crystals

Review
Polyaniline–Titanium Dioxide Heterostructures as Efficient
Photocatalysts: A Review
Yongqiang Fu and Marcin Janczarek *

Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of
Technology, Berdychowo 4, 60-965 Poznan, Poland; [email protected]
* Correspondence: [email protected]

Abstract: This review paper focuses on present issues concerning the use of polyaniline–TiO2 het-
erostructures as potentially efficient photocatalysts. Conducting polymers such as polyaniline (PANI)
are used in the preparation of heterojunction systems with metal oxides like titania to overcome
their inherent limitations, e.g., their sole absorption of UV light and overly fast recombination of
charge carriers. This review discusses preparation methods, the properties of resultant products and
mechanistic aspects. An important part of this paper is its presentation of the major challenges and
future perspectives of such photocatalytic materials.

Keywords: photocatalysis; titanium dioxide; polyaniline

1. Introduction
Titanium dioxide (TiO2 ; titania) has been recognized as the most promising photocat-
alytic material, with high application potential in the fields of water or air treatment (mainly
in the photooxidation of organic compounds) and in solar energy’s conversion into chemical
energy in the obtention of valuable products such as hydrogen and hydrocarbons [1–5]. Its
main strengths include the optimal positions of conduction (CB) and valence bands (VB) in
a semiconductor band structure, corresponding to the redox potentials of various important
chemical transformations; its low cost and perfect stability toward photocorrosion and
Citation: Fu, Y.; Janczarek, M. relative nontoxicity are the reasons for researchers’ widespread interest.
Polyaniline–Titanium Dioxide However, to better utilize light (solar or artificial cheap sources, e.g., light-emitting
Heterostructures as Efficient diodes (LEDs)) and thus increase photocatalytic efficiency, it is necessary to overcome
Photocatalysts: A Review. Crystals the weak points of titania. The first is the relatively wide band gap of TiO2 (3.0–3.2 eV),
2023, 13, 1637. https://doi.org/ which only corresponds to the photoabsorption of UV light. As this has been calculated in
10.3390/cryst13121637 Abe’s review, if all UV light (in solar spectrum) up to 400 nm were utilized, the solar light
Academic Editor: Maria Milanova
conversion efficiency for photocatalytic water splitting would only be 2% [4]. The possibility
of utilizing visible light up to 600 nm or 800 nm will lead to efficiencies of 16% and 32%,
Received: 22 October 2023 respectively (Figure 1). The second limitation is the recombination of photogenerated
Revised: 9 November 2023 charge carriers (electrons and holes), which reduces overall quantum efficiency [6]. During
Accepted: 13 November 2023 the recombination process, the excited electron reverts to the valence band without reacting
Published: 26 November 2023
to adsorbed species.
Many strategies have been designed to improve the photocatalytic performance of tita-
nia and overcome the above-mentioned problems. These range from intrinsic modifications
Copyright: © 2023 by the authors.
of TiO2 in fields such as particle morphology, particle size, specific surface area, porosity
Licensee MDPI, Basel, Switzerland. and density of surface or bulk defects [3,7–11] to chemical modifications. Therefore, the
This article is an open access article introduction of visible light activity into titania chemical modifications is required, although
distributed under the terms and the preparation of defective titanium dioxide could also be a promising direction [3]. Most
conditions of the Creative Commons of these chemical modifications concern the metal and non-metal modification/doping
Attribution (CC BY) license (https:// of TiO2 , dye-sensitization and the design of titania–other semiconductor heterojunction
creativecommons.org/licenses/by/ systems [1,3,12–26]. In comparison to other modification strategies, the usage of non-metal
4.0/). components is still very promising. The use of noble metals or metal complexes could be

Crystals 2023, 13, 1637. https://doi.org/10.3390/cryst13121637 https://www.mdpi.com/journal/crystals

Crystals 2023, 13, 1637 2 of 22

an unreasonable solution because of the cost of these components, which can limit their
practical applications. The use of carbon-, nitrogen-, boron- or sulfur- doping/modification
is much cheaper than the metals enumerated above. It is necessary to mention that a
consequence of the application of some carbon (e.g., pentaerythritol) or nitrogen (e.g., urea)
precursors in the modification process of TiO2 can be the formation of specific organic sen-
sitizers on the titania surface, which is responsible for visible-light-induced photocatalytic
activity [14,16]. Another possibility regarding the use of an organic sensitizer for titania is
the application of conducting polymers such as polyaniline. The conductivity of polyaniline
changes upon its addition to TiO2 ; therefore, perspectives regarding the application of
such materials not only focus on photocatalysis but also on other fields, e.g., metal oxide
semiconductor devices and microactuators [27]. In this review, a brief overview of titania–
polyaniline systems as photocatalysts is presented in relation to current knowledge and
Crystals 2023, 13, x FOR PEER REVIEW 2 of 25
perspectives of application. This review also indicates the main problems in interpreting
the research (including mechanistic aspects) and the reproducibility of the results.

Figure Solarspectrum
Figure 1. Solar spectrum and
and maximum
maximum solar
solar lightlight conversion
conversion efficiencies
efficiencies for a photocatalytic
for a photocatalytic water-
splitting reaction.
water-splitting Reprinted
reaction. with permission
Reprinted from [4].
with permission Copyright
from 2011, Elsevier.
[4]. Copyright 2011, Elsevier.

2. Electronic and Optical

Many strategies haveProperties of Polyaniline
been designed to improve the photocatalytic performance of
Polyaniline (PANI) is an example
titania and overcome the above-mentioned of a polymer belonging
problems. to therange
These conducting
from polymer
intrinsic
(CP) group. One
modifications can2 in
of TiO classify this group
fields such as containing
as particle morphology, electrically conducting
particle size, specificorganic
surface
polymeric compounds.
area, porosity Other
and density ofexamples
surface orofbulk
CPs are polypyrrole
defects [3,7–11](PPy), polythiophene
to chemical (PTh),
modifications.
poly(3,4-ethylenedioxythiophene)
Therefore, the introduction of visible (PEDOT) and polyacetylene
light activity (PAc). CPs
into titania chemical can act as is
modifications a
semiconductor or a conductor. These compounds are conjugated
required, although the preparation of defective titanium dioxide could also be a and show π electron
delocalization along their
promising direction polymer
[3]. Most backbone.
of these chemical This main property
modifications determines
concern the metaltheir
andunique
non-
electrical and optical properties [26,28–31]. The conjugated structure
metal modification/doping of TiO2, dye-sensitization and the design of titania–other of CPs is a necessary
condition for theheterojunction
semiconductor formation of delocalized electronicInstates.
systems [1,3,12–26]. The degree
comparison of delocalization
to other modification
influences
strategies, the
thevalue
usageofofband gap energy,
non-metal which determines
components is still very the conductivity
promising. Theofuse
CPs.ofSingle
noble
and double bonds contain a localized σ-bond (chemically strong). In
metals or metal complexes could be an unreasonable solution because of the cost of these the case of double
bonds, it is also
components, possible
which to distinguish
can limit a localized
their practical π-bond The
applications. (lessuse
strong than thenitrogen-,
of carbon-, σ-bond).
Therefore, π-bonds are responsible for an easier delocalization of
boron- or sulfur- doping/modification is much cheaper than the metals enumerated electrons (Figure 2) [29,32].
PANI has many advantages, such as its low cost, its high environmental
above. It is necessary to mention that a consequence of the application of some carbon stability
and its ability to enact electric switching between its conductive and resistive states via
(e.g., pentaerythritol) or nitrogen (e.g., urea) precursors in the modification process of
doping processes; it is important to emphasize that PANI is characterized by its diversity
TiO2 can be the formation of specific organic sensitizers on the titania surface, which is
of structural forms [33]. Polyaniline is a mixed oxidation state-conducting polymer, which
responsible for visible-light-induced photocatalytic activity [14,16]. Another possibility
consists of reduced benzenoid amine units (–NH–) and oxidized quinoid imine units (=N–)
regarding the use of an organic sensitizer for titania is the application of conducting
(Figure 3). PANI’s average oxidation state is denoted as 1 − x. When 1 − x = 0 PANI exists
polymers such as polyaniline. The conductivity of polyaniline changes upon its addition
as fully reduced leucoemeraldine (LE). If the value 1 − x is equal to 0.5, the half-oxidized
to TiO2; therefore, perspectives regarding the application of such materials not only focus
on photocatalysis but also on other fields, e.g., metal oxide semiconductor devices and
microactuators [27]. In this review, a brief overview of titania–polyaniline systems as
photocatalysts is presented in relation to current knowledge and perspectives of
application. This review also indicates the main problems in interpreting the research
 condition for the formation of delocalized electronic states. The degree of delocalization
influences the value of band gap energy, which determines the conductivity of CPs. Single
Crystals 2023, 13, 1637 and double bonds contain a localized σ-bond (chemically strong). In the case of double3 of 22
bonds, it is also possible to distinguish a localized π-bond (less strong than the σ-bond).
Therefore, π-bonds are responsible for an easier delocalization of electrons (Figure 2)
Figure 2. A representation of a conjugated backbone [32].
[29,32].
emeraldine base (EB) is present. The fully oxidized form of PANI is pernigraniline (PE)
when 1 − xhas
PANI = 1many
[28,34].
advantages, such as its low cost, its high environmental stability and
its ability to enact electric switching between its conductive and resistive states via doping
processes; it is important to emphasize that PANI is characterized by its diversity of
structural forms [33]. Polyaniline is a mixed oxidation state-conducting polymer, which
consists of reduced benzenoid amine units (–NH–) and oxidized quinoid imine units (=N–
) (Figure 3). PANI’s average oxidation state is denoted as 1 − x. When 1 − x = 0 PANI exists
as fully reduced leucoemeraldine (LE). If the value 1 − x is equal to 0.5, the half-oxidized
emeraldine base (EB) is present. The fully oxidized form of PANI is pernigraniline (PE)
when 1 − x = 1 [28,34].

Figure 2. A representation of a conjugated backbone [32].

Figure 2. A representation of a conjugated backbone [32].

PANI has many advantages, such as its low cost, its high environmental stability and
its ability to enact electric switching between its conductive and resistive states via doping
processes; it is important to emphasize that PANI is characterized by its diversity of
structural
Figure forms [33].structure
3. General Polyaniline is a mixed oxidation state-conducting polymer, which
of polyaniline.
Figure 3. General structure of polyaniline.
consists of reduced benzenoid amine units (–NH–) and oxidized quinoid imine units (=N–
) (Figure If3).the EB form
PANI’s averageof PANI is doped
oxidation state iswith inorganic
denoted as 1 − acids
x. Whenand1 −organic acidsexists
x = 0 PANI such as
If the EB
phosphoric form
acid, of PANI is
hydrochloric doped
acid, with inorganic
sulfosalicylic acid and acids andacid,
sulfuric organic acids such
emeraldine as
salt (ES)
as fully reduced leucoemeraldine (LE). If the value 1 − x is equal to 0.5, the half-oxidized
phosphoric acid,Inhydrochloric
is then formed. this process,Theacid, sulfosalicylic
imine nitrogen acid and by
is protonated sulfuric
acid, acid,
and theemeraldine
conductivitysalt
emeraldine base (EB) is present. fully oxidized form of PANI is pernigraniline (PE) of
(ES) is then
ES1significantlyformed. In this process, imine nitrogen is protonated by acid,
increases in comparison to other forms of PANI (Table 1) [35]. Furthermore, and the
when − x = 1 [28,34].
conductivity of ES significantly increases in comparison to other forms of
as has been presented in Table 1, enumerated forms of PANI are characterized by different PANI (Table 1)
[35]. Furthermore, as has been presented in Table 1, enumerated forms
values of band gap energy. The colors of these materials are white, blue/violet, blue and of PANI are
characterized
green for LE, PE,by different
EB and ES, values of band[34,35].
respectively gap energy. The colors of these materials are
white, blue/violet, blue and green for LE, PE, EB and ES, respectively [34,35].
Table 1. The main properties of different forms of PANI [34–38].
Table 1. The main properties of different forms of PANI [34–38].
PANI Form Conductivity/S cm−1 Band Gap Energy/eV
PANI Form Conductivity/S cm−1 Band Gap Energy/eV
Leucoemeraldine 10−5 –10− 10 3–4
Figure 3.Leucoemeraldine
General structure
Pernigraniline of polyaniline. 10 −5–10− −10
5
10 –10 − 10 3–4
1.4–2.2
Pernigraniline
Emeraldine base 10−5–10−101–5 1.4–2.2
3–4
If the EB formbase
Emeraldine
Emeraldine of salt
PANI is doped with inorganic acids and organic3–4
1–5 30–200 acids
2.7 such as
phosphoric acid, hydrochloric
Emeraldine salt acid, sulfosalicylic
30–200 acid and sulfuric acid, emeraldine 2.7 salt
(ES) is then
The ES form of PANI is the main candidate for a good photocatalytic material,the
formed. In this process, imine nitrogen is protonated by acid, and owing
conductivity
to its highofelectron
ES significantly
transfer increases
propertiesinincomparison
conjunctiontowith otheritsforms of PANI
low band gap(Table 1) The
energy.
[35].reason
Furthermore, as has been presented in Table 1, enumerated forms
for this can be the polaron band formation that occurs. Furthermore, the result ofof PANI are
characterized by different
partial oxidation values of band
is the occurrence gap energy.
of crystal The colors
lattice distortion, of these
which materials
can be are for
responsible
white, blue/violet, blue and green for LE, PE, EB and ES, respectively [34,35].
the formation of polaron and bipolaron bands. Polaron formation is due to an upward shift
in the highest occupied molecular orbital (HOMO) and a downward shift in the lowest
Table 1. The mainmolecular
unoccupied properties orbital
of different forms of
(LUMO), [34–38]
PANIresults
which in. a reduction in band gap energy. In
general,
PANIthe π–π* conjugate
Form electron and polaron
Conductivity/S cm−1 band transition system
Band Gap improves electron
Energy/eV
mobility, positively influencing photocatalytic properties through a reduction in the charge
Leucoemeraldine 10−5–10−10 3–4
carrier recombination effect [35,39]. The low band gap is mainly due to the charge transfer
Pernigraniline 10−5–10−10 1.4–2.2
exciton, such as the transition of the benzenoid rings from the HOMO (πb ) to the LUMO
Emeraldine base 1–5 3–4
(πq ). Another transition, referred to as the UV region, is assigned to the πb → π* transition.
Emeraldine salt
Furthermore, ES-PANI behaves as 30–200
a p-type semiconductor [37]. 2.7
The optical properties of PANI are closely related to the form of PANI and prepa-
ration/modification conditions. For example, Figure 4 shows changes in the absorption
spectrum of EB under different conditions of its protonation [34]. EB has an absorption
peak at 2.1 eV due to electronic excitation from the benzenoid (πb ) to the quinoid rings (πq ).
When pH changes to 3, absorption at 2.1 eV shifts to 1.5 eV. The reason for this is the lattice
distortion of polyaniline into a polaronic structure as a result of the protonation of imine
nitrogen atoms. Its peak at 3.9 eV can be attributed to the following transitions: (1) π–π*
 preparation/modification conditions. For example, Figure 4 shows changes in the
absorption spectrum of EB under different conditions of its protonation [34]. EB has an
absorption peak at 2.1 eV due to electronic excitation from the benzenoid (πb) to the
quinoid rings (πq). When pH changes to 3, absorption at 2.1 eV shifts to 1.5 eV. The reason
for this is the lattice distortion of polyaniline into a polaronic structure as a result of the
Crystals 2023, 13, 1637 protonation of imine nitrogen atoms. Its peak at 3.9 eV can be attributed to the following 4 of 22
transitions: (1) π–π* transition, which is similar to that of LE; (2) the transition from low-
lying orbitals to the πq orbital. However, an absorption study on the different
concentrations
transition, whichof is
ESsimilar
in 80% to acetic
that ofacid didthe
LE; (2) not show any
transition interchain
from low-lyinginteractions [34].
orbitals to the πq
Generally, regardless
orbital. However, of the form,study
an absorption PANI onhas
theadifferent
high absorbance coefficient
concentrations of ES over
in 80% a wide
acetic
spectral
acid didrange, fromany
not show theinterchain
Vis to IR region [35]. [34]. Generally, regardless of the form, PANI
interactions
has a high absorbance coefficient over a wide spectral range, from the Vis to IR region [35].

Figure 4. Changes in the photoabsorption properties of PANI (emeraldine base) during its proto-
Figure 4. Changes in the photoabsorption properties of PANI (emeraldine base) during its
−4 2 ×2 10 −4 −4 M HCl, 4.5 h;
nation: (A) pH
protonation: (A) 6,
pH166,h;16(B)
h; 10
(B) 10M−4 HCl, 24 24
M HCl, h; (C)
h; (C) × 10−4MMHCl,
HCl,33h; (D)44×
h;(D) 10−4
× 10 M HCl, 4.5 h;
(E)66×× − 4 − 4 − 3
(E) 1010 M HCl,
−4 M HCl,2 h;2(F) 8 × 810× 10
h; (F) −4 M HCl,M HCl,
16 h; 16
(G)h;10(G)M
−3 10HCl,M2HCl, 2 h. Reprinted
h. Reprinted with permission
with permission from
from
[34] [34]. Copyright
. Copyright 1993, Elsevier.
1993, Elsevier.

3. The Concept of Improving Photocatalytic Activity via Binary System: Metal

3.Oxide—Polyaniline
The Concept of Improving Photocatalytic
Heterostructure Activity via Binary System: Metal Oxide
Nanocomposites
—Polyaniline Heterostructure Nanocomposites
Referring to the previous chapter, the chemical structure and form of PANI determine
its electronic and optical properties. It is known that PANI usually behaves as a p-type
semiconductor. This means that PANI has an Ef (Fermi level) close to the HOMO—it can
receive electrons and demonstrate downward band bending [38]. PANI has the LUMO
level in the range of −1 to −2 V vs. NHE and has the HOMO level in the range of
0.4–0.6 V [35,37,40]. Therefore, the formation of heterojunctions between PANI and metal
oxides such as TiO2 is possible.
First, if two semiconductors with different redox energy levels are coupled, it can
lead to an increase in photocatalytic performance by improving charge carrier separation.
Second, it is important that the conditions for an efficient interparticle transfer between
the semiconductor and TiO2 are met; the CB of titania is more anodic than the correspond-
ing band of the sensitizer. Then, if one only considers the visible light activation of a
semiconductor–sensitizer, this component is excited, and electrons photoexcited to its CB
are injected into the conduction band of the titania [22,24,41–43].
The coupling of an n-type semiconductor (e.g., TiO2 ) with a p-type semiconductor
(e.g., PANI) is advantageous from a photocatalytic point of view. This combination of
semiconductors can ensure an efficient electron transfer between them [43]. Given the
band positions of PANI and n-type semiconductors, such as metal oxides, it is possible to
design a heterojunction system with a high photocatalytic performance (Figure 5, left). The
band positions of PANI and TiO2 form a type II heterojunction (staggered band pattern)
(Figure 5, right). Considering the fact that PANI can be activated by visible light, the follow-
ing main advantages of TiO2 properties can be mentioned: (1) the visible light sensitization
of a titania-containing system, (2) the improvement of charge carrier separation. Therefore,
 semiconductors can ensure an efficient electron transfer between them [43]. Given the
band positions of PANI and n-type semiconductors, such as metal oxides, it is possible to
design a heterojunction system with a high photocatalytic performance (Figure 5, left).
The band positions of PANI and TiO2 form a type II heterojunction (staggered band
pattern) (Figure 5, right). Considering the fact that PANI can be activated by visible light,
Crystals 2023, 13, 1637 the following main advantages of TiO2 properties can be mentioned: (1) the visible light 5 of 22

sensitization of a titania-containing system, (2) the improvement of charge carrier

separation. Therefore, a synergistic effect from these two semiconductor components can
beaexpected.
synergisticAs for from
effect the PANI/TiO ratio, the influence
these two2 semiconductor of this can
components issue
be on photocatalytic
expected. As for the
PANI/TiO
activity 2 ratio,
is often the influence
studied; in most of this issue
research on photocatalytic
reports, the amount activity is is
of titania often studied;
higher than in
most research reports, the amount of titania is higher than PANI.
PANI.

Figure 5. Band positions and band gap energies of PANI and exemplary n-type metal oxide semicon-
ductors. Data collected from [43,44] (left). Symbolic presentation of a type II heterojunction system
Figure 5. Band positions and band gap energies of PANI and exemplary n-type metal oxide
of coupled semiconductors; A—TiO2 , B—PANI (right).
semiconductors. Data collected from [43,44] (left). Symbolic presentation of a type II heterojunction
system of coupled semiconductors; A—TiO 2, B—PANI (right).
4. PANI–TiO Binary Heterojunction Systems—The State of the Art
2
A prospective photocatalytic material with high application potential should meet
4. PANI–TiO2 Binary Heterojunction Systems—The State of the Art
three main criteria: (1) high photocatalytic performance over a broad light spectrum in
A prospective
major photocatalytic
reactions, such material of
as the degradation with highpollutants,
organic applicationhydrogen
potentialproduction
should meetand
three
CO2main criteria:
reduction in (1) high photocatalytic
high-value-added performance
products; over a broad
(2) reasonable light
cost for spectrum in
reproducible and
major reactions,
large-scale such as the
production; (3)degradation of (the
high stability organic pollutants,
retention hydrogen production
of photocatalytic propertiesand
after
CO many cycles).in
2 reduction A high-value-added
major problem concerning
products;these
(2) standards
reasonableis that,
cost as
formore components
reproducible andare
introduced into the structure of the resultant material, its stability tends to decrease. There-
fore, this review focuses on binary PANI and TiO2 heterojunctions to better understand the
great potential of this type of material. However, many examples of ternary or multicom-
ponent composites containing both PANI and TiO2 can be found in the literature [45–56].
Table 2 summarizes the binary PANI–TiO2 heterostructures acting as photocatalysts. Three
main areas were considered: preparation conditions, photocatalytic efficiency and aspects
of the photocatalytic mechanism.

4.1. Preparation Conditions

The main method for the preparation of PANI–TiO2 composites is the in situ chemical
oxidative polymerization of aniline, using ammonium persulfate (APS) as an oxidant. This
process occurs in the presence of TiO2 or a titania precursor. Key reaction parameters,
such as the molar ratio of aniline/APS and aniline/TiO2 , are different. Furthermore,
polymerization conditions vary as well: polymerization time ranges from 1 h to 20 days,
and process temperature ranges from ice bath conditions to room temperature. It is therefore
difficult to find the optimal variant for this method. However, there are several reports
that take into account the dominant amount of PANI. It is usually possible to find the best
PANI/TiO2 ratio for photocatalytic performance. Figure 6 shows this type of study with 2%
PANI content as the best amount for photocatalytic activity [57]. In general, these values
vary in other reports according to experimental conditions.
 and process temperature ranges from ice bath conditions to room temperature. It is
therefore difficult to find the optimal variant for this method. However, there are several
reports that take into account the dominant amount of PANI. It is usually possible to find
the best PANI/TiO2 ratio for photocatalytic performance. Figure 6 shows this type of study
with 2% PANI content as the best amount for photocatalytic activity [57]. In general, these
Crystals 2023, 13, 1637 6 of 22
values vary in other reports according to experimental conditions.

Figure
Figure6. Plots
6. of the photodegradation
Plots of (A) methylene
of the photodegradation bluemethylene
of (A) and (B) Rhodamine
blue andB over
(B)PANI/TiO
Rhodamine2 B over
photocatalysts under visible light irradiation with λ > 450 nm: (a) blank, (b) TiO2, (c) mechanical
PANI/TiO2 photocatalysts under visible light irradiation with λ > 450 nm: (a)7 blank, (b) TiO2 ,
Crystals 2023, 13, x FOR PEER REVIEW
mixture of PANI and TiO2 (3:100), (d) PANI (1.0%)/TiO2, (e) PANI (5.0%)/TiO2, (f) PANI (2.0%)/TiO of 25
2,
(c) mechanical mixture of PANI and TiO2 (3:100), (d) PANI (1.0%)/TiO2 , (e) PANI (5.0%)/TiO2 ,
(g) PANI (3.0%)/TiO2. Reprinted with permission from [57]. Copyright 2008, American Chemical
(f) PANI (2.0%)/TiO2 , (g) PANI (3.0%)/TiO2 . Reprinted with permission from [57]. Copyright 2008,
Society.
American
A muchChemical Society. of papers consider other preparation methods. Some reports
smaller number
include PANI and TiO2 impregnation procedures [58–61]. A novel, green and promising
A much smaller number of papers consider other preparation methods. Some reports
procedure for the preparation of PANI/TiO2 was proposed by Cionti et al. [62]. Figure 7
include PANIsteps
shows the main andof TiO 2 impregnation
this procedures
procedure: (1) UV [58–61].
light-mediated A novel,
growth of PANIgreen and promising
oligomers
procedure for the preparation of PANI/TiO was proposed
on a TiO2 surface, (2) polymerization of the oligomers with H2O2.
2 by Cionti et al. [62]. Figure 7
shows the main steps of this procedure: (1) UV light-mediated growth of PANI oligomers
on a TiO2 surface, (2) polymerization of the oligomers with H2 O2 .

Figure
Figure 7. UV
7. UV light-mediated
light-mediated PANI/TiO
PANI/TiO 2 preparation
2 preparation method.method.
ReprintedReprinted from [62]. from [62].
with permission
with permission
Copyright
Copyright2018, Royal
2018, Chemical
Royal Society.
Chemical Society.

AsAsforfor
thetheform
formof of
TiO 2 that
TiO forms a part of the composites discussed, it is a
2 that forms a part of the composites discussed, it is a com-
commercial
mercial material in many cases, such
material in many cases, such as
asP25,
P25,which
whichcontains
containsa mixture
a mixture of anatase
of anatase (85%)
(85%) and rutile (15%). Some authors directly used a titania precursor in a polymerization
and rutile (15%). Some authors directly used a titania precursor in a polymerization
procedure. Attempts have also been made to obtain special morphological forms of TiO2,
procedure. Attempts have also been made to obtain special morphological forms of
such as a self-assembled monolayer [63], mesoporous material [64–66], flowerlike NPs
TiO2 , such as a self-assembled monolayer [63], mesoporous material [64–66], flowerlike
[67], nanotubes [68,69], nanosheets [60], nanofiber membranes [70], fiber films [59] and
NPs [67],
nanorods nanotubes
[71]. Some works [68,69],
havenanosheets
described the[60], nanofiber
possibility membranes
of using defective[70], fiber
forms of films [59]
titania, e.g., grey or black titania [72,73]. There are also reports of modified forms of TiO2 forms of
and nanorods [71]. Some works have described the possibility of using defective
titania,
with noblee.g., grey
metals or black
such as Au,titania
Pt and [72,73]. There core–shell
Ag [58,74–76], are also reports of modified
structures with SiO2 forms
[77] of TiO2
and combinations with reduced graphene oxide [78]. Furthermore, several applicable
forms of PANI/TiO2 have been considered, such as gypsum plasters [79], acrylic pseudo-
paints [80], cotton fabric [81] and polyurethane foam [82].
The identification of the PANI form (oxidation state) present in a resultant product
is not a common procedure. Only some authors include information about the PANI form.
Crystals 2023, 13, 1637 7 of 22

with noble metals such as Au, Pt and Ag [58,74–76], core–shell structures with SiO2 [77] and
combinations with reduced graphene oxide [78]. Furthermore, several applicable forms of
PANI/TiO2 have been considered, such as gypsum plasters [79], acrylic pseudo-paints [80],
cotton fabric [81] and polyurethane foam [82].
The identification of the PANI form (oxidation state) present in a resultant product is
not a common procedure. Only some authors include information about the PANI form. As
explained earlier, the form of PANI directly affects its photocatalytic properties. Therefore,
it is difficult to discuss the mechanism of photocatalytic action without this knowledge.
There are also a very limited number of approaches for obtaining PANI with different
morphological forms [83].

4.2. Photocatalytic Efficiency

Testing the photocatalytic efficiencies of PANI/TiO2 is another crucial issue. As many
as 65% of reports concern the use of organic dyes as model compounds, such as methylene
blue, rhodamine B or methyl orange. This approach is highly controversial, especially for
testing under visible light conditions [84]. The photosensitizing effect of the dye itself,
induced by visible light, can cause the misconception that a given photocatalyst enacts real
activity under visible light. Fortunately, authors included colorless organic compounds,
such as phenol or 4-chlorophenol, in some of their reports. Another issue is the need
to study the effect of dye adsorption and include this information in the graphs. There-
Crystals 2023, 13, x FOR PEER REVIEWfore, the selection of dyes as model compounds for photocatalytic experiments 8 of 25 requires
careful planning.
When the types of photocatalytic reactions are considered, most of the publications are
concerned
When the with
types theof photocatalytic oxidation
photocatalytic reactions are of organic compounds,
considered, and the photocatalytic
most of the publications
are concernedreported
efficiencies with the in photocatalytic
both UV and Vis oxidation of organic
were high in this compounds,
field, but theand the
materials from some
photocatalytic
of the papers, efficiencies
especially reported
wheninmethylene
both UV andblue Vis were high inunder
was used this field, but the
visible light conditions,
materials from some of the papers, especially when methylene blue was used under
should probably be retested, using other model compounds. As shown in Figure 8, more
visible light conditions, should probably be retested, using other model compounds. As
than 80% of 4-chlorophenol was degraded after 7 h, confirming the synergistic effect of
shown in Figure 8, more than 80% of 4-chlorophenol was degraded after 7 h, confirming
PANI
the and TiO
synergistic 2 [64].
effect Considering
of PANI and TiO2 [64].other reaction other
Considering types, only 12%
reaction types,of the12%
only publications are
concerned
of with testing
the publications are hydrogen
concerned evolution
with testingprocess [72,75,76,78,85],
hydrogen evolution and processone report deals
with photocatalytic
[72,75,76,78,85], reduction
and one report in carbon
deals with dioxide
photocatalytic [86]. These
reduction reaction
in carbon dioxidefields
[86]. still require
These
furtherreaction
researchfieldsinstill require
order further
to test theresearch in order
suitability to testmaterials.
of these the suitability of these be noted that
It should
materials. It should be
most PANI/TiO noted that most
photocatalysts thatPANI/TiO
are 2 photocatalysts that are active in
active in hydrogen evolution contain modified
2
hydrogen evolution contain modified titania (with noble metals or with defective
titania (with noble metals or with defective structure—grey titania). Moreover, the work
structure—grey titania). Moreover, the work of El-Bery et al. (Figure 9) demonstrated that
of El-Bery
the PANI/TiO et2 al. (Figure
sample 9) demonstrated
is more that the PANI/TiO
active in photocatalytic 2 sample than
hydrogen evolution is more active in
photocatalytic
PEDOT/TiO hydrogen evolution than PEDOT/TiO and PPy/TiO2 , confirming
2 and PPy/TiO2, confirming the good prospects 2of PANI composites with the good
prospects
titania of PANI
compared composites
to other conductivewith titania
polymers compared to other conductive polymers [61].
[61].

Figure
Figure8. 8.
Photocatalytic
Photocatalyticdegradation of 4-chlorophenol
degradation under visible
of 4-chlorophenol light visible
under irradiation (λ >irradiation
light 400 nm); (λ > 400 nm);
(a) direct photolysis, (b) M(mesoporous)-TiO2, (c) 6% PANI/M-TiO2 in the dark, (d) PANI-NP-TiO2,
(a) direct photolysis, (b) M(mesoporous)-TiO2 , (c) 6% PANI/M-TiO2 in the dark, (d) PANI-NP-TiO2 ,
(e) 6% PANI/M-TiO2. Reprinted with permission from [64]. Copyright 2011, Elsevier.
(e) 6% PANI/M-TiO2 . Reprinted with permission from [64]. Copyright 2011, Elsevier.
 Figure 8. Photocatalytic degradation of 4-chlorophenol under visible light irradiation (λ > 400 nm);
Crystals 2023, 13, 1637 (a) direct photolysis, (b) M(mesoporous)-TiO2, (c) 6% PANI/M-TiO2 in the dark, (d) PANI-NP-TiO2, 8 of 22
(e) 6% PANI/M-TiO2. Reprinted with permission from [64]. Copyright 2011, Elsevier.

Figure 9. Comparison of TiO2 (P25), PEDOT/TiO2 , PPy/TiO2 , PANI/TiO2 photocatalytic activities in

the process of hydrogen evolution [61].

4.3. Photocatalytic Mechanism

Upon analyzing the mechanisms of photocatalytic reactions based on the PANI/TiO2
materials presented in the publications surveyed, there is general agreement on the mecha-
nistic routes. Figure 10 shows the mechanism of reactive oxygen species generation under
UV and Vis conditions using PANI/TiO2 photocatalysts. As shown in Figure 5, the HOMO
of PANI is located between the VB and CB bands of titania, while the LUMO of PANI is
located higher than the CB of TiO2 . This has been experimentally verified and reported
by Hidalgo et al. [85]. Considering UV radiation (Figure 10a), both PANI and TiO2 absorb
photons. The charge is immediately transferred from the HOMO to LUMO levels in PANI.
Photogenerated electrons are transferred from the LUMO of PANI to the CB of TiO2 . An
electron center is formed. Charge separation is enhanced, and superoxide radicals are
generated in the presence of oxygen (reduction reaction). Subsequently, these radicals
react with water to form hydroxyl radicals (OH• ). Simultaneously, photogenerated holes
from the VB of TiO2 migrate to the surface of the HOMO of PANI. A hole center is then
formed, which is involved in the oxidation of water to OH• (oxidation reaction). The
resulting reactive oxygen species (mainly hydroxyl radicals) participate in the oxidation of
organic compounds. The synergistic effect of PANI and TiO2 relates to an efficient charge
carrier separation, which reduces the recombination effect and increases photocatalytic
activity [87,88].
Under visible light irradiation, only the PANI component is excited (Figure 10b). The
charge migrates from the HOMO to LUMO of PANI. The excited-state electrons from PANI
can then be transferred from the LUMO of PANI to the CB of TiO2 . An electron center
is formed. Simultaneously, the transitions π → polaron and polaron → π* in PANI are
induced. Photogenerated holes in the π orbital of PANI are transferred to the interface
and react with water to form hydroxyl radicals. The synergistic effect of PANI and TiO2
is associated not only with visible light sensitization of TiO2 through PANI but also with
improved charge separation [87,88].
There are also reports of modifications to the PANI–TiO2 binary system. The modifica-
tion of the mechanism is the result of such a concept. For example, Zhang et al. modified
the PANI–TiO2 composite with gold [58]. In this mechanism, additional hot electrons
from Au NPs are injected into the CB of titania, inducing a visible-light-mediated surface
plasmon resonance (LSPR) mechanism (Figure 11). The presence of Au NPs in this system
enhances the charge separation and visible light sensitization effect due to the additional
synergy between Au@TiO2 and PANI–TiO2 .
Crystals 2023, 13, x FOR PEER REVIEW 10 of 25
Crystals 2023, 13, 1637 9 of 22

Figure10.
Figure Mechanismof
10.Mechanism ofthe
the generation
generation of
ofreactive
reactiveoxygen
oxygenspecies
speciesunder (a)(a)
under UVUV
and (b)(b)
and visible lightlight
visible by a
PANI–TiO
by 2 nanocomposite
a PANI–TiO photocatalyst.
2 nanocomposite Reprinted
photocatalyst. with permission
Reprinted with permission from [88]2021,
from [88]. Copyright Elsevier.
. Copyright
2021, Elsevier.
Table 2. Summary of binary PANI–TiO2 heterostructures with photocatalytic properties.
There are also reports of modifications to the PANI–TiO2 binary system. The
PANI–TiO2 Type of Photocatalytic
Preparation Conditions
modification Photocatalytic
of the mechanism Efficiency
is the result For example, ZhangRef.
of such a concept.Mechanism et al.
Material
modified the PANI–TiO2 composite with gold [58]. In this mechanism, additional hot
A self-assembled TiO2 monolayer Photodegradation of methylene
electrons from Au NPs are injected into the CB of titania, inducing
Proposedasensitization
visible-light-mediated
PANI/SAM- was used during aniline orange was performed under
surface plasmon resonance (LSPR) mechanism (Figure mechanism
11). The of TiO
presence by NPs [63]
of2 Au in this
TiO2 polymerization in the presence of sunlight. Almost all the amounts
system enhances the charge separation and visible light PANI.
sensitization effect due to the
HCl for 4 h; PANI was in ES form. of MO degraded during 150 min.
additional synergy between Au@TiO2 and PANI–TiO2.
Photodegradation of methylene
blue and rhodamine B was
performed under UV and Vis
(λ > 450 nm). The activities under Proposed
Vis for the PANI/TiO2 (3 wt%) heterojunction,
PANI and TiO2 (P25) were mixed
sample were k = 0.0071 min−1 providing enhanced
in tetrahydrofuran. An optimum
PANI/TiO2 (MO) and k = 0.0229 min−1 . The charge separation (UV). [57]
synergetic effect was found for
activities under UV for the Proposed sensitization
3 wt% of PANI.
PANI/TiO2 (3 wt%) sample were mechanism of TiO2 by
k = 0.0091 min−1 (MO), PANI (Vis).
k = 0.099 min−1 in comparison to
pure TiO2 ; k = 0.046 min−1 (MO)
and k = 0.066 min−1 .
Aniline (0.058 M) was used as a
Photodegradation of Allura Red
precursor; 1 h polymerization Proposed
◦ (ALR) and Quinoline Yellow (QY)
occurred atFigure
25 C in11.the
Mechanism
presence of the photocatalytic degradation of RhB by heterojunction,
the Au-PANI@TiO2 NPs under
PANI/TiO2 under UV light (λ = 254 nm). [89]
of TiO2 (0.5 visible
g—the light
best conditions)
irradiation. Reprinted with permission from [58]. providing
Copyrightenhanced
2016, Royal Chemical
kALR = 10.7 × 10−4 s−1 ;
and acid—the best efficiency for
Society. charge separation.
kQY = 13.02 × 10−4 s−1 .
H2 SO4 ; PANI was in ES form.
Table 2. Summary of binary PANI–TiO2 heterostructures with photocatalytic properties.
Crystals 2023, 13, 1637 10 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
Camphorsulfonic acid-doped
Photodegradation of methylene
PANI was prepared first; aniline
blue was performed under visible Proposed sensitization
was used as a precursor; 24 h
PANI/TiO2 light (λ > 400 nm). mechanism of TiO2 [90]
polymerization occurred at 0◦ . The
k = 0.01515 min−1 in comparison by PANI.
best mass ratio of PANI and TiO2
to pure TiO2 , k = 0.00963 min−1 .
(P25) was 1:500.
Aniline (0.5 g) was used as a Photodegradation of methylene
precursor; 29 h polymerization blue was performed under
PANI/TiO2 occurred at 0◦ in the presence of sunlight. MB decolorization rate,
Not studied [59]
fiber film HCl and TiO2 multi-pore fiber film. using PANI/TiO2 film, was nearly
Photocatalytic activity correlated similar to the pristine TiO2 film
to the crystal structure of titania. after 240 min irradiation.
Photodegradation of rhodamine B
PANI and M-TiO2 (mesoporous
and 4-chlorophenol under visible
titania) were mixed in The role of the
PANI/M-TiO2 light (λ > 400 nm). The activities
tetrahydrofuran. The optimum core–shell structure in [64]
(core–shell) for the PANI/TiO2 (6 wt%) sample
synergetic effect was found at visible light activity.
were 99.8% (RhB, 30 min) and
6 wt% of PANI.
82.4% (4-CP, 7 h).
Aniline (0.91 mL) was used as a
Photodegradation of methylene
precursor; 24 h polymerization UV: proposed
blue and rhodamine B was
occurred at 0◦ in the presence of passivation of
performed under UV and Vis
HCl. Finally, the product was photocatalytic activity
PANI (λ > 420 nm). UV: activity (both
dispersed in absolute ethanol to by PANI layer; Vis: [83]
nanofibers/TiO2 MB and RhB) was similar to pure
form the nonaqueous suspension proposed sensitization
TiO2 ; Vis: activity was 8 and
of PANI nanofibers. The mechanism of TiO2
2.5 times better than pure titania
PANI/TiO2 mass ratio of 1/100 by PANI.
for MB and RhB, respectively.
was optimal.
Aniline (0.09 M) was dissolved in
HCl; titania precursors were
Photodegradation of methyl
added to an aniline and APS
orange was performed under UV
solution; subsequent Proposed sensitization
and Vis (λ > 420 nm). The best
PANI/TiO2 hydrothermal conditions were mechanism of TiO2 [91]
activity for the sample calcined at
maintained at 100 ◦ C for 4 h; next, by PANI.
200 ◦ C; UV: k = 2.484 h−1 ;
thermal treatment occurred at
Vis: k = 0.5316 h−1. .
different temperatures,
100–300 ◦ C.
Aniline was used as a precursor; Photodegradation of MB and RhB
20-day polymerization occurred in was performed under a solar
Proposed
the presence of TiO2 ; TiO2 /ANI simulator. The best activity
PANI/colloidal heterojunction (UV)
mole had ratios of 50 (TP-50), reported for TP-50/TP-100 [88]
TiO2 NPs and sensitization
100 (TP-100), 150 (TP-150). TP-50: samples: RhB completely
mechanism (Vis).
PANI-ES; TP-100: both PANI-ES degraded after 6 h, while MB
and PANI-EB. degraded 60%.
Aniline was used as a precursor;
24 h polymerization occurred at
Photodegradation of methylene
room temperature in the presence
blue was performed under UV
of a peroxo–titanium complex and
PANI/TiO2 (λ = 365 nm). Almost 17% Not studied [92]
H2 SO4 ; optimal AN/Ti ratio of
degradation occurred during
1/1; conductivity of
100 min.
nanocomposite:
2.08 × 10−2 s cm−1 .
Crystals 2023, 13, 1637 11 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
Photodegradation of methyl
orange and orange II was
Aniline (2 mmol) was used as a Proposed
performed under UV; the
PANI/TiO2 precursor; 24 h polymerization heterojunction,
synergistic effect of both [68]
nanotubes occurred at room temperature in providing enhanced
components was confirmed in
the presence of TiO2 . charge separation.
comparison with single
PANI nanotubes.
Photodegradation of methylene
Aniline was used as a precursor; blue was performed under visible
24 h polymerization occurred at light (λ > 400 nm). More than 80% Proposed sensitization
PANI/TiO2 4 ◦ C in the presence of TiO2 ; of MB degraded during 5 h; the mechanism of TiO2 [93]
titania/aniline ratio of 1:1 wt%; synergistic effect of both by PANI.
dark green composite was formed. components was confirmed in
comparison with single PANI.
Photodegradation of methylene
Aniline (0.4 M) solution in blue was performed under visible
aqueous H2 SO4 (one sample light (λ > 400 nm).
Proposed sensitization
sonicated; another one without Photodecomposition studies of
PANI/TiO2 mechanism of TiO2 [94]
sonication); 24 h polymerization MB with PANI, TiO2 ,
by PANI.
occurred at 0 ◦ C in the presence of PANI–TiO2 –S, and PANI–TiO2
TiO2 (0.5 g). showed efficiencies of 58, 71, 77
and 65%, respectively.
Photodegradation of methyl
Aniline polymerization occurred
orange blue was performed under
on the surface of TiO2 /SiO2 ;
PANI/TiO2 / visible light (λ > 420 nm). The best Proposed sensitization
aniline was dissolved in HCl
SiO2 nanofiber activity for the sample: PANI mechanism of TiO2 [70]
solution; different polymerization
membranes loading of 2.3%; 87% of MO by PANI.
times were used; PANI-ES
degradation occurred during
was obtained.
90 min.
Photodegradation of Congo red
and methyl orange was performed
under UV and solar light; optimal UV: proposed
Aniline was used as a precursor;
photocatalytic performance: passivation of
polymerization for 4 h at 0 ◦ C
Ti/ANI molar ratio of 1:1: photocatalytic activity
occurred in the presence of
3D flowerlike degradation under UV: 92% (MO) by PANI layer;
colloidal TiO2 and HCl; different [67]
TiO2 /PANI and 96% (CR) for 2 h, being far Sunlight: proposed
Ti/ANI molar ratios were
better than for P25 (50%); for sensitization
prepared: 2:1, 1:2, 1:5; dark green
sunlight: k = 0.031 h−1 (MO); mechanism of TiO2
powder was obtained.
k = 0.037 h−1 (CR) in comparison by PANI.
to P25: k = 0.011 h−1 (MO);
k = 0.012 h−1 (CR).
Aniline was used as a precursor;
Photodegradation of 4-nitrophenol
polymerization for 3 h occurred at
was performed under visible light
0 ◦ C in the presence of 2.5 g TiO2
(λ > 400 nm); the molar ratio
PANI/TiO2 and HCl; hydrothermal treatment Not studied. [95]
(TiO2 /aniline) 2:1 was optimal for
was subsequently performed;
the photocatalytic performance:
different molar ratios of TiO2 and
90% of degradation of 4-NP.
aniline were used: 4:1, 2:1 and 1:1.
Crystals 2023, 13, 1637 12 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
Photoelectrochemical behavior
PANI was first synthesized from
was evaluated under UV–Vis,
aniline dimer with the addition of
using prepared photoanodes for
poly (sodium 4-styrenesulfonate),
the water photoelectrolysis
which was used as an emulsioning Enhanced electron
reaction in a NaOH solution; an
PANI/TiO2 film and doping agent to stabilize a transfer and efficient [85]
increase in photocatalytic activity
structure; next, green powder of charge separation.
was observed compared to
PANI was deposited in the TiO2
unmodified titania; ES form of
films through
PANI was more active than
a dip-coating method.
the PE form.
Photodegradations of rhodamine
Aniline (2.5 mmol) was used as a B, methylene blue and phenol
precursor; polymerization were performed under UV light;
occurred for 12 h in the presence photocatalyst with 20 wt% of
PANI/TiO2 of various amounts of TiO2 with titania displayed the highest Not studied. [96]
respect to aniline: 0, 5, 10, 15 and activity (>80% for RhB after 3 h of
20 wt%; dark green powder irradiation). All modified
was obtained. photocatalysts were more active
than pristine TiO2 .
Photodegradations of rhodamine
Aniline (2.5 mmol) was used as a B and methylene blue were
precursor; polymerization performed under visible light
Proposed sensitization
occurred for 12 h in the presence (λ > 400 nm). The
PANI/MS-TiO2 mechanism of TiO2 [65]
of 0.5 g MS (mesoporous)-TiO2 photodegradation efficiencies for
by PANI.
with respect to aniline molar ratios: RhB and MB were 99% and 97%,
20:1, 40:1, 60:1 and 80:1. respectively, for the sample with
the molar ratio (TiO2 /ANI) 40:1.
Aniline was used as a precursor; Photodegradation of rhodamine B
Proposed sensitization
polymerization occurred for 12 h was performed under visible light
mechanism of TiO2 by
in the presence of 400 mg TiO2 and (λ > 420 nm). Photocatalytic
PANI, supported by the
Au-PANI/TiO2 chloroauric acid; different weight efficiencies for TiO2 , Au-TiO2 and [58]
presence of Au NPs
ratios of aniline to titania were Au-PANI/TiO2 (1:100) were
(surface plasmon
considered: 1/30, 1/60, 1/80, k = 0.00379 min−1, k = 0.00379 min−1
resonance effect).
1/100. and k = 0.01016 min−1 .
Photodegradation of Reactive Red
45 was performed under UVA and
Aniline was used as a precursor;
solar irradiation (solar simulator).
polymerization occurred for 24 h
Photocatalytic activity under UVA
at room temperature in the
(TOC removal) for sample 15/1
presence of 0.8 g TiO2 ; different
PANI/TiO2 and pristine TiO2 were 80% and Not studied. [97]
weight ratios of PANI to titania
35%; under solar irradiation,
were considered: 10/1, 15/1, 20/1,
complete degradation occurred;
25/1. Highest conductivity
and 83% degradation occurred for
occurred in sample 20/1.
samples 15/1 and TiO2 during
90 min.
Aniline was used as a precursor; Photodegradation of RB5 was
polymerization occurred for 24 h performed under visible light; the Proposed sensitization
PANI/TiO2 at 0 ◦ C in the presence of TiO2 ; best activity for the sample with mechanism of TiO2 [98]
different amounts of titania were 10 wt% of titania content resulted by PANI.
used at 10, 20, 40 wt%. in 96% of degradation.
Crystals 2023, 13, 1637 13 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
Photodegradations of rhodamine
Aniline was used as a precursor;
B and methylene blue were
polymerization occurred for The role of the
performed under simulated solar
3 days in the presence of TiO2 ; in carbonization
irradiation; photocatalytic
Carbonized the next step, carbonization in process—changes in
performance was optimum for [99]
PANI/TiO2 argon atmosphere was performed; TiO2 structures—for
molar ratio 80:1: almost 100% of
different mole ratios of the improvement of
MB degradation (60 min) and 97%
titania/aniline were considered: charge separation.
of RhB degradation
20, 50 and 80.
(90 min) occurred.
Photodegradation methylene blue
Aniline was used as a precursor; was performed
polymerization occurred for 24 h under UV/Vis irradiation;
at room temperature in the the optimum photocatalytic Proposed sensitization
PANI/TiO2 presence of 0.512 g of TiO2 ; performance was for the sample mechanism of TiO2 [100]
different molar ratios of aniline to with molar ratio 1/5: 60% of MB by PANI.
titania were considered: 1/6, 1/5, degradation occurred during
1 1
4 , 2 , 1/1, 2/1, 3/1, 4/1. 180 min, and for pristine titania, it
was 30%.
Photodegradations of rhodamine
B and hydrogen evolution were PANI serves as a
performed under visible light co-catalyst in
Aniline was used as a precursor;
(λ > 420 nm). The most active promoting separation
polymerization occurred for 3 h at
sample for aniline weight content of photoinduced
PANI/grey- 0 ◦ C in the presence of 2 g of
of 5 wt%; for RhB resulted in charges, and [72]
TiO2 grey-TiO2 ; different weight
almost 100% degradation photoelectrons and
percentages for aniline were
(180 min); for H2 evolution: holes can efficiently
considered: 2.5, 5 and 12 wt%.
9 mmol/g after 5 h of irradiation; transfer at the interface
activities were better than for of PANI and grey-TiO2 .
single grey-TiO2 .
Photodegradation of methyl
orange was performed under
Aniline (0.2 M) was used as a
PANI/black visible light (λ > 450 nm).
precursor; polymerization
anatase TiO2 Photodegradation efficiency of Not studied. [73]
occurred for 16 h at 0–4 ◦ C in the
(BAT) PANI/BAT sample was better than
presence of 0.2 g of BAT.
for single BAT or single PANI: 60%
of MO after 40 min.
Photodegradation of methyl
A novel preparation procedure of
orange was performed under UV
highly porous (HP) PANI/TiO2 :
irradiation; high photocatalytic
(1) UV-mediated PANI oligomer
HP-PANI/TiO2 efficiency was present for Not studied. [62]
growth on the TiO2 surface was
HP-PANI/TiO2 : 97% of
used; (2) oligomer polymerization
degradation during 20 min
was conducted with H2 O2 .
of irradiation.
PANI was obtained as a chemical; The photo-electro-catalytic
TiO2 in the P25 was used; reduced degradation efficiencies of
graphene oxide–PANI/TiO2 rGH-PANI/TiO2 for the
Proposed
composite (rGH-PANI/TiO2 ) with degradation of phenol,
rGH- heterojunction,
a three-dimensional 2,4-dichlorophenol, and [101]
PANI/TiO2 providing enhanced
(3D) network structure was BPA were tested under UV
charge separation.
synthesized by a two-step method, (λ > 320 nm); this reached 100%
involving a hybridization process degradation after 7 h, 3.5 h and
and a water bath approach. 4.5 h, respectively.
Crystals 2023, 13, 1637 14 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
Photodegradation of Reactive Proposed
Blue-19 was performed under UV, heterojunction,
Aniline (1 mL) was used as a
visible and solar light; providing enhanced
precursor; polymerization
PANI/TiO2 photocatalytic efficiency was charge separation (UV). [87]
occurred for 4 h at 0 ◦ C in the
similar for all sources of light: Proposed sensitization
presence of 0.1 g of TiO2 (P25).
almost 100% degradation during mechanism of TiO2 by
120 min. PANI (Vis).
Photodegradation of biologically
active compounds was carried out
Aniline was used as a precursor; in a cell under UV degradation; for
polymerization occurred 20 days amitriptyline, sample
in the presence of TiO2 ; TiO2 /ANI TP-100—45% degradation
PANI/colloidal
mole ratios of 50 (TP-50), 100 (60 min); for sulcotrione, sample Not studied. [102]
TiO2 NPs
(TP-100), 150 (TP-150). TP-50: TP-150 (same as pristine
PANI-ES; TP-100: both PANI-ES TiO2 )—97% degradation (60 min);
and PANI-EB. for clomazone, sample
TP-150—33% degradation
(60 min).
Photodegradation of RB5 was
performed under UV and visible
Titania nanotubes (TNT) were
light; under UV conditions,
used as a substrate for the
photoactivities for TNT,
deposition of PANI via vacuumed
PANI/TiO2 PANI(25 W)/TNT and PANI
rotating-bed plasma-enhanced Not studied. [69]
nanotubes (50 W)/TNT were similar (near
vapor deposition; different plasma
100% degradation); for Vis
powers were used: 25, 50
conditions, the highest degradation
and 75 W.
was for PANI (50 W)/TNT sample
(56.4% degradation).
Photodegradation of benzene was
performed under UV and Vis light;
adding nanocomposites into the
Aniline was used as a precursor;
acrylic film improved the
polymerization occurred for 6 h at
photocatalytic
5 ◦ C in the presence of 1 g of TiO2 ;
performance under visible light
dark green materials were
PANI/TiO2 but decreased activity
obtained; for the preparation of
(acrylic under UV light. The photocatalytic Not studied. [80]
pseudo-paint films, the aqueous
pseudo-paints) pseudo paints containing
dispersion of dodecyl benzene
PANI/TiO2 nanocomposites
sulfonic acid and PANI/TiO2 were
degraded approximately 16%
prepared and added to
benzene under
the acrylic latex.
visible light, suggesting its use as a
practical solution for indoor air
purification.
Aniline (0.5 mol/L) was added
Photodegradation of Rhodamine B
into a TiO2 homogeneous
was performed under simulated
suspension; the cotton fabrics after
sunlight; PANI/
plasma pretreatment underwent
TiO2 /cotton composite fabric had
the “dip-pad” method with the
PANI/TiO2 / good adsorption and
solution mentioned. Not studied. [81]
cotton photocatalytic
Aniline-adsorbed cotton fabrics
performance, and the total
were immersed in a solution
efficiency of adsorption and
containing APS, and a
degradation for
polymerization process was
RhB was up to 87.7%.
conducted for 4 h at 0 ◦ C.
Crystals 2023, 13, 1637 15 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
PANI NPs were introduced into
Photodegradation of Rhodamine B
the interlayer space of titanate
was performed under visible light Proposed sensitization
lattice by the addition of Ti0.91 O2
PANI/Ti0.91 O2 (λ > 420 nm). Photocatalytic mechanism of Ti0.91 O2 [60]
colloidal suspension to the turbid
efficiency resulted in an almost by PANI.
PANI NPs suspension, stirring for
complete degradation during 6 h.
2 h; green products were obtained.
Pt-loaded TiO2 NPs were prepared Photocatalytic hydrogen
via photoreduction method; next, generation was performed under
aniline was used as a precursor; visible light (λ > 420 nm). The Proposed sensitization
PANI/Pt-TiO2 polymerization occurred for 6 h at rates of hydrogen evolution (µmol mechanism of Pt-TiO2 [76]
0 ◦ C in the presence of 0.5 g of h−1 g−1 ) for TiO2 , Pt-TiO2 , by PANI.
Pt-TiO2 ; aniline/titania ratio was PANI–TiO2 and PANI/Pt-TiO2
4/100. were 0, 0, 3 and 60, respectively.
Aniline was used as a precursor;
polymerization occurred for 12 h Photocatalytic reduction of Cr(VI)
Proposed
at 0 ◦ C in the presence of 1.04 g of to Cr(III) was performed under UV;
heterojunction,
PANI/M-TiO2 mesoporous TiO2 ; by varying the maximum reaction rate was [66]
providing enhanced
aniline amounts, samples with 0.62 min−1 for samples containing
charge separation.
different content of PANI were 3 wt% of PANI.
obtained: 1, 3, 5, 7, 10 wt%.
The enhanced
Photodegradations of Rhodamine
photocatalytic
B and hydrogen production were
performance is
performed under visible light
attributed to the rapid
(λ > 420 nm); photodegradation
photoinduced charge
efficiencies after 90 min of
Aniline (in different amounts: separation and
irradiation for TiO2 , TiO2 -rGO,
0.225 mmol, 0.45 mmol, 0.9 mmol) efficiently suppressed
PANI/TiO2 -rGO(0.225),
was used as a precursor; charge recombination
PANI/TiO2 -rGO(0.45),
PANI/TiO2 - polymerization occurred for 24 h caused
PANI/TiO2 -rGO (0.9) were 22%, [78]
rGO at 5 ◦ C in the presence of by the synergy between
62%, 80%, 90% and 85%,
TiO2 -rGO (rGO-reduced graphene PANI, TiO2 , and rGO.
respectively; hydrogen production
oxide); dark green material Moreover, the interfacial
efficiencies for TiO2 , TiO2 -rGO,
was obtained. charge transfer in PANI
PANI/TiO2 -rGO(0.225),
and rGO with the
PANI/TiO2 -rGO(0.45),
p-conjugated group
PANI/TiO2 -rGO (0.9) were (in
used for photocatalytic
mmol h−1 g−1 ) 0.08, 0.45, 0.57, 0.8
performance is of great
and 0.72, respectively.
significance.
Photodegradation of methylene
Aniline was used as a precursor; blue was performed under UV; Proposed
polymerization occurred overnight For samples containing 0.6 M of heterojunction,
PANI/TiO2 in the presence of TiO2 ; different titania, the efficiency was highest providing enhanced [103]
contents of titania were used (86.35%), because large amounts of charge separation and
(0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M). TiO2 in the PANI matrix can visible light activity.
produce many reactive sites.
The first step: synthesis of titania Photodegradation of bisphenol A
nanorods (hydrothermal was performed under UV;
Proposed
conditions); the second step: using photocatalytic efficiency was
PANI/TiO2 heterojunction,
aniline as a precursor; higher for PANI/TiO2 than for [71]
nanorods providing enhanced
polymerization occurred for 12 h TiO2 : 79.8% and 60.7% of
charge separation.
in the presence of TiO2 nanorods; bisphenol A degradation after
green product was obtained. 80 min.
Crystals 2023, 13, 1637 16 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
Photodegradation of phenol was
performed under UV/Vis and
visible light ((λ > 400 nm and
λ > 420 nm), using non-gypsum
Aniline was used as a precursor;
materials; UV/Vis—TiO2 :
polymerization occurred for 24 h
4.63 µmol h−1 , PANI–TiO2 :
at 0 ◦ C in the presence of TiO2
2.01 µmol h−1 ,Vis(400)—TiO2 :
(molar ratio of aniline to titania Proposed
0.4 µmol h−1 , PANI–TiO2 :
PANI/TiO2 - was 1:5); the photocatalytic heterojunction,
0.07 µmol h−1 , Vis(420): TiO2 :
gypsum gypsum plaster was prepared by providing enhanced [79]
0.12 µmol h−1 , PANI–TiO2 :
plaster blending commercial gypsum charge separation and
0.26 µmol h−1 ; photodegradation
plaster and distilled water to visible light activity.
of toluene in the presence of
obtain a paste form; PANI–TiO2 in
gypsum plasters containing
10 wt% to the dry mass of
composites; using 460 nm LED
the plaster.
activity of the gypsum containing
PANI–TiO2 was higher than the
one containing TiO2 ; this was the
opposite if 380 nm LED was used.
Aniline was used as a precursor; Polystyrene composite sheets were
polymerization occurred for 12 h in exposed to UV radiation
Proposed
the presence of TiO2 ; PANI contents (λ = 253 nm); the optimum
heterojunction,
PANI/TiO2 were: 3%, 10%, 30%; photodegradation performance [104]
providing enhanced
green powder was formed; prepared was reported for TiO2 -10% PANI,
charge separation.
composite (3 wt%) was added to and it was almost two times
polystyrene dissolved in toluene. higher than for single TiO2 .
Different methods of combining
polyurethane foam with
Photodegradation of Rhodamine B
PANI/TiO2 to form floating
was performed under simulated
composites were used: (1) in situ
Polyurethane- sunlight; the composite prepared
polymerization, (2) Not studied. [82]
PANI/TiO2 by method (4) had the best activity:
immobilization, (3) in situ
almost 100% of RhB degradation
UV-assisted polymerization,
occurred during 30 min.
(4) impregnation by organic
dopant-modified PANIs solutions.
Photocatalytic hydrogen
production was performed under
UV light (LED). The highest
PANI synthesis: aniline was used
efficiency was for samples with
as a precursor; polymerization
5 wt% content of PANI; 15 mmol g−1 Proposed sensitization
occurred for 6 h at 5 ◦ C; next step—
PANI/TiO2 of hydrogen evolved during 5 h; mechanism of TiO2 [61]
the impregnation of PANI and
this result was better than for other by PANI.
TiO2 , using porcelain crucible and
titania composites containing
a DMF solution.
different conducting polymers such
as PEDOT (10 mmol g−1 ) and PPy
(9.5 mmol g−1 ).
The first step: the preparation of Photocatalytic disinfection activity
Ag-TiO2 NPs; was tested using E. coli under visible
The second step: the use of aniline light; the best sample for
as a precursor; polymerization disinfection efficiency was a
PANI/
occurred for 4 h in ice bath composite with 13 wt% content of Not studied. [74]
TiO2 -Ag
conditions in the presence of Ag-TiO2 ; photodegradation of
Ag-TiO2 ; different amounts of lipopolysaccharides were performed
Ag-TiO2 were used: 5 wt%, 9 wt%, under visible light; ca. 40% of
11 wt% and 13 wt%. endotoxin was degraded in 180 min.
Crystals 2023, 13, 1637 17 of 22

Table 2. Cont.

PANI–TiO2 Type of Photocatalytic

Preparation Conditions Photocatalytic Efficiency Ref.
Material Mechanism
The first step was the preparation
of core–shell SiO2 @TiO2 particles; Photodegradation of phenol was
subsequently, PANI was deposited tested under visible light (LED).
on SiO2 @TiO2 ; aniline was used as The highest photocatalytic
PANI/ a precursor; polymerization performance was reported in
Not studied. [77]
SiO2 @TiO2 occurred in the presence of samples with 1:80 molar ratio and
SiO2 @TiO2 ; molar ratios between a mesoporous core; 35% of phenol
aniline and TiO2 were as follows: degradation occurred during
1:80, 1:60, 1:40; mesoporous and 190 min.
non-porous SiO2 were used.
Polymeric nanocomposite films
were produced via layer-by-layer Photocatalytic reaction for
Proposed sensitization
technique using poly(allyamine hydrogen production was
mechanism of TiO2 by
hydrochloride), poly(acrylic acid), performed in a quartz reactor,
PANI/ PANI, supported by the
TiO2 NPs, tetrachloroauric(III) using a solar simulator; hydrogen [75]
TiO2 -Au presence of Au NPs
acid and mercaptoethane sodium evolution rate for the best sample
(surface plasmon
sulfonate solutions; the films were was 1300 µmol g−1 during
resonance effect).
assembled on FTO glass; PANI 180 min.
was in the form of ES.
Photocatalytic reduction in carbon
dioxide was performed under
visible light;
Aniline (1 mL) was used as a the yield of formaldehyde
precursor; polymerization and formic acid formed per gram Proposed
occurred for 4 h in the presence of of catalyst increased as the TiO2 heterojunction,
PANI/TiO2 TiO2 (P25); different weight content in the PANI–TiO2 providing enhanced [86]
contents of titania were nanocomposites varied from 9.4% charge separation and
considered: 9.4%, 12%, 18.2%, to 18.2%; however, a further visible light activity.
29.1% and 35%. increase in TiO2 content to 29.1 or
35% resulted in a decrease in the
yields of products (formaldehyde
and formic acid).
Photodegradations of Thymol
Blue and Rose Bengal dyes were
performed under visible light; the
Combination of aniline, titanium
photodegradation efficiencies of
isopropoxide and graphene oxide;
PANI/TiO2 , TiO2 /PANI/GO, TiO2 /PANI, and
polymerization occurred for 2 h; Not studied. [105]
PANI/TiO2 /GO TiO2 for Thymol Blue were 96%,
finally, HCl treatment was used to
87% and 21%, respectively, after
obtain conductive PANI.
irradiation for 180 min; for Rose
Bengal, they were 97%, 93% and
14%, respectively.
Photodegradation of RfOM
(refractory organic matter) was
performed under simulated
sunlight; the synergistic effect
PANI-ES/TiO2 composites were
between PANI and TiO2
PANI/TiO2 synthesized via in situ chemical Not studied. [106]
was more pronounced in lower
oxidation polymerization method.
PANI ratios, whereas higher PANI
ratios reflected a retardation effect
up to a specific mass ratio of
polyaniline to TiO2 .
 modification of the mechanism is the result of such a concept. For example, Zhang et al.
modified the PANI–TiO2 composite with gold [58]. In this mechanism, additional hot
electrons from Au NPs are injected into the CB of titania, inducing a visible-light-mediated
surface plasmon resonance (LSPR) mechanism (Figure 11). The presence of Au NPs in this
Crystals 2023, 13, 1637 system enhances the charge separation and visible light sensitization effect due to the18 of 22
additional synergy between Au@TiO2 and PANI–TiO2.

Figure 11. Mechanism of the photocatalytic degradation of RhB by the Au-PANI@TiO NPs under
Figure 11. Mechanism of the photocatalytic degradation of RhB by the Au-PANI@TiO2 NPs 2under
visible light irradiation. Reprinted with permission from [58]. Copyright 2016, Royal Chemical Society.
visible light irradiation. Reprinted with permission from [58]. Copyright 2016, Royal Chemical
Society.
5. Conclusions
Binary PANI–TiO heterostructures are very promising photocatalytic materials. They
2
Table 2. Summary of binary PANI–TiO2 heterostructures with photocatalytic properties.
can be used in many types of reactions, such as the photooxidation of organic compounds,
photocatalytic hydrogen generation and carbon dioxide reduction. These materials can be
efficient in both UV and Vis due to the synergistic effect of both components. This effect
manifests itself in two aspects: (1) the presence of PANI as an effective visible light sensitizer
of titania and (2) the formation of a heterojunction (type II) between PANI and TiO2 , which
is a decisive factor in reducing the charge carrier recombination effect and increasing the
efficiency of UV-induced reactions. Based on the literature survey, the following conclusions
and remarks can be drawn: (I) there are reports on the use of different morphological forms
of titania, but there are still too few reports on the influence of different forms of TiO2 used
in heterostructures with PANI on the efficiency of these binary systems; (II) there are almost
no reports on the evaluation of the influence of PANI with different properties, e.g., particle
size on photocatalytic activity, including the use of different preparation methods of PANI
or PANI–TiO2 heterostructures; (III) the model organic compounds in the photooxidation
reactions were mainly dyes, making it advisable to use other, preferably colorless, organics,
e.g., phenols, especially for visible light-induced reactions; (IV) mechanistic studies of
photocatalytic reactions based on PANI–TiO2 materials should be further investigated
via experiments to confirm existing concepts or to propose other mechanism variants;
(V) research into alternative, simple and low-cost preparation methods of PANI–TiO2
structures with high application potential is highly desirable; (VI) studies on the stability of
these heterostructures should be more frequently included in research reports.

Author Contributions: Y.F. and M.J. wrote the paper. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was supported by the Polish Ministry of Education and Science subsidy from
the Poznan University of Technology.
Conflicts of Interest: The authors declare no conflict of interest.

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