Available online at www.sciencedirect.
com Current Opinion in
ScienceDirect
Review Article
Visible light–driven photoelectrocatalytic
semiconductor heterojunction anodes for water
treatment applications
Omotayo A. Arotiba1,2, Benjamin O. Orimolade1,a and
Babatunde A. Koiki1,a,b
Abstract
Research interest in photoelectrocatalysis or photo-
electrochemical oxidation processes for water treatment is on
the increase. This is because this method has the ability to
abate a wide range of recalcitrant organic pollutants from
wastewater. The application of visible or solar light, which has
the potential to reduce cost, increase safety, and increase
sustainability, is a recent direction in this novel electrochemical
technology for water treatment. This review focuses on the use
of semiconductor heterojunctions as a way of tuning the
photoanode towards visible light activation. The classifications,
preparations and various applications of semiconductor
heterojunction for the removal of organic pollutants from water
in the past two years are presented with concluding remarks
and future perspective.
Addresses
1
Department of Chemical Sciences, University of Johannesburg,
Doornfontein, South Africa
2
Centre for Nanomaterials Science Research, University of Johan-
nesburg, South Africa
Corresponding author: Arotiba, Omotayo A (oarotiba@uj.ac.za)
a
Authors with equal contributions.b Formerly known as Department
of Applied Chemistry, University of Johannesburg, South Africa
Current Opinion in Electrochemistry 2020, 22:25–34
This review comes from a themed issue on Environmental
Electrochemistry
Edited by Richard D. Webster
For a complete overview see the Issue and the Editorial
Available online 4 April 2020
https://doi.org/10.1016/j.coelec.2020.03.018
2451-9103/© 2020 Elsevier B.V. All rights reserved.
Keywords
Semiconductor heterojunction, Visible light photoelectrocatalysis,
Photoelectrochemical degradation, Water Treatment, Organic
pollutants.
Introduction
The availability of fresh and potable water is a global
challenge. For sustenance of life and meeting human
needs, water (surface water, ground water and
www.sciencedirect.com
Electrochemistry
wastewater) should be used, treated, and reused more
effectively and efficiently [1]. Unfortunately, the effi-
cient and effective treatment of wastewater is becoming
more challenging owing to the chemical complexity and
the recalcitrant nature of some pollutants now found in
water. Reports on the presence of some organic pollut-
ants in ground water, surface water and treated water
suggest: (1) the effect of poor industrial effluent
disposal; (2) the presence of previously uncommon
pollutants now termed emerging pollutants; (3) the
recalcitrant nature of some pollutants against treatment
and (4) the poor performance or lapses in the conven-
tional wastewater treatment [2]. The increase in the
burden of pollutants in wastewater adds to the cost of
wastewater treatment and has adverse environmental
effects. Table 1 presents some draw backs in the most
common water treatment techniques. Although there
may not be a one size fits all water treatment method,
there is need to develop methods to mitigate some
current challenges experienced by the conventional
treatment techniques. The development of alternative
and/or complementary water treatment methods that
are low-cost, efficient, robust (towards a myriad of pol-
lutants) and sustainable should be pursued. Such newer
methods should be able to address the issue of the
removal of recalcitrant pollutants while leaving behind a
low foot print on the environment (i.e. green in its
approach). A group of method called advanced oxidation
processes (AOPs) seem to fit into some of the expec-
tations discussed previously.
AOPs have been shown to be a set of effective tech-
niques for the abatement of recalcitrant toxic organic
pollutants owing to the in situ generation of hydroxyl
radicals (
OH), which are known to be non-specific in
action and possesses the ability to completely break-
down recalcitrant organics [3,4]. The predominant
AOPs are chemical, photochemical and photocatalytic
techniques. Examples include hydrogen peroxide with
ultraviolet C (H2O2/UVC) radiation, ozone and ozone
related processes (O3, O3/UVC, O3/H2O2 and O3/H2O2/
UVC), titanium dioxide related processes (TiO2/UV and
TiO2/H2O2/UV) and Fenton’s reaction related tech-
niques (Fenton (Fe2þ/H2O2) and photo-Fenton (Fe2þ/
H2O2/UV)) [5,6].
Current Opinion in Electrochemistry 2020, 22:25–34
26 Environmental Electrochemistry

Table 1

Conventional wastewater treatment methods and their drawbacks.

Water treatment Method Merits Drawbacks References

Physicochemical techniques
Biological treatment
Coagulation, Precipitation
and Flocculation
Chemical disinfectants
Reverse osmosis (RO)
Ultraviolet irradiation
Simple process
Less disruptive
Simple equipment
Removal of pathogenic organisms
Production of portable water from
brackish and sea water sources
It is chemical free and comes
with ease of operation
High cost of equipment cost and low effectiveness [6]
Longer operation time, not realistic under harsh [6,9]
environmental conditions
Expensive when feed water has high pollution load, [2]
secondary waste, sludge that is difficult to dewater
Production of toxic by-products during disinfection [10]
High cost of energy due to thermal treatment of the [10]
concentrate as well as fouling of membrane
surface
High energy consumption and it also gives rise to [11]
bacteria growth

Photocatalysis has distinguished itself as a viable tech-

nique in wastewater treatment owing to the ease of 2Mð
O HÞ / 2MO þ H2 O2 (2)
operation, wide range of application, nontoxicity, ability
to completely mineralise recalcitrant contaminants,
environmental friendliness, and elimination of target 3H2 O / O3 þ 6H þ þ 6e (3)
pollutants without transfer from one medium to another.
It has been reported lately as an efficient technique in
the treatment of water laden with dyes, emerging pol- Several anodic materials have been reported for elec-
lutants such as pharmaceuticals, and other endocrine trochemical oxidation applications and common exam-
disruptors [7,8]. Low photonic efficiency, laborious re- ples are boron doped diamond [16] and dimensionally
covery of the photocatalyst for the purpose of reusability stable anode [17].
and the speedy rate at which the photogenerated charge
carriers recombine are the major setback to photo- Photoelectrochemical degradation of
catalysis. A more efficient method that will address the organics
drawbacks of photocatalysis application should therefore Photoelectrochemical degradation or photo-
the sought. electrocatalysis (PEC) is a recent form of electro-
chemical AOP where both heterogenous photocatalysis
Electrochemical AOPs and electrochemical oxidation techniques are combined
Recently, electrochemical advanced oxidation processes for the enhanced removal of organic pollutants in
(EAOPs) have proven to be novel water treatment wastewater. Basically, metal oxide semiconductors are
methods for the removal of a wide range of pharma- used as anodic material and just as in typical photo-
ceutical compounds and other recalcitrant organics from catalysis, photogenerated electronehole pairs are pro-
wastewater. EAOPs are simple to operate, offer excel- duced when the anodic material absorbs photon from
lent reusability, high energy efficiency, environmentally light irradiation. The mechanism is summarised in Eqs.
friendly and are very versatile [12,13]. The most (4)e(7).
common type of EAOP for wastewater treatment is the
electrochemical oxidation (anodic oxidation) process. In hv þ semiconductor/hþ þ e (4)
electrochemical oxidation, the degradation of organics in
electrolytic system occur through two steps namely the hþ þ H2 O/
O H þ H þ (5)
electron transfer to the anode and oxidation of organics
by the reactive oxygen species generated from water at
the anode [14]. As described in Eqs. (1)e(3), where M e  þ O2 /
O
2 (6)
stands for anode, the reactive oxygen species produced
in electrochemical oxidation include physisorbed hy-

droxyl radical on anode, hydrogen peroxide and ozone O2 þ H þ /
H O2 (7)
[15].

M þ H2 O/Mð
O HÞ þ H þ þ e (1) However, unlike photocatalysis, bias potential is applied

in photoelectrochemical degradation process [6]. The
combined effect of both electrical and light energy

Current Opinion in Electrochemistry 2020, 22:25–34 www.sciencedirect.com


results in a higher removal efficiency in photo-
electrochemical degradation as several reactive oxygen
species such as hydroxyl radicals and superoxide radi-
cals, as well as holes are available for oxidising organic
pollutants in water. A major advantage of photo-
electrochemical degradation over photocatalysis is the
remarkable reduction in rapid recombination of photo-
generated electronehole pairs and this is achieved
through the application of a bias potential which helps
in driving away electrons from the anode and conse-
quently making more photogenerated holes available for
mineralisation reactions [18*]. In addition, because
semiconducting metal oxide photocatalyst are used to
fabricate compact electrode, photoelectrochemical
degradation offers easy recovery and reusability. The
electric energy consumed in photoelectrochemical
degradation is also reduced as compared with anodic
oxidation that often requires higher cell voltage for
substantial mineralisation of organics. Generally, the
overall efficiency of photoelectrochemical degradation
process depends on photocatalytic activity of the anodic
material, the source of irradiation and the design of
reactor cell.
The most extensively used metal oxide semiconductor
for anode in photoelectrochemical degradation process
(and also in photocatalysis) is anatase titanium dioxide
(TiO2) which has been used for the degradation of
several organic pollutants [19,20]. The major short-
coming of titanium dioxide is that pristine TiO2 absorbs
photon better with UV irradiation than under visible
light irradiation, and the use of UV sources is not cost-
effective and safe. Several approaches such as doping
and metal loading have been used to enhance the visible
light harvesting capacity of TiO2 under visible light
irradiation. For instance, Yilmaz et al. [21] improved the
visible light photoelectrocatalytic activity of TiO2 by
loading it with palladium metal (Pd/TiO2) and achieved
Figure 1
Different types of band alignment in heterojunction.
www.sciencedirect.com
Semiconductor heterojunction photoanodes Arotiba et al. 27
higher mineralisation of rhodamine B dye under visible
light irradiation than with pristine TiO2. Codoping TiO2
with fluorine and tin also resulted in higher PEC
degradation efficiency than pristine TiO2 as reported by
Liu et al. [22]. The quest for the use of visible light
irradiation and ultimately solar energy in photo-
electrochemical degradation has led to the investigation
of other visible light active metal oxide semiconductors
such as WO3 [23**], MoS2 [24], BiVO4 [25] and Cu2O
[26].
Semiconductor – semiconductor
heterojunction
The major drawback of many visible light semi-
conductor with narrow band gap is the fast recombi-
nation of energetically unstable photogenerated
electronehole pairs which limits their photocatalytic
efficiency. To improve the visible light efficiency of
semiconductors through the enhancement of charge
separation, several methods such as loading the
photocatalyst with noble metals, morphology control
by fabricating different nanostructures of the photo-
catalyst, the use of sacrificial agent, doping and
fabricating of heterojunctions have been used. It has
been demonstrated that the construction of hetero-
junction is an effective way of limiting rapid recom-
bination of charge carriers in photocatalyst by
promoting effective separation of photogenerated
electronehole pairs resulting in better photocatalytic
efficiency. Heterojunction refer to the interface
formed when two semiconductors of unequal band gap
combine in such a way that result in band alignment
[27]. Heterostructure photocatalysts have been
extensively applied towards photoelectrochemical
water splitting applications where higher photo-
catalytic efficiencies have been recorded in compari-
son to single or pristine semiconductor [28,29].
Current Opinion in Electrochemistry 2020, 22:25–34
28 Environmental Electrochemistry
Classification
Though semiconductor/cocatalyst junctions, semi-
conductor/metal junctions, semiconductor/nonmetal
junctions and surface heterojunctions exist, the focus of
this review is on semiconductor/semiconductor hetero-
junctions which is simply referred to as heterojunctions.
Based on the type of semiconductors involved, a
heterojunction can simply be classified as pep (between
two p-type semiconductors), nen (between two n-type
semiconductors) and pen (one p-type and one n-type
semiconductor) heterojunctions [30].
Another mode of classification of heterojunctions is
based on their band alignment. There are three possible
band alignments in semiconductor/semiconductor
heterojunction, and these band alignments are illus-
trated in Figure 1. It has been established that electrons
migrate from a more negative conduction band to a less
negative conduction band, whereas holes migrate from a
more positive valence band to a less positive valence
band within a heterojunction [31*]. In type I, which is
called straddling gap band alignment, the conduction
band edge of semiconductor A (SC-A) is higher (more
negative) than that of semiconductor B (SCeB),
whereas the valence band of SC-A is lower (more posi-
tive) than that of SC-B and therefore both the electrons
and holes from SC-A are transported to the conduction
band and valence band of SC-B respectively which
would not result in better charge separation. However,
since band alignment depends on Fermi energy level of
semiconductors (for nonintrinsic semiconductors) the
movement of either electrons and holes can be hindered
in a particular direction depending on the direction of
internal electric field, that is, electrons may transport to
SC-B but the movement of holes to SC-B is hindered
which results in charge separation. The type II band
alignment (staggered gap) offers the best charge sepa-
ration because the relative positions of the valence and
conduction bands allow the mobility of electrons from
the conduction band of SC-A to that of SC-B, whereas
the holes are moved from the valence band of SC-B to
that of SC-A. Another kind of charge separation is
possible in type II band alignment which is commonly
called the Z-scheme where the holes of SC-A combine
with the electrons of SC-B at the interface and conse-
quently making the electrons of SC-A and holes of SC-B
available for photocatalytic activity [32]. In the type III
(broken gap) band alignment, the relative positions of
valence and conduction bands of SC-A and SC-B do not
favour the transport of photogenerated electron and
holes in either direction and therefore no charge sepa-
ration is possible [31*].
Heterojunction preparation
Semiconductor/semiconductor heterojunctions can be
prepared using inexpensive techniques such as solegel
method, electrodeposition process, chemical
Current Opinion in Electrochemistry 2020, 22:25–34
precipitation, hydrothermal route and chemical bath
deposition method [30]. Hydrothermal route is a
common method for the preparation of metal oxides and
chalcogenides of different morphologies using high
temperature and pressure. For example, Tahmasebi
et al. [33] reported the preparation of Bi2WO6/BiOCl p-
n heterojunction through hydrothermal route. This was
carried out by preparing a precursor solution containing
sodium tungstate, bismuth nitrate pentahydrate and
hydrochloric acid. The precursor solution was trans-
ferred into an autoclave and the hydrothermal reaction
temperature was 180 C for 12 h. The morphologies of
Bi2WO6 and BiOCl were nanosheets and microsphere,
respectively. Similarly, Zhao et al., [34] used hydro-
thermal synthesis for the preparation of type II p-n
heterostructures of Co3O4/BiVO4 at a reaction temper-
ature of 180 C for 10 h. Other semiconductor hetero-
junctions have been prepared through the hydrothermal
route [35e37].
In electrodeposition method, electrochemical reactions
are used to prepare heterojunctions in a two-step pro-
cedure. In the works of Bai et al. [38], Cu2O/BiVO4 with
p-n heterojunction was prepared through electrodepo-
sition. In the first step, thin films of BiVO4 were elec-
trodeposited on Flourine-doped tin oxide (FTO) glass
at a potential of 0.6 V vs Ag/AgCl in a three-electrode
system set-up. In the second step, Cu2O was then
electrodeposited on the prepared FTOeBiVO4 elec-
trode at a constant potential between 0.25 and 0.5 V
using voltammetric technique. Similarly, electrodeposi-
tion technique has been used to prepare BiOI/BiPO4
[39], Cu2O/TiO2 [40] and CuS/TiO2 [41]
heterojunctions.
Provided the two semiconductors forming hetero-
junction can be synthesized under similar experimental
conditions, one-pot synthesis can be used to construct
the heterojunction. This is usually carried out by mixing
the precursors of the two semiconductors together in a
single container. Koiki et al. [8] have reported the suc-
cessful preparation of type II p-n heterojunction of
Cu2O/g-C3N4 using this approach. This was carried out
by mixing Cu(NO3).23H2O, NaOH, glucose and g-C3N4
in deionised water in a single beaker at a temperature of
80 C. A notable advantage in this synthesis approach
was the short reaction time of 10 min. Another simple
method for the preparation of heterojunction is through
successive ion layer adsorption/reaction (SILAR) which
is a form of liquid-phase chemical deposition. However,
this method often requires the preparation of the first
semiconductor through other techniques. The prepared
semiconductor is then dipped successively into solu-
tions containing the ions of the other semiconductor. For
example, Gupta et al., [42] adopted SILAR method for
the preparation of ZnO/CuI p-n heterojunction. Hy-
drothermal technique was first used to grow ZnO
nanorod films on FTO glass. The FTOeZnO was then
www.sciencedirect.com

Figure 2
Separation of electrons and holes in an n–n heterojunction of BiVO4/WO3
consisting of type II band alignment (Reproduced with permission from a
study by Du et al. [43]).
dipped alternatively in solutions of copper sulphate and
potassium iodide to obtain FTO-ZnO/CuI films.
Heterojunctions in PEC water treatment
n–n heterojunction
The photoelectrocatalytic oxidation of organic pollut-
ants using nen semiconductor heterojunctions have
been well studied. For instance, Du et al. [43] carried
out the photoelectrocatalytic degradation of norfloxacin
using BiVO4/WO3 anode which consist of nen
Figure 3
Charge separation within type II band alignment of BiVO4/BiOI p-n heterojunction (Reproduced with permission from Ref. [46*]).
www.sciencedirect.com
Semiconductor heterojunction photoanodes Arotiba et al. 29
heterojunction. The type II heterojunction was pre-
pared through hydrothermal and SILAR. The composite
electrode showed better charge separation and achieved
highest percentage removal (67%) of norfloxacin with
applied potential of 1.0 V for 3 h under visible light
irradiation. The separation of photogenerated electrone
hole pairs within the heterojunction is depicted in
Figure 2. Cao et al. [44*] reported complete removal of 5
mgL1 norfloxacin with the photoelectrocatalytic
degradation using type II nen Ag2PO4/BiVO4 within
90 min with the application of 0.5 V external potential.
The heterojunction was prepared through electrodepo-
sition method and the impressive photocatalytic effi-
ciency was attributed to reduction in recombination of
charge carriers in the heterojunction.
p–p heterojunction
Limited studies are available on PEC degradation using
pep heterojunction. This could be because of weaker
internal field within pep heterojunction. In addition, n-
type semiconductors are more conductive than p-type
semiconductors since electrons are the major charge
carriers in n-type. In the works of Wang et al. [45],
bismuth modified BiOI/Bi2O3 consisting of pep heter-
ojunction (type II band alignment) was used for the
PEC removal of phenol. A percentage removal of about
95% for phenol (5 mgL1) was achieved within a reac-
tion time of 150 min with 2.5 V applied potential.
Degradation of phenol in the presence of Cr(VI) was
also carried out using the electrode and 92.4% phenol
removal was recorded with simultaneous complete
reduction of Cr(VI) near the cathode.
Current Opinion in Electrochemistry 2020, 22:25–34
Current Opinion in Electrochemistry 2020, 22:25–34

30 Environmental Electrochemistry
Table 2

Recent studies on degradation of organics in water using photoelectrocatalysis.

Anode Type Preparation method PEC application Reference

Bi–Bi2O3/TiO2 p–n Solvothermal method 80% removal of rhodamine B (26% TOC) and 75% removal of methylene [49]
Z Scheme orange (57% TOC);
After 3 h with applied bias potential of 1.0 V vs Ag/AgCl;
500 W Xenon lamp as light source
TiO2/gC3N4 n–n Hydrothermal/Calcination 99.7% removal of 10 mgL−1 bisphenol A after 4 h with applied bias potential [50]
Type II of 1.3 V vs SCE using a 300 W Xenon lamp (full wavelength)
P–ZnO/ACN/MnO2 P–n–n Thermal polymerization and electrodeposition 88.2% removal of 4 mgL−1 Methylene Blue at pH 7 after 1 h with applied [51]
Z Scheme potential of 1.5 V vs Ag/AgCl using 300 W Xe lamp (l > 420 nm)
Bi–BiOI/Bi2O3 p–p Drop coating, etching, UV reduction method 94.6% removal of 5 mgL−1 phenol (92.4% Phenol: 100% Cr(VI) reduction in [45]
Type II a simultaneous process) after 2.5 h with applied potential of 2.5 V using
300 W Xe lamp (l > 420 nm)
TiO2/BiVO4 P–n Sol–gel hydrothermal method 93.9% removal of 10 mgL−1 rhodamine B (pH 5.3) after 5 h with a potential [52]
Type II of 4.0 V using 300 W Xenon lamp (no filter)
Bi2O3/WO3 P–n Hydrothermal method 73.4% removal of 10 mgL−1 rhodamine B after 3 h and 88.4% removal of [36]
Type II norfloxacin after 6 h;
Bias potential of1. 0 V vs SCE;
300 W Xenon lamp (l > 420 nm)
Cu2O/a-Fe2O3 P–n Electrodeposition and liquid-phase deposition 73.3% removal of 10 mgL−1 oxytetracycline after 1 h with applied bias [53]
Type II potential of 0.5 V vs Ag/AgCl using 300 W Xenon lamp (l > 420 nm)
Fe2O3/TiO2 n–n Sol–gel and forced hydrolysis method 92.3% removal of 10 mgL−1 rhodamine B. Using a 300 W Xenon lamp [54]
Type I (l > 400 nm) as light source
Fe2O3/Bi2WO6 n–n Wet chemical synthesis and atomic layer deposition 95% removal 20 mgL−1 tetracycline after 90 min with applied bias potential [55*]
Type II of 0.6 V vs Ag/AgCl using a solar simulator with 150 W Xenon lamp
(l > 400 nm)
Ag3PO4/Ag4P2O7/TiO2 n–n Hydrothermal method 99.39% removal of methylene blue after 1 h with applied potential of 0.5 V [35]
Type II using 500 W Xenon lamp
BiOI/BiPO4 p-n Electrodeposition method 80% removal of 10 mgL−1 tetracycline after 4 h with applied bias potential of [39]
Type II 1.2 V vs SCE using 500 W Xenon lamp
CuS/TiO2 p-n Electrodeposition 99.1% removal of 5 mgL−1 Penicillin G after 150 min with applied bias [41]
Type II potential of 0.4 V vs SCE using 35 W Xenon lamp (l > 420 nm)
TiO2/g-C3N4 n–n Thermal condensation 93% removal of 10 mgL−1 of tetracycline after 3 h with applied bias potential [47**]
Type II of 1.0 V vs Ag/AgCl using 300 W Xenon lamp (l 200–800 nm)
Cu2O/TiO2 P–n Electrodeposition 73% removal of 10 mgL−1 of ciprofloxacin after 4 h with applied bias [40]
Type II potential of 1.5 V vs Ag/AgCl using a solar simulator (100 W Xenon lamp
l > 400 nm)
BiVO4/WO3 n–n Hydrothermal and SILAR method 67% removal of 10 mgL−1 norfloxacin after 3 h with applied bias potential of [43]
Type II 1.0 V vs SCE
300 W Xenon lamp (l > 420 nm)
www.sciencedirect.com

ZnO/CuI p–n Hydrothermal and SILAR method 55.27% removal of chloramphenicol after 1 h with potential of 1.0 V vs Ag/ [42]
Type II AgCl
Ag3PO4/BiVO4 n–n Electrodeposition 100% removal 5 mgL−1 norfloxacin after 90 min with applied potential of [44*]
Type II 0.5 V vs SCE using 300 W Xenon lamp (l > 420 nm)
BiVO4/ZnO n–n Liquid phase deposition and SILAR 66.1% removal of 20 mgL−1 of tetracycline after 2 h with applied bias [56]
Type I potential of 0.8 V vs SCE using 300 W Xenon lamp (l > 420 nm)
BiVO4/MnO2 n–n Electrodeposition method [57]
Type II
 Semiconductor heterojunction photoanodes Arotiba et al. 31

p-n heterojunction
The most extensively used heterojunction for water

[48**]
[46*]

[58]

[37]

[59]

[60]
treatment applications is pen heterojunction because
the internal electric generated between the semi-
conductors further accelerates charge separation [27].

93.73% removal of 10 mgL−1 phenol after 5 h with applied potential of 2.5 V

96.5% decay of 5 mgL−1 oxytetracycline (pH 5.8) after 6 h with applied bias
76% removal of 10 mgL−1 ciprofloxacin after 2 h with applied bias potential

acetaminophen after 2 h with applied bias potential of 1.5 V vs Ag/AgCl

with constant current density of 10 mAcm−2 and using a solar simulator

47.4% removal of rhodamine B after 80 min with applied bias potential of

For instance, the application of pen heterostructured
78.5% removal of 20 mgL−1 ciprofloxacin (39.7% TOC removal) after 3 h
62% removal of 10 mgL-1 ciprofloxacin and 68% removal of 10 mgL−1

BiVO4/BiOI for the degradation of organics was studied

maintaining a current density of 10 mAcm−2 using a solar simulator
91% removal of 10 mgL−1 rhodamine B (74% TOC removal) after 4 h

of 1.0 V vs Ag/AgCl using 36 W blue LED lamp (l 450–460 nm)

of 1.5 V vs Ag/AgCl using a solar simulator (100 W Xenon lamp

by Orimolade et al. [46*]. The type II pen BiVO4/BiOI

was prepared through two-step electrodeposition and
the binary electrode showed enhanced photo-
using a solar simulator (100 W Xenon lamp l > 400 nm)

electrochemical properties such has high photocurrent

response. The PEC degradation of ciprofloxacin, acet-
aminophen and orange 2 dye were studied using the
prepared electrode at a neutral pH with visible light
irradiation using a solar simulator with 100 W xenon
0.6 V vs SCE with AM 1.5 G irradiation

using 300 W Xenon lamp (l > 420 nm)

lamp and application of 1.5 V bias potential. The per-

centage removal after 2 h was 62%, 68% and 85% for
(100 W Xenon lamp l > 400 nm)

ciprofloxacin, acetaminophen and orange 2 dye,

(100 W Xe lamp l > 400 nm)

respectively. These values were higher than those

achieved with pristine BiVO4 and BiOI electrodes. The
mechanism of charge separation as presented in Figure 3
revealed that holes from BiVO4 were transported to the
valence band of BiOI while electrons from BiOI
l > 400 nm)

migrated to the conduction band of BiVO4 which

resulted in better PEC performance. The simultaneous
degradation of the pharmaceuticals in a cocktail solution
was also achieved with the electrode. Similarly, Koiki
et al. achieved an 73% photoelectrocatalytic removal of
ciprofloxacin within 4 h with the application of 1.5 V bias
potential using Cu2O/TiO2 photoanode. The composite
photoanode consisted of pen heterojunction and was
Electrodeposition and hydrothermal method

prepared through electrodeposition. The photocatalytic

efficiency of the photoanode was far higher than bare
TiO2 electrode [40].

Attempts on the photoelectrochemical degradation of

Thermal treatment method

pollutants have also been made with real wastewater

Electrodeposition method

Electrodeposition method

Hydrothermal and SILAR

sample. For example, Tang et al. [47**] applied heter-

Hydrothermal method

ostructured photoanode for the PEC treatment of an-

tibiotics in real wastewater sample both in a static and
continuous flow process. The photoanode was TiO2/g-
C3N4 with pen heterojunction which was prepared
through thermal condensation. A 100 W Xenon lamp was
used as simulated solar light source. In the static pro-
cess, 93% removal of 10 mgL1 tetracycline was
SILAR, successive ion layer adsorption/reaction.

achieved with the application of bias potential of 1 V vs

Ag/AgCl after 3 h. The continuous flow PEC was carried
Type II

Type II

Type II

Type II

Type II
Type I

out at a flow rate of 0.84 mLmin1 with a solution

N–n–n
P–n

P–n

P–n

P–n
n–n

retention time of 1 h in the reactor. The real water

sample was spiked to attain a concentration of 10
mgL1, and 80% removal was achieved, and the per-
centage removal remained stable even after 20 h. This
ZnO/TiO2/Ag2Se

study demonstrated the real-life application of PEC for

Pi-Fe2O3/MoS2
Au–TiO2/PbS

water treatment using heterojunction anode. Similarly,

MoS2/SnO2
BiVO4/ZnO
BiVO4/BiOI

Changanaqui et al. achieved 91% oxytetracycline

removal in a matrix consisting of urban wastewater
[48**]. The recent works on PEC for water treatments

www.sciencedirect.com Current Opinion in Electrochemistry 2020, 22:25–34

32 Environmental Electrochemistry
applications using heterostructured photoanode are
summarised in Table 2.
Concluding remarks
The tuning of the semiconductors towards visible light
catalysis by the formation of heterojunctions is a notable
advancement in photoelectrochemical degradation of
pollutants in water. The possibility of using visible light
and sunlight in some cases, have introduced the much
desired sustainability into electrochemically AOP. With
the preparation of new semiconductors in various ap-
plications other than PEC, there are more possibilities
of the formation of newer heterojunctions which may
exhibit improved PEC degradation performance. It
should be noted that it is difficult to compare the per-
formance of different types of PEC systems in terms of
percentage removal and other performance matrices
from the literature. This is because of the variations in
experimental set-up/conditions. For example, volume of
wastewater, electrode surface area, applied potential and
current, light source, initial concentrations of pollutants,
etc vary from report to report. Future work research
should seek to establish some common baselines that
can be used for comparison of performance. Notwith-
standing, the current reports have shown promising re-
sults and thus future research should tend more toward
cocktail of pollutants, dissolution of organic pollutants in
real waste water and real industrials wastewater samples.
For upscaling this electrochemical technology, contin-
uous flow reactor designs are plausible approaches.
Conflict of interest statement
Nothing declared.
Acknowledgements
The authors wish to acknowledge the National Research Foundation of
South Africa (CPRR Grant number 118546); Centre for Nanomaterials Sci-
ence Research, University of Johannesburg for financial supports. B.A.K. is
grateful to TWAS-NRF for PhD scholarship. B.O.O. acknowledges Global
Excellence and Stature (GES) doctoral support, University of Johannesburg
and he is grateful to University of Ilorin, Nigeria for study leave.
References
Papers of particular interest, published within the period of review,
have been highlighted as:
* of special interest
* * of outstanding interest
1. Morsi R, Bilal M, Iqbal HMN, Ashraf SS: Laccases and peroxi-
dases: the smart, greener and futuristic biocatalytic tools to
mitigate recalcitrant emerging pollutants. Sci Total Environ
2020, 714:136572.
2. ska J, Kotowska U: Removal of organic pollution in the
Karpin
water environment. Water (Switzerland) 2019:11.
3. Brillas E, Martínez-Huitle CA: Decontamination of wastewaters
containing synthetic organic dyes by electrochemical
methods. An updated review. Appl Catal B Environ 2015,
166–167:603–643.
4. Oturan MA, Aaron JJ: Advanced oxidation processes in water/
wastewater treatment: principles and applications. A review.
Crit Rev Environ Sci Technol 2014, 44:2577–2641.
Current Opinion in Electrochemistry 2020, 22:25–34
5. Chong S, Zhang G, Wei Z, Zhang N, Huang T, Liu Y: Sonoca-
talytic degradation of diclofenac with FeCeOx particles in
water. Ultrason Sonochem 2017, 34:418–425.
6. Garcia-Segura S, Brillas E: Applied photoelectrocatalysis on
the degradation of organic pollutants in wastewaters.
J Photochem Photobiol C Photochem Rev 2017, 31:1–35.
7. Ponnaiah SK, Prakash P, Arumuganathan T, Jeyaprabha B:
Effectual light-harvesting and electron-hole separation for
enhanced photocatalytic decontamination of endocrine
disruptor using Cu2O/BiOI nanocomposite. J Photochem
Photobiol A Chem 2019, 380:111860.
8. Koiki BA, Orimolade BO, Peleyeju GM, Arotiba OA: Rapid and
template-free synthesis of copper(I) oxide-graphitic carbon
nitride heterojunction for photocatalytic degradation of
orange II dye in water. Solid State Sci 2019, 97:105994.
9. Al-Maqdi KA, Hisaindee SM, Rauf MA, Ashraf SS: Comparative
degradation of a thiazole pollutant by an advanced oxidation
process and an enzymatic approach. Biomolecules 2017, 7:64.
10. Huang JJ, Hu HY, Tang F, Li Y, Lu SQ, Lu Y: Inactivation and
reactivation of antibiotic-resistant bacteria by chlorination in
secondary effluents of a municipal wastewater treatment
plant. Water Res 2011, 45:2775–2781.
11. Haaken D, Schmalz V, Dittmar T, Worch E: Limits of UV disin-
fection: UV/electrolysis hybrid technology as a promising
alternative for direct reuse of biologically treated wastewater.
J Water Supply Res Technol - AQUA 2013, 62:442–451.
12. Moreira FC, Boaventura RAR, Brillas E, Vilar VJP: Electro-
chemical advanced oxidation processes: a review on their
application to synthetic and real wastewaters. Appl Catal B
Environ 2017, 202:217–261.
13. Geneste F: Catalytic electrochemical pre-treatment for the
degradation of persistent organic pollutants. Curr Opin Elec-
trochem 2018, 11:19–24.
14. Martínez-Huitle CA, Panizza M: Electrochemical oxidation of
organic pollutants for wastewater treatment. Curr Opin Elec-
trochem 2018, 11:62–71.
15. Sirés I, Brillas E: Remediation of water pollution caused by
pharmaceutical residues based on electrochemical separa-
tion and degradation technologies : a review. Environ Int 2012,
40:212–229.
16. Lan Y, Coetsier C, Causserand C, Groenen Serrano K: An
experimental and modelling study of the electrochemical
oxidation of pharmaceuticals using a boron-doped diamond
anode. Chem Eng J 2018, 333:486–494.
17. Baddouh A, Bessegato GG, Rguiti MM, El Ibrahimi B, Bazzi L,
Hilali M, Zanoni MVB: Electrochemical decolorization of
Rhodamine B dye: influence of anode material, chloride
concentration and current density. J Environ Chem Eng 2018,
6:2041–2047.
18. Peleyeju MG, Arotiba OA: Recent trend in visible-light photo-
* electrocatalytic systems for degradation of organic contam-
inants in water/wastewater. Environ Sci Water Res Technol
2018, 4:1389–1411.
This review reported the application of PEC for water treatment. The
mechanism and experimental requieremnts for PEC applications.
Much attention was given to the use of visible-light active semi-
conductor photocatalysts.
19. Song T, Li R, Li N, Gao Y: Research progress on the applica-
tion of nanometer TiO2 photoelectrocatalysis technology in
wastewater treatment. Sci Adv Mater 2019, 11:158–165.
20. Peleyeju MG, Umukoro EH, Tshwenya L, Moutloali R,
Babalola JO, Arotiba OA: Photoelectrocatalytic water treat-
ment systems: degradation, kinetics and intermediate prod-
ucts studies of sulfamethoxazole on a TiO2-exfoliated
graphite electrode. RSC Adv 2017, 7:40571–40580.
21. Yilmaz P, Lacerda AM, Larrosa I, Dunn S: Photoelectrocatalysis
of rhodamine B and solar hydrogen production by TiO2 and
Pd/TiO2 catalyst systems. Electrochim Acta 2017, 231:
641–649.
www.sciencedirect.com

22. Liu D, Zhou J, Wang J, Tian R, Li X, Nie E, Piao X, Sun Z:
Enhanced visible light photoelectrocatalytic degradation of
organic contaminants by F and Sn co-doped TiO2 photo-
electrode. Chem Eng J 2018, 344:332–341.
23. Umukoro EH, Peleyeju MG, Ngila JC, Arotiba OA: Towards
* * wastewater treatment: photo-assisted electrochemical
degradation of 2-nitrophenol and orange II dye at a tungsten
trioxide-exfoliated graphite composite electrode. Chem Eng J
2017, 317:290–301.
This study presented versatility of using visible acticve semiconductor
photode anode in degradating vast spectrums of organics. Exfoliated
graphite was used as conducting substrate for the first time. The
mineralization of phenols and dye using the same anodic material was
achieved. It further reported the mineralization pathways of the
organics.
24. Zhou Y, Fan X, Zhang G, Dong W: Fabricating MoS2 nanoflakes
photoanode with unprecedented high photoelectrochemical
performance and multi-pollutants degradation test for water
treatment. Chem Eng J 2019, 356:1003–1013.
25. Orimolade BO, Arotiba OA: An exfoliated graphite-bismuth
vanadate composite photoanode for the photo-
electrochemical degradation of acid orange 7 dye. Electro-
catalysis 2019, 10:429–435.
26. Sang W, Zhang G, Lan H, An X, Liu H: The effect of different
exposed facets on the photoelectrocatalytic degradation of o-
chlorophenol using p-type Cu2O crystals. Electrochim Acta
2017, 231:429–436.
27. Low J, Yu J, Jaroniec M, Wageh S, Al-Ghamdi AA: Hetero-
junction photocatalysts. Adv Mater 2017, 29:1–20.
28. Kalanoor BS, Seo H, Kalanur SS: Recent developments in
photoelectrochemical water-splitting using WO3/BiVO4
heterojunction photoanode: a review. Mater Sci Energy Tech-
nol 2018, 1:49–62.
29. Li F, Leung DYC: Highly enhanced performance of hetero-
junction Bi2S3/BiVO4 photoanode for photoelectrocatalytic
hydrogen production under solar light irradiation. Chem Eng
Sci 2020, 211:115266.
30. Wang S, Yun JH, Luo B, Butburee T, Peerakiatkhajohn P,
Thaweesak S, Xiao M, Wang L: Recent progress on visible
light responsive heterojunctions for photocatalytic applica-
tions. J Mater Sci Technol 2017, 33:1–22.
31. Zhang L, Jaroniec M: Toward designing semiconductor-
* semiconductor heterojunctions for photocatalytic applica-
tions. Appl Surf Sci 2018, 430:2–17.
This review described in detail the concept of semiconductor – semi-
conductor heterojunctions. The mobility of charge carriers within
different types of band alignment was also discussed.
32. Low J, Jiang C, Cheng B, Wageh S, Al-Ghamdi AA, Yu J:
A review of direct Z-scheme photocatalysts. Small Methods
2017, 1:1700080.
33. Tahmasebi N, Maleki Z, Farahnak P: Enhanced photocatalytic
activities of Bi2WO6/BiOCl composite synthesized by one-
step hydrothermal method with the assistance of HCl. Mater
Sci Semicond Process 2019, 89:32–40.
34. Zhao X, Lu Z, Ma W, Zhang M, Ji R, Yi C, Yan Y: One-step
fabrication of carbon decorated Co3O4/BiVO4 p-n hetero-
structure for enhanced visible-light photocatalytic properties.
Chem Phys Lett 2018, 706:440–447.
35. Qiu L, Cui Y, Tan X, Zheng S, Zhang H, Xu J, Wang Q: Con-
struction of Ag3PO4/Ag4P2O7 nanospheres sensitized hier-
archical titanium dioxide nanotube mesh for
photoelectrocatalytic degradation of methylene blue. Separ
Purif Technol 2019, 215:619–624.
36. Jiang T, Cheng L, Han Y, Feng J, Zhang J: One-pot hydro-
thermal synthesis of Bi2O3-WO3 p-n heterojunction film for
photoelectrocatalytic degradation of norfloxacin. Separ Purif
Technol 2019, 238:116428.
37. Umukoro EH, Kumar N, Ngila JC, Arotiba OA: Expanded
graphite supported p-n MoS2-SnO2 heterojunction nano-
composite electrode for enhanced photo-electrocatalytic
www.sciencedirect.com
Semiconductor heterojunction photoanodes Arotiba et al. 33
degradation of a pharmaceutical pollutant. J Electroanal Chem
2018, 827:193–203.
38. Bai S, Liu J, Cui M, Luo R, He J, Chen A: Two-step electrode-
position to fabricate the p-n heterojunction of a Cu2O/BiVO4
photoanode for the enhancement of photoelectrochemical
water splitting. Dalton Trans 2018, 47:6763–6771.
39. Liu S, Zhao M, He Z, Zhong Y, Ding H, Chen D: Preparation of a
p-n heterojunction 2D BiOI nanosheet/1DBiPO4 nanorod
composite electrode for enhanced visible light photo-
electrocatalysis. Chin J Catal 2019, 40:446–457.
40. Koiki BA, Orimolade BO, Zwane BN, Nkosi D, Mabuba N,
Arotiba OA: Cu2O on anodised TiO2 nanotube arrays: a
heterojunction photoanode for visible light assisted electro-
chemical degradation of pharmaceuticals in water. Electro-
chim Acta 2020, 340:135944.
41. Ma Q, Zhang H, Guo R, Li B, Zhang X, Cheng X, Xie M, Cheng Q:
Construction of CuS/TiO2 nano-tube arrays photoelectrode
and its enhanced visible light photoelectrocatalytic decom-
position and mechanism of penicillin G. Electrochim Acta
2018, 283:1154–1162.
42. Gupta R, Modak JM, Madras G: Behavioral analysis of simul-
taneous photo-electro-catalytic degradation of antibiotic
resistant E. coli and antibiotic via ZnO/CuI: a kinetic and
mechanistic study. Nanoscale Adv 2019, 1:3992–4008.
43. Du H, Pu W, Wang Y, Yan K, Feng J, Zhang J, Yang C, Gong J:
Synthesis of BiVO4/WO3 composite film for highly efficient
visible light induced photoelectrocatalytic oxidation of
norfloxacin. J Alloys Compd 2019, 787:284–294.
44. Cao D, Wang Y, Qiao M, Zhao X: Enhanced photo-
* electrocatalytic degradation of norfloxacin by an Ag3PO4/
BiVO4 electrode with low bias. J Catal 2018, 360:240–249.
Total removal of pharmaceutical was achieved with low bias potential
within a short time using heterostructured photoanode. It also re-
ported the degradation pathway of the pharmaceutical revealing that
formation of lowere carboxylic acid acids happened before total
mineralization.
45. Wang Q, Gao Q, Wu H, Fan Y, Lin D, He Q, Zhang Y, Cong Y: In
situ construction of semimetal Bi modified BiOI-Bi2O3 film
with highly enhanced photoelectrocatalytic performance.
Separ Purif Technol 2019, 226:232–240.
46. Orimolade BO, Koiki BA, Peleyeju GM, Arotiba OA: Visible light
* driven photoelectrocatalysis on a FTO/BiVO4/BiOI anode for
water treatment involving emerging pharmaceutical pollut-
ants. Electrochim Acta 2019, 307:285–292.
This study demonstrated the simultaneous PEC degradation of two
different pharamaceuticals in a cocktail solution. Simple two-step
electrodeposition was used to fabricate the heterostructured anode.
The mechanism of charge separation between the two semiconductors
was within the heterojunction was presented.
47. Tang H, Shang Q, Tang Y, Yi X, Wei Y, Yin K, Liu M, Liu C: Static
* * and continuous flow photoelectrocatalytic treatment of anti-
biotic wastewater over mesh of TiO2 nanotubes implanted
with g-C3N4 nanosheets. J Hazard Mater 2020, 384:121248.
This work demonstrated the real-life application of PEC for degradation
of real effluents using both static and continous flow process
48. Changanaqui K, Brillas E, Alarcón H, Sirés I: ZnO/TiO2/Ag2Se
* * nanostructures as photoelectrocatalysts for the degradation
of oxytetracycline in water. Electrochim Acta 2020, 331:135194.
The effect of aqueous matrix on degradation of oxytetracycline was
studied using urban wastewater and 91% removal was still achieved
49. Liu Z, Wang Q, Tan X, Zheng S, Zhang H, Wang Y, Gao S:
Solvothermal preparation of Bi/Bi2O3 nanoparticles on TiO2
NTs for the enhanced photoelectrocatalytic degradation of
pollutants. J Alloys Compd 2020, 815:152478.
50. Wang W-K, Zhu W, Mao L, Zhang J, Zhou Z, Zhao G: Two-
dimensional TiO2-g-C3N4 with both Ti–N and C–O bridges
with excellent conductivity for synergistic photo-
electrocatalytic degradation of bisphenol A. J Colloid Interface
Sci 2019, 557:227–235.
51. He S, Xiao K, Chen XZ, Li T, Ouyang T, Wang Z, Guo ML, Liu ZQ:
Enhanced photoelectrocatalytic activity of direct Z-scheme
Current Opinion in Electrochemistry 2020, 22:25–34
34 Environmental Electrochemistry
porous amorphous carbon nitride/manganese dioxide nano-
rod arrays. J Colloid Interface Sci 2019, 557:644–654.
52. Wang Y, Lu N, Luo M, Fan L, Zhao K, Qu J, Guan J, Yuan X:
Enhancement mechanism of fiddlehead-shaped TiO2-BiVO4
type II heterojunction in SPEC towards RhB degradation and
detoxification. Appl Surf Sci 2019, 463:234–243.
53. Cheng L, Tian Y, Zhang J: Construction of p-n heterojunction
film of Cu2O/a-Fe2O3 for efficiently photoelectrocatalytic
degradation of oxytetracycline. J Colloid Interface Sci 2018,
526:470–479.
54. Tang W, Zhang Y, Chen X, Zeng X: Fe2O3/TiO2 film electrodes
prepared by the forced hydrolysis method and their photo-
electrocatalytic performance. Mater Lett 2018, 217:109–112.
55. Adhikari S, Selvaraj S, Kim DH: Construction of heterojunction
* photoelectrode via atomic layer deposition of Fe2O3 on
Bi2WO6 for highly efficient photoelectrochemical sensing and
degradation of tetracycline. Appl Catal B Environ 2019, 244:
11–24.
In this study the concentration of the pharmaceutical is relatively high
(20 mgL−1) and 95% removal of was still achieved within just 90 min
with low bias of 0.6 V. Furthermore, atomic layer deposition was used
for the first time to prepare heterojunction
Current Opinion in Electrochemistry 2020, 22:25–34
56. Feng J, Cheng L, Zhang J, Okoth OK, Chen F: Preparation of
BiVO4/ZnO composite film with enhanced visible-light
photoelectrocatalytic activity. Ceram Int 2018, 44:3672–3677.
57. Orimolade BO, Zwane BN, Koiki BA, Tshwenya L, Peleyeju GM,
Mabuba N, Zhou M, Arotiba OA: Solar photoelectrocatalytic
degradation of ciprofloxacin at a FTO/BiVO4/MnO2 anode:
kinetics, intermediate products and degradation pathway
studies. J Environ Chem Eng 2020, 8.
58. Orimolade BO, Koiki BA, Zwane BN, Peleyeju GM, Mabuba N,
Arotiba OA: Interrogating solar photoelectrocatalysis on an
exfoliated graphite–BiVO4/ZnO composite electrode towards
water treatment. RSC Adv 2019, 9:16586–16595.
59. Guo H, Su C, Zhang Y, Yu D, Li L, Liu Z: Facile synthesis of
TiO2/PbS heterojunction with Au doped for photo-
electrocatalytic degradation. Mater Lett 2020, 264:3–6.
60. Cong Y, Ding W, Zhang W, Zhang T, Wang Q, Zhang Y: Fabri-
cation of a novel 3D E-Fe2O3-Pi-MoS2 film with highly
enhanced carrier mobility and photoelectrocatalytic activity.
Electrochim Acta 2020, 337:135748.
www.sciencedirect.com