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Synthesis of Poly(methacrylic acid)/Montmorillonite Hydrogel

Nanocomposite for Efficient Adsorption of Amoxicillin and
Diclofenac from Aqueous Environment: Kinetic, Isotherm,
Reusability, and Thermodynamic Investigations
Suhail Ayoub Khan, Mohammad Fuzail Siddiqui, and Tabrez Alam Khan*
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sı Supporting Information

ABSTRACT: Herein, a simplistic redox polymerization strategy was

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utilized for the fabrication of a poly(methacrylic acid)/montmorillonite

hydrogel nanocomposite (PMA/nMMT) and probed as a sorbent for
sequestration of two pharmaceutical contaminants, viz., amoxicillin
(AMX) and diclofenac (DF), from wastewater. The synthesized
hydrogel nanocomposite was characterized by the Fourier transform
infrared, X-ray diffraction, X-ray photoelectron spectroscopy, scanning
electron microscopy−energy dispersive X-ray spectroscopy, and trans-
mission electron microscopy techniques to analyze structural character-
istics and sorption interactions. The efficacy of PMA/nMMT was
thoroughly investigated for the sequestration of AMX and DF from the
aquatic phase with a variation in operative variables like agitation time,
sorbent dosage, pH, and initial sorbate concentration. The reaction
kinetics was essentially consistent with the pseudo-second-order model with rate dominated by the intraparticle diffusion model as
well as the film diffusion mechanism. The Freundlich isotherm appropriated the equilibrium data over the entire range of
concentration. Thermodynamic investigation explored the spontaneous and endothermic nature of the process. The most possible
mechanism has been explained, which includes electrostatic interaction, hydrogen bonding, cationic exchange, and partition
mechanism. Economic feasibility, better sorption capacity (152.65 for AMX and 152.86 mg/g for DF), and efficient regeneration and
reusability even after four consecutive sorption−desorption cycles ascertained PMA/nMMT as a potential sorbent for AMX and DF
uptake from the aqueous phase.

■ INTRODUCTION
Aqueous effluents emanating from pharmaceutical industries,
due to incompetent sewage system.7 It is reported8 that both
amoxicillin and diclofenac cause chronic effects like gastro-
hospitals, municipal areas, and body discharges1 are generally intestinal and renal tissue damage in many vertebrates,
contaminated with numerous hazardous organic pollutants, reduction in size, and hatchability among various fish species.
which are rarely biodegradable even at a low concentration Human health can be adversely affected by the consumption of
range.2 The release of emerging contaminants into the contaminated potable water.9 Thus, to safeguard the environ-
ecosystem has obnoxious effects on ecological species and ment from toxicities related to pharmaceutical pollutants, there
poses a substantial threat to the human and aquatic health.3 is a critical requirement of their removal from aqueous sources.
Among the pollutants derived from pharmaceutical industries, Several remediation strategies have been probed for the
amoxicillin (AMX) and diclofenac (DF) were selected as probe uptake of the pharmaceutical-laden wastewater, including
molecules because they are extensively used and ubiquitously solid-phase separation,10 flocculation, coagulation,11 ultrasonic
found in aqueous bodies.4 Amoxicillin belongs to the group of degradation,12 photodegradation,13 electrochemical degrada-
β-lactam antibiotics with characteristic properties of treating tion,14 and advanced oxidation processes.15 These technologies
bacterial infection, pneumonia, strep throat, and urinary tract suffer from various flaws as they are technically sophisticated or
and skin infection.5 Diclofenac being an anti-inflammatory and
nonsteroidal drug is broadly used to appease inflammation, Received: October 28, 2019
pain caused by migraine, arthritis, gout, and some other Accepted: January 23, 2020
illnesses.6 However, they are not entirely metabolized upon
consumption and approximately 10−15% of these compounds
are excreted and subsequently discharged into the environment

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economically unfavorable. Moreover, they generate toxic

effluents and have a limited removal efficacy.16
Adsorption offers a prominent method for treating effluents
due to its simplicity, economic feasibility, nonproduction of
secondary products and free radicals, and high surface area, as
well as the presence of functional groups with developed pore
assembly.17 Carbon-based sorbents such as activated carbon
derived from olive stones,18 vine wood,19 guava seeds,20
Moringa oleifera,21 pine tree,22 and Mn-impregnated activated
carbon23 have been ubiquitously used for the uptake of
amoxicillin and diclofenac from wastewater. However, due to
their high cost24 and difficulty in separation from aqueous
solution, the development of highly effective sorbents is
considerably important.
Clay-based hydrogel nanocomposites are envisioned to be
potential super adsorbents for the uptake of inorganic and/or
organic contaminants from an aqueous solution due to the
combining characteristics of both clays and polymers, such as
biodegradability, biocompatibility, economic viability, abun-
dance, high specific surface area, three-dimensional network, Figure 1. Chemical structures and the corresponding FTIR spectra of
and swelling−deswelling properties.25 Recently, many clay- AMX and DF.
based hydrogel composites have been explored for the
confiscation of dyes26,27 and metals28−31 mainly because of
their chemically reactive functional groups and porous obtained on a D8 Advance diffractometer (Bruker) with Cu
structures. A perusal of the literature reveals that there is little target (λ = 0.154 nm) at 40 kV. X-ray photoelectron
work on the removal of pharmaceutical pollutants by clay− spectroscopy (XPS) was done on ESCA+ (Omicron Nano-
hydrogel nanocomposites; therefore, the main motive was to technology Oxford Instruments, Germany, Al Kα radiation hν
explore the efficacy of poly(methacrylic acid)/montmorillonite = 1486.7 eV). Scanning electron microscopy (SEM) micro-
hydrogel (PMA/nMMT) nanocomposite toward the uptake of graphs were obtained on a Phenom ProX (Nanoscience
amoxicillin and diclofenac from wastewater. The nanoscale Instruments, Phoenix, AZ) equipped with an energy-disperse
MMT (nMMT) expectedly with improved cation−exchange X-ray (EDX) instrument under an extra high tension of 15 kV
capacity, hydrophilicity, adsorption capacity, interactive surface at a working distance of 3.8 mm with an aperture width of 30
functional groups, and increased surface-to-volume ratio was μm. Transmission electron microscopy (TEM) images were
used as a filler, which could elevate the mechanical strength, recorded on a transmission electron microscope (HRTEM 200
increase active sites for maximum sorption, high surface area, kV model, FEI Tecnai). The residual concentrations of AMX
and improved regenerative ability of PMA/nMMT nano- and DF at 455 and 520 nm (λmax), respectively, were analyzed
composite. The increase in the adsorption capacity and by a UV−vis spectrophotometer (T80+, PG Instruments Ltd,
reusability is crucial from the practical viewpoint. Further, to U.K.).
comprehend the adsorption mechanism, the impact of Preparation of Nanomontmorillonite Clay (nMMT).
operative variables such as dose, agitation time, pH, and initial Nanomontmorillonite (nMMT) was framed following the
sorbate concentration was explored. Equilibrium data were procedure illustrated by Khan et al.31 Briefly, 50 g of MMT was
analyzed using various kinetic and isotherm models and washed three to four times with double-distilled water, left as
thermodynamic parameters to gain significant insight into the such overnight and finely grated. This clay (12 g) was
process. The regeneration potential was investigated to probe dispersed in 100 mL of double-distilled water in a 500 mL
the sustainability of the synthesized sorbent.

■
beaker containing dil. HCl (4 mL). The mixture was heated at
70 °C on a heating mantle for 30 min and finally dispersed in
EXPERIMENTAL SECTION 50 mL of CTAB (0.5 M) with stirring for 12 h at 70 °C by a
Chemicals and Instruments. Methacrylic acid, mont- magnetic stirrer. The clay was filtered off and dried for 48 h at
morillonite (MMT), amoxicillin trihydrate (AMX, 99%), 80 °C in an oven. Finally, it was ground to nano-
diclofenac sodium (DF, 99%), cetyltrimethylammonium bro- montmorillonite (nMMT) powder, which was stored in glass
mide (CTAB), N,N,N,N-tetramethylethylenediamine bottles.
(TEMED), sodium nitrite, 2,2′-bipyridine, ferric chloride, Preparation of Poly(methacrylic acid)/Montmorillon-
ammonium persulfate (APS), and sodium carbonate were ite (PMA/nMMT) Hydrogel Nanocomposite. A PMA/
obtained from Merck, India. Sulfanilic acid was procured from nMMT hydrogel nanocomposite was prepared via ultrasound-
CDH and HCl from Fischer Scientific, India. All chemicals/ assisted redox polymerization. Typically, 1.0 g of nMMT was
reagents were of A.R grade and used as received. The chemical dispersed in 50 mL of distilled water with ultrasonic vibration
structures of AMX and DF with their corresponding Fourier for 2 h to form a homogeneous dispersion. The ultrasound
transform infrared (FTIR) spectra are depicted in Figure 1. helps in the improved dispersion of clay, resulting in an
FTIR spectra of montmorillonite (MMT), nanomontmor- enhancement of the mechanical properties and adsorption
illonite (nMMT), poly(methacrylic acid)/montmorillonite capacity of the hydrogels. Methacrylic acid monomer (30 mL)
hydrogel nanocomposite (PMA/nMMT), and AMX- or DF- was added dropwise to the suspension. Initiator ammonium
loaded nanocomposite were obtained on a PerkinElmer BX persulfate (APS) (0.1 M) was added to the mixture followed
FTIR spectrophotometer. X-ray diffraction (XRD) pattern was by 1.0 mL of TEMED accelerator. The dispersion was
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vigorously stirred for 4 h at 50 °C by a magnetic stirrer. The

resulting sticky mass was acetone-washed and desiccated for 48
h at 70 °C in an oven. The resulting product was ground and
stored in a glass bottle. Different nanocomposites were
synthesized by varying the nMMT in quantities of 0.5, 1.0,
1.5, and 2.0 g. The nanocomposite prepared using 1.0 g of
nMMT depicted better adsorption results than the rest of
composites and was therefore used for further adsorption
investigation.
Adsorption Studies. Batch mode was employed to
investigate the impact of process parameters on the adsorption
of AMX and DF onto PMA/nMMT. A fixed mass of PMA/
nMMT (0.2−1.8 g) was taken in conical flasks (50 mL)
containing 25 mL of a sorbate solution (40−90 mg/L) and
shaken on a water bath shaker for 40 min at 303, 313, and 323
K. The impact of the initial solution pH was examined by
changing the pH from 2 to 10 by adding NaOH or HCl (0.1
M) solution. When the equilibrium was attained, the solution
was centrifuged at 1500 rpm for 5 min, and the residual
concentration of AMX or DF in supernatant was spectrophoto-
metrically determined. For absorbance measurement, an Figure 2. FTIR spectra of MMT, nMMT, PMA/nMMT hydrogel
equimolar (0.1 M) mixture of HCl, NaNO3, and sulfanilic nanocomposite, and AMX- and DF-loaded nanocomposite.
acid (1.0 mL each) was coupled with Na2CO3 (0.1 M, 1.0
mL), and an AMX solution was added to it, which developed 2922 and 2850 cm−1 represent stretching modes of the CH3
an orange-colored solution32 with λmax at 455 nm. The DF and CH2 groups of CTAB.38 Moreover, the C−C−C flexural
solution was treated with a FeCl3 solution (0.1 M, 1.0 mL) and vibration of the methylene group associated with the
then subsequently reacted with 2,2′-bipyridine (0.1 M, 1.0 cetyltrimethylammonium ion peak is exhibited at 1480 cm−1,
mL) to form a red solution,33 which absorbed at 520 nm which confirms the successful modification of montmorillonite.
(λmax). The parameters of sorption capacity, qe, and removal The reduction in the intensity of absorption peaks in the

ÅÄÅ ÑÉÑ
efficiency (%), were assessed using eqs 1 and 2, respectively PMA/nMMT spectrum at 2922 and 2850 cm−1 along with the
Å C − Ce Ñ
qe = ÅÅÅÅ i × V ÑÑÑÑ
appearance of new sharp peaks at 1730 and 1252 cm−1
ÅÅ WM ÑÑ
corresponding to CO and C−O stretching vibrations of

ÄÅ ÉÑ
(1) the carboxylic group39 supports the formation of hydrogel
ÅÅ C − Ce ÑÑ
removal efficiency(%) = ÅÅÅÅ i × 100ÑÑÑÑ
nanocomposite. In the spectra of PMA/nMMT-loaded AMX

ÅÅ Ci ÑÑ
and DF, the appearance of characteristic absorption bands
(2) corresponding to the C−N stretching of the amine group
(1384 cm−1) and the O−CO stretching of the carboxylic
where Ce and Ci are the equilibrium and initial sorbate group (1565 cm−1) reveals the successful sorption of AMX and
concentrations (mg/L), V represents volume (L) of sorbate DF onto PMA/nMMT. A red shift from 3440 to 3454 cm−1
solution, and WM is the sorbent mass (g). Isotherm studies indicates the participation of the −OH group in hydrogen
were investigated by shaking 25 mL (40−90 mg/L) of sorbate bonding during the sorption process. The structural vibration
solution with PMA/nMMT (1.2 or 1.4 g for AMX or DF) for regions of PMA/nMMT show no significant changes after
40 min at 303, 313, and 323 K. The kinetic investigations were sorption, depicting the structural stability of PMA/nMMT
accomplished by shaking 25 mL (60−80 mg/L) of sorbate after AMX and DF sorption.
solution with PMA/nMMT (AMX: 1.2 g; DF: 1.4 g) for 40 XRD diffractograms of MMT, nMMT, and PMA/nMMT
min at 323 K.

■
are displayed in Figure 3. MMT having a 2:1 layered structure
of smectite class is represented by a sharp peak at 2θ = 26.80°
RESULTS AND DISCUSSION corresponding to quartz mineral,41 while the peak at 2θ =
Characterization of PMA/nMMT Hydrogel Nano- 19.82° confirms the presence of random stacked layers. The
composite. The binding of pollutants is determined by the basal (001) space of MMT is displayed at 2θ = 6.29°. The
existence of functional groups on the surface of the adsorbent. diffractogram of nMMT exhibits a change in peak intensities
Thus, the FTIR technique was employed to verify the chemical attributed to structural modifications in existing planes with
functionality. The FTIR spectra of MMT, nMMT, PMA/ the formation of new layers. Moreover, the average crystallite
nMMT, and AMX- or DF-loaded PMA/nMMT are compared sizes (L) of MMT and nMMT using Scherer’s equation (L =
in Figure 2. A broad peak at 3440 cm−1 and a sharper one at 0.9λ/β cos θ) were 103.3 and 55.3 nm, respectively. The
1637 cm −1 correspond to the O−H stretching and diffractogram pattern of PMA/nMMT displays an amorphous
deformation vibrations, respectively.34 The peak at 3631 halo at 14.29°. The disappearance of the basal peak indicates
cm−1 is assigned to O−H stretching vibrations of the Si− exfoliation of nMMT layers into the PMA matrix,42 which
OH and Al−OH groups of montmorillonite.35 The absorption suggests the formation of the PMA/nMMT hydrogel nano-
band observed at 1031 cm−1 is attributed to in-plane stretching composite.
vibrations of the Si−O group,36 whereas the peaks at 528 and The chemical states of PMA/nMMT, before and after
455 cm−1 represent Al−O−Si and Si−O−Si bending adsorption of AMX and DF, were analyzed by XPS, and are
vibrations, respectively.37 The absorption bands in nMMT at depicted in Figure 4. The study illustrates the existence of C,
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are visible, which depicts the complete exfoliation of nMMT

into the PMA matrix. After AMX or DF sorption, changes in
the PMA/nMMT morphology are observed. The surface
becomes asymmetric with an increase in the rough texture.
TEM investigation was used to assess the structural insights
of nMMT and PMA/nMMT. The TEM micrographs of
nMMT shown in Figure 6a exhibit nearly spherical particles of
7−15 nm diameter. The presence of CTAB in the interlamellar
space of nMMT prevents its agglomeration to a large extent.
The TEM images of PMA/nMMT (Figure 6b) display a PMA
network shown as the light zone in which nMMT as the dark
zone is uniformly dispersed.
Effect of Operational Parameters. To figure out the
impact of sorbent dosage on the removal efficiency, different
varying amounts (0.2−1.4 g/L) of PMA/nMMT were used.
With increasing sorbent dose, a sharp escalation in the removal
efficiency for AMX (74.3−98.6%) and DF (75.8−96.0%) is
observed, which can be credited to an overall increase in the
sorbent surface regions. However, a fall in the adsorption
Figure 3. XRD spectra of MMT, nMMT, and PMA/nMMT hydrogel
nanocomposite.
capacity for AMX occurs from 111.5 to 20.6 mg/g and for DF
from 151.7 to 27.4 mg/g (Figure S6). This antagonistic effect
could be associated with the aggregation of sorbent at higher
doses, which enlarges the diffusional pathway for AMX and DF
to reach the binding sites.44 Therefore, the optimized dose for
AMX (1.2 g/L) and DF (1.4 g/L) at which maximum removal
was attained when the pollutant concentration was 40 mg/L
was taken for subsequent experiments.
Contact time is a prime factor that affects the adsorption
process. To illustrate the impact of contact time on the
adsorption of AMX and DF onto PMA/nMMT, experiments
were conducted for 10−60 min with a 10 min time interval,
keeping the concentration (40 mg/L) and sorbent dose (1.2
and 1.4 g/L for AMX and DF, respectively) constant. It can be
inferred from Figure S7 that the increase in the uptake
efficiency within the initial 40 min is rapid but exhibits a steady
trend with further increase in time, which may be attributed to
the occurrence of available sorption sites on the sorbent during
the initial stage of the sorption process and the increase in the
collision frequency of AMX or DF on the surface of PMA/
Figure 4. XPS spectra of PMA/nMMT hydrogel nanocomposite and nMMT. The maximum % efficacy and sorption capacity is
AMX-/DF-loaded nanocomposite. achieved at 40 min, which is subsequently used in further
investigations. The scavenging potential of PMA/nMMT
O, Al, Si, and Mg in the hydrogel nanocomposite. The C 1s (95.80% for AMX and 95.14% for DF) within a time period
peak is assigned to the presence of PMA, while the peaks of Si of 40 min qualifies it as a potential sorbent.
2p, Al 2p, and Mg 2s are attributed to MMT.43 The peak of Na The pH of the reaction environment is a critical aspect that
1s determines the presence of sodium on the MMT surface. governs the protonation and deprotonation of pollutants in the
The O 1s peak is due to both PMA and MMT. The presence aqueous phase, which affects pollutant binding onto the
of N 1s peak and an increase in carbon and oxygen intensities sorbent surface. To determine the effect of initial solution pH
in the spectra of PMA/nMMT after sorption depict the on the sorption of AMX and DF on the PMA/nMMT surface,
successful grafting of AMX or DF onto the surface of PMA/ pH was changed from 2 to 10 (Figure 7), keeping rest of the
nMMT. parameters such as contact time (40 min), dose (1.2 and 1.4 g/
The SEM micrographs recorded at a magnification of 1.00 L for AMX and DF, respectively), and initial concentration (40
KX along with the EDX of MMT, nMMT, PMA/nMMT, and mg/L) constant. It is evident that AMX contains three
AMX- or DF-loaded PMA/nMMT are illustrated in Figure 5. functional groups with different pKa valuescarboxyl (pKa =
It is observed that raw MMT owes a layered sheet structure 2.68), amine (pKa = 7.49), and hydroxyl (pKa = 9.63), which
showing the presence of larger grains. After modification, the means AMX is cationic at pH < 2.68, anionic at pH > 7.49, and
sheets of MMT are exfoliated into tiny particles, which may be zwitterionic at neutral pH.45 At pH 2, cationic exchange takes
due to the elimination of Si2+ and Al3+ from the octahedral place between positively charged AMX and the sorbent as
sites. The EDX spectrum of nMMT exhibits a high percentage pHpzc of PMA/nMMT is 3.98.46 When the pH is increased
of carbon, which may primarily be due to the surfactant from 3 to 4, stronger electrostatic interactions between
utilized for modification as the main constituent of CTAB negatively charged amoxicillin and positive PMA/nMMT
(C19H42BrN) is carbon (84%). PMA/nMMT displays a surface are observed, escalating the removal efficiency. As the
coherent and near-co-continuous structure. Further, no pores solution pH is increased further, AMX becomes neutral and is
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Figure 5. SEM−EDX micrographs of (a) MMT, (b) nMMT, (c) PMA/nMMT, and (d) AMX- and (e) DF-loaded nanocomposite.

adsorbed onto the surface of PMA/nMMT by the partition increasing pH. At pH < pKa (4.2), the DF becomes neutral48
mechanism. Further increase in pH increases the electrostatic and the PMA/nMMT surface is positive; therefore, instead of
repulsion, thereby decreasing the adsorption.47 The removal electrostatic attraction, the hydrogen bonding may dominate
efficiency of DF is quite high at acidic pH and falls off with the removal mechanism.
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Figure 6. TEM micrographs of (a) nMMT and (b) PMA/nMMT.

Figure 7. Effect of pH on (a) AMX and (b) DF removal.

The effect of the initial concentration of pollutants on the

removal efficacy of PMA/nMMT for the uptake of AMX and
DF is shown in Figure 8. It reveals that with an increase in the
initial sorbate concentration from 40 to 90 mg/L, an escalation
in the sorption capacity for AMX (from 32.37 to 71.66 mg/g)
and DF (from 27.29 to 61.62 mg/g) may be accredited to a
large driving force provided by higher initial concentration that
reduces the mass transfer resistance, leading to an increase in
the adsorption amount.49 Also, at the initial stage, both the
pollutants adhere conveniently on the PMA/nMMT surface
Figure 8. Effect of Initial concentration for (a) AMX and (b) DF
due to the availability of active sites, which boosts the sorption removal.
capacity till equilibrium is attained. At a low concentration, the
relative number of active sites and sorbate molecules is high,
which makes the sorbate molecules interact with the sorbent Besides, the applicability of isotherm models was appraised
and results in prompt uptake from the solution. On increasing based on correlation coefficient (R2) and standard error of
the concentration, the removal efficacy represents a fall estimation (SEE) that were calculated for each model and are
attributed to the saturation of binding sites. presented in Table 1.
Adsorption Isotherm Studies. Adsorption isotherm is a The Langmuir model presumes adsorption to occur via
fundamental tool that illuminates the interaction between monolayer formation on the homogeneous surface.50 It further
sorbate and sorbent and further describes the maximum assumes that active sites are finite and no lateral interaction is
sorption capacity. To design the process and to figure out the observed between the adsorbed molecules on adjacent
best-fit model, the nonlinear form of various isotherm models sorption sites. Equation 3 expresses nonlinear regression of
was coordinated with equilibrium data at 303, 313, and 323 K. the Langmuir model
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Table 1. Isotherm Parameters

AMX DF
isotherm isotherm constant 303 K 313 K 323 K 303 K 313 K 323 K
Langmuir Qm 119.07 130.37 152.65 137.15 146.25 152.86
b 0.285 0.305 0.295 0.151 0.184 0.139
RL 0.055 0.051 0.053 0.086 0.072 0.093
R2 0.983 0.989 0.992 0.981 0.985 0.992
SEE 1.869 1.531 1.309 1.954 1.515 1.392
Freundlich Kf 28.91 32.06 35.53 20.02 20.44 24.22
1/nf 0.564 0.595 0.653 0.680 0.689 0.694
R2 0.990 0.991 0.994 0.988 0.992 0.996
SEE 1.659 1.362 0.135 1.317 0.887 0.790
Temkin Kt 2.50 2.67 2.81 1.67 1.68 2.10
bt 0.091 0.086 0.080 0.094 0.093 0.091
R2 0.977 0.985 0.988 0.962 0.968 0.971
SEE 2.189 1.776 1.584 2.692 2.494 2.377
D−R qD 98.71 106.89 118.70 92.41 97.30 99.44
E 1.26 1.35 1.42 1.10 1.14 1.28
R2 0.972 0.986 0.988 0.958 0.967 0.973
SEE 2.570 1.954 1.606 2.833 2.517 2.284

Q maxbCe factor, RL =
1
(0.053 for AMX and 0.093 for DF),
qe = 1 + bCo
(1 + bCe) (3) illustrate the sorption process to be favorable.
where Ce (mg/L) is the equilibrium concentration of sorbate The Freundlich model elucidates the multilayer sorption
in solution, b (L/mg) is the Langmuir binding constant, qe and pattern onto the heterogenous surface.60 The nonlinear form is
Qmax (mg/g) are the amount of sorbate adsorbed at described by eq 4
equilibrium and the maximum sorption capacity, respectively. 1
The values of Qmax, b, and R2 were investigated from the plot qe = (K f Ce)
nf (4)
of qe vs Ce at 303−323 K (Figure S1). An increment in b values
with a rise in temperature depicts a stronger interaction where Kf (L/mg) attributes to the Freundlich constant
between sorbent and sorbate. The Qmax values turn out to be associated with the sorption capacity and 1/nf is the
152.65 mg/g for AMX and 152.86 mg/g for DF, which are heterogeneity factor, which depicts whether adsorption is
significantly higher than those of reported sorbents (Table 2). favorable (1/nf < 1) or unfavorable (1/nf > 1). The parameters
Kf and 1/nf were assessed from the plot of qe vs Ce (Figure 9),
Table 2. Comparison of Qmax (mg/g) Values which suggests the isotherm to be favorable as the values of 1/
nf (0.56−0.65 for AMX and 0.68−0.69 for DF) are less than
Qmax (mg/
sorbate sorbent g) reference unity (Table 1). The values of 1/nf may be due to the surface
site distribution, which limits the sorbate−sorbent interaction
amoxicillin CS-Fe/Ni 29.63 51
with an increase in surface density.
O-clays 33.51 40
Temkin isotherm speculates reduction in the heat of
O-MMT 48.6 52
adsorption of all molecules in the layer with increased
modified bio-hydrochar 92.87 53
sorbent−sorbate interaction and further specifies the uniform
magnetic graphene nanoparticles 106.38 47
distribution of binding energies. Equation 5 expresses the
Mn-impregnated activated carbon 131.57 23
nonlinear form of the Temkin isotherm model
PMA/nMMT 152.65 this work
diclofenac MWCNT 4.18 54 qe = βt ln(K t Ce) (5)
PPhA 21.11 55
CTAB-ZIF-76 60.58 56 where Kt (L/g) is the binding constant related to the maximum
Terminalia catappa fruit shell 96.1 57 binding energy and bt (=RT/βt) is a constant relevant to heat
coconut shell activated carbon 103.0 58 of adsorption (kJ/mol). The values of Kt and bt were calculated
orange peel activated carbon 144 59 from the qe vs Ce plot (Figure S2), which depicts a significant
PMA/nMMT 152.86 this work sorbate−sorbent interaction and a minor change in the heat of
sorption with temperature change, respectively. The obtained
values of bt (Table 1) substantiate the physisorption to
dominate the sorption process.
This observation establishes the superiority of PMA/nMMT The D−R isotherm is a generalized model that is not
nanocomposite over many other sorbents for AMX and DF restricted to the homogeneous surface or constant adsorption
removal. The enhancement in maximum sorption capacity with potential.61 This model differentiates between physical and
the rise in temperature is indicative of the endothermic nature chemical adsorption because of the mean energy of adsorption
of the process. Thus, at a higher temperature, more energy is (E). It is reported62 that if the value of E (kJ/mol) is between 1
supplied, which augments the physical attachment of sorbate and 8 kJ/mol, then the physical interaction dominates the
on the binding sites of the sorbent. The values of separation adsorption process and an ion-exchange phenomenon is
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To analyze the best-fit model, statistical parameters such as

correlation coefficient (R2) and standard error of estimation
(SEE) were utilized (Table 1). Higher R2 values (0.994 for
AMX and 0.996 for DF) and lower SEE values (0.135 for AMX
and 0.790 for DF) verify that the Freundlich model best
describes the equilibrium data implying multilayer sorption of
AMX and DF on the heterogeneous surface of PMA/nMMT.
Kinetic Investigations. Adsorption rate is a prime factor
that determines the adsorption efficiency of an adsorbent. It
illustrates the mechanism of control of the sorption process,
which may be surface adsorption, chemical reaction, or
penetration mechanism. The kinetics of AMX and DF
adsorption onto PMA/nMMT was evaluated by pseudo-first-
order and pseudo-second-order models. Nonlinear forms of
the models are expressed as (eqs 7 and 8)

qt = qe(1 − e−k1t ) (7)

(k 2qe2t )
qt =
(1 + k 2qet ) (8)

where k1 (1/min) and k2 (g/(mg min)) correspond to rate

constants of pseudo-first-order and pseudo-second-order
models, respectively. The values of qe, k1, and k2 (Table 3)
of pseudo-first-order (Figure S4) and pseudo-second-order
rate equations (Figure 10) were determined from the plot of qt
vs t. It is inferred that the pseudo-second-order model provides
the best representation of sorption kinetics based on higher R2
(AMX: 0.96; DF: 0.97) and lower SSE values (AMX: 0.48−
0.58; DF: 0.34−0.37), which implies that the sorption rate of
PMA/nMMT is influenced by the number of binding sites
Figure 9. Freundlich isotherm plot for (a) AMX and (b) DF removal. rather than the concentration of AMX or DF in solution.
Moreover, the k parameter has a relatively higher value, which
qualifies PMA/nMMT as a rapid scavenger of AMX or DF
from the aqueous phase.
observed between 8 and 16 kJ/mol, and above 16 kJ/mol, Diffusion models were further related with equilibrium data
chemical interaction is the main force. Equation 6 enunciates to elucidate the diffusion mechanism and the rate-controlling
ÄÅ 2 |Ñ
É
ÅÅ l i ÑÑ
the nonlinear equation of the D−R model
o o
step. The adsorption kinetics usually involves four steps: (a)
ÅÅ o
o j y
z o
o ÑÑ
Å
qe = qD expÅÅ−KDm j
lnjj1 + z
z} ÑÑ
mass transfer of sorbate from bulk solution to the external

ÅÅ o
o j z
z o
o ÑÑ
o { ~ÑÑÑÖ
o
1

ÅÅÇ n k
surface of sorbent (film diffusion), (b) boundary layer
Ce
diffusion, (c) mass movement of sorbate from the external
(6) layer into interior pores of the sorbent (intraparticle diffusion),
where qD (mg/g) is the D−R constant and KD (=βadR2T2) and (d) coverage of all binding sites by adsorbate.63 The
corresponds to the activity coefficient. Isotherm parameters boundary layer and coverage of active sites have a meager
were determined from the plots of qe vs Ce (Figure S3). The impact, while film diffusion and intraparticle diffusion affect the
mean adsorption energy was calculated using E =
1
. The kinetics considerably.
2βad Generally, the intraparticle diffusion model64 based on
value of adsorption energy (E) for AMX (1.26−1.42 kJ/mol) surface and pore diffusion is utilized to determine the rate-
and DF (1.10−1.28 kJ/mol) falls in the range of physisorption controlling step. It is expressed in the mathematical form as
(1−8 kJ/mol) supporting the findings of the Temkin model. (eq 9)

Table 3. Kinetic Parameters

pseudo-first-order pseudo-second-order
−2
sorbate concn (mg/L) k1 (1/min) R 2
SEE qe (cal) (mg/g) qe (exp) (mg/g) k2 × 10 (g/(mg min)) qe (cal) (mg/g) R2 SEE
AMX 60 0.233 0.66 1.205 48.15 48.22 0.012 50.20 0.94 0.485
70 0.240 0.71 1.341 55.76 55.80 0.012 57.98 0.95 0.552
80 0.245 0.74 1.386 63.32 63.70 0.011 65.70 0.96 0.581
DF 60 0.245 0.72 0.939 40.93 41.46 0.017 42.49 0.95 0.377
70 0.253 0.75 0.918 47.17 47.94 0.016 48.79 0.96 0.346
80 0.255 0.76 1.001 53.69 54.78 0.014 55.50 0.97 0.343

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sorption kinetics. However, the plots exhibit multilinearity

and deviate from the origin (Figure 11), which implies that

Figure 10. Pseudo-second-order kinetics plot for (a) AMX and (b)
DF removal.

qt = K it 0.5 + Ci (9)
0.5
where Ki (mg/(g min )) implies the intraparticle rate
constant and Ci is a constant related to the thickness of the
boundary layer. The values of Ki and Ci were determined from
the slope and intercept, respectively, of qt vs t0.5 plots, and are
Figure 11. Intraparticle diffusion plots for (a) AMX and (b) DF
presented in Table 4. It is evident from the plots that mainly removal.
three steps are involved in AMX and DF sorption onto PMA/
nMMT. The initial portion portrays immediate sorption on the
external surface. The gradual coverage of active sites due to
intraparticle diffusion of AMX and DF is represented by the intraparticle diffusion is not the sole rate-limiting step.
second stage. The decrease in the intraparticle diffusion rate Moreover, larger values of the intercept for AMX (40.39−
due to extremely low sorbate concentration and lower 54.29) and DF (34.99−46.81) reveal a greater boundary layer
availability of active sites is described by the final step.65 As effect.66
described by eq 9, if the plot of qt vs t0.5 is linear and passes The Boyd kinetic model67 was further employed to appraise
through the origin, intraparticle diffusion dominates the kinetic data, which is expressed as (eq 10)

Table 4. Diffusion Parameters

intraparticle diffusion liquid-film diffusion

0.5 2
sorbate concn (mg/L) Ki (mg/(g min )) Ci R SEE KA (1/min) R2 SEE
AMX 60 1.209 40.39 0.96 0.605 0.061 0.98 0.003
70 1.320 47.30 0.97 0.528 0.058 0.97 0.004
80 1.407 54.29 0.95 0.758 0.069 0.96 0.006
DF 60 0.927 34.99 0.97 0.428 0.061 0.98 0.039
70 0.962 41.00 0.95 0.529 0053 0.99 0.016
80 1.073 46.81 0.95 0.609 0.053 0.99 0.014

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−ln(1 − F ) = KAt (10) Simultaneous Removal of AMX and DF and the Effect
of NaCl on % Sorption by the PMA/nMMT Nano-
where F (qt/qe) represents the fractional equilibrium, KA (1/ composite. Simultaneous sequestration of pollutants specifies
min) is the liquid-film diffusion constant. The deviation of the the portion of binding sites occupied by each of the pollutants
straight-line plots of −ln(1 − F) vs t (Figure S5) from the on the surface of sorbent.69 It further evaluates the interaction
origin represents that the liquid-film diffusion is not the sole of one sorbate on the sorbent surface in the companionship of
controlling step,68 which illustrates both intraparticle and other sorbate molecules. To investigate the simultaneous
liquid-film models governing the diffusive mechanism. sorption, a binary system of AMX-DF with an initial
Thermodynamic Investigations. Comprehensive infor- concentration of 40−90 mg/L and PMA/nMMT (1.5 g/L)
mation regarding innate energy changes associated with the was shaken for 40 min on a water bath shaker. Equation 13 was
adsorption process is specified by thermodynamic parameters. utilized to calculate the ratio of % removal efficiencies
The standard enthalpy change (ΔH°), standard entropy
change (ΔS°), and standard Gibbs free-energy change R = qa /qm (13)
(ΔG°) were analyzed at 303, 313, and 323 K, and the values
are provided in Table 5. The thermodynamic parameters were where qa and qm are the removal efficiencies of AMX and DF in
the binary system and monocomponent system with the same
Table 5. Thermodynamic Parameters initial concentration, respectively. Simultaneous sorption
process might fall under three cases based on the values of
−ΔG° (kJ/mol)
R. If R > 1, a synergistic effect is observed, i.e., both the sorbate
concn ΔH° (kJ/ ΔS° (kJ/(mol molecules work in association that results in an escalation in %
sorbate (mg/L) mol) K)) 303 K 313 K 323 K
removal. If R < 1, the antagonistic effect is dominant, which
AMX 50 20.06 0.083 5.22 6.06 6.89 implies the suppression of one pollutant in the presence of
DF 50 18.83 0.081 5.70 6.51 7.32 other, which leads to a decrease in the removal efficacy. If R =
1, no interaction can be seen, which means that % removal is
determined using the van’t Hoff plot of log(qe/Ce) vs 1/T independent of the impact of binary mixture.70 In this work,

ij q yz
(Figure 12) employing eq 11 and Gibbs equation (eq 12) the antagonistic effect was observed as R values are less than

logjjj e zzz =
unity (Figure 13a), which suggests that competitive sorption is
j Ce z 2.303R
ΔS o ΔH o
k {
− prevalent between both the drugs.
2.303RT (11) The salinity of the solution has a prominent impact on the
o o o
adsorption process. To illustrate the effect of Cl− on %
ΔG = ΔH − T ΔS (12) sorption of AMX and DF, NaCl solutions of varying
concentrations (0.1, 0.5, 0.7, 1.0, 1.5 M) were used. Figure
13b demonstrates that both pharmaceutical contaminants
exhibit a monotonic decrease in % removal with the rise in
salinity. The observed trend may be due to the competitive
sorption of sorbate and the ions from the solution onto the
available binding sites on the PMA/nMMT surface. This
validates the electrostatic interaction as the main mechanism
for sequestration, which is consistent with the pH inves-
tigations.
Desorption and Reusability of Adsorbent. Long-term
reusability and ease in the recovery of the sorbent is a critical
factor for its industrial application as it has a significant impact
on economic conceivability and reduces the disposal problem
of the used sorbent. The reusability potential of PMA/nMMT
was assessed by performing four desorption−adsorption cycles.
PMA/nMMT (2 g/L) was saturated with AMX and DF (60
mg/L) for 3 h and then dried. Sorption sites were regenerated
using HCl (0.1 M). The sorbent exhibits a better regeneration
potential for AMX and DF up to four cycles (Table 6), which
Figure 12. van’t Hoff plots. signifies PMA/nMMT as a potential sorbent. The removal
efficiency diminishes owing to unadsorbed pollutants and
weight loss of PMA/nMMT during the sorption−desorption
where R (8.314 J/(K mol)) represents the ideal gas constant
cycles.
and T (K) is the absolute temperature. The ΔG° values are
found to be negative at all studied temperatures for AMX
(−5.22, −6.06, and −6.89) and DF (−5.70, −6.51, and
−7.32), confirming the feasibility and spontaneity of the
■ CONCLUSIONS
This work demonstrated the successful preparation of a
sorption process. The positive values of ΔS° demonstrate an poly(methacrylic acid)/montmorillonite hydrogel nanocompo-
increase in the disorder of AMX (0.083 kJ/mol) and DF site via redox polymerization and its subsequent usage in AMX
(0.081 kJ/mol) molecules at the sorbate−sorbent interface. and DF uptake from the aqueous phase. The structural
The ΔH° values for AMX (20.06 kJ/mol) and DF (18.83 kJ/ characteristics of PMA/nMMT were investigated employing
mol) specify the endothermic nature of sorption on the surface FTIR, XRD, XPS, scanning electron microscopy−energy
of PMA/nMMT. dispersive X-ray spectroscopy (SEM−EDS), and TEM
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Figure 13. Effect of (a) simultaneous sorption and (b) NaCl on AMX and DF sorption.

Table 6. Sorption−Desorption Cycle Langmuir isotherm plots (Figure S1); Temkin isotherm
plots (Figure S2); D−R isotherm plots (Figure S3);
regeneration % sorption % desorption % sorption % desorption
cycle AMX AMX DF DF pseudo-first-order plots (Figure S4); liquid-film diffusion
1 87.34 91.24 88.42 91.34
plots (Figure S5); effect of adsorbent dose (Figure S6);
and effect of contact time (Figure S7) (PDF)

■
2 80.20 85.14 80.45 82.36
3 71.16 75.16 70.21 71.97
4 63.53 64.49 61.88 62.03 AUTHOR INFORMATION
Corresponding Author
Tabrez Alam Khan − Department of Chemistry, Jamia Millia
Islamia, New Delhi 110 025, India; orcid.org/0000-0002-
techniques. The impact of operative variables was evaluated, 2562-8836; Phone: +91 11 26985938; Email: takhan@
and the optimal conditions were found to be dose (1.2 g/L for jmi.ac.in, [email protected]
AMX and 1.4 g/L for DF), agitation time (40 min), pH (6 for
AMX and 2 for DF), and initial concentration (80 mg/L). Authors
Various isotherm models were utilized, among which the Suhail Ayoub Khan − Department of Chemistry, Jamia Millia
Freundlich model appropriately suited the equilibrium data, Islamia, New Delhi 110 025, India
suggesting multilayer adsorption onto the heterogeneous Mohammad Fuzail Siddiqui − Department of Chemistry,
surface. The maximum sorption capacity was found to be Jamia Millia Islamia, New Delhi 110 025, India
156.65 for AMX and 152.86 mg/g for DF, which is better than Complete contact information is available at:
most of the reported sorbents establishing the high perform- https://pubs.acs.org/10.1021/acsomega.9b03617
ance of PMA/nMMT hydrogel nanocomposite. The adsorp-
tion kinetics was dominated by pseudo-second order with both Notes
intraparticle and film diffusion controlling the rate. The The authors declare no competing financial interest.

■
synergistic effect of cationic exchange, electrostatic interaction,
partition mechanism, and hydrogen bonding could elucidate ACKNOWLEDGMENTS
the enhanced adsorption of AMX and DF onto PMA/nMMT. One of the authors S.A.K. is thankful to the University Grants
Thermodynamic parameters revealed that AMX and DF Commission (UGC), New Delhi, India, for financial assistance
sorption onto PMA/nMMT was spontaneous and endother- and Amity University, Noida, India, for SEM analysis.

■
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