catalysts

Review
Key Principles of Advanced Oxidation Processes: A Systematic
Analysis of Current and Future Perspectives of the Removal of
Antibiotics from Wastewater
Giovanina-Iuliana Lupu 1 , Cristina Orbeci 1, *, Liliana Bobirică 1 , Constantin Bobirică 1
and Luoana Florentina Pascu 2

1 Department of Analytical Chemistry and Environmental Engineering, Faculty of Chemical Engineering

and Biotechnologies, National University of Science and Technology Politehnica Bucharest,
060042 Bucharest, Romania; giovanina.lupu@upb.ro (G.-I.L.); liliana.bobirica@upb.ro (L.B.);
constantin.bobirica@upb.ro (C.B.)
2 National Research and Development Institute for Industrial Ecology, 57-73 Drumul Podu Dambovitei,
060652 Bucharest, Romania; luoanapascu@yahoo.com
* Correspondence: cristina.orbeci@upb.ro

Abstract: In line with the development of industrial society, wastewater has caused multiple en-
vironmental problems. Contaminants of emerging concern (CECs) in water and wastewater are
persistent, and for this reason they can cause serious problems for human health, animal health,
and the whole environment. Therefore, it is absolutely necessary to apply efficient methods for the
treatment of wastewater that has a high concentration of organic compounds. Over recent years, the
prescribed and non-prescribed consumption of antibiotics has increased significantly worldwide.
Large quantities of antibiotics are discharged into wastewater because of their incomplete absorption
by living organisms. However, even small concentrations present in aquatic environments represent
a major risk to human health and environment protection. This paper presents the main advantages
and disadvantages of advanced oxidation processes, and the current state and new perspectives in
the field of environment protection. This study summarizes data from the most recent specialized
scientific literature that focuses on the topic of advanced oxidation processes, thus bringing all these
Citation: Lupu, G.-I.; Orbeci, C.;
aspects to the attention of researchers in a single work that adds comments and interpretations
Bobirică, L.; Bobirică, C.; Pascu, L.F.
related to the presented processes. Advanced oxidation processes (AOPs) are often used in the
Key Principles of Advanced
treatment of different types of wastewater. AOPs are based on physicochemical processes that create
Oxidation Processes: A Systematic
Analysis of Current and Future
significant structural changes in chemical species. The majority of antibiotics may be eliminated using
Perspectives of the Removal of physicochemical processes, such as photo-Fenton oxidation, photolysis, ozonation, electrooxidation,
Antibiotics from Wastewater. heterogeneous catalysis, and other bioprocesses. In comparison to conventional chemical processes,
Catalysts 2023, 13, 1280. https:// AOPs provide superior oxidation efficiency, ideal operating costs, and zero secondary pollutants.
doi.org/10.3390/catal13091280
Keywords: advanced oxidation processes; organic pollutants; wastewater pollution; antibiotics
Academic Editor: Gassan Hodaifa
removal; photocatalysis
Received: 2 August 2023
Revised: 30 August 2023
Accepted: 2 September 2023
Published: 6 September 2023 1. Introduction
The most important natural resource found on Earth is water. It is essential for human
life and contributes to the good health of the environment. As is well known, water is
Copyright: © 2023 by the authors.
unequally allocated in different parts of the world, and the quality is different on all the
Licensee MDPI, Basel, Switzerland. continents. Conversely, the planet is home to an abundance of aquatic resources; however,
This article is an open access article the majority of these resources are either inaccessible to humans in their current state or
distributed under the terms and are isolated from them. Some examples of these resources include the salty water found in
conditions of the Creative Commons oceans and seas, as well as glaciers [1,2]. However, continuous access to water and energy
Attribution (CC BY) license (https:// is essential to ensure the prosperity and development of the global population. Good
creativecommons.org/licenses/by/ management of the two resources is also essential to sustain and improve the health of the
4.0/). environment, and of the human population, respectively [3].

Catalysts 2023, 13, 1280. https://doi.org/10.3390/catal13091280 https://www.mdpi.com/journal/catalysts

Catalysts 2023, 13, 1280 2 of 26

Recently, the availability of fresh water, especially for drinking, has become one of the
biggest problems in the world. One of the major causes of this problem, especially in the
case of developing countries, is the pollution of surface water by effluent discharges into
the surface water from various sectors of activity, such as the chemical and petrochemical
industry, the pharmaceutical and cosmetics industry, and the electrical and electronic
components manufacturing industry [4–6]. Among the many pollutants, persistent organic
compounds have a strong negative impact on aquatic flora and fauna [7,8]. Thus, a
wide range of technologies have been developed and perfected to remove these organic
compounds from effluents before they are discharged into surface water [8]. Among
these, the most widely used are advanced oxidation processes (AOPs) such as Fenton
oxidation, photo-Fenton oxidation, photocatalysis, and electrochemical and sonochemical
advanced oxidation.
AOPs have the potential to be used in the treatment of hazardous effluents, such as
those found in hospitals and slaughterhouses, in addition to industrial effluents, which
include wastewater from agrochemical and distillery operations, oilfields, textile and phar-
maceutical production, and metal plating [1,7]. It is supposed that different contaminants
of water, from hazardous contaminants of pesticides, herbicides, detergents, and cosmetics
products, to pathogenic agents, can be efficiently removed by photocatalytic processes [1,8].

2. Approaches for Removal of Antibiotics from Wastewater

Pharmaceutical compounds have been a growing concern in recent years due to
their negative effects on the environment. In recent years, compounds such as analgesics,
antibiotics, and steroids have been detected in public water systems worldwide. A large
number of pharmaceutical compounds are used in human and veterinary medicine, and
these products are finally discharged into the environment through metabolic processes.
These compounds have been introduced in the category of emerging pollutants [8,9].
Antibiotics are produced by the pharmaceutical industry to treat infectious (microbial)
diseases and are used extensively in both human and veterinary medicine. The growing
demand for antibiotics has led to an increase in their production and, implicitly, in the
effluents generated from them, especially those in wastewaters, which have a high content
of these compounds. In many cases, due to their poor treatment, these wastewaters end up
in surface water in high concentrations [10,11]. Many antibiotics are not totally metabolized
by humans and animals, leading to their release in sewage treatment plants and, finally,
the environment [12,13].
In the past two years, it has been observed that the pandemic period has contributed
to a sudden increase in global antibiotics consumption [14]. Because bacterial co-infections
are a viral disease, antibiotics, especially azithromycin, have been used for treatment.
Recent reviews have identified that more than 50% of COVID-19 patients receive antibiotics
therapy, although less than 10% have a bacterial infection [15]. The fast development pace
during the pandemic period represented a direct threat to patients’ safety and public health
via an over-prescription of antibiotics [15].
Antibiotics could be considered to be persistent compounds due to the fact that their
rate of elimination from the environment is much lower than their rate of their entry into
it [16,17]. In addition, the presence of antibiotic residues in the environment is correlated
with the pharmacokinetic properties of the compounds. Pharmacies provide different
types of antibiotics with oral administration and intravenous administration, and those
addressed to different groups (humans, animals) [16].
Several types of antibiotics have been found in industrial, household, pharmaceutical,
and hospital wastewaters in different countries worldwide. Depending on the geographical
region, seasonal changes, and demographic data, it was found that the concentration value
of antibiotics in wastewater may fluctuate from ng/L to µg/L [14]. As a result, numerous
natural environments, including groundwater, surface water, soil, and sediments, have
been shown to contain antibiotics. The presence of antibiotics in water bodies for extended
periods of time may pose a risk to the integrity of ecological systems since it can lead
Catalysts 2023, 13, 1280 3 of 26

to the evolution of bacteria that are resistant to antibiotics (known as ARBs), as well as
genes that are resistant to antibiotics (ARGs) [18,19]. So, in this respect, negative effects of
antibiotic resistance and higher antibiotics concentrations in wastewater are reported in
some legislation documents (e.g., annual reports from World Health Organization).
One recent analysis estimated that, in the past twenty years, the antibiotics consump-
tion expressed in definite daily doses (DDD) has increased rapidly, by more than 65%. It
is estimated that, in the coming years, there will be an increase of up to 200% if major
changes are not taken soon. Numerous factors, such as the lack of information, poor health
knowledge, the pandemic situation, and fear of disease, drive an excessive use of antibi-
otics. Setting the quantity of antibiotic residues is very important in establishing a relation
between their presence in the environment and their biological effects and ecotoxicological
evaluation [16].
Antibiotics can be classified into two basic categories based on the type of action,
namely bacteriostatic (which inhibit the growth and reproduction of bacteria) and bacterici-
dal (which cause the death of bacteria cells) [18]. The occurrence of antibiotics in different
wastewaters is shown in Figure 1. Sulfamethoxazole, ciprofloxacin, and trimethoprim are
antibiotics that are used to treat a large number of infections of the urinary tract, respiratory
system, and gastrointestinal tract. They were detected in hospital, urban, and pharma-
ceutical wastewaters, often in high concentrations. Antibiotic degradation is a process of
breaking down antibiotics into smaller, less harmful substances. This is important because
antibiotics that are designed to kill bacteria can have unintended effects on the environment
and human health. When antibiotics are not completely degraded, they can persist in
the
Catalysts 2023, 13, xenvironment,
FOR PEER REVIEWleading to the development of antibiotic-resistant bacteria and other 4 of 28
negative consequences.

Figure 1. Occurrence of some antibiotics in different types of wastewater (adapted from [14]): (a)
Figure 1. Occurrence of some
wastewater antibiotics
sources in reported
of antibiotics differentin types of wastewater
recent studies; (adapted
antibiotic types from
and their [14]):
detection
(a) wastewater sources of antibiotics
frequency in: (b) urbanreported in recent
wastewater, studies;
(c) hospital antibiotic
wastewater, types andfrom
(d) wastewater their
thedetection
production
of food,
frequency in: (b) urban (e) industrial(c)
wastewater, wastewater.
hospital wastewater, (d) wastewater from the production of
food, (e) industrial wastewater.
The degradation of antibiotics in the environment is a complex process that is influ-
enced by many factors. Some of the most important factors that contribute to the degra-
dation of antibiotics include the type of antibiotic, the presence of other substances in the
environment, and the conditions of the environment, such as temperature, pH, and mois-
ture. The effectiveness of antibiotic degradation is also influenced by the presence of other
pollutants in the environment, as well as the presence of other microorganisms that may
compete for the same resources.
Despite the importance of antibiotic degradation, there is still much that is unknown
Catalysts 2023, 13, 1280 4 of 26

There are several different mechanisms of antibiotic degradation, including chemical,

physical, and biological processes. Chemical degradation of antibiotics occurs through
reactions with other substances, or water, as well with sunlight, which can break down the
chemical structure of the antibiotics. Physical degradation of antibiotics occurs when they
are broken down into smaller particles through processes such as grinding or crushing.
Biological degradation of antibiotics, on the other hand, is the process by which
microorganisms such as bacteria and fungi break down the antibiotics into smaller, less
harmful substances. This is a crucial process because it helps reduce the quantity of
antibiotics that persist in the environment. Additionally, by breaking down antibiotics,
these microorganisms can help reduce the risk of antibiotic resistance and the spread of
antibiotic-resistant bacteria.
The degradation of antibiotics in the environment is a complex process that is in-
fluenced by many factors. Some of the most important factors that contribute to the
degradation of antibiotics include the type of antibiotic, the presence of other substances
in the environment, and the conditions of the environment, such as temperature, pH, and
moisture. The effectiveness of antibiotic degradation is also influenced by the presence of
other pollutants in the environment, as well as the presence of other microorganisms that
may compete for the same resources.
Despite the importance of antibiotic degradation, there is still much that is unknown
about this process. To better understand the degradation of antibiotics, researchers have
developed a few methods for measuring and tracking the degradation of these compounds
in the environment. Some of these methods include the use of bioreactors, which allow
researchers to study the degradation of antibiotics in controlled environments, and the
use of analytical techniques such as mass spectrometry and chromatography, which allow
researchers to identify and quantify the products of degradation.
To help to reduce the negative impact of antibiotics on the environment and human
health, it is important to develop new methods for managing the degradation of antibiotics.
This may involve developing new methods for removing antibiotics from the environment,
such as through the use of bioreactors or other treatment technologies, as well as improving
our understanding of the factors that contribute to antibiotic degradation. Additionally, it
may be important to develop new antibiotics that are more biodegradable and less likely
to persist in the environment, as well as to encourage the responsible use of antibiotics by
healthcare providers and patients.

3. Advanced Oxidation Processes—Principles, Mechanisms, and Their Applications

Advanced oxidation processes, often known as AOPs, are methods that generate
extremely reactive radicals in order to destroy organic molecules, particularly resistant
chemical compounds that are found in aqueous environments. Degradation can be partial,
with the formation of organic intermediates, or complete when the mineralization of organic
compounds takes place (Figure 2) [18,19]. So, by partial degradation, some compounds are
created that are more hydrophilic and biodegradable, have fewer electrons, and are smaller
in terms of molecular mass compared with the basic pollutants [20]. These compounds are
more easily handled in the next steps of treatment technology [21]. The advanced oxidation
processes can be classified depending on the method of generation of reactive radicals,
such as chemical, electrochemical, sonochemical, and photochemical, or depending on the
reactive phase (homogeneous and heterogeneous) [8,22]. Recently, significant efforts have
been made to use solar energy instead of ultraviolet or visible lamps to reduce reactors’
operating costs. However, the results obtained were not always good, thus highlighting
the fact that important steps still need to be taken to achieve high efficiencies. In most
cases, in order to achieve high efficiencies, advanced oxidation processes using solar energy
are placed in ultrasonic or microwave fields, which increases the operating costs of the
reactors [8,23]. In addition, regarding the efficiency of the advanced oxidation processes,
it must be taken into account that they are based on the strong reactivity of the radicals
generated in the system. However, these radicals are non-selective and will act both on
 ciencies. In most cases, in order to achieve high efficiencies, advanced oxidation processes
using solar energy are placed in ultrasonic or microwave fields, which increases the oper-
ating costs of the reactors [8,23]. In addition, regarding the efficiency of the advanced ox-
idation
Catalysts 2023, 13,processes,
1280 it must be taken into account that they are based on the strong reactivity 5 of 26
of the radicals generated in the system. However, these radicals are non-selective and will
act both on the target compounds in the system, which are usually in low concentrations,
and on the natural organic the targetmaterial
compoundsin in the system.
this system, which are usually
Therefore, theindegradation
low concentrations, and on the
efficiency
natural organic material in this system. Therefore, the degradation efficiency of the target
of the target compounds may be much lower compared to the overall degradation effi-
compounds may be much lower compared to the overall degradation efficiency of the
ciency of the organicorganic material present
material in in
present the
thesystem.
system.

Effluent
O2

Treated
Water
O2-•

Superoxide
anion Conduction
Band

hv

Energy H2O
Source Valence
Band
Free Radical
-
OH• + OH
Effluent

Treated
Water

Figure 2. Advanced oxidation

Figure 2. process—schematic of the mechanism.
Advanced oxidation process—schematic of the mechanism.

The advanced oxidation of inhibitory and refractory organic pollutants having low
The advanced oxidation of inhibitory and refractory organic pollutants having low
biodegradability and high chemical stability involves the generation of reactive oxygen
biodegradability andspecies
high (ROS),
chemical stability
including involves
hydroxyl radicalsthe generation
(•OH), superoxide ofradicals
reactive (•Ooxygen
−
2 ), and sul-
•−
species (ROS), including
phateshydroxyl
radicals (SOradicals
4 (•OH),
). All these superoxide
species are able to beradicals (•Owater
derived from 2 ), and
− sul-
via the use of
hydrogen peroxide (H2 O2 ), ozone (O3 ), and peroxy-sulphates (PSs), with or without the
phates radicals (SO4 ). All these species are able to be derived from water via the use of
•−
application of a suitable catalyst or the utilization of solar energy, electrical energy, or sound
hydrogen peroxide (H 2O2), ozone (O3), and peroxy-sulphates (PSs), with or without the
energy [1,18]. Generally, there are differences in the degradation efficiency of different
application of a suitable
AOPs catalyst
for organicorpollutants.
the utilization of solarofenergy,
The combination different electrical
AOPs, includingenergy,
UV/H or2 O2 ,
ultrasonic/photocatalytic oxidation, UV/O3 and UV/Fe2+ /H2 O2 , and photo/sono/electro-
assisted Fenton reaction processes, has been developed to address the limitations of a
single AOP in terms of efficient ROS (reactive oxygen species) generation and operating
parameters (Figure 3). Due to the synergistic effect of different substances, the combina-
tion of different AOPs can significantly improve the oxidation efficiency of contaminants
compared with individual treatment technology [6]. The redox potentials of a selection of
typical oxidants are shown in Table 1 as a summary in relation to the normal hydrogen
electrode (NHE) [1].
 limitations of a single AOP in terms of efficient ROS (reactive oxygen species) generation
and operating parameters (Figure 3). Due to the synergistic effect of different substances
the combination of different AOPs can significantly improve the oxidation efficiency of
contaminants compared with individual treatment technology [6]. The redox potentials
Catalysts 2023, 13, 1280 6 of 26 to the
of a selection of typical oxidants are shown in Table 1 as a summary in relation
normal hydrogen electrode (NHE) [1].

Figure 3. Advanced
Figure oxidation
3. Advanced oxidationprocesses thatgenerate
processes that generate reactive
reactive oxygen
oxygen species
species (adapted
(adapted from [1,24])
from [1,24]).

Table 1. Redox
Table potentials
1. Redox potentialsof
of common oxidants
common oxidants in in reference
reference to a normal
to a normal hydrogen
hydrogen electrode
electrode [1]. [1].
Redox Potentialsofof Some
Some Oxidants Species ◦
E0 (V,Et 0=(V,
25 tC)= 25 °C)
Redox Potentials Oxidants Species
fluorine (F
fluorine (F22)) 3.03 3.03
hydroxyl radical (•OH) 2.80
hydroxyl
sulphateradical
radical (SO (•OH)
4
•− ) 2.5–3.1 2.80
sulphate
atomicradical
oxygen(SO (O) 4•−) 2.422.5–3.1
ozone (O3 ) 2.07
atomic oxygen (O)
hydrogen peroxide (H2 O2 ) 1.78
2.42
ozone (O )
perhydroxyl radical (HO2 )
3 • 1.70 2.07
permanganate (MnO −) 1.68
hydrogen peroxide (H 4 2O2) 1.78
chlorine dioxide (ClO2 ) 1.57
•
perhydroxyl
hypochlorous radical
acid (HOCl)(HO2 ) 1.49 1.70
chlorine (Cl
permanganate 2)
(MnO 4 )
− 1.36 1.68
bromine (Br2 ) 1.09
chlorine iodine
dioxide(I2 ) (ClO2) 0.54 1.57
hypochlorous acid (HOCl) 1.49
chlorineperoxide
When hydrogen (Cl2) comes into contact with active surfaces, 1.36
such as catalysts,
bromine
which typically have a (Br large 2) specific surface area, it is more likely to 1.09
undergo a chain
reaction that results in
iodine (I2)the release of oxygen in the form of a number 0.54of different free
radicals. Some of these radicals include •OH and HO2 • . Therefore, when combined with
an effective catalyst, hydrogen peroxide demonstrates good reactivity and application
When hydrogen peroxide comes into contact with active surfaces, such as catalysts
efficiency, therefore lowering the high operating costs [1]. Regarding the toxicity of H2 O2 , if
which typically
ingested, haveofahydrogen
solutions large specific
peroxidesurface area, it is more
up to concentrations likely
of 9% to undergo
are generally a chain re-
nontoxic;
action that results in the release of oxygen in the form of a number of different
however, even a 3% solution is mildly irritating to mucosal tissue and may cause vomiting. free radi-
cals.Ingestion
Some ofofthese radicals include
industrial-strength •OH(10%)
solutions and HO •
2 . Therefore,
causes whenand
systemic toxicity combined
has beenwith an
associated with fatalities. In general, the most important mechanisms involved
effective catalyst, hydrogen peroxide demonstrates good reactivity and application in advanced
oxidation are broken down and discussed in Figure 4.
 efficiency, therefore lowering the high operating costs [1]. Regarding the toxicity of H2O2,
if ingested, solutions of hydrogen peroxide up to concentrations of 9% are generally non-
toxic; however, even a 3% solution is mildly irritating to mucosal tissue and may cause
vomiting. Ingestion of industrial-strength solutions (10%) causes systemic toxicity and has
Catalysts 2023, 13, 1280 been associated with fatalities. In general, the most important mechanisms involved 7 of in
26
advanced oxidation are broken down and discussed in Figure 4.

Radicals species react Radicals species react

with pollutants with biodegradable
intermediate products

generate biodegradable
reactive CO2, H2O and
intermediate inorganic salts
radical products
species

Figure 4.
Figure 4. The
The processes involved in
processes involved in advanced
advanced oxidation
oxidation processes.
processes.

Briefly, the
Briefly, the main
main characteristics
characteristics of
of the
the AOPs
AOPs are
are presented
presented as
asfollows:
follows:
- The possibility
possibility of controlling the oxidation of inorganic chemicals and ions such as
chlorides and nitrates, as well as the mineralization of organic organic contaminants
contaminants of of CO
CO22
(carbon dioxide) and H22O O22 (water).
(water).
- Non-selective reactivity
reactivitywith
withpractically
practicallyallallorganic
organicsubstances
substances is necessary
is necessaryto avoid the
to avoid
existence
the of potentially
existence hazardous
of potentially hazardousintermediates
intermediates produced
producedfromfromprimary pollutants.
primary pollu-
This non-selective
tants. reactivity
This non-selective may bemay
reactivity achieved using ausing
be achieved variety of methods
a variety that dothat
of methods not
entail the entire oxidation of the pollutant.
do not entail the entire oxidation of the pollutant.
- One of of the
themain
maindisadvantages
disadvantagesofof AOPs
AOPs is the
is the high
high costcost of employing
of employing expensive
expensive rea-
reagents
gents (H2O (H O2 ) the
2)2and andincreased
the increased
energyenergy
usage usage (generation
(generation of O3 orofUV O3radiation)
or UV radia- [21].
tion) [21].
4. Advantages and Disadvantages of AOPs
4. Advantages and Disadvantages of AOPs
The AOP processes are relevant for the removal of antibiotics from wastewater, but
The AOP processes are relevant for the removal of antibiotics from wastewater, but
they have a series of advantages and disadvantages that depend on the type of processes
they have a series of advantages and disadvantages that depend on the type of processes
applied and working conditions; thus, all these aspects are reflected in the efficiency of
applied and working conditions; thus, all these aspects are reflected in the efficiency of
the treatment of wastewater. Next, we synthesize these advantages and disadvantages.
the treatment of wastewater. Next, we synthesize these advantages and disadvantages.
The advantages include the following: organic compounds are transformed into stable
The advantages include the following: organic compounds are transformed into stable
inorganic compounds such as carbon dioxide, water, and salts; they have high reaction
inorganic compounds such as carbon dioxide, water, and salts; they have high reaction
rates [3]; they have the potential to reduce toxicity and completely mineralize organic con-
rates [3]; they have the potential to reduce toxicity and completely mineralize organic
taminants; there is no need to concentrate waste for further treatment through methods
contaminants; there is no need to concentrate waste for further treatment through methods
using membranes or activated carbon adsorption [25]; different organics can be treated at
using membranes or activated carbon adsorption [25]; different organics can be treated
the same time; the cost is relatively low compared with other technologies; during oxida-
at the same time; the cost is relatively low compared with other technologies; during
tion processes, heavy metals could precipitate as hydroxides and can be removed in a
oxidation processes, heavy metals could precipitate as hydroxides and can be removed in a
subsequent stage
subsequent stage[8,23];
[8,23];hydroxyl
hydroxylradicals
radicalscould
could help
help in in
thethe disinfection
disinfection process
process during
during the
the wastewater treatment simultaneously with the degradation of
wastewater treatment simultaneously with the degradation of organic compounds [8]; and organic compounds [8];
andnew
no no new organic
organic compounds
compounds withwith
higherhigher toxicity
toxicity are formed
are formed [2,8].[2,8].
In addition to these advantages, the advanced oxidation processes
In addition to these advantages, the advanced oxidation processes have
have some
some disad-
disad-
vantages, including
vantages, including the the following:
following: aa large
large consumption
consumption of of acid
acid and
and base
base is
is determined
determined by by
the AOP (Fenton oxidation), which is usually conducted in acid conditions
the AOP (Fenton oxidation), which is usually conducted in acid conditions [4]; the use of [4]; the use of
H 2O2 can be dangerous for humans; the efficiency of the process depends on the dosage,
H2 O2 can be dangerous for humans; the efficiency of the process depends on the dosage, so
soisitimportant
it is important to use
to use the the
rightright amount
amount in order
in order to form
to form an appropriate
an appropriate amountamount of hy-
of hydroxyl
droxyl radicals [4]; the cost of AOPs can be high because of the need
radicals [4]; the cost of AOPs can be high because of the need for chemicals and the high for chemicals and the
high energy
energy consumption,
consumption, as wellasaswell as the possibility
the possibility of formingof forming
unknown, unknown,
persistentpersistent
by-products; by-
and AOPs are used for the elimination of radicals by non-target substances, but they are
not effective for toxic compounds that resist hydroxyl radical involvement [4,8].

5. Fenton and Photo-Fenton Oxidation Processes

The first considered AOP is the Fenton process. Using Fenton oxidation, it is possible
to treat complex wastewater with the increase in the biodegradability of the effluent’s
recalcitrant organic compounds, such as antibiotics, decreasing the toxicity and removing
Catalysts 2023, 13, 1280 8 of 26

the remnant COD and the color [26,27]. In the Fenton treatment process, a mixture of
H2 O2 and ferrous iron salts (Fe2+ ), which form the Fenton reagent generates reactive (•OH)
radicals, causing the organic removal of wastewater by involving a complex reaction
sequence [23]. The generation of •OH radicals is caused by the decomposition of H2 O2 in
acidic conditions initiated and catalyzed by the Fe2+ . The mechanism of Fenton oxidation
is presented in the following reaction:

Fe2+ + H2 O2 → Fe3+ + HO− + HO• (1)

According to Equation (2), ferric ions can be reduced by the hydrogen peroxide
reaction to reconstruct ferrous ions, but also to produce additional radicals. This type of
reaction is called a Fenton-like reaction.

Fe3+ + H2 O2 → Fe2+ + H+ + HO2 • (2)

While iron is considered a catalyst, the consumption of hydrogen peroxide is contin-

uous as it serves both as a generator of hydroxyl radicals and as a radical scavenger, as
demonstrated in Equation (3):

HO• + H2 O2 → H2 O + HO2 • (3)

Figure 5 shows a diagram of the Fenton process. The primary advantages of this
method are its ability to be performed under normal conditions (room temperature and
atmospheric pressure) and the availability of readily accessible and easy to store and handle
chemicals. Another advantage is that mass transfer is minimal due to its uniform structure;
therefore, the reactor design is easy. However, this mechanism has two drawbacks: self-
decomposition and oxidant loss due to the radical scavenging action of H2 O2 , as shown in
Equation (4) [23].
Catalysts 2023, 13, x FOR PEER REVIEW 9 of 28
2 H2 O2 → 2 H2 O + O2 (4)

Figure 5. Diagram of the Fenton process (adapted from [23]).

Figure 5. Diagram of the Fenton process (adapted from [23]).
The second downside refers to the pH conditions. The pH value has to be around the
value of 3 because the value of the pH is dependent on the Fenton reaction. In most cases,
the pH must be decreased before the treatment because most wastewaters do not have a
pH value around 3. In the next phase, it was observed that, in order to precipitate the
excess iron, the pH has to be increased with the further solid sludge formation [10].
The concentration of the hydrogen peroxide has a significative role in this process. It
Catalysts 2023, 13, 1280 9 of 26

The second downside refers to the pH conditions. The pH value has to be around
the value of 3 because the value of the pH is dependent on the Fenton reaction. In most
cases, the pH must be decreased before the treatment because most wastewaters do not
have a pH value around 3. In the next phase, it was observed that, in order to precipitate
the excess iron, the pH has to be increased with the further solid sludge formation [10].
The concentration of the hydrogen peroxide has a significative role in this process. It
was highlighted that a higher concentration of H2 O2 leads to greater removal of organic
compounds. However, care must be taken with the toxicity induced by high concentrations
of hydrogen peroxide in aqueous systems. In this respect, for proper control of the con-
centration, a continuous dosage of the hydrogen peroxide during the oxidative treatment
is preferred [2,23]. It was also highlighted that when the temperature is increased, the
reaction rate could also be increased. On the other hand, for low organic concentrations,
the temperature could be increased by a few degrees because the reaction of H2 O2 with the
catalyst is an exothermal one. When organic contaminants are present in large quantities
in the wastewater, hydrogen peroxide decomposition (Equation (22)) might be expedited,
resulting in increased consumption and higher operational costs [2,23]. It was observed
that three other categories of processes derived from Fenton technology were used, namely:
• Fenton-like;
• Heterogeneous Fenton;
• Zero-valent iron (ZVI).

Influencing Factors of the Fenton and Photo-Fenton Oxidation Processes

• Fenton catalysts
Even if the Fenton oxidation process can efficiently degrade organic pollutants, in
practical applications some problems may occur. Thus, if the usage rate of H2 O2 is low, it
could cause a low decomposition rate of pollutants. Furthermore, as stated in the preceding
sections, the Fenton process requires a pH of 3, which is lower than the pH used in actual
wastewater. As a conclusion, adjusting the pH value could increase the operational costs.
Finally, the heterogeneous Fenton or Fenton-like processes can be performed over a broad
pH range and the catalyst can be reused repeatedly. These characteristics may help to
reduce the development of iron sludge [2,10].
Heterogeneous Fenton catalysts can contain:
• Iron minerals, such as ferrite and magnetite.
• Zero-valent iron.
• Metals and metal oxides such as MnO2 .
• Materials containing iron and iron oxide; typically, the supports used include activated
carbon, alumina, silica, and zeolite.
• Metal-organic frameworks are crystalline functional materials made of a combination
of transition metal ions and organic ligands [10].
• Catalyst dosage
The amount of catalyst used, which plays a major role in breaking down organic
pollutants, is a crucial factor in the Fenton and Fenton-like oxidation processes. Overuse
of the catalyst may reduce the formation of hydroxyl radicals (•OH) and hinder the
degradation of contaminants. As a result, overdosing on catalyst might raise operational
expenses [26].
• Concentration of H2 O2
H2 O2 is the primary generator of hydroxyl radicals (•OH), and it plays a crucial role
in the Fenton oxidation process. The reduction in the degradation efficiency is possible if
an insufficient H2 O2 dosage leads to an insufficient amount of hydroxyl radicals (•OH).
The actual added H2 O2 concentration is frequently more than the estimated amount based
on the chemical equations, which can be evaluated by preparatory tests [2,23].
Catalysts 2023, 13, 1280 10 of 26

• pH value
As shown above, in Fenton and Fenton processes, the pH value has a significant role
and is an important parameter for efficient treatment of wastewater. The ideal pH value for
the homogeneous Fenton process is 3, and the appropriate pH value in the Fenton process
is contingent on the reaction system, especially when the reaction mechanisms depend on
the catalyst’s efficacy Table 2 [28].

Table 2. Removal of antibiotics by Fenton and Fenton-like oxidation.

Chemical Formula and Molecular

Antibiotics Catalyst (Dosage); pH Range Removal Efficiency (%) References
Weight, Mw (g/mol)
Zero-valent iron (nZVI)- concentration between
0.2–2 g/L;
pH range = 2–5 86.5
C16 H19 N3 O5 S Fe(II) (0.32–24.3 mM); pH range = 2–4 80
Amoxicillin (AMX) [29]
Mw = 365.4 g/mol H2 O2 /Fe2+ molar ratio = 2.0–50; 100
pH range = 2–4 80.9
H2 O2 /Fe2+ molar ratio = 1–50;
pH range = 1–9
Fe(II) (53–87 lM); pH range = 2.3–5.7
90.2
C16 H18 N3 NaO4 S Fe(II) (0.32–24.3 mM); pH range = 2–4
Ampicillin (AMP) 80 [10,29]
Mw = 349.406 g/mol H2 O2 /Fe+ molar ratio = 2.0–150;
100
pH range = 2.0–4.0
C38 H72 N2 O12
Azithromycin (AZT) H2 O2 /Fe2+ molar ratio = 1.75 mM; pH = 3 95 [30]
Mw = 749.0 g/mol
Concentration of Fe3 O4 between 1.0 and 2.5 g/L;
pH range = 3–11
89
C17 H18 FN3 O3 CNTs/FeS between 5 and 35 mg;
Ciprofloxacin (CPR) 91.03 [31,32]
Mw = 331.346 g/mol pH range = 1–12
95
H2 O2 /Fe2+ molar ratio = 1.75 mM;
pH range = 3
Fe0 (0.3 mM)
100
C22 H24 N2 O8 CFO (0.05–0.2 g/L)
Tetracycline (TTR) 84 [33]
Mw = 444.435 g/mol Concentration of Fe0 /CeO2 = 0.01–0.2 g/L)
93
pH range = 3–7
C10 H10 N4 O2 S
Sulfadiazine (SDZ) Fe0 (0.3 mM) 100 [34]
Mw = 250.278 g/mol
FeNi3 /SiO2 nanocomposite, concentration
Metronidazole C6 H9 N3 O3
between 0.005 and 0.1 g/L; 95.3 [35]
(MTR) Mw = 171.16 g/mol
pH range = 3–11
C22 H22 N2 O8
Metacycline (MTC) spinel copper cobaltate CuCo2 O4 (0.1–0.3 g/L) 95.1 [36]
Mw = 442.419 g/mol

There are several strategies for optimizing the Fenton technology. To avoid sludge
production, the operation conditions have to be near a neutral pH value to bypass the
neutralization acidification and to operate with a low iron concentration. On the other hand,
this technology might be placed in microwave or ultrasound fields. Regarding operation
conditions, several strategies are described below:
1. One of the strategies is to use some chelating agents such as oxalate, citrate, EDDS
(ethylenediamine-N,N’-disuccinic acid), or EDTA (ethylenediaminetetraacetic acid)
in order to build an iron ligand complex that can continue to be at a neutral pH in
the solution.
2. Copper, manganese, and cobalt are other metals that can be a good alternative to
ferrous iron. These are derived in the Fenton-like processes.
3. Another strategy is to immobilize the ferrous iron on the mesoporous materials, which
can be used to conduct a heterogeneous Fenton process [23].
The Fenton process contributes to the generation of reactive species by having Fe(II)
and H2 O2 in solution, which also leads to the elimination of organic pollutants through
the photolysis of H2 O2 to produce hydroxyl radicals. It has been observed that the photo-
Fenton technology takes place when these three elements are applied [23]. Furthermore,
compared with the classical Fenton process, the main improvement is the continuous
generation of the catalyst as described in Equation (5). The key results are that a lower
Catalysts 2023, 13, 1280 11 of 26

amount of iron salt is needed, and a smaller amount of iron residue is produced. Both
factors lead to cost reductions and improved process efficiency [23].

Fe3+ + H2 O + hv → Fe2+ + HO• + H+ (5)

Solar energy, on the other hand, is appealing from a sustainability viewpoint. More-
over, it was observed that when the Fe(OH)2+ is present in the solution, the pH is around
the value of 3.0 because of the photoactivity of the Fe(OH)2+ , and the process is very
efficient [23]. However, the pH adjustment cannot be avoided due to the implications of
higher reagent costs, and in these circumstances pH limits remain a concern. It is also
suggested that various catalysts should be developed that are more efficient at pH levels
near to neutrality. An alternative to using humic acids is chelating agents such as EDTA
(ethylenediaminetetraacetic acid), citrate, and oxalate. Furthermore, if sunlight is employed
as a source of radiation, the wavelength might shift closer to the visible range depending
on the chelating agent. However, the costs will be increased if a chelating agent is used, but
the
Catalysts 2023,value
13, x FORof TOC
PEER (total organic carbon) will be increased [23,37,38].
REVIEW 12 of 28

Lower efficiency is obtained when an excess of H2 O2 concentration is used, causing a

scavenging effect.(ethylenediaminetetraacetic
Moreover, some undesirable results can be obtained in the improbable
acid), citrate, and oxalate. Furthermore, if sunlight is em-
case of using a catalyst ployed asthat canofdecrease
a source radiation, thethe efficiency.
wavelength mightAsshiftacloser
conclusion,
to the visibleall these
range de- variables
have to be studied pending
for on the chelating
every singleagent.
case However,
[23]. the costs will
Under be increased if irradiation,
appropriate a chelating agentsolid iron
is used, but the value of TOC (total organic carbon) will be increased [23,37,38].
oxides such as hematite might behave
Lower efficiency is obtained as
when semiconductors, creating
an excess of H2O2 concentration electron–hole
is used, causing a pairs.
Additionally, their zero-point charge might vary, leading to substantial differences in their
scavenging effect. Moreover, some undesirable results can be obtained in the improbable
case of using a catalyst that can decrease the efficiency. As a conclusion, all these variables
effectiveness at various pH levels.
have to be studied for every single case [23]. Under appropriate irradiation, solid iron
Adding ultrasoundoxides such to the system
as hematite leadsas to
might behave a furthercreating
semiconductors, increase in hydroxyl
electron–hole pairs. radical
production, resulting in the
Additionally, theirsono-photo-Fenton
zero-point charge might vary, process. In this differences
leading to substantial case, thein their
intermediate
species producedeffectiveness with Feat3+various
can be pH levels.
converted to Fe2+ not only through photolysis, but
Adding ultrasound to the system leads to a further increase in hydroxyl radical pro-
also through sonolysis. However,
duction, resulting the energy needed
in the sono-photo-Fenton process. Inforthisultrasonic generation
case, the intermediate species increases
the process’s energy produced with Fe3+ can be converted
consumption when using to Fe2+ not onlytechnique
this through photolysis,[2,23].but also
Thethrough
entire energy
sonolysis. However, the energy needed for ultrasonic generation increases the process’s
consumption canenergy be lowered
consumptionwhen solar
when using thislight is [2,23].
technique used. TheHowever, if the treatment
entire energy consumption can time
is too long or if there arewhen
be lowered geographical limitations,
solar light is used. However, if theresearch
treatment time might
is too consider alternative
long or if there
parameters, suchare asgeographical
the electricallimitations, research might consider alternative parameters, such as the
energy per order (EEO ) [23,26].
electrical energy per order (EEO) [23,26]. Figure 6 shows
Figure 6 shows a typical
a typical SWOT analysis for a
SWOT analysis for a photo-Fenton
photo-Fenton process. process.

Strengths Weaknesses
- catalyst regeneration - restriction of pH
- operate with solar light - formation of sludge

Opportunities
Threats
- combination with
semiconductors - dependence on light
- use of organic ligands - costs associated with
to extend pH range and use of H2O2 and energy
use visible light

Figure 6. SWOT analysis for the photo-Fenton process (adapted from [25]).
Figure 6. SWOT analysis for the photo-Fenton process (adapted from [25]).
Catalysts 2023, 13, 1280 12 of 26

6. Photochemical Advanced Oxidation Processes

In photochemical accelerated oxidation processes, light energy is the principal source
of transient species production. Compared to previous AOPs, this procedure is clean,
reasonably inexpensive, straightforward, and much more efficient. In photochemical AOPs,
UV/Visible light radiations are linked with potent oxidants such as O3 and H2 O2 and
catalysts such as titanium dioxide (TiO2 ). These photochemical reactions may destroy
pollutants via three distinct mechanisms: photodecomposition in the presence of O3 under
UV irradiation, photooxidation in the presence of H2 O2 , and oxidation by photocatalysis [1].

6.1. Photo-Peroxidation (H2 O2 /UV)

H2 O2 can be photolyzed by UV radiations at different wavelengths ranging from 200
to 300 nm. Homolytic fission of the O–O bond of the H2 O2 molecule is possible and leads
to the formation of •OH radicals through a series of successive reactions, as shown in the
following equations:
H2 O2 + hv → 2•OH (6)

•OH + H2 O2 → H2 O + HO2 • (7)

HO2 • + H2 O2 → •OH + H2 O + O2 (8)

•OH + HO2 − → HO2 • + OH− (9)

2HO2 • → H2 O2 + O2 (10)

•OH + HO2 • → H2 O + O2 (11)

2•OH → H2 O2 (12)
The reaction rate is faster in an alkaline medium at a value of pH >10, as the UV
radiations can produce the free radicals HO2 • and •OH. However, the molar absorption
coefficient of H2 O2 in the UV area is quite low; therefore, a higher concentration of hydrogen
peroxide is required for the safe destruction of target contaminants [1,2].

6.2. Photo-Ozonation (O3 /UV)

Ozone dissolved in water effectively absorbs UV radiation in the range of 200–360 nm,
with the highest absorption occurring at 253.7 nm. This absorption is measured by the
molar absorption coefficient, εmax , which has a value of 3600 L mol−1 cm−1 . Due to this high
εmax value, the process of ozone photolysis in water is more efficient than the photolysis of
hydrogen peroxide. The photolysis of ozone in water leads to the formation of •OH radicals,
which are highly reactive and effective oxidizing agents. These radicals can participate in a
series of chemical reactions, as shown in the following equations [23]:

O3 + H2 O + hv → 2•OH + O2 (13)

O3 + •OH → HO2 • + O2 (14)

O3 + HO2 • → •OH + 2 O2 (15)

•OH + HO2 • → H2 O + O2 (16)

The use of nanoparticles made from ZnO and TiO2 as catalysts in the photo-ozonation
process has yielded significant results. These materials have proven to be effective in
producing oxidizing agents when they are exposed to light [1].
13, x FOR PEER REVIEW 14 of 28

Catalysts 2023, 13, 1280 13 of 26

6.3. Heterogeneous Photocatalysis
Photocatalysis is a process in which a chemical reaction is accelerated by a catalyst
that is activated6.3.by
Heterogeneous
the absorptionPhotocatalysis
of photons with energy above its bandgap. The term
heterogeneous refers Photocatalysis is a process
to the fact that in which
pollutants are apresent
chemicalinreaction
a fluid is accelerated
phase whileby thea catalyst
cat-
alyst is in a solid phase [39]. Various methods of this technique have been attempted, re-term
that is activated by the absorption of photons with energy above its bandgap. The
heterogeneous refers to the fact that pollutants are present in a fluid phase while the catalyst
sulting in the development of a new advanced oxidation process (AOP) technology for
is in a solid phase [39]. Various methods of this technique have been attempted, resulting in
environmentalthe and energy applications
development of a new advanced basedoxidation
on semiconductor
process (AOP)photocatalysis [1].
technology for environmental
When a semiconductor is exposed
and energy applications basedto light with ultra-bandgap
on semiconductor energy,
photocatalysis [1]. a valence band
electron is excited to the conduction band, leaving a photogenerated hole
When a semiconductor is exposed to light with ultra-bandgap (h+) ainvalence
energy, the va-band
+
lence band [39].electron
The eis excited
−/h + pairstocan
the conduction
then migrate band, toleaving a photogenerated
the surface hole (h ) in theand
of the semiconductor valence
band [39]. The e− /h+ pairs can then migrate to the surface of the semiconductor and
participate in redox reactions that generate hydroxyl radicals (•OH), h , and+ superoxide +
participate in redox reactions that generate hydroxyl radicals (•OH), h , and superoxide
ion radicals (•O ion2−) in the photocatalytic degradation
radicals (•O2 − ) in the photocatalytic of pollutants
degradation in wetinconditions,
of pollutants wet conditions,as as
shown in Figure 7 [40]. The photogenerated h + is considered + an oxidant that
shown in Figure 7 [40]. The photogenerated h is considered an oxidant that directly directly de-
grades organicdegrades
contaminants,
organic and its effectiveness
contaminants, is determined
and its effectiveness by the catalyst
is determined by theused and
catalyst used
and the
the oxidation states [1]. oxidation states [1].

Figure 7. Mechanism of photocatalysis. Superoxide anions and hydroxyl radicals produced by

Figure 7. Mechanism of photocatalysis. Superoxide anions and hydroxyl radicals produced by elec-
electron–hole pairs completely degrade pollutants (adapted from [1]).
tron–hole pairs completely degrade pollutants (adapted from [1]).
In this process, when the catalyst surfaces are exposed to photoirradiation, valence
band holes
In this process, when and conduction
the band electrons
catalyst surfaces are generated.
are exposed When the valencevalence
to photoirradiation, band holes
with water, •
band holes and conduction band electrons are generated. When the valence band molecular
react OH radicals are generated, whereas when they react with holes
oxygen absorbed on the catalyst surface, superoxide radical anions are generated.
react with water, •OH radicals are generated, whereas when they react with molecular
Different classes of therapeutic drugs, such as analgesics, antibiotics, anticonvulsants,
oxygen absorbed andon the catalyst
psychiatric surface,
drugs, superoxide
are oxidized radical2anions
by the UV/TiO Different. operational
are generated
photocatalyst.
Different classes of therapeutic drugs, such as analgesics, antibiotics, anticonvul-
parameters, such as initial concentration of the substrate, catalyst loading, type of TiO2 pho-
tocatalyst, wavelength/light intensity, pH of the solution, and the
sants, and psychiatric drugs, are oxidized by the UV/TiO2 photocatalyst. Different opera- water matrix, influence
the degradation kinetics for pharmaceutical pollutants.
tional parameters, such as initial concentration of the substrate, catalyst loading, type of
Heterogeneous photocatalysis requires several items to be fulfilled, such as the following:
TiO2 photocatalyst, wavelength/light intensity, pH of the solution, and the water matrix,
(a) A photon emitted at the suitable wavelength.
influence the degradation kinetics for
(b) A semiconductor as a catalyst. pollutants.
pharmaceutical
material
Heterogeneous
(c) Aphotocatalysis
strong oxidizing requires
agent. several items to be fulfilled, such as the fol-
lowing:
(a) A photon emitted at the suitable wavelength.
(b) A semiconductor material as a catalyst.
(c) A strong oxidizing agent.
Catalysts 2023, 13, x FOR PEER REVIEW 15 of 28
Catalysts 2023, 13, 1280 14 of 26

The main challenge is connected to the growth of new types of catalysts with im-
proved
Thequality. There are
main challenge some restrictions
is connected that need
to the growth to be
of new detailed,
types as follows:
of catalysts with improved
quality. There are
1. Bandgap some restrictions
regulation to obtain athat need
type to be detailed,
of catalyst that hasasactivity
follows:in the visible range.
1.2. Morphology
Bandgap improvement,
regulation which
to obtain a typecan
of optimize shape
catalyst that hasand size. in the visible range.
activity
3.
2. Delay or avoidance
Morphology of recombination
improvement, which canofoptimize
electronshape
holes and
[23].size.
3. Delay
Figureor
8 avoidance of recombination
shows a typical SWOT analysisof electron
for theholes [23].
heterogeneous photocatalysis pro-
cess.Figure 8 shows a typical SWOT analysis for the heterogeneous photocatalysis process.

Weaknesses
Strengths
- limitations of visible light
- favorable properties and catalyst
good price of catalyst (TiO2)
- high turbidity of aqueous
- simultaneous disinfection solution causes low-efficiency
photon absorption

Opportunities
- new reactor designs
Threats
- challenges in development - catalyst reuse: it is neccesary
of nanomaterials to separate or immobilize the
catalyst when this is in
- new progress on LED suspension
technology

Figure 8. SWOT
Figure8. SWOT analysis forthe
analysis for theheterogeneous
heterogeneous photocatalysis
photocatalysis process
process (adapted
(adapted from [25]).
from [25]).

The
Thecurrent
currenttrend
trendisistotodevelop
developnew,
new,mixed advanced
mixed advancedoxidation processes
oxidation thatthat
processes combine
com-
microwaves or ultrasounds. Some preliminary results show that the reaction
bine microwaves or ultrasounds. Some preliminary results show that the reaction rate rate cancan
be
increased to an acceptable level and a successful rate of removing organic substrate
be increased to an acceptable level and a successful rate of removing organic substrate can can be
reached. Solar energy could be used, in association with some photovoltaic panels,
be reached. Solar energy could be used, in association with some photovoltaic panels, to to reduce
the operation
reduce costs regarding
the operation the implementation
costs regarding of the AOPsofon
the implementation a large
the AOPsscale.
on aThis
largesystem
scale.
has
This system has some major advantages, such as the reduced costs of operation it
some major advantages, such as the reduced costs of operation and maintenance; is
and
considered a clean energy; the process of energy generation is noiseless; and it can
maintenance; it is considered a clean energy; the process of energy generation is noiseless;be close
to the final consumer. It was observed that this system still has significant problems, such
and it can be close to the final consumer. It was observed that this system still has signifi-
as the limited ability of the system, the high-rate initial cost, the large area of land required
cant problems, such as the limited ability of the system, the high-rate initial cost, the large
for the system to be installed, and the inability to install the system in a geographical area
area of land required for the system to be installed, and the inability to install the system
that has low rates of solar radiation [23].
in a geographical area that has low rates of solar radiation [23].
6.4. TiO2 /UV System
6.4. TiO2/UV System
The process of photocatalytic oxidation is a widely recognized technique for eliminat-
ing a The process
variety of photocatalytic
of organic compounds.oxidation is a involves
This process widely recognized technique
the combination of UV forlight,
elimi-
a
nating a variety of organic compounds. This process involves the combination of UV
photocatalyst (typically TiO2 ), and air or oxygen. However, it is not widely implemented light,
Catalysts 2023, 13, 1280 15 of 26

due to the need to separate the photocatalyst, despite its relatively simple application.
TiO2 is highly effective when used in powder form, with particle sizes in the range of
tens of nanometers. Moreover, the light that reaches the photocatalyst surface must have
low energy for the promotion of electrons from the semiconductor’s valence band to the
conduction band, thus enabling electron–hole pairs to be created [2].
In this case, TiO2 radiation in the near-ultraviolet spectrum is needed. Because of its
relatively broad bandgap, TiO2 may absorb up to 5% of the solar spectrum (UV radiation
with a wavelength of 380 nm) [41]. Consequently, researchers have paid more attention
to the catalytic activity of TiO2 within the visible zone of the solar spectrum in recent
years [42].
In this respect, efforts were made to improve the photocatalytic properties of TiO2
under visible irradiation, such as surface modification with organic molecules or nanoparti-
cles, or doping with metal and non-metal ions [43]. Table 3 summarizes the results, and it
can be stated that the UV-TiO2 system is effective at removing antibiotics from wastewater.
However, when significant catalyst dosages are used, the process efficiency drops. Nonethe-
less, the most significant impediment to the adoption of this technology is probably the
difficulty in separating and reusing a costly photocatalyst, such as TiO2 [2].

Table 3. Removal efficiency of antibiotics from wastewaters by TiO2 /UV.

Antibiotic Matrix Operation Conditions Removal Efficiency Observations References

Graphitized
Complete mineralization realized in
mesoporous carbon
90 min.
Ciprofloxacin and TiO2 Maximum efficiency
Ultrapure water The primary degradation processes [32]
C17 H18 FN3 O3 nanocomposite used (100%) in 45 min
are hydroxylation and
as a catalyst (0.35 g/L)
decarboxylation.
UV lamp (λ = 254 nm)
Ultrapure water, Concentration of TiO2 photocatalysis has higher
Cloxacillin Efficiency was
synthetic solutions of TiO2 = 2.0 g/L degradation and mineralization [44]
C19 H18 ClN3 O5 S approximately 100%
pharmaceuticals wastewater UV light = 150W efficiencies than other processes.
Complex aqueous Except for glucose, the presence of
Concentration of Efficiency was
Metronidazole matrix solutions common water matrix components
TiO2 = 1.5 g/L approximately 88% in [45]
C6 H9 N3 O3 (include anions, interferes with
UV light = 6.5 mW cm−2 30 min
cations and glucose) medication degradation.
TiO2 photocatalysis is the
Concentration of
second most
Norfloxacin TiO2 = 0.3 g/L Efficiency was
Ultrapure water efficienct process for the removal of [46]
C16 H18 FN3 O3 Low-pressure approximately 90%
norfloxacin, after photo-Fenton
UV lamp (λ = 254 nm)
(efficiency was approximately 96%).
Concentration of
TiO2 = 0.5 g/L Efficiency was
Oxacillin Efficiency was ~90% mineralization
Ultrapure water Mercury high-pressure approximately 100% in [47]
C19 H19 N3 O5 S realized in 135 min.
lamp (λ = 365 nm) 45 min
UV lamp = 150 W
Concentration of
100% in 45 min
Synthetic solutions TiO2 = 0.5 g/L
(without additives) The additives had the least effect on
of pharmaceuticals High-pressure mercury [44]
100% in 60 min TiO2 photocatalytic treatment.
wastewater lamp (λ = 365 nm)
(with additives)
UV lamp = 150 W

7. Sustainable Photocatalytic Wastewater Treatment

To increase the biodegradability of dangerous and non-biodegradable contaminants,
such as persistent organic pollutants and antibiotics, photocatalytic degradation can be used
as an efficient and advantageous treatment technology for wastewater. This technology allows
the transformation of chemical pollutants into less toxic compounds with structural features
that are much more readily biodegradable. The photocatalytic treatment process consists
of the combination of oxidizing agents with an appropriate catalyst and/or light [10,44].
For the treatment of effluents containing toxic compounds for which biological process
are not efficient, the photocatalytic oxidation process may be used. Photoexcitation of a
semiconductor that is solid, sometimes due to the absorption of electromagnetic radiation
but not always in the near-UV spectrum, is the basic stage of photocatalysis [26,48].
Over the years, several photocatalytic oxidation processes that could be effective for
the degradation of various types of organic contaminants have been investigated. As an
example, some semi-conductor materials, including TiO2 , ZnS, WO3 , and SnO2 , are used as
photocatalysts. A photocatalyst must absorb energy in order to produce electrons (e− ) with
Catalysts 2023, 13, 1280 16 of 26

strong reducing capacity, according to numerous studies. Moreover, the excited electrons
(e− ) could be used to reduce the quantity of O2 to form superoxide radicals (•O2 − ), whereas
holes (h+ ) go to the photocatalyst surface where they oxidize water to generate hydroxyl
radicals (•OH), which will begin to break down the organic contaminants. After that, either
the superoxide radicals (•O2 − ) or hydroxyl radicals (•OH) are generated. It was found that
titanium dioxide, due to its high catalytic efficiency and stability, is the most significant
catalyst [10,49].
The mechanisms of photocatalytic oxidation using TiO2 as a catalyst are presented in
Figure 9 and are described by the following equations:

TiO2 + hv → TiO2 + h+ + e− (17)

h+ + OH− → •OH (18)

h+ + H2 O +O2 → •OH + H+ + •O2 − (19)

O2 + e − → O2 − (20)

O2 − + H+ → HO2 − (21)

2HO2 − → O2 + H2 O2 (22)

Catalysts 2023, 13, x FOR PEER REVIEW 18 of 28

H2 O2 + •O2 − → •OH + OH− + O2 (23)

Figure 9. Mechanism of oxidative radicals’ development [50].

Figure 9. Mechanism of oxidative radicals’ development [50].
7.1. Photocatalytic Materials
A photocatalytic reaction is a redox process and a photochemical reaction that takes
place between a photocatalyst and the substrates on its surface, such as hydrogen perox-
ide, oxygen, and target pollutants, when light is applied. Photocatalysts are relevant com-
ponents in photocatalytic processes. The photocatalysts can be classified into two main
Catalysts 2023, 13, 1280 17 of 26

7.1. Photocatalytic Materials

A photocatalytic reaction is a redox process and a photochemical reaction that takes
place between a photocatalyst and the substrates on its surface, such as hydrogen per-
oxide, oxygen, and target pollutants, when light is applied. Photocatalysts are relevant
components in photocatalytic processes. The photocatalysts can be classified into two main
categories:
• Oxide photocatalysts: TiO2 -based photocatalysts, Bi2 O3 -based photocatalysts, and
other oxide photocatalysts such as ZnO, WO3 , or Fe2 O3 .
• Non-oxide photocatalyst: CdS series photocatalysts, CuS series photocatalysts, ZnS
series photocatalysts, and nitride series photocatalysts.
To enhance the efficiency of the photodegradation process, some photocatalysts, such
as metal oxides (i.e., titanium dioxide, zinc oxide), metal sulfides (i.e., CdS), precious
metal semiconductors (i.e., BiOBr, BiOCl, BiVO4 , Ag3 O4 , SmVO4 , GdVO4 ), and non-
metallic semiconductors (i.e., g-C3 N4 ) have been tested in the photochemical oxidation
process [10,51].
TiO2 photocatalysts were used in the living world and wastewater treatment for the
elimination of hazardous organic pollutants, notably antibiotics, due to higher photocat-
alytic activity, non-toxicity, and high photo-stability [51]. Another important photocatalyst,
zinc oxide (ZnO), has been studied in the literature for the degradation of a series of an-
tibiotics (such as ciprofloxacin, norfloxacin, sulfamethoxazole, cefixime trihydrate, and
tetracycline hydrochloride), due to its reduced cost, non-toxicity, raised redox potential,
and environmentally friendly properties [10].

Photocatalyst Preparation Methods

All types of photocatalyst are obtained by different techniques. Over time, a large
number of methods to prepare photocatalysts have been developed. For example, the
electrospinning, solid phase, gas phase, liquid phase, sol–gel, precipitation, liquid depo-
sition, and hydrothermal methods are the most commonly used methods for obtaining
photocatalysts [52].
 Electrospinning method
The electrospinning method is used to directly produce polymer nanofibers. This
technique has been used to make a variety of nanofibers, including organic and inorganic
composites. The electrospinning process requires several components: a nozzle, a liquid
supply device, a fiber-receiving device, and a high-voltage power source. The high-voltage
power supply, which uses a direct current, produces thousands of volts and generates an
electromagnetic field to polarize and charge the liquid. The fiber-receiving device, which
may take the form of a rotating metallic roller, is located on the opposite side of the nozzle,
ground with a thread, and connected to the negative electrode of the high-voltage power
supply. The most important factors that contribute to a highly efficient electrospinning
process include the voltage, surface tension, solution viscosity, conductivity, and solvent
evaporation rate [52,53].
 Solid Phase method
The solid phase method is a process where the reactant ingredients are ground and
blended together in a specified ratio, and then calcined at a specific temperature to yield
the desired product [52]. This method has many benefits, such as simple setup, low cost,
ease of use, uniform particle size, and controlled reaction conditions [54]. The absence of
a solvent also minimizes the formation of hard agglomerates and reduces environmental
pollution. However, this method also has some drawbacks, such as a tendency for particle
aggregation, a coarser powder, and a higher likelihood of ion oxidation, as well as easy
impurity contamination [52,54].
Catalysts 2023, 13, 1280 18 of 26

 Gas Phase method

The gas phase method involves directly using gas or converting a substance into gas
to allow it to react either physically or chemically in the gas phase. During the cooling
process, the nanoparticles can then aggregate and form [52]. This method results in
high-purity nanoparticles with desirable properties, but it requires advanced techniques
and equipment. It encompasses various vapor phase methods, including physical vapor
deposition, chemical vapor deposition, and molecular beam epitaxy.
The chemical vapor deposition (CVD) process involves the use of chemical reactions
between vapor phase components to produce thin films on a substrate surface. This
technique can be used to deposit various materials, such as metals, nitrides, and oxides.
CVD can be further divided into four categories, namely atmospheric pressure CVD, low
pressure CVD, plasma pressure CVD, and laser pressure CVD, depending on the conditions
under which it is performed. However, there are certain limitations to the CVD process,
such as inconsistent surface roughness and particle size (ranging from 50 to 150 nm) [52,55].
The physical vapor deposition (PVD) technique involves physically vaporizing a paint
to create a film on the surface of a substrate. This method has advantages over conventional
vacuum deposition techniques, such as ion beam deposition, ion plating, and ion-beam-
assisted deposition. Additionally, the PVD process operates at low deposition temperatures
and does not result in substrate deformation or cracking. This process has been used to
deposit ceramic compounds, polymer films, and metal and alloy films [52,56].
The molecular beam epitaxy (MBE) method is a cutting-edge film production process
that allows for the creation of single crystal films. In this process, a hot beam of atoms or
molecules is directed onto the surface of a heated substrate under vacuum conditions. The
MBE technique offers several benefits, such as the ability to precisely control beam intensity
and shape the surface of the epitaxial material, which can be transformed into a multi-layer
structure with various compositions [52].
 Liquid Phase method
The liquid phase method, also referred to as the wet chemical method, is a process
for producing material. To start, a soluble metal salt must be selected based on the desired
composition of the material. The metal ions in the solution must then be precipitated or
crystallized using appropriate agents. Finally, the desired raw material powder is produced
through thermal decomposition of the precipitate [57].
 Sol–Gel method
The sol–gel method is a common technique for preparing photocatalysts. It involves
dissolving a precursor in a solvent to form a sol via hydrolysis. The sol–gel process is
influenced by various parameters such as the pH of the solution, concentration, reaction
time, and temperature. The sol–gel process has numerous benefits, including high purity
and homogeneity, low synthesis temperature, and easy control of reaction parameters.
However, it also has some drawbacks, such as the high cost of titanium alkoxide raw
material, the use of a large amount of organic solvent, high cost of film production due to
high-temperature heat treatment, low film adhesion, and weak transparency [52].
 Precipitation method
The precipitation method is a commonly used technique for synthesizing nanomate-
rials. In this method, a precipitant is added to form a precursor precipitate which is then
mixed with other substances having various chemical components. However, some heavy
metals introduced during the precipitation process may not react in solution and could
potentially introduce impurities into the solution, affecting the usage of this approach. The
reaction temperature, duration, pH value, and titration rate all have an effect on the mate-
rial manufacture throughout this method’s operation. Some advantages of the precipitation
method are the low cost of operation and its simple and safe process [58,59].
Catalysts 2023, 13, 1280 19 of 26

 Liquid deposition method

In this method, a uniform film is put into the substrate, before which the substrate is
placed in a reaction solution. For this method, a high temperature during film formation or
expensive equipment are not needed. This approach may also be used to create composite
oxide films, multicomponent oxide films, metal fine particle dispersion oxide films, and
laminated oxide films [52,60]. The most significant advantages are that environmental
pollution is minimal and the benefit-to-cost ratio is high. It has these advantages because
all of the problems have been solved; as a result, the liquid deposition method has a broad
application area [60].
 Hydrothermal method
In this method, an enhanced inorganic material is created by combining an inorganic
or organic component with water under high pressure at temperatures ranging from 100 ◦ C
to 300 ◦ C. The resulting inorganic compound is filtered, washed, and dried to produce
ultrafine particles of high purity. Some advantages of the hydrothermal method are mild
conditions, stable system, easy process, low cost, and low environmental pollution. Other
advantages are that films obtained using this method have good uniformity and are not
limited by the shape and size of the substrate [52]. On the other hand, by adjusting the
amount of the product using the hydrothermal approach, homogenous nanocomposites
may be obtained.

7.2. Factors That Influence the Photocatalytic Oxidation Process

• pH value
An important parameter of the photocatalytic oxidation processes is the pH of the
aqueous solutions. It was discovered that the charge on the surface of the catalyst can vary
depending on whether the pH is above or below the potential of zero charge. Likewise,
if the pH is higher or lower than the pKa (acid dissociation constant), the substrates may
exhibit a different charge form [61]. In certain studies, a UV-A/TiO2 photocatalyst was
used to degrade amoxicillin, and it was discovered that the degradation was unaffected
by the rise in pH from 5.0 to 7.5. This rise may be ascribed to the ionization states of both
the catalyst and the pollutant. The mineralization of amoxicillin was reduced from 95%
to 75% when the pH was increased from 5 to 7. Moreover, the photocatalytic degradation
of cefotaxime in various aqueous solutions was studied by employing TiO2 and ZnO as a
photocatalyst. It was discovered that, when the pH of cefotaxime was elevated from 4 to 6.2
using TiO2 as a catalyst, the removal rate rose, but it decreased when the pH was increased
from 6.2 to 7.6. Other results were noted in scientific papers in the case of cefotaxime
degradation using ZnO as a catalyst [10,62].
• Catalyst dosage
Another significant parameter in the photocatalytic oxidation process is the photo-
catalyst dosage. It has been discovered that having a higher amount of photocatalyst in
the system can result in more active sites and an improved ability to remove pollutants
through oxidation and mineralization. However, having too much catalyst can also obstruct
light energy from reaching the system and reduce the effectiveness of light energy due to
reflection, scattering, and light blockage caused by solid particles [2,10].
• Mineralization of antibiotics
It has been frequently remarked that the degradation efficiency due to the formation
of short-term organic intermediates that are formed during the photocatalytic process
is higher than the mineralization efficiency [63]. In this respect, it was found that for
oxytetracycline degradation under UV irradiation for 10 h, the total organic carbon (TOC)
removal was only 9.5%. It was also found that in the case of tetracycline under UV radiation
for 5 h with the addition of 0.2 g/L (multi-walled carbon nanotube) MWCNT/TiO2 , TOC
removal reached 83%. Flumequine’s mineralization ratio reached 74% after 15 min of UV
Catalysts 2023, 13, 1280 20 of 26

irradiation, and it remained unchanged after 60 min, or even extended the irradiation times.
It was observed that some aromatic organic intermediates remained intact after they were
exposed several times to irradiation, for a longer time [10,64] Table 4.

Table 4. Removal of several antibiotics by photocatalytic oxidation.

Chemical Formula and

Antibiotics Molecular Weight, Photo-Catalysts Removal Efficiency (%) References
Mw (g/mol)
C16 H19 N3 O5 S
Amoxicillin (AMX) UV-A/TiO2 100% [65]
Mw = 365.4 g/mol
UV/TiO2 /PLA/Fiberglass fabric plain
95.2%
C16 H18 N3 NaO4 S woven-type membrane
Ampicillin (AMP) [66]
Mw = 349.406 g/mol UV/TiO2 /PLA/Fiberglass mat-type membrane 83%
UV/TiO2 /PLA/Fiberglass fabric one-fold
79.7%
edge-type membrane
C16 H15 N5 O7 S2 Nitrogen-doped titanium
Cefixime (CFX) 80% [67]
Mw = 453.452 g/mol dioxide/graphene oxide (N-TiO2 /GO)
C16 H21 N5 O10 S2
Cefixime trihydrate Zinc oxide/iron oxide (ZnO/a-Fe2 O3 ) 99.1% [68]
Mw = 507.50 g/mol
C16 H17 N5 O7 S2
Cefotaxime (CFT) Titanium dioxide/zinc oxide (TiO2 /ZnO) 84.2% [69].
Mw = 455.47 g/mol
C11 H12 Cl2 N2 O5
Chloramphenicol (CHL) Titanium dioxide (TiO2 ) 85% [70]
Mw = 323.132 g/mol
TiO2 /carbon dots
Reduced graphene oxide (rGO)/bismuth 91.1%
vanadate (BiVO4 ) 68.2%
C17 H18 FN3 O3 Ag/AgBr/BiVO4 photocatalyst 91.4%
Ciprofloxacin (CPR) [67,71–75]
Mw = 331.346 g/mol Zinc oxide (ZnO) 100%
Cadmium sulfide (CdS)/strontium titanate (SrTiO3 ) 93.7%
Ternary photocatalyst, graphitic carbon nitride (g-C3 N4 ), 100%
iron oxide) Fe3 O4 /g-C3 N4
C19 H22 FN3 O3 Cadmium sulfide/strontium titanate CdS/SrTiO3 93.7%
Enrofloxacin (ENF) [74,75]
Mw = 359.4 g/mol g-C3 N4 , Fe3 O4 /g-C3 N4 100%
C16 H18 FN3 O3 Bismuth vanadate/tungsten trioxide (BiVO4 /WO3 ) 70%
Norfloxacin (NRF) [76,77]
Mw = 319.331 g/mol Zinc oxide ZnO/CuOx >80%
Titanium dioxide (TiO2 )
100
C22 H24 N2 O9 Multi-walled carbon nanotube/Bismuth vanadate
Oxytetracycline (OXY) 88.8 [78–82]
Mw = 460.434 g/mol (MWCNT/BiVO4 )
100
Titanium dioxide (TiO2 )
C9 H11 N2 O4 S Cadmium sulfide/strontium titanate (CdS/SrTiO3 ) 93.7
Penicillin (PNC) [83]
Mw = 334.4 g/mol Bismuth vanadate (BiVO4 ) 100
C12 H14 N4 O2 S Graphene modified anatase/titanate
Sulfamethazine (SMZ) 96.1 [84]
Mw = 278.33 g/mol nanosheets (G/A/TNS)
C10 H11 N3 O3 S
Sulfamethoxazole (SLF) UVC lamp (10 W) 95.8 [85]
Mw = 253.279 g/mol
C14 H12 N4 O2 S
Sulfaquinoxaline (SLQ) Titanium dioxide 100 [86]
Mw = 300.366 g/mol
C66 H75 Cl2 N9 O24
Vancomycin (VAN) Titanium dioxide (TiO2 ) 95 [87]
Mw = 1.449.3 g/mol

7.3. Photocatalysis—Challenges and Opportunities

In many applications areas, such as environmental remediation, energy production,
chemical engineering, medicine/biochemistry, and agriculture, the heterogeneous photo-
catalysis has shown great efficiency [88]. The applicability of the photocatalytic technology
for wastewater treatment is constrained by some important technical issues that need more
research in the near future, such as the following:
• The first issue is if the photocatalytic process is a pre-treatment or a separate system.
• The photocatalytic process can be used as a pre-treatment step to improve the biodegra-
dation of recalcitrant organic pollutants before biological wastewater treatment due
to the non-selective reactivity of the non-biodegradable wastewater soluble pollu-
tants [89].
In order to try to obtain significant results regarding the efficiency of this process, it is
necessary to consider other technical aspects, from catalyst development to reactor design
and process optimization, such as the following:
• Catalyst improvement for high photo-efficiency.
• Catalyst immobilization to ensure a cost-effective solid–liquid separation.
• Improvement in the photocatalytic operation for a wider pH range and for a mini-
mization of the addition of oxidant additives.
Catalysts 2023, 13, 1280 21 of 26

• A new, integrated or coupling system for improved photo-mineralization or photo-

disinfection kinetics.
• An efficient design of the reactor photocatalytic system or the use of solar energy to
reduce the electricity costs [89].
Therefore, a photocatalytic wastewater treatment process with large-scale applicability,
high efficiency, and low costs of operation, using solar energy, can be realized in order to
perform a rapid evaluation of different possible issues and ambiguities that may appear.
Nevertheless, the applicability of heterogeneous photocatalysis based on ZnO and
TiO2 is still doubtful due to some limitations:
• The quantum efficiency is reduced under sunlight because of the use of large bandgap energy.
• An e− /h+ pair is generated by high energy consumption.
• The photocatalytic activities are decreased due to reactive oxidative species reduction
of a rapid e− /h+ pair recombination.
• There is limited ability to extend the approach due to the complex modification process
needed to increase the photocatalysis.
• The kinetic reaction rate decreases due to a fast active surface site and the activation
by interaction with intermediate secondary products.
• The low photocatalyst stability reduces the reuse of its lifetime services.
• The solid photocatalyst is eliminated as a secondary solid waste.
• A low photocatalytic efficiency against high concentrations of pollutants at high air
and water flow rates [88].
As a remark, water can also be considered as a solvent or a chemical component
because the water properties are changed due to the rapid increases in the temperature or
the applied pressure. The operation and synthesis costs depend on many factors involved in
the usage of catalyst, such as energy consumption, the regeneration process, the long-term
stability, and the individual component costs [90].

8. Opportunities and Future Perspectives

In recent years, scientists have been involved in looking for a strategy to allow for total
removal of the low concentration of contaminants found in wastewater that was previously
treated with conventional removal techniques. Furthermore, it has been observed that
using AOPs is a proper option in which the pollutants are adsorbed in a porous material
that is removed following in situ AOP reactions; these reactions could take place on the
surface of the exhausted adsorbent [24,91,92].
Advanced oxidation processes could be considered suitable technologies that can
used to treat wastewaters when they include recalcitrant or toxic organic compounds. In
some cases, an excellent option could be when the full mineralization can be obtained
with suitable costs and time. These processes are efficient and some of them could be
seen as “green” technologies. The combination of two or three methods can increase the
mineralization efficiencies in eliminating pesticide pollutants. This approach not only
transforms organic compounds into non-toxic by-products, but also proves to be cost
effective as it requires minimal space and chemicals, and generates little to no sludge.
It has been observed that most of the heterogeneous photocatalysis research was
conducted using bench setups in unrealistic conditions that are too different from the real
conditions. Only some limited efforts have been made to test the real performance of the
heterogeneous photocatalysis using water and air feed streams. On the other hand, it has
been discovered that there are many inconsistent data in the existing research regarding
heterogeneous photocatalysis application for the environment [89].
Moreover, the scalability of the heterogeneous photocatalysis technology has barely
been implemented for industrial purposes such as wastewater treatment or air purification.
The most recent studies suggest that the photocatalytic splitting of water into hydrogen,
which could be used as a renewable energy, is impractical, because it requires expensive
sacrificial agents or electron donors, for example, methanol, glucose, or isopropanol.
Catalysts 2023, 13, 1280 22 of 26

9. Conclusions
Antibiotics are widespread contaminants found in a wide range of surface waters,
wastewaters, WWTPs (wastewater treatment plants), and hospital effluents. Furthermore,
the presence of antibiotics in wastewater may have negative consequences for human
health and may enhance the resistance of bacteria to antibiotics. Advanced oxidation
processes have frequently proven their great efficacy in the removal of a wide range of
contaminants, including antibiotics.
The high efficiency and non-selectiveness of AOPs have made them a highly sought-
after method for removing organic pollutants in various matrices, as evidenced by the high
removal rates, effective remediation of water, and low energy consumption. Therefore,
it is important to consider harnessing the full potential of AOPs in future developments
by implementing them on an industrial scale for removing organic pollutants. These
techniques show great promise as effective tools for wastewater treatment and further
research should focus on improving the stability of solid catalysts, as well as on evaluating
the cost effectiveness and long-term efficacy of large-scale AOP applications. From the
point of view of the photochemical properties, some AOPs such as UV/H2 O2 can be
considered to be undisguised, and their development will be consistent with new UV light
sources such as LEDs. In some places with high insolation, solar-powered photo-Fenton
and heterogeneous photocatalysis may be advantageous for the future implementation of
the technology. From these perspectives, it is clear that a significant effort is taking place
in order to develop new catalysts for heterogenous photocatalysis, to thereby increase the
efficiency of this technology and reach the commercial stage.
AOPs have the potential to effectively eliminate a wide range of stubborn organic
compounds due to their high oxidation capability, which can be further enhanced by
pairing with various oxidants and catalysts. One of the promising advanced oxidation
process technologies for industrial applications, such as wastewater treatment, is photo-
catalysis. Selecting an appropriate photocatalyst and optimizing conditions can result in
high degradation rates of persistent organic contaminants from wastewater. Therefore, the
main motivation for AOPs is the use of renewable energy sources to reduce the costs and
perhaps to substitute electricity with them. An area of future research that could prove to be
of interest is the use of solar energy on a large scale, which has the potential to significantly
reduce the environmental impact, by over 90%.
Future developments will have to occur with the direct participation of engineers,
analytical chemists, and electrochemists, to create and conduct research for an efficient
application and operation of the advanced oxidation processes. AOPs could represent an
efficient, important, and environmentally friendly method to remove or to degrade a series
of organic pollutants from wastewaters.

Author Contributions: All authors contributed to the study conception and design. Material prepa-
ration and data collection were performed by G.-I.L., C.B., C.O., L.B. and L.F.P. The first draft of the
manuscript was written by the first author, G.-I.L. and all authors commented on previous versions
of the manuscript. All authors have read and agreed to the published version of the manuscript.
Funding: This work has been funded by the European Social Fund from the Sectoral Operational
Programme Human Capital 2014–2020, through the Financial Agreement with the title “Training
of PhD students and postdoctoral researchers in order to acquire applied research skills-SMART”,
Contract no. 13530/16.06.2022-SMIS code: 153734.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare that they have no competing interest.

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