Colloid and Polymer Science (2018) 296:653–667

https://doi.org/10.1007/s00396-018-4277-z

ORIGINAL CONTRIBUTION

Preparation and characterization of poly(acrylic acid-co-acrylamide)

/montmorillonite composite and its application for methylene blue
adsorption
Congcong Wei 1,2 & Zhiqun Xu 1,2 & Fuhao Han 1,2 & Wenkai Xu 1,2 & Junjie Gu 1,2 & Minrui Ou 1,2 & Xiaoping Xu 1,2

Received: 28 October 2017 / Revised: 6 January 2018 / Accepted: 19 January 2018 / Published online: 21 February 2018
# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
A series of poly(acrylic acid-co-acrylamide)/montmorillonite composite (poly(AA-co-AM)/MMT) was prepared by radical
polymerization. The composite was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron micro-
scope (SEM), energy dispersive X-ray (EDX) and X-ray diffraction (XRD). Batch adsorption experiments of methylene blue
(MB) from aqueous solutions were carried out with poly(AA-co-AM)/MMT composite. The effects of montmorillonite (MMT)
content, initial pH of MB solutions, adsorption temperature, and ionic strength on the adsorption were investigated. Furthermore,
the adsorption kinetics and isotherms were studied by analyzing the effect of adsorption time and initial MB concentration on the
adsorption capacity. The results indicated that the addition of a small amount of MMT could improve the adsorption capacity of
the poly(AA-co-AM). The maximum adsorption capacity of poly (AA-co-AM)/MMT (2%) composite was 1964.1 mg g−1. The
adsorption kinetics were in good agreement with the pseudo-second-order equation, and the adsorption isotherms were better
fitted for the Langmuir equation. In addition, desorption studies show that the composites have good regenerative properties. The
experimental results show that the poly(AA-co-AM)/MMT can be used as promising adsorbent for the removal of MB from
wastewater.

Keywords Composites . Hydrogels . Montmorillonite . Adsorption . Methylene blue

Introduction water bodies and hinder the photosynthesis of aquatic plants

[3]. In addition, some dyes or their metabolites are biological-
Synthetic dyes were widely used in textile, paper, leather, ly toxic, even carcinogenic and mutagenic, which poses a
food, cosmetics, plastics, and other fields [1]. A large amount huge threat to human health [4]. For example, methylene blue
of untreated dye wastewater was discharged directly into nat- (MB) is a widely used cationic dye, which can cause eye
ural water bodies every year. Dye wastewater was character- burns. And through oral intake, it will produce burning sensa-
ized by high organic content, high chromaticity, complex tion, causing nausea, vomiting, sweating, mental disorders, or
composition, and poor biodegradability, so it was widely rec- methemoglobinemia [5]. Therefore, the effective treatment of
ognized as one of the intractable industrial wastewaters [2]. dye wastewater is still an important field of widespread
Even if a small amount of dye wastewater was discharged into concern.
the water, it also can greatly reduce the light transmittance of There are many methods to remove dyes from wastewater,
such as membrane separation [6], coagulation and flocculation
[7], electrocatalysis [8], oxidation or ozonation [9], biodegra-
* Xiaoping Xu dation [10], and adsorption. Among these methods, the ad-
[email protected] sorption method, with its low cost, high speed, and large ca-
pacity and that its adsorbent can be recycled and other advan-
1
Key Laboratory of Pharmaceutical preparations, College of tages, becomes the most effective and commonly used waste-
Chemistry, Fuzhou University, Fuzhou 350108, People’s Republic of
China
water decolorization method [11]. At present, activated carbon
2
is the most widely used commercial adsorbent. However, the
Key Laboratory of Bipharmaceutical, College of Chemistry, Fuzhou
University, Fuzhou 350108, People’s Republic of China
market price of industrial-grade activated carbon is considered
654 Colloid Polym Sci (2018) 296:653–667

very expensive (average cost about US$7.5/kg) [12]. In addi- dispersive X-ray (EDX), and X-ray diffraction (XRD). The
tion, activated carbon has some disadvantages such as low effects of MMT content, pH value, interference ionic strength,
adsorption capacity, complicated and expensive regeneration and adsorption temperature were studied. In addition, the ad-
process, large loss of adsorbent, and no selectivity and inef- sorption kinetics and adsorption isotherm parameters were
fectiveness for disperse dyes and vat dyes [13]. These short- also evaluated in detail. Finally, the desorption and reusability
comings have greatly restricted the practical value of activated of the composites were also investigated. The experimental
carbon and prompted many researchers to find more econom- results show that the poly(AA-co-AM)/MMT composite can
ical adsorbents. be used as promising adsorbent for the removal of cationic dye
Hydrogel is a kind of polymer material with three- from wastewater.
dimensional network structure, which is composed of hydro-
philic homopolymer or copolymer [14]. It can swell in aque-
ous solution; has good water permeability, biocompatibility, Materials and method
and biodegradability; and can perceive and respond to envi-
ronmental changes [15]. Hydrogel contains a large number of Materials
functional groups, such as hydroxyl, amino, carboxyl, and
amide groups, which have strong binding capacity for cationic Acrylic acid (AA), acrylamide (AM), methylene blue (MB),
dyes. However, these polymers have some limitations such as N,N,-methylenebisacrylamide (MBA), sodium nitrate
poor mechanical properties, poor thermal stability, and low (NaNO3), and magnesium nitrate hexahydrate (Mg(NO3)2·
porosity [16]. Due to its low cost, abundant distribution, and 6H2O) and iron(III) nitrate nonahydrate (Fe(NO3)3·9H2O)
high adsorption properties, natural clay minerals can be used were all obtained from Sinopharm Chemical Reagent Co.,
as wastewater treatment adsorbents. According to different Ltd. Sodium hydrogen sulfite (SHS), sodium hydroxide
layered structures, clay minerals are mainly divided into mont- (NaOH), and hydrochloric acid were all purchased from
morillonite, mica, kaolinite, apatite, vermiculite, and sepiolite Xilong Chemical Co., Ltd. Ammonium persulfate (APS)
[17]. Among them, montmorillonite clay has the largest sur- w a s s u p p l i e d b y Sh a n g h a i S A N G O N B i o l o g i c a l
face area and cation exchange capacity, and the current market Engineering Co., Ltd. Sodium montmorillonite (Na-MMT)
price (about US$0.04–0.12/kg) is much lower than of activat- was supplied by Nanocor Inc., USA. The cationic exchange
ed carbon [13]. The excellent adsorption property and low capacity (CEC) of MMT-Na is 145 mequiv/100 g, with a
price of montmorillonite clay have attracted the attention of purity greater than 98%, with a methylene blue adsorption
many researchers [18–20]. However, in practical applications, capacity of 437.7 mg L−1 and with 16–22 μm particle size.
clay adsorbent still has the disadvantages of poor The chemical compositions of MMT-Na are given in Table 1.
dispersibility, difficulty in solid-liquid separation, and poor All chemicals were of analytical grade and used without fur-
reusability [21]. ther purification. All aqueous solutions were prepared with
In recent years, researchers have prepared a series of deionized water.
polymer/clay composites by doping clay minerals in polymer
systems. Marrakchi, F [22] reported a cross-linked chitosan/ Preparation of poly(AA-co-AM)/MMT composite
sepiolite composite for the adsorption of methylene blue and adsorbent
reactive orange 16 dyes. Shirsath, SR [23] synthesized poly
(acrylamide)-kaolin composite hydrogel by ultrasonic- In this paper, a series of poly(AA-co-AM)/MMT composite
assisted in situ emulsion polymerization to remove crystal was prepared by radical polymerization. The specific prepara-
violet dye from wastewater. Ayazi, Z [24] synthesized tion method was as follows. First, 8 g of AA and 20 mL of
alginate-montmorillonite-polyaniline nanocomposite and op- distilled water were placed in a 100-mL beaker with mechan-
timized the reactive orange 13 adsorption conditions by the ical stirring at room temperature. Then, 3.55 g of NaOH was
response surface methodology. Polymer/clay mineral com- dissolved in 10 mL of distilled water and added drop-wise to
posite combines the advantages of both, maintaining high ad- the mixture in an ice bath so that AA was partially neutralized
sorption capacity while dramatically reducing costs and im- to 80%. Then, 2 g of AM and different amounts of MMT were
proving material properties (mechanical strength, thermal sta- added and stirred for 30 min. Then, 0.08 g of MBA was dis-
bility, material porosity, and reusability). solved in 5 mL of distilled water, added to the mixture, and
In this paper, we report a novel composite of poly(AA-co- stirred for 15 min. Finally, 0.06 g of APS and 0.06 g of SHS
AM)/montmorillonite (MMT), which is used as an adsorbent were dissolved in 5 mL of distilled water and added to the
for the removal of cationic dye MB (molecular structure is mixture to initiate the polymerization reaction. The mixture
shown in Scheme 1a) in aqueous solutions. The composites was reacted in a water bath at 50 °C for 1 h and then reacted at
were characterized by Fourier transform infrared spectroscopy 70 °C for 2 h. After completion of the polymerization reaction,
(FTIR), scanning electron microscope (SEM), energy the sample was chopped and rinsed with deionized water until
Colloid Polym Sci (2018) 296:653–667 655

Scheme 1 a Structure of MB. b Synthesis process of poly(AA-co-AM)/MMT composite

the unreacted material was completely removed and dried in a the adsorption capacity and adsorption efficiency of adsorbent
vacuum freeze drier for 24 h to constant weight. The product to MB was calculated according to the following formula:
was then milled and passed through a 100-mesh screen and
ð C0 −Ce Þ V
used for further experiments. Synthesis process of composite qe ¼ ð1Þ
material is as shown in Scheme 1b. m
C0 −Ce
%adsorption ¼ ð2Þ
Characterization methods C0

where qe is the equilibrium adsorption capacity of adsorbent

FTIR spectra of the samples were recorded by a Fourier trans- (mg g−1); C0 and Ce are the initial and equilibrium concentra-
form infrared spectrometer (Nicolet Magna 670) in the range tion of the MB solution, respectively (mg L−1); m is the weight
of 4000–400 cm−1. The morphology and composition of the of the adsorbent (mg), and V is the volume of the MB solution
samples were measured by field-emission scanning electron (mL).
microscopy (FE-SEM, Nova NanoSEM 230, FEI, USA) and The effect of MMT content on MB removal was studied by
energy dispersive X-ray (EDX) spectrometer. The crystal adding adsorbents with different MMT contents to MB solution
structures of the samples were characterized by an X-ray dif- (2000 mg L−1, pH 5.0) and adsorbing at 25 °C for 120 min. The
fractometer (XRD, Empyrean, PANalytical, Netherlands) MB solution (2000 mg L−1) was adjusted to different pH by
with Cu Kα radiation. The MB concentrations in aqueous using a pH meter and adsorbed at 25 °C for 120 min to study
solutions were determined using a UV-Vis spectrophotometer the effect of pH on MB removal. The effect of temperature on
(UV-1780, Shimadzu, Japan) at 665 nm according to the cal- MB removal was investigated by adjusting the thermostatic shak-
ibration curve. er to different temperature and adsorbing MB solution
(2000 mg L−1, pH 5.0) for 120 min. The effect of ionic strength
Adsorption experiments on MB removal was investigated by adding different concentra-
tions of interfering ions to the MB solution (2000 mg L−1,
All batch adsorption experiments were carried out in 20 mL of pH 5.0) and adsorbing at 25 °C for 120 min. In addition, the
MB aqueous solution with 20 mg of the adsorbent and shak- adsorption kinetics were studied by adding 20 mg of adsorbent to
ing at 150 rpm on a thermostatic shaker. After a certain period 20 mL of MB solution (2000 mg L−1, pH 5.0) and shaking at
of time, the sample was taken from the shaker and the mixture 25 °C for predetermined time interval. The adsorption isotherms
was centrifuged by a high-speed centrifuge. The absorbance was investigated by adding 20 mg of adsorbent to 20 mL of
of MB in the supernatant was measured at 665 nm using a UV- different concentrations of MB solution (pH 5.0) and adsorbing
Vis spectrophotometer, and the MB concentration remaining at 25 °C for 120 min. Each experiment was run in triplicate and
in the solution was calculated by the calibration curve. Finally, the average data were presented.

Table 1 The chemical composition of sodium montmorillonite (wt%)

Composition SiO2 Al2O3 Na2O MgO Fe2O3 CaO K2O Ti2O

Proportion 61.932 23.278 6.415 3.913 3.217 0.294 0.217 0.184

656 Colloid Polym Sci (2018) 296:653–667

Desorption and reusability studies and symmetrical stretching vibration of –COO−, respectively
[26]. In addition, C=C stretching vibration in AA and AM did
The desorption performance of the adsorbent for MB was not appear, indicating that copolymerization of AA and AM
evaluated by the following method. First, 20 mg of the adsor- monomers occurred.
bent was added to 20 mL of MB solution (2000 mg L−1, For the poly(AA-co-AM)/MMT30%(Fig. 1c), 3350 cm−1 is
pH 5.0) and shaken at 25 °C for 120 min. The adsorbent is attributed to the superposition of the stretching vibrations of O–
then recovered with a high-speed centrifuge and washed thor- H and N–H in poly(AA-co-AM); 2941 cm−1 corresponds to CH
oughly with distilled water to remove unadsorbed dyes. stretching vibration, 1663; and 1550, 1450, and 1403 cm−1 cor-
Distilled water (20 mL) of different pH was used as the eluent, respond to the characteristic peaks of poly(AA-co-AM).
and then the loaded adsorbent was placed in different pH Compared with Fig. 1b, c, the new peaks at 1031, 513, and
eluate and shaken at 25 °C for 60 min. Finally, the MB con- 452 cm−1 are attributed to Si–O–Si stretching vibration, Si–
centration in supernatant and eluate was measured by UV-Vis O–M coupling vibration, and M–O coupling vibration in mont-
spectrophotometer, respectively, and the desorption rate was morillonite, respectively. In addition, the Al–O–H stretching
calculated by the following formula: vibration (3618 cm−1) due to the MMT surface almost disap-
pears, indicating that montmorillonite is not simply mixed in the
Cd
%desorption ¼ ð3Þ polymer matrix, and the Al–O–H on the MMTsurface may also
C0 −Ce be involved in the copolymerization.
where C0 and Ce are the initial and equilibrium concentration of The infrared spectra of MB (Fig. 1d) and poly(AA-co-
the MB solution in the adsorption experiment, respectively (mg AM)/MMT30%/MB (Fig. 1e) were analyzed comparatively.
L−1), and Cd is the equilibrium concentration of MB in the eluent. It can be seen that the new peaks at 1598 and 1489 cm−1(Fig.
The reusability of the adsorbent was studied by five cycles 1e) belonged to the aromatic ring skeleton stretching vibration
of continuous adsorption-desorption. First, the adsorption ex- of MB. In addition, the new peaks at 1334, 1138, and
periment was carried out in the same manner as the desorption 885 cm−1 correspond to the –CH3 symmetrical bending vibra-
experiment, and then 20 mg of the loaded adsorbent was tion, C–S stretching vibration, and C–H surface bending vi-
desorbed in HCl solution (20 mL, 0.1 M) for 60 min. The bration of MB, respectively [27], indicating that MB was suc-
sample was then placed in NaOH solution (20 mL, 0.1 M) cessfully adsorbed on poly(AA-co-AM)/MMT composites.
and shaken at 25 °C for 20 min to neutralize the residual
hydrochloric acid. Finally, the adsorbent is sufficiently XRD characterization
washed with distilled water for a new adsorption-desorption
cycle. Each experiment was run in triplicate and the average The main diffraction peaks of the MMT minerals in Fig. 2 have
data were presented. been labeled, among which 001, 002, 110, 004, 220, 310, and
330 are the characteristic diffraction peaks of Na-MMT, while
100, 101, and 112 are the characteristic diffraction peaks of
detrital minerals (α-quartz) in MMT minerals [28]. The strong
Results and discussion diffraction peak of MMTat 2θ = 7.12° is the reflection from the
(001) basal plane [29], and the corresponding interlayer spacing
FTIR characterization d001 = 1.241 nm is calculated by the Bragg equation (2dsinθ =
nλ). In addition, poly(AA-co-AM) is completely amorphous
The infrared spectra of MMT, poly(AA-co-AM), poly(AA-co- with no diffraction peaks. The characteristic diffraction peaks
AM)/MMT30%, MB, and poly(AA-co-AM)/MMT30%/MB of MMT in poly(AA-co-AM)/MMT30% composites still exist,
are shown in Fig. 1. For the MMT (Fig. 1a), 3618 and which proves that MMT was effectively incorporated into
912 cm−1 respectively correspond to the Al–O–H stretching poly(AA-co-AM) matrix. And the d001 value is almost un-
and bending vibration of the montmorillonite sheet surface, changed, indicating that the monomers are mainly polymerized
3424 and 1636 cm−1 respectively correspond to the H–O–H between the montmorillonite particles. In addition, the charac-
stretching and bending vibration of the water molecules in the teristic diffraction peaks of MMT in poly(AA-co-AM)/
montmorillonite layer, 1012 cm−1 due to Si–O–Si stretching MMT2% composites are hardly observed. This may be due to
vibration, 797 cm−1 is attributed to the α-quartz in montmoril- the relatively low content of montmorillonite in the composite.
lonite, and 512 cm−1 due to Si–O–M coupling vibration [25].
For the poly(AA-co-AM) (Fig. 1b), 3346 cm−1 corresponds to Structural and morphology characterization
N–H stretching vibration of AM, 2944 cm−1 corresponds to C–H
stretching vibration, 1663 cm−1 corresponds to C=O bending The SEM images of poly(AA-co-AM) and poly(AA-co-AM)/
vibration of AA, 1450 cm−1 due to the C–N stretching vibration MMT30% (before and after adsorption) are shown in Fig. 3.
of AM, and 1550 and 1403 cm−1 are attributed to the asymmetric SEM analysis showed that the surface of poly(AA-co-AM)
Colloid Polym Sci (2018) 296:653–667 657

Fig. 1 FTIR spectra of a MMT, b

poly(AA-co-AM), c poly(AA-co-
AM)/MMT30%, d MB, and e
poly(AA-co-AM)/MMT30%
/MB

was dense and smooth, and the introduction of MMT made SEM images of poly(AA-co-AM)/MMT30% before and after
the composite surface rough and porous. This facilitates dye adsorption, it was found that the irregular sheet structure on
penetration and adsorption onto the polymer network, thereby the surface of the adsorbent disappeared and covered with
increasing adsorption capacity. In addition, comparing the many particles.

Fig. 2 XRD patterns of MMT, poly(AA-co-AM)/MMT, poly(AA-co-AM)/MMT2%, and poly(AA-co-AM)/MMT30%

658 Colloid Polym Sci (2018) 296:653–667

Fig. 3 SEM images of a poly(AA-co-AM), b poly(AA-co-AM)/MMT30%, and c poly(AA-co-AM)/MMT30%/MB

The EDX spectra of poly(AA-co-AM) and poly(AA-co- adsorption capacity(437.7 mg L−1) and a higher MMT content
AM)/MMT30% (before and after adsorption) are shown in reduces the content of –COO– groups in the polymer compos-
Fig. 4. EDX analysis showed that the poly(AA-co-AM)/ ite, which is also an important reason for the decrease of ad-
MMT contains characteristic elements (Mg, Al, Si) of mont- sorption capacity [32]. Therefore, we selected blank samples,
morillonite, indicating that the poly(AA-co-AM)/MMT com- the best samples (containing 2% MMT), and the cheapest
posite has been successfully prepared. The characteristic ele- samples (including 30% MMT) for further experiments.
ment (S) of MB appeared on the EDX spectra of poly(AA-co-
AM)/MMT (after adsorption), indicating that MB was suc- Effect of pH value on adsorption
cessfully adsorbed onto poly(AA-co-AM)/MMT. In addition,
comparing the EDX spectra of poly(AA-co-AM)/MMT (be- The pH of dye solution can affect the degree of ionization of
fore and after adsorption), it was found that the content of Na adsorbent and the molecular structure of dye, which is an
decreases while the content of S increases. This may be that important factor affecting the removal of dye [33]. The effect
the MB cationic dye replaced the Na ion in the –COONa of the pH value of the dye solution on the adsorption of
group by ion exchange. Alternatively, –COONa was ionized poly(AA-co-AM)/MMT is shown in Fig. 6. The adsorption
in an alkaline environment to produce –COO–, which adsorbs capacity of the adsorbent increased sharply with the increase
the MB cationic dye by electrostatic attraction. of the initial pH value. However, when the pH was increased
to 5.0, the adsorption amount of MB was almost constant.
Effect of MMT content (wt%) on adsorption This is because when the pH is low, the excess H+ in the
solution causes the carboxyl groups in the adsorbent to be
The introduction of inorganic clay components can reduce the mostly in the form of –COOH. At the same time, H+ also
cost of materials, and the clay content has an important effect competes with cationic dye MB for the adsorption site of the
on the performance of the polymer system [30]. The influence adsorbent. When the pH value is gradually increased, the –
of MMT content on the adsorption of poly(AA-co-AM)/MMT COOH groups in the adsorbent dissociate to form –COO–,
composite is shown in Fig. 5. The adsorption capacity of the increasing the electrostatic attraction of the adsorbent to MB,
polymer system was increased from 1878 to 1935 mg g−1 after thus increasing the adsorption capacity of MB. In addition,
the introduction of 2% MMT. According to the FTIR analysis electrostatic repulsion between adjacent –COO− groups in
of the composites, the –OH of the montmorillonite surface the polymer network causes the adsorbent to swell highly in
participates in the polymerization reaction and acts as a the dye solution, which is also an important reason for the
crosslinking point in the network, which can improve the increased adsorption capacity. And the pKa of polyacrylic
polymer network structure and adsorption capacity. In addi- acid is about 4.7 [34]; the adsorption capacity of MB is almost
tion, according to XRD and SEM analysis, the introduction of constant due to the buffering effect between –COOH and –
MMT made the composite surface rough and porous, which is COO– groups when the pH reaches 5.0. Thus, further studies
conducive to dye penetration and adsorption to the polymer of MB adsorption on poly(AA-co-AM)/MMT were carried
network, thereby enhancing the adsorption capacity. out at pH = 5.0.
However, a further increase in MMT content reduced the ad-
sorption capacity of the composite. The higher MMT content Effect of temperature on adsorption
will produce excessive crosslinking point, which leads to
higher crosslinking densities and lower elasticity of the poly- The effect of ambient temperature on the adsorption of
mer chains, thereby reducing the adsorption capacity of com- poly(AA-co-AM)/MMT is shown in Fig. 7. When the tem-
posites [31]. Furthermore, pure MMT has a lower MB perature rose from 15 to 35 °C, the adsorption capacity of
Colloid Polym Sci (2018) 296:653–667 659

Fig. 4 EDX spectra of a

poly(AA-co-AM), b poly(AA-co-
AM)/MMT30%, and c poly(AA-
co-AM)/MMT30%/MB
660 Colloid Polym Sci (2018) 296:653–667

Fig. 5 Effect of MMT content on

adsorption of poly(AA-co-AM)/
MMT (initial concentrations
2000 mg L−1, adsorption time 2 h,
temperature 25 °C and pH value
5.0)

the composites increased. But when the temperature is fur- Effect of ionic strength on adsorption
ther increased, the adsorption capacity of the composite
material began to decline. The results can be attributed to Figure 8 shows the effect of ionic strength of different cations
the following factors. Appropriate elevate temperatures on the adsorption efficiency of poly(AA-co-AM)/MMT. It
can increase the swelling degree of the adsorbent, which was found that as the ionic strength of the cation in the solu-
contributes to the diffusion of dye molecules into the inte- tion increases, the adsorption efficiency of the adsorbent to
rior of the adsorbent. At the same time, increasing the tem- MB decreases. This is due to the fact that coexisting cations
perature properly can increase the dye diffusion rate and in solution competed with the MB cationic dye for adsorption
reduce the mass transfer resistance, thus enhancing the ad- sites on poly(AA-co-AM)/MMT. In addition, the coexisting
sorption capacity of adsorbent [35]. However, too high cations in the solution may shield the adsorption sites on the
temperature destroys the network structure of the polymer adsorbent, weaken the electrostatic attraction between adsor-
and separates the dye molecules that combine with the bent and MB, resulting in a decrease in MB removal efficien-
adsorbent [36]. In addition, since the adsorption process cy. In addition, under the same concentration, the effect of
of the MB is exothermic, the high temperature weakens high-valence cations on adsorption efficiency is greater than
the bond between the adsorbent site and the dye molecule, that of low-valence cations, which may be due to the greater
thereby reducing the adsorption capacity of adsorbent [37]. contribution of high-valence cation to ionic strength.

Fig. 6 Effect of the pH on

adsorption of poly(AA-co-AM)/
MMT (initial concentrations
2000 mg L−1, adsorption time 2 h,
and temperature 25 °C)
Colloid Polym Sci (2018) 296:653–667 661

Fig. 7 Effect of the temperature

on adsorption of poly(AA-co-
AM)/MMT (initial concentrations
2000 mg L−1, adsorption time 2 h,
and pH value 5.0)

Adsorption kinetics The pseudo-first-order kinetics model is expressed as

logðqe −qt Þ ¼ logqe −k1 t ð4Þ
The effect of adsorption time on the adsorption of poly(AA-
co-AM)/MMT is shown in Fig. 9a. The adsorption amount of The pseudo-second-order kinetics model is expressed as
MB increased rapidly in the first 15 min, exceeding 90% of
the total amount of adsorption. Then, the MB adsorption ca- t 1 t
¼ 2
þ ð5Þ
pacity slowly increased and reached equilibrium after qt k 2 q e q e
120 min. In order to study the dynamic interaction between
the adsorbate and the adsorbent, the adsorption mechanism The intra-particle diffusion model is expressed as
was further understood. The adsorption kinetics of MB by
qt ¼ ki t1=2 þ C ð6Þ
poly(AA-co-AM)/MMT was studied by pseudo-first-order ki-
netics model [38], pseudo-second-order kinetics model [39], where t is the adsorption time (min); qe and qt are the adsorp-
and intra-particle diffusion model [40]. tion capacity (mg g−1) of MB by adsorbent at adsorption equi-

Fig. 8 Effect of the ionic strength

on adsorption of poly(AA-co-
AM)/MMT (initial concentrations
1000 mg L−1, adsorption time 2 h,
temperature 25 °C, pH value 5.0,
and MMT content 30%)
662 Colloid Polym Sci (2018) 296:653–667

librium and time t; k1 and k2 are pseudo-first-order rate con- surface, the adsorption rate of the fastest. The second
stants (min−1) and pseudo-second-order rate constants (g stage is the intra-particle diffusion stage, and the MB
mg−1 min−1), respectively; ki is the intra-particle diffusion rate molecules begin to diffuse into the pores for adsorption.
constants (mg g−1 min-1/2); and C is a constant related to the Finally, the adsorption capacity does not change with
thickness of the boundary layer. time, indicating that the adsorption reaction has reached
The obtained kinetic parameters and correlation coeffi- equilibrium [41]. Among them, the intra-particle diffusion
cients are shown in Table 2, and the results of the kinetic stage is the rate control step of the adsorption reaction,
fitting curve are shown in Fig. 9. It can be seen from where qt has a good linear relationship with t1/2. But the
Table 2 that the experimental data are in good agreement fitting curve does not go through the origin, indicating
with the pseudo-second-order model, and the correlation that the intra-particle diffusion is not the only control step
coefficient (R 2 ) of the pseudo-second-order model is of the adsorption process. The adsorption process may
0 . 9 9 9 9 . I n a d d i t i o n , t h e t h e o r e ti c a l a d s o r p t i o n also be affected by the surface adsorption and liquid-
capacity(qe,cal) calculated by the pseudo-second-order ki- film diffusion mechanism [42].
netic model is very close to the experimental adsorption
capacity(qe,exp). The results show that the adsorption pro- Adsorption isotherms
cess of MB by poly(AA-co-AM)/MMT follows the
pseudo-second-order kinetics model. The effect of MB initial concentration on the adsorption of
As shown in Fig. 9b, the entire adsorption process can poly(AA-co-AM)/MMT is shown in Fig. 10. The results showed
be divided into three parts. First is the surface adsorption that when the initial concentration of MB increased from 1600 to
stage, MB molecules from the solution to the adsorbent 2000 mg L−1, the adsorption capacity of the composites

Fig. 9 a Effect of the adsorption time on adsorption of poly(AA-co-AM)/MMT, b intra-particle diffusion model, c pseudo-first-order model, and d
pseudo-second-order model
Colloid Polym Sci (2018) 296:653–667 663

Table 2 Kinetic parameters for the adsorption of MB on poly(AA-co-AM)/MMT

MMT(wt%) qe,exp Pseudo-first-order model Pseudo-second-order model

qe,cal k1 × 10−2 R2 qe,cal k2 × 10−4 R2

0 1883.2 314.2 1.758 0.6026 1889.9 7.065 0.9999

2 1943.5 269.2 1.669 0.5679 1948.4 8.984 0.9999
20 1809.8 461.9 1.676 0.6823 1819.2 4.365 0.9999

increased rapidly. However, when the initial concentration of The adsorption isotherm can be used to study the interaction
MB is further increased, the adsorption capacity of the composite between the adsorbent and the adsorbate, thus further explaining
is almost invariable, while the removal rate of MB decreases the adsorption mechanism [43]. The Langmuir and Freundlich
rapidly. This may be due to that the three-dimensional network models are two typical adsorption isothermal models. The
space of poly(AA-co-AM)/MMT is substantially filled with MB Langmuir isothermal model assumes that the adsorbate is mono-
molecules, so that excess MB molecules are difficult to continue layer adsorbed on the adsorbent surface, and the adsorption sites
to diffuse into the adsorbent. on the adsorbent surface are evenly distributed, and the adsorbed

Fig. 10 Effect of the initial MB concentration on adsorption of poly(AA-co-AM)/MMT. a Adsorption capacity. b Removal rate. Adsorption isotherm
plots of MB adsorption onto poly(AA-co-AM)/MMT. c Langmuir. d Freundlich
664 Colloid Polym Sci (2018) 296:653–667

Table 3 Isotherm parameters for the adsorption of MB on poly(AA-co-AM)/MMT

MMT (wt%) qm,exp Langmuir isotherm Freundlich isotherm

qm,cal (mg g−1) KL (L mg−1) RL × 10−3 R2 kF 1/n R2

0 1884.8 1900.3 0.421 1.08–1.48 0.9999 1446.6 0.0503 0.8574

2 1947.6 1964.1 0.512 0.98–1.22 0.9999 1466.73 0.0569 0.7842
20 1800.4 1820.4 0.273 1.66–2.28 0.9999 1391.3 0.0463 0.8689

molecules do not react with each other [44]. RL is an important the better the adsorption performance, and the 1/n > 2 is difficult
dimensionless parameter of the Langmuir isothermal model. The to adsorb [47].
Freundlich model is an empirical adsorption isotherm describing The adsorption isotherm parameters and correlation coeffi-
multilayer adsorption and assumes that the adsorption surface is cients obtained by fitting the experimental data are shown in
heterogeneous [45]. The equations are represented by the follow- Table 3, and the results of the isotherm fitting curve are shown
ing formulas: in Fig. 10. It can be seen from Table 3 that the experimental
data agree well with the Langmuir isothermal model with a
Ce 1 Ce correlation coefficient of R2 > 0.9999. And the theoretical
¼ þ ð7Þ
qe bqm qm maximum adsorption capacity (qm,cal) is similar to the exper-
imental adsorption capacity (qm,exp). The results showed that
1
logqe ¼ logK f þ logCe ð8Þ the adsorption process of poly(AA-co-AM)/MMT on MB was
n monolayer. In addition, the separation factor RL is in the range
1 of 0 to 1, and the Freundlich constant 1/n is much smaller than
RL ¼ ð9Þ
1 þ bC0 2, indicating that the adsorption reaction is prone to occur.
where C0 and Ce are the initial and equilibrium concentration of
the adsorbate respectively (mg L−1); qe and qm are the equilib- Desorption and reusability studies
rium and saturated adsorption capacity of the adsorbent, respec-
tively (mg g−1); b is the Langmuir adsorption equilibrium con- Desorption studies can further study the mechanism of ad-
stant (L mg−1); RL is the separation factor, which can be used to sorption processes. If the distilled water can elute the dye, it
determine whether it is suitable for adsorption, unfavorable ad- can be deduced that the dye molecules are fixed to the adsor-
sorption (RL > 1), linear adsorption(RL = 1), favorable adsorp- bent via the weak bond. If the dye is to be eluted with a strong
tion(0 < RL < 1), and irreversible adsorption(RL = 0) [46]; KF is acid solution, it can be deduced that the dye molecules are
the Freundlich adsorption equilibrium constant; and n is the immobilized on the adsorbent by ion exchange or electrostatic
constant of adsorption strength, where the smaller the 1/n value, absorption [48]. Thus, the dye-supported poly(AA-co-AM)/

Fig. 11 a Effect of pH on desorption percentage of dye from dye-loaded poly(AA-co-AM)/MMT. b Reusability of the dye-loaded poly(AA-co-AM)/
MMT (initial concentrations 2000 mg L−1, adsorption time 2 h, temperature 25 °C, pH value 5.0, and MMT content 30%)
Colloid Polym Sci (2018) 296:653–667 665

Table 4 Comparison of adsorption capacity of MB by various Adsorption mechanism

adsorbents

Adsorbent qmax (mg g−1) The microstructure and surface groups of poly(AA-co-AM)/
Reference MMT, the structure of MB dyes, and the interaction between
the binding sites and other factors all affect the adsorption
Fe3O4/activated montmorillonite 106.38 [20]
properties of adsorbents. First, combined with FTIR, EDX,
PAA/MGO composites 290.7 [49]
pH effects, and desorption studies, we propose three possible
poly(AM-IA)/DAM/Zr(OH)4 composite 102 [50]
mechanisms for MB adsorption. The first is the electrostatic
HNTs/Fe3O4/poly(DA + KH550) 714.29 [51]
interaction between the –COO– of the adsorbent surface and
nanohybrids
Cr(OH)3–NPs–CNC hybrid nanocomposite 106 [52] the positively charged groups in the MB cationic dye. The
Graphene nanosheet/magnetite composite 43.82 [53] second is that –COOH adsorbs MB cationic dyes directly
M-MWCNTs adsorbent 48.86 [54] through ion exchange. The third is the hydrogen bond inter-
Poly(AA-co-AM)/MMT composites 1964.1 This action between O–H in the polymer and the positively charged
work groups in the MB cationic dye. Secondly, the influence of
MMT content, XRD, and SEM shows that the introduction
of small amounts of MMT can produce loose porous struc-
tures, so as to improve the adsorption capacity of the compos-
MMT was subjected to desorption experiments using HCl ites. Finally, the adsorption kinetics showed that the adsorp-
solutions of different pH as eluent. As shown in Fig. 11a, tion process was controlled by surface adsorption, intra-
the desorption rate of the adsorbent was the highest (85.1%) particle diffusion, and liquid-film diffusion mechanism.
under strong acid (pH 2.0) conditions and decreased rapidly Adsorption isotherm studies show that MB is monolayer
with the increase of eluent pH and reached a minimum value adsorbed on the adsorbent surface.
(0.23%) at pH 9.0. The results show that the MB molecule is
immobilized on poly(AA-co-AM)/MMT by ion exchange or
electrostatic attraction, and the effect of pH on adsorption is
confirmed. Conclusions
Reusability is an important indicator of the practical appli-
cation of adsorbents. The effect of adsorption-desorption cy- In this study, we successfully prepared a series of poly(AA-co-
cle on the adsorption performance of poly(AA-co-AM)/MMT AM)/MMT composites by free radical polymerization and
is shown in Fig. 11b. After five adsorption-desorption cycles, characterized by XRD, FTIR, SEM, and EDX. Batch adsorp-
the adsorbent adsorption capacity decreased slightly but still tion experiments of MB show that the adsorption process of
reached 96% of the initial capacity. The results show that MB depends on MMT content, initial pH value, adsorption
poly(AA-co-AM)/MMT composites have good reusability temperature, and ionic strength. The introduction of a small
and can effectively remove methylene blue in water after re- amount of MMT can produce a loose porous structure, which
peated treatment. can improve the adsorption capacity of composite materials.
The adsorption amount of MB on the composite increases
with the increase of pH and is affected by the temperature
Comparison with other adsorbents change. The adsorption kinetic data are in good agreement
with the pseudo-second-order kinetics model, and the adsorp-
Poly(AA-co-AM)/MMT composites have a very high adsorp- tion process is controlled by the intra-particle diffusion and
tion capacity for methylene blue compared to other reported liquid-film diffusion mechanism. The adsorption equilibrium
montmorillonite, acrylic, or acrylamide-modified adsorbents. data agrees well with the Langmuir isothermal model, indicat-
In addition, the preparation process of adsorbents such as ing that MB is monolayer adsorbed on the composite surface,
HNTs/Fe3O4/poly(DA + KH550) nanohybrids and Cr(OH)3– and the theoretical maximum adsorption capacity is
NPs–CNC hybrid nanocomposite are relatively complicated, 1964.1 mg g−1. Desorption studies show that the desorption
while the adsorption activity of materials such as M- rate of the composites was as high as 85.1%, and the adsorbent
MWCNTs adsorbent and graphene nanosheet/magnetite com- retains 96% of the initial adsorption capacity after five
posite is too low. Compared with the reported adsorbents adsorption-desorption cycles. In addition, the study shows that
(Table 4), poly(AA-co-AM)/MMT composites show very the composite mainly adsorbs MB dye molecules through
high adsorption activity, simple preparation process, and low electrostatic attraction, ion exchange, and hydrogen bonding
preparation cost. Therefore, poly(AA-co-AM)/MMT compos- interaction. Therefore, poly(AA-co-AM)/MMT composites
ites can be used as efficient adsorbents for removing cationic can be used as an economically efficient adsorbent for remov-
dyes in wastewater. ing MB from wastewater.
666 Colloid Polym Sci (2018) 296:653–667

Funding information We would like to thank the University of Fuzhou 15. Alvarez-Lorenzo C, Concheiro A (2002) Reversible adsorption by
(School of Chemistry) for its financial and technical support. a pH- and temperature-sensitive acrylic hydrogel. J Control Release
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