Industrial Crops & Products 218 (2024) 118979

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Industrial Crops & Products

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Carboxymethyl cellulose/ microfibrillated cellulose hydrogel beads for

phosphate recovery: Templating effects of in situ-grown CaCO3
nanoparticles from CO2
Jialin Fu a, Jia Xin Yap a, Choe Peng Leo a, *, Chun Kiat Chang b
a
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Nibong Tebal, Penang 14300, Malaysia
b
River Engineering and Urban Drainage Research Centre (REDAC), Universiti Sains Malaysia, Engineering Campus, Nibong Tebal, Penang 14300, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: Carboxymethyl cellulose (CMC) hydrogel is a promising adsorbent. However, its weak chemical interaction with
Cellulose phosphate restricts the adsorption capacity and selectivity for nutrient recovery. In this study, CaCO3 nano­
Hydrogel particles were grown with microfibrillated cellulose using CO2 before crosslinking CMC into hydrogel beads to
Calcium carbonate
improve phosphate adsorption through chemical interactions. Scanning electron microscope showed the rough
Template
Phosphate
surface with wrinkles and the slightly porous surface after removing CaCO3. Fourier-transform infrared spec­
troscopy confirmed calcite formation in CMC hydrogel and the removal through chelation based on the calcite
peak at 852 cm− 1. However, the calcite crystallinity was absent in the X-ray diffraction analysis due to the
hindrance of the amorphous hydrogel. The phosphate adsorption capacity was increased to 109.87 mg/g by
growing CaCO3 nanoparticles instead of blending. After removing CaCO3 nanoparticles, the phosphate adsorp­
tion capacity was further raised to 132.21 mg/g due to the increment of active sites and surface area. The
adsorption was stable between pH 3 and pH 7, and it was only significantly affected by HCO-3 due to alkalinity
changes. The selective phosphate adsorption was driven by chemical interaction, as proven by the pseudo-
second-order kinetic model and Langmuir isotherm. After 6 cycles, the adsorption capacity was maintained
more than 80 %.

1. Introduction adsorption. Wu et al. (2019) incorporated β-FeOOH nanoparticles into

polyacrylamide hydrogel to enhance phosphate adsorption capacity of
Phosphate run-off from agricultural land and sewage is one of the 8.2 mg/g, which was reduced by 31.6 % after 3 cycles. The presence of
main causes of harmful algal blooms (Zahed et al., 2022). Harmful algal HCO-3 and SO2- 4 further reduced the phosphate removal efficiency
blooms can result in toxins produced by cyanobacteria besides dead significantly due to pH increment and large electronegativity, respec­
zones with limited light and low oxygen content for other aquatic life in tively. Xi et al. (2021) modified bentonite with zirconium oxychloride
our water resources. Hydrogels have been extensively developed in octahydrate before immobilizing it into sodium alginate hydrogel to
recent years to remove phosphate from water. Unlike other adsorbents promote phosphate adsorption via electrostatic interaction and ligand
with high selectivity towards heavy metals (Chai et al., 2021; Rajendran exchange, followed by inner complexation. The adsorption capacity of
et al., 2022; Song et al., 2019), the phosphate-rich hydrogels could be 63.61 mg/g was also significantly affected by the presence of HCO-3 and
reused as a fertilizer with slow-release properties. The weak chemical F- anions. Moreover, the desorption reduced significantly after 5 cycles.
interaction between hydrogels and phosphate constitutes the primary Zhang et al. (2022a) used the MIL-101 metal-organic framework to
gap to commercial viability due to its negative impact on adsorption promote phosphate adsorption by chitosan hydrogel. The adsorption
capacity and nutrient recovery selectivity. capacity of 49.8 mg/g was driven by electrostatic attraction and ligand
Incorporating different inorganic fillers was widely adopted in exchange. Other anions, such as Cl-, NO-3, CO2- 2-
3 , and SO,4 did not affect
developing hydrogels for phosphate adsorption. The state-of-the-art the adsorption capacity significantly. Song et al. (2023) crosslinked
involved the creation of chemical interactions for phosphate sodium alginate in the presence of Ti3C2 MXenen besides zirconium. The

* Corresponding author.
E-mail address: [email protected] (C.P. Leo).

https://doi.org/10.1016/j.indcrop.2024.118979
Received 27 October 2023; Received in revised form 21 May 2024; Accepted 10 June 2024
Available online 13 June 2024
0926-6690/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
J. Fu et al. Industrial Crops & Products 218 (2024) 118979

formation of Zr–O–P and Ti–O–P complexes improved phosphate iron-rich biochar for phosphate removal through chemical precipitation
adsorption. Although experimental results showed a maximum adsorp­ at a capacity of 17.33 mg/g. Tang et al. (2023) loaded the SBA-15
tion capacity near 160 mg/g, a theoretical adsorption capacity of metal-organic framework with calcium carbonate to reach a phos­
492.55 mg/g was predicted. Lin et al. (2023) incorporated yttrium oxide phate desorption capacity of 92.0 mg/g through the formation of a
(Y2O3) in the sodium alginate hydrogel to improve phosphate adsorp­ phosphate-calcium complex. Incorporating calcium carbonate in
tion capacity to 48.54 mg/g through inner complexion, as described by different hydrogels for phosphate recovery was recently reported. Pap
Freundlich isotherm and the pseudo-second-order model. A high selec­ et al. (2023) described the implementation of chitosan-calcite hydrogel
tivity of 62.5 was reported in the presence of coexisting anions. Past to recover phosphate from wastewater at a pilot scale. The phosphate
studies exhibited the importance of ion selectivity studies after creating was adsorbed through microprecipitation and ligand exchange and then
selective interaction with phosphate using different inorganic fillers in released to promote the growth of perennial ryegrass. Wang et al.
hydrogels. Among different inorganic fillers, lanthanum was extensively (2023b) grafted polyethyleneimine on chitosan before loading with
reported to promote phosphate adsorption by hydrogels as it resulted in 3-(methacrylamido) propyl-trimethylammonium chloride modified La
significant improvement in phosphate adsorption capacity. Wang et al. (OH)3 and calcium carbonate for phosphate removal at a capacity of
(2020) reported a maximum adsorption capacity of 16.4 mg P/g be­ 107.23 ± 4.96 mg P/g.
tween pH 4 and 6 after incorporating talc and lanthanum in the prep­ Biodegradable cellulose, nanocellulose, and cellulose derivatives
aration of sodium alginate hydrogel. The addition of SO2- 4 reduced from sustainable sources are abundantly available in the market. Due to
phosphate adsorption due to competitive adsorption. Li et al. (2021) their large surface area, abundant hydroxyl groups, and non-toxic
polymerized (3-acrylamidopropyl) trimethylammonium chloride in the properties, they have been widely used to stabilize different types of
presence of La(OH)3. Phosphate was adsorbed at a capacity of 39.14 nanoparticles (Alam et al., 2020; Amornkitbamrung et al., 2020;
±0.31 mg/g within 2 h through electrostatic adsorption on –N+(CH3)3, El-Naggar et al., 2022; Hazra et al., 2024; Musino et al., 2021; Wang
ligand exchange to La(OH)3, and inner complexing. The adsorption was et al., 2022; Yan et al., 2019). Cellulose-based composites could be easily
not significantly affected by other anions, but the adsorption capacity prepared using a coagulation bath (Allouss et al., 2019; Baek and Park,
dropped 36.6 % after 10 cycles. Shan et al. (2022) encapsulated rice 2021; Brondi et al., 2022; Hazra et al., 2021; Hua et al., 2019; Liu et al.,
husk biochar and MgAl2O4 into carboxymethyl cellulose/lanthanum 2022; Maaloul et al., 2020; Xia et al., 2022; Zhang et al., 2024). Hence,
hydrogel. The phosphate adsorption capacity of 89.65 mg/g was carboxymethyl cellulose was selected as the major building block of
recorded at pH 3 due to electrostatic interaction, ligand exchange, and hydrogel for phosphate recovery in this study. Since the previous work
inner completion. Although the adsorption was not affected by other (Fu et al., 2023) showed that calcium carbonate further improved the
anions, it dropped significantly after 5 reuse cycles. Chen et al. (2022) phosphate adsorption capacity of carboxymethyl cellulose/sodium
synthesized sodium alginate hydrogel containing amorphous lanthanum alginate hydrogel containing bentonite to 90.31 mg/g, calcium car­
silicate and Fe3O4 for phosphate removal through precipitation, ligand bonate was continuously studied in this study. Different from the
exchange, and complexation. The adsorption capacity of 40.14 mg/g blending approach reported in the previous work (Fu et al., 2023),
was not affected by other anions. Qing et al. (2022) reduced the solution calcium carbonate was grown in the presence of microfibrillated cellu­
pH to pH 3 for improving phosphate adsorption capacity of sodium lose using CO2 before crosslinking carboxymethyl cellulose in this study.
alginate/zirconium hydrogel from 122.68 mg/g to 256.79 mg/g. The The main objective was to promote phosphate adsorption by carbox­
adsorption through ligand exchange was converted into electrostatic ymethyl cellulose hydrogels using the homogeneously grown calcium
interactions and hydrogen bondings. The coexisting anions affected carbonate. The in-situ growth method promotes carbon capture, utili­
phosphate insignificantly at pH 3, but resulted in competitive inner zation, and storage (CCUS) in hydrogel production (Tan et al., 2021).
complexation between pH 5 and 7. Kong et al. (2023) crosslinked chi­ Besides studying the effects of calcium loading on the hydrogel prop­
tosan with the presence of attapulgite and lanthanum to form a porous erties and phosphate adsorption capacity, their templating effects on
hydrogel that could adsorb phosphate up to 114.1 mg/g in less than hydrogel properties, phosphate adsorption, selectivity, and reusability
400 min. The phosphate adsorption through precipitation, electrostatic were evaluated.
interaction, ligand exchange, and complexion was affected by other
coexisting anions when they appeared at a high concentration. The use 2. Materials and methods
of lanthanum in hydrogel to promote phosphate adsorption is still
limited by the drop in selectivity in the presence of other water pollut­ 2.1. Materials
ants besides its high cost.
Phosphate adsorption could also be promoted by biocompatible Calcium chloride (CaCl2, purity > 95 %, R&M Chemicals, Malaysia),
calcium carbonate, which is commercially abundant and low in cost (Shi sodium dodecyl sulfates (SDS > 99 %, Sigma-Aldrich, United States),
et al., 2022). Calcium-rich waste has been widely used to adsorb phos­ poly(ethylene glycol) (PEG, 10 kDa, Sigma-Aldrich, United States), and
phate. Arslanoğlu (2021) reported that calcium carbonate in the gran­ NaOH (purity > 99.0 %, R&M Chemicals, Malaysia) are used to syn­
ular cake of carbonatization sludge could adsorb 65.16 mg P/g. Jeong thesize calcium carbonate. Carboxymethyl cellulose (CMC, food grade,
and Kim (2023) utilized coal bottom ash and oyster shells with abundant DCHemie, Malaysia), microfibrillated cellulose (10 wt%, Exilva, Borre­
calcium to remove phosphate through precipitation into calcium phos­ gaard, Norway), ethylenediaminetetraacetic acid (EDTA, purity >
phate and hydroxyapatite at a capacity of 1.403 mg P/g. Lee et al. 99.4 %, R&M Chemicals, Malaysia), and iron chloride (FeCl3, purity ≥
(2023) reported using calcium-rich wood bottom ash to remove phos­ 97.0 %, Fluka Chemicals, United Kingdom) were acquired to produce
phate, reaching an adsorption capacity of 76.8 mg/g. Hernández-Na­ hydrogel beads. Meanwhile, KH2PO4 (purity > 99 %, Bendosen), NaCl
varro et al. (2023) used calcium-rich Sargassum macroalgae to adsorb (Systerm, Malaysia, purity > 99 %), Na2SO4 (R&M Chemicals, Malaysia,
phosphate up to 224.6 mg/g. Pérez et al. (2022) further explained that purity > 99 %), NaNO3 (Merck, Germany, purity > 99.5 %), and
the Ca-P complex formed due to ion exchange between CO2- 3 and PO3
3-
NaHCO3 (R&M Chemicals, Malaysia, purity > 99.5 %) were used in the
during phosphate adsorption on eggshell-palm mesocarp fiber compos­ adsorption and recovery tests without further purification.
ite. Flower et al. (2022) further developed a surface complexation model
for P adsorption by calcite. Subsequently, more phosphate adsorbents 2.2. Synthesis and characterization of hydrogel beads
were developed by modifying waste with calcium. Samaraweera et al.
(2021) modified lignite with Ca2+ and Mg2+ cations to remove phos­ SDS and PEG were dissolved in distilled water at a weight ratio 1:1
phate at an adsorption capacity of 80.6 mg/g through precipitation. Yu under stirring to form complex micelles to limit the growth of calcium
et al. (2022) pyrolyzed paper mill sludge under CO2 to form calcium and carbonate in nano size. After adding 1 g of micelles and 2 g of

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J. Fu et al. Industrial Crops & Products 218 (2024) 118979

Fig. 1. The synthesis steps for 1CaCl2, 2CaCl2, and 3 CaCl2 hydrogel beads.

microfibrillated cellulose, different amounts of CaCl2 (1, 2, or 3 g) were with a diamond crystal. The freeze-dried hydrogel beads were ground
dissolved into distilled waterThe mixture of micelles and micro­ into powder form and pelletized with KBr for FTIR analysis from
fibrillated cellulose with different amounts of CaCl2 was added into 4000 cm− 1 to 550 cm− 1.
NaOH solution (0.02 M, 80 ml), followed by CO2 bubbling at a rate of The crystallinity of selected hydrogel beads with intermediate con­
600 ml/min for 3 min. CaCO3 nanoparticles smaller than 100 nm were tent of CaCl2 was further analyzed. The freeze-dried hydrogel beads
expected to be produced, similar to our previous work (Tan et al., were ground into powder before crystallinity analysis. X-ray diffraction
2021a). The final solution (100 ml) with carbonate precipitate was later patterns (XRD, Bruker D8 Advance) were collected from 20 ◦ to 80 ◦ for
used as the solvent of CMC hydrogel beads. examining crystallinity under Cu Kα radiation.
The 1CaCl2, 2CaCl2, and 3CaCl2 hydrogel beads were later produced The Brunauer–Emmett–Teller (BET) surface area of selected hydro­
from hydrogel dope solution by dissolving 2 g of carboxymethyl cellu­ gel beads was also determined (Micromertics ASAP 2020 BET Analyzer).
lose into the solution containing carbonate precipitate under stirring at Prior to analysis, the freeze-dried hydrogel beads in the powder form
500 rpm for 3 h. The 1CaCl2, 2CaCl2, and 3CaCl2 hydrogel beads were degassed at 200 ◦ C for 8 h.
contained calcium carbonate precipitates of the mixture of micelles, The water uptake capacity of hydrogel beads was determined. The
microfibrillated cellulose with 1, 2, an 3 g of CaCl2, respectively. The freeze-dried hydrogel beads were immersed in water. The surface water
homogenous dope solution was sonicated for 2 h to remove bubbles on the swollen hydrogel beads was removed using filter paper. Then, the
before being dripped into 3 % FeCl3 solution using a syringe. The swollen hydrogel beads were weighed, and the percentage of water
hydrogel beads were crosslinked in FeCl3 solution for 25 min at room uptake capacity was determined using the following equation.
temperature. Fig. 1 illustrates the synthesis of 1CaCl2, 2CaCl2, and
Ms − Md
3CaCl2 hydrogel beads. The crosslinked hydrogel beads were washed 5 S% = × 100 (1)
Md
times using distilled water before being frozen at − 85 ◦ C for 24 h and
freeze-drying for 16 h. EDTA was later used to form 2CaCl2/EDTA where S is the equilibrium water absorbency (%), Ms is the weight of the
hydrogel. CaCO3 leaching from hydrogels using acids and EDTA has swollen hydrogel beads (g), and Md is the weight of the freeze-dried
been widely reported in the development of drug delivery systems (Fu hydrogel beads (g).
et al., 2022). However, the stability of CaCO3 nanoparticles in the
hydrogel can be extended under the dry condition. Hence, hydrogel
beads in this study were freeze-dried after synthesis. 2CaCl2 hydrogel 2.3. Adsorption and recovery tests
beads were immersed in EDTA solution (0.002 M) for 5 min. The
modified hydrogel beads were washed, frozen, and dried. The The hydrogel beads were immersed in water, and the total dissolved
freeze-dried hydrogel beads were subsequently characterized and solid (TDS) was measured at 30 min invertal time. The TDS reading
tested. remained the same after 3 h. CaCO3 leaching through dissolution was
The hydrogel beads were characterized using equipment in the not detected. The stability of CaCO3 in the hydrogel beads was consid­
School of Chemical Engineering, Universiti Sains Malaysia. The ered acceptable for adsorption tests. The hydrogel beads were compared
morphology of freeze-dried hydrogel beads was examined using a in phosphate adsorption using phosphate solution without pH adjust­
scanning electron microscope (SEM, Quanta 450 FEI) after sputter ment under orbital shaking (MS-NOR-30, Major Science) at 130 rpm.
coating with gold. The hydrogel beads were tested at 25 ◦ C during adsorption tests. The
The chemical properties of hydrogel hydrogel beads were studied initial concentration of phosphate solution was 500 mg/L, and the
using Fourier transform infrared (FTIR) spectrometry (Nicolet iS10) adsorbent loading was kept at 1 mg/ml. The phosphate concentration of

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J. Fu et al. Industrial Crops & Products 218 (2024) 118979

Fig. 2. SEM images of (a) 1CaCl2, (b) 2CaCl2, (c) 3CaCl2 and (d) 2CaCl2/EDTA hydrogel beads.

adsorbent samples was analyzed using a UV-spectrophotometer (Cary The phosphate adsorption kinetics using the selected hydrogel beads
60 UV-Vis, Agilent Technologies) at a wavelength of 700 nm (Marsie­ with the highest phosphate adsorption capacity were further studied
zade and Javanbakht, 2020). The phosphate concentration was deter­ using the pseudo-first-order, pseudo-second-order, and intra-particle
mined using the calibration curves (Fig. S1). The following equations diffusion models. The pseudo-first-order model and pseudo-second-
were used to calculate the adsorption capacity (qt, mg/g) and removal order model are expressed in the following equations.
percentage (R, %) at the time, t (Abdi and Abedini, 2020).
ln(qe − qt ) = lnqe − k1 t (4)
(C0 − Ct )V
qt = (2) qe k2 t
m qt = (5)
1 + k2 qe t
C0 − Ct
R= × 100% (3)
C0 where qe is the amount of adsorbate adsorbed (mg/g) at equilibrium and
qt represents the amount of adsorbate adsorbed at a given time t. The
where C0 is the initial phosphate concentration (mg/L), Ct is the phos­ rate constant of the pseudo-first-order model is k1 (min− 1), while the
phate concentration (mg/L) at the time of t, V is the absorbate volume rate constant of the pseudo-second-order model k2 (g/mg⋅min).
(L), and m is the adsorbent weight (g). The intra-particle diffusion equation is stated below.
The effects of pH on the selected hydrogel beads with the highest
phosphate adsorption capacity were studied. The pH of the phosphate qt = kp t 1/2 + C (6)
solution with an initial concentration of 50 mg/L was adjusted using HCl
solution or NaOH solution. The adsorbent loading was kept at 0.6 mg/ where kp is the rate constant of intraparticle diffusion (mol/g⋅min1/2).
ml. The phosphate concentration and adsorption capacity were deter­ The value of C gives a good impression of the boundary layer.
mined, as mentioned earlier. The effects of coexisting anions (Cl-, SO2-
4,
The phosphate adsorption capacity of the selected hydrogel beads
NO-3, and HCO-3) on phosphate removal efficiency of the selected with the highest phosphate adsorption capacity was fitted to Langmuir
hydrogel beads with the highest phosphate adsorption capacity were and Freundlich models to understand changes in the adsorption
studied by adding one of the coexisting anions with a concentration of behavior. The single-layer adsorption is well described by the Langmuir
0.01 M or 0.1 M to phosphate solution (10 mg/L) in the adsorption test. model, but the heterogeneous adsorption is represented by the
The concentration of anions, PO2- - 2- - -
4 , Cl , SO4 , NO3, and HCO3 were
Freundlich. The Langmuir and Freundlich are listed here.
photometrically determined (HI83399, Hanna Instruments) using re­ qm KL Ce
agent test kits, HI93717A, HI93753A, HI93751, and HI3811, respec­ qe = (7)
1 + KL Ce
tively. The anion adsorption selectivity of two selected hydrogel beads
with high phosphate adsorption capacities was compared using a 1
qe = KF Ce n (8)
mixture of anions with an initial concentration of 100 mg/L each.

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J. Fu et al. Industrial Crops & Products 218 (2024) 118979

where KL (L/mg) is a Langmuir constant, qm (mg/g) is the maximum

adsorption ability, 1/n (mg/L) is the intensity parameter, and KF (mg/g)
is the capacity factor.
The reusability of the selected hydrogel beads with the highest
phosphate adsorption capacity was evaluated after phosphate adsorp­
tion. The recovery was conducted using HCl solution with a concen­
tration of 0.15 M and a volume of 10 ml under stirring at 120 rpm and
25 ◦ C for 10 min. The solution pH was neutralized using NaOH solution
before the subsequent adsorption cycle. The adsorption and reusability
tests were conducted with 3 replicates before calculating standard
deviations.

3. Results and discussion

Fig. 3. FTIR spectra of 1CaCl2, 2CaCl2, 3CaCl2 and 2CaCl2/EDTA hydro­
3.1. Hydrogel characteristics gel beads.

The close-up images of the freeze-dried 1CaCl2, 2CaCl2, 3CaCl2 and

2CaCl2/EDTA hydrogel beads are shown in Fig. S2. The hydrogel beads
with particle size near to 2 mm under ImagJ analysis showed irregular
shapes due to the structure rupture after removing the trapped water
through freeze drying. The formation of hydrogel beads could be further
improved based on the rheology properties of the CMC solution, which is
well described by the Power law (Salehi et al., 2023). A rheology study
should be conducted in future works to form highly porous beads with
the desired dimension. The morphological characterization could
further reveal the filler aggregates and templating effects in this study.
The surface morphology of 1CaCl2, 2CaCl2, 3CaCl2, and 2CaCl2/EDTA
hydrogel beads was compared using SEM images in Fig. 2. The surface of
these CMC hydrogel beads was considered rough after growing car­
bonate nanoparticles from CaCl2 in the microfibrillated cellulose
network under CO2 bubbling before polymer crosslinking. The micro­
Fig. 4. XRD spectrum of 2CaCl2 hydrogel beads.
fibrillated cellulose with a solid content of 1.5–2.4 % and a viscosity
higher than 14000 mPa⋅s in water (2 %) consists of a three-dimensional
be applied for in-situ growth of other nanoparticles in the future work
fiber network containing microfibers and some nanofibers (Molinari
(Liu et al., 2018). The 2CaCl2 hydrogel beads with the intermediate
et al., 2021). During hydrogel formation, the crosslinking was initiated
CaCl2 content were further treated with EDTA to study the templating
by the coordination of Fe3+ by hydrogen bonds between the anionic
effects of CaCO3. After EDTA treatment, 2CaCl2/EDTA hydrogel beads
CMC polymer chains and multivalent cations, subsequently leading to
exhibited a slightly porous surface. CaCO3 nanoparticles have been
ionic crosslinking (Zhang et al., 2022b). However, the increasing
extensively applied as the template in drug delivery systems to create
loading of CaCl2 did not reduce surface roughness like graphene oxide.
porous structures [26]. However, studies on their templating effects
Graphene oxide nanosheets could cover the rough surface of CMC
were limited to several hydrogels, such as polyacrylamide, alginate, and
hydrogel, but CaCO3 nanoparticles only induced the formation of hier­
poly(ethylene glycol) diacrylamide. The recent work (Fu et al., 2024)
archical roughness. Large CaCO3 aggregates were observed from the
confirmed that the porous structure created in CMC hydrogel after
surface of 1CaCl2, 2CaCl2, and 3CaCl2 hydrogel beads compared to
templating helped to enhance phosphate adsorption. In addition to
CMC/CaCO3 hydrogel with the incorporation of sodium alginate in our
crosslinking and gel swelling degrees, the crosslinking agent also affects
previous work (Fu et al., 2023). However, the aggregates were homo­
the tension strength and thermostability of beads (Morozkina et al.,
genously grown due to the presence of microfibrillated cellulose in these
2022).
hydrogel beads. Wu et al. (2023) showed the transmission electron
The FTIR spectra of 1CaCl2, 2CaCl2, 3CaCl2, and 2CaCl2/EDTA
microscopy image of calcium carbonate grown and wrapped around
hydrogel beads are studied using Fig. 3 to understand their differences in
cellulose nanofibrils. Unlike cellulose nanofibrils, microfibrillated cel­
terms of chemical properties. The absorption peak at 3496 cm− 1 could
lulose could affect the interaction and change the size of CaCO3 nano­
be related to the hydroxyl group (OH) of CMC and microfibrallated
particles differently. The microfibrillated cellulose dispersed CaCO3
cellulose (Maslamani et al., 2021; 2022). This peak could also be asso­
nanoparticles in the hydrogel network through intercalation (Ng and
ciated with–OH stretching in EDTA, while the peak at 1091 cm− 1
Leo, 2019). Nanoparticles showed a great tendency to attach to the
showed the -OH bending vibration. The presence of carboxylate groups
fibrous cellulose network, resulting in homogenous nucleation and
(-COO-) in CMC caused the narrow peak at 1600 cm− 1. The successful
growth of nanoparticles before the formation of CMC hydrogel. Karim
growth of CaCO3 nanoparticles was indicated by the calcite character­
et al. (2020) reported the zeta potential of microbrillated cellulose was
istic peaks at 852 cm− 1 (Tan et al., 2021a). This calcite peak was shown
− 47 ± 2.2 mV, while Wang et al. (2023) recorded positive zeta potential
clearly in the FTIR spectra of 1CaCl2, 2CaCl2, and 3CaCl2 hydrogel
values below pH 11 for calcium carbonate produced using PEG-SDS.
beads. However, this calcite peak vanished from the FTIR spectrum of
Hence, electrostatic interactions are proposed during the growth of
2CaCl2/EDTA hydrogel bead after EDTA chelation. The vanished peak
calcium carbonate in the presence of microfibrillated cellulose. XPS
explained the template removal using EDTA, resulting in a slightly
analysis should be conducted in future works to understand the inter­
porous surface. The sharp peak located at 1431 cm− 1 could be correlated
action between microfibrillated cellulose and CaCO3 nanoparticles.
to -CN- bonding in EDTA or asymmetric bending from the internal
Although CMC hydrogel (Td of 230 ◦ C) exhibited slightly lower thermal
oscillation of CO2-3 ions. The presence of CaCO3 nanoparticles could
decomposition temperature than the pulp (Td of 310 ◦ C) due to crys­
promote phosphate adsorption, as reported in previous works (Fu et al.,
tallinity loss, the thermal stability of CMC hydrogel is still sufficient to
2023; 2024).

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J. Fu et al. Industrial Crops & Products 218 (2024) 118979

Table 1 pattern. The 2CaCl2 hydrogel beads were considered nonporous since
Water uptake capacity of 1CaCl2, 2CaCl2, 3CaCl2, and 2CaCl2/EDTA only the single point surface area of 0.0484 m2/g was detected at P/P0 of
hydrogel beads. 0.0694, and BET surface area could not be calculated. The BET surface
Hydrogel beads Water uptake capacity (%) area of 0.4747 m2/g was recorded for 2CaCl2/EDTA hydrogel beads
1CaCl2 190.27 ± 32.02
after removing the template, CaCO3 using EDTA. The N2
2CaCl2 281.15 ± 56.12 adsorption-desorption isotherm of 2CaCl2/EDTA hydrogel beads has
3CaCl2 209.68 ± 41.09 been presented in Fig. S3. As summarized in Table S1, Large mesopores
2CaCl2/EDTA 367.24 ± 46.57 of 2CaCl2 hydrogel beads (BJH adsorption average pore diameter of
1618.272 Å) could promote diffusion, while small mesopores of
2CaCl2/EDTA hydrogel beads (BJH adsorption average pore diameter of
The crystallinity and templating effects of CaCO3 nanoparticles in
262.648 Å) could provide more adsorption sites (Tan et al., 2021b). The
hydrogel beads could be studied using XRD patterns and BET surface
water uptake of CMC hydrogel beads could be improved by nearly
area, respectively. The crystalline CaCO3 nanoparticles in CMC hydrogel
2500 % to improve diffusion based on a study conducted by (Büyü­
beads were expected to be calcite with characteristic planes of (012) (2θ
küstün et al., 2020). In this work, the water uptake of 1CaCl2, 2CaCl2,
= 23.09), (104) (2θ = 29.42), (110) (2θ = 36.00), (113) (2θ = 39.43),
3CaCl2, and 2CaCl2/EDTA has been summarized in Table 1. Although
(202) (2θ = 43.18), (018) (2θ = 47.47, (116) (2θ = 48.50) and (122) (2θ
these hydrogel beads showed a low water uptake capacity in general, the
= 57.42). However, the growth of CaCO3 nanoparticles in the CMC
water uptake capacity of 2CaCl2/EDTA hydrogel beads increased
hydrogel beads before crosslinking did not result in these characteristic
significantly compared to 2CaCl2 hydrogel beads due to the porosity
peaks in the XRD spectrum of 2CaCl2 hydrogel bead (Fig. 4). The
increment after removing templates using EDTA. The porous structure of
crystallinity of CaCO3 nanoparticles could be hindered by amorphous
2CaCl2/EDTA hydrogel beads remained after water uptake at pH 11 but
CMC hydrogel, unlike blending CaCO3 nanoparticles into hydrogel re­
not at pH 2 (Fig. S4). The disappearance of the porous structure at pH 2
ported in our previous work (Fu et al., 2023). Moreover, the calcification
could be caused by a pore rupture caused by the further disassociation of
could take longer to form the desired crystallinity with clear XRD
the remaining CaCO3 at a low pH.
characteristic peaks (Milovanovic et al., 2020). Unlike cellulose, CMC
only exhibited an amorphous pattern in XRD analysis. Meanwhile, CaCl2
was dissolved in the water before the growth of CaCO3 nanoparticles.
3.2. Adsorption and hydrogel recovery
Although microfibrillated cellulose should exhibit a crystalline phase in
XRD analysis, the low microfibrillated cellulose content in CMC
The phosphate adsorption capacity and removal percentage of
hydrogel was not expected to induce any crystalline peaks in the XRD
1CaCl2, 2CaCl2, 3CaCl2, and 2CaCl2/EDTA hydrogel beads were

Fig. 5. Phosphate adsorption by 1CaCl2, 2CaCl2, 3CaCl2 and 2CaCl2/EDTA adsorbent hydrogel beads using phosphate solution with initial concentration of
500 mg/L, adsorbent dosage of 1 mg/ml at pH 7.

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J. Fu et al. Industrial Crops & Products 218 (2024) 118979

Fig. 6. Effect of solution pH on phosphate adsorption by 2CaCl2/EDTA

hydrogel beads using phosphate solution with initial concentration of 50 mg/L
Fig. 7. Effects of co-existing anions on phosphate removal from the mixture of
and adsorbent dosage of 0.6 mg/ml.
10 mg/L of phosphate and 0.01 M or 0.1 M of anion using 2CaCl2/EDTA
hydrogel beads at an adsorbent dosage of 1 mg/ml.
compared, as shown in Fig. 5. The absorbance changes over time are
presented in Fig. S5. After 2 h, all hydrogel beads developed in this work
attained the maximum phosphate removal capacity and percentage. The
phosphate adsorption capacity of 1CaCl2 and 3CaCl2 hydrogel beads in
this study was slightly lower than that of CMC/alginate hydrogel beads
blended with CaCO3 nanoparticles in our previous study (Fu et al.,
2023). Unlike blending, the in-situ growth of CaCO3 nanoparticles in
hydrogels allows carbon capture, utilization, and storage (CCUS) using
calcium-rich waste such as brine in the future (Tan et al., 2021). The
loading of CaCO3 nanoparticles in the 1CaCl2 hydrogel bead was ex­
pected to be low and insufficient for effective phosphate adsorption.
Meanwhile, particle agglomeration could occur in the 3CaCl2 hydrogel
bead due to its high calcium content. Particle agglomeration frequently
resulted in a low adsorption capacity. However, 1CaCl2 and 3CaCl2
hydrogel beads attained maximum adsorption faster than the CMC/al­
ginate/CaCO3 hydrogel beads reported in our previous work (Fu et al., Fig. 8. Anion adsorption from mixture of 100 mg/L of phosphate and 100 mg/
2023). The wrinkles on these CMC hydrogel beads provided a large L of anions using 2CaCl2 and 2CaCl2/EDTA hydrogel beads with adsorbent
dosage of 1 mg/ml.
surface for fast adsorption. The 2CaCl2 hydrogel bead with the appro­
priate amount of CaCO3 nanoparticles attained the maximum phosphate
adsorption capacity of 109.87 mg/g after 2 h. This adsorption capacity Table 2
was higher than CMC/alginate/CaCO3 hydrogels developed in our pre­ Adsorption kinetic parameters of 2CaCl2/EDTA hydrogel beads.
vious work. Compared to hydrogels containing lanthanum (Chen et al.,
Ci (mg/L) Pseudo-first order kinetic
2022; Feng et al., 2022; Liu et al., 2023), the phosphate adsorption ca­
pacity of 2CaCl2 hydrogel bead was still considered high. After template qe,cal (mg/g) k1 (min− 1) R2

removal using EDTA, the phosphate adsorption capacity of 100 86.53 0.0259 0.9665
2CaCl2/EDTA hydrogel bead was even raised to 132.21 mg/g. The pore Ci (mg/L) Pseudo-second order kinetic
qe,cal (mg/g) k2 (min− 1) R2
construction through templating was considered necessary in devel­
100 107.06 7.2049×10− 4 0.9957
oping hydrogel adsorbent, even though the improvement of hydrogel Ci = 100 mg/L Intra-particle diffusion
porosity was less significant, as shown in SEM images. The access to C (mg/g) kp (mol/g⋅min1/2) R2
internal active sites could be improved through pore creation in the C1 -6.4545 4.6089 0.9811
hydrogel. Although the phosphate adsorption capacity was affected by C2 17.4092 1.4683 0.9683
C3 32.4815 0.1955 0.9437
CaCl2 loading and the template removal, the maximum adsorption of
phosphate was achieved by all hydrogel beads within 120 min.
The phosphate adsorption changes and reusability of 2CaCl2/EDTA removal efficiency of the 2CalCl2/EDTA hydrogel bead were presented
hydrogel beads were further investigated. The adsorption mechanism in Fig. 7. The phosphate removal efficiency was significantly affected by
could be affected by solution pH (Arslanoğlu, 2021). the presence of HCO-3 but slightly affected by SO2-
4 at high concentration.
A similar observation was reported by Shan et al. (2022), who produced
Ca2+ + H2PO4- → CaH2PO+
4 (pK = -1.08) (8)
CMC/lanthanum hydrogel containing biochar/Mg-Al spinel for phos­
Ca 2+
+ HPO2-
4 → CaHPO4 (pK = -7.0) (9) phate removal. The presence of HCO-3 affected solution alkalinity and
2+
resulted in surface charge changes, reducing phosphate adsorption.
Ca + PO3-
4 → CaPO-4 (pK = -6.5) (10) Fig. 8 further shows that 2CaCl2 and 2CaCl2/EDTA hydrogel beads
The phosphate adsorption on 2CaCl2/EDTA hydrogel bead was not adsorbed PO3- - - 2-
4 and NO3 more than Cl and SO4 from a mixture of anions.

significantly affected by solution pH between pH 3 and pH 7 (Fig. 6). They showed great potential in nutrient recovery from wastewater. The
This cationic hydrogel bead was expected to be neutralized by the phosphate adsorption kinetics were further studied using pseudo-first
alkaline solution. The phosphate adsorption was affected by surface order, pseudo-second order, and intra-particle diffusion kinetic
charge changes besides pore rupture at low pH due to the disassociation models. The kinetic parameters are listed in Table 2 and illustrated in
of remaining CaCO3. Such observation is compatible with the phosphate Fig. 9. The kinetics of phosphate adsorption on 2CaCl2/EDTA hydrogel
adsorption by chitosan/lanthanum hydrogel, which was reduced beads were described well by the pseudo-second-order kinetic model.
beyond pH 6 as the hydrogel became neutral in the pH range of 8.5–9.5 The rate-limiting factor in such chemisorption was the calcium content
(Liu et al., 2023). The effects of coexisting ions on the phosphate of this hydrogel bead since chemisorption occurred during phosphate

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J. Fu et al. Industrial Crops & Products 218 (2024) 118979

Table 3
Adsorption isotherms for 2CaCl2/EDTA hydrogel beads.
Models Parameters Phosphate adsorption

Langmuir qm (mg/g) 118.73

KL (L/mg) 0.0295
R2 0.9991
Freundlich KF ((mg/g/(mg/L)n) 53.70
N (L/mg) 0.1166
R2 0.8823

Fig. 11. Reusability of 2CaCl2/EDTA hydrogel beads in phosphate adsorption

from 50 mg/L of phosphate solution with pH 7 using adsorbent dosage at
1 mg/ml.

while Table 3 summarizes the fitting parameters. The phosphate

adsorption was well described by Langmuir adsorption isotherm.
Phosphate adsorption only involved single-layer adsorption under
chemical interaction. Fig. 11 shows that the phosphate adsorption ca­
pacity of the 2CaCl2/EDTA hydrogel bead dropped about 15 % after 5
cycles although no physical changes on hydrogel beads were observed.
Table 4 shows that the phosphate adsorption capacity and reusability of
the 2CaCl2/EDTA hydrogel bead were comparable with other hydrogel
Fig. 9. The fitting of (a) pseudo-first-order, (b) pseudo-second-order, and (c) beads reported in recent works.
intra-particle diffusion models to the phosphate adsorption kinetics of 2CaCl2/
EDTA hydrogel beads using 100 mg/L of phosphate solution at pH 7 and an 4. Conclusions
adsorbent dosage of 0.4 mg/ml.
This study showed the potential of fertilizer production from the
recovered nutrient using CO2, supporting CCUS. CaCO3 nanoparticles
were homogenously grown in the presence of microfibrillated cellulose
before crosslinking CMC into hydrogel beads with a mean diameter in
the range of 1.618 – 2.464 mm. The particle aggregates appeared on the
hydrogel surface, as shown in SEM images. FTIR spectra proved the
presence of calcite, but the calcite crystallinity in the XRD spectrum was
hindered by the amorphous hydrogel. The calcium loading should be
adjusted to form an appropriate amount of CaCO3 for phosphate
adsorption. A low calcium loading was insufficient for phosphate
adsorption, while a high calcium loading could result in agglomeration
and reduce phosphate adsorption. An appropriate amount of calcium
loading initiated the homogenous growth of CaCO3 nanoparticles in situ
for producing CMC/microfibrillated cellulose hydrogel with phosphate
Fig. 10. Langmuir and Freundlich models fitting on the phosphate removal adsorption capacity higher than the similar hydrogel blended with
from 50 mg/L of phosphate solution with pH 7 using 2CaCl2/EDTA hydrogel CaCO3 nanoparticles. After EDTA chelation, the hydrogel surface
beads at an adsorbent dosage of 1 mg/ml.
became slightly porous. The calcite peak in the FTIR spectrum vanished
after EDTA chelation. EDTA chelation further enhanced phosphate
adsorption. The pseudo-first-order kinetic model could not be used to adsorption to 132.21 mg/g in 2 h without much change between pH 3
explain phosphate adsorption on 2CalCl2/EDTA since the electrostatic and pH 7. It was only significantly affected by the presence of HCO3 due
attraction of mass transfer and the formation of outer sphere complexes to alkalinity changes, and it was slightly affected by SO2- 4 under
were considered weak. Phosphate was effectively adsorbed by the competitive adsorption while maintaining the high selective adsorption
2CaCl2/EDTA hydrogel beads because of the chemical interaction with of PO3- -
4 and NO3. The fitting to the pseudo-second-order kinetic model
remaining CaCO3 nanoparticles through the porous structure. Langmuir and the Langmuir isotherm proved the phosphate adsorption through
and Freundlich isotherms were used to understand the phosphate chemical interactions. The phosphate removal percentage could be
adsorption by 2CaCl2/EDTA hydrogel beads. Fig. 10 shows the fitting, recovered by more than 80 % even after 5 adsorption cycles. However,

8
J. Fu et al. Industrial Crops & Products 218 (2024) 118979

Table 4
Comparison of phosphate adsorption capacity between 2CaCl2/EDTA hydrogel beads and hydrogels reported in recent works.
Hydrogels Phosphate adsorption Adsorption isotherm and kinetic model Adsorption Reference
capacity (mg/g) reusability

Sodium alginate/zirconium 122.68 mg/g Redlich-Peterson isotherm, pseudo-second- - Qing et al.

(256.79 mg/g at pH3) order model and intraparticle diffusion (2022)
model
Chitosan/attapulgite/lanthanum 114.1 mg/g Langmuir isotherm and >60 % after 5 Kong et al.,
pseudo-second-order model cycles (2023)
Chitosan/calcite 1.859 mg/g - - Pap et al.,
(2023)
Polyethyleneimine modified chitosan/ 3-(methacrylamido) propyl- 107.23 ± 4.96 mg P/g Sips isotherm and pseudo-second-order Wang et al.
trimethylammonium chloride modified La(OH)3 and calcium model (2023)
carbonate
Carboxymethyl cellulose/sodium alginate /bentonite/CaCO3 90.31 Langmuir isotherm and Fu et al.,
pseudo-second-order model (2023)
Carboxymethyl cellulose/CaCO3 (blending)
2CaCl2/EDTA 132.21 mg/g Langmuir isotherm and > 80 % after 8 This work
pseudo-second-order model cycles

the adjustment of phosphate release to meet the specific plant or fer­ Amornkitbamrung, L., Bračič, D., Bračič, M., Hribernik, S., Malešič, J., Hirn, U., Vesel, A.,
Kleinschek, K.S., Kargl, R., Mohan, T., 2020. Comparison of trimethylsilyl cellulose-
tilizer standards still remains challenging. Future works should focus on
stabilized carbonate and hydroxide nanoparticles for deacidification and
different strategies to control the nutrient release profiles. strengthening of cellulose-based cultural heritage. ACS Omega 5, 29243–29256.
Arslanoğlu, H., 2021. Production of low-cost adsorbent with small particle size from
calcium carbonate rich residue carbonatation cake and their high performance
CRediT authorship contribution statement
phosphate adsorption applications. J. Mater. Res. Technol. 11, 428–447.
Baek, S.-Y., Park, S.-Y., 2021. Highly-porous uniformly-sized amidoxime-functionalized
Jia Xin Yap: Investigation, Writing – review & editing. Choe Peng cellulose beads prepared by microfluidics with N-methylmorpholine N-oxide.
Leo: Writing – review & editing, Formal analysis, Conceptualization. Cellulose 28, 5401–5419.
Brondi, M., Florencio, C., Mattoso, L., Ribeiro, C., Farinas, C., 2022. Encapsulation of
Jialin Fu: Writing – original draft, Methodology, Investigation. Chun Trichoderma harzianum with nanocellulose/carboxymethyl cellulose
Kiat Chang: Writing – review & editing, Funding acquisition. nanocomposite. Carbohydr. Polym. 295, 119876.
Büyüküstün, A.D., Erışır, E., Gümüşkaya, E., 2020. Cellulosic superabsorbent production
with acid crosslinking method. Sigma J. Eng. Nat. Sci. 11, 185–191.
Declaration of Competing Interest Chai, W.S., Cheun, J.Y., Kumar, P.S., Mubashir, M., Majeed, Z., Banat, F., Ho, S.-H.,
Show, P.L., 2021. A review on conventional and novel materials towards heavy
metal adsorption in wastewater treatment application. J. Clean. Prod. 296, 126589.
The authors declare the following financial interests/personal re­
Chen, H., Zeng, H., Yang, H., 2022. Phosphate removal from wastewater by magnetic
lationships which may be considered as potential competing interests: amorphous lanthanum silicate alginate hydrogel beads. Minerals 12, 171.
Chun Kiat Chang reports financial support was provided by Royal El-Naggar, M.E., Hasanin, M., Hashem, A.H., 2022. Eco-friendly synthesis of
superhydrophobic antimicrobial film based on cellulose acetate/polycaprolactone
Academy of Engineering. Choe Peng Leo has patent #PI2022006944
loaded with the green biosynthesized copper nanoparticles for food packaging
pending to Universiti Sains Malaysia. If there are other authors, they application. J. Polym. Environ. 30, 1820–1832.
declare that they have no known competing financial interests or per­ Feng, L., Zhang, Q., Ji, F., Jiang, L., Liu, C., Shen, Q., Liu, Q., 2022. Phosphate removal
sonal relationships that could have appeared to influence the work re­ performances of layered double hydroxides (LDH) embedded polyvinyl alcohol /
lanthanum alginate hydrogels. Chem. Eng. J. 430, 123754.
ported in this paper. Flower, H., Rains, M., Taşcı, Y., Zhang, J.-Z., Trout, K., Lewis, D., Das, A., Dalton, R.,
2022. Why is calcite a strong phosphorus sink in freshwater? Investigating the
Data availability adsorption mechanism using batch experiments and surface complexation modeling.
Chemosphere 286, 131596.
Fu, J., Leo, C.P., Chang, C.K., 2024. Nutrient recovery and pollutant removal using
Data will be made available on request. carboxymethyl cellulose/microfibrillated cellulose hydrogel: templating effects of
CaCO3 nanoparticles. J. Water Process. Eng. 58, 104869.
Fu, J., Leo, C.P., Show, P.L., 2022. Recent advances in the synthesis and applications of
Acknowledgements pH-responsive CaCO3. Biochem. Eng. J. 187, 108446.
Fu, J., Yap, J.X., Leo, C.P., Chang, C.K., 2023. Carboxymethyl cellulose/sodium alginate
This work is funded through Engineering X, an international beads incorporated with calcium carbonate nanoparticles and bentonite for
phosphate recovery. Int. J. Biol. Macromol. 234, 123642.
collaboration funded by the Royal Academy of Engineering and Lloyd’s Hazra, R.S., Dutta, D., Mamnoon, B., Nair, G., Knight, A., Mallik, S., Ganai, S., Reindl, K.,
Register Foundation. Jiang, L., Quadir, M., 2021. Polymeric composite matrix with high biobased content
as pharmaceutically relevant molecular encapsulation and release platform. ACS
Appl. Mater. Interfaces 13, 40229–40248.
Appendix A. Supporting information Hazra, R.S., Kale, N., Boyle, C., Molina, K.B., D’Souza, A., Aland, G., Jiang, L.,
Chaturvedi, P., Ghosh, S., Mallik, S., Khandare, J., Quadir, M., 2024. Magnetically-
Supplementary data associated with this article can be found in the activated, nanostructured cellulose for efficient capture of circulating tumor cells
from the blood sample of head and neck cancer patients. Carbohydr. Polym. 323,
online version at doi:10.1016/j.indcrop.2024.118979.
121418.
Hernández-Navarro, C., Pérez, S., Flórez, E., Acelas, N., Muñoz-Saldaña, J., 2023.
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