Journal of Electroanalytical Chemistry 878 (2020) 114724

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Journal of Electroanalytical Chemistry

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

Review

Bismuth vanadate in photoelectrocatalytic water treatment systems for the

degradation of organics: A review on recent trends
Benjamin O. Orimolade a, Omotayo A. Arotiba a,b,
⁎
a
Department of Chemical Sciences (Department of Applied Chemistry), University of Johannesburg, South Africa
b
Centre for Nanomaterials Science Research, University of Johannesburg, South Africa

A R T I C L E I N F O A B S T R A C T

Article history: Photoelectrocatalytic degradation, an advanced oxidation process, which combines both light and electrical
Received 27 June 2020 energy for chemical reaction has proven to be an efficient method for the degradation of organics in waste-
Received in revised form 7 September 2020 water. The efficiency of photoelectrocatalytic degradation depends greatly on the choice of material for
Accepted 24 September 2020
photoanode. Bismuth vanadate (BiVO 4 ) has been identified as a suitable electrode material and it has
Available online 28 September 2020
been widely applied in visible light mediated photocatalysis, photoelectrochemical water splitting and
Keywords:
photoelectrocatalytic water treatment applications. These applications are due to its attractive properties
Photoelectrocatalysis such as narrow band gap, low toxicity and excellent physicochemical stability. In the past, much focus has
Water treatment been on photocatalysis and photoelectrochemical water splitting applications of BiVO 4. However, due to
Bismuth vanadate the recent interest in the application of BiVO4 in photoelectrocatalysis for wastewater treatment applica-
Photoanode tions, there is a need to present to the electrochemistry community (and other related science and engineer-
Heterojunction ing communities on water and materials), a review on the recent applications of BiVO4 based photoanodes
for the photoelectrocatalytic degradation of recalcitrant organic pollutants in wastewater. Additionally,
brief insights into the synthesis and strategies of improving the efficiency of BiVO4 are presented. This re-
view provides relevant information that will be beneficial for future works on the use of BiVO4 for water
treatment applications.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Basic concept of photoelectrocatalysis for water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Bismuth vanadate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Structural, electronic and optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Preparation of BiVO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.3. Improving photoelectrocatalytic efficiency of BiVO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.1. Morphology control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.2. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.3. Formation of heterojunction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Photoelectrocatalytic degradation of organics using BiVO4 photoanodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1. Application BiVO4 heterostructures in photoelectrocatalytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2. BiVO4 in coupled systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5. Conclusion and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

⁎ Corresponding author.
E-mail address: oarotiba@uj.ac.za. (O.A. Arotiba).

http://dx.doi.org/10.1016/j.jelechem.2020.114724
1572-6657/© 2020 Elsevier B.V. All rights reserved.
B.O. Orimolade, O.A. Arotiba /
1. Introduction
Water remains an indispensable natural resource for the sustenance of
human and animal lives. Increase in water pollution as a result of organic
compounds emanating from industrial and urban human activities is a
major worldwide problem as many of the organic pollutants are persistent
in nature and have been discovered in considerable concentrations in sur-
face water, underground water as well as in drinking water. Rapid industri-
alization and urbanization are major factors leading to increase in the
occurrence of these recalcitrant organics in water [1]. These organic pollut-
ants constitute serious environmental and health problems mainly due to
their toxicity and potential hazardous health effects on living organisms, in-
cluding human beings [2]. Dyes are among the major group of organics
found in the water environment. Synthetic dyes are major materials in
many manufacturing industries and statistics have shown that over
800,000 tons of dyes are produced worldwide yearly [3]. In fact, textile in-
dustries release more than 100 tons of dyes and pigments to the water en-
vironment yearly [4]. Of greater concern are the pharmaceutical wastes
which have been classified as emerging pollutants because they remain un-
regulated or are presently undergoing a regularization process. Pharmaceu-
ticals, both prescriptive and non-prescriptive, such as analgesics,
antibiotics, hormones, antiseptics, chemotherapy drugs, have been de-
tected in surface water, wastewaters, and ground water over the last three
decades [5–7]. The occurrence of these pharmaceutical waste is of concern
due to their adverse health effect, which include the disruption of hormone
actions (leading to development and reproductive problems), the hin-
drance of metabolic processes, erosion problem in liver, when consumed
by human and aquatic species [8,9]. Furthermore, antibiotics like ciproflox-
acin and sulfamethoxazole are nonbiodegradable, genotoxic, and have
been reported to be harmful at concentrations as low as 17 μg/L to micro-
organisms in treatment plants as well as the microbial flora in which the
wastes are discharged [10–12].
In order to eliminate these recalcitrant organic compounds from waste-
water and consequently increase the availability of clean water, several
water treatment methods have been extensively studied for possible indus-
trial applications. Examples of conventional water treatment methods that
have been applied include adsorption, chlorination, deconjugation, coagu-
lation and filtration [13–18]. Unfortunately, conventional waste treatment
methods are ineffective for the complete removal of these recalcitrant or-
ganics. For instance, concentrations of residual pharmaceuticals have
been observed to be up to 60% of initial pharmaceutical concentration
after treatments with chlorination, sorption and filtration [14]. This is un-
derstandable because chlorination has low oxidative power to degrade
pharmaceuticals and its metabolites in sewage treatment plants [13]. Addi-
tionally, most conventional treatment methods such as adsorption tech-
nique generate secondary pollutants since pollutants are merely
transferred from aqueous solution to another medium. Other problems as-
sociated with conventional water treatment methods include the use toxic
chemicals and high cost of operation [19]. It is therefore vital to adopt
methods that are capable of achieving complete removal of these recalci-
trant organics for wastewater treatment applications.
Contrary to the limited success achieved with conventional water treat-
ment methods for removing organic pollutants from wastewater, impres-
sive results have been achieved with the applications of water treatment
methods based on advanced oxidation processes (AOPs). In AOPs, oxidising
radicals such as hydroxyl radicals are used to degrade organic molecules
present in aqueous solutions non-selectively. These radicals are generated
in situ through several reactions of water molecules with other chemical
compounds [20]. Unlike in conventional water treatment methods, the
powerful hydroxyl radicals (second strongest radical) generated in AOPs
make the total mineralisation of organics to water and carbon dioxide
achievable over a period of time or degradation to smaller non-toxic
small chain aliphatic carbons within a short treatment time [21]. AOPs
commonly applied for mineralisation of pharmaceuticals and other persis-
tent organics can be categorised into photochemical, non-photochemical
and hybrid processes [22,23]. Heterogenous photocatalysis, where metal
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Journal of Electroanalytical Chemistry 878 (2020) 114724
oxides semiconductor photocatalysts are used to generate hydroxyl radi-
cals, is a prominent example of AOPs commonly applied for water treat-
ment. Although titanium dioxide is the most studied photocatalyst for
degradation of both dyes [24–27] and pharmaceutical pollutants
[28–31], much attention has been given to visible light active semiconduc-
tors in recent years [32–35] in order to harness the solar energy for irradi-
ation. Other major challenges of photocatalysis are rapid recombination of
photogenerated electron – hole pairs and difficulty in the recovery and
reuse of photocatalysts. Development of photoelectrocatalysis whereby
bias potential is applied to electrode consisting of semiconductor has
been used to address some of these setbacks.
Among the numbers of visible light active metal oxide semiconductors
that have been used as photoanode in photoelectrocatalytic water
treatment, bismuth vanadate (BiVO4) has received much attention by re-
searchers due to its narrow band gap (2.4 eV) and excellent photocatalytic
properties. BiVO4 has been mostly applied in photocatalysis for water treat-
ment and some review articles have documented this [36–40]. It is also
worth noting that the most common photoelectrochemical application of
BiVO4 is towards water splitting and there are existing review articles on
this as well [41–47]. However, the photoelectrochemical application of
BiVO4 for water treatment purposes have only received attention in recent
years and it is essential to present researchers with current research devel-
opment in this field. Therefore, this review concentrates on the
photoelectrocatalytic degradation of organics (phenols, dyes and pharma-
ceuticals) using BiVO4 based photoanodes. Other aspects related to the
focus of this review such as introduction to photoelectrocatalysis; the syn-
thesis, characterisation and band gap manipulations of BiVO4; are
discussed.
2. Basic concept of photoelectrocatalysis for water treatment
Photoelectrocatalysis is an example of electrochemical advanced oxida-
tion processes (EAOP) that combines both photocatalysis and electrochem-
ical oxidation for the degradation of organics in aqueous solution. As an
EAOP, photoelectrocatalysis is an environmental friendly process since it
uses a clean reagent (electron) [48].The combined effect of light and elec-
trical energy, which results in higher removal efficiency of organic pollut-
ants, is a major advantage of this process [49]. Similar to traditional
heterogenous photocatalysis, oxidising radicals are produced through the
irradiation of semiconducting metal oxides which serve as anode in
photoelectrocatalytic system. Upon irradiation, electrons are excited to
the conduction band while vacant holes occupy the valence band. The reac-
tion of photogenerated holes with water molecules produces hydroxyl rad-
icals which are strong oxidants capable of breaking down recalcitrant
organic molecules. In fact, hydroxyl radicals have been identified as the sec-
ond strongest oxidants (after fluorine) due to its high standard reduction
potential (Eo ·OH/H2O) of about 2.8 V vs SHE [23]. Unfortunately, the life-
time of photogenerated holes are very short due to their rapid recombina-
tion with electrons and this is a major setback in photocatalysis.
However, in photoelectrocatalysis, an applied bias potential helps in driv-
ing away photogenerated electrons from the anode surface thereby
prolonging the lifetime of photogenerated holes [50]. Since more
photogenerated holes are produced in photoelectrocatalysis, more hy-
droxyl radicals can be generated within the solution and this consequently
results in higher mineralisation of organic molecules. In addition to
holes and hydroxyl radicals which attack organic compound in
photoelectrocatalysis, other reactive oxygen species are generated within
the reaction system which also contribute to the mineralisation of organic
molecules. These weaker oxidising species include superoxide radicals
and hydroperoxyl radicals. The stepwise formation of oxidising radicals in
photoelectrocatalytic system is summarised in eqs. 1–5 [2,50].
hv þ semiconductor→hþ þ e− ð1Þ
hþ þ H 2 O→ • OH þ H þ ð2Þ
B.O. Orimolade, O.A. Arotiba /
− •
e þ O2 → O−
2 ð3Þ
•
O− þ •
2 þ H → HO2 ð4Þ
2• HO2 →H 2 O2 þ O2 ð5Þ
An additional advantage of photoelectrocatalytic degradation over typ-
ical photocatalysis is the ease of reusability of the material. Since semicon-
ducting metal oxides are used to fabricate a compact electrode in
photoelectrocatalytic system, electrode can easily be rinsed, dried and
reused whereas in photocatalysis, where photocatalysts are used in pow-
dery or granular form, recovery after first use may be time consuming, dif-
ficult and may involve the use of hazardous reagents [51].
Photoelectrocatalysis also an improvement over another type of electro-
chemical method of water treatment called anodic oxidation. In anodic
oxidation, higher cell voltage is required to achieve effective degrada-
tion of organics whereas total mineralisation of organics through
photoelectrocatalysis can be achieved with substantially low applied cell
potential [13] owing to the added light stimulation of the process. There-
fore, photoelectrocatalysis also offers impressive energy efficiency.
Similar to photocatalysis, anatase titanium dioxide (TiO2) is also the
most extensively applied metal oxide semiconductor as anodic material in
photoelectrocatalysis. Numerous literatures exist on the application of
TiO2 for degradation of phenols, dyes and pharmaceuticals [52,53]. Unfor-
tunately, because TiO2 has a relatively large band gap energy (3.5 eV),
higher removal efficiency of organics can be only be achieved when TiO2
photoanode is irradiated with UV light [54]. The application of solar irradi-
ation as light source when using TiO2 often give unimpressive results be-
cause UV radiation constitute less than 5% of solar spectrum. Therefore,
the use of TiO2 is not cost efficient since UV lamps are expensive and also
exposure to UV irradiation is associated with health hazards. In order to re-
duce the cost associated with the use of TiO2 in photoelectrocatalytic water
treatment, many strategies have been employed to make TiO2 more respon-
sive to visible light irradiation which makes up the larger percentage of the
solar spectrum. Examples of such strategies include doping, morphological
control and metal loading. For instance, self-doped TiO2 nanotube (blue
TiO2) has been reported to achieve a higher removal of 2,4-
dichlorophenoxyacetic acid than pristine TiO2 photoanode with simulated
sunlight [55]. Similar enhanced performance has also been reported by
doping TiO2 with fluorine and tin [56].
In recent years, much focus has been directed to the application of visible
light active metal oxide semiconductors as suitable anodic materials for the
removal of organic pollutants in aqueous solution. These semiconductors
have relatively low band gap energy which make excitation with visible
light irradiation possible. A prominent example is tungsten trioxide (WO3)
Fig. 1. Schematic diagram for photoelectrocatalytic degradation of organic using BiVO4 photoanode.
3
Journal of Electroanalytical Chemistry 878 (2020) 114724
with a band gap energy of about 2.8 eV which has been applied for the
photoelectrocatalytic degradation of phenols, dyes and pharmaceuticals in
water [57,58]. Other visible light active semiconductors in
photoelectrocatalytic water treatment include g-C3N4 [59], Cu2O [60],
MoS2 [61], Fe2O3 [62], BiOI [63] and BiVO4. Over the last few years, consid-
erable attention has been given to BiVO4 in photoelectrocatalytic water
treatment applications. Fig. 1 presents a schematic diagram for
photoelectrocatalytic degradation of organics using BiVO4 anode. Visible
light is used to irradiate the photoanode to excite electrons to the conduction
band (CB) while photogenerated holes (which remain in the valence band)
react with water molecules to form hydroxyl radicals. Though this happens
on the electrode surface, the radicals formed diffuse into the solution to react
with organic molecules. Additionally, bias potential drives away electrons to
the cathode and these electrons also produce superoxide radicals when they
react with oxygen molecules in the solution. Therefore, the degradation of
organic molecules also takes place in the bulk of the solution.
3. Bismuth vanadate
3.1. Structural, electronic and optical properties
Bismuth vanadate (BiVO4) is a non-toxic and low-cost n-type semicon-
ductor with remarkable chemical and photostability. In recent years,
BiVO4 has attracted wide technological applications in the many fields due
to its photocatalytic, acousto-optical, ferroelasticity and ionic conductivity
properties [40]. It has been established that these properties are highly de-
pendent on its crystal and electronic structures [64]. Generally, BiVO4 exists
in three polymorphs with different corresponding crystal structures and
these polymorphs are dreyerite, pucherite and clinobisvanite. The naturally
occurring mineral of BiVO4 is the pucherite polymorph and it has an ortho-
rhombic crystal structure [65]. Dreyerite has a tetragonal zircon crystal
structure while clinobisvanite can either adopt a monoclinic scheelite or te-
tragonal scheelite structure. As shown in Fig. 2(a–c), in tetragonal zircon,
monoclinic and tetragonal structures of BiVO4, four oxygen atoms stabilize
vanadium ion and bismuth ion is coordinated by eight oxygen atoms. How-
ever, the oxygen atoms surrounding bismuth ion are from eight different
VO4 tetrahedral units in the scheelite structures; while the oxygen surround-
ing bismuth ion are from just six VO4 units in the tetragonal zircon structure.
The major difference between tetragonal scheelite and monoclinic scheelite
structure is that the distortion of local environments of bismuth ion and va-
nadium ion in monoclinic scheelite are more [66].
Furthermore, the occurrence of different crystals structures of BiVO4 is
highly temperature dependent and transitions from one crystal structure
to another is common. For instance, when BiVO4 with tetragonal zircon
structure is subjected to elevated temperatures between 670 and 770 K
B.O. Orimolade, O.A. Arotiba /
Fig. 2. Crystal structure of (a) tetragonal scheelite; (b) monoclinic scheelite and (c) zircon structure of BiVO4 (where purple is Bi, red is V and gray is O) (Reproduced with
permission from ref. [66]).(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
(about 400–500 °C) and cooled to room temperature, monoclinic scheelite
structure is obtained but this transition is irreversible. However, at a tem-
perature of 528 K, a reversible transition occurs between tetragonal schee-
lite structure and monoclinic scheelite structure [64,67]. This transition is
depicted in Fig. 3. In addition, transformation of BiVO4 from tetragonal
structure to monoclinic structure through mechanical grinding at room
temperature has been confirmed [65].
Among the different crystal structures of BiVO4, monoclinic scheelite
has been established to possess the highest photocatalytic activity for
water oxidation under visible light irradiation [67] and this has been attrib-
uted to the distortion of local environments of VO4 and BiO8. This distortion
results from the hybridization or overlap of bismuth ion in 6 s orbital and
with oxygen 2p orbital at the top of the valence band which promotes in-
creased mobility of photogenerated electrons and thereby limiting recom-
bination of electron – hole pairs [68]. Additionally, the distortion permits
a shorter transition of photoexcited electron to the vanadium 3d orbitals
in the conduction band of monoclinic scheelite BiVO4 and this accounts
for its smaller band gap energy resulting in better optical properties [36].
Specifically, the energy band gap of monoclinic structure BiVO4 is approx-
imately 2.4 eV while that of tetragonal structure falls within 2.9–3.1 eV
[47,69]. Due to the impressive photocatalytic activity of monoclinic
BiVO4, it has been extensively applied in the photodegradation of a wide
range of organic pollutants [70–73]. Additionally, it is a material of interest
in the fabrication of photoanode for hydrogen evolution in water splitting
due to its well positioned valence band [74–77]. BiVO4 has also been
used for the fabrication of photoelectrochemical sensors [78].
Fig. 3. Phase transition between different crystal structures of BiVO4 at different
temperatures (Adapted from ref. [37]).
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Journal of Electroanalytical Chemistry 878 (2020) 114724
3.2. Preparation of BiVO4
Ever since BiVO4 was first prepared in the laboratory through solid state
and melting reaction in 1963 by Roth and Waring [79], numerous other
synthesis routes have been applied for the preparation of BiVO4. These
methods include hydrothermal synthesis, electrochemical deposition,
chemical vapour deposition, metal organic decomposition, sol-gel synthe-
sis, co-precipitation method, ultrasonic/microwave assisted methods and
pulse layer deposition. Selection of appropriate method for BiVO4 synthesis
is a critical step that affects its photocatalytic activity because the morphol-
ogy, crystal structure and phase formation depend largely on the synthesis
method adopted [39,80].
Hydrothermal synthesis has been extensively used for the prepara-
tion of BiVO4 [78,81–83]. This is because the morphology and crystal-
linity of BiVO 4 can easily be controlled in the hydrothermal route
through the variation of pH or temperature and the addition of surfac-
tants. For instance, in the works of Lin et al., different microstructures
of BiVO4 were obtained at different pH values (0.5, 2, 7, 12) [84]. The
crystalline sizes of the monoclinic BiVO4 obtained at the different pH
revealed that smaller sizes are formed at higher pH value. Additionally,
as shown in Fig. 4 (a – d), hollow spheres, decahedron crystals with
well-defined edges, coralline shaped structure and needle like struc-
tures were obtained at pH 0.5, 2, 7 and 12 respectively. Furthermore,
the obtained BiVO4 at pH 7 showed highest photocatalytic activity
[84]. The use of ultrasonication with hydrothermal method has been
reported to produce BiVO4 with higher photoelectrocatalytic activity
as compared with BiVO 4 prepared with conventional hydrothermal
route [85]. This can be seen in the photocurrent response and better
stability shown in Fig. 4e and f. Similar observation has been reported
with microwave assisted hydrothermal synthesis [86].
Recently, thin films of BiVO4 have shown to possess better
photoelectrochemical properties and pulsed laser deposition have been
identified as a suitable preparation method [87]. Pulsed laser deposition
is an example of physical vapour deposition suitable for producing semi-
conducting films with outstanding electronic attributes [88]. For instance,
Kolbach et al. successfully prepared BiVO4 thin films with high
photoelectrocatalytic performance through pulsed layer deposition by al-
ternating the ablation of Bi2O3 and V2O5 [87]. In the review article by
Zhang and Li, the three major techniques for the preparation of BiVO4
thin films (molecular beam epitaxy, pulsed layer deposition and chemical
vapour deposition) are well presented [89].
B.O. Orimolade, O.A. Arotiba / Journal of Electroanalytical Chemistry 878 (2020) 114724

Fig. 4. Microstructures of BiVO4 obtained through hydrothermal synthesis at pH (a) 0.5; (b) 2; (c) 7 and (d) 12 (Reproduced with permission from [84]). Photocurrent
response of BiVO4 prepared through hydrothermal (H-BiVO4) and sonochemical assisted hydrothermal (S-BiVO4) (f) and corresponding I-t stability curves (Bias potential
of 1.2 V vs SCE; 0.5 M Na2SO4 at pH 7) (Reproduced with permission from ref. [85]).

5
B.O. Orimolade, O.A. Arotiba / Journal of Electroanalytical Chemistry 878 (2020) 114724

3.3. Improving photoelectrocatalytic efficiency of BiVO4
Even though monoclinic scheelite BiVO4 has attracted much attention
for photoelectrocatalytic applications, there are still some limitations to
its performance and these limitations are largely related to its photocata-
lytic efficiency. BiVO4, owing to its narrow band gap with short hole diffu-
sion length, suffers from excessive spontaneous recombination of
photogenerated electron – hole pairs and this reduces its photon efficiency
[47]. In addition to this, BiVO4 has poor electron mobility and slow oxida-
tion kinetics [90,91]. Several strategies have been applied to overcome
these limitations and they include morphology control, metal loading, dop-
ing and formation of heterojunction.
3.3.1. Morphology control
In order to improve the photocatalytic efficiency of BiVO4, it has been
prepared on the nanoscale with different interesting morphologies such
as nanorods, nanoplates, nanowires, nanofibers, nanotubes, hollow spheres
and nanobelts [92–95]. For instance, in the works of Deshpande et al., they
reported that the nanostructured morphology and crystal facets of BiVO4
greatly affect its photoelectrocatalytic efficiency. Different morphologies
and crystal facets were prepared by manipulating the ratio of Bi to V (Bi/
V) through spin coating process and highest photocurrent response (1.98
mAcm−2 vs RHE) was recorded with Bi/V = 3 having a nanoporous dual
morphology of nanospheres and decahedral shaped particles [96].
3.3.2. Doping
Several metals and non-metals have been introduced in little quantity
within the crystal structures of BiVO4 to facilitate photocatalytic efficiency.
Doping is an effective strategy to enhance the efficiency of BiVO4 because
the crystal structure BiVO4 has some intrinsic defects that can serve as trap-
ping sites for dopants such as Bi3+, V5+ and O2− [46]. The effectiveness of
BiVO4 doping depends on the chemical state, size and the quantity of dop-
ants introduced into the crystal structure of BiVO4. As a n-type semiconduc-
tor, the n-type conductivity and charge separation of BiVO4 can be
improved through introduction of n-type dopants which functions as do-
nors. Metal dopants such as tungsten and molybdenum, which are n-type,

Fig. 5. (a) Atomic super cell structures of the monoclinic BiVO4, from which the tunneled structure and the interconnected VO4 tetrahedra can be observed clearly;
(b) Qualitative band diagrams under illuminative for the photoanode and electrolyte interface. Dashed lines are the Fermi level of holes/electrons after photoexcitated
(reproduced with permission from ref. [97]); (c) Spin polarized density of state (DOS) of BiVO4 and Cu doped BiVO4 and corresponding (d) Partial density of states
(reproduced with permission from ref. [108]).

6
B.O. Orimolade, O.A. Arotiba /
have been found to be effective in increasing the efficiency of BiVO4 by act-
ing as shallow donors. When BiVO4 are doped with Mo and W, they often
replace the V5+ sites in the unit cell of BiVO4 [45]. This is illustrated in
Fig. 5a. Improved charge oxidation kinetics has been observed in Mo
doped BiVO4 due to the formation of high photovoltage between
photoanode and electrolyte interface resulting in faster
photoelectrocatalytic activity [97]. As shown in steady-band diagram in
Fig. 5b, the doping leads to increase in the concentration of holes and the
Fermi energy falls from the electron level (Ff,n) to quasi-Fermi (Ef,p) level
under illumination which results into the generation of photovoltage
(Vph) at the interface of electrolyte and doped BiVO4 photoanode. Further-
more, the introduction of tungsten and molybdenum into BiVO4 often in-
crease electron mobility and charge carrier density of BiVO4 resulting in
substantial enhancement in photoelectrocatalytic efficiency of BiVO.4
Thus, tungsten and molybdenum have been extensively applied as suitable
dopants for BiVO4 [45,98–100]. Copper has also been used as a dopant for
BiVO4 as reported by Regmi et al. [101]. In their study, Cu-doped BiVO4
was prepared through microwave assisted hydrothermal synthesis and
the Cu-doped showed a better photocatalytic activity in the degradation
of methylene blue and ibuprofen with inactivation of E.coli than the
undoped BiVO4. The higher photocatalytic efficiency of the doped BiVO4
was attributed to the formation of in-gap energy state which resulted in a
wider optical absorption range under visible light irradiation [101]. The
in-gap energy state formed in the Cu doped BiVO4 can be clearly seen in
the spin polarized density of states (DOS) diagram shown in Fig. 5c. It
was evident that the in-gap energy state formed originated from Cu as
shown in the partial density of states (PDOS) of individual elements
(Fig. 5d). The formation of this in-gap state is common when BiVO4 is
doped with metals. Unfortunately, the in-gap states can also act as centres
for recombination of charge carriers which consequently reduce the effi-
ciency of semiconductors [102]. Due to this challenge, non-metals have
been proposed to be more effective as dopants for BiVO4.
Improved efficiency of BiVO4 has been achieved by doping with suit-
able non-metals such as carbon, phosphorus and nitrogen. Non-metal dop-
ants often increase the photocatalytic efficiency as well as the
photoelectrochemical performance of BiVO4 through the formation of a
new valence band position which reduces the band gap energy, enhances
charge separation and extends the range of visible light absorption. In the
case of phosphorus doping of BiVO4, the V5+ in the BiVO4 lattice often
act as the sites for P5+ which is similar to the mechanism of metal doping.
Given the similar electronic levels of phosphorus and oxygen, the electronic
structure of BiVO4 can be modified through the hybridization of 2p and 2 s
orbitals of phosphorus and oxygen respectively and this often yield im-
proved efficiency of BiVO4 under visible light illumination [103,104]. As
reported by Xia et al., impressive photoelectrochemical performance was
observed when BiVO4 was doped with phosphorus [105]. The P-doped
BiVO4 photoanode was prepared by dip-coating fluorine doped tin oxide
(FTO) glass with a precursor solution of BiVO4 containing specified
amounts of phosphoric acid. It was observed that the band gap of BiVO4 re-
duced slightly with the introduction of phosphorus dopants which gave
Fig. 6. (a) Charge separation mechanism in a typical Type II heterojunction; (b) Charge separation mechanism in a Z-scheme heterojunction (Reproduced with permission
from ref. [110].
7
Journal of Electroanalytical Chemistry 878 (2020) 114724
evidence of improved visible light absorption. The P-doped BiVO4 gave a
photocurrent density of 0.28 mAcm−2 (applied potential of 1.23 V vs
RHE) which was almost three times higher than that of the undoped
BiVO4. The improved photoelectrochemical performance achieved was at-
tributed to efficient charge separation within the doped BiVO4
photoanodes. This explanation was rightly justified by measurement of
charge separation efficiency which was carried out through the addition
of hydrogen peroxide to scavenge the photo-generated holes and it was ev-
ident that the yield of photogenerated holes reaching the photoanode/elec-
trolyte interface was high in the doped BiVO4. Obviously, the significant
yield was due to efficient separation of charge carriers due to the incorpo-
ration of phosphorus dopants. Therefore, P-doped BiVO4 photoanodes
have great prospects for photoelectrocatalytic degradation of organics. In
another study, improved photocatalytic activity of BiVO4 was achieved by
doping with nitrogen [106]. However, unlike with metals and phosphorus
dopants, when BiVO4 was doped with nitrogen, two atoms of oxygen in the
unit cell of BiVO4 was replaced with nitrogen atoms. Both the experimental
results and theoretical calculations revealed that there was pronounced re-
duction of the band gap energy of BiVO4 which resulted in better visible
light absorption.
Even though the visible light absorption of BiVO4 can be increased
through doping with both non-metals and metals, doping could also result
in the decrease in the activity of BiVO4 if not properly applied. For example,
with increase in the concentration of dopants, low photoactivity has been
observed [101,107]. If the amounts or concentration of dopants introduced
into BiVO4 is relatively too high (>3%), the crystal structure of BiVO4 can
be altered and transformation from monoclinic scheelite to tetragonal
scheelite occur resulting in low photocatalytic performance [46]. There-
fore, when it comes to improving the efficiency of BiVO4 through doping,
great caution should be applied.
3.3.3. Formation of heterojunction
Among the various ways of improving the photoelectrocatalytic effi-
ciency of BiVO4, the formation of heterojunction has proven to be an excel-
lent approach. This is because doping may introduce new centres of
recombination of electron – hole pairs while morphology manipulation
can lead to increase in band gap [109,110]. A semiconductor – semiconduc-
tor heterojunction is formed when two semiconductors of unequal band
gap combine in such a way that results in band alignment. Though, there
are different band alignments possible in heterojunctions, type II (including
Z scheme) has been observed to promote efficient charge separations in
semiconductors [111–113]. In type II heterojunction (Fig. 6), charge sepa-
ration within the heterojunction interface generally follow two mecha-
nisms depending on the Fermi energy level (EF) of the two
semiconductors. In the first mechanism, electrons migrate from the conduc-
tion band of one of the semiconductors (SC-1) to that of the other semicon-
ductor (SC-2) while holes migrate from the valence band of SC-2 into the
valence band of SC-1 (Fig. 6a) and this happens when the Fermi energy
level of SC-1 (p-type) is less than that of SC-2 (n-type). On the other hand,
when the Fermi energy level of SC-1 is higher than that of SC-2, after the
B.O. Orimolade, O.A. Arotiba /
band alignment in the heterojunction, the electrons from SC-2 combines
with the holes from SC-1 making available holes in SC-2 and electrons in
SC-1 for photoelectrocatalytic activity. This kind of charge separation
mechanism is called Z-scheme (Fig. 6b) [110].
One way of classifying semiconductor – semiconductor heterojunctions
is based on if the semiconductors are n-type or p-type. Accordingly,
heterojunctions can be classified as p-p, p-n or n-n heterojunctions. Since
BiVO4 is n-type semiconductor, its heterojunction can either be p-n (when
the other semiconductor is p-type) or n-n (when the other semiconductor
is also n-type). Many researchers have confirmed enhanced efficiency of
BiVO4 based heterostructured photoanodes prepared through different
methods including hydrothermal, electrodeposition, sol-gel, calcination
and successive ion adsorption/reaction.
BiVO4 based heterojunctions consisting of either n-n and p-n junctions
have been successfully prepared using the hydrothermal route. For exam-
ple, in the works of Lu et al., hydrothermal synthesis was used to fabricate
a n-n heterojunction of BiVO4/CeVO4 using ammonium nitrate, cerium ni-
trate and bismuth nitrate as precursors [114]. The presence of both micro-
spheres of BiVO4 and hedgehog-like structure of CeVO4 were clearly
observed in the scanning electron microscopic image of BiVO4/CeVO4.
The formation of heterojunction resulted in enhanced
photoelectrochemical performance which was observed in the photocur-
rent response of BiVO4/CeVO4 which was three-fold greater than that of
pristine BiVO4. The mechanism, as depicted in Fig. 7, reveals that enhanced
separation of photogenerated carriers was achieved through the formation
of a typical type II band alignment within the BiVO4/CeVO4 heterojunction
interface which facilitated the migration of BiVO4 holes into the valence
band of CeVO4 while electrons from CeVO4 were transported into the con-
duction band of BiVO4. The efficient separation consequently resulted in
better visible light activity of BiVO4. Similar enhanced charge separations
have been achieved in other BiVO4 composites consisting of n-n
heterojunctions which were prepared using hydrothermal synthesis. Exam-
ples include BiVO4/FeVO4 [115] and BiVO4/BiPO4 [116]. Hydrothermal
synthesis have equally been employed in the prepared of p-n
heterojunctions of BiVO4 such as BiVO4/Co3O4 [117] and BiVO4/BiOBr
[118] heterostructures which possess impressive photocatalytic efficiencies
far higher than pristine BiVO4. Therefore, hydrothermal technique remains
a suitable technique for the preparation of BiVO4 heterostructures. Soltani
et al. have also demonstrated the feasibility of preparing BiVO4
heterojunction through ultrasonic assisted hydrothermal synthesis by suc-
cessful constructing BiVO4/BiFeO3 heterojunction [119]. The BiVO4/
BiFeO3 contains a p-n junction which greatly reduce rapid recombination
of photo induced charge carriers through formation of type II band
alignment.
Two step electrodeposition technique has also been successfully used in
the construction of BiVO4 based heterojunction with a n-n junction. For in-
stance, as shown in the schematic diagram in Fig. 8a, BiVO4/MnO2
heterojunction was prepared through electrodeposition on FTO glass by
Fig. 7. Possible Type II mechanism of charge separation between n-n junction of
BiVO4/CeVO4. (Reproduced with permission from ref. [114]).
8
Journal of Electroanalytical Chemistry 878 (2020) 114724
Arotiba and co-workers [120]. BiOI was electrodeposited and vanadium so-
lution was drop casted. Upon calcination at 420 °C, BiVO4 was obtained.
MnO2 was then electrodeposited on the prepared FTO-BiVO4 to obtain
FTO-BiVO4/MnO2. The prepared BiVO4 heterostructure gave better photo-
current response than pristine BiVO4 which revealed that the formation of
heterojunction led to better charge separation which resulted in enhanced
photoelectrochemical activity (Fig. 8b) [120]. The mechanism of the
charge separation within the n-n junction interface was found to proceed
through a type II mechanism. Similar electrodeposition approach has
been used to construct BiVO4/BiOI [121] and BiVO4/Cu2O [122]
heterojunctions with p-n junctions with a type II charge separation mecha-
nism which resulted in improved photocatalytic activity.
Furthermore, successive ion layer adsorption/reaction (SILAR) has
proven to be an effective way of preparing BiVO4 based heterojunctions
consisting of either n-n or p-n junctions. Usually, one of the semiconductors
forming the heterojunction is prepared through other synthesis routes such
as hydrothermal and electrodeposition, then the other semiconductor will
be combined with it through SILAR reaction. For example, BiVO4/Ag2S
has been prepared by Guan et al. using SILAR method [123]. The BiVO4
was firstly prepared by electrodeposition on FTO glass and this was then
followed by the addition of Ag2S through SILAR. This was carried out by
successively immersing the prepared FTO-BiVO4 into solutions of silver ni-
trate and thiourea. The procedure is illustrated in Fig. 8c [123]. The pre-
pared BiVO4/Ag2S achieved an impressive photocurrent density of 1.91
mAcm−2 at 1.23 V vs RHE which was more than threefold higher than
that of pristine BiVO4 [123]. The enhanced photoelectrochemical perfor-
mance of the BiVO4/Ag2S photoanode was credited to the p-n junction
formed between the two semiconductors which favoured electron mobility
and efficient separation of photogenerated charge carriers through a type II
mechanism. Similarly, Du et al., prepared BiVO4/WO3 consisting of n-n
heterojunction using SILAR approach [124]. However, the WO3 was ini-
tially prepared through hydrothermal synthesis while BiVO4 was added
through SILAR from solutions of bismuth nitrate and ammonium vanadate.
The photoelectrocatalytic efficiency of BiVO4/WO3 was also significantly
higher than that of BiVO4 only.
Evidently, combining BiVO4 with another semiconductor to form
heterojunction remains an appropriate technique to improving the
photoelectrocatalytic performance of BiVO4 photoanodes. However, not
all semiconductor heterojunctions favour efficient charge separation
[110]. Therefore, serious considerations need to be given to the choice of
the other semiconductor in order to form suitable BiVO4 heterojunctions
that will result in better photoelectrocatalytic efficiency. Generally, since
the formation of heterojunction depends largely on band edge positions
and Fermi energy levels, theoretical evaluations can be carried out (if this
information is available) on the semiconductors to inform on the likelihood
of a suitable heterojunction and possible charge separation mechanism
beforehand.
4. Photoelectrocatalytic degradation of organics using BiVO4
photoanodes
Photoanodes of BiVO4 have been successfully employed for the
photoelectrocatalytic degradation of phenols, dyes and pharmaceuticals.
In most applications, fluorine doped tin oxide glass (FTO) is often used as
the conducting substrate for BiVO4. For example, Bennani et al. reported
the photoelectrocatalytic degradation of phenol using BiVO4 thin films
[125]. Spray pyrolysis was used to prepare the thin films of monoclinic
scheelite BiVO4 on FTO glass from a precursor solution. The degradation
setup used was a three-electrode system where FTO-BiVO4, platinum wire
and Ag/AgCl electrode were the working, counter and reference electrode
respectively. The working solution consisted a 250 mL solution of
20 mgL−1 phenol in the presence of 14.2 gL−1 Na2SO4. Xenon lamp with
intensity of 60 Wm−2 was used as a source of visible light irradiation.
The prepared BiVO4 photoanode achieved 70% removal of phenol concen-
tration with applied potential of 1.0 V vs Ag/AgCl electrode after 4 h. The
performance of the BiVO4 in the degradation of phenol was also compared
B.O. Orimolade, O.A. Arotiba / Journal of Electroanalytical Chemistry 878 (2020) 114724

Fig. 8. Schematic diagram of (a) electrodeposition of BiVO4/MnO2 and (b) corresponding photocurrent response (Bias potential of 1.5 V vs Ag/AgCl; 0.1 M Na2SO4 at pH 7 as
supporting electrolyte) (reproduced with permission from ref. [120]); (c) Schematic diagram for SILAR preparation of BiVO4/Ag2S (reproduced with permission from ref. [123]).

9
B.O. Orimolade, O.A. Arotiba /
with that of TiO2 and it was observed that TiO2 achieved a lower percent-
age removal of 56% after 4 h. The degradation reaction rate constants
were 0.005 min−1 and 0.0024 min−1 for BiVO4 and TiO2 respectively.
The improve performance achieved with BiVO4 was rightly attributed to
better visible light absorption.
Similarly, the photoelectrocatalytic degradation of methyl orange (an
azo dye) using BiVO4 prepared on FTO glass was investigated by Bacha
et al. [126]. The BiVO4 photoanode was prepared through drop coating
and calcination at 500 °C for 3 h. The degradation setup consisted of a
three-electrode system with FTO-BiVO4, Ag/AgCl and platinum wire as
working, reference and counter electrode respectively. The source of visible
light irradiation was a 300 W Xenon lamp with an intensity of 100
mWcm−2. The initial concentration of methyl orange solution used was
10 mgL−1 at pH 7.5 while the volume used was 40 mL. The effect of
sulphite radicals which are also reactive species in the degradation of or-
ganic pollutants, was also studied by the addition of different concentra-
tions of Na2SO3. It was observed that without sulphite the percentage
removal of methyl orange was just 10.9% while the percentage removal in-
creased with increase in sulphite concentration and the highest removal of
96.6% was achieved in the presence of 16 mM sulphite after 2 h with ap-
plied bias potential of 2.0 V vs Ag/AgCl. Scavenging experiments carried
out by the addition of EDTA, NaNO3 and isopropanol revealed that holes
and hydroxyl radicals were largely responsible for the mineralisation of
methyl orange on by BiVO4 photoanode. In another study conducted by
Shao et al., the photoelectrocatalytic degradation of Bisphenol A using
BiVO4 photoanode was significantly improved by the addition of peroxy-
monosulfate [127]. The total removal of 10 mgL−1 bisphenol A was
achieved after 2 h with 0.25 V vs SCE applied potential with visible light ir-
radiation. The mechanism of the reaction is depicted in Fig. 9 and it can be
seen that peroxymonosulfate acts as electron acceptor for BiVO4 while the
holes are then available for the oxidation of the organics. Generally, sul-
phate or sulphite radicals are suitable secondary radicals that can be used
to improve the performance of BiVO4 photoanodes in degradation of or-
ganics. Furthermore, both sulphates and sulphites can equally promote en-
hanced charge separation within BiVO4 which also result in increased
efficiency.
In addition to the use of supporting radicals to improve the performance
of BiVO4 photoanodes, the conducting substrate used for BiVO4
photoanode has also been investigated. Though FTO has been widely
used as the substrate for semiconductors in photoelectrocatalytic degrada-
tion experiments, exfoliated graphite (EG) has also been explored as a
Fig. 9. Mechanism of photoelectrocatalytic degradation of bisphenol in the
presence of peroxymonosulfate at a FTO-BiVO4 anode (reproduced with
permission from ref. [127]).
10
Journal of Electroanalytical Chemistry 878 (2020) 114724
suitable substrate due to its remarkable conductivity and low cost by
Arotiba and co-workers [49,61,128,129]. The use of EG as photoanode sub-
strate was further extended to BiVO4 by this same research group [130].
The EG-BiVO4 photoanode anode achieved 88% percentage removal of or-
ange 2 dye after 90 min with applied current density of 10 mAcm−2. It was
observed that EG significantly increase the electron mobility within the
photoanode. Additionally, better separation of photoinduced charge car-
riers achieved in BiVO4 because EG also act as electron sink for BiVO4
thereby increasing the efficiency and kinetics of the degradation process.
4.1. Application BiVO4 heterostructures in photoelectrocatalytic degradation
Due to the poor performance of bare BiVO4 in photoelectrocatalytic
degradation, BiVO4 based heterostructures with efficient charge separation
have been widely applied in photoelectrocatalysis for water treatment.
Both BiVO4 based heterostructured photoanodes with p-n or n-n junctions
have been applied accordingly. For instance, Cao et al. reported the
photoelectrocatalytic degradation of antibiotic norfloxacin using BiVO4/
Ag3PO4 electrode [131]. The photoelectocatalysis experiments were con-
ducted with 5 mgL−1 norfloxacin solution in a three-electrode system
where BiVO4/Ag3PO4, platinum wire and SCE were working electrode,
counter electrode and reference electrode respectively. A 300 W xenon
lamp with UV cut-off filter was used as the source of visible light irradia-
tion. After photoelectrocatalytic degradation time of 90 min with an ap-
plied low bias potential of 0.5 V, the binary BiVO4/Ag3PO4 electrode
achieved 100% removal of norfloxacin while the bare BiVO4 photoanode
achieved only 61.4% removal. The reaction rate of the binary electrode
was also faster than that of bare BiVO4. The remarkable efficiency recorded
on the BiVO4/Ag3PO4 electrode was due to enhanced charge separation in-
duced by the formation of heterojunction. The mechanism of the reaction
process indeed confirmed the charge separation happening within the n-n
junction and this was proposed through scavenger studies and electron
spin resonance. It was found that more photogenerated holes were pro-
duced in the composite electrode which favoured high production of hy-
droxyl radicals and this was because the holes from BiVO4 were
efficiently separated into the valence band of Ag3PO4 following a type II
heterojunction mechanism. However, the prepared photoanode was unable
to achieve total mineralisation of norfloxacin within the reaction time as
only about 27% total organic carbon (TOC) was removed. Regardless of
the low TOC removal, the heterostructured photoanode generally per-
formed better than bare BiVO4 and was also effective in the removal of
other antibiotics. In addition to these, the prepared heterostructured
photoanode demonstrated impressive stability with no sign of
photocorrosion after four cycles of usage.
Another BiVO4 based heterostructured photoanode with n-n junction
that has been used for the photoelectrocatalytic removal of norfloxacin is
BiVO4/WO3 photoanode as reported by Du et al. [124]. The BiVO4/WO3
heterostructured photoanode was prepared using hydrothermal and
SILAR synthesis routes. After a photoelectrocatalytic degradation time of
3 h with applied bias of 1.0 V vs SCE, the BiVO4/WO3 photoanode achieved
67% removal of norfloxacin (10 mgL−1) which was significantly higher
than about 40% recorded with the use of pristine BiVO4 photoanode. The
formation of BiVO4/WO3 heterojunction resulted in increased
photoelectrocatalytic efficiency through the suppression of rapid recombi-
nation of photogenerated electron – hole pairs and this resulted in better
performance of the heterostructured anode. The authors confirmed the
charge separation happening within the n-n junction through trapping ex-
periments and it was observed that when photogenerated holes were sup-
pressed by the addition of EDTA salt, the percentage removal of
norfloxacin decreased significantly which suggested that the process relied
on the photogenerated holes. Accordingly, the mechanism of charge sepa-
ration revealed that a type II heterojunction was formed whereby the elec-
trons from BiVO4 were prevented from recombining with holes since they
are transferred to the conduction band of WO3. The holes from both WO3
and BiVO4, which were separated in the valence band of BiVO4, then facil-
itated the oxidation of norfloxacin. The stability and reusability of the
B.O. Orimolade, O.A. Arotiba / Journal of Electroanalytical Chemistry 878 (2020) 114724

Table 1
Summary of recent reports using BiVO4 based photoanode for photoelectrocatalytic degradation of organics.
Photoanode Preparation Reactor cell Light source Analyte %removal Rate constant Ref
method concentration

FTO-BiVO4 Spin coating and Three electrode system; Pt wire and 160 W Hg lamp (100 Methylene Blue 96% after 5 h −1.06 × 10−2 min−1 [96]
annealing Ag/AgCl as counter and reference mWcm−2). (20 mgL−1)
electrodes respectively Congo Red 86% after −1.87 × 10−2 min−1
(20 mgL−1) 90 min
BiVO4/MnO2 Electrodeposition Three electrode system; Pt sheet and 100 W Xe lamp Ciprofloxacin 76% after 2 h 1.05 × 10−2 min−1 [120]
Ag/AgCl as counter and reference (λ ≥ 420 nm). (10 mgL−1)
electrodes respectively.
Bias potential: 1.5 V vs Ag/AgCl
FTO-BiVO4 Spray pyrolysis Three electrode system; Pt wire and Xenon lamp with Phenol (20 mgL−1) 70% after 4 h 0.005 min−1 [125]
Ag/AgCl as counter and reference light intensity of 60
electrodes respectively. Wm−2.
Bias potential: 1.0 V vs Ag/AgCl
FTO-BiVO4 Drop coating and Three electrode system; Pt wire as 300 W Xe lamp (100 Methyl orange 96.6% after 0.029 min−1 [126]
calcination counter electrode and Ag/AgCl as mWcm−2). (10 mgL−1) 2h
reference electrode.
Bias potential: 2 V vs Ag/AgCl
FTO-BiVO4 Electrodeposition Three electrode system; Pt wire and 300 W Xe lamp Bisphenol A 100% after 2 h 0.041 min−1 [127]
SCE as counter and reference electrode (λ ≥ 420 nm). (10 mgL−1)
respectively.
Bias potential: 0.25 V vs SCE
EG-BiVO4 Hydrothermal Pt sheet and Ag/AgCl as counter and 100 W Xe lamp Acid orange 7 88% after 0.016 min−1 [130]
synthesis reference electrodes respectively. (λ ≥ 420 nm). (10 mgL−1) 90 min
Current density of 10 mAcm−2
BiVO4/Ag3PO4 Electrodeposition Three electrode system; Pt wire and 300 W Xe lamp Norfloxacin 100% after 7.94 × 10−4 min−1 [131]
and in situ growth SCE as counter and reference electrode (λ ≥ 420 nm). (5 mgL−1) 90 min
respectively.
Bias potential: 0.5 V vs SCE
BiWO4/WO3 Hydrothermal Three electrode system; Pt plate and 300 W Xe lamp Norfloxacin 67% after 3 h 2.68 × 10−3 min−1 [124]
and SILAR SCE as counter and reference electrode (λ ≥ 420 nm) with (10 mgL−1)
respectively. intensity of 1
Bias potential: 1.0 V vs SCE mWcm−2.
BiWO4/WO3 Chemical Three electrode system; Pt foil and SCE 300 W Xe lamp Tetracycline 76.1% 0.683 h−1 [132]
reduction and as counter and reference electrode (λ ≥ 420 nm) with hydrochloride 71.5% 0.385 h−1
spin coating respectively. intensity of 100 Phenol 94.8% after 1.05 h−1
Bias potential: 1.0 V vs SCE Wcm−2. Congo red 3h
(10 mgL−1 each)
BiVO4/Ag2S Electrodeposition Three electrode system; Pt sheet and 100 W Xe lamp Ciprofloxacin 80% 0.014 min−1 [133]
and SILAR Ag/AgCl as counter and reference (λ ≥ 420 nm). (10 mgL−1)
−1
electrodes respectively. Sulfamethoxazole 86% after 2 h 0.015 m
Bias potential: 1.2 V vs Ag/AgCl (10 mgL−1)
BiVO4/TiO2 Sol-gel and Three electrode system; Pt wire and 300 W Xe lamp Rhodamine B 93.9% after [134]
hydrothermal Ag/AgCl as counter and reference (λ ≥ 420 nm) with (10 mgL−1) 5h
electrodes respectively. intensity of 200
Bias potential: 4 V vs Ag/AgCl mWcm−2.
EG-BiVO4/ZnO Hydrothermal Three electrode system; Pt sheet and 100 W Xe lamp Rhodamine B 91% after 4 h 9.21 × 10−3 min−1 [135]
and annealing Ag/AgCl as counter and reference (λ ≥ 420 nm). (10 mgL−1)
electrodes respectively.
Current density of 10 mAcm−2
BiVO4/BiOI Electrodeposition Porous carbon felt as cathode. Paracetamol 92% after 4 h [136]
Current density of 10 mAcm−2 (0.1 mM) (TOC)
BiVO4/WO3 Impregnation, PFC setup with MnO2/graphene oxide 300 W Xe lamp Rhodamine B 81.6% after 0.286 h−1 [137]
drop coating and cathode. (λ ≥ 420 nm) with (0.02 mM) 6h
annealing intensity of 100
mWcm−2.
FTO-BiVO4 Electrodeposition PFC setup with CuO/Cu2O cathode 300 W Xe lamp Phenol (5 mgL−1) 100% after 2 h 2.568 h−1 [138]
(λ ≥ 420 nm).
BiVO4/TiO2 Anodization and PFC setup with Cu2O/TiO2 cathode 300 W Xe lamp Tetracycline 30.5% after 0.307 h−1 [139]
electrodeposition (λ ≥ 420 nm) with hydrochloride 2h
intensity of 100 (10 mgL−1)
mWcm−2.
FTO-BiVO4 Electrodeposition Coupled system with Hemin/Cu and 300 W Xe lamp Rhodamine B 88.5% after [140]
carbon cloth as dual cathode (λ ≥ 420 nm). 1h
Bias potential: 0.8 V Tetracycline 93.6% after
2h
FTO-BiVO4 Solvothermal Three electrode system; polydopamine 300 W Xe lamp Ofloxacin 99.3% after 0.077 min−1 [141]
modified carbon felt as counter (λ ≥ 420 nm). (8 mgL−1) 2h
electrode and Ag/AgCl as reference
electrode.
Bias potential: 1.5 V
BiVO4/WO3 Electrodeposition Three electrode system; Pt foil and SCE Light intensity of 0.1 Levofloxacin 60% [142]
and anodization as counter and reference electrode Wcm−2. (10 mgL−1)
respectively. Ketoprofen 80% after 5 h.
(10 mgL−1)

(continued on next page)

11
B.O. Orimolade, O.A. Arotiba / Journal of Electroanalytical Chemistry 878 (2020) 114724

Table 1 (continued)

Photoanode Preparation Reactor cell Light source Analyte %removal Rate constant Ref
method concentration

Bias potential: 1.2 V for ketoprofen and

1.5 V for levofloxacin
Yb-BiVO4/Bi2O3 Hydrothermal Three electrode system; Pt wire and 500 W Xe lamp Methylene blue 83.2% [143]
SCE as counter and reference electrodes (λ ≥ 420 nm). Methyl orange 93.3%
respectively. Tetracycline 78.7%
Bias potential: 1.0 V Chlorophenol 70.2% after
(10 mgL−1 each) 2 h.
BiVO4/CuO Thermal Three electrode system; Pt foil and White LED 44 W 4-nitrophenol 50.2% after 3.11 × 10−4 s−1 [144]
decomposition Ag/AgCl as counter and reference (λ ≥ 420 nm). (30 mgL−1) 8 h (TOC)
electrodes respectively.
Bias potential: 4.0 V
BiVO4/Fe2O3 Spin coating and Three electrode system; Pt foil and 350 W xenon lamp Phenol (50 mgL−1) 68.89% after [145]
SILAR Ag/AgCl as counter and reference (100 mWcm−2) 2h
electrode respectively.
Bias potential: 0.6 V
BiVO4/TiO2 Hydrothermal PFC setup with ZnO/CuO cathode 350 W Xe lamp Methyl Orange 76% 0.018 min−1
and spin coating (λ ≥ 420 nm) with Methylene Blue 83% 0.029 min−1 [146]
intensity of 100 Congo red 90% after 0.022 min−1
mWcm−2. (20 mgL−1 each) 80 min
BiVO4/ZnO Liquid phase Three electrode system; Pt foil and SCE 300 W Xe lamp Tetracycline 66.1% after 1.94 × 10−3 min−1 [147]
deposition and as counter and reference electrode (λ ≥ 420 nm) (20 mgL−1) 2h
SILAR respectively.
Bias potential: 0.8 V
BiVO4/g-C3N4 Electrospinning Three electrode system; Pt wire and Xe lamp Diclofenac sodium 30.1% after 3.23 × 10−3 min−1 [148]
and calcination SCE as counter and reference electrode (λ ≥ 420 nm) (10 mgL−1) 2h
respectively.
Bias potential: 1.0 V
FTO-BiVO4 Electrodeposition Au decorated silicon photovoltaic cell 500 W xenon lamp Rhodamine B 77.98% – [149]
(100 mWcm−2) Methyl orange 89.15%
Methylene blue 93.2% after
(10 mgL−1 each) 2 h.
BiVO4/Ag/AgCl/g-C3N4 Dip coating and Two-cell chamber separated by a 150 W solar Ibuprofen Degradation – [150]
annealing proton exchange membrane simulator efficiency of
Potential: 1.23 V vs RHE 11.15%
h−1 cm−2.
BiVO4/TiO2 Hydrothermal Three electrode system; Pt foil and 350 W xenon lamp Methylene blue 91.8% after – [151]
and liquid phase Ag/AgCl as counter and reference (100 mWcm−2) (10 mgL−1) 80 min.
deposition electrode respectively.
Bias potential: 1.0 V
BiVO4/WO3 Dip coating and PEC setup with solar cell and stainless 20 W visible light. Methylene blue 94% – [152]
calcination steel as cathode. (5 mgL−1)
Bias potential: 2.0 V Rhodamine B 93% after 3 h.
(5 mgL−1)
Co-BiVO4 Impregnation Two electrode system; Pt foil counter 300 W xenon lamp Bisphenol A 99.16% after 0.0803 min−1 [153]
electrode. (100 mWcm−2) (10 mgL−1) 1h
Bias potential: 1.2 V
Mo-BiVO4/WO3 Hydrothermal Pd/Ni foam as counter electrode. – 2,4-dichlorophenol 99% after 3 h – [154]
and drop coating Bias potential: 1.0 V vs Ag/AgCl (100 mgL−1)
BiVO4/BiOI Electrodeposition Pt sheet and Ag/AgCl as counter and 100 W Xe Ciprofloxacin 62% – [155]
reference electrodes respectively. lamp (λ ≥ 420 nm). Acetaminophen 68%
Bias potential: 1.5 V vs Ag/AgCl Orange 2 dye 85% after 2 h
(10 mgL−1 each)
CNP/B-BiVO4/WO3 Hydrothermal Pt sheet and Ag/AgCl as counter and 100 W Xe lamp Orange 2 dye 56% after 3 h 0.845 h−1 [156]
reference electrodes respectively. (λ ≥ 420 nm). (50 mgL−1)
Bias potential: 1.2 V vs Ag/AgCl

photoanode after three cycles were assessed, it was observed that the
photoanode was susceptible to minimal surface adsorption of undegraded
norfloxacin as well as degraded byproducts which lead to slight decrease
in the percentage removal after the third cycle. However, the photoanode
demonstrated a degree of acceptable stability. A similar heterojunction of
BiVO4/WO3 with a type II charge separation mechanism has been used
for successful photoelectrocatalytic degradation of tetracycline hydrochlo-
ride with visible light irradiation as reported by Zheng et al. [132]. Even
though the efficiencies achieved with the use of BiVO4/WO3 photoanode
is often less than hundred percent, BiVO4/WO3 heterojunction remains
the most common BiVO4 based heterojunction used in
photoelectrocatalytic oxidation of organic pollutants (Table 1). In all the
studies, the charge separation mechanism within BiVO4/WO3 n-n
heterojunction follows similar route. However, the performance and stabil-
ity of the electrode largely depends on the analyte concentration, applied
potential as well as the heterojunction synthesis method.
BiVO4 based heterostructured photoanodes with p-n junction has also
been successfully used for the photoelectrocatalytic removal of organics.
For example, in our research group, Ag2S was used to form a p-n
heterojunction with BiVO4 and applied for the photoelectrocatalytic re-
moval of ciprofloxacin and sulfamethoxazole [133]. In the study, BiVO4/
Ag2S heterojunction was prepared through electrodeposition and SILAR ap-
proach. A three-electrode system using the prepared material, platinum
sheet and Ag/AgCl (3.0 M KCl) as working electrode, counter electrode
and reference electrodes respectively was used for the degradation process.
With an applied potential of 1.2 V vs Ag/AgCl, percentage removal of 80%

12
B.O. Orimolade, O.A. Arotiba / Journal of Electroanalytical Chemistry 878 (2020) 114724

and 86% were obtained for ciprofloxacin and sulfamethoxazole respec- photoanode in a coupled photoelectrocatalysis and electro-Fenton system
tively after 2 h. These values were significantly higher than what was for mineralisation of paracetamol has been studied by Arotiba and co-
achieved using bare BiVO4 photoanode. The improved performance of workers [136]. The photoanode used consisted of BiVO4/BiOI
BiVO4/Ag2S was due to the formation of type II heterojunction and the elec- heterojunction with p-n junction and it achieved a total removal of paracet-
tron lifespan was calculated to be longer than that of BiVO4 which evidently amol within 2 h but with less than 60% TOC removal when platinum sheet
confirmed the reduction in rapid recombination of electron hole pairs. Con- was used as cathode (photoelectrocatalysis alone). The mechanism of the
sequently, the mechanism of charge separation was proposed as shown in photoelectrocatalysis process revealed that the charge separation within
Fig. 10a where the charge separation mechanism within the p-n the heterostructured anode enhanced the degradation efficiency. However,
heterojunction follows a type II pattern whereby holes and electrons were when the cathode was replaced with carbon felt to establish a
separated into the valence band of Ag2S and conduction band of BiVO4 re- photoelectrocatalysis – electro-Fenton system, the TOC removal increased
spectively. The improved charge separation therefore justified the better appreciably to more than 90%. It was observed that coupling the two pro-
performance of BiVO4/Ag2S than both bare BiVO4 and Ag2S photoanode cesses favoured the production of more hydroxyl radicals within the system
as shown in Fig. 10b. The BiVO4/Ag2S further displayed good stability as the scavenger studies confirmed that hydroxyl radicals play a major role
and reusability over three experimental cycles of 2 h each (Fig. 10c). in the degradation process of paracetamol. Furthermore, coupling
After the third cycle (6 h), the electrode showed no sign of leaching or photoelectrocatalytic process with electro-Fenton also resulted in efficient
photocorrosion and still maintained its removal efficiency. energy consumption for the mineralisation process. The findings from this
The versatility of BiVO4 heterostructured photoanodes has also been study established the suitability of using BiVO4 photoanodes in coupled
demonstrated for the photoelectrocatalytic degradation of dyes. Wang photoelectrocatalytic – electro-Fenton degradation system.
et al. reported enhanced photoelectrocatalytic degradation of rhodamine
B dye on a BiVO4/TiO2 n-n heterostructured anode [134]. The
heterojunction was prepared using sol-gel and hydrothermal method. A
three-electrode system comprising of the prepared material, platinum
wire and Ag/AgCl as working, counter and reference electrode respectively
was used for photoelectrocatalytic degradation of 100 mL solution of rho-
damine B dye. The light source was a 300 W Xenon lamp with an intensity
of 200 mWcm−2. After a reaction time of 5 h with applied potential of
4.0 V, a degradation efficiency of 93.9% for the removal of rhodamine B
dye was achieved. This degradation efficiency was greater than that re-
corded with BiVO4 electrode which suggested that the type II
heterojunction facilitated photoelectrocatalytic efficiency in BiVO4/TiO2
electrode. The superiority of degrading rhodamine by using BiVO4/TiO2
in photoelectrocatalytic process over photocatalytic process was also con-
firmed and the mechanism of charge separation in the two processes
were proposed. From the mechanism study, the photogenerated electrons
from the BiVO4 were migrated to the conduction band of TiO2 while
photogenerated holes were retained in the valence band of BiVO4. The
mechanism revealed that the separated electrons played predominant role
in photocatalysis while photogenerated holes played the major roles in
photoelectrocatalysis. Furthermore, in the acute toxicity tests, less toxic in-
termediate products were formed in the photoelectrocatalysis process and
the photoanode has good stability after 18 h.
Similarly, Arotiba and co-workers studied the photoelectrocatalytic
degradation of rhodamine B dye on another type of BiVO4 heterostructured
photoanode. BiVO4/ZnO photoanode with n-n heterojunction was fabri-
cated through hydrothermal synthesis. The composite photoanode
achieved 91% photoelectrocatalytic removal of rhodamine B after 4 h
[135]. The performance of the heterostructured anode was significantly
higher than that of pristine BiVO4 photoanode due to reduced recombina-
tion of photogenerated charge carriers. It was observed that the charge sep-
aration within the n-n junction followed a type I mechanism, however,
efficient charge separation of holes in the valence band of BiVO4 was
achieved and this accounted for the improved photoelectrocatalytic perfor-
mance. Additionally, the EG used as substrate helped in trapping
photogenerated holes. The results further confirmed that the formation of
heterojunction is an ideal strategy for enhancing the efficiency of BiVO4
photoanodes.

4.2. BiVO4 in coupled systems

The efficiency of photoelectrocatalytic degradation of organics can be

enhanced by coupling the process with other suitable water treatment pro-
cesses. In photoelectrocatalysis, the oxidation of organics is facilitated at
the anode while platinum sheet or plate is often used as cathode. Therefore,
it is possible to improve the efficiency of the process by combining it with Fig. 10. (a) Charge separation mechanism within BiVO4/Ag2S heterojunction in
another electrochemical advanced oxidation process which depends on photoelectrocatalytic degradation of ciprofloxacin and (b) corresponding
cathode such as electro-Fenton. The feasibility of using BiVO4 based concentration decay pattern (reproduced with permission from ref. [133]).

13
B.O. Orimolade, O.A. Arotiba /
Another dual functional system where BiVO4 photoanodes have found
significant application is in photocatalytic fuel cells (PFC) in which
photoelectrocatalytic process is used for simultaneous power generation
and organic pollutant degradation. The performance of PFC systems signif-
icantly depends on the efficiencies of both photoanode and cathode. In the
works of Ouyang et al., a PFC system with two electrode configuration
consisting of BiVO4/WO3 photoanode and MnO2/graphene oxide cathode
was used for the simultaneous degradation of rhodamine B dye and energy
production [137]. The source of the visible light irradiation was a 300 W
Xenon lamp with intensity of 100 mWcm−2. The percentage
photoelectrocatalytic removal of rhodamine B after 6 h was 81.6% which
was significantly higher than the 61.4% recorded using the prepared
BiVO4/WO3 for photocatalytic degradation. Attempts were made to un-
derstand the mechanism of the degradation process taking place within
the system and photoluminescence spectra revealed that significant quan-
tities of hydroxyl radicals were produce from the photoanode. As shown
in Fig. 11, the efficient charge separation within the n-n heterojunction of
BiVO4/WO3 is responsible for the availability of photogenerated holes
which produced hydroxyl radicals. Additionally, the photogenerated elec-
trons separated in the conduction band of WO3 migrated through the ex-
ternal circuit to the MnO2/GO cathode. The performance of the PFC cell
is credited to these two processes. More so, the large surface area of the
cathode greatly reduced charge transfer resistance and the system also
displayed remarkable stability after 30 h of use. In another study involv-
ing the removal of another organic pollutant – phenol, Li et al., used a
PFC system consisting of BiVO4 photoanode and Cu2O/CuO photocath-
ode to obtain improved photoelectrocatalytic degradation [138]. The sys-
tem was a self-bias system which was induced due to the mismatch Fermi
energy levels of BiVO4 photoanode and Cu2O/CuO cathode. The dual
electrode system PFC achieved 100% photoelectrocatalytic removal of
phenol after a long period of 21 h with corresponding TOC removal of
40.3%. Impressively, with the introduction of H2O2 into the PFC system,
complete removal of phenol was achieved within 2 h with TOC removal
of 44.6%. It was proposed that photogenerated electrons at Cu2O/CuO
activated the added H2O2 to generate more hydroxyl radicals within the
system through a Fenton like reaction and this complemented the hy-
droxyl radicals produced at the photoanode. Furthermore, a PFC system
consisting of BiVO4/TiO2 photoanode and Cu2O/TiO2 photocathode has
also been successfully applied for the photoelectrocatalytic removal of tet-
racycline hydrochloride [139]. The mechanism of the degradation pro-
cess equally revealed that hydroxyl radicals produced from
photoinduced holes at the BiVO4 photoanode and superoxide radicals
Fig. 11. Schematic diagram for PFC cell showing the charge transfer mechanism
within BiVO4/WO3 photoanode (reproduced with permission from ref. [137]).
14
Journal of Electroanalytical Chemistry 878 (2020) 114724
produced from the reaction of electrons at the cathode were responsible
for the oxidation of the pharmaceutical.
Furthermore, BiVO4 photoanode has also been employed in the degra-
dation of organics in a coupled system of photoelectrocatalysis and
electroenzymatic catalysis [140]. The degradation setup consisted of
BiVO4 photoanode and a dual cathode of hemin/Cu and carbon cloth
with a 300 W xenon lamp as light source and air was continuously purged
into the system to facilitate electrogeneration of H2O2 at the cathode. The
system achieved 88.5% removal of 5 mgL−1 rhodamine B dye after 1 h
and 93.6% removal of tetracycline after 2 h was also reported and these
values were significantly higher than the single process. The remarkable
degradation of organics recorded was attributed to the synergistic effect be-
tween photoelectrocatalytic process and electroenzymatic and the system
showed good stability and reusability after four cycles of usage. Overall,
BiVO4 based photoanodes have been found to be suitable for applications
whereby photoelectrocatalytic process is combined with other electro-
chemical processes.
The summary of other works involving the application of BiVO4 in
photoelectrocatalytic degradation of organics in water are presented in
Table 1. However, there is still need to understand the mechanism of the
processes happening in details as the proposed mechanism relied solely
on the estimation of radicals formed during the reaction.
5. Conclusion and future perspectives
BiVO4 has indeed lent itself to many applications in energy and the
environment. Relative to some applications such as water splitting, its
use in the photoelectrocatalytic treatment of organic pollutants in water
and wastewater is fewer and recent. This review has provided a compre-
hensive overview on recent progress on the applications of bismuth van-
adate based photoanodes in visible light mediated photoelectrocatalytic
removal of organics in wastewater. The choice of BiVO4 as a suitable
photoanode over the years has been because of its attractive attributes
such as low toxicity, narrow band gap, ease of fabrication and low poten-
tial for water oxidation. These attributes, no doubt, are being exploited in
the removal of a myriad of organic pollutants through various
photoelectrocatalytic systems. Furthermore, these attributes have helped
in improving the sustainability of photoelectrocatalysis by the introduc-
tion of visible light or solar light in lieu of the less environmentally
friendly UV light. While the rapid recombination of photogenerated elec-
tron – hole pairs and poor conductivity drawbacks of BiVO4 are acknowl-
edged, the several ways of mitigating these limitations such as
morphology control, doping, metal loading and construction of
heterojunction with suitable semiconductors, are captured in this review.
Another trend of note is the application of BiVO4 in coupled systems such
as photoelectroctalysis and electro-Fenton, photoelectrocatalysis and
electroenzymatic catalysis, and photoelectrocatalytic fuel cells for the re-
moval of organics and power generation. These approaches have
achieved impressive results with good energy efficiencies.
The results from the photoelectrocatalytic degradation studies using
BiVO4 based photoanodes revealed that the efficiency is also dependent
on the selected supporting electrolyte. Though Na2SO4 remains the most
commonly used supporting electrolyte, impressive results have also been
obtained with the use of NaClO4. Furthermore, enhanced removal effi-
ciency has been observed when peroxymonosulphate (PMS) are introduced
into the reaction media. This is because sulphate radicals, which are capa-
ble of also oxidising organics, are produced when PMS is activated through
visible light irradiation. Since BiVO4 photoanodes perform well with visible
light irradiation, addition of PMS has proven to be a suitable strategy to im-
prove the overall performance.
Additionally, photoelectrocatalytic removal efficiency largely depends
on the production of active radicals from the excitation of BiVO4 electrodes.
In other to promote the production of hydroxyl radicals, several kinds of
BiVO4 heterostructures consisting of either p-p, p-n or n-n heterojunctions
have been investigated. However, better results have been obtained with
the use of BiVO4 heterostructures consisting of p-n heterojunctions. This
B.O. Orimolade, O.A. Arotiba /
is because combining n type BiVO4 with a p-type semiconductor often re-
sults in type II heterojunction which readily promotes effective charge sep-
aration and this makes available more holes which facilitates the
production of hydroxyl radicals.
In our opinion, there are still a lot to study and understand in
photoelectrocatalytic applications of BiVO4 and photoelectrocatalysis in
general. For example, more studies attempting to unravel the mechanism
of degradation of the pollutants will be welcomed. These studies may be
linked to the efficiency of the catalysis and also form a base of comparison.
While the ideal degradation products are CO2 and H2O, such complete deg-
radation are almost never achieved. It will thus be of importance to investi-
gate the degradation products. These products, along with toxicity
investigations, will shed more light on strength and weakness of this elec-
trochemical technology. Earlier reports on photoelectrocatalytic degrada-
tion of wastewater were based on dyes. It is interesting to note that other
applications are evolving and the degradation of a wider class of organic
pollutants such as pharmaceuticals are now reported and this direction is
encouraged. The application of BiVO4 based photoanode in real wastewater
samples are worthy of further investigation so as to test the robustness of
this semiconductor. Additionally, since BiVO4 has good visible light absorp-
tion, it would be interesting and beneficial if future works pay much atten-
tion to the use of direct solar light as source of irradiation rather than using
commercial simulated solar light. It has been observed that most studies
reporting the application of BiVO4 for photoelectrocatalytic degradation
of organics provided limited insight on how the preparation method of
BiVO4 and the structural property affects the efficiency of the process.
Therefore, future studies also need to pay keen attention to how these fac-
tors affect the performance of photoanodes.
Certainly, BiVO4 is a suitable material for fabricating photoanodes for
water treatment applications and with the progress made so far, in due
time BiVO4 based photoanodes will find extensive applications on indus-
trial scales.
Declaration of Competing Interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgements
The following are gratefully acknowledged: The National Research
Foundation (CPRR Grant number: 118546); Global Excellence and Stature
(GES) doctoral support (for B.O.O), University of Johannesburg; B. O. O.
is grateful to University of Ilorin, Nigeria for study leave.
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