Hindawi

Adsorption Science & Technology

Volume 2022, Article ID 3823008, 15 pages
https://doi.org/10.1155/2022/3823008

Review Article
Recent Review of Titania-Clay-Based Composites Emerging as
Advanced Adsorbents and Photocatalysts for Degradation of
Dyes over the Last Decade

Asma Raza,1 Rabia Rehman ,1 and Madeeha Batool2

1
Centre for Inorganic Chemistry, School of Chemistry, University of the Punjab, Lahore, Pakistan
2
Centre for Analytical Chemistry, School of Chemistry, University of the Punjab, Lahore, Punjab, Pakistan

Correspondence should be addressed to Rabia Rehman; [email protected]

Received 28 March 2022; Accepted 19 May 2022; Published 3 June 2022

Academic Editor: Chinenye Adaobi Igwegbe

Copyright © 2022 Asma Raza et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Textile industry being one of the most flourishing industries keeps growing and developing every year, and the consequences are
not very pleasant. Even though its contribution towards economy of a country is indisputable, there are many pros and cons
associated with it that should not be brushed aside, one of them being textile dye waste which is also growing at alarming rate.
Many techniques have been designed to deal with this environmental crisis including adsorption and photodegradation of dye
waste by various substances, both natural and synthetic. TiO2 and clay both have gained immense popularity in this area. Over
the last decade, many successful attempts have been made to design TiO2-clay-based composites to combine and make the
most of their individual capabilities to degrade textile dye waste. While clay is an effective adsorbent, inexpensive, innocuous,
and a great ion exchanger, TiO2 provides supplementary active sites and free radicals and speeds up the degradation rate of
dyes. This review summarizes various features of TiO2-clay-based composites including their surface characteristics, their role
as dye adsorbents and photocatalysts, challenges in their implementation, and modifications to overcome these challenges
made over the last decade.

1. Introduction in water per year [6, 7]. Some examples of commonly used
dyes have been listed in Table 1. Most of them are used
Color is defined as optical interpretation originating from extensively in textile and chemical industries, like brilliant
the brain when visible light stimulates the human eye [1]. green, Congo red, methylene blue, and indigo carmine.
The discovery of earliest dye (aniline purple) dates back to Many dyes are stable towards degradation and it is hard to
the 1860s by W.H. Perkin who laid the foundation for decompose them, resulting effluents using ordinary methods
worldwide production of dyes for commercial purposes of wastewater treatment [8]. These dye effluents have been
[2]. Initially, the world relied on Europe for manufacture reported to cause cancer, allergies, and skin diseases; there-
and supply of dyes, but currently, South Asia has overtaken fore, their proper treatment is inevitable [9]. Figure 1 gives
it [3]. Gross production of dyes is expected to be 1,000,000 a brief description of procedures involved in textile waste
tons per year [4]. These dyes are used in the fabrics, process- water treatment.
ing of leather, publication, lithography, medicinal, and It involves various physical and chemical treatment
beauty sectors. Some of them are also used as coloring agents methodologies, like coagulation, ozonation, bioremediation,
for food items [5]. This universal reliance of industrial sec- filtration, photochemical degradation, and electrolysis, either
tors on dyes means that a bulk amount of dye effluents are individually or in combination to produce clean water. That
being produced and dumped over by every industry all over water in turn is used for secondary purposes, like watering
the world and most of it is discarded into water bodies. It has plants, washing, steam generators, and leaching. Some types
been reported that 200 BL dye effluents are being discharged of water treatments even produce pure water that can be
2 Adsorption Science & Technology

Table 1: List of some commonly used dyes and their abbreviations.

AAT o-Aminoazotoluene CR Congo red PPD Paraphenylene diamine

AB Azure B CV Crystal violet PR Procion red
AC1 Alizarin complex one DB 291 Disperse blue 291 RB 19 Reactive blue 19
AOP Advance oxidation process DR 1 Dispersive red 1 RBR Reactive brilliant red
AO7 Acid orange 7 Es Eosin RhB Rhodamine B
AR 3R Acid red 3R GV Gentian violet Rh 6G Rhodamine 6G
ARB Acid red B MB Methyl blue SI Sudan I
ARG Acid red G MO Methyl orange SBE Sumifix blue Exf
AV 90 Acid violet 90 MV Methyl violet SRhB Sulforhodamine B
BB 41 Basic blue-41 MY Methyl yellow SY Sunset yellow
Bzd Benzidine NBB Naphthol blue black Ttz Tartrazine
CB Conduction band NR Neutral red TY Titan yellow
Ch Chrysoidine OG Orange G TyB Trypan blue
CN Cyanide OII Orange II VB Valence band

Coagulation Bio-remediation Electrolysis Photo-

degradation

Ion
Filtration
exchange Adsorption

Processed H2O

Figure 1: Schematic representation of textile waste water treatment plants.

used for drinking, like in Sri Lanka and Malaysia, and desa- hydrides screen the light from entering the aqueous streams
lination and ion exchange processes are used to convert sew- which leads to a deleterious effects on aquatic environment.
age and sea water into drinkable one. Half of these dye effluents may have chlorine in their com-
position which is a mutagen and cancerous in nature. Some
1.1. Toxicological Profile of Dyes. Dye effluents mainly pol- dyes may also consist of metal ions, like Hg, Cd, As, Cr, and
lute environment in the form of water pollutants which are Pb which cannot be decomposed biologically, so they have
released into water system without treatment. It causes a sig- the tendency to accumulate in our immune system, causing
nificant drop in oxygen concentration of water as sulfur deterioration and inducing different maladies. Unprocessed
Adsorption Science & Technology 3

Table 2: Toxic effects of some synthetic colorants on human post sorption has limited its usage. Therefore, scientists have
health. been engrossed in designing such adsorbents which are not
only effective in action but also strong, durable, renewable,
Dyes Toxicity Source cost-efficient, and eco-friendly [31].
DR 1 Chromosomal mutation [11]
CV Chronic kidney disease [12] 1.2.2. Adsorption Kinetics. The adsorption potential of an
DB 291 Necroptosis [13]
adsorbent is represented graphically using different models
such as Freundlich and Langmuir [32]. These graphs are
AC 1 Disturbance in blood plasma proteins [14]
based on concentration of adsorbate adsorbed by adsorbent
CR Skin irritant [15] at constant parameters (temperature and pressure) [33].
PPD Loss of vision [16] The Langmuir model (Equation (1)) perfectly represents
PPD Coryza [17] a single-layer adsorption unit. It is based on the assumption
RhB Skin cancer [18] that dye particles when adsorbed on adsorbent arrange
MY Neural degeneration [19] themselves in a single layer, all the adsorbed particles having
SI Imbalanced digestive system [20]
equal amount of Ea [34]. It also suggests that single-dye par-
ticle binds per active site. Moreover, this theory overlooks
Bzd Urothelial carcinoma [21]
the interactivity between individual dye particles [35].
SY White blood cell damage [22]
Ttz Anxiety [23] K L Qm C e
AAT Atopic dermatitis [24] Qe = , ð1Þ
1 + K L Ce
MY Hepatocellular carcinoma [25]
TyB Abnormal development [26]
where Qe : Adsorption potential at equilibrium (mgg-1), Qm :
Ch Toxicity in blood plasma [27] Max adsorption potential (mgg-1), C e : Conc. of adsorbed
TY Skin irritant [28] dyes at equilibrium (mgL-1), K L : Equilibrium constant of
adsorption (Lmg-1).
Contrary to the Langmuir model, the Freundlich model
or partly decomposed dye pollutants are destructive for both
(Equation (2)) represents an adsorption theory where dye
aquatic and human life [10]. Table 2 enlists chief human
particles are adsorbed and arrange in more than one layer
maladies caused by dye pollutants.
and this arrangement is nonlinear [36]. Mostly, the Freun-
dlich model is used where more refined adsorbents with
1.2. Degradation Methods of Dye Effluents. Since the time,
enlarged surfaces and better pore morphology are being
the pathological effects of dye effluents have been analyzed,
studied for adsorption or to describe the adsorption of
and researchers have been working on various effective tech-
extremely reactive organic dyes [37]. Although these equa-
niques for their decomposition and removal from wastewa-
tions are perfectly applicable at low pressure, the values
ter. Some of these techniques have been showcased in
become more uncertain at high pressure [38].
Figure 2. They are widely explored all over the world by dif-
ferent researchers. Most of them were employed on indus-
trial level for wastewater treatment or for converting sea Qe = K F ðC e Þ1n , ð2Þ
water into pure water.
where Qe : Adsorption potential at equilibrium (mgg-1), K F :
1.2.1. Adsorption. Amongst all these methods, adsorption Adsorption potential (mmolg-1), Ce: Conc. of adsorbed dyes
has emerged as an exceptionally effective and facile method at equilibrium (mgL-1), n: Constant of adsorption strength.
for the removal of dye effluents (Table 3) [29]. Adsorption Both these models have been used to study kinetics of
is a physical phenomenon of separation of any element adsorption for various adsorbents [39–41]. Some other
between two surfaces, e.g., liquid/solid. It can be carried models that have also been proved quite successful are Tem-
out by physical or chemical means. One of its main features kin [42] and Henry’s [43]. Koyuncu and Okur used all these
is regeneration of adsorbent. The adsorption potential of a four models to study adsorption potential of C2M1 for AV
substance depends on its surface area, resistance to abrasion, 90 dye where the Freundlich model proved to be superior
pore diameter and structure, etc. [30]. It is quite simplistic than others having highest correlation factor (R2 > 0:94)
and economically favorable and involves swift recollection [44], while Kulasooriya et al. investigated adsorption poten-
and reusability of adsorbent without needing to deal with tial of brick clays for SBE dye where the Langmuir model
sludge or unsafe side products. However, the success of showed better results, max adsorption potential being
adsorption procedure depends on performance of adsor- 1667 mg kg-1 [45].
bents which should be comprehensive in its actions. Some-
times an adsorbent may observe a very high adsorption 1.2.3. Parameters for Effective Adsorption of Dyes. The pro-
potential but lack other important features. For instance, cess of adsorption is dependent on parameters like pH, heat,
activated carbon is a commonly used adsorbent having a and quantity of adsorbent. Different parameters have differ-
high SSA (specific surface area), void fraction, and adsorp- ent impact on different adsorbents. Some conditions could
tion efficiency, but its heavy price and complexed isolation be more ideal for one adsorbent but not for others.
4 Adsorption Science & Technology

Ion Fenton
exchange process
Electrochem Membrane
oxidation filtration

Electrolytic Phyto-
precipitation remediation

Bio-
Flocculation remediation

Dye
Photo-
Adsorption removal
catalysis
methods

Figure 2: Degradation methods of dye effluents.

Table 3: Shortcomings of dye removal techniques. tion at higher pH, while it is opposite for anionic dyes [50].
Cationic dyes show greater adsorptions if pH of solution is
Sr. higher than pHpzc, while it is opposite for anionic dyes [51].
Method Shortcomings
no.
1 Flocculation Sludge formation 1.2.4. Photocatalysis. Unlike adsorption, photocatalysis is an
Electrolytic advanced technique which has been proved as an effective
2 Time consuming remediation for waste water treatment. This procedure does
precipitation
Electrochemical not require the usage of any strong chemical specie, so the
3 Expensive due to electricity usage chances of production of hazardous side products are very
oxidation
4 Ion exchange Only effective for selective dyes little. Photocatalysis is powerful enough to decompose oth-
erwise highly stable dyes into harmless products [52]. The
5 Fenton process Excessive formation of anions
fundamental principle of photocatalysis involves the contact
6 Membrane filtration Unstable and expensive between dye pollutants and their loading onto the photoca-
7 Phytoremediation Not permanent treatment talyst. The dye pollutants get adsorbed on its exterior where
8 Bioremediation Impedes microbial development redox reactions transpire as a result of generation of elec-
Photocatalytic Source of light required which is trons from conduction band (CB) and holes from valence
9
degradation expensive band (VB). The resultant products finally detach from the
photocatalyst and are discarded into the aqueous media
Therefore, optimum parameters are decided for every adsor- [53]. The reaction mechanism can be simplified as follows:
bent on hit and trial basis.
UV
Photocatalyst + ⟶ HolesðVBÞ + eðCBÞ
(1) Temperature. Adsorption is either exothermic or endo- Vis
thermic so temperature is a major parameter here. In an endo- HolesðVBÞ + eðCBÞ ⟶ EðΔhÞ
thermic procedure, the value of Qmax rises at higher
temperature due to enhanced motion of the dye particles HolesðVBÞ + H2 O ⟶ ∙ OH + H+ ð3Þ
and increased active sites of adsorbents [46]. However in some
cases, value of Qmax falls at higher temperature as motion of eðCBÞ + O2 ⟶ ∙ O2
∙
dye particles slows down and adsorption is exothermic [47]. OH + Dye ⟶ H2 O + CO2
∙
(2) Quantity of Adsorbent. Usually, the greater the quantity O2 + Dye ⟶ H2 O + CO2
of adsorbents, the greater the number of active sites available
and hence the higher is adsorption potential [48]. However, Various studies have proved that photocatalysis is a
financially feasible adsorbents are those that show higher highly efficient and result-oriented technique for degrada-
potential with minimum quantity [49]. tion of dyes.
Photocatalysis can be carried out via batch as well as
(3) pH. pH is another major parameter that impacts adsorp- continuous process as shown in Figure 3.
tion procedure determined by pzc (point of zero charge). pH This review mainly focuses on progress made on clay-
can control rate of ionization of the adsorbents. Cationic based TiO2 composites over the period of past decade. It
dyes show lower adsorptions at lower pH and higher adsorp- summarizes the data on the synthesis and implementation
Adsorption Science & Technology 5

UV light UV lamp

Water
outlet

TiO2 Spectrometer
coating
Peristaltic pump
Ceramic
substrate

Water
inlet

23ºC

Dye solution
(a) (b)

Figure 3: (a) Batch process setup vs. (b) continuous process setup for photocatalytic degradation of dye.

O2
of clay-TiO2 composites for treatment of industrial waste
water, both as adsorbent or as a photocatalyst. A literature CB O2–
review based on selective experimental approaches was – – – –
made which highlights the advantage of degradation of dyes UV EG = 3.2ev
by clay-based TiO2 composites. rays

+ + + +
2. TiO2 as Adsorbent and Photocatalyst and VB OH•
Its Limitations Pure TiO2 H2O

TiO2 is an excellent adsorbent based on its abundance, ease

Figure 4: Mechanism of Photocatalytic degradation by TiO2.
of excitability, modifiable physical properties, and a very fit-
ting PCZ of 6–6.8, which enables it to adsorb dye particles
[54]. TiO2 is also a widely used photocatalyst owing to its core of photodegradation mechanism [64]. The mechanism
degradation potential [55]. Photocatalysis obviously cannot is briefly explained through Figure 4 graphically.
be carried out without adsorption of dyes onto TiO2. This
adsorption brings out the interaction between the dye parti-
cles and photogenerated species, which kick starts photoca- 2.1. Drawbacks and Challenges. However, TiO2 has few
talysis [56]. Thus, the photocatalytic activity of TiO2 is also drawbacks [65] that can make it less effective and various
determined by its adsorption potential. Adsorption is a sur- methods have been adopted to overcome them.
face phenomenon which is dependent on form, area, and
structural regularity of TiO2 crystals [57]. (1) A very large band gap of anatase limits its ability to
TiO2 is highly stable both chemically and physically and adsorb light in UV region only, so it cannot make
mild and inexpensive which make it a perfect photocatalyst proper use of spectrum. To overcome this problem,
[58]. TiO2 exhibits polymorphism and its 3 mineral forms TiO2 has been modified by induction of metallic
are anatase, brookite, and rutile [59, 60]. Anatase and rutile [66, 67] and certain nonmetallic [68, 69] compounds
are reported to have greater photocatalytic activity. Anatase which shrink the band gap as shown in Figure 5
is a better photocatalyst owing to its indirect band gap that (2) Lesser attraction for organic dyes and lesser volume
gives a greater life span to electron-hole pair, while rutile of pores per surface area reduce its adsorption
produces electron-hole pair of a shorter life span based on potential. So adsorption capacity of organic dyes is
its direct band gap [61]. CB and VB of TiO2 have a gap of improved by layering its surface with carbon-based
3.2 eV (anatase) and 3.0 eV (rutile) [62]. Thus, anatase has organic compounds [70, 71]
a λmax of 387.5 and rutile has 400 nm in UV region [63].
TiO2 on photoexcitation produces a number of electrons (3) Irregular distribution of TiO2 particles and agglom-
and holes in CB and VB simultaneously. These charged spe- eration of its NPs can block the active sites and hin-
cies further create bunch of free radicals which forms the der the interaction with incoming light. To avoid
6 Adsorption Science & Technology

Light
Source

Vis
rays ray
s
UV

O2
O2– O2
CB
CB O2–
e– e– e– e–
e– e– e– e–

EG < 3.2 ev
EG = 3.2 ev Addition of metals/
non-metals

VB VB
OH• OH•
h+ h+ h+ h+
h+ h+ h+ h+
H2O
Modified TiO2
H2O TiO2

Figure 5: Photocatalytic activity of TiO2 vs. modified TiO2.

this, TiO2 is immobilized with different supports (2) Cations are present in between the layers of clay
which break off clustering of its particles and block- structure which captures the electrons. Thus, the
age of light [72, 73] holes in VB of TiO2 are free and available for oxidi-
zation. This reduces the overall rate of charge recom-
(4) It often ends up making a slurry in liquid media and bination in TiO2-clay composites and increases its
its regeneration gets difficult which makes its use less photocatalytic potential [86]
cost-effective. Functionalization by magnetization of
TiO2 can make its recovery easier [74, 75] (3) Regeneration and recovery of TiO2-clay composites
are easier due to the presence of charged species on
clay which make the composite separable from aque-
2.1.1. Clay as an Adsorbent and an Effective Support for
ous media and the reaction becomes more feasible
Titania. Clay is a mineral naturally found on earth crust.
economically
Its chief composition is finely grounded substances (mostly
sheet silicates) that impart a unique plasticity in aqueous 2.2. Preparation of TiO2-Clay Composites. TiO2-clay-based
media, while it hardens up in dry conditions [76]. Clay com- composites can be synthesized using various techniques as
position involves uniformly grounded hydrated alumino- shown in Figure 6. They are reported by various researchers
silicates. The structure of these alumino-silicates contains from all over the world with good yields and various
tetrahedral sheets of Si-O and octahedral sheets of Al. Clay applications.
has the potential to clean wastewater system up to 70% by
adsorbing impurities [77]. The extent to which these impu- 2.2.1. Adsorption of Dyes via TiO2-Clay Composites. TiO2/
rities are adsorbed onto clay depends on how strongly they stishovite clay composite was simply prepared by mixing
interact with natural clay and mineral oxides on its surface stishovite and TiO2 and stirring with alcohol for 5-6 hours,
[78–82]. The adsorption procedure is regulated by a few fac- precipitating overnight, and vacuum drying. The resultant
tors such as nature of ions (cationic or anionic), number of composite was used for adsorption of MV dye. 88% of dye
ions, pH, temperature, and nature of dye being treated [83, was adsorbed. The adsorption data shows that adsorbent’s
84]. surface was covered by a single layer. Adsorption process
Clays have emerged as popular supports for TiO2 for dye was endothermic and it observed pseudo 2nd order. How-
degradation. ever, the recovery rate of adsorbent was not up to the
mark [92].
(1) Pure TiO2 has lower photocatalytic potential than Likewise, a TiO2-bentonite composite was prepared by
clay-based TiO2 composite. Clay imparts TiO2 a larger mixing TiO2 with clay and double distilled H2O followed
surface area, increases the number of active sites, and by stirring and drying, and the resulting composite was used
hence improves its adsorption potential [85] for degradation of RhB via batch process and results were
Adsorption Science & Technology 7

Table 4: Summary of TiO2-clay composite preparation

methodologies and their consumption for adsorption of dyes in
Sol-gel the last decade.

Adsorbent Preparation Adsorption Reference

TiO2-Mnt-PAN Spin coating MB [100]
TiO2-Ht Sol-gel MB [101]
Pillaring Solvothermal
Methods of TiO2-Mnt-PVA Immobilization MB [102]
preparing TiO2-Knt Sol-gel OII [103]
TiO2-clay
composites TiO2-Bnt Sol-gel NBB [104]
TiO2-Knt Impregnation PR [105]

Immobilization Hydrothermal
thermal method, while CTAB was used as a surface active
agent and adsorption of MB was studied. The studies suggest
that graphene having layers of sp2 hybridized C is bestowed
with a huge surface area, greater affinity for H2O, and uni-
Figure 6: Methods of preparation of TiO2-clay composites form distribution which makes it an ideal support. Likewise,
[87–91]. palygorskite has exceptional adsorption potential owing to
its enormous surface area and heat resistance. C=O groups
studied using the Langmuir isotherm. TiO2-bentonite adsor- on the surface of adsorbent provided the active sites where
bent removed up to 98.9% RhB which was higher than nat- MB molecules were seem to be bound by H-bonds (on OH
ural clay adsorbent [93]. groups). The adsorbent showed commendable adsorption
TiO2 has the ability to make composites with a variety of even after 5 recovery cycles. The max adsorption potential
clays. TiO2-rectorite composite was synthesized by mixing was 134.59 mgg-1 [96].
titanium butoxide/HCl suspension with rectorite/dd H2O Clay composites of TiO2 can be further improved by
suspension followed by stirring, drying, centrifugation, microwave treatment. TiO2-bentonite composite was syn-
washing, and finally drying. Then, it was magnetized with thesized via impregnation where bentonite was added to a
iron oxide and used for adsorption of MB dye showing water suspension of TiO2 followed by heating and stirring.
max adsorption potential of 169.20 mgg-1. Iron oxide was The thoroughly mixed solution was subjected to microwave
reported to increase the number of active sites by rupturing irradiation; the product was removed and desiccated. It was
the sheets of TiO2-rectorite composite and created large cav- further used to study adsorption behavior using RhB and
ities which adsorbed greater number of MB molecules. Mag- MB dyes using the Langmuir equation. Structural analysis
netization also made desorption easier [94]. shows that the integration of TiO2 particles onto bentonite
The degradation potential of TiO2-clay composites can via impregnation enhanced its adsorption potential, and
be enhanced by incorporation of metal oxides. TiO2-WO3- OH● on TiO2 act as potential active sites and amplify the
bentonite composites were synthesized through hydrother- adsorption process [97].
mal method by adding a mixture of Na+-bentonite and A TiO2-Rouge clay composite was synthesized via
sodium tungstate dihydrate mixture to titanium tetrachlo- hydrothermal synthesis. Carefully refined and pretreated
ride with constant mixing in a cold bath followed by treat- clay (with NaOH) was purified and desiccated and stored
ment with ultrasound radiations for ½ hr. This mixture for 12 hours. Equal weight of functionalized clay and TiO2
was heated in an autoclave with H2O at 443.15 K for 10 h. were mixed in the presence of NaOH at 373.15 K and
The resultant composite was separated through filtration 5 atm. The adsorbent was used for adsorption of MB dye;
and washed and dried at 25°C. This composite was used it was reported to remove 91.19% dye. Morphological analy-
for adsorption studies of MB dye. WO3 has been reported sis indicates that the clay undergoes structural rearrange-
to escalate TiO2’s sensitivity for gaseous species as well as ment post combination with TiO2 and adsorbent shows a
improves its acidic strength and increases its affinity for comparatively uneven and granulated surface with multiple
dye contaminants. The unique pretreatment of bentonite active sites which escalates adsorption rate [98].
with ultrasound radiations allowed a thorough disruptor of Lately, halloysite nanotubes (financially feasible clays)
Na+-bentonite matrix and uniform insertion and intercala- have enticed deep interest owing to their hollow tube-like
tion of TiO2-WO3 particles in between its layers. The adsor- structure, enlarged surface area, and distinctive surface fea-
bent exhibited excellent adsorbent potential, a smooth tures. A TiO2-halloysite composite was doped with Fe using
desorption, and an easy recovery. Moreover, the adsorption hydrothermal procedure and used for adsorption of RhB
potential of pretreated adsorbent increased by 50% possibly and MB dyes. The multilayer tubes have anionic Si–OH on
due to increase in number of active sites by ultrasound irra- the exterior side and cationic Al–OH on the interior side
diation [95]. which attract impurities of different nature via electrostatic
Mixing of TiO2 with clay and organic material like gra- interactions. Moreover, they are harmless, inexpensive, eas-
phene imparts its tremendous adsorption properties. TiO2- ily accessible, and nonhazardous. TiO2-Fe composites were
palygorskite-graphene composite was prepared via hydro- seen to stick to the exterior of the tubes which increased
8 Adsorption Science & Technology

Table 5: Summary of preparation and photocatalytic degradation of TiO2-clay composites over the last decade.

Photocatalyst Preparation Photocatalysis Source Removal efficiency (%) Reference

TiO2-Spt Sol-gel ARG UV 99.2 [114]
TiO2-Knt Hydrolysis AO7 UV-Vis 60 [115]
TiO2-Rtr Sol-gel ARG UV 98 [116]
TiO2-Atp-AgBr Impregnation MB Solar 98.8 [117]
TiO2-Rtr Intercalation ARG UV 18 [118]
TiO2-Mnt-PMMA Emulsion polymerization/sputtering MB UV 29.3 [119]
TiO2-Mnt-V Sol-gel SRhB Vis 67.1 [120]
TiO2-Lpt Intercalation ARB UV 98.3 [121]
TiO2-Bnt-Ce Sol-gel NR Solar 99 [122]
TiO2-Bnt Pillarization MO UV 98.8 [123]
TiO2-Mnt Pillarization MB UV-Vis 98 [124]
TiO2-Mnt Pillarization MO UV 98.08 [125]
TiO2-Portuguese clay Immobilization MB UV 96.5 [126]
TiO2-Mnt-Pan Sono-chemical AB Vis light 59 [127]
TiO2-Ht Low temperature GV Vis light 60 [128]
TiO2-Bnt Sol-gel AR 3R UV 96.7 [129]
TiO2-Mnt-Ptp Intercalation/polymerization Rh 6G Solar/ultrasound/UV 96 [130]
TiO2-Plg Sol-gel OG UV 96 [131]
TiO2-Tunisian clay Impregnation RB 19 UV 99 [132]
TiO2-Mnt Impregnation CV UV A 97.1 [133]
TiO2-Atp-BiOBr In situ deposition MO Vis light 96.8 [134]
TiO2-Svs Solvothermal OG UV 80 [135]
TiO2-Sep-Au Sol-gel MO UV 90 [136]
TiO2-Plg-CdS Hydrolysis MB Vis 37 [137]
TiO2-Spt-Ag2O Sol-gel+impregnation ARG Vis 98 [138]
TiO2-Bnt-Fe3O4 Co-precipitation/sol-gel MB UV 90 [139]
TiO2-C-N-Ht Precipitation/recrystallization MB Solar 95 [140]
TiO2-Y3+-Mnt Acid-sol MO UV/Vis 65 [141]
TiO2-AM-Ht Biosynthesis MB UV 90 [142]
TiO2-Spt Hydrothermal OG UV 98.8 [143]
TiO2-Ivorian clay Hydrothermal sol-gel MO UV 60 [144]
TiO2-Spt Sol-gel Es UV 72 [145]

their dispersion in aqueous phase, and the greater the dis- negative CB so these electrons diffuse to brookite. These
persion, greater the contact with dye contaminants present electrons undergo a series of reactions and produce •OH
in water and hence the higher the adsorption [99]. which oxidizes dye particles. Likewise, photoactivated holes
Table 4 gives a brief summary of synthesis methodolo- in brookite diffuse to anatase due to its high VB potential
gies and application of some of TiO2-clay-based composites and interact with dye particles. Thus, the mixing of different
in degradation of dyes via adsorption. phases and resulting heterojunction between them can
improve TiO2’s photocatalysis [106].
2.2.2. Photocatalysis of Dyes via TiO2-Clay Composites. Mix- The amount of clay used in the composite plays an
ing different phases of TiO2 with clay gives amazing results important role in its potential to remove impurities. A
in photocatalysis. A novel TiO2-kaolinite photocatalyst was TiO2/clinoptilolite photocatalyst was prepared via sol-gel
prepared using various phases of TiO2 which was used for method in different ratios and used for degradation of CN
photocatalytic degradation of ARG dye. According to XRD and MV-2B dye. The charge on the surface was dependent
data, the photocatalyst seemed to be composed of mixtures on clay’s ratio which is an important factor in determining
of 3 different phases of TiO2, i.e., anatase, rutile, and brook- the affinity of charged dye particles towards the photocata-
ite, in different combinations. The anatase/brookite combi- lyst. 90/10 turned out to be the best ratio; the lower the clay
nation was reported to have highest photoactivity. Both of ratio, the higher was the surface area and photocatalysis. The
them were stimulated by UV light which leads to photoge- lower ratio of clay also prevented accumulation of TiO2 in
neration of free electrons in anatase. Anatase has a highly aqueous phase and improved its recovery [107].
Adsorption Science & Technology 9

Rapsomanikis et al. prepared TiO2-halloysite clay com- tributes to porosity of the TiO2-clay composite that adds to
posites using sol-gel method for photocatalysis of BB41. photocatalytic potential. Urea addition can also lead to
The unique feature of this photocatalyst was that its surface shrinkage of the band gap of the TiO2-clay composite from
was modified with Ag particles by treating composite’s films 3.35 to 2.92 eV and makes it visible light activated. It is
with 1.0 mM AgNO3 sol for 10-20 minutes followed by rins- reported to enhance the degradation rate of dyes by 2.3
ing with double distilled H2O and drying by N2 gas. Later, times under visible lights. Moreover, it is inexpensive and
the Ag ions were reduced to Ag0 by UV irradiation of films. easily available which makes it even a better additive [112].
These Ag particles were reported to improve TiO2’s effi- Photocatalytic degradation coupled with ultrasound
ciency to separate charge carrying species which led to an treatment has been proved a very effective technique to
enhanced photocatalytic activity [108]. enhance photoactivity of TiO2-clay composites. During
Even though TiO2-clay photocatalyst show a remarkable photocatalysis, the efficiency of photocatalyst is reduced
potential to degrade dyes and are economically feasible, over the time due to blockage of active sites and hindrance
some of them (e.g., TiO2-palygorskite) have limited applica- of UV light. Ultrasonic treatment solves this problem by
tions as they can only be stimulated by ultraviolet light acting as an irradiation sources and activates TiO2 to carry
owing to their large EG . Various experiments have been car- out sono-catalysis in the absence of UV light. Ultrasound
ried out to make them responsive to visible light, some of waves also induce turbulence in the liquid phase which
which include hybridization and doping with other metals results in particle sizing and deagglomeration and hence
especially transition metals. The plasmonic effects of Ag increase number of active sites available. Moreover, treat-
nanoparticles enable it to improve the visible light sensitivity ment of these titania-clay composites with ultrasound
of TiO2-clay photocatalysts and expand their area of usage. waves leads to formation of supplementary OH• radicals.
A TiO2-Palgorskite composite was doped with Ag-AgCl par- All these factors are reported to escalate photoactivity of
ticles through deposition-photoreduction method and used titania-clay composites and speed up the removal rate of
for photocatalytic degradation of RhB. Due to the surface dye [113].
plasmonic effect, Ag nanoparticles improved the photoactiv- Table 5 gives a brief summary of synthesis methodolo-
ity of the catalyst under visible light [109]. gies and application of some of titania-clay-based compos-
The sensitivity of TiO2 towards light spectrum can also ites in degradation of dyes via photocatalytic degradation.
be broadened by merging it with other metal oxides like It is evident from Tables 4 and 5 comparisons that sol-
Fe2O3 which are highly photoactive under visible light due gel and coprecipitation methods are more used for synthe-
to Fenton mechanism. Therefore, its fusion with TiO2 sizing titania-clay composites as compared to other
imparts an exceptional photoactivity under natural day light, methodologies.
which is a mixture of ultraviolet (5%) and visible (40%) and
IR light (55%). One such photocatalyst was prepared
through sol-gel procedure where bentonite-supported TiO2 3. Conclusion
was doped with Fe2O3 and used for photocatalysis of MB.
The dye was completely degraded in 2 hours. Fe2O3 not only (i) TiO2 as both photocatalyst and adsorbent is exten-
improved the photoactivity by absorption of light in visible sively and effectively used for treatment of textile
region, but its magnetic nature also helped to retrieve and waste water
reuse the photocatalyst making it economically favor- (ii) The factors that limit TiO2’s efficacy of dye degra-
able [110]. dation can be overcome by using different supports
Another such attempt to exploit visible light for photo- like clays, silica, etc.
degradation by TiO2-clay composites was made by deposit-
ing g-C3N4 onto TiO2-bentonite via wet impregnation. For (iii) Clays like rectorite, bentonite, montmorillonite,
this purpose, TiO2-bentonite composite was mixed with attapulgite, kaolinite, and halloysite are most com-
highly concentrated slurry of g-C3N4, sonicated for 120 monly used as supports for TiO2 using various
minutes, stirred overnight, and dried at 333.15 K. Samples techniques
of such composites with varying weight of g-C3N4 were pre- (iv) Clay as a support provides TiO2 with a high sur-
pared. These composites were applied for photodegradation faces area, porosity, improved morphology, more
of RBR dye. 90% of the dye was degraded within 1.6 hour active sites, and better adsorption of dyes
under visible light. This brilliant outcome was ascribed to
strong interaction between clay and g-C3N4 leading to (v) Loading of TiO2 on clays helps preventing the
enhanced dispersity, increased number of active sites, and aggregation of TiO2 and its loss to environment
their uniform distribution and better optical activity. (vi) The efficacy of these TiO2-clay composites can be
Another reason was rate of charge recombination declined enhanced by further addition of various metallic
due to electron transfer from g-C3N4 to TiO2 and photoin- and nonmetallic substances, ultrasonic irradiation,
duction under visible light. The photocatalyst was reusable and experimenting with different phases and parti-
for 5 successive cycles [111]. cle size of TiO2
Incorporation of nonmetallic additives like urea into
TiO2-clay composites can be quite favorable. Urea is (vii) These TiO2-clay composites are energy-efficient,
reported to promote formation of anatase phase and con- nonhazardous, and economically feasible
10 Adsorption Science & Technology

(viii) The study on TiO2-clay-based composites and [13] M. Tsuboy, J. P. F. Angeli, M. S. Mantovani, S. Knasmüller,
their modifications for treatment of textile waste G. A. Umbuzeiro, and L. R. Ribeiro, “Genotoxic, mutagenic
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Data Availability
[14] F. Ding, L. Zhang, J. X. Diao, X. N. Li, L. Ma, and Y. Sun,
All data related to this work is presented in results section “Human serum albumin stability and toxicity of anthraqui-
along with references. none dye alizarin complexone: an albumin-dye model,” Eco-
toxicology and Environmental Safety, vol. 79, pp. 238–246,
2012.
Conflicts of Interest [15] S. Chawla, H. Uppal, M. Yadav, N. Bahadur, and N. Singh,
The authors declare that they have no conflicts of interest “Zinc peroxide nanomaterial as an adsorbent for removal of
Congo red dye from waste water,” Ecotoxicology and Envi-
regarding the publications of this review.
ronmental Safety, vol. 135, pp. 68–74, 2017.
[16] H. Yagi, A. M. el Hendi, A. Diab, and A. A. Elshikh, “Para-
Acknowledgments phenylenediamine induced optic atrophy following hair dye
poisoning,” Human & Experimental Toxicology, vol. 15,
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