catalysts

Review
Semiconductor Electrode Materials Applied in
Photoelectrocatalytic Wastewater
Treatment—an Overview
Elzbieta Kusmierek
Institute of General and Ecological Chemistry, Faculty of Chemistry, Lodz University of Technology,
Zeromskiego 116 St., 90-924 Lodz, Poland; [email protected]; Tel.: +48-42-631-31-30




Received: 14 March 2020; Accepted: 16 April 2020; Published: 18 April 2020


Abstract: Industrial sources of environmental pollution generate huge amounts of industrial

wastewater containing various recalcitrant organic and inorganic pollutants that are hazardous
to the environment. On the other hand, industrial wastewater can be regarded as a prospective
source of fresh water, energy, and valuable raw materials. Conventional sewage treatment systems
are often not efficient enough for the complete degradation of pollutants and they are characterized
by high energy consumption. Moreover, the chemical energy that is stored in the wastewater is
wasted. A solution to these problems is an application of photoelectrocatalytic treatment methods,
especially when they are coupled with energy generation. The paper presents a general overview
of the semiconductor materials applied as photoelectrodes in the treatment of various pollutants.
The fundamentals of photoelectrocatalytic reactions and the mechanism of pollutants treatment as
well as parameters affecting the treatment process are presented. Examples of different semiconductor
photoelectrodes that are applied in treatment processes are described in order to present the strengths
and weaknesses of the photoelectrocatalytic treatment of industrial wastewater. This overview is
an addition to the existing knowledge with a particular focus on the main experimental conditions
employed in the photoelectrocatalytic degradation of various pollutants with the application of
semiconductor photoelectrodes.

Keywords: semiconductors; photoelectrocatalysis; photoelectrodes; wastewater treatment

1. Introduction
In the XXI century, energy crisis and environmental pollution constitute two main problems in
sustainable development, which is defined as the ability of natural systems to supply the natural
resources and ecosystems while meeting current human needs, not affecting the ability of the future
generations to meet their needs and without deteriorating of the integrity and stability of
the natural systems.
Environmental pollution results in serious climate changes and is the most important threat to
human population on a global scale nowadays. Thus, it is important to significantly limit the emission
of pollutants to the environment. Industrial sources of environmental pollution generate huge amounts
of industrial wastewater, which have serious impact on the environment. Although the industrial
wastewater contains various recalcitrant organic and inorganic pollutants, it can be regarded as
a prospective source of fresh water, energy, and valuable raw materials. Pollutants that are present
in wastewater can be treated and simultaneously converted into methane in microbial fuel cells
(MFC) [1–8], becoming a potential source of energy. Conventional sewage treatment systems are often
not efficient enough for the complete degradation of pollutants present in the industrial wastewater
and they are characterized by high energy consumption. On the other hand, the primary energy

Catalysts 2020, 10, 439; doi:10.3390/catal10040439 www.mdpi.com/journal/catalysts

Catalysts 2020, 10, 439 2 of 49

is still supplied from fossil fuels. Their combustion leads to the greenhouse effect and dangerous
climate changes [9,10]. The pollution of the environment and increasing demand for energy supply
has resulted in the development of renewable energy sources. Sunlight seems to be the cleanest and
most abundant renewable source of energy, which should be applied in the industrial wastewater
treatment [11].
Industrial wastewater usually contains different recalcitrant pollutants and its composition is
complex. The wastewater pollutants include textile dyes, pharmaceuticals, pesticides, heavy metals,
pulp and paper, surfactants, and other chemicals. Thus, an application of advanced treatment
technologies might be required in order to remove or utilize them. Conventional sewage treatment
systems are not efficient enough to completely degrade pollutants present in the industrial wastewater.
Moreover, the chemical energy stored in the wastewater is wasted [12]. Therefore, it is important to
apply clean, environmentally friendly, and efficient wastewater treatment technologies that can totally
remove pollutants, recover fresh water and raw materials, and simultaneously recover the chemical
energy contained in the wastewater. One of the alternatives to commonly applied wastewater
treatment is heterogeneous photocatalysis. However, this technology has some drawbacks. Although
many semiconductor photocatalysts are easily photoexcited by UV or VIS irradiation, are stable, and
non-toxic, they suffer from low photocatalytic efficiency due to the fast recombination of holes and
electron [13–15]. The photocatalytic treatment of wastewater usually does not degrade pollutants
completely but results in a decrease of pollutant concentration and formation of intermediated
products. The second alternative to the commonly applied wastewater treatment is electrocatalysis,
especially electrochemical advanced oxidation processes (EAOPs) that are applied in the case of
organic pollutants treatment [16–19]. However, total degradation of organic compounds present in
the wastewater often requires so-called “deep electrooxidation” due to the necessity of high voltages
application in order to degrade the pollutants to inorganic compounds, such as CO2 , H2 O, N2 , etc., or
to simple organic compounds that are easily biodegradable. These methods are characterized by high
energy consumption, making the treatment process uneconomical. The photoelectrocatalytic treatment
of industrial wastewater should overcome this problem, especially when it is coupled with energy
generation. However, the selection of proper electrode materials applied in the photoelectrocatalytic
degradation is very important for achieving a decrease in electrical energy consumption. Special
attention should be paid to possible photoexcitation of electrode material by visible light (solar
irradiation) instead of harmful and more energetic ultraviolet light. Moreover, high long-term stability,
mechanical strength, high corrosion resistance, high efficiency of degradation processes, and low costs
should characterize electrode materials.
Solar irradiation is regarded as a clean, safe and limitless source of photons. However,
the photoexcitation of electrode materials by low energy photons requires the application of special
semiconductors or coupled semiconductors or doped semiconductors that are capable of absorbing
sunlight in order to degrade organic pollutants present in the industrial wastewater. Thus, three factors
should be considered in the selection of semiconductors applied as electrode materials [20]:

(1) absorption of UV and VIS irradiation;

(2) charge-carrier transport within the semiconductor; and,
(3) interfacial charge transfer.

Besides these parameters, the semiconductor should also be characterized by appropriate position
of valence and conduction bands related to oxidation and reduction potentials of pollutants, good
electrical conductivity and sufficient stability to be applied in treatment processes implemented
in practical applications on a large scale. The above-mentioned parameters are important in both
wastewater treatment and energy generation.
The aim of this paper is to present a general overview on the semiconductor materials that are
applied as photoelectrodes in the photoelectrocatalytic treatment of pollutants present in the industrial
wastewater. The fundamentals of photoelectrocatalytic reactions and mechanism of pollutants treatment
Catalysts 2020, 10, 439 3 of 49

as well as parameters affecting the treatment process are presented first. They are followed by examples
of various semiconductor materials applied as photoelectrodes in the treatment of different kinds of
pollutants in order to prove the advantages of photoelectrocatalytic treatment processes. This overview
is an addition to the existing knowledge with a particular focus on the main experimental conditions
employed in the photoelectrocatalytic degradation of various pollutants.

2. Mechanism of Photoelectrocatalysis Applied in Wastewater Treatment

Photoelectrocatalytic (PEC) treatment of wastewater is a combination of heterogeneous
photocatalysis and electrochemical degradation. This technique is based on the application of
a semiconductor material as an electrode, which is irradiated by light with energy equal to or greater
than its band gap energy and simultaneously biased by a potential or current. Thus, a description of
the photoelectrocatalytic processes should include photocatalytic and electrochemical reactions.
Generally, the semiconductor materials applied in the photoelectrochemical processes can be
divided into two groups: photoanodes (n-type) when oxidation reactions take place at the interface
and photocathodes (p-type) when the reduction is the main process. The reactions that proceed during
the photoelectrocatalytic treatment of pollutants are various and depend on the semiconductor type.
The photocatalytic reactions that take place at n-type semiconductors are presented below [21–25].

2.1. n-Type Semiconductor (SC)

 
+
SC + hν → SC e− CB + hVB (1)
 
+
SC hVB + H2 O → SC + H+ + OH• (2)
 
+
SC hVB + OH− → SC + OH• (3)
 
•−
SC e−CB + O2 → SC + O2 (4)

O•− + •
2 + H → HO2 (5)

2HO•2 → H2 O2 + O2 (6)
 
• −
H2 O2 + SC e−
CB → SC + OH + OH (7)

where SC denotes semiconductor, hν—photon energy, VB—valence band in SC, CB—conduction band
in SC, h+ —hole, and e− —electron.
Organic pollutants (OP) are degraded in photocatalytic processes according to the reactions [24,25]:

OP + OH• → OP•− + H2 O(OH• ) → OP degradation products (8)

+
OP + hVB → OP•+ → OP oxidation products (9)
•−
OP + e−
CB → OP → OP reduction products (10)

If chlorides are present in the solution, then the following photocatalytic reactions are
possible [24,26,27]:
Cl− + OH• → Cl• + OH− (11)

Cl− + h+ → Cl• (12)

Cl• + Cl− ↔ Cl•−

2 (13)

Organic pollutants (OP) photooxidation in the presence of chloride ions proceeds according to
the reactions [27–29]:
OP + Cl•− •
2 → OP + 2Cl
−
(14)
Catalysts 2020, 10, 439 4 of 49

OP•+ + O2 → OP oxidation products + CO2 (15)

Processes, including hydrogen evolution reaction (HER), formation of hydroperoxyl radical and
hydrogen peroxide, can be carried out on p-type semiconductor electrodes [25] under UV or VIS
irradiation and they are described by the reactions presented below.

2.2. p-Type Semiconductor (SC)

 
+
SC + hν → SC e−
CB + hVB
(16)
−
S + e−
CB → S (17)

S − + H + → S + H• (18)
+ •
e−
CB + H → H (19)
+ •
e−
CB + H + H → H2 (20)

S − + H + + H• → H2 + S (21)
+
hVB + H• → H + (22)
+
hVB + S− → S (23)
+ •
e−
CB + O2 + H → HO2 (24)

HO•2 + H+ → H2 O2 + h+ (25)

where S represents a surface state.

The photocatalytic degradation of pollutants often requires the application of UV irradiation instead
of VIS light or more accessible solar light [30–32] due to relatively large band gap of semiconductors
that were applied in the process. Moreover, the rapid recombination of photogenerated electrons and
holes (e− /h+ ) pairs decreases the efficiency of the degradation. The electrochemical degradation of
pollutants seems to be an alternative to their photocatalytic degradation, although an application of
electrochemical methods also suffers from some limitations.
The electrochemical degradation of pollutants present in the wastewater can proceed directly or
indirectly [33–35]. Direct degradation is relatively slow and it requires an application of high voltages
or high current densities [36,37], resulting in high energy consumption and high costs. Moreover, it is
difficult to achieve the complete degradation of organic pollutants to CO2 , H2 O, N2 , HCl, etc., or to
simple organic compounds that are easily biodegradable [36,38]. The electrochemical degradation of
pollutants can also proceed indirectly by reactive oxygen species and it is based on the electrogeneration
of hydroxyl radicals during oxygen evolution on the anode surface (M) [34,35,39]:

M + H2 O → M(OH• ) + H+ + e− (26)

which are converted to oxygen in the following reactions [40]:

M(OH• ) + H2 O → M + O2 + 3H+ + 3e− (27)

2M(OH• ) → 2M + O2 + 2H+ + 2e− (28)

Although OH• radicals are formed at the electrode surface, their reactivity is limited to about
1µm [41], resulting in significant limitation of oxidation efficiency.
The indirect degradation of pollutants can proceed by in situ electrogenerated chlorine species if
chloride ions are present in wastewater. Chlorine electrogenerated at the anode quickly diffuses to
Catalysts 2020, 10, 439 5 of 49

the bulk solution and undergoes the subsequent reactions, resulting in the formation of other species
that can degrade pollutants. Subsequently, the following reactions are possible [40,42]:

2Cl− → Cl2 + 2e− (29)

Cl2 + H2 O → HClO + Cl− + H+ (30)

HClO− ↔ ClO− + H+ (31)

Moreover, chloride ions can react with photogenerated OH• radicals forming another radical,
according to the reactions [43]:
Cl− + OH• ↔ ClOH•− (32)

ClOH•− + H+ ↔ Cl• + H2 O (33)

Cl− + Cl• ↔ Cl•−

2 (34)

In sulphate medium, two other oxidants (peroxodisulphate ions and ozone) can be formed at
the anode, according to the following reactions [44,45]:

2HSO− 2− +
4 → S2 O8 + 2H + 2e
−
(35)

3H2 O → O3 + 6H+ + 6e− (36)

Further reaction of peroxodisulphate ions with photogenerated electrons is thermodynamically

probable [46]:
− •−
S2 O2−
8 + eCB → SOCB + SO4
2−
(37)

Sulphate radicals (SO4 •− ) reveal high reactivity like OH• . Table 1 presents the redox
potential of various oxidants and radical species, which can be formed in photochemical and
electrochemical processes.

Table 1. Comparison of standard potentials determined for some oxidants and radical species [47–49].

Species E0 , V (vs. NHE)

OH• 2.80
SO4 •− 2.60
Cl• 2.47
O3 2.07
S2 O8 2− 2.01
Cl2 •− 2.09
H2 O2 1.78
HO2 • 1.68
ClO− 1.49
Cl2 1.36
O2 1.23

In the case of electrochemical degradation, it is important to select suitable electrode material,

which should be not only stable enough during the process, but should also guarantee the formation of
highly reactive radicals and oxidant species, resulting in high efficiency of pollutant treatment.
The efficiency of pollutants treatment achieved in the photocatalytic and electrochemical processes
can be enhanced by a combination of these two types of processes. The photoelectrocatalytic degradation
of pollutants present in the industrial wastewater has been developed during the last few years due
Catalysts 2020, 10, 439 6 of 49

to the significant development of semiconductor materials applied as photoelectrode materials.

The application of external potential or current significantly improves the photocatalytic degradation
efficiency, due to the decrease in recombination rate and formation of radicals simultaneously in
both (photocatalytic and electrochemical) processes. In the case of photoanodes, the photo-generated
electrons are transferred to the external circuit and they are concentrated in the cathode, while
photo-generated holes are accumulated in the anode, which guarantees a significant decrease in e− /h+
Catalysts 2020, 10, 439
recombination 6 of
rate [50]. Reactive radicals and highly oxidant species formed both on the cathode and49
anode can react with pollutants present in wastewater. Figure 1 presents the overall mechanism of
wastewater. Figure degradation
photoelectrocatalytic 1 presents the overall mechanism of photoelectrocatalytic degradation of
of pollutants.
pollutants.

1. The
Figure 1. Theoverall
overallmechanism
mechanismofof
photoelectrocatalytic degradation
photoelectrocatalytic of pollutants
degradation in wastewater
of pollutants with
in wastewater
the
withapplication of n-type
the application and p-type
of n-type semiconductor
and p-type electrodes.
semiconductor electrodes.

The
The photoelectrochemical reactions in
photoelectrochemical reactions in the
the case
case ofof n-type
n-type semiconductor
semiconductor applied
applied as
as working
working
electrode are, as follows [51,52]:
electrode are, as follows [51,52]:
photoanode—irradiation
photoanode—irradiation 
+

SC + hν → SC e− CB + hVB (38)
SC + hν → SC(e− CB + h +
VB ) (38)
anode  
anode
+
SC hVB + H2 O → SC + 1/2O2 + 2H+ (39)
 
+ + •
SC SC(h
hVB +H O O →
VB ) +2H2ads
→SCSC+−½OOH + 2H
2 ads
+ +H+ (40)
(39)
 
+ • •
SC+
SC(h VB )++
hVB Oads−
H2OH ads→→ SCSC − OH
− OH + H+
ads ads (41)
(40)
••+
 
++ ) −
SC(h
SC hVB VB ++OP
OHads → SC
ads → SC −
+ OH
OPadsads
(42)
(41)
•+
cathode SC(h+
VB ) + OPads → SC + OPads (42)
− −
H2 O + e → 1/2H2 + OH (43)
cathode
Similar reactions proceed while p-type semiconductor is applied as a photocathode:
photocathode—irradiation H2 O + e− → ½H
 2 + OH 
−
(43)
− +
SC + hν → SC eCB + hVB (44)
Similar reactions proceed while p-type semiconductor is applied as a photocathode:
cathode
photocathode—irradiation    
+ +
SC e−
CB + O2 + 2H → −H2 O2 ++ SC hVB (45)
 SC + hν → SC(eCB + hVB ) (44)
− •
SC e− CB + H2 O2 → OH + OH (46)
cathode  
SC e− CB + OX+→ SC + RED + (47)
SC(e−CB ) + O2 + 2H → H2 O2 + SC(hVB ) (45)
•
SC(e− −
CB ) + H2 O2 → OH + OH (46)

SC(e−
CB ) + OX → SC + RED (47)
Catalysts 2020, 10, 439 7 of 49

anode
2H2 O → O2 + 4H+ + 4e− (48)

The photoelectrocatalytic degradation of pollutants present in wastewater takes advantage of

heterogeneous photocatalysis with simultaneous electrocatalysis by using a biased potential or current
at a photoanode or photocathode. This results in an increase in the pollutant removal efficiency due
to the fact that different radicals are formed both in the electrocatalytic and photocatalytic processes
simultaneously. The improvement of pollutant removal efficiency in the photoelectrocatalytic process
requires the consideration of all parameters influencing both electrochemical and photochemical
processes and including the proper selection of a semiconductor material as well as the process
parameters. The most important factors influencing efficiency of the photoelectrocatalytic process are,
as follows [53]:

photoelectrode type;
light source and its intensity;
pH solution value;
supporting electrolyte—its type and concentration;
counter electrode type;
thickness of semiconductor film on electrode surface;
applied potential or current; and,
design of photoelectrochemical reactor.

Photoelectrode Type
Photoelectrodes applied in photoelectrocatalytic cells consist of a semiconductor supported on
a conductive substrate. Semiconductor material must be selected while taking the position of CB
and VB into consideration. In the case of water splitting, CB position should be more negative than
the potential at which H2 generation occurs. Similarly, VB position should be more positive than
the potential at which O2 generation is observed [11]. That means relatively wide absorption band,
which is undesirable in the case of solar light absorption.
The redox reactions occurring at photoelectrodes can be controlled by the applied potential or
current, which means the improvement of reaction selectivity. Moreover, the application of potential
or current enables controlling the Fermi level in a semiconductor, resulting in the improvement of
charge separation.
The photocatalytic material (semiconductor) should be immobilized at the electrode surface in
order to avoid the complicated separation of the photocatalyst applied in the slurry system. In the proper
reactor arrangement, the immobilization of the photocatalyst does not decrease its photocatalytic
activity [50].
Applied Potential or Current
The photoelectrocatalytic treatment of wastewater requires an application of constant bias potential
to a photoelectrode or constant current [53]. Photoreactors are usually equipped with three or two
electrode systems, depending on the operation conditions. The potential or current range within which
photoelectrocatalytic treatment is performed should be properly selected taking into consideration
the efficiency of treatment process and stability of materials applied as electrodes. The treatment
efficiency strongly depends on the recombination of e− /h+ , which can be prevented by external potential
or current supplied to photoelectrodes. The external current is even more advantageous due to less
complicated reactors with a set of two electrodes instead of three electrodes.
Supporting Electrolyte
The photoelectrochemical treatment of wastewater should be carried out in the presence of
a supporting electrolyte. The supporting electrolyte increases the conductivity of a solution that must
Catalysts 2020, 10, 439 8 of 49

guarantee good ion transfer in the treated wastewater. The conductivity also prevents recombination of
e− /h+ pairs. Moreover, it has significant impact on the applied bias potential or current and the resulting
consumption of electrical energy. The type of supporting electrolyte influences the efficiency of
the photoelectrocatalytic degradation of pollutants present in wastewater due to formation of different
oxidant or reductant species including various radicals with different reactivity [54,55]. The most
common electrolytes include NaCl and Na2 SO4 solutions. In the case of NaCl, active chlorine
species and radicals are formed, except for OH• radicals, and take part in pollutants degradation.
In the presence of Na2 SO4 , peroxodisulphate ions and sulphate radicals with comparable reactivity
as OH• radicals can be also generated and take part in the degradation of pollutants. An increase
in supporting electrolyte concentration results in the enhancement in pollutants degradation due to
formation of higher amounts of reactive species and higher conductivity of the solution [56,57]. On
the other hand, the supporting electrolyte affects not only pathway of pollutant degradation, but also
the corrosion of photoelectrodes [58].
pH Solution Value
The pH value determined for treated watewater is related to the supporting electrolyte and it is
another parameter that is important in photoelectrocatalytic processes. This parameter strongly affects
adsorption and dissociation of substrate molecules and distribution of charges on the photocatayst
surface and potential of CB and VB [54,55]. Moreover, pH affects the formation of reactive species and
radicals. For example, OH• radicals are regarded as predominant oxidation species at neutral and high
pH values, while, at low pH values, the positive holes are considered as the major oxidant species [59].
Generally, the photoelectrocatalytic degradation of organic pollutants proceeds easier at higher pH
values due to a higher number of hydroxyl groups, which can be easily oxidized to very reactive OH•
radicals. At low pH values, the reduction of electrons in CB takes part in the degradation of organic
pollutants, resulting in reductive cleavage of azo bonds [60]. The pH of wastewater also influences
the stability and corrosion of photoelectrodes.
Light Source and Its Intensity
Light intensity has significant impact on the extent of photogenerated e− /h+ pairs and the kinetics
of photocatalytic reactions due to increasing concentration of reactive radicals [55,61–63]. The higher
light intensity causes higher probability of the photocatalysts excitation and the recombined electrons
re-excitation. It was reported that, under low light intensities (below 250 W m−2 ), the photoreaction
rate is proportional to the light intensity. If moderate light intensities (higher than 250 W m−2 ) are
applied, then the photoreaction rate is proportional to square root of the light intensity, but, under high
light intensities, the photoreaction rate does not depend on the light intensity [64,65]. On the other
hand, the higher intensity causes sometimes more energy waste instead of more efficient degradation
of pollutants. The energy band structure of a semiconductor plays important role in the utilization of
light energy. In heterogeneous systems applied in PEC degradation of wastewater, light energy losses
include five reasons [64]:

(1) photons with energy lower than a band gap in a semiconductor do not excite e− /h+ pairs and are
wasted as a heat;
(2) photons with energy higher than a band gap in a semiconductor are absorbed and the energy
equal to Eg is used in e− /h+ pair excitation, while the remaining energy is lost as a heat;
(3) some part of a light can be reflected by semiconductor surface and absorbed by the surface of
other objects resulting in energy losses;
(4) light transmitted through a semiconductor layer can be absorbed by a support and cause light
losses; and,
(5) recombination of e− /h+ pairs cause that photons are not utilized effectively and heat is released.
Catalysts 2020, 10, 439 9 of 49

These energy losses can be eliminated by an appropriate wavelength range of light emitted by
the lamp, a decrease in the reflection of semiconductor surface, appropriate semiconductor thickness,
and light intensity.
Taking into consideration that the light intensity is not uniformly distributed inside
the photoreactor [66], it is important to determine the optimum light intensity in order to increase
the efficiency of the photoelectrocatalytic degradation and minimize the energy consumption.
The distribution of the light inside the photoreactor and, in fact, inside wastewater, depends on
lamp-reactor geometry. Three common geometrical configurations of photoreactors are known: annual,
elliptical, and parabolic [66]. The annular photoreactor is characterized by the placement of a lamp
at the center of the cylindrical vessel. One of the drawback of this geometry is a nonuniform light
intensity distribution, depending on a distance inside the reactor which can be overcome by smaller
annular region with the thickness lower than 2 cm. Another drawback is related to heat removal which
can be also overcome by continuous flow of a solution. In the case of elliptical geometry, a light source
is placed at one of ellipse foci and the reactor tube at the other one. However, the surface of the vessel
should reflect most of the light that is emitted by the light source. This geometrical configuration is
applied when heat must be removed from the lamp and it is also released from highly exothermic
reactions. The elliptical reactors are applied in the case of opaque liquids when the reflectivity of
container is very important.
Moreover, light sources emitting harmful UV irradiation should be replaced with VIS irradiation
or solar light. This requires the proper selection of a semiconductor material that can be excited by
light photons with lower energy and can decrease light energy losses.
Counter Electrode
In the case the photoelectrochemical reactor, the counter electrode is a cathode or anode, depending
on the working electrode—photoanode or photocathode. The counter electrode plays an important
role in the inhibition of recombination between e− and h+ by using the external constant potential or
current [21,50]. Other factors, like scavengers, should also be considered along with the external bias,
since they can reduce recombinations, due to bulk and surface recombinations. However, very fast
recombinations with lifetime of picoseconds or nanoseconds are possible, and result in low quantum
yield [53].
The role of the counter electrode is still underestimated. Besides the recombination inhibition,
this electrode can be useful in the generation of additional oxidant or reductant species, including
reactive radicals. In the case of the photoelectrochemical cell with a photoanode and a cathode,
the electroreduction of oxygen and the formation of H2 O2 is possible [34]. Furthermore, this electrode
is capable of generating OH• radicals from H2 O2 under UV irradiation [35]. This results in an increase
in the efficiency of photoelectrocatalytic degradation of organic pollutants in wastewater.
Semiconductor Thickness
The amount of a semiconductor that is immobilized on a substrate related to its thickness has
significant influence on the efficiency of the photoelectrocatalytic degradation of pollutants due to
the penetration of the light inside the semiconductor film. The semiconductor film should not be too thin
because of the insufficient absorption of the light resulting in low efficiency of a photoelectrocatalytic
process. Semiconductor film that is too thick can scatter or screen the light and also causes the efficiency
of the process to be too low [53]. This is related to dense and compact films of a semiconductor.
Semiconductor film thickness affects light energy conversion and electron transfer. In the case
of higher thickness of semiconductor film, relatively high resistance to electron transfer can result in
the lower efficiency of the photoelectrodegradation [63].
Reactor Design
The reactor design is a parameter that influences not only the efficiency of photoelectrocatalytic
degradation of pollutants present in wastewater, but is also important in the implementation of this
Catalysts 2020, 10, 439 10 of 49

process in industrial application. Parameters affecting the reactor design are similar to those that are
mentioned above, i.e. photoelectrode type, supporting electrolyte, pH of wastewater, applied external
potential or current, light source, load of organic pollutants, etc. However, additional parameters should
be also taken under consideration: temperature, dissolved oxygen, etc. [53]. The immobilized system
seems to have more advantages due to the elimination of necessary post treatment of wastewater used
in order to remove a photocatalyst. It is important to consider the positioning of the light source versus
the solution and photoelectrodes, due to its significant impact on the process efficiency. The simple
configuration of the reactor consists of a single chamber, but often with separated compartment for
anode and cathode [61]. Flat photoelectrodes allow for maximum light exposure and can be applied in
a simple design.

3. Semiconductor Materials Applied in Photoelectrocatalytic Wastewater Treatment

Semiconductor materials are often applied in the photocatalytic treatment of wastewater. However,
photocatalysis in wastewater treatment reveals some inconveniences. Photocatalytic treatment can be
performed in two modes: suspension and immobilized system [67–70]. The application of suspended
semiconductors requires subsequent processes of semiconductor separation and its recycling from
the treated wastewater. Both of the processes are time-consuming and increase the treatment cost.
Moreover, photocatalyst particle absorbed UV irradiation and its penetration inside wastewater solution
is limited [71]. These inconveniences can be overcome by the immobilization of a semiconductor on
a proper support [69,71,72]. On the other hand, the immobilization of the semiconductor results in
lower surface area of a photocatalyst and a decrease in a reaction rate [67]. Additionally, semiconductor
photocatalysts reveal relatively low photocatalytic efficiency due to the recombination of electrons and
holes [73].
The above-mentioned inconveniences make the photocatalytic treatment of wastewater difficult
to implement in practical applications on a large scale. A solution to these problems seems to be
combination of a photocatalytic treatment with electrochemical oxidation. Subsequently, photoactive
material, i.e. semiconductor, can be immobilized on a conductive support to which a bias potential or
current is supplied [74]. The immobilization of the semiconductor results in a decrease in its losses
during the recovery process.
During the photocatalytic processes, the semiconductor is irradiated by light photons with
the energy being equal to or higher than its band gap energy. If the photocatalytic process is
combined with the electrochemical degradation, photogenerated e− /h+ pairs are separated by the bias
potential supplied to the semiconductor [22,51,75–77]. Additionally, combination of photocatalytic and
electrochemical techniques results in an increase in wastewater treatment due to the generation of highly
reactive hydroxyl radicals (OH• ). These radicals are generated by the conducting electrode material
and simultaneously by the photoactive material that is irradiated by UV or VIS light. Hydroxyl radicals
degrade organic pollutants that are present in wastewater with high rate and non-selectively [78–80].
In the case of photoelectrocatalytic treatment of wastewater, it is important to apply the optimum
potential supplied to a semiconductor electrode. This potential should be low enough to prevent
the destruction of the semiconductor electrode, and to avoid undesired reactions occurring at specified
potentials and consuming the electrical charge, e.g., oxygen evolution reaction in the case of an anode.
Moreover, the applied potential has a significant effect on the consumption of electrical energy and
the costs of the process. On the other hand, lower potential can decrease the electrochemical treatment
efficiency [81]. Thus, it is necessary to optimize the applied potential in order to ensure the high
stability of the semiconductor electrode and high efficiency of wastewater treatment resulting from
the electrochemical process.
One of the methods for improving the efficiency of photoelectrocatalytic wastewater treatment is
the application of semiconductors in the form of nanomaterials. Highly ordered nanomaterials, such as
nanotubes, nanwires, nanorods, and nanowalls, are characterized by high surface area compensating
Catalysts 2020, 10, 439 11 of 49

the incoveniences that are related to the semiconductor immobilization. Moreover, nanomaterials are
characterized by very good electronic transport [51,82,83].
Special attention should be also paid to the development of highly stable semiconductor materials,
which could be activated by solar irradiation. This should result in a decrease of photoelectrocatalytic
treatment costs.
A semiconductor reveals electrical conductivity between a conductor and insulator. Three regions
can be distinguished in its electronic energy structure: the valence band (VB), the conduction band
(CB), and the band gap. At absolute zero, a semiconductor is an insulator due to the fact that the VB is
completely filled with electrons, while the conduction band is completely empty [84]. Under irradiation,
if the light energy is higher than the band gap in the semiconductor, then electrons are transferred from
VB to CB and e− /h+ pairs are generated. These pairs can recombine with a release of thermal energy or
they can be separated and transferred to the semiconductor surface. In the latter case, they take part in
oxidation and reduction processes with pollutants being adsorbed at the surface [85]. However, the VB
and CB levels should be thermodynamically consistent with the redox potentials of the adsorbates.
The band gap (Eg ) is the main parameter characterizing semiconductors applied as a photoelectrode
material. This parameter characterizes the electronic structure of semiconductors and the efficiency of
photon absorption is related to its value [86]. Eg can be defined in different ways as the fundamental gap,
optical gap, electronic gap, and HOMO-LUMO gap. The fundamental gap is defined as the difference
in energy between the first electron affinity (EA) and the first ionization potential (IP), according to
the equation [87]:
Eg (fund) = EA − IP (49)

The optical gap is the energy of transition between the ground state and the first excited state. Its
value is close to the value of Eg (fund) and it can be described by the equation [87]:

Eg (opt) = EA − IP − Eb (50)

where Eb is the exciton formation energy significantly lower in comparison with Eg (fund).
The band gap can be also defined as a difference between the top of valence band (EVB ) and
the bottom of the conduction band (ECB ), which can be denoted as the HOMO-LUMO band gap or
the mono electronic band gap [87]:

Eg (mono) = ECB − EVB (51)

In the case of solids, it can be assumed that Eg (fund) is almost equal to Eg (mono).
The band gap position is another important parameter that characterizes semiconductors applied
as photoelectrocatalytic material. In the case of a photoanode or photocathode, the positions of
the quasi-Fermi levels of the holes (EFh ) and electrons (EFe ) defines the ability of the semiconductor to
oxidation or reduction reactions by presenting the chemical potentials of these charge carriers [87–89].
The quasi-Fermi levels can be calculated according to the following equations:
!
Neff,C
EFe = EC − kB × T × ln (52)
ne
!
Neff,V
EFh = EV − kB × T × ln (53)
nh
where kB —the Boltzmann constant, T—temperature, Neff,c/v —effective density of states in CB or VB,
and ne/h —the concentration of electrons or holes.
Taking into consideration the order of values determined for effective density of states in CB or
VB and typical charge carrier densities [90,91], the quasi-Fermi levels are close to the minimum and
maximum energy of CB and VB, respectively. In photoelectrocatalytic investigations, the minimum
Catalysts 2020, 10, 439 12 of 49

and maximum energy of CB and VB is applied in the evaluation of the redox potentials of
the semiconductor [87].
Semiconductor materials commonly applied in wastewater treatment, as electrodes can be generally
characterized as n-type and p-type. Figure 2 presents energy level diagrams for n-type semiconductors
under equilibrium conditions after semiconductor-electrolyte contact, after illumination, and after
subsequent
Catalysts 2020,bias potential supplied.
10, 439 12 of 49

Figure 2. Energy diagram of n-type semiconductor; band positions in a semiconductor under

Figure 2. Energy diagram of n-type semiconductor; band positions in a semiconductor under
equilibrium condictions, after semiconductor-electrolyte contact (A), after irradiation (B) and after
equilibrium condictions, after semiconductor-electrolyte contact (A), after irradiation (B) and after
irradiation and applying a bias potential E > Efb (C); Efb —flat band potential, SCL—space charge layer,
irradiation and applying a bias potential E > Efb (C); Efb—flat band potential, SCL—space charge layer,
BSC —band bending in the semiconductor.
BSC—band bending in the semiconductor.

In the case of n-type semiconductor, if the position of Fermi level in the redox electrolyte lies below
In the case of n-type semiconductor, if the position of Fermi level in the redox electrolyte lies
the Fermi level in the semiconductor, and then electrons will be transferred from the semiconductor to
below the Fermi level in the semiconductor, and then electrons will be transferred from the
the oxidized speces in a solution until the equilibrium is achieved. This leads to the formation of a space
semiconductor to the oxidized speces in a solution until the equilibrium is achieved. This leads to the
charge layer of
formation SCL (i.e., depletion
a space layer SCL
charge layer due to removal
(i.e., depletion of electrons)
layer due in to
theremoval
semiconductor and theinFermi
of electrons) the
levels in both phases must be equal at equilibrium [85]. A bending
semiconductor and the Fermi levels in both phases must be equal at equilibrium [85]. A bending ofof bands upward toward the surface
takes
bands place. The band
upward toward bending is equal
the surface takesto the difference
place. The band between
bending theisFermi
equal levels
to theof the semiconductor
difference between
and the redox electrolyte [85]. The band bending is defined
the Fermi levels of the semiconductor and the redox electrolyte [85]. The band bending by the parameter B SC (Figure 2A) and
is defined byit
results in a potential
the parameter barrier2A)
BSC (Figure against
and electron
it resultstransfer
in a potentialin the barrier
n-type semiconductor
against electron[88]. transfer in the n-
Under the irradiation,
type semiconductor [88]. the semiconductor is photoexcited by the light energy and e− /h+ pairs are
generated.
UnderThe theFermi level the
irradiation, risessemiconductor
up upon irradiation [88]. Photoexcitation
is photoexcited by the light energy splitsandtheeFermi
−/h+ pairs level areof
the semiconductor
generated. The Fermi intolevel
tworises
quasi-Fermi levels: the [88].
up upon irradiation quasi-Fermi level ofsplits
Photoexcitation electrons for the
the Fermi CBof(Ethe
level F,e− )
and the quasi-Fermi
semiconductor intolevel of holes for the
two quasi-Fermi VB (E
levels: theF,h + ). The
quasi-Fermi quasi-Fermi
level of level of
electrons majority
for the charge
CB (E F,e−carriers
) and
remains close to the
the quasi-Fermi original
level Fermi
of holes for level,
the VB while
(EF,h+the quasiFermi
). The quasi-Fermi levellevel
of minority
of majoritycharge carriers
charge shifts
carriers
away
remainsfromclose
the original FermiFermi
to the original level (Figure
level, while2B). the quasiFermi level of minority charge carriers shifts
away The application
from the originalof a Fermi
bias potential is a method
level (Figure 2B). for controlling the Fermi level in the semiconductor,
which The application
results in the change of a inbias potential
the band bendingis a [51,84,89].
method for If thecontrolling the Fermi
applied potential level the
flattens in band
the
semiconductor,
edges, whichflat
then it is called results
bandinpotential
the change Efbin the
. In band
this case,bending [51,84,89].
the potential If the
drops appliedsurface
between potential and
flattens
the bulk of thetheband edges, then is
semiconductor it zero.
is called flatapplied
If the band potential
potentialEfbis. higher
In this than
case, Ethe
fb >
potential
(E E fb ) drops
then an
between surface and the bulk of the semiconductor is zero. If the applied
increase in band bending and SCL occurs [51,82]. The electrons are depleted and holes are enriched at potential is higher than E fb

(Esurface
the > Efb) then
of theansemiconductor
increase in band bending
(Figure 2C).and SCL occurs
Electrons [51,82].
that have beenThe electrons
excited in theare depleted and
conduction band
holes are enriched at the surface of the semiconductor (Figure
move through external circuit to the counter electrode where redution reactions may occur. 2C). Electrons that have been excited
in the
In theconduction
case of p-typeband semiconductor
move through (Figure external3), circuit
quite to the counter
inverse processes electrode
proceed. where redution
Its Fermi level
reactions may occur.
is located above the VB top. The depletion layer in this type of the semiconductor is characterized
by theIn the case of
depletion of the
p-type semiconductor
majority (Figure 3), quite
of the carriers—holes inverse
in this case.processes
The applied proceed. Its Fermi
potential lowerlevel than
is located above the VB top. The depletion layer in this type of the
Efb (E < Efb ) results in enrichment of the electrons on the semiconductor surface while the wholes semiconductor is characterized by
the depletion of the majority of the carriers—holes in this case.
are depleted [50]. The reduction reactions are observed on the semiconductor (photocathode) and The applied potential lower than E fb

(E < Efb) results in enrichment of the electrons on the semiconductor surface while the wholes are
oxidation reactions proceed on the counter electrode.
depleted [50]. The reduction reactions are observed on the semiconductor (photocathode) and
oxidation reactions proceed on the counter electrode.
Catalysts 2020, 10, 439 13 of 49
Catalysts 2020, 10, 439 13 of 49

Figure 3. Energy diagram of p-type semiconductor; band positions in a semiconductor under

Figure 3. Energy diagram of p-type semiconductor; band positions in a semiconductor under
equilibrium conditions, after semiconductor-electrolyte contact (A), after irradiation (B) and after
equilibrium conditions, after semiconductor-electrolyte contact (A), after irradiation (B) and after
irradiation and applying a bias potential E < Efb (C); Efb —flat band potential, SCL—space charge layer,
irradiation and applying a bias potential E < Efb (C); Efb—flat band potential, SCL—space charge layer,
BSC —band bending in the semiconductor.
BSC—band bending in the semiconductor.
The semiconductor materials that are applied in photoelectrocatalytic treatment of wastewater
The semiconductor materials that are applied in photoelectrocatalytic treatment of wastewater
include photoanodes (n-type) and photocathodes (p-type) if oxidation or reduction is the main process
include photoanodes (n-type) and photocathodes (p-type) if oxidation or reduction is the main
at the interface [84]. Thus, photoelectrocatalysis is developed in such wastewater treatment field as:
process at the interface [84]. Thus, photoelectrocatalysis is developed in such wastewater treatment
field as:
organic compounds oxidation [92,93];
organic compounds
inorganic oxidation
ions reduction [94,95];[92,93];
inorganic ions
disinfection reduction [94,95];
[96–98];
metal [96–98]; [99–102]; and,
removal/recovery
disinfection
simultaneous generation of
metal removal/recovery –102]; and,and hydrogen [12,103–105].
[99electricity
simultaneous generation of electricity and hydrogen [12,103–105].
The appropriate semiconductor material applied in photoelectrocatalytic wastewater treatment
The appropriate semiconductor material applied in photoelectrocatalytic wastewater treatment
should meet some requirements. The most important requirements are as follows [11]:
should meet some requirements. The most important requirements are as follows [11]:
wide
widelight
lightabsorption
absorptionspectra
spectrarange;
range;
suitable
suitableband
bandenergies;
energies;
high
highcharge
chargemobility
mobilityand
andlong
longcharge
chargecarrier
carrierdiffusion;
diffusion;
high catalytic activity;
high catalytic activity;
high stability; and,
high stability; and,
sustainability and low cost.
sustainability and low cost.
Theserequirements
These requirementsare are partially
partially fulfilled
fulfilled by semiconductor
by single single semiconductor materials,
materials, compositecomposite
materials,
materials,
and and doped semiconductors.
doped semiconductors. However, the However,
materialsthe materials
applied applied as photoelectrodes
as photoelectrodes still need
still need improvement
inimprovement
order to make intheorder to make the
implementation implementation
of the of thetreatment
photoelectrocatalytic photoelectrocatalytic treatment of
of industrial wastewater on
industrial
a large scalewastewater
possible. on a large scale possible.

3.1.
3.1.Single
SingleSemiconductor
SemiconductorPhotoelectrode
PhotoelectrodeMaterials
Materials

AAsemiconductor
semiconductorshouldshouldbe beimmobilized
immobilized on an appropriate
appropriate substrate
substrateto toform
formaaphotoelectrode.
photoelectrode.
Thesubstrate
The substrateplays
plays important
important rolerole in
in electron
electrontransfer
transferthrough
through thethe
semiconductor
semiconductor film.film.
Thus,Thus,
the
substrate should fulfil some criteria: strong adherence, chemical and electrochemical
the substrate should fulfil some criteria: strong adherence, chemical and electrochemical stability, stability,
relativelyhigh
relatively highconductivity,
conductivity, high
high specific
specific surface
surface area,
area, and strong
strong adsorption
adsorption affinity
affinity towards
towards
pollutants
pollutants [106].The
[106]. Themost
mostcommon
commonsubstrates
substrates that
that are
are applied
applied inin supporting
supportingsemiconductors
semiconductorsinclude
include
silica gel, metals, ceramics, fibres, carbons, graphites, fibres, polymers cellulose, zeolites,
silica gel, metals, ceramics, fibres, carbons, graphites, fibres, polymers cellulose, zeolites, glass glass coated
with indium
coated tin oxide
with indium tinoroxide
fluorine
or doped
fluorinetindoped
oxide glass, etc. [63].
tin oxide Generally,
glass, conductive
etc. [63]. Generally,glasses reveal
conductive
not enough connection with the semiconductor film (e.g. TiO 2), which results in low transfer
glasses reveal not enough connection with the semiconductor film (e.g., TiO2 ), which results in
efficiency
low transfer [63,84].
efficiencyThe application
[63,84]. of metalof supports
The application metal supportsallowsallows
for one
for oneto to
achieve
achievehigher
higher
photoelectrocatalytic activity of the photoelectrode due to the lower resistance in chargetransfer
photoelectrocatalytic activity of the photoelectrode due to the lower resistance in charge transfer[84].
[84].
Catalysts 2020, 10, 439 14 of 49

3.1.1. TiO2 Photoelectrodes

Titanium dioxide is the most common semiconductor material that is applied in
photoelectrocatalytic treatment of wastewater as electrode material, due to its low cost, nontoxicity,
and resistance to photocorrosion [107]. TiO2 occurs in three polymorphs—the stable rutile, metastable
anatase, and brookite, showing different properties and band gaps, i.e. 3.0, 3.22, and 3.23 eV,
respectively [108,109]. The three polymorphs of TiO2 were investigated in the photocatalytic
degradation of methyl orange (MO) under UV irradiation. During the two-hour experiment, anatase
degraded MO in 90%, rutile—60% while brookite—45% [108]. Thus, anatase and rutile forms are
mainly applied as photocatalysts. Anatase reveals higher photocatalytic activity than rutile in many
cases due to different lattice structure and electronic band structure. The properties of TiO2 strongly
depends on methods of its preparation [110]. In the case of photoelectrodes, TiO2 can be immobilized
on different substrates, e.g., titanium, stainless steel, glass, graphite, etc. The photoelectrodes with
TiO2 as a semiconductor were applied in various photoelectrocatalytic systems for the degradation
of organic and inorganic pollutants that are present in wastewater. Table 2 presents an overview of
photoelectrodes with TiO2 applied in degradation of different pollutants under various conditions,
over the last two decades.
Catalysts 2020, 10, 439 15 of 49

Table 2. Photoelectrocatalytic degradation of various pollutants with the application of TiO2 as a semiconductor photoelectrode material.

Degradation
Pollutant, Light Source Supporting Other Exp.
Semicond./Support Counter Electrode Efficiency Ref.
Concentration Applied Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
98% Simultaneous
TiO2 NTs/Ti Pt/C MO, 5 mg/L 150 W Xe lamp 0.05 M Na2 SO4 [111]
(4 h) electricity generation
MO—100%,
UV light (254 nm)
TiO2 NTs/Ti Ni MO, 50 mg/L 0.01 M Na2 SO4 COD > 80% - [112]
0.75 V
(3 h)
4 W UV lamp (254 nm)
80%
TiO2 NTAs/Ti Pt MO, 20 mg/L 1.0 mW/cm2 0.01 M Na2 SO4 - [113]
(3 h)
0.5 V vs. Ag/AgCl
8 W mercury lamp (365 nm)
TiO2 /Ti RVC (reticulated 0.01 M Na2 SO4 , 50%
Orange G, 0.1 mM 0.68 mW/cm2 - [114]
mesh vitreous carbon) pH = 6.2 (5 h)
0.71 V vs SCE
8 W mercury lamp (365 nm)
0.1 M Na2 SO4 , 54.3%
TiO2 /Ti Graphite Orange G, 0.1 mM 0.66 mW/m2 - [115]
pH = 3 (3 h)
5.5 V
4 W UV lamp (365 nm)
TiO2 /SS 0.01 M Na2 SO4 , DOC—38.8%
Graphite Orange G, 64 mg/L 0.33 mW/cm2 - [116]
mesh pH=3 (3 h)
1.0 V vs. SCE
UV light
(365 nm) H2 SO4 , 60%
TiO2 NTs/Ti Graphite Orange G - [117]
1 mW/cm2 pH = 3 (3 h)
1 mA
250 W tungsten-halogen
TiO2 /EG 0.1 M Na2 SO4 , 85%
Pt MB, 20 mg/L lamp - [118]
NPs pH = 7 (4 h)
2.5 V
300 W Xe lamp
90.2%
TiO2 /PI/Ni Pt MB, 0.05 mM (>430 nm) 0.1 M Na2 SO4 - [93]
(1.5 h)
0.4 V vs SCE
Reactive Black 5
RB—77%,
TiO2 /SS (RB), Simultaneous
Graphite UV light 0.14 M Na2 SO4 KHP —98%, [104]
NPs 100 mg/L; KHP, hydrogen generation
(40 min)
875 mg/L
Catalysts 2020, 10, 439 16 of 49

Table 2. Cont.

Degradation
Pollutant, Light Source Supporting Other Exp.
Semicond./Support Counter Electrode Efficiency Ref.
Concentration Applied Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
Acid Orange 7 AO7—100% (2 h),
Carbon-PTFE-air- Sunlight irradiation
TiO2 /SS (AO7), 0.05 M Na2 SO4 TOC—40% [119]
diffusion-electrode 1 mA/cm2
15 mg/L (4 h)
DB–72% (0.4 MPa),
Direct Black 22 In the presence of
COD–58% (0.7
TiO2 /Ti Pt (DB), Fluorescent lamp 0.1 M Na2 SO4 dissolved oxygen at [120]
MPa),
20 mg/L various pressures
(2 h)
Drimaren Red
30 W UV lamp (254 nm) 93%
TiO2 /Ti Steel mesh 243X-6BN dye, 25 4.2 mM KCl - [121]
1.5 V (1 h)
mg/L
500 W Xe lamp
Rhodamine B, 5 0.1 M phosphate, 52.8%
NP-TiO2 /Ti Pt 2 mW/cm2 - [122]
mg/L pH = 7 (2 h)
0.5 V vs Ag/AgCl
4 Leds (3 W)
0.1 M Na2 SO4 , 73.8%
TiO2 /FTO Pt Phenol, 10 mg/L 25 mW/cm2 EEO = 599.8 kWh/l [123]
pH = 5 (2 h)
1.84 V vs Ag/AgCl
3 Xe lamps (solar light)
0.1 M Na2 SO4 , 88.5% EEC =1 kWh/m3 ,
TiO2 /Ti Graphite Phenol, 2 mg/L 60 W/m2 [124]
pH = 7.2 (6h) (50% effic. 115 min)
1.0 V vs Ag/AgCl
TiO2 /Ti RVC (reticulated 2,4,6-trichlorophenol, 8 W UV-A lamp (365 nm) 99% with electrogenerated
0.01 M Na2 SO4 [125]
mesh vitreous carbon) 10 mg/L 2.5 V vs SCE (1 h) H2 O2
UV Hg-Xe lamp
TiO2 /Ti 80%
Pt Phenol, 20 mg/L 3.1 mW/cm2 0.01 M Na2 SO4 - [126]
NTAs (7 h)
0.6 V vs Ag/AgCl
2-nitrophenol
UV lamp 2-NPH—90%,
TiO2 /Ti (2-NPH), 0.1 mM;
Pt 2 mW/cm2 0.5 M NaOH 4-NPH—95%, - [127]
NTs 4-nitrophenol
0.6 V vs Ag/AgCl (1.5 h)
(4-NPH), 0.1 mM
300 W Xe lamp (>320 nm) 4-CP—100%,
TiO2 /Ti 4-chlorophenol Simultaneous
SS 1 W/cm2 0.1 M Na2 SO4 TOC—38%, [103]
Blue-TNTs (4-CP), 100 µM hydrogen generation
1.64 V vs NHE (2 h)
Catalysts 2020, 10, 439 17 of 49

Table 2. Cont.

Degradation
Pollutant, Light Source Supporting Other Exp.
Semicond./Support Counter Electrode Efficiency Ref.
Concentration Applied Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
Ascorbic acid
MnO2 /carbon (AA), 60 µM;
60 W tungsten lamp AA > 90% (4 h),
paper/Ni Catechol (CAT), Simultaneous
TiO2 /CI (carbon ink) (633 nm, AA) 0.1 M KCl CAT—25% (3.5 h), [128]
mesh/Teflon air 0.5 mM; electricity generation
150 W Xe lamp (IPA, CAT) IPA—57% (3 h)
cathode 2-propanol (IPA),
13.9 mM
Bisphenol-A, 200 150 W Xe lamp (>280 nm) 5 mM HClO4 , pH 100%
TiO2 /ITO BDD - [129]
µg/L 0.32 mA/cm2 =1 (1.5 h)
Act > 95%,
Acetaminophen 14 UV lamp (275 nm)
TiO2 NTs/Ti Ti 0.02 M Na2 SO4 TOC—53%, EEO = 67 kWh/m3 [130]
(Act), 10 mg/L 8.0 V
(5 h)
100 W Xe lamp (AM 1.5G
Sulfamethoxazole, 0.1 M Na2 SO4 COD—60%,
TiO2 /EG Pt filter) - [131]
25 mg/L pH = 6.3 (6 h)
100 mW/cm2 , 10 mA/cm2
Hg lamp (254 nm)
Atrazine (AA), 100 AA—99.8% (0.5 h),
TiO2-x /Ti Graphite 5.4 mW/cm2 , 0.03 M Na2 SO4 - [132]
µg/L DOC—45.8% (3 h)
4 mA/cm2
MO—100%
300 W mercury lamp (AM
(12 min), Simultaneous
TiO2 @TiO2−x /FTO Pt MO, 0.1 M 1.5 G filter) 0.1 M NaOH [133]
TOC—72% (20 hydrogen generation
100 mW/cm2
min)
TiO2 /Ti Tetracycline, 20 4 W GE UV lamp 96.4%
Pt 0.1 M Na2 SO4 , - [134]
NTAs mg/L 5 mW/cm2 , 2.0 V (1 h)
TiO2 /FTO 4 W UV lamp (254 nm)
Tetracycline, 10 80%
NPs Pt 2.5 mW/cm2 0.02 M Na2 SO4 - [23]
mg/L (3 h)
nanoporous 0.5 V vs Ag/AgCl
CTC—98%,
Hg lamp (254 nm)
Chlortetracycline 0.5 M Na2 SO4 , TOC—67%, Simultaneous H2 O2
TiO2 /Ti Vitreous carbon 6.0 mW/cm2 , [135]
(CTC), 32 µg/L pH = 8 TN—69%, generation
0.39 A
(2 h)
TiO2 /Ti Sulphamethoxazole, 4 W UV-A lamp 100%
Pt 10 mM Na2 SO4 - [43]
nanorods 2 mg/L 0.5 V vs Ag/AgCl (70 min)
Catalysts 2020, 10, 439 18 of 49

Table 2. Cont.

Degradation
Pollutant, Light Source Supporting Other Exp.
Semicond./Support Counter Electrode Efficiency Ref.
Concentration Applied Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
Hg lamp (254 nm) CBZ—73.5%,
TiO2 /Ti Carbamazapine
Vitreous carbon 6.9 mW/cm2 , 0.05 M Na2 SO4 TOC—21.2%, - [136]
Nanostructure (CBZ), 10 mg/L
0.3 A (2 h)
125 W Hg lamp
Tamol—anionic Tamol—100%,
TiO2 /Ti (315–400 nm) 0.1 M Na2 SO4 ,
Pt surfactant, 0.009% TOC—94%, - [137]
Nanostructure 9.23 W/m2 pH = 2
(m/v) (1.5 h)
1.0 V vs Ag/AgCl
8 W bacteria lamp (254 nm)
0.5 M citric acid, 100%
TiO2 NTs/Ti Ti mesh Cr (VI), 17.7 mg/L 3.1 mW/cm2 - [138]
1 M NaCl, pH = 2.5 (1 h)
1.5 V
300 W UV lamp
TiO2 /ITO Ag+ , Pb2+ , Cu2+ , 100% Simultaneous
Pt (311 nm) 05 M NaCl [99]
NPs Cr2 O7 2− , 0.2 mM (160 min) electricity generation
21.5 W/m2
300 W Xe lamp (AM 1.5 G
TiO2 /FTO filter) 0.1 M NaCl, >99%
Pt U(VI), 0.5 mM - [139]
Nanorods 100 mW/cm2 ethanol (12 h)
0.45 V vs SCE
Pharmaceutical
250 W Hg lamp (≥365 nm) Color—78.5%,
MWCNTs air wastewater, COD, 0.1 M NaCl,
nano-TiO2 /Ni 6.17 mW/cm2 COD—93.5%, - [140]
cathode 3150 mg/L, Color pH = 3
10 V (2 h)
(units)—825
Real textile
PPy/CC 11 W Hg lamp (254 nm), COD—74.1%, Simultaneous
TiO2 NTs/Ti wastewater pH = 3 [141]
Nanostructure 3 mW/cm2 (4 h) electricity generation
COD, 108 mg/L
Abbreviations: MO—methyl orange, MB—methylene blue, NTs—nanotubes, NTAs—nanotube arrays, NPs—nanoparticles, FTO—fluorine doped tin oxide glass, ITO—indium tin oxide
glass, SS—stainless steel, EG—exfoliated graphite, DOC—dissolved organic carbon, TOC—total organic carbon, TN—total nitrogen, EEC—electrical energy consumption.
Catalysts 2020, 10, 439 19 of 49

Table 2 presents a comparison of results of degradation of various pollutants with the application
of TiO2 as photoelectrode in the photoelectrocatalytic process, as described by several authors. TiO2
was deposited on various substrates including Ti, W, ITO, FTO, SS, and EG. TiO2 was also deposited
in the form of nanoparticles, nanotubes, nanorods, and in nanocrystalline form, strongly affecting
TiO2 properties, depending on the method of preparation. The application of TiO2 as a nano material
was one of the methods for band gap modification and enabled photoexcitation of photoanodes by
visible light. Counter electrodes applied in PEC systems was usually Pt, but also stainless steel, carbon,
graphite, or BDD was applied. The counter electrode had significant effect on the PEC efficiency as it
was described in [114]. The light sources supplied irradiation from the UV or VIS region with different
intensities. Generally, PEC was applied in the degradation of organic compounds, including azo dyes,
pharmaceuticals, and pesticides. However, it was also possible to remove metal ions, e.g., Ag(I), Pb(II),
Cu(II), Cr(VI), and U(VI). The degradation efficiency was relatively high and significantly higher
than in the photocatalytic process without external bias potential or current, or in the electrocatalytic
process. However, it should be noted that the degradation efficiency was usually related to a decrease
in pollutant concentration or the decolorization of the solution, especially in the case of dyes. This does
not indicate solution mineralization and total degradation of pollutants with the formation of inorganic
compounds or simple organic compounds that can be easily degraded with the application biological
methods. Some authors described also determination of changes in TOC or COD values which can be
attributed to the mineralization of pollutants. It is worth noting that a decrease in TOC or COD values
were clearly lower in comparison with the degradation efficiency and required higher times of PEC
treatment. Moreover, the concentration of the pollutants in all of the described processes was relatively
low. Taking into consideration, especially dyes, their possible concentrations in wastewater can be
significantly higher, even up to 2 g/L [142], which means higher colouration of wastewater solution
and lower penetration of the irradiation, resulting in lower degradation efficiency.
Among TiO2 photoelectrode materials, a bifunctional electrode draws attention. This electrode
was applied in 2-nitrophenol degradation in the PEC process [143]. TiO2 photocatalyst was coated on
one side of the Ti substrate, while Ta2 O5 -IrO2 was coated on the other side and it formed electrocatalytic
thin film. During a 3 h process, the degradation efficiency of the organic compound achieved the value
of 90%. The hydroxyl radicals participating in the organic compound degradation were formed in
the photoelectrocatalytic and electrocatalytic processes occurring at both sides of the electrode.
The selection of an effective semiconductor applied as a photoelectrode in wastewater treatment
requires the consideration of several factors. These factors include PEC degradation efficiency,
semiconductor stability, treatment conditions, regulations, wastewater post-treatment conditions, PEC
costs, etc. Among these factors, the costs of the process are very important. They include electrical
energy consumption, which constitutes the main part of the operating costs [48,51]. PEC processes
of wastewater treatment are regarded as consuming electrical energy and are usually characterized
by the consumption of electrical energy per mass EEM (kWh/kg) or electrical energy per order EEO
(kWh/m3 /order), as described by the following equations [51,144]:

P × t × 106
EEM = (54)
V × ( C0 − Ct )

P × t × 1000
EEO = (55)
V × lg(M0 /Mt )
where: P—the rated power (kW) of the system, V—volume of treated wastewater (L), t—treatment
time (h), C0 and Ct —initial and final mass concentrations (mg/L), M0 and Mt—initial and final molar
concentrations (mol/L), and V—volume of treated wastewater (L). The electrical energy consumption
per order is the electrical energy used in degradation of a pollutant by one order magnitude in
unit volume of wastewater. The electrical energy consumption seems to be relatively high in PEC
processes, although being lower than in other alternative treatment methods. The EEO values
Catalysts 2020, 10, 439 20 of 49

achieved in the degradation of phenol in photocatalytic process and anodic oxidation were 3732.6 and
8367.7 kWh/L, while photoelectrocatalytic degradation resulted in 599.8 kWh/L [124]. However, the EEO
value determined for acetaminophen degradation in the PEC process was only 67 kWh/m3 [130].
The costs of PEC process can be decreased by the application of semiconductor photoelectrodes
activated by solar light.

3.1.2. Other Single Semiconductor Photoelectrode Materials

TiO2 is not the only semiconductor applied as photoelectrode material. There are several papers
describing application of ZnO, Fe2 O3 , SnO2 , CuO/Cu2 O, BiPO4 , BiVO4 , WO3 , etc., semiconductor
photoelectrodes in the degradation of various pollutants that are present in wastewater. These
semiconductors are characterized by band gaps that are different than in TiO2 , except for ZnO (Table 3).

Table 3. Band gaps of semiconductors applied as photoelectrodes in the photoelectrocatalytic

degradation of various pollutants.

Semiconductor Band Gap, eV Ref.

SnO2 3.8 [107,145]
ZnO 3.2 [84]
WO3 2.6 [84,107]
CdS 2.25 [107]
Fe2 O3 2.1–2.2 [84,107]
MoS2 1.7–1.9 [146]
MoO3 3.2 [147,148]
Cu2 O 1.95–2.2 [84]
ZrO2 ca. 5.0 [149]
BiVO4 2.4–2.5 [150,151]
Bi2 MoO6 2.5–2.8 [152]
Bi2 WO6 2.82 [153]

ZnO is an n-type semiconductor with similar photocatalytic properties as TiO2 . However, its
chemical instability in aqueous solutions is its main drawback related to the following reactions [107]:

ZnO + 2H+ ↔ Zn2+ + H2 O (56)

ZnO + H2 O ↔ Zn(OH)2 (57)

This results in limited pH range in which ZnO is stable. Nevertheless, ZnO was investigated as
a semiconductor material being applied in photoelectrocatalytic degradation of various pollutants
present in wastewater (Table 4).
SnO2 is also an n-type semiconductor, but with relatively high band gap (3.8 eV) resulting in
necessity of UV irradiation application for its photoexcitation. Moreover, the position of CB in SnO2
makes this semiconductor incapable of reducing oxygen [145]. Thus, this semiconductor has not
been applied as photoelectrode material in wastewater treatment However, its coupling with other
semiconductor materials has been widely described and it is presented in the next section.
The other semiconductors that are presented in Table 3 reveal lower band gaps and they can
be excited by visible irradiation. Especially, WO3 draws attention due to its high stability in acidic
solutions, resistance to photocorrosion, high conductivity, and the possibility of photoexcitation by VIS
irradiation or sunlight [107,145]. Thus, this semiconductor seems to be most commonly applied in
photodegradation of pollutants present in wastewater, except for TiO2 (Table 4).
Catalysts 2020, 10, 439 21 of 49

α-Fe2 O3 (hematite) is a semiconductor with low energy of its band gap (2.1–2.2 eV). Furthermore,
this semiconductor is characterized by low costs, nontoxicity, and good chemical stability in most
aqueous solutions at pH > 3 [154,155]. α-Fe2 O3 can be applied in photoelectrocatalytic degradation of
pollutants rather than in photocatalytic processes due to its high recombination rate of photoinduced
e− /h+ pairs. This oxide is also characterized by low conductivity, which can be a drawback in its
application as a photoelectrode material. However, this drawback can be eliminated by doping α-Fe2 O3
with suitable metals.
Bismuth vanadate (BiVO4 ) is another semiconductor with relatively low energy of a band gap
(2.4–2.5 eV), which can be excited by sun light [21]. This oxide is non-toxic, but only stable at almost
neutral pH. Although this oxide is characterized by low photon-efficiency and is susceptible to
photocorrosion [156], it is often coupled with other semiconductors, e.g., WO3 [157].
CdS is a semiconductor with higher VB and lower resistance to photocorrosion by photogenerated
holes [107]. However, it was not only applied in photoelectrocatalytic degradation of organic
compounds, but also in solar cells and optoelectronic devices [158].
Catalysts 2020, 10, 439 22 of 49

Table 4. Photoelectrocatalytic degradation of various pollutants with the application of other single semiconductor photoelectrode materials.

Degradation Other Exp.

Pollutant, Light Source, Applied Supporting
Semicond./Support Counter Electrode Efficiency Conditions— Ref.
Concentration Voltage/Current Electrolyte
(Process Time) Remarks
1000 W Xe lamp (420 nm), Cf—95%,
WO3 /W Chlorfenvinphos (Cf),
Pt 100 mW/cm2 , pH = 1 TOC—65% - [92]
Nanorods 20 ppm
1 V vs Ag/AgCl (6 h)
150 W Xe lamp (AM 1.5G
Cu2+ —100%,
Cu2+ —500 ppm, filter) (UV—4.1%,
Ni2+ —100%,
WO3 /Ti Pt Ni2+ —500 ppm, VIS—54.7%, IR—41.2%), 0.5 M NaCl - [159]
MB > 70%
MB—10 ppm 100 mW/cm2
(10 h)
0.6 V—Cu2+ , 0.8 V—Ni2+
100 W Xe lamp, (AM 1.5 G 2-NPH—82% and
2-nitrophenol 0.1 M Na2 SO4 ,
WO3 /EG filter) TOC—69% (3 h),
Pt (2-NPH), 20 ppm, pH = 6 (3 h), - [160]
NPs 100 mW/cm2 , Orange II—96%
Orange II, 30 ppm pH = 5.5 (2 h)
10 A/cm2 TOC—67% (2 h)
350 W Xe lamp (AM 1.5 Urea—100%,
0.05 M Na2 SO4 ,
WO3 /FTO Pd/Au/PM Urea, filter), TOC—50.9%,
0.05 M NaCl, - [161]
Nanoplate arrays PM—porous metal 30 mg/L 100 mW/cm2 , TN—99.4%
pH = 5
1.2 V vs SCE (1 h)
Phenol (Ph), Ph—58%,
Cu2 O/Cu 350 W Xe lamp (AM 1.5 Simultaneous
WO3 /W Rhodamine B (RhB), 0.1 M KH2 PO4 , RhB—66%,
photocathode filter), electricity [162]
Nanocrystals Congo Red (CR), pH = 7 CR—73%
Nanowires 100 mW/cm2 generation
20 mg/L (5 h)
500 W Xe lamp (>400 nm),
WO3 /W MO 0.1 M NaH2 PO4 , MO—99% (3 h),
Pt 0.1 W/cm2 , - [163]
Nanoporous 61.1 µmol/L pH = 7 TOC—81.7% (7 h)
1.0 V vs SCE
WO3 /Ti Atrazine (Atr) 1000 W Xe lamp (360 nm), Atr—100% (3 h),
Pt 0.1 M H2 SO4 - [164]
Nanosheets 20 mg/L 40 mW/cm2 , 1.0 V TOC—72% (22 h)
MO, 5 mg/L 300 W Tungsten lamp (>
MO—79.1 2 (2 h),
α-Fe2 O3 /Ti Pt p-nitrophenol (PNP), 400 nm), 9·104 lux, 0.1 M Na2 SO4 - [155]
PNP—46.8%, (4 h)
0.05 mM 1.0 V vs SCE
Catalysts 2020, 10, 439 23 of 49

Table 4. Cont.

Degradation Other Exp.

Pollutant, Light Source, Applied Supporting
Semicond./Support Counter Electrode Efficiency Conditions— Ref.
Concentration Voltage/Current Electrolyte
(Process Time) Remarks
Simulated sunlight (AM In the presence
MB 1.0 M NaHCO3 ,
Fe2 O3 /FTO Pt 1.5G filter), 100 mW/cm2 , >90% (1 h) of 1.0 mM [165]
10 mg/L pH = 2.5
0.2 mA Mn(II)
Ammonia nitrogen
(AN), 20 mg/L 300 W Xe lamp (> 420 nm),
MoS2 /ITO 0.1 M Na2 SO3 , AN—80% (6 h)
Pt Bovine Serum 95.5 mW/cm2 , - [166]
Nanosheets pH = 10 BSA—70% (4 h)
Albumine (BSA), 10 0.6 V vs Ag/AgCl
mg/L
Color—93%,
ZnO/FTO Metal Textile effluent UV illumination - COD—69% - [167]
(3 h)
300 W Quartz
ZnO/EG Eosin yellowish dye, 0.1 M Na2 SO4 ,
Pt tungsten-halogen lamp, 95% (2 h) - [168]
Nanostructure 0.1·10−4 M pH = 1.5
UV light filter, 1.0 V
Eosin yellowish dye 250 W quartz EY > 90%,
ZrO2 /EG
Pt (EY), tungsten-halogen lamp, 0.1 M Na2 SO4 TOC—60% - [81]
NPs
20 ppm 2.5 V (1 h)
MB, MB—89%,
MoO3 /EG 400 W Spectrum solar
Pt Methyl red (MR), 0.1 M Na2 SO4 MR—92% - [169]
Nanorods simulator
1·10−4 M (3 h)
300 W Xe lamp (> 400 nm), Ag—87.7%, In the presence
Ag(CN)2− , 0.05 M Na2 SO4 ,
g-C3 N4 Ti 19 mW/cm2 , CN- —74.1% of [170]
0.45 mM pH = 12
1.0 vs SCE (2.5 h) 20 mM H2 O2
Simulated sunlight, NP—99.4%,
Bi2 WO6 /CA Nonylphenol (NP), with
- 500 mW/cm2 , pH=10 TOC—66.1% [171]
CA—carbon aerogel 1 mg/L electrosorption
0.6 V vs SCE (8 h)
1 mM Na2 SO4 ,
CN—99.8%,
Cu(CN)3 2− , 150 W Xe lamp (> 420 nm), 1 mM NaOH, Simultaneous
Bi2 MoO6 /ITO Ti Cu—91.0% [172]
250 mg/L 2.0 V vs SCE pH = 11, recovery of Cu
(2 h)
EDTA/CN = 5:1
Catalysts 2020, 10, 439 24 of 49

Table 4. Cont.

Degradation Other Exp.

Pollutant, Light Source, Applied Supporting
Semicond./Support Counter Electrode Efficiency Conditions— Ref.
Concentration Voltage/Current Electrolyte
(Process Time) Remarks
Ibuprofen (IB), IB—85% and
10 mg/L, 150 W Xe lamp (> 420 nm), TOC—76% (2 h),
Bi2 MoO6 /BDD Pt 0.1 M Na2 SO4 - [173]
Naproxen (NP), 2.0 V NP—85% and
15 mg/L TOC—78% (6 h)
Tungsten lamp
CdS/ITO Bisphenol A, (400–1100 nm),
Ti 0.05 M NaCl 94.1% (20 min) - [158]
Nanoparticles 0.1 mM 0.18 mW/cm2 ,
0.8 V vs. Ag/AgCl
Abbreviations: MO—methyl orange, MB—methylene blue, NTs—nanotubes, NTAs—nanotube arrays, NPs—nanoparticles, FTO—fluorine doped tin oxide glass, ITO—indium tin oxide
glass, SS—stainless steel, EG—exfoliated graphite, DOC—dissolved organic carbon, TOC—total organic carbon, TN—total nitrogen.
 Catalysts 2020, 10, 439 25 of 49

Tables 3 and 4 present such semiconductor photoelectrodes as MoS, ZrO2 , MoO3 , Bi2 WO6 , BiVO4 ,
and Bi2 MoO6 , which were applied in the photoelectrocatalytic degradation of various pollutants.
Catalysts 2020, 10, 439 26 of 49
Their band gaps are lower than 3 eV, except for ZrO2 (5.0 eV), MoO3 (3.2 eV), and SnO2 (3.8 eV). All
ofTables
them3degraded mainly
and 4 present suchorganic pollutants,
semiconductor including dyes
photoelectrodes and
as MoS, ZrOpharmaceuticals. In the
2, MoO3, Bi2WO6, BiVO 4, case of

and Bi2MoO6, which were applied in the photoelectrocatalytic degradation of various pollutants. under
MoS, this semiconductor photoelectrode was applied in the degradation of ammonia nitrate
VISband
Their irradiation.
gaps are lower than 3 eV, except for ZrO2 (5.0 eV), MoO3 (3.2 eV), and SnO2 (3.8 eV). All
Similarly,mainly
of them degraded as in the case of
organic TiO2 semiconductor
pollutants, including dyesphotoelectrodes, the concentrations
and pharmaceuticals. of pollutants
In the case of MoS,
thiswere
semiconductor
low and thephotoelectrode was applied
degradation efficiency wasin the but
high, degradation
a decreaseof in
ammonia
COD and nitrate
TOC under VIS lower
was usually
irradiation.
than decolorization of solutions or decrease in the concentration. Only a few authors also investigated
Similarly,
the stabilityasofinthe
thephotoelectrodes
case of TiO2 semiconductor photoelectrodes,
in accelerated theeven
stability tests, concentrations
though this of pollutants
parameter is very
were low and the degradation efficiency was high,
important in wastewater treatment on the large scale. but a decrease in COD and TOC was usually lower
than decolorization of solutions or decrease in the concentration. Only a few authors also investigated
the 3.2. Composite
stability of theSemiconductor
photoelectrodes Photoelectrode Materials
in accelerated stability tests, even though this parameter is very
important in wastewater treatment on the large scale.
A combination of two or more semiconductors with appropriately selected band gaps and
3.2.the energySemiconductor
Composite of CB and VBPhotoelectrode
is a method Materials
of improvement of photocatalyst activity [174]. Such combined
semiconductors are applied as photoelectrode materials in wastewater treatment. The reason of
A combinationcoupling
semiconductor of two orismore semiconductors
not only enhancementwith appropriately
in utilization selectedinband
of sunlight gaps and the
photoelectrode excitation,
energy of CB and VB is a method of improvement of photocatalyst activity [174]. Such combined
but also the reduction of e− /h+ pairs recombination [175,176]. Three combinations of n-type and p-type
semiconductors are applied as photoelectrode materials in wastewater treatment. The reason of
semiconductors are possible [21]:
semiconductor coupling is not only enhancement in utilization of sunlight in photoelectrode
excitation,
(1) p-n but also the reduction of e−/h+ pairs recombination [175,176]. Three combinations of n-type
heterojunction;
and(2)p-typen-n heterojunction;are
semiconductors possible [21]:
and,
(1) p-n
(3) heterojunction;
p-p heterojunction.
(2) n-n heterojunction; and,
The p-n heterojunction is characterized by the migration of holes from the p-type to n-type
(3) p-p heterojunction.
semiconductor and electrons from the n-type to p-type semiconductor due to the fact that electrons are
The p-n heterojunction is characterized by the migration of holes from the p-type to n-type
predominant charge carriers in the n-type semiconductors, while holes are the main charge carriers in
semiconductor and electrons from the n-type to p-type semiconductor due to the fact that electrons
the p-type semiconductors.
are predominant charge carriers in the n-type semiconductors, while holes are the main charge
carriers inTaking into consideration
the p-type semiconductors. the position of CB and VB in two coupled semiconductors (A and B),
three types of heterojunctions can
Taking into consideration the position be distinguished
of CB and VB[177,178]:
in two coupled semiconductors (A and B),
three types of heterojunctions can be distinguished [177,178]:
(1) type I with straddling gap—CB in semiconductor A is higher than CB in semiconductor B, while
(1) type IVB
with
in straddling gap—CB
semiconductor A isin semiconductor
lower than VB inAsemiconductor
is higher than CB
B; in semiconductor B, while
VB (2)
in semiconductor
type II withAstaggered
is lower than VB in semiconductor
gap—CB B;
and VB in semiconductor A are higher than CB and VB in
(2) type II
thewith staggered gap—CB
semiconductor B; and, and VB in semiconductor A are higher than CB and VB in the
semiconductor
(3) type IIIB;with
and, broken gap.
(3) type III with broken gap.
Figure 4 presents these three types of heterojunctions.
Figure 4 presents these three types of heterojunctions.

Figure 4. Three types of heterojunction photocatalysts with conduction band (CB) and valence band
Figure 4. Three types of heterojunction photocatalysts with conduction band (CB) and valence band
(VB) position.
(VB) position.
In the case of the type I heterojunction, electrons and holes photogenerated in the semiconductor
A are transferred to the semiconductor B and the redox reactions take place at the surface of the
Catalysts 2020, 10, 439 26 of 49

In the case of the type I heterojunction, electrons and holes photogenerated in the semiconductor
A are transferred to the semiconductor B and the redox reactions take place at the surface of
the semiconductor B. Thus, the redox ability of the coupled semiconductors might be lower. The type
II heterojunction is characterized by migration of the photogenerated electrons from the semiconductor
A to CB in the semiconductor B, while the photogenerated holes migrate in the opposite direction, i.e.,
from the semiconductor B to VB in the semiconductor A and this is convenient for the separation of e− /h+
pairs. In the case of the type III heterojunction, the band gaps of two semiconductor do not overlap and
the migration of electrons and holes between two semiconductors does not occur. However, the charge
transfer between semiconductors is possible due to broken gap alignment with increasing overall
voltage [179,180]. Such heterojunction is unsuitable for the enhancement of photogenerated electrons
and holes separation. Photocatalytic activity can be the mostly improved in the case of the type II
heterojunction due to the separation of holes and electrons, which makes this heterojunction commonly
applied. The coupled semiconductor materials, like SnO2 /TiO2 , TiO2 /g-C3 N4 , or BiVO4 /WO3 , are
classified as the type II heterojunction, and are applied as photoelectrodes in photoelectrocatalytic
degradation of various pollutants that are present in wastewater (Table 5). Ag/AgCl/g-C3 N4 is
a semiconductor material that belongs to type I heterojunctions, while Ag/AgBr/g-C3 N4 is type II
heterojunction [178].
The aforementioned heterojunctions are not the only heterojunctions of semiconductors applied
in wastewater treatment as photoelectrodes. The new generation of heterojunctions includes [177]:

(1) p-n heterojunction—coupling of a p-type semiconductor with an n-type semiconductor which

results in more efficient separation of photogenerated e− /h+ pairs;
(2) surface heterojunction—creation of heterojunction between two crystal facets of a single
semiconductor due to their different band structures;
(3) Z-scheme heterojunction, coupling of two different semiconductors and an electron acceptor/donor
pair; and,
(4) semiconductor/carbon heterojunction—combination of a semiconductor with carbonaceous
nanomaterials, i.e. carbon dots (CDs), carbon nanotubes (CNTs) and graphene.

The semiconductor materials, like BiOI/CeO2 , are classified as p-n heterojunction, g-C3 N4 -TiO2
as direct Z-scheme heterojunction and CNT-TiO2 is an example of semiconductor/carbon
heterojunction [178].
Catalysts 2020, 10, 439 27 of 49

Table 5. Photoelectrocatalytic degradation of various pollutants with the application of composite semiconductors as photoelectrode materials.

Degradation
Counter Pollutant, Light Source, Applied Supporting Other Exp.
Semicond./Support Efficiency Ref.
Electrode Concentration Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
125 W Hg lamp, RB5—100%,
Reactive Black 5 (RB5), 0.1 M Na2 SO4 , Simultaneous
TiO2 /WO3 /Ti Pt 12.55 mW/cm2 , TOC—85% [181]
0.01 mM pH = 6 hydrogen generation
1.0 V vs. Ag/AgCl (2 h)
Deuterium lamp,
MO, 0.1 M K2 SO4 , 100%
TiO2 /Cu2 O/FTO Pt 2 mW/cm2 , - [182]
20 mg/L pH = 10 8h
1.5 V vs SCE
MO MO—75.67% (3 h),
500 W Xe lamp, solar
TiO2 NTs/Bi2 WO6 RhB 0.1 M Na2 SO4 , RhB—66.07% (3 h),
Pt irradiation simulated, - [183]
Nanosheets MB 0.1 M KCl (Cr(VI)) MB—95.21% (2 h),
1.0 V vs Ag/AgCl
Cr(VI) Cr(VI)—74.18% (3 h)
MO 500 W Xe lamp, MO—71.97% (3 h),
RhB 1.0 V (MO, RhB, MB) RhB—59.88% (3 h),
TiO2 NTs/Ag-AgBr Pt 0.1 M Na2 SO4 - [184]
MB and 0.5 V (Cr(VI)) vs. MB—80.76% (2 h),
Cr(VI) Ag/AgCl Cr(VI)—52.24% (3 h)
TiO2 /SnO2 /BDD Bisphenol A (BPA), 300 W UV lamp, BPA—100% (3 h),
Pt 0.1 M Na2 SO4 - [185]
nanostructure 100 mg/L 20 mA/cm2 COD—100% (6 h)
Textile industrial
wastewater
(TWW-COD = 237 TWW—211.2 kWh/kg
UV light (365 nm), TWW-COD—58%,
mg/L), COD,
TiO2 NTs/Sb-SNO2 /Ti Pt 10 mW/cm2 , - CWW-COD—54% [186]
Coffee process. CWW—311.2 kWh/kg
30 mA/cm2 (5 h)
wastewater COD
(CWW-COD = 686
mg/L)
Phenol, 300 W UV-free Xe lamp, 0.1 M NaClO4 , 58.3%
CNT-TiO2 /ITO Pt - [187]
20 ppm 1.2 V vs. Ag/AgCl pH = 7 (2 h)
Methanol [(M, COD =
Xe lamp (AM 1.5 filter), M-COD—35%,
WO3 /TiO2 /Ti 5000 ppm)], Simultaneous
Pt 100 mW/cm2 , 0.1 M H2 SO4 F-COD—42% [20]
NTs Formaldehyde (F, 3000 hydrogen generation
0.8 V vs Ag/AgCl (5 h)
ppm)
Catalysts 2020, 10, 439 28 of 49

Table 5. Cont.

Degradation
Counter Pollutant, Light Source, Applied Supporting Other Exp.
Semicond./Support Efficiency Ref.
Electrode Concentration Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
WO3 /ZnO/FTO Sugarcane factory 94.44%
SS Sunlight illumination - - [188]
NPs wastewater (100 min)
150 W Xe lamp,
WO3 /BiVO4 /FTO Cr(VI), In the presence of
Ti 50 mW/cm2 , pH = 2.5 100% (40 min) [156]
Nanostructure 20 mg/L citric acid
1.7 V
Ibuprofen (IB), 100 W Hg lamp, IB—100% (1.5 h), Simultaneous
Cu2 O/TNAs/Ti Pt - [189]
10 ppm 0.5 V vs Ag/AgCl TOC—49.96% (4 h) hydrogen generation
125 W Hg lamp
98%,
Sn3 O4 /TiO2 /Ti DSA Acid yellow 17, 9320–400 nm), 0.1 M Na2 SO4 ,
COD—83% - [190]
Nanostructure electrode 10 mg/L 72.2 mW/cm2 , pH = 2
(30 min)
0.5 V vs Ag/AgCl
MO, 500 W UV light source, 97.4%
SnO2 /PbO2 /Ti Cu pH = 2.5 - [191]
50 mg/L 1.5 V vs Ag/AgCl (40 min)
Sb-doped
Phenol red dye, 10 W UV lamp, ca. 90%
Sn80%- W20% -Ox /Ti SS 0.1 M KH2 PO4 - [192]
0.1 mM 20 mA/cm2 (2 h)
Nanostructure
PNP—98%,
p-nitrophenol (PNP), 300 W UV lamp, 0.1 M
SnO2 /TiO2 NTs Ti TOC—91% - [193]
200 mg/L 20 mA/cm2 Na2 SO4
(4 h)
150 W Xe lamp (400
Phenol—75%,
CdTe/ZnO/ITO Phenol, nm),
Pt 0.07 M Na2 SO4 TOC—53.2% - [194]
Nanorods 100 mg/L 130 mW/cm2 ,
(2.5 h)
1.0 V vs SCE
300 W Xe lamp
MO, 99.2%
CdS/TiO2 NTs Pt (>400 nm), 0.05 M K2 SO4 - [195]
0.05 mM (3 h)
0.5 V vs SCE
300 W Xe lamp
MO, 85.2% Simultaneous
CdSe/TiO2 NTAs/Ti Pt (>400 nm), 0.2 M Na2 S [196]
10 ppm (3 h) hydrogen generation
0.5 V vs SCE
Catalysts 2020, 10, 439 29 of 49

Table 5. Cont.

Degradation
Counter Pollutant, Light Source, Applied Supporting Other Exp.
Semicond./Support Efficiency Ref.
Electrode Concentration Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
Reactive Brilliant Blue
PbO2 /Co3 O4 NWs/Ti 175 W Xe lamp, 83%
Ti KN-R dye, 0.1 M Na2 SO4 - [197]
Nanowire arrays 35 mA/cm2 (22 h)
60 mg/L
Xe lamp
Cr(VI), (>420 nm), 93.6% In the presence of
AgI/TiO2 NTs/Ti Ti 0.2 M Na2 SO4 [102]
0.08 mM 100 mW/cm2 , (70 min) 0.1 M EDTA
2.0 V vs Ag/AgCl
150 W solar simulator
g-C3 N4 /Ag/AgCl/ Benzophenone/sewage, 11.15% (h−1 ·cm−2 ) Simultaneous
Pt (AM 1.5 filter), - [96]
BiVO4 /ITO 2 ppm (2 h) hydrogen generation
1.23 V vs RHE
300 W Xe lamp
Ag3 PO4 /BiVO4 Norfloxacin, 100%
Pt (>420 nm), 10 mM NaClO4 - [198]
Nanostructure 5 mg/L (1.5 h)
0.5 V vs SCE
Urban wastewater with
estrogen (EE2), EE2—100%,
Simultaneous
0.56 mg/L TOC—100%,
Ag/AgCl@chiral Solar simulation (AM generation of
Pt/FTO Cu2+ , 1.03 mg/L, - Cu2+ —100%, [199]
TiO2 /FTO 1.5G filter) hydrogen and
TOC—0.56 mg/L, TN—70%
electricity
DO—6.7 mg/L, (2 h)
TN—13 mg/L
Abbreviations: MO—methyl orange, MB—methylene blue, NTs—nanotubes, NTAs—nanotube arrays, NPs—nanoparticles, FTO—fluorine doped tin oxide glass, ITO—indium tin oxide
glass, SS—stainless steel, EG—exfoliated graphite, DOC—dissolved organic carbon, TOC—total organic carbon, TN—total nitrogen.
Catalysts 2020, 10, 439 30 of 49

TiO2 coupled with WO3 is a typical example of two n-type semiconductors heterojunction. WO3 is
characterized by lower band gap energy (2.6 eV) in comparison with TiO2 (3.2 eV). Composite WO3 /TiO2
nanostructures were applied in the PEC degradation of methanol and formaldehyde [20]. The coupling
of these two semiconductors resulted in clearly higher COD reduction in the PEC process in comparison
with TiO2 or WO3 alone. This was attributed to the improvement of the solar spectrum absorption and,
additionally, by the enhancement of the photogenerated carrier transport. The coupling of WO3 with
TiO2 was also applied in Reactive Black 5 degradation in the PEC process [181]. The bicomponent
material applied as a photoanode provided faster dye degradation combined with simultaneous
improved hydrogen generation in comparison with the unmodified photoelectrode. CdS is another
n-type semiconductor that was coupled with TiO2 nanotubes and applied as a photoelectrode material
in the PEC degradation of methyl orange [195]. Its band gap energy is lower than in TiO2 and it
is equal to 2.4 eV. The coupling of these two semiconductors resulted in a significant increase in
the PEC degradation of methyl orange in comparison with unmodified TNTs, under not only UV, but
also VIS irradiation. Cu2 O coupled with TiO2 is an example of p-n heterojunction. Such composite
semiconductor was applied in the PEC degradation of methyl orange [182] and ibuprofen [189]. Cu2 O
is characterized by the band gap energy that is equal to 2.0–2.2 eV. In the case of methyl orange
degradation, its total decolorization was achieved during eight hours of the PEC process if the coupled
semiconductor was applied. If the unmodified TiO2 was applied as photoelectrode material, then total
decolorization of the dye solution required 8 h process performed with the application of 1.5 V bias
potential. In the case of Cu2 O/TiO2 photoelectrode, the comparable apparent rate constant of methyl
orange degradation was achieved of the bias potential of −0.4 V. It was explained by the improvement
in charge separation and extended light absorption spectrum to the visible region. The best degradation
efficiency of ibuprofen was achieved at the Cu2 O/TNAs-20 photoelectrode, which revealed the band
gap energy of 1.64 eV. The total removal of ibuprofen was observed during the 1.5 h PEC process, while
the removal efficiency achieved in photocatalytic process was only 60.4%. Similarly, a decrease in
the TOC value was 50% and 30.5% in 4 h PEC process and PC process, respectively. The PEC process was
performed with simultaneous hydrogen generation. CdSe is another semiconductor that was coupled
with TiO2 nanotube arrays and applied in the PEC degradation of methyl orange [196]. CdSe is a n-type
semiconductor with the band gap energy of 1.7 eV. The composite material revealed high efficiency in
methyl orange degradation (PEC process) combined with simultaneous hydrogen generation under
visible light irradiation due to the high dispersity of CdSe nanoparticles on outside and inside part
of the pore walls of TiO2 NTAs. The AgI/TiO2 -NT composites were applied as photoelectrodes in
the PEC removal of Cr(VI) under visible light irradiation [102]. This semiconductor material was
characterized by enhanced PEC reduction of Cr(VI) due to the easier generation and separation of
e− /h+ pairs and reduced charge transfer resistance. The total removal of Cr(VI) was achieved in
a 70 min process. TiO2 NTs/Ag-AgBr photoelectrode showed the removal efficiency of methyl orange,
rhodamine b, methylene blue and Cr(VI) in the PEC process under visible light irradiation [184].
This photoelectrode properties were attributed to high activity of solar absorption and electron
separation in comparison with TiO2 NTs/Ag photoelectrode. g-C3 N4 /Ag/AgCl/BiVO4 heterojunction
was applied as the photoelectrode in the PEC degradation of benzophenone sewage with simultaneous
hydrogen generation. The application of this photoelectrode resulted in the highest removal efficiency
in comparison with other photoelectrodes such as g-C3 N4 /BiVO4 , g-C3 N4 , Ag/AgCl/BiVO4 , and
BiVO4 . This was explained by more efficient transport of electrons towards the cathode and reduced
recombination rate of the charge carriers, which resulted in the formation of high energetic reactive
species, like hydroxyl radicals.
TiO2 is most commonly applied among the coupled semiconductors. However, the coupled
semiconductors without TiO2 are also applied as photoelectrodes in the degradation of various
pollutants. For example, WO3 was coupled with ZnO and BiVO4 while ZnO was coupled with CdTe.
The application of WO3 /ZnO photoelectrode in the PEC treatment of sugarcane factory wastewater
under sunlight irradiation [188] seems to be especially interesting. The wastewater degradation
Catalysts 2020, 10, 439 31 of 49

with 99.4% efficiency was achieved in a 1.7 h PEC process. The photostability and reusability of
the photoelectrode was investigated and resulted in the conclusion that this photoelectrode was stable
and did not undergo photocorrosion. BiVO4 with the monoclinic structure is a semiconductor with
a band gap energy of 2.4 eV, which makes it favourable to couple with WO3 . WO3 /BiVO4 was applied
as a photoelectrode in Cr(VI) removal [156]. The CB in the coupled semiconductors was more positive
than in the pure WO3 photoelectrode and it resulted in higher reduction ability of photoexcited
electrons. Moreover, the heterojunction structure broadened light absorbance range and revealed
higher photocurrents due to more efficient e− /h+ separation.
The enhanced efficiency of the PEC degradation of norfloxacin was observed in the case of
Ag3 PO4 -modified BiVO4 photoelectrode [198]. The band gap that was determined for Ag3 PO4 , BiVO4 ,
and Ag3 PO4 /BiVO4 film was equal to 2.42, 2.54, and 2.51 eV. The enhanced photoelectrocatalytic
activity of the tested photoelectrode under visible light irradiation and at low bias potential (0.5 V)
was attributed to a better separation of the photogenerated e- /h+ pairs. The degradation efficiency
increased with higher bias potential and lower norfloxacin concentration due to the contribution of
hydroxyl radicals and holes in the oxidation of the organic compound.
CdTe is a semiconductor with the narrow band gap (1.5 eV) that is suitable to absorb solar light.
CdTe-ZnO composite nanorods were applied in the PEC degradation of phenol under visible light
irradiation [194]. Approximately 75% degradation of phenol was achieved at CdTe-ZnO photoelectrode
while the application of ZnO nanorods in the PEC process resulted in 40% degradation. Furthermore,
the PC and EC degradation of phenol with the application of CdTe-ZnO composite nanorods resulted
in comparable (about 20%) and much lower efficiency than in the case of the PEC process that was
performed under visible light irradiation.
Co3 O4 is a promising photoelectrode material due to its high stability, low cost, and narrow
bandgap of 2.07 eV. The compoites of PbO2 with Co3 O4 nanowire arrays presented higher PEC activity
in the degradation of Reactive Brilliant Blue dye in comparison to Co3 O4 nanowires, which was
attributed to lower charge transfer resistance, larger electroactive surface area and higher ability for
the generation of hydroxyl radicals [197].
SnO2 is another n-type semiconductor worth mentioning due to its application in different
composite photoelectrode materials succesfully applied in the PEC degradation of organic pollutants,
i.e. p-nitrophenol [193], methyl orange [191], and bisphenol A [185]. TiO2 -NTs/Sb-SnO2 was
the photoelectrode material that was applied in the PEC treatment of textile industrial wastewater
and coffee processing wastewater [186]. The decrease in COD value for both types of wastewater was
higher than 50% under UV irradiation. The energy consumption was calculated to be 211.2 kWh/kg
COD (textile wastewater) and 311.2 kWh/kg COD (coffee processing wastewater). The high service life
and reusability of the tested photoelectrode suggested its potential application for the treatment of
industrial wastewater on a large scale.

3.3. Doped and Metal-Deposited Semiconductor Photoelectrode Materials

The doping of semiconductors is applied in order to enhance their photocatalytic activity and
make their photoexcitation with visible light irradiation possible. Thus, doping is related to band
gap engineering. Furthermore, doping can enhance electrical conductivity of a single semiconductor.
This is especially important in the case of TiO2 , which is characterized by high electrical resistance
at room temperature, resulting in a low rate of electron transfer [52]. If both disadvantages, e.g.,
low photocatalytic activity and low electrical conductivity, are overcome, then it is possible to
minimize the costs of the photoelectrocatalytic treatment of pollutants that are present in wastewater.
The semiconductor properties can be modified by doping with [200]:
(1) alkali metals: Li, Mg, Ca;
(2) anions (nonmetal dopants): C, N, F, S, B, I;
(3) different metalloids: B, Si, Ge, Sb;
(4) transition metals: Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta;
Catalysts 2020, 10, 439 32 of 49

(5) post-transition metals: Al, Ga, In, Sn; and,

(6) lanthanides: La, Ce, Nd, Sm, Eu.

Moreover, a semiconductor can be co-doped or tri-doped with two or even three dopants. Doping
results in the replacement of oxygen with the dopant in the crystal lattice.
Photocatalytic activity of semiconductor materials applied as photoanodes can also be enhanced
by combining with noble metals (Au, Ag, Pt, and Pd) on a nanometer scale. This is related to different
Fermi levels in the semiconductor and noble metal dopant, being characterized by the work function
of the dopant and band structure of the semiconductor. Doping results in the formation of Schottky
barrier in the doped material [84,107]. Subsequently, the noble metal acts as an electron trap and
promotes the interfacial electron transfer from CB of the semiconductor into the metal nanoparticles
and recombination of photogenerated e− /h+ pairs is reduced. Metal semiconductor materials, such as
Ag/TiO2 , Pt/TiO2 , and Au/TiO2 , are synthetized by photodeposition from metal precursors (AgNO3 ,
HAuCl4 , or H2 PtCl6 ) dissolved in the solution [201].
The deposition of metals on a semiconductor surface is another way to enhance the photocatalytic
activity of a semiconductor material [107]. The metal deposition can be performed with an application
of electrochemical reduction [202] or dip coating method, followed by a photoassisted reduction of
metal ions in aqueous solution under UV irradiation [107,203]. This modification of semiconductor
surface is also called “decoration”. ZnO that is decorated with Ag nanoparticles is an example of
the semiconductor material with enhanced photocatalytic activity [204–206].
Doped and metal-deposited semiconductors were successfully applied as photoelectrode materials
in the photoelectrocatalytic degradation of different pollutants that are present in wastewater (Table 6).
Catalysts 2020, 10, 439 33 of 49

Table 6. Photoelectrocatalytic degradation of various pollutants with the application of doped and metal-deposited semiconductors as photoelectrode materials.

Degradation
Counter Pollutant, Light Source, Applied Supporting Other Exp.
Semicond./Support Efficiency Ref.
Electrode Concentration Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
125 W Hg lamp, AR29—100%,
Acid Red 29 (AR29), 0.1 M Na2 SO4 ,
Pt-TiO2 NTs/Ti Pt 9.2 W/m2 , TOC—92% - [202]
85.4 mg/L pH = 3
2.0 V vs Ag/AgCl (2 h)
500 W UV lamp,
Formic acid, 15 mM, COD > 95%
Pt-TiO2 /ITO Pt 3.12 mW/cm2 , pH = 2.73 - [203]
COD = 239 mg/L (1 h)
1.0 V vs Ag/AgCl
Rhodamine B (RhB), 60 W lamp (>450 nm),
RhB—72% (3 h),
Ti3+ -TiO2 /Ti Pt 0.01 mM, 86610 lux, 0.1 M Na2 SO4 - [207]
Phenol—68% (5 h)
Phenol, 10 mg/L 0.6 V vs SCE
150 W Xenon lamp (AM CTC—99.6%,
Chlortetracycline
Vitreous 1.5 filter), TOC—92.5%,
N-TiO2 /Ti (CTC), 0.07 M Na2 SO4 - [208]
carbon 6.9 mW/cm2 , TN—90.3%
0.1 mg/L
0.6 A (3 h)
36 W Visible light
N-TiO2 / Diazinon, 0.042 M Na2 SO4 , 80% Process with
Pt lamps, [209]
graphene/Ti 9 mg/L pH = 6 (3 h) electrosorption
0.9 V vs SCE
300 W tungsten lamp MB—65.3%,
MB, 80 mg/L,
(>420 nm), RhB—44.7%,
N-TNTs/Ti Pt RhB, 80 mg/L, 0.1 M Na2 SO4 - [210]
213 µW/cm2 , BPA—34.3%
BPA, 50 mg/L
2V (80 min)
MO, 450 W Xe lamp, 0.5 M Na2 SO4 , 54.5%
Au/TiO2 NTs/Ti Ti - [211]
5 mg/L 0.5 V vs. SCE pH = 7 (6 h)
N-S-TiO2 NCs/ MB, 35 W Xe lamp, 93.9%
Pt 0.1 M Na2 SO4 - [212]
TNTAs 5 mg/L 0.4 V vs SCE (2 h)
100 W Hg lamp,
Perfluorooctanoic acid, 56.1% Simultaneous
N-C-TNTAs/Ti Pt 3.12 mW/cm2 , pH = 4 [213]
40 mg/L (3 h) hydrogen generation
1.0 V vs Ag/AgCl
50 W tungsten lamp,
Malachite green, >80%
La-N-TiO2 /Ni Carbon stick 80.4 mW/cm2 , 0.5 M Na2 SO4 - [214]
30 mg/L (4 h)
4 V vs SCE
Catalysts 2020, 10, 439 34 of 49

Table 6. Cont.

Degradation
Counter Pollutant, Light Source, Applied Supporting Other Exp.
Semicond./Support Efficiency Ref.
Electrode Concentration Voltage/Current Electrolyte Conditions—Remarks
(Process Time)
AY1—100%,
Acid yellow 1 (AY1), 125 Hg lamp,
B-TiO2 NTs/Ti Ti/Ru 0.01 M Na2 SO4 TOC—95% - [215]
100 ppm 1.2 v vs Ag/AgCl
(2 h)
35 W Xe lamp
Tetrabromobisphenol A, 95%
TiO2 NBs/AuNPs/Ti Pt (>400 nm), 0.1 M Na2 SO4 - [216]
5 mg/L (100 min)
1.5 V vs SCE
500 W Xe lamp (AM 1.5
MO—0.1 M K2 SO4 , MO—98%,
MO filter),
TiO2 NTs/Ag@Au/Ti Pt Cr(VI)—0.1 M Cr(VI)—70% - [217]
Cr(VI) 1.0 V (MO),
NaCl (2 h)
0.5 V (Cr(VI))
50 W tungsten lamp,
Landfill leachate, 76.9%
Cu/N-TiO2 /Ti Graphite 80.1 mW/cm2 , pH = 2 - [59]
COD—186.68 mg/L (2.5 h)
20 V
500 W Xe lamp (>400
RhB—95.7%(2 h),
Rhodamine B (RhB), nm), 0.1M K2 SO4 ,
Cu/TiO2 NTs/Ti Pt Cr(VI) —50.7% - [218]
Cr(VI) 0.5 V (RhB), 0.1M KCl
(2.5 h)
1.0 V (Cr(VI))
Reactive brilliant blue RB > 80%,
150 W Xe lamp,
F-PbO2 /Ti Ti KN-R (RB), 0.1 M Na2 SO4 TOC—14.2% - [219]
35 mA/cm2
60 mg/L (2.5 h)
MB, 250 W solar symulator, 0.1M Na2 SO4 , 93%
Ag-ZrO2 /EG Pt - [37]
20 mg/L 2V pH = 11 (4 h)
150 W vapour metallic BPA—ca. 80%,
Bisphenol A (BPA), 0.5 M Na2 SO4 ,
Cu-WO3 /FTO Pt lamp, TOC—75% EEC = 11.73 kWh/kg [220]
60 ppm pH = 8
10 mA/cm2 (8 h)
300 W Xe lamp (>420
Rhodamine B, nm), 24%
Y0.05 Bi0.95 VO4 /FTO Pt 0.5 M Na2 SO4 - [221]
0.2 mg/L 100 mW/cm2 , (3 h)
0.7 V vs. Ag/AgCl
Abbreviations: MO—methyl orange, MB—methylene blue, NTs—nanotubes, NTAs—nanotube arrays, NPs—nanoparticles, NBs—nanobelts, FTO—fluorine doped tin oxide glass,
ITO—indium tin oxide glass, SS—stainless steel, EG—exfoliated graphite, DOC—dissolved organic carbon, TOC—total organic carbon, TN—total nitrogen, EEC—electrical
energy consumption.
Catalysts 2020, 10, 439 35 of 49

Pt decorated TiO2 nanotubes were applied as photoanodes in the photoelectrocatalytic (PEC)

degradation of Acid Red 29 dye [202]. The decoration with Pt resulted in a decrease of TiO2 NT band
gap from 3.21 to 2.87 eV. Simultaneously, the decrease in TOC value was 92% in the case of the doped
photoelectrode during a 2 h process, while only 66% decrease in TOC was achieved in the same time at
the undoped photoelectrode. The improvement of the degradation process was attributed to a better
separation of e- /h+ pairs, and the generation of additional OH• radicals due to higher photocatalytic
activity of the doped photoelectrode. The degradation efficiency of formic acid was clearly higher in its
PEC degradation with the application of Pt deposited TiO2 photoelectrode [203] and was dependent
on the amount of Pt deposited. COD removal efficiencies were higher (>95%) than in the case
the photocatalytic process (PC) or PEC process with the application of the undecorated photoelectrode.
Additionally, the rates for the PC oxidation or PEC oxidation on Pt-TiO2 photoelectrode were more than
4 and 5.4 times higher than in the case of the PC oxidation on the undecorated electrode. The deposition
of Au at TiO2 nanotubes resulted in enhanced absorption of visible light and higher activity of PEC
degradation of methylene blue under solar light irradiation [211], due to the facilitation of the charge
separation and transfer. Doped TiO2 nanobelts with Au nanoparticles were found to be efficient
photoelectrode material in the PEC degradation of tetrabromobisphenol A [216]. The modification of
the photoelectrode with AuNPs facilitated the direct utilization of the photogenerated holes in the PEC
degradation of the pollutant. TiO2 nanotubes that were decorated with Ag@Au nanoparticles were
applied as photoelectrodes in the PEC degradation of methyl orange and the removal of Cr(VI) [217].
Bimetallic Ag-Au nanoparticles showed a remarkable influence on solar response and PEC activity
ofTiO2 NTs, which was attributed to the plasmon mediated electron transfer from Au to Ag sites within
core-shell structures. The PEC efficiency of methylene blue and Cr(VI) removal was significantly
higher in the case of TiO2 NTs/Ag@Au photoelectrode in comparison with TiO2 NTs and TiO2 NTs/Ag
photoelectrodes, and achieved the value of 98% (MO) and 70% (Cr(VI)) during a 2 h process. N doped
TiO2 photoelectrode was applied in the PEC degradation of chlortetracycline [208]. Doping with N
resulted in a band gap decrease from 3.2 to 2.3 eV in the case of the photoelectrode that was doped
with 3.4 at. % N. This significantly improved a decrease in the pollutant concentration and in TOC, in
comparison with the undoped photoelectrode and with the photoelectrodes that were doped with
lower amounts of nitrogen. TiO2 nanotubes doped with N revealed a decrease in a band gap from
3.07 eV (TNTs) to 2.77 eV for N-10-TNTs photoelectrode with the optimum amount of N [210]. This
photoelectrode was applied in the PEC degradation of methylene blue, rhodamine B, and bisphenol A
with the degradation efficiency of 65.3, 44.7, and 34.3%, respectively, under visible light. The enhanced
activity of the photoelectrode material was attributed to the reduction of the transfer resistance of
the photoelectrons. N and S co-doped TiO2 nano-crystallites (NCs) decorated TiO2 nano-tube arrays
(N-S-TiO2 NCs/TNTAs) photoelectrodes revealed a decrease in the band gap from 3.2 (TNTAs) to
2.25 eV [212]. The degradation of methylene proceeded on this photoelectrode with the removal
efficiency of 94%, while, in the photocatalytic process, the efficiency was only 58% under the same
conditions. The enhancement in the PEC efficiency of the pollutant degradation was attributed to
the enhancement of the light absorption in the visible region and the improvement of the transfer and
separation of photoinduced charge carriers. C and N co-doped TiO2 nanotube arrays (C-N-TNTAs) were
applied as photoelectrodes in hydrogen generation combined with the simultaneous PEC degradation
of perfluorooctanoic acid [213]. Doping with C and N resulted in a band gap decrease from 3.2 eV
(TNTAs) to 2.9 eV. The PEC process was the most efficient in the case of the pollutant degradation (56%)
in comparison with the PC process (18%) and EC process (5%). Another TiO2 semiconductor material
that was co-doped with La and N was applied in malachite green dye degradation [214]. Doping
resulted in a narrowing of the band gap to 2.79 eV and an increase in photocatalytic activity under
visible light irradiation in comparison with the undoped TiO2 , which was attributed to the prevention
of the phase transition between anatase and rutile phase, and to slow the recombination rate of
the photogenerated e− /h+ pairs. The co-doped photoelectrode presented higher PEC activity in
the degradation of the dye under VIS irradiation, but under relatively high bias voltage of 4 V. TiO2
Catalysts 2020, 10, 439 36 of 49

self-doped with Ti3+ was obtained by the electrochemical reduction method [207] and applied in
the PEC degradation of Rhodamine B and phenol. The enhancement of the photoelectrocatalytic
responses for the self-doped photoelectrodes in UV and visible region was proved. The doped
photoelectrode generated hydroxyl radicals under visible irradiation and revealed higher efficiency
in the PEC degradation of the tested pollutants in comparison with the undoped photoelectrode.
The doping of TiO2 nanotubes with boron (B-TiO2 NTs) resulted in a band gap decrease to 2.22 eV [215].
The boron-doped photoelectrode was successfully applied in Acid Yellow 1 dye degradation performed
in the PEC process with the rate two times higher than in the PC process under solar irradiation.
TiO2 is a semiconductor that is most commonly modified by doping and applied as
a photoelectrode material. Nonetheless, there are also other doped semiconductors that are applied
in the photoelectrocatalytic treatment of different pollutants. Cu doped WO3 was applied as
a photoelectrode in the PEC degradation of bisphenol A [220]. Doping with Cu did not result
in a significant change in the band gap of the modified semiconductor, because its value for 1% Cu
was 2.96 eV, while WO3 presented relatively wide band gap energy of 2.6–3.0 eV. Doping with 1%
Cu was most beneficial when taking into consideration the removal of the pollutant. The Ag doped
ZrO2 /EG semiconductor material presented a band gap of 5.16 eV, i.e. lower than in the case of
ZrO2 /EG (5.42 eV) and was applied as photoelectrode in the degradation of methylene blue under
solar light [37]. Although this semiconductor material presented minimal degradation efficiency
in photocatalytic degradation, the PEC process resulted in a significant degradation of MB, which
was attributed to the synergistic effects of Ag and EG (exfoliated graphite). BiVO4 semiconductor
doped with Y was applied in the degradation of Rhodamine B dye [221]. Doping with Y resulted
in a very slight change in band gap energy. BiVO4 revealed a band gap of 2.5 eV, while the most
advantageous modified semiconductor (Y0.05 Bi0.95 VO4 ) was characterized by the band gap of 2.52 eV.
Photocatalytic degradation of the dye in the presence of the tested photoelectrode was characterized by
the degradation efficiency of 18%, while this value increased to 24% in the PEC process. The authors
attributed the increase in the degradation efficiency to the applied bias potential, which could promote
the separation and transfer of photogenerated holes and electrons in Y0.05 Bi0.95 VO4 thin film electrode.
The degradation efficiency of different pollutants that were achieved in the photolectrocatalytic
process applied with doped semiconductor materials as photoelectrodes was relatively high in most
examples presented in Table 6. The mineralization of the pollutant solutions expressed as a decrease in
COD or TOC was also high. However, it required a relatively long duration of the PEC process. Only
in a few cases, electrical energy consumption was calculated, and the results of accelerated stability
tests were presented.

4. Conclusions and Future Perspectives

An overview of semiconductor electrode materials applied in photoelectrocatalytic treatment of
various pollutants, including organic compounds, inorganic compounds and metals, was presented.
Photoelectrocatalytic reactions and parameters affecting the treatment process were described.
Examples of various semiconductor materials with main experimental conditions and results of
the pollutants degradation were included in the presentation of strengths and weaknesses of
the photoelectrocatalytic process. Undoubtedly, the photoelectrocatalytic degradation of pollutants
present in industrial wastewater is a very promising technique in wastewater treatment with potential
application on a large scale. In many cases, the photoelectrocatalytic processes are characterized
by higher efficiency in comparison with the photocatalytic and electrocatalytic processes, because
the applied bias potential or current can significantly facilitate the transfer of photocarriers and
simultaneously hinder the recombination of photogenerated electrons and holes. The advantage of
the PEC treatment processes results from the synergetic effect of UV or VIS irradiation and external
electrical field. Nonetheless, the selection of a proper method for wastewater treatment requires
the consideration of not only efficiency of pollutant removal, but also the mineralization degree of
wastewater, with possible products formed during pollutant degradation, recovery of water and
Catalysts 2020, 10, 439 37 of 49

raw materials, energy consumption connected with process costs, etc. The PEC processes with
the application of semiconductors as photoelectrode materials have many advantages since they
are environmentally friendly—no toxic chemicals are required in the treatment, they are easy to
operate, and safe due to the ambient conditions of wastewater treatment, sustainable (possible
application of sunlight), and cost effective if an appropriate semiconductor material is applied. Thus,
the semiconductor materials should still be improved, and some key points should be taken into
consideration. First of all, the semiconductor material should be excited by the sunlight, which is
commonly available, and the photon absorption should be maximized. This can be achieved by
narrowing the band gap. The band gap engineering suggests a few methods for a decrease in the band
gap energy, such as coupling of two or more semiconductors or doping with transition metals or
non-metal. Moreover, the VBM (valence band maximum) and CBM (conduction band minimum) of
the semiconductor need to be correlated with the redox potential of the catalysed reactions in order to
make the reactions thermodynamically accessible upon photon absorption and guarantee the high
efficiency of the treatment process. Tuning the band edge positions in the semiconductors can also be
achieved by band gap engineering. For example, an increase in the energy of the VBM is possible by
less electronegative anion substitutions if the VBM is dominated by O 2p states. Similarly, a decrease
in the CBM energy can be reached by more electronegative transition metal cations substitutions
if the CBM is dominated by empty metal d-states [222]. This requires the appropriate selection of
the semiconductor modification in order to reach not only the change in the band edge position, but
also the band gap narrowing.
Taking the fact that the semiconductor materials are applied as electrodes in the PEC treatment
of wastewater into consideration, their active surface area should be high. It can be achieved by
the application of nanostructured semiconductors in the form of nanotubes, nanowires, nanofibres,
nanorods, and nanowalls. The nanostructured semiconductors can be easily obtained by electrochemical
methods. The nanostructures are characterized not only by high surface area, but also by ability
to minimize charge transfer recombination [84]. The surface area of the electrodes is connected
with their catalytic activity, which should be improved in the case of semiconductors applied as
photoelectrodes. This requires the lowering of the overpotential, which is related to the overall kinetic
barrier to the photoelectrochemical reaction. The photoelectrode material should also be characterized
by high conductivity. It also requires an appropriate modification of semiconductor materials, e.g.,
by dopants donating electron/hole carriers to the host materials without creating traps and with
simultaneous reduction of activation barriers for carrier transfer [222]. When considering possible
practical application of the PEC processes in wastewater treatment, the stability of semiconductor
materials should also be taken into account. This parameter can seriously limit the practical application
on a large scale. Although so many semiconductors were tested as photoelectrodes in the PEC treatment
of various pollutants, only in a few cases, their stability was determined. Thus, accelerated stability tests
seem to be necessary in the characterization of semiconductor materials. In this aspect, the substrates
on which semiconductors are supported should also be properly selected and be characterized by high
stability and conductivity. The preparation methods of photoelectrodes should be directed not only to
their highest stability, activity, and conductivity, but also to the strong adherence of semiconductors to
the conductive substrates.
The PEC processes of pollutants treatment with the application of semiconductor materials as
photoelectrodes presented in this paper have some disadvantages. The long duration of treatment
attracts attention in many cases. This results in a high energy consumption and high costs, making
the PEC process questionable in practical use. Moreover, in many cases, the degradation efficiency of
the PEC process was estimated as a decrease in pollutant concentration (sometimes only decolorization
of a pollutant solution) without the determination of the final products, which can be toxic. The almost
complete mineralisation of pollutant solutions was only achieved in few cases and usually required
a significantly higher duration of the treatment process. Thus, a combination of the PEC process with
other treatment methods, e.g., physicochemical or biological methods, is worth considering. This
Catalysts 2020, 10, 439 38 of 49

should result in a reduction of operating costs as well as in shorter duration of the PEC process. In
this case, the conversion of toxic and recalcitrant pollutants into biodegradable compounds that were
achieved in the PEC process can be followed by the subsequent biological process.
Additionally, the chemical energy stored in industrial wastewater is often wasted. Thus, it is
important to develop clean and efficient wastewater treatment methods for the simultaneous removal of
pollutants and recovery of energy stored in the wastewater. A solution to this problem is an application
of photoelectrochemical fuel cells with efficient semiconductor photoanodes and photocathodes.
Furthermore, the pollutants that are present in the wastewater should be simultaneously degraded at
the photoanode and photocathode. This process requires an application of appropriate semiconductor
materials as photoelectrodes and optimization of the operational parameters. A combination of
photoelectrocatalytic anode for the oxidation of organic pollutants and photoelectrocatalytic cathode
for the reduction of inorganic pollutants should be developed and improved as an efficient and
environmentally friendly approach to wastewater treatment.
In summary, the development of semiconductor materials that were applied as photoelectrodes in
wastewater treatment should be directed to the utilization of sunlight irradiation and the increase in
their photoelectrocatalytic activity in order to increase the rate of pollutants degradation and decrease
the costs of the treatment. Moreover, the semiconductor photoanodes and photocathodes should
facilitate simultaneous energy generation in order to make the treatment processes self-sufficient and
enable their practical application.

Funding: This research received no external funding.

Conflicts of Interest: The author declares no conflict of interest.

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