Applied Clay Science 173 (2019) 46–64

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Applied Clay Science

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

Research Paper

Efficient and selective removal of cationic organic dyes from their aqueous T
solutions by a nanocomposite hydrogel, katira gum-cl-poly(acrylic acid-co-N,
N-dimethylacrylamide)@bentonite
⁎
Subinoy Jana, Jagabandhu Ray, Barun Mondal, Tridib Tripathy
Postgraduate Division of Chemistry, Midnapore College (Autonomous), Midnapore, Paschim Medinipur 721101, West Bengal, India

A R T I C LE I N FO A B S T R A C T

Keywords: A pH sensitive nanocomposite (NC) hydrogel based on katira gum-cl-poly(acrylic acid-co-N, N-dimethylacryla-
Nanocomposite hydrogel mide) incorporated bentonite (BT) nano clay (KG-cl-poly(AA-co-DMA)@BT abbreviated as KGNCH) is prepared
Katira gum by in-situ crosslinked co-polymerization technique using N, N′-methylene-bis-acrylamide (MBA) as crosslinker
Acrylic acid and potassium peroxodisulphate (KPS) as a free radical initiator. Various nanocomposite hydrogels (KGNCH-1 to
N, N-dimethylacrylamide
KGNCH-4) are prepared by varying weight percentage of bentonite clay. The best one is selected (KGNCH-3)
Cationic dyes
with respect to their highest swelling percentage in aqueous medium. The prepared KGNCH-3 is characterized by
Adsorption
the FTIR, FESEM, XRD and EDS analysis and is used for the removal of cationic dyes [Methylene blue (MB),
Crystal violet (CV) and Auramine-O (AO)] from their aqueous solutions. The adsorption of cationic dyes onto the
KGNCH-3 is found to be pH dependent, the adsorption isotherm and kinetic data are best fitted with the
Freundlich isotherm and pseudo second order kinetic model respectively and maximum adsorption capacity
(qmax) is found to be at pH = 8.0 for MB, pH = 7.5 for CV and pH = 10 for AO. Calculation of different ther-
modynamic parameters shows the spontaneous and endothermic nature of the adsorption. The KGNCH-3 also
exhibits excellent regeneration capacity at different pH using five cycle of adsorption-desorption studies. From
the selectivity study the order of adsorption capacity of the KGNCH-3 is found to be MB > CV > AO.

1. Introduction
Synthetic dyes are used in several industries like art, textiles, lea-
ther, plastics, printing and personal care products (e.g. hair dyes) (Zhou
et al., 2018) for increasing brightness and attractiveness of their pro-
ducts (Gupta et al., 2006). But such dyes are toxic in nature and create
severe water pollution when discharged as waste products from the
industries into the environment. The most synthetic organic dyes are
carcinogenic and mutagenic in nature which shows adverse effects on
human health and marine organisms (Crini, 2006). Dyes can also cause
allergic dermatitis and skin irritation (Saka et al., 2012). Due to their
higher solubility in water and complex aromatic molecular structures
(Saka and Sahin, 2011), which make dyes are non-biodegradable and
resistant to aerobic oxidation (Crini, 2006).
The basic functionalities present in the coloured organic dyes are
chromophoric (–NR2, –NHR, –NH2, –COOH, –OH) and auxochromic
groups (eN2, –NO and –NO2) (Gupta, 2009). Various type of dyes are
used for the dying purpose including acid dyes (anionic), basic dyes
(cationic), direct dyes, dispersed dyes, reactive dyes, vat dyes (non-
ionic) etc. (Salleh et al., 2011). Among the various dyes, basic dyes are
used in paper, tannin mordant cotton, silk and wool industries (Salleh
et al., 2011). Such basic dyes are soluble in water and formed cations
hence are called cationic (Bouatay et al., 2016). Common examples of
cationic dyes are malachite green, basic yellow 28, crystal violet, me-
thylene blue and auramine-O etc.
MB is a heterocyclic aromatic dye, deep blue in colour with broad
application in various industries like leather, plastics, cosmetics, and
used as strainers in medicinal surgery (Levin et al., 2004; Patel, 2006).
MB causes retching, stun, cyanosis and tissue necrosis in human body
when comes into contact with the human skin (Kumar et al., 2005).
CV is a triarylmethane cationic dye widely used for purple col-
ouration in textile industries for dying cotton, temporary hair colorant
and wools (Li, 2010). It is also used in medical purpose as a biological
strain and is active ingredient in gram stain. CV is bacteiostatic agent
for animal and veterinary medicine and is also used as dermatological
agent for human (Puri and Sumana, 2018). It causes some harmful ef-
fects to the human body such as eye and skin irritation, increase heart
beat, cyanosis, and also lead to respiratory and kidney failures at

⁎
Corresponding author.
E-mail address: tridib.tripathy@midnaporecollege.ac.in (T. Tripathy).

https://doi.org/10.1016/j.clay.2019.03.009
Received 15 October 2018; Received in revised form 3 March 2019; Accepted 5 March 2019
0169-1317/ © 2019 Elsevier B.V. All rights reserved.
S. Jana, et al.
extreme degree (Li, 2010).
Auramine-O (AO) is bis [4-(dimethylamino) phenyl] methanimi-
nium chloride, a cationic dye, used in paper, textile leather industries
for colouring the products (Martelli et al., 1998). It is used as an anti-
septic and fungicide in medical community. Internal Agency for Re-
search on Cancer (IARC) exhibits sufficient evidence of the carcino-
genicity effect of AO dye due to its bio-transformation to reactive
species in target organs of both rats and humans (Asfaram et al., 2015a,
2015b).
Therefore, it is necessary to remove these dyes from industrial ef-
fluents and wastewater before their release into the environment.
Several treatment techniques, such as flocculation/coagulation (Allegre
et al., 2004), Activated carbon (Baytar et al., 2018) membrane se-
paration (Miao et al., 2012), chemical precipitation (An et al., 2014),
electrochemical process (Körbahti et al., 2011) and adsorption are used
to remove different dyes from the wastewater (Kyzas et al., 2010). Most
of these techniques are should be expansive, high operational cost and
less selectivity. Among the aforementioned treatment processes, ad-
sorption is one of the most useful methods because of its cost effec-
tiveness, simplicity of operational design, higher efficiency, and re-
cyclability of the adsorbents (Saha et al., 2010).
In recent years, hydrogels based on polysaccharides are used as
adsorbents for the removal of dyes from aqueous solution (Jana et al.,
2017). Hydrogels are three dimensional crosslinked hydrophilic poly-
meric networks, absorb water due to the presence of hydrophilic
functional groups like amino, hydroxyl, carboxylic and sulfonic acid but
are insoluble by the application of physiological conditions such as
temperature, pH and ionic strength of the water. Because of some
specific properties of hydrogels, they are widely used in drug delivery,
waste water treatment, tissue engineering and manufacturing of beauty
care products (Hinkley et al., 2004; Mahkam, 2005; Zhang et al., 2005).
Lots of researches are carried out using hydrogel as an adsorbent for
remove pollutants from wastewater due to their high adsorption limit,
low toxicity and regeneration capacities. Recently special attention is
given to the nanocomposite hydrogels used as adsorbents for the ad-
sorption of toxic substances from the water medium. The incorporation
of inorganic filler into the hydrogel polymer matrix not only increases
the strength but also increase the stiffness of the hydrogels (Ghorai
et al., 2012). Among the inorganic compounds, mineral clays are used
for the nanocomposite hydrogel preparation because of their smaller
size, large surface capacities, swelling and cation exchange properties
(Yang et al., 2018). Inclusions of nano-clay into the crosslinked hy-
drogel not only increase strength (Mittal and Mishra, 2014) but also
increase the rate of their adsorption capacities (Yadav and Rhee, 2012).
Nanocomposite hydrogel containing clay such as montmorillonite
(MMT) (Lee and Yang, 2004), kaoline (Wan et al., 2006), attapulgite
(Chen and Wang, 2009), laponite (Li et al., 2009), bentonite (Tao et al.,
2006) are synthesized and used as the dye and metal adsorbents from
the aqueous solutions.
Bentonite clay (BT) is aluminium phyllosilicates containing reactive
–OH groups and high cation exchange capacity and surface area (Sahin
et al., 2015). It possesses some special properties such as large specific
surface area, swelling, stiffness, specific active sites which enhance
adsorbing capacity of cationic, anionic and organic pollutant (Yavuz
and Saka, 2013; Chinoune et al., 2016). Katira gum (KG) is a branched
acidic naturally occurring polysaccharide obtained from Co-
chlospermanrelogiosum tree. The main constituents of KG are L-rham-
nose, D-galactose and D-galacturonic acid and the main chain of the
structure of KG is (1→4)-α-D-Galp-(1→4)-α-L-Rahp. The side chain is
made by β-Galactose and β-Raphinose residues which are (1→2) linked
alternatively at every α-L-Rahp and α-D-Galp residue. The structure of
katira gum is given in our previous communication (Jana et al., 2018a).
In the present investigation, a novel pH sensitive NC hydrogel is
prepared based on KG with a mixture of acrylic acid, N, N dimethyla-
crylamide (DMA) and BT clay by using in-situ crosslinked copolymer-
ization technique in the presence of MBA as the crosslinking agent
47
Applied Clay Science 173 (2019) 46–64
which to be used as an efficient and selective dye adsorber from the
mixture of ternary cationic dyes (MB, CV, and AO) from their aqueous
solution. A comparative study will also be made between the hydrogel
with bentonite nano clay and without the clay to see whether the dye
adsorbing property will be enhanced when bentonite nano clay will be
incorporated into the hydrogel matrix. To the best of our knowledge the
removal of cationic dyes by such type of nano composite hydrogel is not
reported so far. The swelling behaviour in water medium is also studied
at different pHs. The aim of this work is to synthesize KGNCH and to
investigate their swelling behaviours under different solution pH in
water. The impact of different parameters affecting the adsorption of
dyes such as contact time, pH, temperature, adsorbent's dosage and
initial dye concentration are studied. Adsorption kinetics, isotherms,
and different thermodynamic parameters are conducted. Furthermore,
comparison of different KGNCHs and their preferential order of dye
adsorption are also evaluated. The regeneration of the KGNCH is ex-
amined by adsorption-desorption studies.
2. Experimental
2.1. Chemicals
Katira gum (KG) is purchased from local market of Midnapore, West
Bengal, India. N, N′-methylene-bis-acrylamide (MBA) is obtained from
SRL, Mumbai, India. N, N-dimethylacrylamide (DMA) is purchased
from the Sigma Aldrich Chemical Co. St. Louis, USA and acrylic acid
(AA) is obtained from Himedia Laboratory, Mumbai, India. Potassium
peroxodisulphate (KPS, K2S2O8), sodium hydroxide (NaOH), hydro-
chloric acid (HCl) and acetone (CH3COCH3) are supplied by E. Merck,
Mumbai, India and used as are obtained. Bentonite clay (BT), MB, CV
and AO are obtained from Loba Chemie, Mumbai, India. Double dis-
tilled water is used for all the experiments.
2.2. Synthesis of katira gum-cl-poly(acrylic acid-co-N, N-
dimethylacrylamide) hydrogel [KG-cl-poly (AA-co-DMA)]
The KG-cl-poly(AA-co-DMA) is synthesized by using KPS as a radical
initiator and MBA as a crosslinking agent by free radical co-poly-
merization method. A typical synthetic procedure is as follows; 1 g KG
is dispersed in distilled water and stirred at 300 rpm at 70 °C in a
250 mL conical flask. After 30 min 5.8 × 10−2 mol acrylic acid and
4.8 × 10−2 mol DMA is added to the above mixture and stirred vigor-
ously after adding 6.48 × 10−4 mol of MBA into the reaction mixture.
Then N2 gas is purged through the mixture in order to remove dissolved
oxygen. Under this condition, 3.69 × 10−5 mol of KPS is added to the
reaction mixture and stirred for 3 h at 70 °C until gel like solution is
formed. After the specific time period, the heating is stopped and the
mixture is allowed to keep at room temperature for 24 h to complete the
polymerization reaction. The gel is precipitated out with excess quan-
tity of acetone and washed thoroughly with ethanol for several times.
The product is dried in a hot air oven at 55 °C. Various crosslinked
hydrogels (KGH-1 to KGH-4) is prepared by varying the amount of AM
and DMA by the similar method. The best one (KGH-3) is identified
with respect to the swelling behaviour of the prepared hydrogel, which
is used for further study. The synthetic details are shown in the Table 1.
2.3. Synthesis of katira gum-cl-poly(acrylic acid-co-N, N-
dimethylacrylamide)/Bentonite NC hydrogel [KGNCH]
A typical procedure for the preparation of KGNCH is as follows; BT
(1 g) is added in the 100 mL of double-distilled water and the mixture is
sonicated using digital ultrasonic cleaner (LABMAN, 40 ± 3 KHz,
India) for 30 min to obtain homogeneous dispersion of bentonite. After
sonication, 1 g of KG is added into the reaction mixture and stirred
vigorously by the magnetic stirrer at 300 rpm followed by the addition
of required amounts of AA, DMA and MBA. Afterwards, N2 gas is
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

Table 1
Synthetic details of various KGH and KGNCH.
KG (g) AA (mol × 10−2) DMA (mol × 10−2) MBA (mol × 10−4) K2 S 2 O8 (mol × 10−5) BT (g) Swelling (%)

(a) Hydrogels
KGH-1 1 5.8 4.8 6.48 3.69 – 452
KGH-2 1 5.8 3.8 6.48 3.69 – 704
KGH-3 1 7.2 3.8 6.48 3.69 – 912
KGH-4 1 7.2 4.8 6.48 3.69 – 864

(b) NC hydrogels
KGNCH-1 1 7.2 3.8 6.48 3.69 0.5 589
KGNCH-2 1 7.2 3.8 6.48 3.69 7.2 780
KGNCH-3 1 7.2 3.8 6.48 3.69 1.5 1130
KGNCH-4 1 7.2 3.8 6.48 3.69 2.0 1014

Hydrogels with maximum swelling are highlighted.

purged through the reaction mixture for next 30 min. Prescribed
amount of KPS is added to the reaction when temperature of the mix-
ture is raised to 80 °C. The reaction is allowed to continue for 3 h at the
same temperature and stirring speed. After completion, heating is
stopped and the product is kept at room temperature (30 °C) for 12 h.
The gel is precipitated using excess acetone. After precipitation, the gel
is washed with mixture of methanol and water (5:1 v/v) in order to
remove homopolymer and unreacted monomer. The KGNCH is dried in
a hot-air oven at 50 °C for 24 h. Different grades of nanocomposite
hydrogel are prepared by varying the amount of BT and is referred to as
KGNCH-1, KGNCH-2, KGNCH-3 and KGNCH-4. The synthetic details
are shown in the Table 1.
2.4. Swelling studies
2.7. Characterization of the KGNCH-3
The chemical structure of KG, BT, AA, DMA, KGH-3, KGNCH-3, and
MB dye loaded KGNCH-3 is analyzed by FTIR spectroscopy using Perkin
Elmer (L16000300 Spectrum Two LiTa, Llantnsant, UK) using KBr
pellet method. X-ray Diffraction (XRD) pattern of KG, BT, KGH-3,
KGNCH-3, MB dye loaded KGNCH-3 and after desorption of MB dye are
performed in an X-ray Diffractometer (Rigaku, Japan), using CuKα
(λ = 1.54 Ǻ) radiation. The surface morphology of the KG, BT, AA,
DMA, KGH-3, KGNCH-3, and MB dye loaded KGNCH-3 are obtained by
a field emission scanning electron microscopy (FESEM) using a Cam
Scan Series (Cambridge Scanning Company, UK). Energy dispersive X-
ray spectroscopy (EDS) analysis of KGNCH-3 is also performed.

Swelling is an important parameter of the hydrogels and most of
their applications depend upon their swelling behaviour. The swelling
experiment of the all the prepared KGNC hydrogels is carried out using
excess double distilled water. The typical experimental procedure is as
follows; accurately weighted 0.3 g of each KGNCH is immersed in
100 mL double distilled water separately at room temperature (30 °C).
After regular time interval (1 h), the hydrogel is taken out from the
water medium and excess surface water is removed gently by using the
tissue paper and weighted again. The experiment is continued until
maximum swelling is reached. After weighing the swollen hydrogel, the
percentage swelling (PS) is calculated by using Eq. (1) (Ali et al., 2006)
We − Wo
%swelling (PS) = × 100
Wo
Percentage swelling is calculated as per gram of water absorbed per
gram of hydrogel (g g−1). Where We and Wo are the weight of the gel
after and before swelling respectively. The hydrogel which has highest
% swelling in water is indentified (KGNCH-3) and used for further in-
vestigations. The experiment is repeated for two times.
2.5. Water retention
The swollen gel (We) which is equilibrated in water is kept at room
temperature (30 °C) for 48 h. After that, its weight is measured and
marked as (Wd). The percentage of water retention is calculated by Eq.
(2) (Bao et al., 2011).
wd
%water retaintion = X 100
we
2.6. Swelling behaviour of KGNCH-3 at various solution pHs
The effect of pH on the equilibrium water uptake behaviour of
KGNCH-3 is studied in different pHs ranges from 2 to 14. The pH is
adjusted by adding 0.1 (M) HCl and 0.1 (M) NaOH as is required.
2.8. Determination of point of zero charge (PZC) of the KGNCH-3
The surface charge of the KGNCH-3 depends upon the pH of the
solution which is determined from is point of zero charge (PZC) de-
termination. A typical experimental procedure is as follows; 0.03 g of
the KGNCH-3 is added to the 30 mL of NaCl (0.1 M) solution with dif-
ferent pHs (2−13). The initial pH of the solution is adjusted by 0.1 (M)
HCl or 0.1 (M) NaOH using a digital pH meter (Systronics model 335,
India). The solution containing KGNCH-3 is stirred by the magnetic
stirrer at 300 rpm for 12 h to reach the equilibrium. After reaching the
equilibrium, final pH of the solution is measured. The PZC is obtained
from the plot of ΔpH (ΔpH = pHf − pHi, pHi, is the initial pH and pHf is
the final pH) versus pHi, where the point of intersection of the graph is
(1) equal to zero.
2.9. Adsorption studies
In a typical experiment 0.03 g of dry KGNCH-3 is put into the 60 mL
of dye mixture solution (20 mL of each dye solution of concentration
20 mg L−1 for MB, 25 mg L−1 for CV and 20 mg L−1 for AO) and the
mixture is stirred at 300 rpm. After regular time intervals 2.5–3 mL of
dye mixture solution is taken out from the dye-hydrogel mixture using a
syringe, and the concentration of unadsorbed MB, CV and AO dye in
solution is measured using UV–Visible spectrophotometer (Shimazdu-
1800, Japan) at λmax 620 nm for MB, 583 nm for CV and 400 nm for
AO. The spectra of individual and mixture of dye solution are shown in
Fig. 1(a). It is obvious from the Fig. 1(a) that the absorbance of the
single dye by NCH is higher compare to the mixture of three dyes. After
(2)
mixing of the three dyes in equal volume, the concentration of the in-
dividual dye in mixture becomes less due to the increase in volume
(dilution effect). Hence, absorbance of the dye in the mixture decreases.
Again the absorbance of dyes decreases further by adding NCH to the
dye mixture due to the adsorption of dyes by the hydrogel. The removal
efficiency or percentage removal (% RE) of dye is calculated by fol-
lowing Eq. (3) (Jana et al., 2018b).

48
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

2.11. Adsorption kinetics

The adsorption kinetic studies of the dyes onto the KGNCH-3 are
performed at regular time interval ranging from 10 min to 80 min. A
typical experimental procedure is as follows; 0.11 g of KGNCH-3 hy-
drogel is added to the 60 mL of dye mixture solution taken in a 100 mL
beaker at room temperature. At fixed time intervals 2.5–3 mL of the dye
solution is taken out from the dye-hydrogel solution using a syringe and
the concentration of unadsorbed dye in solution is analyzed by the si-
milar way as described earlier. The amount of MB, CV and AO dye
adsorbed at different time interval is calculated using the Eq. (5)
(Kumar et al., 2016).

V
qt = (C0 − Ct )
m (5)

where qt is the amount of dye adsorbed per unit mass of the adsorbent
(mg g−1) at time t. Ct is the concentration of dye (mg L−1) at time t.

2.12. Comparison of dye removal efficiency with different grades of

KGNCH

The dye adsorption efficiency of the different grades of KGNCH is

compared under the same optimum conditions as is obtained from the
batch adsorption studies with the KGNCH-3. A typical experimental
procedure is as follows; 0.11 g of the each KGNCH (KGNCH-1 to
KGNCH-4) is added separately into the 60 mL solution of dye mixture
(each of 20 mL dye solution of concentration 20 mg L−1 for MB,
25 mg L−1 for CV and 20 mg L−1 for AO) at pre-optimized time, pH and
temperature. The sample solution is stirred at 300 rpm using a magnetic
stirrer. After optimum time period, 2.5–3 mL of dye mixture solution is
taken out from the dye-hydrogel solution. Concentration of unadsorbed
dye remains in the solution after adsorption is measured using the
UV–Visible (Shimadzu-1800, Japan) spectrophotometer and % removal
efficiency is calculated by Eq. (3).

Fig. 1. (a) The UV–Visspectra of individual dye, before adsorptionand UV–Vis

spectra after adsorption of the dye mixture. (b)Percentage of swelling (PS) be- 2.13. Preferential adsorption studies of MB, CV and AO by the KGNCH-3
haviours of different grades of KGNCH.
The selectivity of adsorption of KGNCH-3 towards the dyes used is
C − Ce ⎞ investigated by mixing of two dyes under optimum conditions. An ex-
%RE = ⎛ 0 ⎜ × 100 ⎟
perimental procedure is as follows; 0.11 g of KGNCH-3 is added sepa-
⎝ C0 ⎠ (3)
rately into the 30 mL solution of a mixture of two dyes namely, MB/CV,
where Co is the initial concentration (mg L−1) and Ce is the equilibrium MB/AO and CV/AO at the fixed concentrations of each dyes (20 mL dye
(mg L−1) of dye. solution of concentration 20 mg L−1 for MB, 25 mg L−1 for CV and
Factors affecting the dye adsorption by the KGNCH-3 like, contact 20 mg L−1 for AO). After reaching the equilibrium, the concentration of
time, solution pH, amount of KGNCH-3, temperature and the initial dye unabsorbed dye in the solution is measured by UV–Vis spectro-
concentration are studied. photometer (UV-1800, Shimadzu, Japan) at their specific λmax values
(λmax = 656 nm for MB, λmax = 583 nm for CV and λmax = 400 nm for
AO respectively). The equilibrium dye uptake is calculated using Eq.
2.10. Adsorption isotherm (4).

Adsorption isotherm studies are conducted at different initial con-
centration of dyes ranging from 20 mg L−1 to 80 mg L−1. In a typical
experimental procedure 0.11 g of KGNCH-3 is added separately into the
60 mL of dye mixture of different initial concentration at pre-optimized
temperature and pH obtained from batch mode adsorption studies. The
equilibrium adsorption (qe) is calculated using Eq. (4) (Ray et al.,
2018).
V
q e = (C0 − Ce )
m (4)
where qe is the equilibrium adsorption of dye per mass of KGNCH-3
(mg g−1), m is the weight of the KGNCH-3 (g) and V is the volume of
the dye solution (L).
2.14. Desorption studies
The desorption and reusability behaviour of KGNCH-3 is studied in
successive five cycles of adsorption-desorption at different pHs (2−12).
Initially 0.11 g of KGNCH-3 is added into the 60 mL dye mixture and
stirred at 300 rpm for 2 h. The dye load KGNCH-3 is taken out from the
dye solution and washes with double distilled water for several times,
and then dried. The dye loaded KGNCH-3 is added into 30 mL 0.1 (M)
HCl and stirred for 6 h. The process is repeated for five successive cy-
cles. The percentage of desorption is calculated using Eq. (6) (Ghorai
et al., 2014).
concentration of desorbed dye (mg L−1)
%desorption = × 100
concentration of adsorbed dye (mg L−1) (6)

49
S. Jana, et al.
Scheme I. Mechanism for the synthesisof KG-cl-poly(AA-co-DMA)@BT nanocomposite hydrogel.
3. Results and discussion
3.1. Synthesis
The KGNCH is synthesized by crosslinked copolymerization of AA
and DMA onto KG using KPS as radical initiator and MBA as crosslinker
with BT clay. The mechanism is based on the generation of free radical
form KPS under heating. Initially, the peroxodisulphate decomposed on
heating to produce sulphate anion radicals. The generated free radical
forms alkoxy radical on the KG backbone by the abstracting hydrogen
radicals from the hydroxyl groups of the KG chain. The formed alkoxy
radicals react with the monomers of AA and DMA which are in close
50
Applied Clay Science 173 (2019) 46–64
vicinity of radical sites to from a macro-radical. Thereafter, they grow
the chain by donating free radical to neighbouring molecules. In the
propagation step, the vinyl group of the crosslinker MBA reacts with the
copolymer chain to form a three dimensional crosslinked chains into
the hydrogel. Finally, the bentonite nano clay is captured by the hy-
drogel in situ to form a three dimensional layer structure with the
crosslinked hydrogel. The proposed mechanism for the incorporation of
bentonite nano clay within the cross-linked KGH is represented in
Scheme I.
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

3.2. Swelling characteristics of the different KGNCH

Fig. 1(b) shows the % swelling behaviours of different KGNCH.

From the Fig. 1(b), it is observed that PS increases with the increase in
amount of BT and reached to a maximum value (1131%) with 1.5 g of
BT clay loading (KGNCH-3), after that, PS value decreases by further
loading of BT. The explanation comes in the following way; initially, PS
of the KGNCH is increased with increasing the amount of BT due to the
increase in amount of the hydrophilic functional groups (–Si-OH) pre-
sent in the BT within the hydrogel framework. However, further in-
crease in the amount of BT increases the synergetic intermolecular in-
teractions between the hydrophilic (–Si-OH) groups of the BT and
different functionalities (–CONMe2, –COOH, –OH) present in the KGH
framework, as a result of which the water uptake and holding capacity
of the KGNCH is increased. But with further increase in the amount of
BT from 1.5–2.0 g, the PS is decreased. This is due to the fact that, in
presence of large amount of BT the synergetic interactions between the
hydrophilic groups of the BT and the functional groups present in the
KGH decreases, resulting decreases in the value of PS (Huang et al.,
2012; Mittal et al., 2015a). Additionally, the crosslinking density within
the different hydrogel network also decreases with increasing amount
of BT in the hydrogel (Mittal et al., 2015a). Since KGNCH-3 shows
maximum PS (1131%), further investigations are carried out using
KGNCH-3.

3.3. Characterization of the NC hydrogel

3.3.1. Fourier transform infrared spectroscopy

The FTIR spectra of BT, KGH-3, KGNCH-3, and MB dye loaded
KGNCH-3 is shown in Fig. 2(a-d). The FTIR spectra of KG, AA and DMA
are given in our previous communications (Ali et al., 2006; Jana et al.,
2017). In the FTIR spectrum of BT (Fig. 2a), the peaks at 3625 cm−1
and 3443 cm−1 are ascribed to the –OH stretching vibrations of inter-
layer and intralayer H-bonding of –OH groups respectively. The peak at
1636 cm−1 is due to –OH bending vibrations of the water molecule in
the BT layer. The peaks at 1038 cm−1 and 794 cm−1 are attributed to
the stretching vibrations of Si-O-Si and Si-O-Al groups respectively. The
peaks at 530 cm−1 and 463 cm−1 are assigned to the bending vibration Fig. 2. FTIR spectra of (a) BT (b) KGH-3 (c) KGNCH-3 (d) MB dye loaded
of Si-O-Al and Si-O-Si groups, respectively (Sasikala et al., 2014). FTIR KGNCH-3.
spectrum of KGH-3 (Fig. 2b), the band appears at 3454 cm−1 is due to
the overlapping of –OH present in (KG and AA) and –NH present in The bending vibrational modes of Si-O-Si and Si-O-Al groups are ob-
(MBA) stretching vibrations which is present in the crosslinked hy- served at 638 cm−1 and 583 cm−1, indicating successful incorporation
drogel. The peak at 2936 cm−1 is responsible for aliphatic –C-H of BT onto the KGH matrix. FTIR spectrum of MB dye loaded KGNCH-3
stretching vibrations present in the hydrogel. The two strong peaks at (Fig. 2d), in addition to the peaks present in the NC hydrogel the
1731 cm−1 and 1258 cm−1 are assigned to the stretching vibrations of O
∥
carboxylic (–C=O and –C-O) groups suggesting the presence of PAA stretching vibrational bands of −C− both the amide and carboxylic acid
chain onto the KGH. The peaks at 1620 cm−1 and 1407 cm−1 are re- functionalities are shifted from 1630 cm−1 to 1625 cm−1 and
O
∥
1731 cm−1 to 1722 cm−1 respectively, and also the stretching vibra-
lated to the stretching vibration of the −C− groups of tertiary amide tional frequencies of Si-O-Si and Si-O-Al are shifted from 638 cm−1 to
(–CONMe2) and –C-N. The characteristic band appears at 1040 cm−1 is 619 cm−1 and 814 cm−1 to 804 cm−1 suggesting adsorption of MB dye
due to the C-O-C stretching vibrations. In FTIR spectrum of KGNCH-3 onto the KGNCH-3.
(Fig. 2c), the peaks at 3625 cm−1 and 3443 cm−1 are for the stretching
vibrations of –OH group in BT that is absent KGNCH. A new peak at 3.3.2. X-ray diffraction studies
3454 cm−1 is appeared in KGNCH-3 due to the overlapping of –OH and The XRD patterns of BT, KGH-3, KGNCH-3, MB dye loaded KGNCH-
–NH stretching bands. The peak at 2936 cm−1 is due to the –C-H 3 and KGNCH-3 after desorption are shown in Fig. 3(a-e) respectively.
stretching vibrations of –CH2 groups. The two peaks at 1731 cm−1 and The XRD plot of BT (Fig. 3a), shows characteristic reflection at
O
∥ 2θ = 6.31°, 19.79°, 26.84°, 34.88°, 50.11°, 54.77°, 61.87° which in-
1248 cm−1 are attributed to −C− stretching vibrations of –COOH with dicating its crystalline character. XRD plot of KG is given in our pre-
O
∥ vious communication (Jana et al., 2018b). From the XRD plot of KGH-3,
−1
lower in intensity. The new characteristics peaks at 1630 cm of −C− it is observed that the reflection at 2θ = 22.44° present in KG is shifted
group of the amide is shifted from 1620 cm−1 indicating the strong H- to at 2θ = 21.05° in KGH-3 (Fig. 3b) which indicates the presence of
O
∥
grafted of poly-acrylic acid and poly-N, N-dimethylacrylamide chains
bonding interaction occurs between the −C− of amide groups and –OH into KG backbone. The XRD pattern of KGNCH-3 shows reflection at
groups of the BT. The peaks at 1045 cm−1 and 814 cm−1 are related to 2θ = 20.93°, 26.80° and 35.22° which implies that BT is effectively in-
the stretching vibrations of the Si-O-Si and Si-O-Al groups respectively. corporated into the crosslinked hydrogel matrix (Fig. 3c). MB dye

51
S. Jana, et al.
Fig. 3. XRD plots of (a) BT (b) KGH-3 (c) KGNCH-3 (d) MB dye loaded KGNCH-
3 (e) after desorption of MB dye.
loaded KGNCH-3 (Fig. 3d) shows the XRD plot at 2θ = 26.38° and
34.72° with low intensity which suggests that BT and other functional
moieties are responsible for the dye adsorption. After desorption of the
dyes the XRD plot of KGNCH-3 is given in Fig. 3e. It is observed that
characteristic reflection at 20.90° 26.78° and 35.20 ° which are similar
to that of before adsorption. This proved that the KGNCH-3 is quite
stable and can be reused several times.
3.3.3. Field emission scanning electron microscopy (FESEM) and energy
dispersive X-ray spectroscopy
FESEM images of KGH-3, KGNCH-3 and MB dye loaded KGNCH-3
are shown in Fig. 4(a-c). The FESEM image of KGH-3 (Fig. 4a) displays
rough surface and irregularities which is due to the crosslinking reac-
tion. On the other hand after incorporation of BT clay within the hy-
drogel matrix, the surface is converted to highly porous and nano fi-
brous structure which confirms that the BT is uniformly distributed into
the hydrogel matrix (Fig. 4b). After MB dye adsorption by the KGNCH-3
(Fig. 4c) the irregular and porous surface is disappeared and a smooth
surface is appeared due to the adsorption of dye molecules by various
interactions into the pores of the KGNCH.EDS spectrum of the KGNCH-
3 is shown in Fig. 4d. The EDS spectrum analysis shows that the
KGNCH-3 shows the presence of characteristic elements (C, O, Al Si, Na,
and K) of the BT which supports that BT is incorporated successfully to
the hydrogel matrix
52
Applied Clay Science 173 (2019) 46–64
3.4. pHPZC of KGNCH-3
Fig. 5a shows the plot of ΔpH of KGNCH-3 with the initial pH in the
NaCl solution. The PZC value of the KGNCH-3 is found to be 5.25. At
pH < pHPZC, the KGNCH-3 surface becomes positively charged (ca-
tionic) on the other hand, at pH > pHPZC the surface of KGNCH-3
hydrogel becomes negatively charged (anionic) as is observed from
Fig. 5a. The above fact is explained by the following way; in acidic
medium, amino groups present in KGNCH-3 get protonated, resulting
higher values of pHPZC. When the pH of the solution increases, the
protonated amino groups become deprotonated and at the same time
the carboxylic groups of the KGNCH is ionized into carboxylate ion, as a
result of which pHPZC is decreased.
3.5. Swelling behaviour of KGNCH-3 different solution pHs
The swelling behaviour of KGNCH-3 is studied at room temperature
in various pHs ranging from 2 to13 and the results are shown in Fig. 5b.
Under acidic pH (pH < pHPZC), most of the carboxylic acid groups
remain in deprotonated form and at the same time dimethylacrylamide
OH
∣
groups get protonated to form −C=⊕NM e2 as a result of which hy-
drogen bonding interaction with water molecule increases resulting
increase in swelling percentage. At pH = pHPZC, the carboxylic acid
groups start to ionize to carboxylate ions, for which the electrostatic
attraction between negatively charged oxygen atom of the carboxylate
ion and positively charged nitrogen atom of the protonated dimethy-
lacrylamide groups is increased. As a result of which extent of hydrogen
bonding with water molecules decreases and hence swelling percentage
also decrease (Nebhani et al., 2016; Jana et al., 2018b). In basic pH
(pH > pHPZC) most of the carboxylic acid groups exists as carboxylate
ions and dimethylacrylamide groups are deprotonated to form
OH
∥
−C‐NM e2 . The electrostatic repulsion between the –COO– groups is
increased which creates larger no of void space inside the polymer
matrix according to which swelling percentage increases (Pourjavadi
and Mahdavinia, 2006; Pourjavadi et al., 2008). The reason for the
decrease in the swelling percentage in highly alkaline medium
(pH > 10) is due to the formation of intimate ion pair (COO−Na+) of
excess Na+ in the aqueous media preventing the anion-anion repulsion
between the carboxylate groups (Jana et al., 2018b), as a result of
which void spaces inside the polymer matrix is reduced.. Similar results
are also reported in our previous communication (Jana et al., 2018b).
3.6. Swelling kinetics
3.6.1. First order kinetics
The swelling mechanism of the KGNCH-3 is investigated by
studying of its swelling kinetics in the water medium. The first order
kinetics of the swelling is expressed by the Eq. (7) (Saber-Samandari
et al., 2014).
We
ln = Kt
We − Wt (7)
where We and Wt are the equilibrium swelling ratio and at time t re-
spectively. K is the first order rate constant. K is calculated from the
slope of the linear plot of ln (We/We–Wt) versus t (Fig. 5c). The cor-
relation coefficient (R2) is found to 0.945 which indicates that the plot
does not fit well into the straight line; therefore swelling of KGNCH-3
does not follow the first order kinetics, due to the various solvent-hy-
drogel interactions between the different functionalities of the hydrogel
and the water molecules.
3.6.2. Second order kinetics
The second order kinetic model is expressed by the Eq. (8) (Ganji
et al., 2010).
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

Fig. 4. SEM photographs of (a) KGH-3 (b) KGNCH-3 (c) MB dye loaded KGNCH-3 (d) EDS of KGNCH-3.

t 1 1 power law equation and can be represented by the Eq. (9) (Narayanan
= + t
wt KW2e We (8) et al., 2014).

We and K values are calculated from the slope ( 1

) and intercept F = Ktn (9)
We
1 t where F is the fractional uptake of the water at time t, K is swelling
( ) of the linear plot of versus t (Fig. 5d). The value We is found to
KW2e Wt
be 1.697 (g g−1) which is closer to the experimental value of We and constant and n is the diffusion exponent. The above equation is written
also R2 value is found to be 0.986 which is higher than the first order in the linear form as
kinetics. Therefore, the swelling of the KGNCH-3 is fitted well with the lnF = lnK + nlnt (10)
second order kinetic model.
the value of K and n are calculated from the intercept and slope of the
linear plot of lnF versus lnt (Fig. 5e). The n value indicates the types of
3.6.3. Diffusion diffusion mechanism. When n = 0.5, the Fickian diffusion is observed,
The diffusion mechanism of water into KGNCH-3 is analyzed by for n = 1, the diffusion is rapid than relaxation process and if

53
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

1.0 1400
(a) (b)
1200
0.5
1000

% Water uptake
pH 0.0
800

-0.5 600

400
-1.0
200
-1.5
2 4 6 8 10 12 14 2 4 6 8 10 12 14
pHi pH

3.0 0.40
KGNC-1.5 (d)
KGNC-1.5
(c)
2.5
0.35

2.0
0.30
ln (We /We -Wt )

1.5 t/Wt
0.25
1.0
0.20
0.5
0.15
0.0
50 100 150 200 250 300 350 400 50 100 150 200 250 300 350 400 450
t (min) t (min)

2.6
KGNC-1.5
2.4
(e)
2.2
2.0
1.8
lnF

1.6
1.4
1.2
1.0
0.8
4.0 4.5 5.0 5.5 6.0 6.5 7.0
lnt
Fig. 5. (a)The point of zero charge of KGNCH-3. (b) effect of pH on the % swelling of the KGNCH-3 (c) swelling kinetics of first order (d) swelling kinetics of second
order (e) swelling kinetics of diffusion.

0.5 < n < 1, the diffusion is non Fickian. In the present case the n
value is observed as 0.77 indicating non diffusion character. The
KGNCH-3 is elastic in nature (rubbery state), as a result of which
KGNCH allows more penetration of the water into the hydrogel matrix
(Narayanan et al., 2014).
3.7. Adsorption dynamics
3.7.1. Effect of contact time
The effect of contact time in the removal efficiency of KGNCH-3 for
the adsorption of MB, CV and AO is represented in Fig. 6a. Initially the
removal efficiency is increased with increasing time and reached a
maximum value (83.93% for MB, 82.35% for CV and 80.28% for AO
dyes) at 80 min. After that, removal efficiency remains constant with

54
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

86
90 (b)
MB (a) MB
84
CV 85 CV
82 AO AO
80

% removal efficiency
% removal efficiency

80
75
78
70
76
65
74
60
72
55
70
50
68
45
0 20 40 60 80 100 120 2 4 6 8 10 12 14
Contact time (min) pH

96 MB 92 MB (d)
(c)
CV 90 CV
92 AO
AO 88
% removal efficiency

% removal efficiency
88 86
84
84
82
80 80
78
76
76
72 74
72
68
70
0.00 0.03 0.06 0.09 0.12 0.15 0.18 20 30 40 50 60 70 80
o
Dose (g) Temperature ( C)
95
94 (e) MB
CV
93 AO
% removal efficiency

92
91
90
89
88
87
86
85
20 30 40 50 60 70 80
Dye concentration (mg/L)
Fig. 6. Effect of (a) contact time (b) solution pH (c) KGNCH-3 dosage (d) temperature (e) initial dye concentration on removal efficiency of dyes from the aqueous
solution by KGNCH-3.

further increase in time. The explanation comes in the following way; at 3.7.2. Effect of solution pH
the beginning of the adsorption large number of adsorption sites is The effect of solution pH in the dye adsorption efficiency is shown in
available for interacting with the dye molecules resulting increase in Fig. 6b which shows that the removal efficiency increases with in-
dye removal efficiency. Whereas, after reaching equilibrium, binding creasing pH and maximum adsorption occurs at pH = 8 (86.87%) for
sites for the adsorption in the adsorbent are not available for further MB, pH = 7.5 (84.29%) for CV and pH = 10 (83.93%) for AO, there-
adsorption of the dye molecules (Srivastava and Sillanpää, 2017). after removal efficiency decreases. The adsorption of cationic dyes onto

55
S. Jana, et al.
the KGNCH-3 occurs due to the ionic interactions controlled by the
surface charge of the adsorbent and adsorbate in aqueous solution
(Mittal et al., 2014; Jana et al., 2018b). The charge on the surface of the
adsorbent is predicted by the PZC. The removal efficiency of cationic
dyes by the KGNCH-3 are favourable at pH > pHPZC. The pHPZC of the
KGNCH-3 is found to be 5.25. So, in the lower pH (pH < pHPZC), the
functional groups present in KGNCH-3 get protonated hence cationic
dyes are less adsorbed by KGNCH-3. Therefore, lower adsorption is
observed in acidic solution. As solution pH increases (pH > pHPZC) the
adsorbent's surface acquires negative charge due to the deprotonation
of carboxylic acid to carboxylate anion and silanol groups present in
bentonite clay to form SieOe anion. As a result of which negative
charge density of the KGNCH-3 surface is increased and hence the
electrostatic attraction between the positively charged heteroatom of
the cationic dyes and the hydrogel increases. The higher removal effi-
ciency of cationic dyes is observed in alkaline medium supports the
above phenomenon. Similar results are also obtained by Garg et al.
(2004) for the effects of the solution pH on the adsorption of MB by
Indian rosewood sawdust.
3.7.3. Effect of KGNCH-3 dosage
The dye adsorption efficiency of KGNCH-3 with increasing amount
of KGNCH-3 is shown in Fig. 6c. It is noticed from the Fig. 6c that, the
dye removal efficiency by the KGNCH-3 is increased with increase in
amount of adsorbent's dose and reaches a maxima then it decreases. The
maximum removal efficiency is observed 93.1% for MB, 91.73% for CV
and 90.9% for AO at 0.11 g of the adsorbent. The results can be at-
tributed to the increase in the available binding sites for the adsorption
with the increase in the amount of the KGNCH-3. However, the removal
efficiency decreases by increasing KGNCH-3 dose at constant dye con-
centration and volume because of the saturation of binding sites present
in the KGNCH-3 (Mittal et al., 2014). Similar observations for the effect
of the adsorbent dose on the adsorption of methylene blue is reported
for GK-cl-P(AA-co-AAM)/SiO2 by Mittal et al. (2015a).
3.7.4. Effect of temperature
Fig. 6d shows the effect of solution temperature in adsorption of
dyes onto the KGNCH-3. It is observed from the Fig. 6d that, the ad-
sorption gradually increases with the increase in temperature form
25 °C to 60 °C and maximum removal efficiency is observed 89.89%,
85.73%, and 87 for MB, AO and CV at 60 °C and 50 °C respectively after
that the dye removal efficiency decreases in case of all the three dyes.
The explanation comes in the following way; at higher temperature
swelling properties of the hydrogel increases and as a result of which
the dye molecules get adsorbed into the hydrogel's surface resulting
enhance in dye removal efficiency. Furthermore, as temperature is in-
creased the removal efficiency also increased due to the increase in
diffusion rate of the dye molecules and also decreases in solution
viscosity of the adsorbent molecules (Chowdhury et al., 2011). On the
other hand, decreasing dye adsorption is observed at much higher
temperature is due to the enhancement in Brownian movement of the
dye molecule and breaking of the intermolecular hydrogen bonding
between the dye molecules and the KGNCH-3 which may cause deso-
rption of dye molecule from the hydrogel's surface (Mittal et al.,
2015b). In the literature, similar observations are reported for the ad-
sorption of methylene blue and methyl violet using h-XG/SiO2-nano-
composites hydrogel.
3.7.5. Effect of initial dye concentration
Effect of initial dye concentration on the dye removal efficiency of
the KGNCH-3 for the adsorption of MB, CV and AO is shown in Fig. 6e.
From the Fig. 6e, it is observed that, increasing initial dye concentra-
tion, the removal efficiency decreases from 94.14% to 86.35% for MB,
92.56% to 86.35% for CV and 91.75% to 85.45% for AO with the
concentration 20 mg L−1 to 80 mg L−1. This is because of the fact that,
the quantities of binding sites of a fixed amount of KGNCH-3 are fixed,
56
Applied Clay Science 173 (2019) 46–64
so, large number of binding sites are available for the adsorption of dye
molecules at the initial stage. At higher dye concentrations, the quantity
of cationic dye molecules is increased in the solution but, the numbers
of available of binding sites on the KGNCH-3 are not available for
further adsorption, resulting decrease in the dye adsorption (Feng et al.,
2018). Similar kinds of results are observed for the adsorption of me-
thylene blue and methyl violet using h-XG/SiO2- nanocomposites hy-
drogel (Ghorai et al., 2013).
3.8. Binding study of KGNCH-3
The dye adsorption capacity of the KGNCH-3 is studied using
binding mechanism (Seow and Lim, 2016). A typical experimental
procedure is as follows; 0.11 g of KGNCH-3 is added to the aqueous
solution of some cationic dyes namely MB, CV, AO and some anionic
dyes such as Congo red (CR), Tartrazine (TA), Indigo blue (IB), Sa-
franine-O (SO) separately and allow to reaching the equilibrium at 3 h.
After equilibrium is established, when KGNCH-3 is removed from the
dye solution by filtration and washing with water it does not show any
colour rather it remains as such (colourless), but in case of cationic dye
solution, the colour of the KGNCH-3 changes to dark colour, indicating
that the cationic dyes are adsorbed by the KGNCH-3 but anionic dyes
remain unaffected. The KGNCH-3 contains ionizable groups in its
backbone (–COOH and Si-OH) which partially ionizes in aqueous so-
lution to become –COO– and –Si-O– as a result of which electrostatic
interactions between the cationic functionalities of the cationic dye
molecules and the negative functionalities (–COO– and –Si-O−) of the
hydrogel occurs, H-bonding interactions also occur between the more
electronegative nitrogen atoms of the cationic dyes and hydrogen atoms
of –NH- groups present in crosslinking chain in the KGNCH-3 frame-
work.
3.9. Mechanism of cationic dye adsorption
Since, the synthesized KGNCH-3 is found to be highly potent for the
removal of cationic dyes (MB, CV and AO), the possible mechanism of
the adsorption of cationic dyes onto the KGNCH-3 is likely to be elec-
trostatic and hydrogen bonding interaction between the dye molecules
and the carboxylate ions, amine groups present in the KGNCH-3
backbone. The removal of MB by KGNCH-3 is due to the electrostatic
interactions between the positive charges (=N+-) present in the dye
molecules and the negative charges of the –COO– groups present in the
adsorbent, and also by the hydrogen bonding between the electro-
negative N residue of the dye molecules with –NH- group of the
crosslinking chains in the adsorbent (Ghorai et al., 2014).
The removal of CV occurs because of the electrostatic attraction
between the deprotonated carboxylic acid groups (–COO−) of the ad-
sorbent and positively charged = N+- moieties present in the dye mo-
lecules. Furthermore, hydrogen bonding occurs between the –OH and
–NH- groups present in the nano gel's surface and nitrogen atom of CV.
Similarly for AO, the major force for its attraction is due to the
formation of hydrogen bonding between –OH and –NH- groups present
in the KGNCH-3 with the electronegative N present in the dye mole-
cules, along with electrostatic attractions between cationic = N+-
groups of the dye molecules and carboxylate moieties of the KGNCH-3
(Sharma et al., 2018). Various interactions are shown in the Fig. 7.
3.10. Types of adsorption isotherm using Gile's model
The nature of adsorption of the dye molecules onto the solid surface,
the adsorbent (KGNCH-3) and adsorbate (dye molecules) is classified
under Gile's classification (Giles et al., 1974). The plot of the amount of
dye adsorbed at equilibrium (qe) versus equilibrium dye concentration
(Ce) is given in the Fig. 8. It is observed from the Fig. 8 that, L type
isotherm curve is originated according to the Gile's classification. The
phenomenon is explained by the following way; Initially binding sites
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

Fig. 7. Schematic interactions of cationic dyes onto KGNCH-3.

50 of the adsorbent are unoccupied, with increasing dye molecules in the

MB solution binding sites of the adsorbent are occupied by the dye mole-
45 CV cules, hence adsorption increases, thereafter, adsorption becomes con-
AO stant. L-type of adsorption isotherm curve is obtained due to the strong
40 ionic interactions between the negatively charged surface of the
35 KGNCH-3 (adsorbent) and positively charged functional groups present
in the MB, CV and AO (adsorbate) molecules.
qe (mg g )
-1

30
3.11. Adsorption isotherms
25
3.11.1. Langmuir adsorption isotherm
20
The linear form of the Langmuir isotherm model is given by Eq. (11)
15 (Langmuir, 1918).
Ce 1 C
10 = + e
qe qm b L qm (11)
0 2 4 6 8 10 12 −1
Where, Ce is the equilibrium concentration of the dye (mg L ), qe is
-1
Ce (mg L ) the amount of dye adsorbed at equilibrium (mg g−1), qm is the max-
imum adsorption capacity of the adsorbent (mg g−1), and bL is the
Fig. 8. Gile's curve for theMB, CV and AO dyes showing L-types adsorption Langmuir constant (L mg−1) related to the free energy and affinity of
[conditions: MB: dye concentration-20 mg L−1, pH-8, time-80 min, adsorbent adsorption. The values of qm and bL are calculated from the slope and
dose-0.11 g/L, and temperature-50 °C, CV: dye concentration-20 mg L−1, pH- intercept of the linear plot of Ce/qe versus Ce (Fig. 9a), which are given
7.5, time-80 min, adsorbent dose-0.11 g/L, and temperature-50 °C and AO: dye
in Table 2. The maximum adsorption capacity is found to be 165.28,
concentration-20 mg L−1, pH-10, time-80 min, adsorbent dose-0.11 g/L, and
158.73, 152.67 mg g−1 for MB, CV and AO respectively. From the
temperature-60 °C].
Table 2, it is observed that higher bL value is obtained for MB than the
other dyes indicating strong affinity of MB dye by the binding sites of
the KGNCH-3 surface. The feasibility of adsorption process is predicted

57
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

4.2
0.27 (d) MB
(a) 4.0
CV
3.8
0.24 AO
3.6
0.21 3.4

ln (qe-qt)
MB 3.2
Ce/qe

0.18 CV 3.0
AO 2.8
0.15 2.6
2.4
0.12
2.2
2.0
0.09
1.8
0 2 4 6 8 10 12 10 20 30 40 50 60 70
-1
Ce (mg L ) t (min)

4.0 2.4
(b) (e) MB
3.8 CV
2.3
3.6 AO
MB 2.2
3.4 CV
lnqe(mg g )

t/qt
-1

3.2 AO 2.1

3.0 2.0
2.8
1.9
2.6
2.4 1.8

0.0 0.5 1.0 1.5 2.0 2.5 3.0 0 10 20 30 40 50 60 70 80 90

-1
lnCe(mg L ) t (min)

50 75
MB
45 (c) 70 (f) CV
65 AO
40
60
35
qe(mg g )

MB 55
-1

30 CV 50
AO
qt

25 45
20 40

15 35
30
10
25
0.0 0.5 1.0 1.5 2.0 2.5
3 4 5 6 7 8 9
-1
lnCe (mg L ) 1/2 1/2
t (min)
Fig. 9. Plots of (a) Langmuir isotherm (b) Freundlich isotherm (c) Temkin isotherm for (d) Pseudo-first order (e) Pseudo second order (f) Intra-particle diffusion
kinetics for the adsorption of cationic dye onto KGNCH-3 [conditions: MB: dye concentration-20 mg L−1, pH-8, time-80 min, adsorbent dose-0.11 g/L, and tem-
perature-50 °C, CV: dye concentration-20 mg L−1, pH-7.5, time-80 min, adsorbent dose-0.11 g/L, and temperature-50 °C and AO: dye concentration-20 mg L−1, pH-
10, time-80 min, adsorbent dose-0.11 g/L, and temperature-60 °C].

58
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

Table 2 Table 3
Langmuir, Freundlich and Temkin isotherm parameters for the adsorption of Pseudo-first order, pseudo-second order kinetic and intraparticle diffusion
cationic dyes onto KGNCH-3. model parameters for the adsorption for the adsorption of cationic dyes onto
KGNCH-3.
Isotherm model parameter Cationic dyes
Kinetics model parameter Cationic dyes
MB CV AO
MB CV AO
Langmuir isotherm
qm (mg g−1) 165.28 158.73 152.67 First-order kinetic model
bL (L mg−1) 6.05 × 10−3 6.30 × 10−3 6.55 × 10−3 qe (mg g−1) 49.651 58.732 67.087
RL 0.647 0.664 0.685 K1 (min−1) 0.0262 0.0273 0.0274
R2 0.989 0.987 0.982 h0,1 (min) 1.290 1.603 1.838
SSE (%) 1.56 × 10−5 1.69 × 10−5 1.76 × 10−5 R2 0.9805 0.990 0.988
SSE (%) 4.84 × 10−3 5.78 × 10−3 7.8 × 10−3
Freundlich isotherm
1/nF 0.633 0.657 0.667 Second-order kinetic model
KF (mg g−1) 11.841 9.845 8.9526 qe (mg g−1) 232.558 222.71 224.75
R2 0.995 0.9954 0.996 K2 (g mg−1 min−1) 1.06 × 10−5 1.148 × 10−5 1.08 × 10−5
SSE (%) 1.16 × 10−3 1.39 × 10−3 1.42 × 10−3 h0,2 (mg g−1 min−1) 0.573 0.565 0.545
R2 0.995 0.994 0.993
Temkin isotherm
SSE (%) 1.22 × 10−4 0.00934 0.0221
bT (J mol−1) 151.82 148.67 145.22
AT (L mg−1) 1.643 1.261 1.093 Intra-particle diffusion model
R2 0.981 0.984 0.982 Kid (mg g−1 min-1/2) 6.512 6.712 6.610
SSE (%) 4.05 4.24 4.60 C (mg g−1) 8.899 8.534 4.350
R2 0.988 0.990 0.981
SSE (%) 0.258 0.0682 0.958
from the value of separation factor (RL) which is a dimensionless con-
stant is calculated from Eq. (12) (Xiong et al., 2018a)
adsorption process. In the present investigation, the pseudo-first order,
1
RL = pseudo second order and intraparticle diffusion model are used to de-
1 + bL C0 (12) scribe the adsorption process.
The value of RL indicates the shape and feasibility of isotherm,
whether the isotherm will be unfavourable (RL > 1), linear (RL = 1), 3.12.1. Pseudo first order kinetics
favourable or irreversible (0 < RL < 1) (Hall et al., 1966). In the The pseudo first order kinetic model (Lagergren, 1898) is used for
present studies, the separation factor (RL) is found to be 0.647, 0.664 the adsorption of solid-liquid system and the linear form is given by Eq.
and 0.685 for MB, CV and AO respectively, which lies in between 0 and (15)
1. So, adsorption of cationic dyes by KGNCH-3 is favourable. ln(q e − qt) = ln q e − K1t (15)

3.11.2. Freundlich adsorption isotherm The initial adsorption rate (h0) is obtained by Eq. (16)
The linear form of the Freundlich isotherm model is given by Eq. h 0,1 = K1q e (16)
(13) (Freundlich, 1907).
where, h0, 1 (min) is the initial adsorption rate, K1 (min−1) is the rate
1
ln q e = ln KF + ln Ce constant of pseudo-first order kinetics. qe and qt are the amount of dye
nF (13) adsorbed (mg g−1) at equilibrium and at any instant time t. The value
where 1/nF is the adsorption intensity. The values of 1/nF and KF are of K1 and qe are estimated from the slope (K1) and the intercept (lnqe) of
calculated from the slope and intercept of the linear plot of ln qe versus the linear plot of ln (qe-qt) versus t (Fig. 9d) respectively and values are
ln Ce (Fig. 9b) and are summarized in Table 2. If1/nF value lies in the given in the Table 3. The lower value of correlation coefficient suggests
range of 0.1 < 1/nF < 1 the adsorption process is said to be favour- the poor quality of linearization. Hence, the adsorption of cationic dyes
able and feasible. In the present study the 1/nF value lies in the range of onto the KGNCH-3 does not follow first order kinetics. Moreover, initial
0.633 to 0.667 for all the three dyes. These results indicate that the sorption rate (h0,1) is higher for MB (1.86) than CV (1.603) and AO
adsorption of cationic dyes by the KGNCH-3 is chemisorption i.e. strong (1.290) at the same initial concentration due to the smaller molecular
electrostatic and hydrogen bonding interactions play vital roles for the volume of MB.
adsorption process.
3.12.2. Pseudo second order kinetics
3.11.3. Temkin adsorption isotherm The integrated form of the pseudo-second-order kinetic model is
The model is expressed in the linear form which is given by Eq. (14) expressed by Eq. (17) (Ho and McKay, 1998).
(Temkin, 1940). t 1 1
= + t
RT RT qt K2q e2 qe (17)
qe = ln AT + ln Ce
bT bT (14)
The initial adsorption rate (h0,) is given by Eq. (18).
where AT (L mg−1) is the equilibrium binding constant related to the
h 0,2 = K2q 2e (18)
maximum binding energy and bT (J mol−1) is the Temkin constant re-
lated to heat of adsorption. The value of bT and AT are calculated from where h0, 2 (mg g−1 min−1) is the initial adsorption rate and K2
the slope and the intercept of the linear plot of qe against ln Ce (Fig. 9c). (g mg−1 min−1) is the overall rate constant of the pseudo-second order
The results are represented in Table 2. kinetics. qt and qe are the amount of dye adsorbed per weight of ad-
sorbent (g) at any particular time t and at equilibrium. The values of qe
3.12. Adsorption kinetics and K2 for all the dyes are calculated from the slope and the intercept of
the plot of t/qt versus t respectively (Fig. 9e). The values of qe, K2, h0,2
The kinetics of adsorption is an important parameter to understand and R2 are given in the Table 3. The calculated value of qe (cal) obtained
the adsorption rate and provides information for modelling the from Eq. (17) is closer to the experimental value of qe (exp) obtained

59
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

2.0 100
(a) (b)
1.8
80
1.6

% removal efficiency
MB
1.4 CV 60
AO
1.2
ln Kc

1.0 40

0.8
20
0.6

0.4 0
-3 -3 -3 -3 -3
3.0x10 3.0x10 3.1x10 3.2x10 3.3x10 3.4x10
-3 KGNCH-1 KGNCH-2 KGNCH-3 KGNCH-4
-1 Various KGNCH
1/T (K )

90
(c)
75

60
qe (mg g )
-1

45

30

15

0
MB /CV MB /CV CV /AO
dye pairs
Fig. 10. (a) Plot of ln KC versus 1/T for the adsorption of cationic dyes onto the KGNCH-3. (b) Dye removal efficiency of different grades of KGNCH. (c) Comparison
of the adsorption of MB, CV and AO dyes by KGNCH-3.

from the equilibrium adsorption. Since, the chemisorption is relatively
dominant in the dye adsorption process (Cao et al., 2018). From the
Fig. 9e it is found that the plot t/qt versus t gives a straight line with
high correlation coefficient and is closest to unity for all the three dyes
used. From Table 3, it is observed that the initial adsorption rate of the
second order (h0, 2) is higher for MB than the other two at the same
initial concentration suggesting, MB is adsorbed more rapidly than CV
and AO. Similar results are also reported for the adsorption of dye by
the hydrogel in literature (Jana et al., 2018b).
3.12.3. Intra-particle diffusion model
Pore and surface diffusion is an important parameter for the solid-
liquid adsorption process. Therefore, intraparticle diffusion model is
used to determine the diffusion mechanism for the adsorption of dyes
onto surface of the KGNCH-3, and most widely used model is given by
Weber and Morris (1963). The linear mathematical form of this model
is described by Eq. (19).
qt = Kid t1/2 + C
−1
where kid is the intraparticle diffusion rate constant (mg g min-0.5)
and C is a constant that is proportional to the thickness of the boundary-
layer (mg g−1). The values of Kid and C are estimated from the slope
(Kid) and intercept (C) from the linear plot of qt versus t1/2, respectively
(Fig. 9f) and are given in the Table 3. According to the Weber and
Morris, if qt versus t1/2 is linear and passes through the origin, then the
rate determining parameters which control the adsorption process is
involved only by the intraparticle diffusion. If the plot does not pass
through the origin the intraparticle diffusion is not the rate limiting step
of the adsorption mechanism. It is observed from the Fig. 9f that, the
adsorption of cationic dyes onto the KGNCH-3 follows a straight line
plot but does not pass through the origin (Fosso-Kankeu et al., 2017).
Therefore, the intraparticle diffusion is not solely controlled the rate
determining step of the dye adsorption (Xiong et al., 2018b). Hence,
adsorption of dye onto the KGNCH-3 is involved diffusion of dye mo-
lecules through the solution to the external surface of the adsorbent (He
et al., 2013).
3.13. Validity of isotherm and kinetic model
The fit linear method is not appropriate for the good fitness of
(19) theoretical model with experimental results. Therefore, in this study the
validity of the isotherm and kinetic models is verified by comparing the
value of sum of square error (SSE) and correlation coefficient. Well
fitting occurs when correlation coefficient is closet to unity and lower
value of SSE (Tseng and Tseng, 2005; Xiong et al., 2017). The value of
SSE is calculated by the following Eq. (20).

60
S. Jana, et al. Applied Clay Science 173 (2019) 46–64

(∑ q e,exp − q e,cal )
2 decreased.
%SSE =
N (20)
3.16. Preferential adsorption studies of MB, CV and AO by the KGNCH-3
where, qe (exp) is the experimentally determined adsorption capacity
(mg g−1), qe (cal) is the theoretical adsorption capacity using a model The preferential adsorption of MB over the CV and AO dyes form
(mg g−1) and N is the number of data points. Among the isotherm and their binary mixture is determined by measuring the selectivity coef-
kinetic models studied, Freundlich isotherm and pseudo second order ficient (αBA) (Liu et al., 2013; Jana et al., 2018a) which is expressed by
kinetic model are best fitted model in the present case. Eq. (24).
qA CB
3.14. Thermodynamics αBA =
CA qB (24)
The spontaneity of the removal efficiency of dyes onto the KGNCH-3 When the selectivity coefficient (αBA) is greater than unity then
is investigated by calculating different thermodynamic parameters such adsorption of A dye is preferred over B, on the other hand if it is
as standard Gibbs free energy change (ΔG0), standard enthalpy change αYXissmaller than unity adsorption of B dye is preferred over A. In the
(ΔH0), and standard entropy change (ΔS0). The standard Gibbs free present study the selectivity coefficient for the ternary dye adsorption is
energy change (ΔG0) of the adsorbent is calculated from the Van't Hoff's given by the following Eqs.
equation which is related to the equilibrium constant by the following
MB qMB CCV
Eqs. (21, 22) (Ghorai et al., 2013). α CV =
CMB qCV
∆S0 −∆H0
ln K C = +
R RT (21) qMB CAO
αMB
AO =
CMB qAO
∆G0 = −RT ln K C (22)
qCV CAO
qe αCV
AO =
KC = CCV qAO
Ce (23)
For MB-CV and MB-AO, the value of selectivity coefficient is higher
where KC is the equilibrium constant, R is the universal gas constant
than unity indicating MB dye molecules are adsorbed preferentially
(8.314 J mol−1 K−1), T is temperature (K), qe is the amount of dye
onto KGNCH-3 than the other two dyes and the results are represented
adsorbed onto the hydrogel per litre of the dye solution at equilibrium
in Fig. 10c. But in the case of CV-AO, the selectivity coefficient is
(mg L−1), and Ce is the equilibrium concentration of the dye in the
greater than unity, which indicates higher affinity of CV onto the
solution (mg L−1). The values of ΔH0 and ΔS0 of the adsorption are
KGNCH-3 surface than the AO. Therefore, the preferential order for the
estimated from the slope (ΔH0/R) and intercept (ΔS0/R) of the linear
adsorption of cationic dyes by KGNCH-3 follows MB > CV > AO. The
plot of ln KC versus 1/T, (Fig. 10a) respectively and the value are re-
reason behind the preferential order is explained in the following way;
presented in Table 4. The negative value of ΔG0 indicates the feasibility
MB is preferentially adsorbed by the NC hydrogel, due to its smaller
and spontaneous nature of the cationic dyes adsorbed onto the KGNCH.
spatial structural arrangement over the other two dyes (Liu et al.,
With increasing temperature, ΔG0 value increases suggesting the fea-
2015). The lower adsorption efficiency of CV and AO is due to their
sibility of the adsorption process at elevated temperature. The positive
larger molecular structure causing steric hindrance by the active sites of
value of ΔS0 indicates an increase in disorder and randomness of dye
the KGNCH during the transfer of dye molecules to the pore of the
molecules at the solid and liquid interface during the adsorption of dye
KGNCH-3.
on the solid surface of KGNCH-3. The positive value of ΔH0 suggests the
endothermic nature of the dye adsorption by the KGNCH-3.
3.17. Comparison of the adsorption capacity of KGNCH-3 with KG, KGH
and the other reported adsorbents
3.15. Comparison of the dye removal efficiency with different grades of
KGNCH
The adsorption capacities of the KGNCH-3 in the present case are
compared (Table 5) to some other reported adsorbents. It is found from
The maximum removal efficiency of different types of KGNCH-3
the Table 5, that the present NC hydrogel is more efficient for the dye
with respect to the time is shown in Fig. 10b. The % removal efficiency
removal over the other adsorbents in the same systems. The reported
increases from KGNCH-1 to KGNCH-3 but decreases for the KGNCH-4
adsorbents are used only to a single dye system where qmax of one or
hydrogel. The maximum removal efficiency is found in case of KGNCH-
two adsorbents become higher (entry 1 and entry 3 for MB, entry 6 and
3. This is due to the optimized surface area of the KGNCH and right
entry 7 for CV and entry 8 for AO) than the present hydrogel NCH but it
degree of BT incorporation. However, further increase in the percentage
(entry 13 in Table 5) shows better performance in all the three cases
of BT results decrease in the removal efficiency, due to the increase in
when compared simultaneously in a mixture than some other reported
crosslinking density between the functional groups present in the
adsorbents. This is due to the fact that, various functionalities
KGNCH-4 which reduces the binding sites of the adsorbent for the ad-
(–CONMe2, –COOH, –OH and –Si-OH) are present in the nanocomposite
sorption of dye molecules. As a result, dye adsorption efficiency is
hydrogel backbone which increases the porosity, surface area and
binding site in the NC hydrogel that are effectively responsible for all
Table 4
Thermodynamic parameters for the adsorption of cationic dyes onto KGNCH-3.
the three dyes adsorption. From the Table 5 it is clearly indicated that
the KGNCH-3 can be used as a potent adsorbent for the removal of
Thermodynamic parameters Cationic dyes cationic dyes from the dye containing waste water. The higher capacity
MB CV AO
of the KGNCH-3 is due to the presence of more number of anionic
binding sites onto KGNCH polymer matrix which effectively take part
T (K) 323 333 323 for the adsorption. Furthermore, the KGNCH-3 exhibits higher ad-
−ΔG0 (kJ/mol) 34.87 29.44 29.37 sorption capacity compared to the KG and KGH. This is attributed to the
ΔH0 (kJ/mol) 30.80 25.40 24.95
higher surface area, optimized crosslinking density and maximum
ΔS0 105.58 91.95 88.95
R2 0.982 0.952 0.977 porosity of the KGNCH resulting by the right incorporation of BT clay
onto the KGNCH-3.

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S. Jana, et al. Applied Clay Science 173 (2019) 46–64

Table 5
Comparison of the maximum dye adsorption capacity (qm) of nanocomposite hydrogel with other reported adsorbents.
Adsorbents Maximum adsorption capacity [(qm) mg g−1] References

MB CV AO

1 Modified bentonite, organoclay-HDTMA 399.7 Anirudhan and Ramachandran (2015)

2 Fe3O4/activated montmorillonite 106.38 – Chang et al. (2016)
3 PAA/MGO composites 290.7 – – Zhang et al. (2015)
4 poly(AM-IA)/DAM/Zr(OH)4 composite 102 – – Hamoud et al. (2014)
5 Car/poly(AAm-co-Na-AA)-MMT – 11 – Mahdavinia et al. (2013)
6 Car-Alg/MMT 277 – Mahdavinia et al. (2012)
7 Poly(Acrylamide-co-Maleic Acid)/Montmorillonite – 178 – Aref et al. (2017)
8 ZnS: Cu nanoparticles loaded on activated carbon – 183.15 Asfaram et al. (2015a)
9 Bagasse fly ash (BFA) – 31.177 Mall et al. (2007)
10 Activated carbon-commercial grade (ACC) 1.509 Mall et al. (2007)
11 Activated carbon-laboratory grade (ACL) 12.552 Mall et al. (2007)
12 ZnS: Cu nanoparticles loaded on activated carbon – – 38.1 Asfaram et al. (2015b)
13 KG-cl-poly(AA-co-DMA)@BT 165.28 158.73 152.67 This study

3.18. Desorption studies
The adsorption-desorption experiment is conducted for evaluating
the regeneration and reusability characteristics of the synthesized hy-
drogel KGNCH-3. Desorption of the adsorbed cationic dye a molecule
(MB, CV and AO) from the surface of the KGNCH-3 is investigated in
aqueous solution at different pHs ranging from 2 to 12 and the results
are shown in Fig. 11(a–c). Desorption behaviour of the KGNCH-3 shows
an opposite trend to its adsorption. The maximum desorption of MB and
CV dyes is observed at pH 2 and for AO maximum desorption is ob-
served at pH 3.5 while minimum desorption is observed in alkaline
solution. Five successive adsorption-desorption cycles are carried out at
pH 2.0 for MB, CV dyes, and at pH 3.5 for AO dye. After every cycle, the
sample is treated with a 0.1 M NaOH solution in order to regenerate the

% adsorption
(a) % desorption % adsorption
(b) % desorption

100
100
80

al
oval

80
after

ter
% dye remov
each cycle

each cycle
efficiency af
% dye rem

60
efficiency

60
40 40
20 20
ad 0 0
so Num 5 5
rp
tio ber 4 ad Nu
n- of so
rp mb4
cy des 3 tio e 3
cle
s
or
pt n- r o f
io
n
2 c y deso 2
cle rp
1 s tio 1
n

% adsorption
% desorption
(c)

100

80

60
al
ter
% dye remov

each cycle

40
efficiency af

20

5 0
ad Nu 4
so m
rp
tio ber 3
n- of
cy deso 2
cle rp 1
s tio
n

Fig. 11. Adsorption-desorption cyclesof (a) MB (b) CV (c) AO respectively using KGNCH-3.

62
S. Jana, et al.
adsorption sites. The pH dependence of the desorption behaviour is
explained by the following way; in acidic pH the carboxylate and amine
groups present in the KGNCH-3 exist as protonated form which des-
orbed the cationic dye molecules from the surface due to the reduction
of electrostatics interaction between the cationic dye molecules and the
functional groups present in the KGNCH-3. The maximum desorption is
observed 81.3% for MB and 88.6% for CV at pH = 2, and 90.1% for AO
at pH = 3.5 after five cycles. CV dye molecule is desorbed faster due to
its large size compare to the other dye molecules (Jana et al., 2018b).
The desorption study suggests that the pH sensitive KGNCH-3 can be
used repeatedly for the adsorption of cationic dyes.
4. Conclusion
The pH sensitive nanocomposite hydrogel KG-cl-poly(AA-co-DMA)@
BT is successfully synthesized using crosslinked co-polymerization
technique. Several morphological and spectroscopic analyses indicate
the successful incorporation of BT into the crosslinked hydrogel matrix.
The nanocomposite hydrogel shows pH dependence in the water
swelling behaviour and maximum PS is observed 1131% at pH = 10.
The adsorption of cationic dyes is also influenced by the pH of the
medium and maximum dye adsorption is found to occur at pH = 7.5 for
MB, pH = 8.0 for CV and pH = 10.0 for AO. The nanocomposite hy-
drogel shows better removal efficiency over the crosslinked hydrogel.
The adsorption of cationic dyes follows the Freundlich isotherm and
pseudo second order kinetic model. Various thermodynamic parameters
indicate spontaneous and endothermic nature of the adsorption.
Furthermore, adsorption-desorption studies show that KGNCH-3 can be
used repeatedly for the removal of cationic dyes from their aqueous
solution. Thus KGNCH-3 has a promising application for the removal of
cationic dyes from such dye enriched wastewater.
Acknowledgments
The financial support of this research work by the West Bengal
Department of Science and Technology [contract grant number 868
(Sanc.)/ST/P/S & T/15G-9/2015] and Higher Education, Science &
Technology and Biotechnology (Biotech.) (Contract Grant Number
60(Sanc.) BT/P/Budget/RD-63/2017) is earnestly acknowledged.
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