV consist peaks at 932.1 eV and 933.7
eV corresponds to reduced species of copper (Cu+ ) and Cu2+ re-
spectively [31, 58]. The peak at 932.1 eV shows lower area than at
933.7 eV and it reveals that Cu2+ exist in higher amount than Cu+
in the surface of sample. The satellite peaks observed at 940.4 eV
and 942.8 eV. The oxygen peaks observed at 529.5 eV, 531.2 eV and
532.4 eV correspond to lattice oxygen, adsorption of O and water
molecules on the surface respectively [58]. Lattice oxygen exists in
the high amount than hydroxyl groups and water molecules.
3.6. Electrochemical impedance analysis
Electrochemical impedance spectroscopic analysis was per-
formed to study the charge transport properties of materials de-
posited on top of fluorine doped tin oxide (FTO glass). Here three
electrode system used to measure the impedance spectroscopic
analysis and 0.5 M Na2 SO4 used as electrolyte solution. The FTO/
CuBi2 O4 , Ag/AgCl, sat., KCl and platinum were used as work-
ing electrode, reference electrode and counter electrodes respec-
tively. The arc of semicircle of Nyquist plot in Figure 8 shows
the charge transport resistance (Rct ) at electrode-electrolyte inter-
face. The arc of Nyquist plot increase with the increasing tempera-
ture shows that the charge transfers resistance of sample increase
with sintered temperature. At low temperature the charge trans-
A. Manjceevan, N. sulaimalebbe and T. Somapala
Figure 7. XPS spectrum of CuBi2 O4 sintered at 300°C (a) survey spectrum (b) deconvolution spectrum of Cu 2p (c) spectrum of Bi 4f and (d) deconvolution spectrum of O
1s.
Figure 8. Electrochemical impedance spectroscopic analysis of CuBi2 O4 sintered at
various temperature performed at dark condition at -0.5 V bias voltage.
port is favourable between electrode and electrolyte interface. This
is due to incomplete formation of products exist at low temper-
ature may facilitates the effective electron-hole charge separation
due to some heterojunction features between CuBi2 O4 and incom-
plete phases and it suppress the recombination of excited electron.
As a result, the sample sintered at low temperature shows lower
charge transfer resistance.
4. Conclusion
The impact of annealing temperature on the structural, opti-
cal and electrochemical properties of CuBi2 O4 sample prepared by
6
Journal of Molecular Structure 1235 (2021) 130205
solution processing methods was investigated. Annealing temper-
ature improve the crystallinity and exist in pure form at 500 °C
as tetragonal CuBi2 O4 crystal with lattice parameters a = 8.4875 Aͦ
and c = 5.7901 Aͦ. Further, average size of crystal increases from
18.27 nm to 45.51 nm and dislocation density decreases with in-
creasing temperature. The optical bandgap of pure CuBi2 O4 was in
1.65 eV and it absorbs wide ranges of spectrum including better
absorbance in visible region of spectrum. The bandgap energy of
low temperature sintered sample varies between 1.35 eV to 1.55 eV
due to presence of incomplete phases of materials and shows bet-
ter charge transfer properties. However, charge transfer resistance
of CuBi2 O4 sintered at higher temperature shows higher value
due to higher recombination of excited electron and it hinder the
charge transport properties between the material-electrolyte inter-
faces. Enhancement of absorbance, less charge transfer resistance
and less defect density of materials are better qualities of mate-
rial for photocatalytic and photovoltic applications. If the charge
transfer properties of CuBi2 O4 material synthesized at higher tem-
perature improved furter, it would be one of the best material for
photocatalytic and photovoltic application.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgements
This work was supported by the South Eastern University of
Sri Lanka, University research grant. The research grant number:
SEU/ASA/RG/2018/05.
A. Manjceevan, N. sulaimalebbe and T. Somapala
References
[1] L.C. Stages, Life Cycle Greenhouse Gas Emissions from Solar Photovoltaics, J.
Ind. Ecol. (2012).
[2] Administration, E.I. and G.P. Office, International Energy Outlook 2016, with
Projections to 2040. 2016: Government Printing Office.
[3] A. Manjceevan, J. Bandara, Optimization of performance and stability of quan-
tum dot sensitized solar cells by manipulating the electrical properties of
different metal sulfide counter electrodes, Electrochimica Acta 235 (2017)
390–398.
[4] N.H. Thomas, et al., Semiconductor-based Multilayer Selective Solar Absorber
for Unconcentrated Solar Thermal Energy Conversion, Scientific Reports 7 (1)
(2017) 5362.
[5] J. Zhao, C. Chen, W. Ma, Photocatalytic Degradation of Organic Pollutants Under
Visible Light Irradiation, Topics in Catalysis 35 (3) (2005) 269–278.
[6] X. Chen, S.S. Mao, Titanium dioxide nanomaterials: synthesis, properties, mod-
ifications, and applications, Chemical reviews 107 (7) (2007) 2891–2959.
[7] G. Yang, Z. Yan, T. Xiao, Preparation and characterization of SnO2/ZnO/TiO2
composite semiconductor with enhanced photocatalytic activity, Applied Sur-
face Science 258 (22) (2012) 8704–8712.
[8] A. Manjceevan, J. Bandara, Robust surface passivation of trap sites in PbS q–
dots by controlling the thickness of CdS layers in PbS/CdS quantum dot solar
cells, Solar Energy Materials and Solar Cells 147 (2016) 157–163.
[9] S. Sujinnapram, S. Moungsrijun, Additive SnO2-ZnO composite photoanode for
improvement of power conversion efficiency in dye-sensitized solar cell, Pro-
cedia Manufacturing 2 (2015) 108–112.
[10] Pal, K., et al., Cutting edge development on graphene derivatives modified by
liquid crystal and CdS/TiO2 hybrid matrix: optoelectronics and biotechnologi-
cal aspects. 2020: p. 1-65.
[11] Y.-L. Lee, C.-F. Chi, S.-Y. Liau, CdS/CdSe Co-Sensitized TiO2 Photoelectrode for
Efficient Hydrogen Generation in a Photoelectrochemical Cell, Chemistry of
Materials 22 (3) (2010) 922–927.
[12] A. Ikram, et al., Improved charge transportation at PbS QDs/TiO2 interface for
efficient PEC hydrogen generation, Physical Chemistry Chemical Physics 18 (23)
(2016) 15815–15821.
[13] J. Jia, et al., Inter-plane heterojunctions within 2D/2D FeSe2/g-C3N4 nanosheet
semiconductors for photocatalytic hydrogen generation, Applied Catalysis B:
Environmental 261 (2020) 118249.
[14] K. Telmani, et al., Synthesis, optical and photo-electrochemical properties of
NiBi2O4 and its photocatalytic activity under solar light irradiation, Optik 207
(2020) 163762.
[15] Feng, K., et al., Magnetron sputtered copper bismuth oxide photocathodes for
solar water reduction. 2020. 53(49): p. 495501.
[16] S. Li, et al., Influence of MnO2 on the photocatalytic activity of P-25 TiO2 in
the degradation of methyl orange, Science in China Series B: Chemistry 51 (2)
(2008) 179–185.
[17] F. Zhang, et al., TiO2-assisted photodegradation of dye pollutants II. Adsorp-
tion and degradation kinetics of eosin in TiO2 dispersions under visible light
irradiation, Applied Catalysis B: Environmental 15 (1) (1998) 147–156.
[18] D. Ayodhya, G. Veerabhadram, A review on recent advances in photodegra-
dation of dyes using doped and heterojunction based semiconductor metal
sulfide nanostructures for environmental protection, Materials Today Energy
9 (2018) 83–113.
[19] S. Ibrahim, et al., Tailoring the structural and optical properties of bismuth
oxide films deposited by reactive magnetron sputtering for photocatalytic ap-
plication, Materials Chemistry and Physics 243 (2020) 122580.
[20] M. Wang, et al., N-type hedgehog-like CuBi2O4 hierarchical microspheres:
room temperature synthesis and their photoelectrochemical properties, Crys-
tEngComm 17 (21) (2015) 4019–4025.
[21] Wang, Y., et al., Short-Time Hydrothermal Synthesis of CuBi2O4 Nanocolumn
Arrays for Efficient Visible-Light Photocatalysis. 2019. 9(9): p. 1257.
[22] Gottesman, R., et al., Pure CuBi2O4 Photoelectrodes with Increased Stability
by Rapid Thermal Processing of Bi2O3/CuO Grown by Pulsed Laser Deposition.
Advanced Functional Materials. n/a(n/a): p. 1910832.
[23] Rodriguez-Gutierrez, I., et al., Charge transfer and recombination dynamics
at inkjet-printed CuBi2O4 electrodes for photoelectrochemical water splitting.
2018. 122(48): p. 27169-27179.
[24] Yang, F., et al., Preparation of Z-scheme CuBi2O4/Bi2O3 nanocomposites us-
ing electrospinning and their enhanced photocatalytic performance. 2020: p.
101735.
[25] S.P. Berglund, et al., Comprehensive Evaluation of CuBi2O4 as a Photocathode
Material for Photoelectrochemical Water Splitting, Chemistry of Materials 28
(12) (2016) 4231–4242.
[26] S.I. Asiya, et al., Reliable optoelectronic switchable device implementation by
CdS nanowires conjugated bent-core liquid crystal matrix, Organic Electronics
82 (2020) 105592.
[27] Zhu, L., et al., Visible light-induced photoeletrochemical and antimicrobial
properties of hierarchical CuBi2O4 by facile hydrothermal synthesis. 2016.
1(8): p. 1518-1524.
[28] D. Cao, et al., p-Type CuBi2O4: an easily accessible photocathodic material for
high-efficiency water splitting, Journal of Materials Chemistry A 4 (23) (2016)
8995–9001.
[29] A.K. Shah, et al., Reduced graphene oxide modified CuBi2O4 as an efficient
and noble metal free photocathode for superior photoelectrochemical hydro-
gen production, Sustainable Energy & Fuels 3 (6) (2019) 1554–1561.
Journal of Molecular Structure 1235 (2021) 130205
[30] Yuan, X., et al., Z-scheme Bi2WO6/CuBi2O4 heterojunction mediated by inter-
facial electric field for efficient visible-light photocatalytic degradation of tetra-
cycline. 2019. 369: p. 292-301.
[31] Zhong, X., et al., Visible Light Driven Spherical CuBi2O4 with Surface Oxygen
Vacancy Enhanced Photocatalytic Activity: Catalyst Fabrication, Performance,
and Reaction Mechanism. 2020. 10(8): p. 945.
[32] Najafian, H., et al., Fabrication of nanocomposite photocatalyst
CuBi2O4/Bi3ClO4 for removal of acid brown 14 as water pollutant under
visible light irradiation. 2019. 361: p. 210-220.
[33] Nogueira, A.C., et al., Improved visible light photoactivity of CuBi2O4/CuO het-
erojunctions for photodegradation of methylene blue and metronidazole. 2019.
123(42): p. 25680-25690.
[34] Wang, L., et al., Fabrication of the flower-flake-like CuBi2O4/Bi2WO6 het-
erostructure as efficient visible-light driven photocatalysts: Performance, kinet-
ics and mechanism insight. 2019. 495: p. 143521.
[35] Cai, F., et al., One Step Synthesis of Tetragonal-CuBi2O4/Amorphous-BiFeO3
Heterojunction with Improved Charge Separation and Enhanced Photocatalytic
Properties. 2020. 10(8): p. 1514.
[36] Cao, H., et al., Photoelectrocatalytic Reduction of CO2 over CuBi2O4/TiO2-NTs
under Simulated Solar Irradiation. 2020. 5(17): p. 5137-5145.
[37] Chen, Q., et al., In situ construction of biocompatible Z-scheme α -
Bi2O3/CuBi2O4 heterojunction for NO removal under visible light. 2020: p.
119008.
[38] Huang, S., et al., A novel CuBi2O4/BiOBr direct Z-scheme photocatalyst for ef-
ficient antibiotics removal: synergy of adsorption and photocatalysis on degra-
dation kinetics and mechanism insight. 2020. 12(17): p. 4431-4445.
[39] Sabri, M., et al., Novel ZnO/CuBi2O4 heterostructures for persulfate-assisted
photocatalytic degradation of dye contaminants under visible light. 2020. 391:
p. 112397.
[40] Shi, H., et al., Visible light driven CuBi2O4/Bi2MoO6 pn heterojunction with
enhanced photocatalytic inactivation of E. coli and mechanism insight. 2020.
381: p. 121006.
[41] Wang, L., et al., The precursor-guided hydrothermal synthesis of CuBi2O4/WO3
heterostructure with enhanced photoactivity under simulated solar light irra-
diation and mechanism insight. 2020. 381: p. 120956.
[42] Zhang, H., et al., Construction of CuBi2O4/MnO2 composite as Z-scheme pho-
toactivator of peroxymonosulfate for degradation of antibiotics. 2020. 386: p.
124011.
[43] Zhang, X., et al., Construction of novel symmetric double Z-scheme
BiFeO3/CuBi2O4/BaTiO3 photocatalyst with enhanced solar-light-driven photo-
catalytic performance for degradation of norfloxacin. 2020: p. 119017.
[44] C.-Y. Lin, et al., Facile room-temperature growth of nanostructured CuBi2O4 for
selective electrochemical reforming and photoelectrochemical hydrogen evolu-
tion reactions, Sustainable Energy & Fuels 4 (2) (2020) 625–632.
[45] Nadi, S.A., et al., Postdeposition Annealing Effect on Cu2ZnSnS4 Thin Films
Grown at Different Substrate Temperature. 2014. 2014.
[46] N. Prasad, B. Karthikeyan, Cu-doping and annealing effect on the optical prop-
erties and enhanced photocatalytic activity of ZnO nanoparticles, Vacuum, 146
(2017) 501–508.
[47] S. K, et al., Solvothermal synthesis of copper cadmium sulphide (CuCdS2)
nanoparticles and its structural, optical and morphological properties, Mate-
rials Science in Semiconductor Processing 93 (2019) 345–356.
[48] P. Bindu, S. Thomas, Estimation of lattice strain in ZnO nanoparticles: X-ray
peak profile analysis, Journal of Theoretical and Applied Physics 8 (4) (2014)
123–134.
[49] M. Dongol, et al., Thermal annealing effect on the structural and the optical
properties of Nano CdTe films, Optik 126 (14) (2015) 1352–1357.
[50] P. Makuła, M. Pacia, W. Macyk, How To Correctly Determine the Band Gap En-
ergy of Modified Semiconductor Photocatalysts Based on UV–Vis Spectra, The
Journal of Physical Chemistry Letters 9 (23) (2018) 6814–6817.
[51] R. Patil, et al., Low temperature grown CuBi 2 O 4 with flower morphology and
its composite with CuO nanosheets for photoelectrochemical water splitting, J.
Mater. Chem. A (2) (2013).
[52] N.R. Dhineshbabu, et al., Study of structural and optical properties of cupric
oxide nanoparticles, Applied Nanoscience 6 (6) (2016) 933–939.
[53] Gao, H., et al., Photocatalytic activity tuning in a novel Ag2S/CQDs/CuBi2O4
composite: Synthesis and photocatalytic mechanism. 2019. 115: p. 140-149.
[54] B. Khaled, Z. Nassira, H. Imene, Eco-friendly synthesis of self-regenerative low–
cost biosorbent by the incorporation of CuO: a photocatalyst sensitive to visi-
ble light irradiation for azo dye removal, Environmental Science and Pollution
Research 27 (25) (2020) 31074–31091.
[55] W.C.J. Ho, et al., Photocatalytic and Adsorption Performances of Faceted
Cuprous Oxide (Cu2 O) Particles for the Removal of Methyl Orange (MO) from
Aqueous Media, Molecules (Basel, Switzerland) 22 (4) (2017) 677.
[56] F. Soleimani, M. Salehi, A. Gholizadeh, Hydrothermal synthesis, structural and
catalytic studies of CuBi2O4 nanoparticles, Journal of Nanoanalysis (2017).
[57] Yuvaraj, S., et al., Surfactant-free hydrothermal synthesis of hierarchically
structured spherical CuBi2O4 as negative electrodes for Li-ion hybrid capaci-
tors. 2016. 469: p. 47-56.
[58] Y. Zhang, et al., Degradation of benzotriazole by a novel Fenton-like reaction
with mesoporous Cu/MnO2: Combination of adsorption and catalysis oxida-
tion, Applied Catalysis B: Environmental 199 (2016) 447–457.