Journal of Molecular Liquids 256 (2018) 395–407

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Dyes adsorption using clay and modified clay: A review

Abida Kausar a,⁎, Munawar Iqbal b,⁎, Anum Javed a, Kiran Aftab a, Zill-i-Huma Nazli a,
Haq Nawaz Bhatti c, Shazia Nouren d
a
Department of Chemistry, Government College Women University Faisalabad, Pakistan
b
Department of Chemistry, University of Lahore, Lahore, Faisalabad, Pakistan
c
Department of Chemistry, University of Agriculture Faisalabad, Pakistan
d
Department of Chemistry, Government College Women University Sialkot, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: The effective use of the sorption properties of different clays as sorbents for the removal of dyes from wastewater
Received 2 October 2017 has currently received much attention because of the eco-friendly nature of clay materials. Dyes are complex
Received in revised form 10 January 2018 class of organic compound having wide range of applications in textile and food industries and a large amount
Accepted 8 February 2018
of dyes are wasted, which get mixed in natural water resources. Mixing of dyes in water resources must be
Available online 10 February 2018
prohibited for the safety of natural ecosystem. The adsorbents (natural and modified) have been successfully
Keywords:
used for the adsorption of dyes form wastewater. This review article highlights the importance of clay (raw
Textile wastewater and modified) as an adsorbent for the adsorption of dyes from textile wastewater. Appropriate conditions for
Dyes-clay interaction clay-dye system and adsorption capacities of a variety of clays are presented and sorption process is critically an-
Adsorption alyzed. Studies reported the clays as an adsorbent from 2004 to 2016 are included and different properties for the
Modified clay utilization of clay and clay-based adsorbents are discussed. Based on studies, it was found that the clays (natural
Characterization and modified) are affective adsorbents for the purification of wastewater containing dyes.
Kinetic © 2018 Published by Elsevier B.V.
Equilibrium

1. Introduction
Dyes are colored organic compounds based on functional groups
such as chromophoric group (NR2, NHR, NH2, COOH and OH) and
auxochromes (N2, NO and NO2) [1]. There are different classes of dyes
used for the dyeing of different substrates (Table 1), i.e., acid dyes are
generally used for silk, wool, modified acrylics and nylon dyeing.
These are also used in cosmetics, paper, food, ink-jet printing and
leather dyeing. The major classes of acid dyes are azine, xanthene, an-
thraquinone, triphenylmethane, nitroso, nitro and azo dyes [2]. Acid
blue 2, acid red 57, methyl orange, orange (I, II) are common acid
dyes. Basic dyes are used for modified polyesters, modified nylons, poly-
acrylonitrile dyeing as well as in paper industry and medicines. These
are also used for tannin mordant cotton, silk and wool [2]. This class of
dyes is soluble in water and yields colored cations and are also called
cationic dyes [3]. The major classes are cyanine, thiazine, acridine,
oxazine, hemicyanine and diazahemicyanine, i.e., basic red 46, mala-
chite green, basic yellow 28, crystal violet, methylene blue, basic
brown and basic red 9 are the basic dyes. Disperse dyes are employed
on cellulose acetate, nylon, acrylic fibers and cellulose fiber. These are
non-ionic dyes and are insoluble in water and from aqueous solutions,
⁎ Corresponding authors.
E-mail addresses: abida.kausar@hotmail.com (A. Kausar),
munawar.iqbal@chem.uol.edu.pk, bosalvee@yahoo.com (M. Iqbal).
used for acrylic fibers also. Main classes are benzodifuranone, nitro,
styryl, azo and anthraquinone group [4] and some common examples
are disperse yellow, disperse blue, disperse orange and disperse red. Di-
rect dyes are used for leather, cotton, rayon dyeing and in paper indus-
try. These dyes have affinity for cellulosic fiber if dying process occurs in
aqueous solution containing electrolytes. The main classes are oxazine,
stilbenes and poly azo compounds. Examples are direct orange 34, di-
rect black, direct violet and direct blue etc. [5]. Reactive dyes are used
on nylon, wool as well as cellulose and cotton fiber. The chromophores
in these dyes are phthalocyanine, azo, triaryl methane and a covalent
bond is formed between the dye and fiber [6]. Common examples are
reactive yellow 2, reactive red, remazol and reactive black 5 etc. Vat
dyes are used for wool, rayon fibers, flax wool and cotton (on cellulosic
fibers mainly) dyeing i.e., indigoids and anthraquinone etc.; vat dyes are
insoluble in water. The common examples of vat dyes are vat green 6,
vat blue and indigo [7].
The use of adsorption using clay sorbent (Bentonite – 0.05–0.2; Red
mud 0.025; Clinoptilolite – 0.14–0.29) U$/kg for effluent treatment will
be cost effective by saving the money that is used in the import of com-
mercial active carbon (0.8–1.1 U$/kg), natural zeolite (0.08 U$/kg), Chi-
tin (15–20 U$/kg), Chitosan (16.5–10 U$/kg) Cross-linked-chitosan
(5–10 U$/kg) [8,9]. At the same time, comparatively, the adsorption
process is technically also considered a better alternative in water and
wastewater treatment because of convenience, ease of operation and
simplicity of design, moreover be helpful to overcome on the problem

https://doi.org/10.1016/j.molliq.2018.02.034
0167-7322/© 2018 Published by Elsevier B.V.
396 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407

Table 1
Different classes of textile dyes and their health effects [13,14].

Dyes Examples Textile industrial products Health effects

Acid Acid blue 25, acid red 57, methyl orange, Congo red Polyamide, fibers, polyurethane, modified Skin and mucous membrane irritation and burns
dyes acrylics, nylon
Basic Basic red 46, malachite green, basic yellow 28, Silk, moderant acrylic, polyester, modified Carcinogens, allergic skin reactions, allergic dermatitis,
dyes methylene blue, basic brown, basic red 9 polyesters, modified nylons, paper. skin Irritation, mutations, cancer.
Direct Direct orange 34, direct black, direct violet, direct blue. Leather, cotton, rayon, paper. Bladder cancer carcinogen
dyes
Disperse Disperse yellow, disperse blue, disperse orange, Polyacrylonitrile, polyamide, nylon, acrylic DNA damage, induction of bladder cancer in humans,
dyes disperse red fibers, cellulose. splenic sarcomas
Reactive Reactive yellow 2, reactive red, remazol, reactive black Nylon, wool, cellulose, cotton. Allergic respiratory problem
dyes 5
Vat dyes Vat green 6, vat blue, indigo Wool, rayon fibers, flax wool cotton Severe burns, skin and mucous membrane irritation

of high energy input (used in reverse osmosis and UV sterilization) as
the most developing countries lacking adequate electricity [10–12].
A large variety of organic (residual dyes) pollutants are introduced
into different water bodies from different sources like pharmaceutical
industries, paper and pulp industries, tannery, bleaching industries, tex-
tile industries and other anthropogenic activities [15–37]. Currently,
there are N100,000 dyes commercially existing (azo dyes, are about
70% on weight basis from these dyes) and over 1 million tons dyes are
manufactured per year, of which 50% are textile dyes [38]. According
to one estimate, the dyes produced are 2% that are directly discharged
in aqueous waste matters, 10% is lost in the coloration procedure subse-
quently, 20% of these colored compounds are entered in the environ-
ment through waste matters [39]. The reported percentage fixation of
different dyes on different substrates and discharge in effluent is
shown in Table 2 [40].
2. Dye separation techniques
Dyes effluent mixed with wastewater may cause potential hazard to
environment [41–43]. Different physico-chemical techniques have been
developed for the remediation of waste of environmental concern
[44–69]. The chemical treatment which includes photolysis and photo-
catalytic processes, whereas biological methods include anaerobic and
aerobic degradation and physiochemical methods include electro ki-
netic coagulation, ion exchange, adsorption and membrane filtration.
exchange of electrons, adsorbate is chemically bounded to the surface.
Whereas, in latter procedure waste matter is attached with adsorbent
surface by physical forces as for instance, hydrogen bonding, polarity,
Vander Waals forces and dipole-dipole interactions etc. However, the
extent of adsorption depends upon adsorbent nature like molecular
size, molecular structure, molecular weight, solution concentration, po-
larity and also on adsorbent surface properties like surface area and par-
ticle size etc. [2]. This separation process discovers extensive use in the
removal of dyes from aqueous medium and is considered as best
method in comparison with others. The efficiency of this method de-
pends on chemical and physical properties of adsorbent and adsorbate,
their cost, availability, ease of operation, surface area and less toxicity
[72]. Numerous biomass types including bacteria, fungi, algae and
yeast have proposed excellent sorbents for waste water treatment
[73–75] intended the biocatalysts such as enzymes for degradation
and mineralization of textile dyes from aqueous solution. Gisi et al.
[75] classified the lowcost adsorbents into following five groups:
(i) agricultural and household wastes, (ii) industrial by-products, (iii)
sludge, (iv) sea materials, (v) soil and ore materials and (vi) novel
low-cost adsorbents and compared their efficacy for different pollutants
like dyes and heavy metals. Furthermore Gisi et al. [75] after
Table 3
Separation techniques and their advantages and disadvantages [2,13].

All methods have their own limitation on the basis of cost, design and Separation Advantages Disadvantages
dye separation efficiency [13,70,71]. But adsorption is the most suitable techniques
method in comparison with others in different respects. A summary of Chemical methods
advantages and disadvantages of these methods are presented in Ozonation No sludge generation Operational cost is very high, half
Table 3. life is short (20 min)
Photo catalyst Operational cost is low Some photo catalyst degrades into
and economically toxic by-products.
2.1. Adsorption for the removal of dyes from textile effluents feasible
Fenton reagent Low-priced reagent Disposal issues and sludge
Adsorption is one of the most important industrial separation pro- and efficient procedure production
cesses for the treatment of waste. It is a mass transfer process through Biological methods

which the solid substance (adsorbent) can selectively remove dissolved Anaerobic By-products can be Under aerobic conditions require
constituents from an aqueous solution by attracting the dissolved solute degradation used as energy more treatment and yield of
toward its surface. The accumulation of concentrated matter at surface resources methane and hydrogen sulphide
Aerobic degradation Operational cost is low Provide suitable environment for
or at the inter phase is involved in this process. The adsorbent can and effective in growth of microorganisms and
exist in liquid, solid, gas or dissolved solute phase. Adsorption can be removal of azo dyes very slow process
classified as chemical or physical; the former procedure is due to the Physicochemical methods

Adsorption/sorption High adsorption Low surface area for some

Table 2 capacity for all dyes. adsorbents, high cost of
Fixation degree of different classes of dyes on different substrates and percentage loss of adsorbents.
dyes in textile effluent [40]. Need to dispose of adsorbents.
Ion exchange No loss of sorbents For disperse dyes not effective
Dye class Fiber type Fixation degree (%) Loss in effluent (%)
Electro kinetic Economically feasible Need further treatments by
Direct Cellulose 70–95 5–30 coagulation flocculation and filtration and
Acid Polyamide 80–95 5–20 production of sludge.
Base Acrylic 95–100 0–5 Membrane filtration Effective for all dyes Suitable for treating low volume
Reactive Cellulose 50–90 10–50 with high quality and production of sludge.
Disperse Polyester 90–100 0–10 effluents
 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407
comprehensive study of previous literature reported that dyes among
different pollutants have maximum affinity for textile dyes. The affinity
of sorbents in removing various pollutants, their applications on real
wastewater, costs and considerations on their reuse after adsorption
processes are available, clay has been proved economically and techni-
cally suited as an adsorbents [57,76]. In spite of a large amount of studies
on clay adsorbents, there is little data containing a full study comparing
the economic viability between these clay adsorbents. Even though a lot
has been done on studies dealing with clay material sorbents, a great
deal of work still needs to be done to predict the performance of the ad-
sorption processes for dye adsorption in real world industrial effluents
under various operating conditions.
3. Clays
Clays are defined as fine grained minerals, which may be plastic in
nature, clays can be hardened when dried or fired and they contain ap-
propriate water contents. Clays generally contain phyllosilicates, how-
ever the other contents present may impart either plasticity or harden
when fried or dried [77]. Clays can be differentiated from other fine
grained soils by their difference in minerology and size. Adeyemo
et al. [78] reported montmorillonite- sematic, kaolinite, Illite, bentonite
and chlorite the main classes of clays. Kaolinite group includes the min-
eral kaolinite, dickite, halloysite and nacrite. The smectite group in-
cludes pyrophyllite, talc, vermiculite, sauconite, saponite, nontronite
and montmorillonite. The illite group includes the clay micas. Illite is
the only common mineral [79]. Chlorites are not always considered
clay; sometimes they are classified as a separate group within the
phyllosilicates. There are approximately 30 different types of “pure”
clays in these categories, but most “natural” clays are mixtures of
these different types, along with other weathered minerals. These dif-
ferences among the clays provide an opportunity to investigate the im-
pact of structure and layer charge on metal ion coordination to
permanent charge sites. In addition, this choice of minerals provided
various arrangements of aluminol and silanol surface hydroxyl sites.
The adsorption capabilities of clay are related to the negative charge
on the structure of fine grain silicate minerals. This negative charge
can be neutralized by the adsorption of positively charged cations
such as dyes. Besides, the clays possessed large surface area, ranging
up to 800 m2/g, which contributes to its high adsorption capacity.
There are many types of clays but montmorillonite clays are expected
to have the highest sorptive capacity in comparison to other [80]. Fur-
ther, clay could be modified to enhance its efficiency for the removal
of pollutants from water and wastewaters. Zeolites are naturally occur-
ring silicate minerals, which can also be synthesized at commercial
level. Probably clinoptilolite is the most abundant of N40 natural zeolite
species. The adsorption properties of zeolites depend upon their ion-
exchange capabilities [5].
3.1. Kaolinite
This group contains trioctahedral minerals like chrysotile,
cronstedite, antigorite, chamosite and dioctahedral minerals for exam-
ple kaolinite, halloysite, dickite and nacrite. It is white and soft plastic
clay, composed of the hydrated aluminium silicate, a mineral kaolinite.
The general structure of the kaolinite group is composed of silicate
sheets (Si2O5) bonded to aluminium oxide/hydroxide layers (Al2(OH)
4) called gibbsite layers [81], which is a layered silicate mineral with
one tetrahedral sheet linked through oxygen atoms to one octahedral
sheet of alumina octahedra. The primary structural unit of this group
is a layer composed of one octahedral sheet condensed with one tetra-
hedral sheet. In the dioctahedral minerals, the octahedral sites are occu-
pied by aluminium, while in the trioctahedral minerals, these sites are
occupied by magnesium and iron. Kaolinite and halloysite are single-
layer structures. Kaolinite, dickite and nacrite occur as plates; halloysite,
which can have a single layer of water between its sheets, occurs in a
397
tubular form. It is formed by the alteration of feldspar and muscovite
[81,82]. The common structure of kaolinite contains silicate sheets,
bounded to aluminium oxide/hydroxide layers, called gibbsite layers,
which is a layered silicate mineral composed of one tetrahedral sheet,
linked through the oxygen atoms to one octahedral sheet of alumina oc-
tahedra. Nacrite, kaolinite and dickite exist as plates, halloysite occurs in
a tubular form, have a single layer of water between its sheets. Rocks
having large amount of kaolinite are referred to as kaolin or china clay
[77]. Kaolinite contains heterogeneous surface charge is a well-known
fact. It is believed that its basal surface has a constant structural charge
which is attributed to isomorphs substitutions of Si4+ by Al3+. The
charge on the edges is due to protonation or deprotonation of surface
hydroxyl groups and so it depends on pH of solution. Adsorption can
occur on flat exposed planes of silica and alumina sheets. It is least reac-
tive clay. Kaolin has no side effects, no health problems till the fine dust
particle is controlled, so it is safe environmentally [83,84].
3.2. Bentonite
Bentonite is aluminium phyllosilicate adsorbent, important impure
clay, generally contains montmorillonite. The structure of montmoril-
lonite is a gibbsite layer sandwiched between two silica sheets to form
the structural unit [85]. The substitutions are mainly within the octahe-
dral layer (Mg2+, Fe2+) and to a much less extent within the silicate
layer (Al3+/Si4+). The chemical composition of the clay mineral is
based on a hydroxyl-aluminosilicate framework. The crystal structures
of the clay minerals are formed by a combination of sheets of silica tet-
rahedral and alumino octahedral. Part of the trivalent Al is substituted
by divalent Mg or Fe in some cases. In such cases, substitution is accom-
panied by the addition of alkaline metals such as Na and K or alkaline
earth metals such as Mg and Ca to provide charge balance. The investi-
gated organoclays vary in the degree of their total cation exchange ca-
pacity (CEC) exchanged by organic counter ions [78,85].
There are different types of bentonite which are named with respect
to the presence of dominant element in them such as calcium, potas-
sium, aluminium and sodium. Bentonite is commonly produced due to
the weathering of volcanic ash mostly in the presence of water. Two
main classes of bentonite are calcium and sodium bentonite, mainly
used for industrial applications. Calcium bentonite is an effective adsor-
bent of ions not only in solution but also in oils and fats. Sodium benton-
ite when added in water; absorb many times as its dry mass present in
water and expand when it is wetted, it is very significant because of its
wonderful colloidal properties. It is used for geotechnical and environ-
mental investigation by drilling mud for oil and gas wells [86,87]. By
ion exchange process, calcium bentonite can be converted into sodium
bentonite, to attain a number of properties of sodium bentonite. Ben-
tonite is environmentally safe and is beneficial in wine making process
to remove extra quantity of protein from white wines. Due to its adsorp-
tion properties, it is also used as desiccant, they have been used to pro-
tect nutraceutical, pharmaceutical and diagnostic products from extend
shelf life and moisture degradation. According to the adsorption proper-
ties of bentonite, it has overall neutral charge on its lattice excessive
negative charge is present which is characterized by a three layer struc-
ture with two silicate layers, enveloped by an aluminate layer as oppo-
site charges attract, negative charge surfaces have affinity for cationic
dye. A number of cationic dyes was absorbed by bentonite clay [88].
So far, clay could possibly be used for the removal of dyes due to its ef-
ficiency, availability, abundance and economically beneficial.
3.3. Sepiolite/palygorskite
Sepiolite/palygorskite are natural clay minerals, composed of mag-
nesium hydrosilicates and belonged to silicate group [89]. Both groups
are Mg silicates but palygorskite have more diversity in structure and
has more Al and less Mg than sepiolite. They are non-swelling and
inert clays. When dispersed in water they produce irregular lattice
398 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407

Table 4
Application of clays (raw and modified) as an adsorbents for different types of dyes.

Sr. Clay Modification Dye pH Efficiency Equilibrium Kinetic TDSa Characterization Ref.
No. (adsorbents) study study

1 Montmorillonite Fe3O4/activated montmorillonite Methylene blue 7.3 99.47% 1 2 – FTIR, XRD [102]
(Fe3O4/Mt) nanocomposite
2 Raw clay Modifications were carried out by Basic Red 46 (BR46) – 2.805, 4.232, 1 2 – FTIR, XRD [3]
calcination at different temperature and Reactive Yellow 1.968, and 2.756
(S2, S3), acidic activation, and 181 (RY181 mmol/g for CI
acetylation. Basic Red 46
0.031, 0.030,
0.046, and 0.050
mmol/g for CI
Reactive Yellow
181
3 Montmorillonite – Methyl green and 5 68.35% for – 2 2 XRD [103]
methyl blue methyl green
95.95% for
methyl blue
4 Montmorillonite – Basic Yellow 2 (BY2 11 434.196 mg g−1 1 2 2 XRD, FTIR [104]
5 Bentonite clay The cold plasma treatment Methylene blue 12 303 mg/g 1 2 FT-IR, XRD, SEM [96]
6 Tunisian raw clay – Direct orange 34 – 7.75 mg/g. 1 2 1 XRD, XRF, FT-IR [15]
7 Vermiculite Expanded vermiculite Basic Red 9 6.8 7.66 × 10−5 2 2 1 XRD, FTIR [72]
mol·g−1
8 Attapulgite Amino-functionalized attapulgite Methylene Blue 10.0 215.73 mg g−1 1 2 1 XRD, FTIR, SEM [105]
clay nanoparticle
9 Bentonite y Cationic surfactant Methylene blue (MB), 9.0 399.74 μmol/g 2 2 – XRD, FTIR, [71]
(Hexadecyltrimenthylammonium Crystal violet (CV) for MB
chloride)/organoclay and Rho-damine B 365.11 μmol/g
(RB) for CV
324.36 μmol/g
for RB
10 Montmorillonite Gemini surfactants Methyl orange – 161.03 to 271.74 1 2 2 XRD, FTIR [94]
mg g−1
11 Montmorillonite Montmorillonite supported porous Methylene blue (MB) – 686.94 mg g−1 1 2 – XRD, FTIR, SEM [106]
carbon nanospheres (MMT-PCN)
12 Bentonite Bentonite (Bt) modification using Telon-Orange, – 108.3 mg/g for 2 1 1 FTIR, XRD TGA [107]
(ortho, meta and para) Telon-Red and Telon-Orange
bis-imidazolium cations Telon-Blue 437 96.7 mg/g
for Telon-Red
82.4 mg/g for
Telon-Blue
13 Montmorillonite Novel kappa-carrageenan/poly Crystal violet – 151 mg g−1 1 2 – FTIR, SEM, XRD, [108]
(vinyl alcohol) nanocomposite and TEM
hydrogels
14 Moroccan Illitic – Methylene Blue(MB) 13,698 mg/g 1 2 1 XRD [109]
15 Bentonite Hexadecyltrimethylammonium Acid red (AR) 3 140.84 μmol/g 1 1 2 FTIR, SEM, XRD, [110]
chloride (HDTMA)-intercalated TGA and
bentonite clay potentiometric
titrations
16 Bentonite New adsorbents derived from Congo red (CR), – 900 mg/g for CR 1 2 – FTIR, SEM, and [111]
tragacanth gum-graft-poly(methyl methyl orange (MO), 750 mg/g for MO TG/DTA
methacrylate) and bentonite and acid blue 113 8.5 mg g−1 for
(TG-g-PMMA/B) (AB-113) AB-113
17 Zeolite Zeolite-reduced graphene oxide methylene blue and – 53.3 mg g−1 for 1 – – [112]
(zeolite-rGO) (reduced graphene malachite green methylene blue
oxide) 48.6 mg g−1 for
malachite green
18 Natural Illitic clay – Methylene blue (MB) – 24.87 mg g−1 1 2 2 [113]
mineral
19 Sodium Nano clay filled composite Congo red and methyl 7 110 mg/g for CR 4 1 1 FTIR, SEM, XRD, [114]
Montmorillonite, hydrogels of poly acrylic acid and violet 111 mg/g for MV DTA–TGA
bentonite polyethylene glycol
20 Montmorillonite Starch-montmorillonite/polyaniline Reactive dye – 91.74 mg g−1 1 2 – FT-IR, XRD, SEM, [115]
(St-MMT/PANI) nanocomposite TGA and TEM
21 Kaolinite Polymer-clay composite Bromophenol blue 5.895 mg/g 2 1 – FTIR, SEM, XRD and [116]
Thermal analysis.
22 Natural – Basic Yellow 2 5.12 833.33 mg/g 1 2 1 FTIR, PSD, TEM, [117]
untreated clay XRD and BET
23 Montmorillonite Dodecyl sulfobetaine. Methylene blue 5 150.2 mg/g 1 2 2 XRD, FTIR, TG [118]
Surfactant-modified
montmorillonite
24 Smectite An alginate-based nanocomposite Methylene blue 10 1843.46 mg/g – 2 – FTIR, XRD and SEM [119]
hydrogel enhanced by
organo-illite/smectite clay
25 Activated clay Methyl orange (MO) b7 13.624–16.779 1 2 1 – [120]
mg/g
26 Bentonite Modified with iron chloride Brilliant blue FCF – 6.16 mg/g for 1 1,2 1 XRD and SEM [121]
natural clay
 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407 399

Table 4 (continued)

Sr. Clay Modification Dye pH Efficiency Equilibrium Kinetic TDSa Characterization Ref.
No. (adsorbents) study study

14.22 mg/g for

iron-modified
clay
27 Montmorillonite Lignocellulose-g-poly(acrylic Methylene blue (MB – 1994.38 mg/g 1 2 – FTIR, XRD, SEM, [122]
acid)/montmorillonite and TEM
(LNC-g-PAA/MMT) hydrogel
nanocomposites
28 Montmorillonite N-vinyl-2-pyrrolidone/itaconic Safranine-T 6 550.0 mg g−1 1 2 – XRD, FTIR, SEM [123]
acid/organo clay nanocomposite
hydrogels
29 Montmorillonite – Basic red 18 4 530.645 mg g−1 2 2 2 – [124]
30 Montmorillonite Paper-like composites of cellulose Acid Scarlet G 5.5 85.7 mg/g 1 1 2 XRD, FTIR, TGA and [125]
acetate–organo-montmorillonite SEM
31 Laponite RD Clay Novel carrgeenan-based hydrogel Crystal violet (CV) – 79.8 mg g−1 1 2 – XRD, SEM TEM [126]
nanocomposites containing laponite
RD
32 Bentonite Modified by thermal and acid Congo red 5.5 95% 2 2 1 SEM [92]
activation
33 Ghassoul – Methyl violet 10. 625 mg/g 1 2 2 XRD [127]
34 Bentonite Glycol bis-N-cetylnicotinate Methyl orange – 99.02%for GN-Bt – – – FTIR and XRD [128]
dibromide, 80.12%for C-BT.
Cetyltrimethylammonium bromide
35 Palygorskite clay Heat-treated Palygorskite Methylene blue 7 78.11 mg/g 1 – – XRD and BET [129]
36 Activated Clay Modified by iron oxide (Fe-clay) Alizarin red s (ARS) – 32.7 mg g−1 1 2 – – [130]
37 Biotite clay Chitosan-g-poly(acrylic Methylene blue (MB – 2125.70 mg/g 1 2 1 – [131]
acid)/biotite (CTS-g-PAA/BT)
hydrogels with unique clay biotite
(BT)
38 Ball Clay Calcined and uncalcined ball clay Crystal violet (CV) – 1.6 × 10–4 mol 1,3 – – XRD, FTIR, GTA [132]
g−1 for calcined
1.9 × 10–4 mol
g−1 for
uncalcined ball
clay
39 Clay minerals of Halloysite nanotube Methyl violet 11 113.64 mg/g 1 2 1 TEM [133]
Halloysite
40 Bentonite Iron-pillared bentonite Rhodamine B 5.0 98.62 mg/g 1 2 – XRD, FTIR [134]
41 Smectite clay Organofunctionalized Amazon Brilliant Orange 3R 4 1.26 mmol g−1 1 2 1 XRD, FTIR [135]
smectite (SMC and SMCAMP.) for SMC
2.07 mmol
g−1for SMCAMP
42 Montmorillonite Montmorillonite/CoFe2O4 Methylene blue 9 97.75 mg g−1 1 2 2 XRD, SEM, VSM [136]
composite
43 Montmorillonite Diphosphonium-intercalated Telon dyes (Red, blue 2 11–26 to 2 1 1 XRD [137]
montmorillonite and orange) 110–160 mg∙g−1
44 Natural clay – Acid Red 88 (AR88) 2 1133.10 mg g−1 1 2 SEM and zeta [138]
potential analysis
−1
45 Pillared clays Alginate encapsulated pillared clays Safranine 6.9 963 μmol∙g 1 2 – FTIR and thermal [139]
analysis
46 Clay materials Lime Congo Red 12 94% 2 2 – XRD, SEM,BET [140]
(bentonite,
kaolin and
zeolite)
47 Granular High-shear wet granulation Basic Yellow 28 6 514 mg/g 1 1 – XRD, FTIR, SEM [141]
inorgano-organo
pillared clays
48 Halloysite Halloysite nanotubes Neutral Red 7 54.85, 59.24 and 1,2 2 2 XRD, FT-IR, TEM [142]
65.45 mg/g at and BET
298, 308 and 318
K
49 Purified Acid activation Methylene blue 500 mg/g. 5 – – X-ray diffraction [143]
Moroccan Clay
mineral
50 Smectite-rich Activated clay (sulphuric Indanthrene Blue RS 6.0 for 13.92 mg/g for 1 – 2 XRD, FT IR [144]
clayey rock acid-activated products) (AYDS) (C.I. Vat Blue 4) AYDS AYD
(AYD) and 7.3 17.85 mg/g for
for AYDS
AYD
51 Natural clay – Nile Blue (NB) and 25 mg/g for NB 2 1 – XRF [145]
Brilliant Cresyl Blue 42 mg/g for BCB
(BCB)
52 Moroccan crude – Basic Red 46 (BR46) 9.5 54 mg/g 1 2 1 XRD [146]
clay
53 Bentonite Humic acid-immobilized amine Cationic dyes 8.0. 99.0% 2 2 – SEM [147]

(continued on next page)

400 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407

Table 4 (continued)

Sr. Clay Modification Dye pH Efficiency Equilibrium Kinetic TDSa Characterization Ref.
No. (adsorbents) study study

modified polyacrylamide/bentonite (Malachite Green

composite (MG), Methylene
Blue (MB) and Crystal
Violet (CV))
54 Bentonite Magnesium-oxide coated bentonite Crystal violet (CV+) 6.5 496 mg/g 1 2 – XRD [148]
(MCB)
−1
55 Clay minerals of – Congo Red 7 19.9 mg g by For kaolin 1, 2 1 SEM, XRD [149]
bentonite, kaolin Sodium Bentonite
and zeolite bentonite and zeolite
5.6 mg g−1 by by the 2 l
kaolin
4.3 mg g−1 by
zeolite
56 Montmorillonite – Methylene blue 11 292.15 mg g−1, 1 2 2 XRD [150]
97.38%.
57 Raw bentonite Manganese oxide-modified (MMB) Crystal violet (CV+) 11.0. 0.32 m mol/g for 1 2 – XRD [151]
(RB) bentonite RB
1.12 m mol/g for
MMB
58 Bentonite Humic acid immobilized Basic dyes (Malachite 8.0. 99.0% 2 2 – XRD, conducto [152]
polymer/bentonite composite Green, Methylene metric and
Blue and Crystal potentiometric
Violet) titrations
59 Bentonite Ca-bentonite Congo red 10 95.92% 2 2 1 – [153]
60 Kaolin – Crystal violet and 7 47.27 mg/g for 1 2 1 BET, XRD [154]
brilliant green Crystal violet
65.42 mg/g for
Brilliant green
61 Montmorillonite Sodium montmorillonite clay Rhodamine- B 7 42.19 mg/g 1 2 1 BET [155]
62 Montmorillonite Chitosan-g-poly(acrylic Methylene blue (MB) 6.5 1859 mg/g 1 2 – IR [156]
acid)/montmorillonite
(CTS-g-PAA/MMT) nanocomposites
63 Attapulgite clay Sonication-surfactant-modified Red MF-3B 1 81.96, 82.64, and 2 2 2 XRD, FTIR, surface [157]
attapulgite clay 85.47 mg/g at 30, area analysis.
50, and 70 °C
64 Spent activated Methylene blue 5.5 2.44 × 10–4 2 2. SEM [158]
clay (SAC) mol/g
65 Bentonite Intercalation of bentonite with a Reactive Yellow 2 – 64.1 mg/g 1 – – XRD, SEM [159]
layered double hydroxide, Mg–Al–Cl (RY2)
LDH
66 Bentonite – Malachite green 9 91% 1,2 and 6 – – UV–Vis [160]
spectrophotometer.
67 Montmorillonite Cr(III)-intercalated montmorillonite Supranol Yellow 4GL, 2.8 58.47 mg/g 1 2 1 XRD [161]
68 Bentonite Organobentonite (modified using Acid Red 151 3 357.14 mg g−1 1 2 – XRD and FT-IR [88]
cationic surfactants) for CDBA-bent
416.66 mg/g for
CP-bent
69 Natural – Acid red 57 – 1.35 × 105 mol 1 – – XRD [89]
mesoporous g−1
Sepiolite
70 Bentonite Dodecyltrimethylammonium Acid Blue 193 1.5 740.5 mg g−1for 2 2 1 EDX, XRD [162]
bromide-modified bentonite DTMA–bentonite
(DTMA–bentonite AND
Na–bentonite.
a
Kinetic Studies 1-Pseudo-first order Kinetic Model, 2-Pseudo-Second Order Kinetic Model. Equilibrium studies 1- Langmuir, 2-Freundlich, 3-Redlich-Peterson isotherm, 4-Fritz–
Schlunder (FS) model, 5-Toth model and 6-D–R adsorption isotherms. Thermodynamic studies (TDS) 1-Exothermic, 2-Endothermic.

that is capable of liquid trapping and give best suspending gelling and
thickening properties [77,78].
3.4. Montmorillonite/smectite
It is a very soft phyllosilicate mineral belongs to smectite. Montmo-
rillonite (a member of the smectite family) has 2:1 expanding crystal
lattice. The smectite group refers to a family of non-metallic clays pri-
marily composed of hydrated sodium calcium aluminium silicate, a
group of monoclinic clay-like minerals with general formula (Ca, Na,
H)(Al, Mg, Fe, Zn)2(Si, Al)4O10(OH)2·nH2O [78,90]. Chemically, it is hy-
drated sodium calcium aluminium magnesium silicate hydroxide (Na,
Ca)x(Al,Mg)2(Si4O10)(OH)2·nH2O. Potassium, iron and other cations
are common substitutes and the exact ratio of cations varies with source
[91]. The basic structural unit is a layer consisting of two inward-
pointing tetrahedral sheets with a central alumina octahedral sheet.
The layers are continuous in the length and width directions, but the
bonds between these layers are weak and have excellent cleavage,
allowing water and other molecules to enter between the layers causing
expansion in the highness direction. Isomorphous substitution gives the
various types of smectite and causes a net permanent charge balanced
by cations in such a manner that water may move between the sheets
of the crystal lattice, giving a reversible cation exchange and very plastic
properties [78,90].The smectite clay is a family of nonmetallic clays pri-
marily consisted of hydrated sodium calcium aluminium silicate, which
is a group of monoclinic clay like minerals, iron, potassium and other
 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407
cations are common substitutes and the exact ratio of these cationic
species varies with source. In these clays the main structural unit is a
layer composed of two inward pointing tetrahedral sheets with a cen-
tral alumina octahedral sheet [86]. Various types of smectite clays are
formed due to isomorphous substitution due to which a net charge is
balanced by cations. During this process water can move between
sheets, gives plastic properties and reversible cation exchange [5]. In
comparison with other clays, montmorillonite expand largely due to
penetration of water in the interlayer molecular space. This expansion
is due to the exchangeable cations. There are many uses of sodium
montmorillonite; it is a main constituent in non-explosive reagents for
rock splitting in natural stone quarries to limit the amount of waste [91].
4. Effect of modifications on adsorption capacity of dye
Clays are one of the most widely used low-cost adsorbent due to
high flexibility. Current studies have established that the adsorption ca-
pability can be improved by modification of adsorbents via physical,
thermal and chemical processes [92,93]. Clay can be modified with dif-
ferent materials like manganese Oxide [148], cationic surfactant
(hexadecyltrimenthylammonium chloride) [71] and gemini surfactants
[94] etc. to enhance the adsorption capacity and mechanical strength of
clay [91,95].
Compared to raw bentonite, efficiency of adsorption capacity of MB
with cold plasma was increased from 168 to 231 mg/g. The active spe-
cies such as high-energy electrons and reactive radicals generated in
the plasma can activate the upper molecular layers of the interface
[96]. From the results obtained it was observed that organoclay is 1.6
times effective than Na-bentonite for the removal of MB. This is due to
the fact that after modification, the surface area and its porosity also in-
creases. Increasing dose increases the partitioning of per gram of adsor-
bent, which leads to an increase in adsorption. As a result, more
adsorbate molecules can be bound to adsorbent surface through chem-
ical bonding [71].
According to Srinivasan [97], clay adsorption capacities are usually
dependent on the net charges, large pore sizes and surface area. Gener-
ally, clays have exchangeable ions that play crucial role in the environ-
ment by being natural pollutant scavengers by way of both cations
and anions take up through adsorption and ion exchange. Ions that
are usually found on surfaces of the clay include H+, K+, Na+, Ca2+,
−
Mg2+, NH+ 4 and Cl , SO4
2−
, PO4 3−, and NO−3 . Cation exchange readily
without affecting the clay mineral's structure [98]. Clay minerals display
a strong attraction to cationic and anionic dyes [99]. Nevertheless, the
adsorption capability for basic dyes (cationic dyes) is comparable
greater than that of acid dyes (anionc dyes). But this generalization is
not always the case, because different physico-chemical variables like
pH, temperature, pulp density, point to zero charge etc., also effect sig-
nificantly on sorption capacity of clays [100,101]. The objective of the
present review were; to investigate the effect of modification to evalu-
ate the adsorption efficiency of adsorbent for the removal of dye from
aqueous solution, to examine the effect of contact time, initial dye con-
centration, pH and temperature on the adsorption process, to determine
the fitting of adsorption kinetics and isotherm data with various models,
to calculate the thermodynamic parameters and to understand the in-
teractions between adsorbent and dye molecule.
5. Effect of pH
Solution pH plays an important role in the sorption process. It ap-
pears to interrupt the solution chemistry of dyes and functional groups
of the adsorbents. Adsorption capacity of dye depends on pH of the so-
lution [163]. Usually, at low pH the percentage of anionic dye removal
from solution increases due to electrostatic attraction between the pos-
itive surface charge of adsorbent and anionic dye. There is an electro-
static attraction between the negatively charged adsorbent and
positively charged dye molecule when solution has high pH (basic),
401
causing decrease in the percentage removal of anionic dye
[58,59,63,164]. Whereas, when solution has high pH the adsorption ca-
pacity and removal of cationic dyes will increase because positive
charges on the dye ensured that they are attracted by anionic adsorbent
so there are electrostatic attractions between positive charges of dye
and negative surface of adsorbent [64,65,165,166].
It is revealed that the pH of solution is optimized for maximum ad-
sorption of dyes (Table 4). The previously reported literature indicates
that optimized pH depends upon nature of dye, type of clay used and
modification of the clay. Sharma et al. [167] investigated the effect of
pH on the removal of methyl green, a cationic dye and methyl blue, an
anionic dye, from aqueous system onto the montmorillonite clay. It
was observed that the adsorption capacity of methyl green onto the
clay was increased and that of methyl blue onto the clay was decreased
with increase of initial pH of the suspension. At low pH, there was abun-
dance of H+ ions on the clay–water suspension, imparting a repulsive
force toward the positively charged methyl green dye molecule. As
the pH increased the amount of OH– ions was also increased. As a con-
sequence, the amount of negative charge on the suspension also in-
creased; facilitating the adsorption of the methyl green dye molecule
onto the montmorillonite clay. While the adsorption of anionic methyl
blue dye molecule was more at low pH due to the high abundance of
positive charge in the suspension [103]. The influence of pH on the ad-
sorption capacity of the adsorbent was monitored in dye solutions of
initial pH values varying from 2.0 to 9.25. The results showed that the
maximum adsorption capacity was observed at around pH 6 for AYDS
and 7.3 for AYD, it was due to the fact that acid activation increases
the number of sites responsible for dye adsorption and at any pH; the
amount of dye adsorbed per unit mass (qe) of acid-activated clay had
a higher adsorption capacity compared to the non-activated clay.
Under the experimental conditions, acid-activated clay could remove
as much as 89.90%, while the untreated clay could remove 84.67%
(pH 6.0) [144].
6. Kinetics studies
The adsorption kinetics is a significant factor for scheming adsorp-
tion process and is essential for choosing the optimum operating condi-
tions for adsorbent-adsorbate interaction [117]. In order to comprehend
the behavior of the adsorbent and to investigate the controlling mecha-
nism of the adsorption procedure, the pseudo first-order, pseudo sec-
ond order and intraparticle diffusion models are useful to check the
kinetic information [127], i.e., Zhou et al. [105] fitted the experimental
data to pseudo-first-order and pseudo second- order kinetic models in
order to investigate the mechanism of adsorption for the adsorptive re-
moval of MB by using amino-functionalized attapulgite clay nanoparti-
cle as adsorbent. Correlation coefficients of the pseudo second-order
kinetic model was relatively greater than that of the pseudo first-
order kinetic model, implying that the MB adsorption can be described
more appropriately by the pseudo-second-order model. It may be ex-
plained by the reason that a large number of vacant surface sites were
available for adsorption during initial stage. Though, with an interval
of adsorption time, the remaining vacant surface sites were difficult to
be occupied due to steric hindrance between MB dye adsorbed on the
surface of ATP@CCS and solution phase. Based on the assumption of
the pseudo-second-order model it can be concluded that the adsorption
of MB onto ATP@CCS was chemical adsorption [105]. Hernández-
Hernández et al. [168] applied three models i.e. pseudo-first-order
model, second-order model (Elovich) and pseudo-second-order model
to determine the adsorption mechanism brilliant blue FCF dye by natu-
ral clay and modified with iron chloride. The best adjustment was found
with the pseudo-second-order model. For unmodified clay, the sorption
constant of Lagergren was higher at 20 and 30 °C and then decreased.
For the iron-modified clay, the adsorption capacities were 1.0 mg/g at
the different temperatures and the pseudo-second-order rate constant
increased as the temperature increased [121]. The results of kinetic
402 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407

Table 5
FT-IR analysis of modified and raw clay used for the adsorption of dyes.

Clay (adsorbents) Raw Modified Reference

Functional group Peaks Functional group Peaks

Bentonite Al\
\Al\
\OH, Si\
\O 918 cm−1, 1100–950 \
\OH deformation band of water to observe raw 1600 cm−1 [96]
cm−1 regions and modified bentonite
Raw clay Al\\Al\\OH– stretching and bending 3694 and 917 cm−1 – – [15]
Bentonite Stretching vibrations bands of Si\
\O\ \MVI 400–550 cm−1 Aromatic C\\H bonds of bis-imidazolium 3035 cm−1 [107]
(M¼Al, Mg, and Fe) molecule
Sharing of the OH group between Fe and Al 913 cm−1 Stretching vibrations of aromatic ring double 1450 and
in octahedral sheets bond 1600 cm−1
Montmorillonite clay Al\\O\\Si deformation 527 cm−1 – – [103]
Si\
\O\ \Si deformation 467 cm−1
Natural bentonite (GZ Weak band of Fe-Ben can be ascribed to 1384 cm−1 – – [134]
Ben) and Fe-Ben the stretching of NO3−.
−1
Halloysite nanotubes \OH
Stretching vibrations of inner-surface\ 3701 and 3626 cm – – [142]
Stretching mode of apical Si\\O 1105 cm−1
Bentonite – – \
\CH3,\
\CH2 for modified bentonite 2921 and [88]
2854 cm−1
Ammonium ion 1469 cm−1
Attapulgite clay Asymmetric stretching modes of Si\\O\\S 1031 cm−1 Asymmetric stretching modes of S\\O\\S for 1032 cm−1 [157]
for attapulgite clay organoclay
−1 −1
OH bending band 985 cm OH bending band 991 cm
C\\N vibrations in quaternary amines absent C\
\N vibrations in quaternary amines 1402 and
1466 cm−1

studies reviewed research articles (Table 4) shows that pseudo-second
order kinetic model is more fitted to the experimental data as compared
to other models, however; depending upon the reaction other kinetic
models also show correlation to the data.
Literature (Table 4) revealed that pseudo second order model is
mostly found but in some papers pseudo first order is also observe
[107] and based on present study, it is suggested that adsorption of tex-
tile dyes was quite rapid initially, the rate of adsorption became slower
with the time and reached a constant value (equilibrium time). The ini-
tial faster rate may be due to the availability of the uncovered surface
area of various sorbents. The intra-particle diffusion model proposed
the involvement of diffusion mechanism. According to this theory, the
adsorbate uptake qt varies almost proportionally with the square root
of the contact time, t½ rather than t.
7. Equilibrium studies
Equilibrium data, generally known as sorption isotherms are ele-
mentary necessity to comprehend the mechanism of the sorption. Ad-
sorption isotherms are used to describe the sorption procedure and
for assessing sorption capability. Adsorption isotherm can be describes
as the equilibrium correlation between the concentration in the adsor-
bent phase on the adsorbent elements and the concentration in the liq-
uid phase at a certain temperature [92]. In order to describe the
adsorption of dye onto the clay, the experimental data is examined by
adsorption isotherms at specific temperature as equilibrium concentra-
tions are temperature dependent. A number of isotherms are used like
Freundlich, Langmuir, Dubinin-Radushkevich, Redlich-Paterson, Halsey
and Sips. Different characteristics of adsorption process are described by
each equilibrium model, but most suitable methods are Langmuir and
Freundlich [163]. A number of linear forms of these isotherms having
different axis have been used. Linear analysis is not so much precise
and reliable. Nonlinear statistical functions are more effective and pre-
cise than linear analysis in such conditions. In recent years, a developing
interest in the utilization of non-linear optimization modeling has been
noted as reported in recent literature of dyes adsorption [169].
Bentahar et al. [170] removed congo red by using clay minerals of
bentonite, kaolin and zeolite. The Freundlich and Langmuir models
were applied to the experimental data. The results indicate that zeolite
and bentonite were best described by the Freundlich model (R2 = 0.90,
0.97) however Langmuir model provided a better fit on the experimen-
tal data of kaolin with high R2 value (R2 = 0.98). The experimental data
followed Freundlich adsorption isotherm for zeolite and bentonite
shows that the adsorption occurs on a heterogeneous surface, due to
the presence of various active sites on sodium bentonite and zeolite
having different attractions to CR molecules. The complete adsorptive
process is dominated as a physical adsorption procedure. Kaolin may
be described at the molecular level by the applicability of single layer
treatment of dye molecules on the surface. There is very slight or no
substitution taking place between layers. So, it is a fact that kaolinite
crystal is balanced due to the structure charge of kaolin. The surface
where adsorption of kaolinite occurs, only equates the exterior surface
area and the edge surface area. It can be seen that the adsorption with
bentonite can take place between interlayer spaces, in contrast. Adsorp-
tion isotherm is probably depended on the affinity and surface proper-
ties of the adsorbent [149]. In the present review, the equilibrium study
of available literature of dyes adsorption proves that Langmuir is better
as compared to Freundlich isotherm in prediction of textile dyes

Table 6
Scanning electron microscopic (SEM) analysis of modified and raw clay used for the adsorption of dyes.

Clay (adsorbents) Raw structure Particle Modified structure Particle References

size size

Bentonite Regular layered structure of bentonite 1 μm The small flakes of LDH nanoparticles seem to be 1 μm [159]
bound onto the bentonite surface
Spent activated clay (SAC) Irregular in shape and porous 6 μm – – [158]
Untreated clay Rough and porous structure of the clay 5 μm – – [138]
Montmorillonite/CoFe2O4 composite It shows an aggregated morphology with the 1 μm Magnetic nanoparticles slightly Modified the flaky 2 μm [136]
with magnetic separation irregular plate-like shapes structure of MMT clay.
Natural bentonite Smooth due to closely packed flakes 10 μm Ragged appearance of the TA bentonite 10 μm [92]
Clay surface more porous for ATA 10 μm
 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407 403

Table 7
Thermogravimetric (TGA) analysis of modified and raw clay used for the adsorption of dyes.

Clay (adsorbents) Raw Modified Reference

Weight loss at Reason Weight loss at temperature Reason

temperature

Montmorillonite 150 °C Due to evaporation of – – [103]

clay water,
670 °C Due to loss of structural
hydroxyl groups
Bis-imidazolium 9.5% weight-loss at the Due to the 245 90% weight loss at the temperature range It is related to the thermal decomposition [107]
modified temperature range of evaporation of the of 350–400 °C for bis-imidazolium cations of the products
bentonite 30–200 °C for organo-Bt desorbed water
molecules
Polymer-clay – – Weight loss of 70.3% at 550 °C. Weight loss started at 505 °C, it may be [116]
composite [P due to the introduction of kaolinite to
(AAm-AA)-Kao] polymer network results in an increase in
thermal stability
Montmorillonite Weight loss of Mt. at Due to dehydration of SB12 completely decomposed at about 350 – [118]
600–700 °C. the structural OH units °C.
of Mt
Weight loss of Mt-SB12 at 350–500 °C Due to the decomposition of dodecyl
sulfobetaine surfactant on Mt
Alginate – – Mass loss at 800 °C was respectively 40%, – [139]
encapsulated 50% and 70% for Al-Mont-EnPILC,
pillared clays CTAB-Al-Mont-PILC and alginate.

adsorption processes. Langmuir adsorption qm is an important Langmuir
constant, representing the maximum capacity at equilibrium. The KL
values of refers to the different in binding strength and capacity of the
dyes with the surface of sorbents in general values of KL decreased
with the rise of temperature [3,94,96,102,104,105,108,117,118] etc.
However, freundlich model did not provide any information about the
saturation adsorption capacity; however the parameters of KF and 1/n
exhibited intense change at higher temperatures. The values of 1/n
(0.1 b 1/n b 1) indicated favorable adsorption of dyes at experimental
conditions [72,92,107,116,124].
8. Thermodynamic studies
Textile industries discharge their wastes at moderately high temper-
atures; therefore, temperature can be a significant parameter in dye re-
moval process. Thermodynamic study of the adsorption process is
helpful in establishing the nature and possibility of reaction. Different
thermodynamic factors which comprise standard enthalpy change
(ΔH°), standard entropy change (ΔS°) and standard Gibbs free energy
change (ΔG°) of adsorption can be calculated from temperature and
sorption procedure [163]. A thermodynamic study of dye adsorption
onto clay shows endothermic and exothermic nature in reported litera-
ture. Ozturk and Malkoc [117] conducted experiments to check out the
effect of temperature on the removal of BY2 by adsorbing it on natural
untreated clay (NUC), at different temperatures 25, 35 and 45 °C. The re-
sults showed that by increasing the temperature of the adsorption pro-
cess there was a decrease in adsorption efficiency and adsorption
capacity, indicating that the process was exothermic. When the temper-
ature of the process was raised, thermal energy of adsorption system
was also increased, by increasing the mobility of the adsorbate causing
desorption, as a result, there was decrease in adsorption capacity. The
values of ΔG° at all studied temperatures showed that the process was
spontaneous [117]. Fan et al. [118] investigated the effect of tempera-
ture on the removal of MB and Cu2+ onto Mt-SB12. The thermodynamic
features provided in-depth information about the energetic changes re-
lated to adsorption process. ΔG° values at different temperatures were
negative and ΔH° values were positive, indicating that the adsorption
process was spontaneous and endothermic. The positive values of ΔS°
reflected an increase in randomness at the solid/solution interface dur-
ing the adsorption of MB and Cu2+ onto Mt-SB12 [118].
In order to evaluate the feasibility and the effect of temperature bet-
ter, for MO adsorption onto activated clay, the thermodynamic parame-
ters such as standard free energy change (ΔG°), standard enthalpy
change (ΔH°), and standard entropy change (ΔS°) were also studied.
The negative value of ΔG° at different temperature indicated the spon-
taneous nature of MO adsorption onto activated clay, and the absolute
term of ΔG° revealed that the adsorption trend decreases with the in-
crease in temperature, which was consistent with the result that the ad-
sorption lessens with increasing in temperature. Enthalpy change (ΔH°
= −12.289 kJ mol−1) was negative, and it was implied that adsorption
process for MO was exothermic [120]. Summary of the thermodynamic
studies shows that the sorption process may be exothermic or endo-
thermic for dyes absorption on to clays.
9. Characterization studies
There are a number of techniques which have been used to describe
the adsorbent and characterization study helps to understand adsorp-
tion process. Different techniques like XRD, FT-IR, SEM, TGA, BET
(Tables 5–9) [171–177] and TEM. FT-IR have been used for

Table 8
Bruner Emmer and Teller (BET) analysis of modified and raw clay used for the adsorption of dyes.

Clay (adsorbents) Surface area Pore volume/pore size References

Raw Modified

Vermiculite 7.8 m2·g − 1 for vermiculite 9.8 m2·g − 1 for expanded vermiculite 0.0043 cm3·g−1 with mesoporous character [72]
Bentonite 64.2 m2/g for raw 65.3 m2/g for cold plasma treated bentonite 0.0923 cm3/g for raw [96]
0.0929 cm3/g for cold plasma treated bentonite
Natural clay 20 m2/g – – [15]
Montmorillonite clay 249 m2/g – 38.34 nm [103]
Bentonite 75.5 m2/g untreated clay 99.6 m2/g iron-modified clay – [121]
404 A. Kausar et al. / Journal of Molecular Liquids 256 (2018) 395–407
Table 9
X-Ray diffraction (XRD) analysis of modified and raw clay used for the adsorption of dyes.
Clay (adsorbents) Chemical composition
Raw
Vermiculite Si4+, Mg2+, Al3+, Fe3+ and K+
Raw clay Halloysite (H) (61%) and kaolinite (K) (39%)
Montmorillonite Illite–montmorillonite-type structure
Natural untreated clay 2Ө = 27.9°, 29.4°,40.5°, 43.2°, 47.5°, 48.6°and 57.3°
Halloysite nanotubes Dehydrated halloysite
Al2Si2O5(OH)4
characterization and clay adsorbents. FT-IR gives information about the
presence of functional group in the adsorbent. This technique also
shows difference in functional group before and after treatment. There
are some functional groups which are common in different clays. For
an instance, Si\\O functional in montmorillonite clay [103], Fe3O4/acti-
vated montmorillonite nanocomposite [102], bentonite clay [96], smec-
tite raw and modified [135] and HNTs [142] have been observed
commonly. Adsorption peak of Si\\O for following clays appears at
1057 and 792 cm−1 for montmorillonite clay, 1030, 791 and 528 cm−
1
for Fe3O4/activated montmorillonite nanocomposite, 1100–950 cm−
1
for bentonite clay, 900 cm−1for raw and modified Smectite and
1105 cm−1 for HNTs [96,167,178,179]. Similarly, Al\\Al\\OH functional
group is common in Tunisian raw and bentonite clay and its adsorption
peak appears at 3694 cm−1 and 918 cm−1 [15,96]. Table 5 presents the
most prominent adsorption peaks for different functional groups for
clays involved in adsorption process. SEM analysis is used for the evalu-
ation of structural ordering determination, morphologies (surface) and
cracks, cavities and fine particles attached to the surface of adsorbent,
the SEM analysis revealed a significant difference before and after treat-
ment of clays. It was revealed that a significant changes have been oc-
curred on the clay surface after adsorption of dyes [149]. Similarly,
TGA gives information about the weight loss of adsorbent on specific
temperatures and their stability at specific temperatures. In TGA analy-
sis, a sample at specific rate is heated and the change in mass as a func-
tion of temperature and time are measured. From TGA, it was observed
that the difference in weight loss between raw and modified clay before
and after treatment was also changed significantly [125]. The average
pore size and specific surface area of the adsorbent can be analyzed by
BET technique. According to the definition stated by the International
Union of Pure and Applied Chemistry (IUPAC), adsorbent pores are cat-
egorized into three groups: (1) micropores (diameter b 2 nm),
(2) mesopores (2–50 nm), and (3) macropores (N50 nm) [117]. Based
on pore size, the nature of clay can be estimated. Studies performed
using montmorillonite, it was observed that clay has mesopores since
pore size was 38.34 nm [103]. Surface area of clay may change after
modification; an increase in surface area indicates the adsorption capac-
ity of clay enhanced and vice versa. XRD is used for determination of
chemical composition of adsorbent before and after adsorption, also
changes in the structure of adsorbent can be predicted [71]. For an in-
stance, the results of XRD analysis for expanded vermiculite showed
that sample contained primarily vermiculite and minor amounts of
mica, illite and hydrobiotite [72].
10. Conclusions
The clays (raw and modified) are low-cost sorbents, which have
been successfully used for the adsorption of dyes from wastewater
since last three decades on laboratory scale. Attempts have not been
made to use clay as sorbent in scale-up process specially using real efflu-
ents. The performance of different types of clays (raw and modified)
was compared for the adsorption of dyes belong to different classes
based on experimental conditions including pH, temperature, particle
size and initial dye concentration. Modified clays offered more effi-
ciency for the adsorption of dyes. The techniques FTIR, XRD, SEM and
Reference
Modified
Si4+, Mg2+, Al3+, Fe3+ and K+ [72]
– [15]
– [103]
– [117]
– [142]
BET have been used for the characterization of clays before and after
the adsorption of dyes, however, most of the studies lack information
about the complete characterization of clays used as an adsorbent,
which needs to be investigated in future studies. Also, the clay-based re-
actors should be designed and the working conditions should be opti-
mized for process scale up. Future studies should be performed in
order to study the real effluent treatment possibility, reusability and
cost of clay-based adsorbents.
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