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Poly(acrylic acid-co-2-acrylamido-2-methyl-1-
propanesulfonic acid)-grafted chitosan hydrogels
Open Access Article. Published on 23 October 2023. Downloaded on 3/30/2024 8:09:14 AM.
Cite this: RSC Adv., 2023, 13, 31002

for effective adsorption and photocatalytic
degradation of dyes
a a
Kunlarat Phonlakan, Panjalak Meetam, Rungthip Chonlaphak,a
b b *a
Piyawan Kongseng, Sirinya Chantarak and Surangkhana Budsombat
As a result of the growth of industrialization and urbanization, the water ecosystem is contaminated by
various pollutants, including heavy metal ions and dyes. The use of low-cost and environmentally
friendly dye adsorbents has been investigated. A hydrogel was fabricated via graft polymerization of
acrylic acid (AA) and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) onto chitosan. The hydrogel
was used as a dye adsorbent and support for a zinc oxide (ZnO) powder photocatalyst. The adsorption
capacity of the bare hydrogel was greater towards cationic dyes than anionic dyes. Grafting P(AA-co-
AMPS) exhibited a 23-time increase in adsorption capacity towards crystal violet (CV) compared to
pristine chitosan. The effect of the AA–AMPS molar ratio on CV adsorption was studied. A hydrogel with
an AA–AMPS ratio of 10 : 1 had the highest adsorption capacity towards CV in water, removing 91% of
the dye in 12 h. The maximum adsorption capacity was 2023 mg g−1. The adsorption kinetics and
isotherm were described by the pseudo-second-order model and the Langmuir model, respectively.
ZnO particles were in situ synthesized within the 10 : 1 hydrogel to facilitate the recovery of the
photocatalyst. The ZnO hydrogel composite could remove 95% and 92% of CV from solutions on the 1st
Received 16th August 2023
Accepted 17th October 2023
and 2nd cycle, respectively. In addition, the hydrogel composite containing only 8.7 wt% of ZnO particles
effectively degraded adsorbed CV under sunlight and could be reused without requiring a chemical
DOI: 10.1039/d3ra05596e
regeneration or photocatalyst recovery procedure. This hydrogel composite is an effective dual-
rsc.li/rsc-advances functional material for the adsorption and photodegradation of dye pollutants in wastewater.
chitosan contribute to its potential as an adsorbent.7 However,

1. Introduction it is unstable in acidic conditions and poor mechanical stability
Wastewater contains harmful, carcinogenic, and stable organic limits its application. To overcome these drawbacks, chitosan
pollutants1 that can endanger the health of living organisms if has been modied or composited with inorganic materials.8–12
released into the environment. Organic dyes have broad Modication by crosslinking and graing also improves the
industrial applications; nevertheless, direct dye discharge into adsorption performance of chitosan.13 For dye adsorption,
water causes potential toxicity and reduced photosynthetic suitable functional groups can be added to chitosan by graing
activity.2 Organic dyes can be removed from wastewater by with other polymers. Polymers used in this way include poly-
various treatment methods. Commonly used methods include acrylamide,14 poly(methacrylic acid) (PMAA),15 poly(sodium 4-
adsorption,3 physicochemical and membrane separation,4,5 styrene sulfonate) (PSSA),16 poly(acrylic acid) (PAA),17 and poly(2-
electrochemical techniques, reverse osmosis, ion exchange, acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS). Micro-
electrodialysis and advanced oxidation processes (AOPs).6 spheres prepared from the gra polymerization of acrylic acid
Adsorption processes have attracted a lot of attention due to and 2-acrylamido-2-methyl-1-propanesulfonic acid (P(AA-co-
their simplicity, versatility, and low cost. AMPS)) onto chitosan demonstrated a high adsorption capacity
Chitosan is an abundant natural polymer. The biocompati- towards methylene blue (MB).18,19 The presence of multifunc-
bility, biodegradability, polyfunctionality, and hydrophilicity of tional groups including amino (–NH2), hydroxyl (–OH),
carboxylic acid (–COOH), and sulfonic acid (–SO3H) groups in
a
Department of Chemistry and Center of Excellence for Innovation in Chemistry, the microspheres accounted for their excellent removal ability.
Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand. E-mail: Hydrogels made from chitosan graed with P(AA-co-AMPS) were
surama@kku.ac.th also used to remove MB and rhodamine B (RhB) in aqueous
b
Division of Physical Science, Faculty of Science, Prince of Songkla University, Hat Yai, solutions.20
Songkhla 90110, Thailand
31002 | RSC Adv., 2023, 13, 31002–31016 © 2023 The Author(s). Published by the Royal Society of Chemistry
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Another method of treating wastewater is photocatalytic sum of moles of AA and AMPS) were then added. The mixture
degradation. Typically, photocatalytic powders absorb energy was stirred for 30 min, purged with nitrogen, and the reaction
from UV light or sunlight, and then reactive radical species are was then conducted at 50 °C for 90 min. The obtained rubbery
generated that oxidize toxic pollutants into non-toxic small gel was thoroughly washed with deionized water before being
molecules.21,22 Zinc oxide (ZnO) is a commonly used inorganic dried in an oven at 50 °C until a constant weight was achieved.
powder photocatalyst that exhibits high chemical stability and
photocatalytic activity at an affordable price. Although powder 2.3 Synthesis of ZnO/P(AA-co-AMPS) hydrogel composite
photocatalysts are not easy to recover aer use, supporting
The hydrogel fabricated with an AA–AMPS molar ratio of 10 : 1 was
materials, including synthetic or natural polymers,23–27 can be
immersed in water until absorption equilibrium was reached. The
impregnated with photocatalytic particles to facilitate the opera-
swollen hydrogel was transferred to 5 mol% ZnAc2 solution and
tion. Immobilizing photocatalysts in biodegradable natural poly-

gently shaken at 100 rpm for 16 h at room temperature. The
mers can reduce the generation of secondary waste.28,29
hydrogel was then soaked in 10 mol% NaOH aqueous solution
In this work, hydrogels of chitosan graed with P(AA-co-
and heated at 60 °C for 1 h. The hydrogel composite was soaked in
AMPS) were synthesized via free radical polymerization with
water for 24 h to remove unreacted ZnAc2 and excess NaOH and
AA–AMPS at various molar ratios to investigate the effect of
then dried in an oven at 60 °C until completely dry.
acidic functional groups on dye adsorption. Potassium persul-
fate (KPS) and N,N′-methylenebis(acrylamide) (MBA) were used
as an initiator and a crosslinker, respectively. The morphology 2.4 Batch adsorption experiment
of the prepared hydrogels was investigated and their adsorption A batch experiment was used to determine the adsorption capacity
performances towards cationic and anionic dyes were explored. of fabricated hydrogels towards the cationic dyes MB, RhB, MG, CV,
The effect of the AA–AMPS molar ratio on MB and CV adsorp- and BG, and the anionic dyes RB5, OG, CR, DY50, and RO16. The
tion was also studied. The most promising hydrogel was then adsorption experiment was performed for 24 h using a hydrogel
further investigated in various CV adsorption conditions of dose of 0.05 g in 50 mL of 1000 mg L−1 aqueous dye solution at
contact time, adsorbent dose, pH, and initial concentration. ambient temperature. The concentration of the dye solution aer
Adsorption kinetics and isotherms were investigated. ZnO adsorption was determined by UV-Vis spectrophotometry.
photocatalyst particles were synthesized and immobilized in To investigate the effect of the AA–AMPS ratio on MB and CV
the chitosan hydrogel graed with the optimal P(AA-co-AMPS). adsorptions, 0.05 g of each preparation of the hydrogel was
The efficiency of photocatalytic dye degradation on ZnO and the soaked in 50 mL of 1000 mg L−1 aqueous dye solution for 24 h.
potential of the hydrogel as a biodegradable adsorbent sup- To optimize the CV adsorption conditions of the hydrogel
porting material were studied. fabricated with an AA–AMPS molar ratio of 10 : 1, 0.01–0.07 g of
the hydrogel was soaked in 50 mL of CV aqueous solution at
initial concentrations of 10–4000 mg L−1, in the pH range of
2. Experimental 2.0–10.0, for 1–24 h, at ambient temperature. Solution pH was
2.1 Materials adjusted using 0.1 M HCl or 0.1 M NaOH solutions.
Chitosan (molecular weight 50 000–190 000 Da, 75–85% deacety- The amount of dye adsorbed at different times (qt, mg g−1) and
lated), AA (99%), AMPS (99%), reactive orange 16 (RO16), direct removal efficiency (R, %) were calculated using eqn (1) and (2),
yellow 50 (DY50), orange G (OG), brilliant green (BG), and reactive respectively.
black 5 (RB5) were purchased from Sigma-Aldrich (USA). MB ðC0 Ct Þ V
(95%), CV (88%), malachite green (MG), and Congo red (CR) were qt ¼ (1)
m
from Loba Chemie (India). RhB was from UNILAB (Philippines).
MBA (98%) was supplied by Fluka (USA). KPS (99.0%) was from C0 Ct
R¼ 100% (2)
VWR (USA). Sodium hydroxide (NaOH, 99%) was purchased from C0
Ajax Finechem (Australia). Zinc acetate dihydrate (ZnAc2, 99.0%) where C0 and Ct (mg L−1) are the initial dye concentration and
was from EMSURE (USA). All chemicals were used as received. the dye concentration at a certain time, respectively. V and m
represent the solution volume (L) and the weight (g) of the
2.2 Synthesis of hydrogels hydrogels, respectively.
Chitosan-based hydrogels were prepared with AA–AMPS feed
molar ratios of 1 : 5, 1 : 1, 5 : 1, 10 : 1 and 1 : 0. Free radical gra 2.5 Water absorption test
copolymerization of chitosan with partially neutralized AA and To measure water absorption capacity (WAC), dry samples were
AMPS was conducted as follows: the desired amount of AA was immersed in water for 24 h. The weight change of the hydrogels
dissolved in 25 mL of NaOH aqueous solution. The molar was measured, and WAC was calculated according to eqn (3).
concentration of NaOH was xed at 80% of the molar concen-
Ws Wo
tration of AA. The desired amount of AMPS and 0.45 g of chi- WAC ¼ (3)
Wo
tosan were added to the solution and stirred for 20 min. The
total weight of the feed monomers was xed. MBA (0.1 mol% of where Wo and Ws (g) are the weights of the hydrogel before and
the sum of moles of AA and AMPS) and KPS (0.1 mole% of the aer water immersion, respectively.
© 2023 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2023, 13, 31002–31016 | 31003
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Scheme 1 Synthetic route and possible chemical structure of P(AA-co-PAMPS)-grafted chitosan hydrogel.
2.6 Photocatalytic degradation test composite dose of 0.05 g/50 mL of CV aqueous solution at a C0 =
10 mg L−1. Aer adsorbing CV for 24 h, the hydrogel composite
The efficiency of photocatalytic degradation on the in situ
was placed under a UV light source (39 mW cm−2) and natural
synthesized ZnO particles was studied using a hydrogel
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obtained with very high yields, with the 1 : 5 P(AA-co-AMPS)

yielding 74% and the other four ratios yielding 91–98%. Gra-
ing percentage (G, %) was determined gravimetrically and
calculated using eqn (4):
Mgrafted copolymer Mchitosan

Grafting percentage ð%Þ ¼ 100%
Mchitosan
(4)
The graing percentages of the 1 : 5, 1 : 1, 5 : 1, 10 : 1 and 1 :

0 P(AA-co-AMPS) chitosan hydrogels were 1550, 2060, 2000,

2210, and 2140%, respectively.
In the FTIR spectrum of chitosan (Fig. 1(a)), the broad
absorption band located at 3000–3500 cm−1 was attributed to
O–H and –NH2 groups. The band near 2862 cm−1 was ascribed
to C–H stretching vibrations. The bands at 1649 and
Fig. 1 FTIR spectra of chitosan (a) and P(AA-co-AMPS)-chitosan 1547 cm−1 corresponded to the C]O stretching vibration of
hydrogels at AA–AMPS ratios of (b) 1 : 5, (c) 1 : 1, (d) 5 : 1, (e) 10 : 1, and (f) amide and the N–H bending vibration, respectively.20 In the
1 : 0.
FTIR spectra of hydrogels (Fig. 1(b)–(f)), the stretching
vibrations of O–H at 3000–3500 cm−1 were signicantly
enhanced due to the presence of the O–H groups of chitosan
sunlight (11 am–2 pm, Songkhla Province, Thailand), while and AA. The band at 2930 cm−1 was due to –CH2 groups
soaking in water. The colors of the hydrogel composite before formed by the copolymerization of AA and AMPS. The bands
and aer the photocatalytic degradation of the adsorbed dye at 1023 and 617 cm−1 were ascribed to the valent oscillation of
were compared. The next cycle was repeated without further the S–O bond and the valent symmetric oscillation of the SO2
purication. At least three replicates were studied for each group of AMPS.20,30
experiment. The effect of the AA–AMPS ratio on the morphology and
porosity of the hydrogels was observed under SEM. The micro-
2.7 Characterizations graphs showed variations in the pore size of the hydrogels
Fourier transform infrared (FTIR) spectrometry (Tensor 27, (Fig. 2). At low AA content, the pores were very large compared
Bruker, Germany) between 4000 and 600 cm−1 in attenuated with the samples that had higher AA content. Increasing the AA
total reection mode was used to produce FTIR spectra that content decreased pore size and increased the uniformity of the
were processed by Opus 7.0 soware. The concentration of dye pore-size distribution. This result was probably due to the
solutions aer adsorption was determined by using UV-Vis reduced steric hindrance between repeating units of the poly-
spectrophotometry (Agilent 8453, USA). Scanning electron mer chains when AA content was higher. The smaller functional
microscopy (SEM, Quanta 400, FEI) was used to examine the groups would promote closer hydrogen bonding, stronger
morphology of fully swollen hydrogels. Samples were frozen in interactions between interconnected porous structures, and
liquid nitrogen, dried under vacuum, and coated with gold. higher crosslinking density.31–33
Chemical compositions were analyzed by energy-dispersive X- The AA–AMPS ratios affected water absorption of the
ray spectroscopy (EDS) coupled with SEM. The morphology of hydrogels. The highest WAC (707.36 g g−1) was obtained from
in situ synthesized ZnO particles in the 10 : 1 hydrogel matrix the 1 : 5 hydrogel (Fig. 3). However, the structural integrity of
was studied using a transmission electron microscope (TEM, this sample was low compared with the other fully swollen
JEM-2010, JOEL). The X-ray diffraction (XRD) patterns of the hydrogels. This result was consistent with the thinner cell wall
10 : 1 hydrogel and the ZnO/hydrogel composite were collected and the larger pore size of the 1 : 5 hydrogel. The hydrogels with
on an EMPYREAN X-ray diffractometer (PANalytical, United smaller pores, absorbed less water but were more mechanically
Kingdom) using Cu-Ka radiation. The thermal stability of the stable.
hydrogels and the hydrogel composite were evaluated by ther-
mogravimetric analysis (TGA) (STA7200, Hitachi, Japan) in the
temperature range of 35–650 °C at a heating rate of 10 °C min−1 3.2 Adsorption performance of the 5 : 1 hydrogel towards
under nitrogen gas. various dyes
In this study, the 5 : 1 hydrogel was used as a representative
3. Results and discussions adsorbent. The adsorption of cationic dyes was superior (Fig. 4)
due to the strong electrostatic interactions between carboxylic
3.1 Synthesis of hydrogels acid and sulfonic acid groups of the hydrogel and cationic dyes.
Chitosan-based hydrogels were prepared with ve different AA– The adsorption capacities towards MB and CV exceeded 860 mg
AMPS feed molar ratios. A possible chemical structure of these g−1. The anionic dye adsorption capacities of this hydrogel were
hydrogels is proposed in Scheme 1.30 Pale yellow gels were between 3 and 45 mg g−1.
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Fig. 2 Micrographs show SEM cross-sections of chitosan-based hydrogels P(AA-co-AMPS) at AA–AMPS ratios of (a) 1 : 5, (b) 1 : 1, (c) 5 : 1, (d) 10 :
1, and (e) 1 : 0. The histogram shows the average pore size and pore size distribution of the hydrogels.
3.3 Effect of AA–AMPS ratio on MB and CV adsorption by was more pronounced in CV adsorption. The adsorption
hydrogel capacity towards CV increased with increments of AA content.
As the total weight of the feed monomers was xed, the hydrogel
As the 5 : 1 hydrogel demonstrated higher adsorption capacities
with a higher AA content had a higher total number of moles of
towards MB and CV, these two dyes were chosen to study the
monomers. Therefore, the enhanced adsorption performance
effect of the AA–AMPS ratio on dye adsorption. All hydrogels
was due to the increase in the number of negatively-charged
demonstrated comparable adsorption capacities of approxi-
functional groups. The 10 : 1 hydrogel exhibited the highest
mately 800 mg g−1 towards MB—about 24 times the adsorption
adsorption capacity of 1032 mg g−1—about 23 times that of
capacity of pristine chitosan (Fig. 5). The inuence of AA and
AMPS contents on MB adsorption was also found to be negli- chitosan. The adsorption capacity of 1 : 5 hydrogel was not re-
ported as the hydrogel broke into small pieces during stirring,
gible in a previous study that used P(AMPS-co-AA) particles as
possibly due to the low degree of crosslinking. This result was in
adsorbents.19 The effect of the AA–AMPS ratio in the hydrogel
good agreement with the water absorption test, in which the
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Fig. 3 Water absorption capacity of chitosan-based P(AA-co-AMPS) Fig. 5 Adsorptions of methylene blue (MB) and crystal violet (CV) by
hydrogels with various AA–AMPS ratios. chitosan-based hydrogels containing P(AA-co-AMPS) at various AA–
AMPS ratios. (Co = 1000 mg L−1, dose = 0.05 g/50 mL, ambient
temperature, contact time = 24 h, unadjusted pH).
Fig. 4 Adsorption capacity of chitosan-based P(AA-co-AMPS) Fig. 6 Adsorption of CV at various contact times of a chitosan-based
hydrogel with an AA–AMPS ratio of 5 : 1 towards various anionic and P(AA-co-AMPS) hydrogel with an AA–AMPS ratio of 10 : 1. (Co =
cationic dyes. (Co = 1000 mg L−1, dose = 0.05 g/50 mL, ambient 1000 mg L−1, dose = 0.05 g/50 mL, ambient temperature, unadjusted
temperature, contact time = 24 h, unadjusted pH). pH).
WAC of the 1 : 5 hydrogel was excessive. The low adsorption 3.5 Kinetics of CV adsorption
capacity of the 1 : 0 hydrogel was possibly due to the low WAC of
To investigate the adsorption process of CV on the hydrogel, the
the hydrogel.
pseudo-rst-order (eqn (5)) and pseudo-second-order (eqn (6))
kinetics models were used:
3.4 Effect of contact time on CV adsorption
Because the 10 : 1 hydrogel had the highest CV adsorption ln(qe − qt) = ln qe − k1t (5)
capacity, it was used for subsequent experiments. The adsorp- t 1 1
tion rate of CV on the 10 : 1 hydrogel was initially fast due to the ¼ þ t (6)
qt k2 qe 2 qe
large number of adsorption sites, which quickly combined with
CV in solution. As contact time progressed, more adsorption where qe and qt were the dye adsorbed (mg g−1) at equilibrium
sites became occupied, and the electrostatic repulsion between and at different times; k1 and k2 were the rate constants of the
adsorbed and unadsorbed CV molecules increased, the rate of pseudo-rst-order model, and the pseudo-second-order model,
adsorption slowed (Fig. 6).34 The hydrogel removed 91% of CV respectively.35
in 12 h and reached equilibrium at about 16 h. The adsorption Fig. 7(a) and (b) show the pseudo-rst-order linear tting
capacity and removal efficiency at equilibrium were 1032 mg and the pseudo-second-order linear tting, respectively. The
g−1 and 94%, respectively. kinetics parameters are listed in Table 1. The correlation
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Fig. 8 Adsorption capacity and removal efficiency of a chitosan-

based P(AA-co-AMPS) hydrogel with an AA–AMPS ratio of 10 : 1
towards aqueous crystal violet at (a) various doses (Co = 1000 mg L−1,
V = 50 mL, ambient temperature, contact time = 24 h, unadjusted pH)
and (b) at various pH values. (Co = 1000 mg L−1, dose = 0.05 g/50 mL,
Fig. 7 Pseudo-first-order linear fitting (a) and pseudo-second-order ambient temperature, contact time = 24 h).
linear fitting (b) of CV adsorption of a chitosan-based P(AA-co-AMPS)
hydrogel with an AA–AMPS ratio of 10 : 1. (Co = 1000 mg L−1, dose =
0.05 g/50 mL, ambient temperature, unadjusted pH).
CV, such as modied rice bran/alginate hydrogel beads (5.69 ×
10−4 g mg−1 min−1),36 husk of agarwood fruit/sodium alginate
hydrogel (1.92 × 10−4 g mg−1 min−1),37 and cellulose/
Table 1 Kinetics parameters
carrageenan magnetic hydrogel microbeads (6.8× 10−3 g
Kinetics parameters mg−1 min−1).38
Experiment qe,exp (mg g−1) 1032

3.6 Effect of hydrogel dose on CV adsorption
Pseudo-rst-order qe,cal (mg g−1) 1515
k1 (min−1) 0.0059 As the adsorbent dose generally affected the efficiency of dye
R2 0.9218 removal, the effect of the 10 : 1 hydrogel dose on CV adsorption
Pseudo-second-order qe,cal (mg g−1) 1250
was investigated. At a low dose of 0.01 g per 50 mL of CV
k2 (g mg−1 min−1) 3.408 × 10−6
R2 0.9839 solution, the adsorption capacity was only 322 mg g−1 and the
removal efficiency was 6% (Fig. 8(a)). Upon increasing the
hydrogel dose up to 0.05 g per 50 mL of CV solution, the
coefficient of the pseudo-second-order model was closer to 1.0 adsorption capacity and removal efficiency increased due to the
and higher than that of the pseudo-rst-order model, indicating increase in the active sites to the dye molecules. At a dose of
that the adsorption rate was controlled by chemisorption. In 0.07 g, the removal efficiency reached 98%, while the adsorption
addition, the calculated qe value was closer to the experimental capacity decreased to 723 mg g−1. The decrease in the adsorp-
qe value for the pseudo-second-order model. It was worth noting tion capacity was attributed to the limited number of dye
that the pseudo-second-order rate constant (k2) of this hydrogel molecules. Therefore, further studies were conducted with
was relatively lower than that of several hydrogel adsorbents for 0.05 g of hydrogel per 50 mL of CV solution.
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Fig. 9 Adsorption capacity at various initial CV concentrations of

a chitosan-based P(AA-co-AMPS) hydrogel with an AA–AMPS ratio of
10 : 1. (Dose = 0.05 g/50 mL, ambient temperature, contact time =
24 h, unadjusted pH).
3.7 Effect of pH on CV adsorption

As solution pH affects the surface charge and active sites of the
adsorbent along with the degree of ionization and structure of
the adsorbate, CV adsorption on the 10 : 1 hydrogel was inves-
tigated in the pH range of 2.0 to 10.0. The pH of the prepared CV
solution was 4.3 and this was adjusted using 0.1 M HCl or 0.1 M
NaOH solutions. In a strong acidic condition (pH = 2.0),
adsorption capacity was low because the hydrogel network
contracted, which prevented the adsorption of dye.39 At pH 4.3,
a sharp increase in adsorption capacity and removal efficiency
was observed (Fig. 8(b)). Since the pKa of AMPS = 1.5 and that of
AA = 4.2,18 the sulfonic acid groups (–SO3H) of PAMPS and
carboxyl groups (–COOH) of PAA were ionized at pH above 4.2.18 Fig. 10 Linear Langmuir isotherm (a) and linear Freundlich isotherm
Therefore, electrostatic interactions with the protonated amine (b) of CV adsorption of a chitosan-based P(AA-co-AMPS) hydrogel
group of CV were stronger. A slight increase in capacity was with an AA–AMPS ratio of 10 : 1. (Dose = 0.05 g/50 mL, ambient
observed at pH 6.0. Above pH 6.0, adsorption capacity temperature, contact time = 24 h, unadjusted pH).
decreased. The decrease in capacity could be attributed to
a decrease in CV cationization, which reduced electrostatic
interactions. Similar ndings were reported in MB adsorption a homogenous surface. The Freundlich model, on the other
on chitosan-g-P(AA-co-AMPS).20 hand, assumes that adsorption sites are heterogenous. The
stronger adsorption sites are occupied rst, and as the coverage
3.8 Effect of initial concentration of CV on adsorption and of the adsorbent surface increases, adsorption affinity
adsorption isotherm
A contact time of 24 h was allowed to elapse to ensure that
adsorption reached equilibrium. Adsorption capacity increased Table 2 Adsorption isotherm parameters
with increments of initial concentration from 10 to 3000 mg L−1
(Fig. 9). At these concentrations, the number of available Isotherm model Isotherm parameters
adsorption sites for bonding was greater than the number of
Langmuir qm (mg g−1) 2500
dye molecules.40 The maximum adsorption capacity was
KL (L mg−1) 0.0054
2023 mg g−1. The decrease in adsorption capacity at the initial RLa 0.1550
concentration of 4000 mg L−1 resulted from the saturation of R2 0.9666
active sites on the hydrogel surface.41 The interaction between Freundlich KF (mg g−1) 18.0185
CV and the hydrogel was investigated using the Langmuir and 1/n 0.7799
R2 0.8899
Freundlich isotherm models. The Langmuir isotherm model
describes the formation of a monolayer adsorption on a
Calculated at the CV concentration of 1000 mg L−1.
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Table 3 Comparison with various adsorbents for CV
Adsorbent qmax (mg g−1) KL (L mg−1) References
Polyaniline@TiO2 80 0.004 43
p(NIPAM-co-MAA1.0)/b-CD0.4 1253.7 0.0136 44

Gum arabic-cl-poly(acrylamide) nanohydrogel 90.9 0.047 45
Rarasaponin–bentonite-activated biochar composite 518.6 0.0741 46
Hydroxypropyl-b-cyclodextrin–polyurethane magnetic nanoconjugates 1269 — 47
Zeolitic imidazolate framework-9 (Z9-600) 26.8 — 48
Modied rice bran/alginate hydrogel beads 454.55 0.011 36
Husk of agarwood fruit/sodium alginate hydrogel 370.37 0.022 37
Cellulose/carrageenan magnetic hydrogel microbeads 217.1 0.0159 38

P(AA-co-AMPS)-graed chitosan hydrogel 2023 0.0054 This study
decreases, resulting in multilayer adsorption.42 The Langmuir 2500 mg g−1, which is higher than many other values reported
and Freundlich isotherm models can be expressed as eqn (7) for CV adsorbents (Table 3).
and (8), respectively: In addition, the separation factor, RL, of the Langmuir model
qm KL Ce was calculated using eqn (9):
qe ¼ (7)
1 þ KL Ce 1
RL ¼ (9)
1 þ KL C0
qe = KFCe1/n (8) where KL (L mg−1) is the Langmuir isotherm constant, and C0
(mg L−1) is the initial dye concentration.
where Ce (mg L−1) is the concentration of CV at equilibrium. qe The RL value indicates the tendency of the adsorption
(mg g−1) is the Langmuir maximum adsorption capacity at process to be irreversible (RL = 0), favorable (0 < RL < 1), linear
equilibrium and KL (L mg−1) is the Langmuir isotherm (RL = 1), or unfavorable (RL > 1).18 The Langmuir isotherm RL
constant. KF (L mg−1) is the Freundlich isotherm constant, and value of 0.1550 indicated a favorable adsorption. The KL value is
n is the heterogeneity factor. related to the affinity of binding sites and is independent of
The linear Langmuir isotherm and linear Freundlich qmax. The relatively low KL value of the 10 : 1 hydrogel suggests
isotherm of CV adsorption are shown in Fig. 10(a) and (b), a low affinity for CV (Table 3).
respectively. The adsorption isotherm parameters are summa-
rized in Table 2. The correlation coefficient of the Langmuir
model was closer to 1.0 and higher than that of the Freundlich 3.9 ZnO/P(AA-co-AMPS) 10 : 1 hydrogel composite
model, suggesting that the Langmuir model better described Fig. 11(a) and (b) show photographs of the 10 : 1 hydrogel and
the adsorption of CV on the 10 : 1 hydrogel. The theoretical ZnO/10 : 1 hydrogel composite. Aer the in situ synthesis of
maximum adsorption capacity (qmax) of this hydrogel was ZnO particles, the transparent hydrogel became partially
Fig. 11 Photographs of (a) 10 : 1 hydrogel and (b) ZnO/10 : 1 hydrogel composite, (c) and (d) TEM micrographs (magnification 150k×) of ZnO
particles, and (e) SEM-EDS cross-section micrograph and the corresponding elemental maps of ZnO/10 : 1 hydrogel composite.
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Fig. 12 SEM-EDS micrographs and the corresponding elemental maps of ZnO/10 : 1 hydrogel composite (a) outer surface and (b) cross-section.
white and opaque except in the outer area of the sample. 357 °C). The temperature shi indicated an increase in thermal
Fig. 11(c) and (d) show TEM micrographs of ZnO particles in stability. Moreover, because ZnO is stable at high temperatures,
the 10 : 1 hydrogel matrix. The particles were well dispersed, the thermal stability of the hydrogel composite could be used to
and agglomerations were small. The average size of the determine the amount of ZnO incorporated in the hydrogel. The
particles was 16.91 ± 1.41 nm but the shape of the particles residual weight of the samples at 650 °C indicated the
was not uniform. SEM-EDS (Fig. 11(e)) of the ZnO/10 : 1 percentage of polymer char. Therefore, the 8.7% difference
hydrogel composite showed that the porosity of the hydrogel between the residual weight of the bare 10 : 1 hydrogel and that
was maintained aer the in situ synthesis of ZnO. In order to of the ZnO/10 : 1 hydrogel composite could be attributed to
observe the distribution of ZnO particles, the image was taken ZnO.
at low magnication. The elemental mappings conrmed that The performance of the hydrogel composite towards the
Zn was evenly distributed and fully covered the surface of cell photocatalytic degradation of adsorbed dye was studied
walls. Zn and O elements almost completely replaced C. SEM- under natural sunlight and articial UV light. Aer 3 h under
EDS micrographs were further analyzed at higher magnica- sunlight (Fig. 14(a)), the color of the hydrogel composite had
tion (Fig. 12) to determine the % element ratio which was changed from dark purple to almost colorless and whitish,
summarized in Table 4. The results show that a very low indicating that the adsorbed dye molecules had been
content of Zn was observed on the outer surface of the degraded. Under UV lamps (Fig. 14(c)), photocatalytic degra-
hydrogel which was consistent with the clear layer as observed dation took longer (6 h) due to the much lower power of
in Fig. 11(b). However, a much higher content of Zn was irradiation. Although the photocatalytic degradation could
observed in the cross-section area indicating a dense incor- not be quantitatively analyzed due to the irregular sample
poration of ZnO particles inside the hydrogel matrix. Na was shapes, the reusability of the hydrogel composite was tested
detected on both the outer surface and the cross-section area, for adsorption and photocatalytic degradation. During pho-
which was the residue of the precipitation. tocatalytic degradation, the hydrogel composite was
Fig. 13(a) depicts XRD patterns of the 10 : 1 hydrogel and immersed in water to remove photodegraded products and
ZnO/10 : 1 hydrogel composite. The hydrogel showed a small simultaneously regenerate the hydrogel composite, thus no
broad peak at 20.1°, corresponding to the amorphous structure solvent desorption or washing step was required. In the rst
of PAA.49 The hydrogel composite showed additional peaks of cycle, the hydrogel composite removed ∼95% of the dye from
the hexagonal phase of the wurtzite structure of ZnO at 30.9°, the solution by adsorption process (Fig. 14(e)). In the second
33.6°, 35.4°, 46.7°, 55.7°, 62.0°, 65.2°, 67.0°, and 68.2° (JCPDS
card no. 36-1451).50 The XRD analysis conrmed the successful
conversion of Zn2+ ions to ZnO particles in the hydrogel matrix
Table 4 Corresponding elemental weight percentages of ZnO/10 : 1
with high purity.
hydrogel composite
TGA thermograms of the 10 : 1 hydrogel and ZnO/10 : 1
hydrogel composite showed a continuous weight loss from 35 to Weight%
350 °C due to the loss of absorbed water molecules and the
degradation of polymeric hydrogel via thermal scission of Element Outer surface Cross-section
pendant groups, crosslinks, and backbones (Fig. 13(b)).51,52 C 37.6 23.6
However, the initial degradation temperature of the hydrogel O 43.9 29.5
composite was higher than that of the bare hydrogel (336 °C vs. Zn 1.5 33.7
Na 17.0 13.2
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90%. The reduction in removal efficiency was due to the

accumulation of degraded products on the surface of the
hydrogel composite that hindered the activities of the free
radical species.53–56
Fig. 14(b)-3 h shows that, in the second cycle, the adsorbed

dye was almost completely degraded by sunlight, however, the
hydrogel composite was obviously less opaque. In the case of
UV light, the darker color of the hydrogel composite was
observed in the second cycle compared with the rst cycle at
the same irradiation time (6 h) (Fig. 14(c)-6 h and (d)-6 h).
These results indicated that ZnO particles disappeared during

irradiation and thus, the degradation performance of the
photocatalytic degradation of CV was reduced due to the loss
of ZnO particles. It has been reported that ZnO particles could
undergo hydrolyzation and were dissolved into Zn2+ ions.57 In
this work, the ZnO leaching increased with an increased
exposure time. Besides, the loss of ZnO particles was probably
due to the very small size of particles compared with the pore
size of the hydrogel. This limitation will be our further study
by reducing ZnO leaching by producing strong interactions
between polymers and ZnO particles and using a powerful
light source to decrease exposure time. Although the photo-
catalytic efficiency decreased and the reusability of the
hydrogel composite was low, the adsorption efficiency of the
hydrogel itself containing 2210% of graing chitosan
remained satisfactory. This composite material is easy to use,
especially in material handling. The problem of photo-
catalytic powder recovery is avoided.
The proposed mechanism of photocatalytic degradation of
CV adsorbed in the hydrogel composite is shown in Fig. 15.
Fig. 13 XRD patterns (a) and TGA thermograms (b) of 10 : 1 hydrogel When ZnO photocatalyst particles were exposed to light, they
and ZnO/10 : 1 hydrogel composite. gained energy and generated electrons (e−) in the conduction
band (CB) and holes (h+) in the valence band (VB). These e− and
h+ further reacted with oxygen (O2) and water (H2O) molecules,
cycle, the removal percentage of the sample regenerated by respectively, producing superoxide radical anions O2c− and
sunlight slightly decreased to 92% whereas the removal hydroxyl radicals (cOH) which decomposed CV molecules into
percentage of the sample regenerated by UV light decreased to non-toxic small molecules.
Fig. 14 Photocatalytic degradation of CV adsorbed in ZnO/10 : 1 hydrogel composite under sunlight (a) cycle 1 and (b) cycle 2 and UV lamps (c)
cycle 1 and (d) cycle 2, and (e) removal efficiency of the hydrogel composite. (Irradiation time is as indicated.)
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Fig. 15 The proposed photocatalytic degradation mechanism of CV by ZnO encapsulated in 10 : 1 hydrogel.
4. Conclusions Science, Research and Innovation. The authors would like to

thank Dr Chonnakarn Panawong for instrumental assistance.
P(AA-co-AMPS)-graed hydrogels were successfully synthesized
via free radical polymerization with high yields (>90%). Graing References
P(AA-co-AMPS) enhanced the adsorption capacity of chitosan,
and the hydrogels showed superior adsorption capacity towards 1 Y. Hong, C. Li, B. Yin, D. Li, Z. Zhang, B. Mao, W. Fan, W. Gu
cationic dyes compared to anionic dyes. The effect of AA and and W. Shi, Promoting visible-light-induced photocatalytic
AMPS contents on adsorption was observed in CV adsorption. degradation of tetracycline by an efficient and stable beta-
The 10 : 1 hydrogel removed 91% of CV in 12 h and reached Bi2O3@g-C3N4 core/shell nanocomposite, Chem. Eng. J.,
equilibrium aer 16 h. The maximum adsorption capacity of 2018, 338, 137–146, DOI: 10.1016/j.cej.2017.12.108.
this hydrogel towards CV was 2023 mg g−1, which is higher than 2 M. Mathur, D. Gola, R. Panja, A. Malik and S. Z. Ahammad,
the reported values of most other CV adsorbents. The adsorp- Performance evaluation of two Aspergillus spp. for the
tion kinetics and adsorption isotherm were described by the decolourization of reactive dyes by bioaccumulation and
pseudo-second-order kinetics model and the Langmuir biosorption, Environ. Sci. Pollut. Res., 2018, 25, 345–352,
isotherm model, respectively. ZnO particles incorporated in the DOI: 10.1007/s11356-017-0417-0.
10 : 1 hydrogel by in situ synthesis yielded a stable hydrogel 3 M. Bilal, I. Ihsanullah, M. U. Hassan Shah, A. V. Bhaskar
composite with photocatalytic properties. The hydrogel Reddy and T. M. Aminabhavi, Recent advances in the
composite could almost completely photodegrade adsorbed CV removal of dyes from wastewater using low-cost
dye under sunlight in less than 3 h. The adsorption capacity of adsorbents, J. Environ. Manage., 2022, 321, 115981, DOI:
the hydrogel composite in the 2nd cycle remained higher than 10.1016/j.jenvman.2022.115981.
90% but photocatalytic degradation decreased. This composite 4 R. Abejón, M. de Cazes, M. P. Belleville and J. Sanchez-
material could be used for wastewater treatment, adsorbing, Marcano, Large-scale enzymatic membrane reactors for
and degrading dye pollutants without requiring a photocatalyst tetracycline degradation in WWTP effluents, Water Res.,
recovery procedure. 2015, 73, 118–131, DOI: 10.1016/j.watres.2015.01.012.
5 Z. Liu, M. Zhu, L. Zhao, C. Deng, J. Ma, Z. Wang, H. Liu and
H. Wang, Aqueous tetracycline degradation by coal-based
Conflicts of interest carbon electrocatalytic ltration membrane: effect of nano
antimony-doped tin dioxide coating, Chem. Eng. J., 2017,
There are no conicts to declare.
314, 59–68, DOI: 10.1016/j.cej.2016.12.093.
6 A. G. Varghese, S. A. Paul and M. S. Latha, Remediation of
Acknowledgements heavy metals and dyes from wastewater using cellulose-
based adsorbents, Environ. Chem. Lett., 2019, 17, 867–877,
This research was supported by the Fundamental Fund of Khon DOI: 10.1007/s10311-018-00843-z.
Kaen University (KKU), and the Center of Excellence for Innova- 7 G. Crini and P. M. Badot, Application of chitosan, a natural
tion in Chemistry (PERCH-CIC), Ministry of Higher Education, aminopolysaccharide, for dye removal from aqueous
View Article Online
RSC Advances Paper
solutions by adsorption processes using batch studies: solutions, RSC Adv., 2017, 7, 47029–47037, DOI: 10.1039/
a review of recent literature, Prog. Polym. Sci., 2008, 33, c7ra06810g.
399–447, DOI: 10.1016/j.progpolymsci.2007.11.001. 19 X. Huang, D. Zhou, Y. Wang, C. He, W. Zhao, S. Sun and
8 S. Ma, M. Zhang, J. Nie, J. Tan, S. Song and Y. Luo, C. Zhao, A green approach towards functional hydrogel
Lightweight and porous cellulose-based foams with high particles from synthetic polymers via spherical capsule
loadings of zeolitic imidazolate frameworks-8 for mini-reactors, Chem. Eng. J., 2019, 359, 1360–1371, DOI:
adsorption applications, Carbohydr. Polym., 2019, 208, 328– 10.1016/j.cej.2018.11.042.
335, DOI: 10.1016/j.carbpol.2018.12.081. 20 Y. Tang, T. He, Y. Liu, B. Zhou, R. Yang and L. Zhu, Sorption
9 Y. Wang, X. Dai, Y. Zhan, X. Ding, M. Wang and X. Wang, In behavior of methylene blue and rhodamine B mixed dyes
situ growth of ZIF-8 nanoparticles on chitosan to form the onto chitosan gra poly(acrylic acid-co-2-acrylamide-2-
hybrid nanocomposites for high-efficiency removal of methyl propane sulfonic acid) hydrogel, Adv. Polym.
Congo Red, Int. J. Biol. Macromol., 2019, 137, 77–86, DOI: Technol., 2018, 37, 2568–2578, DOI: 10.1002/adv.21932.
10.1016/j.ijbiomac.2019.06.195. 21 J. Guo, H. Sun, X. Yuan, L. Jiang, Z. Wu, H. Yu, N. Tang,
10 Y. Wang, G. Xia, C. Wu, J. Sun, R. Song and W. Huang, M. Yu, M. Yan and J. Liang, Photocatalytic degradation of
Porous chitosan doped with graphene oxide as highly persistent organic pollutants by Co-Cl bond reinforced
effective adsorbent for methyl orange and amido black CoAl-LDH/Bi12O17Cl2 photocatalyst: mechanism and
10B, Carbohydr. Polym., 2015, 115, 686–693, DOI: 10.1016/ application prospect evaluation, Water Res., 2022, 219,
j.carbpol.2014.09.041. 118558, DOI: 10.1016/J.WATRES.2022.118558.
11 S. Kang, L. Qin, Y. Zhao, W. Wang, T. Zhang, L. Yang, F. Rao 22 S. Sharma and S. Basu, Highly reusable visible light active
and S. Song, Enhanced removal of methyl orange on hierarchical porous WO3/SiO2 monolith in centimeter
exfoliated montmorillonite/chitosan gel in presence of length scale for enhanced photocatalytic degradation of
methylene blue, Chemosphere, 2020, 238, 124693, DOI: toxic pollutants, Sep. Purif. Technol., 2020, 231, 115916,
10.1016/j.chemosphere.2019.124693. DOI: 10.1016/j.seppur.2019.115916.
12 K. Phonlakan, B. Khamsuk, N. Soontonhong, C. Panawong, 23 Y. Li, H. Zhang, X. Hu, X. Zhao and M. Han, Efficient Visible-
P. Kongseng, S. Chantarak and S. Budsombat, Composite Light-Induced Photocatalytic Activity of a 3D-Ordered
beads from chitosan and zeolitic imidazolate framework-8 Titania Hybrid Photocatalyst with a Core/Shell Structure of
for the adsorption and photocatalytic degradation of Dye-Containing Polymer/Titania, J. Phys. Chem. C, 2008,
reactive red 141, RSC Adv., 2023, 13, 12295–12308, DOI: 112, 14973–14979, DOI: 10.1021/jp8055152.
10.1039/d3ra01187a. 24 C. Ma, J. Zhou, Z. Cui, Y. Wang and Z. Zou, In situ growth
13 M. Vakili, M. Rafatullah, B. Salamatinia, A. Z. Abdullah, MoO3 nanoake on conjugated polymer: an advanced
M. H. Ibrahim, K. B. Tan, Z. Gholami and P. Amouzgar, photocatalyst for hydrogen evolution from water solution
Application of chitosan and its derivatives as adsorbents under solar light, Sol. Energy Mater. Sol. Cells, 2016, 150,
for dye removal from water and wastewater: a review, 102–111, DOI: 10.1016/j.solmat.2016.02.010.
Carbohydr. Polym., 2014, 113, 115–130, DOI: 10.1016/ 25 D. Ponnamma, J.-J. Cabibihan, M. Rajan, S. S. Pethaiah,
j.carbpol.2014.07.007. K. Deshmukh, J. P. Gogoi, S. K. K. Pasha, M. B. Ahamed,
14 Z. Yang, H. Yang, Z. Jiang, T. Cai, H. Li, H. Li, A. Li and J. Krishnegowda, B. N. Chandrashekar, A. R. Polu and
R. Cheng, Flocculation of both anionic and cationic dyes C. Cheng, Synthesis, optimization and applications of
in aqueous solutions by the amphoteric graing occulant ZnO/polymer nanocomposites, Mater. Sci. Eng., C, 2019, 98,
carboxymethyl chitosan-gra-polyacrylamide, J. Hazard. 1210–1240, DOI: 10.1016/j.msec.2019.01.081.
Mater., 2013, 254–255, 36–45, DOI: 10.1016/ 26 Y. Zhang, S. Wei, H. Zhang, S. Liu, F. Nawaz and F.-S. Xiao,
j.jhazmat.2013.03.053. Nanoporous polymer monoliths as adsorptive supports for
15 J. Maity and S. K. Ray, Enhanced adsorption of methyl violet robust photocatalyst of Degussa P25, J. Colloid Interface
and congo red by using semi and full IPN of polymethacrylic Sci., 2009, 339, 434–438, DOI: 10.1016/j.jcis.2009.07.050.
acid and chitosan, Carbohydr. Polym., 2014, 104, 8–16, DOI: 27 P. Maijan, P. Amornpitoksuk and S. Chantarak, Synthesis
10.1016/j.carbpol.2013.12.086. and characterization of poly(vinyl alcohol-g-acrylamide)/
16 J. Men, H. Shi, C. Dong, Y. Yang, Y. Han, R. Wang, Y. Zhang, SiO2@ZnO photocatalytic hydrogel composite for removal
T. Zhao and J. Li, Preparation of poly(sodium 4-styrene and degradation of methylene blue, Polymer, 2020, 203,
sulfonate) graed magnetic chitosan microspheres for 122771, DOI: 10.1016/j.polymer.2020.122771.
adsorption of cationic dyes, Int. J. Biol. Macromol., 2021, 28 B. Zhang, H. Yu, Y. Zhang, Z. Luo, W. Han, W. Qiu and
181, 810–823, DOI: 10.1016/j.ijbiomac.2021.04.079. T. Zhao, Bacterial cellulose derived monolithic titania
17 L. Wang, J. Zhang and A. Wang, Fast removal of methylene aerogel consisting of 3D reticulate titania nanobers,
blue from aqueous solution by adsorption onto chitosan-g- Cellulose, 2018, 25, 7189–7196, DOI: 10.1007/s10570-018-
poly(acrylic acid)/attapulgite composite, Desalination, 2011, 2073-z.
266, 33–39, DOI: 10.1016/j.desal.2010.07.065. 29 M. Alavi and A. Nokhodchi, An overview on antimicrobial
18 B. Xu, C. Zheng, H. Zheng, Y. Wang, C. Zhao, C. Zhao and and wound healing properties of ZnO nanobiolms,
S. Zhang, Polymer-graed magnetic microspheres for hydrogels, and bionanocomposites based on cellulose,
enhanced removal of methylene blue from aqueous
View Article Online
Paper RSC Advances
chitosan, and alginate polymers, Carbohydr. Polym., 2020, adsorbents: equilibrium, kinetics, and thermodynamics, J.
227, 115349, DOI: 10.1016/j.carbpol.2019.115349. Chem. Eng. Data, 2016, 61, 3266–3276, DOI: 10.1021/
30 A. M. K. Najjar, W. M. Z. W. Yunus, M. B. Ahmad and acs.jced.6b00340.
M. Z. A. Rahman, Preparation and characterization of 42 H. Yan, H. Yang, A. Li and R. Cheng, pH-tunable surface
poly(2-acrylamido-2-methylpropane-sulfonic acid) graed charge of chitosan/graphene oxide composite adsorbent

chitosan using potassium persulfate as redox initiator, J. for efficient removal of multiple pollutants from water,
Appl. Polym. Sci., 2000, 77, 2314–2318, DOI: 10.1002/1097- Chem. Eng. J., 2016, 284, 1397–1405, DOI: 10.1016/
4628(20000906)77:10<2314::AID-APP25>3.0.CO;2-7. j.cej.2015.06.030.
31 Y. Liu, Y. Zheng and A. Wang, Enhanced adsorption of 43 M. Maruthapandi, L. Eswaran, J. H. T. Luong and
methylene blue from aqueous solution by chitosan-g-poly A. Gedanken, Sonochemical preparation of
(acrylic acid)/vermiculite hydrogel composites, J. Environ. polyaniline@TiO2 and polyaniline@SiO2 for the removal of
Sci., 2010, 22, 486–493, DOI: 10.1016/s1001-0742(09)60134-0. anionic and cationic dyes, Ultrason. Sonochem., 2020, 62,
32 K. Varaprasad, K. Vimala, S. Ravindra, N. Narayana Reddy, 104864, DOI: 10.1016/j.ultsonch.2019.104864.
G. Siva Mohana Reddy and K. Mohana Raju, 44 S. Jia, D. Tang, J. Peng, Z. Sun and X. Yang, b-Cyclodextrin
Biodegradable chitosan hydrogels for in vitro drug release modied electrospinning bers with good regeneration for
studies of 5-urouracil an anticancer drug, J. Polym. efficient temperature-enhanced adsorption of crystal violet,
Environ., 2012, 20, 573–582, DOI: 10.1007/s10924-012-0412-y. Carbohydr. Polym., 2019, 208, 486–494, DOI: 10.1016/
33 Y. Zhao, J. Kang and T. Tan, Salt-, pH- and temperature- j.carbpol.2018.12.075.
responsive semi-interpenetrating polymer network 45 G. Sharma, A. Kumar, M. Naushad, A. Garcı́a-Peñas, A. H. Al-
hydrogel based on poly(aspartic acid) and poly(acrylic Muhtaseb, A. A. Ghfar, V. Sharma, T. Ahamad and
acid), Polymer, 2006, 47, 7702–7710, DOI: 10.1016/ F. J. Stadler, Fabrication and characterization of gum
j.polymer.2006.08.056. arabic-cl-poly(acrylamide) nanohydrogel for effective
34 H. Zhang, Q. Dang, C. Liu, D. Yu, Y. Wang, X. Pu, Y. Liu, adsorption of crystal violet dye, Carbohydr. Polym., 2018,
Y. Liang and D. Cha, Fabrication of methyl acrylate and 202, 444–453, DOI: 10.1016/j.carbpol.2018.09.004.
tetraethylenepentamine graed magnetic chitosan 46 L. Laysandra, F. H. Santosa, V. Austen, F. E. Soetaredjo,
microparticles for capture of Cd(II) from aqueous K. Foe, J. N. Putro, Y.-H. Ju and S. Ismadji, Rarasaponin-
solutions, J. Hazard. Mater., 2019, 366, 346–357, DOI: bentonite-activated biochar from durian shells composite
10.1016/j.jhazmat.2018.12.006. for removal of crystal violet and Cr(VI) from aqueous
35 E. D. Revellame, D. L. Fortela, W. Sharp, R. Hernandez and solution, Environ. Sci. Pollut. Res., 2018, 25, 30680–30695,
M. E. Zappi, Adsorption kinetic modeling using pseudo- DOI: 10.1007/s11356-018-3104-x.
rst order and pseudo-second order rate laws: a review, 47 S. Nasiri and N. Alizadeh, Synthesis and adsorption behavior
Cleaner Engineering and Technology, 2020, 1, 100032, DOI: of hydroxypropyl-b-cyclodextrin–polyurethane magnetic
10.1016/j.clet.2020.100032. nanoconjugates for crystal and methyl violet dyes removal
36 G.-B. Hong, T.-J. Yu, H.-C. Lee and C.-M. Ma, Using rice bran from aqueous solutions, RSC Adv., 2019, 9, 24603–24616,
hydrogel beads to remove dye from aqueous solutions, DOI: 10.1039/c9ra03335a.
Sustainability, 2021, 13, 5640, DOI: 10.3390/su13105640. 48 T.-T. Han, H.-L. Bai, Y.-Y. Liu and J.-F. Ma, Synthesis of
37 C. M. Ma, B.-Y. Yang and G.-B. Hong, Husk of agarwood nanoporous cobalt/carbon materials by a carbonized
fruit-based hydrogel beads for adsorption of cationic and zeolitic imidazolate framework-9 and adsorption of dyes,
anionic dyes in aqueous solutions, Molecules, 2021, 26, New J. Chem., 2018, 42, 717–724, DOI: 10.1039/c7nj03745g.
1437, DOI: 10.3390/molecules26051437. 49 S. Moulay and N. Bensacia, Removal of heavy metals by
38 S. Park, Y. Oh, J. Yun, E. Yoo, D. Jung, K. K. Oh and S. H. Lee, homolytically functionalized poly(acrylic acid) with
Cellulose/biopolymer/Fe3O4 hydrogel microbeads for dye hydroquinone, Int. J. Ind. Chem., 2016, 7, 369–389, DOI:
and protein adsorption, Cellulose, 2020, 27, 2757–2773, 10.1007/s40090-016-0097-5.
DOI: 10.1007/s10570-020-02974-5. 50 S. Li, P. C. Chiang, L. Ding, K. J. Shah, Q. Chen and S. Chen,
39 L. Zhu, C. Guan, B. Zhou, Z. Zhang, R. Yang, Y. Tang and ZnO-chitosan/rectorite nanocomposite exhibiting high
J. Yang, Adsorption of dyes onto sodium alginate gra photocatalytic activities under visible-light irradiation, J.
poly(acrylic acid-co-2-acrylamide-2-methyl propane sulfonic Wuhan Univ. Technol., Mater. Sci. Ed., 2020, 35, 310–319,
acid)/kaolin hydrogel composite, Polym. Polym. Compos., DOI: 10.1007/s11595-020-2258-9.
2017, 25, 627–634, DOI: 10.1177/096739111702500808. 51 M. A. Abu-Saied, E. A. Soliman and E. A. A. Desouki,
40 P. Kongseng, P. Amornpitoksuk and S. Chantarak, Development of proton exchange membranes based on
Development of multifunctional hydrogel composite based chitosan blended with poly(2-acrylamido-2-methylpropane
on poly(vinyl alcohol-g-acrylamide) for removal and sulfonic acid) for fuel cells applications, Mater. Today
photocatalytic degradation of organic dyes, React. Funct. Commun., 2020, 25, 101536, DOI: 10.1016/
Polym., 2022, 172, 105207, DOI: 10.1016/ j.mtcomm.2020.101536.
j.reactfunctpolym.2022.105207. 52 M. Mohammadian, R. Sahraei and M. Ghaemy, Synthesis
41 Y. Wang, L. Zhao, H. Peng, J. Wu, Z. Liu and X. Guo, Removal and fabrication of antibacterial hydrogel beads based on
of anionic dyes from aqueous solutions by cellulose-based modied-gum tragacanth/poly(vinyl alcohol)/Ag0 highly
View Article Online
RSC Advances Paper
efficient sorbent for hard water soening, Chemosphere, 55 M. Thomas, G. A. Naikoo, M. U. D. Sheikh, M. Bano and
2019, 225, 259–269, DOI: 10.1016/ F. Khan, Effective photocatalytic degradation of Congo red
j.chemosphere.2019.03.040. dye using alginate/carboxymethyl cellulose/TiO2
53 G. Sharma, A. Kumar, M. Naushad, B. Thakur, D.-V. N. Vo, nanocomposite hydrogel under direct sunlight irradiation,
B. Gao, A. A. Al-Kahtani and F. J. Stadler, Adsorptional- J. Photochem. Photobiol., A, 2016, 327, 33–43, DOI: 10.1016/
photocatalytic removal of fast sulphon black dye by using j.jphotochem.2016.05.005.
chitin-cl-poly(itaconic acid-co-acrylamide)/zirconium 56 L. Zhang, P. Ma, L. Dai, S. Li, W. Yu and J. Guan, In situ
tungstate nanocomposite hydrogel, J. Hazard. Mater., 2021, crystallization and growth of TiO2 nanospheres between
416, 125714, DOI: 10.1016/j.jhazmat.2021.125714. MXene layers for improved adsorption and visible light
54 N. Kumar, H. Mittal, S. M. Alhassan and S. S. Ray, photocatalysis, Catal. Sci. Technol., 2021, 11, 3834–3844,
Bionanocomposite hydrogel for the adsorption of dye and DOI: 10.1039/D1CY00239B.

reusability of generated waste for the photodegradation of 57 M. Malekkiani, A. Heshmati Jannat Magham, F. Ravari and
ciprooxacin: a demonstration of the circularity concept M. Dadmehr, Facile fabrication of ternary MWCNTs/ZnO/
for water purication, ACS Sustain. Chem. Eng., 2018, 6, chitosan nanocomposite for enhanced photocatalytic
17011–17025, DOI: 10.1021/acssuschemeng.8b04347. degradation of methylene blue and antibacterial activity,
Sci. Rep., 2022, 12, 5927, DOI: 10.1038/s41598-022-09571-5.

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