Chemical Engineering Journal 452 (2023) 139261

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Removal of heavy metals from water by macro-mesoporous calcium

alginate–exfoliated clay composite sponges
Shella Permatasari Santoso a, b, *, 1, Alfin Kurniawan a, c, 1, Artik Elisa Angkawijaya d, e,
Hardy Shuwanto f, g, I.D.A.A. Warmadewanthi h, Chang-Wei Hsieh i, j, Hsien-Yi Hsu k, l,
Felycia Edi Soetaredjo a, b, Suryadi Ismadji a, b, Kuan-Chen Cheng m, n, o, p
a
Department of Chemical Engineering, Widya Mandala Surabaya Catholic University, Kalijudan 37, Surabaya 60114, Indonesia
b
Collaborative Research Center for Zero Waste and Sustainability, Jl. Kalijudan 37, Surabaya 60114, East Java, Indonesia
c
Research Group for Advanced Materials and Sustainable Catalysis (AMSC), State Key Laboratory Breeding Base of Green Chemistry and Synthesis Technology, College
of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China
d
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, No. 43, Sec 4, Keelung Road, Taipei 106, Taiwan
e
Plant Lipid Research Team, RIKEN Center for Sustainable Resource Science, Yokohama 230-0045, Japan
f
Department of Materials Science and Engineering, National Taiwan University of Science and Technology, No. 43, Sec. 4, Keelung Road, Taipei 106, Taiwan
g
Department of Industrial Engineering, Universitas Prima Indonesia, Jalan Sampul No. 4, Medan 20118, North Sumatra, Indonesia
h
Department of Environmental Engineering, Faculty of Civil, Environmental, and Geo Engineering, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya
60111, Indonesia
i
Department of Food Science and Biotechnology, National Chung Hsing University, South Dist., Taichung City 40227, Taiwan
j
Department of Medical Research, China Medical University Hospital, North Dist., Taichung City 404333, Taiwan
k
School of Energy and Environment, Department of Materials Science and Engineering, City University of Hong Kong, Kowloon Tong, Hong Kong, China
l
Shenzhen Research Institute of City University of Hong Kong, Shenzhen 518057, China
m
Institute of Food Science and Technology, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan
n
Institute of Biotechnology, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan
o
Department of Medical Research, China Medical University Hospital, Taichung 40402, Taiwan
p
Department of Optometry, Asia University, 500, Lioufeng Road, Wufeng, Taichung 41354, Taiwan

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

Keywords: The contamination of drinking water and freshwater by heavy metals has become a growing concern for human
Alginate health and environment that calls for immediate remedial action. Adsorption process has been proved to be a
Organoclay promising technology for producing treated water that complies with drinking water standards. In this work, we
Exfoliation
describe a facile and low-cost approach to fabricate porous calcium alginate composite sponges containing
Porous composite
Adsorption
exfoliated bentonite clay (denoted as CRAB) by saponin-assisted foaming and external gelation techniques for
Heavy metals efficient removal of Cu2+ and Cr6+ ions from aqueous solution and real world water samples. The formation of
exfoliated organoclay within the composite matrix was achieved by intercalation of saponin into the interlayer
spacing of bentonite and subsequent penetration of alginate chains. Morphological and textural characterizations
revealed that the resultant CRAB sponges mainly exhibited meso- and macropores in their interior. The formation
of calcium alginate-organoclay exfoliated composites was also verified by the XRD results. The performance of
CRAB sponges in removing Cu2+ and Cr6+ ions from aqueous solution was evaluated under different environ­
mental conditions including temperature, pH, ionic strength, and background electrolyte. The results demon­
strated that the uptake capacity of Cu(II) and Cr(VI) increased with increasing temperature, suggesting the
endothermic nature of the adsorption process. The Freundlich isotherm model was found to better interpret the
equilibrium adsorption behaviors of Cu2+ and Cr6+ ions onto the investigated sorbents than the Langmuir model.
The sorption kinetics for these metal ions followed a pseudo-first-order model. Reusability tests for CRAB sponge
demonstrated that the sorption capacity of the sorbent is well maintained over three successive adsorp­
tion–desorption cycles. Together, these results indicate the great potential of low-cost and sustainable CRAB
sponges for remediation of water polluted with copper and hexavalent chromium ions.

* Corresponding author at: Department of Chemical Engineering, Widya Mandala Surabaya Catholic University, Kalijudan 37, Surabaya 60114, Indonesia.
E-mail address: shella@ukwms.ac.id (S.P. Santoso).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.cej.2022.139261
Received 13 June 2022; Received in revised form 22 August 2022; Accepted 13 September 2022
Available online 17 September 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
S.P. Santoso et al.
1. Introduction
Copper and its alloys, such as copper-titanium (CuTi), copper-nickel
(CuNi), and copper-chromium (CuCr) are among the most industrially
important materials used in building applications, as well as various
electronic and consumer products. Specifically, CuCr alloys are of
particular interest, due to their high thermal (323.4 W/m⋅K) and elec­
trical (85 % IACS) conductivities, enhanced mechanical properties,
excellent corrosion and arc erosion resistance, and low welding ten­
dency, which make them ideally suited as a contact material for medium
and high voltage circuit breakers [1,2]. Despite its pivotal importance in
many consumer and industrial sectors, the discharge of wastewater ef­
fluents bearing copper and chromium ions leads to severe water quality
degradation and poses a serious risk to public health and aquatic or­
ganisms. The prevalence and source of copper and chromium in aquatic
ecosystems are also inevitably associated with various industrial activ­
ities. The typical concentrations of copper (Cu2+) and chromium in
major industrial effluents (e.g., metal plating, mining, tannery) vary
widely from tens to a few thousand ppm. For example, wastewater
discharges from ore mining and hydrometallurgical industries contain
relatively high copper concentrations of about hundreds of ppm [3,4],
while lower concentration levels of 10–50 ppm are found in electro­
plating waste streams [5,6]. For chromium, the total concentrations
(Cr6+ and Cr3+) ranging from 150 to 600 ppm and from 3000 to 15000
ppm were reported for the composite discharge and rinse waters in
chrome plating operation, respectively [6]. Chromium ions (as Cr6+) are
also ubiquitously present in the tannery and textile effluents at low to
moderate concentrations of 1–40 ppm [6–9], while a much higher
concentration (~410 ppm) has been detected in the wastewater stream
from stainless steel manufacturing plant [10]. The presence of copper in
water bodies imparts an undesirable greenish-bluish stain, as well as a
metallic and bitter taste. Although copper is well known for its pivotal
role in several biological functions, acute and chronic exposures to this
metal through contaminated water sources at levels beyond its safe
upper limit (1.3 ppm based on the U.S. EPA guideline) can lead to
various symptoms and multiple organ failure including heart, liver, and
kidneys [11]. Meanwhile, environmentally mediated human exposure to
highly toxic and carcinogen Cr6+ via drinking water has been linked to
adverse health effects, such as DNA damage, reproductive dysfunction,
and kidney diseases [12,13], as well as an increased risk for multiple
cancers or even death. The U.S. EPA has also listed chromium as one of
the priority pollutant metals of public health concern with the maximum
contaminant level in drinking water at 0.1 ppm [14]. Given these
problems, the elimination of such toxic heavy metal ions from aqueous
environments is an urgent necessity to protect both water resources and
public health.
Various technologies to remove heavy metal ions from water and
wastewater have been investigated including membrane filtration [15],
electrodeposition [16], solvent extraction [17], chemical precipitation
[18], biological treatment [19], phytoremediation [20], and adsorption
[21–23]. While these conventional methods are technically feasible,
they have several disadvantages including low efficiency in removing
trace amounts of metal ions, high economic and energy costs, surface
fouling, and the production of large volumes of toxic chemical sludge
[22]. On the other hand, adsorption method has attracted wide attention
due to its merits, such as low cost, ease of operation and simplicity of
design, high removal efficiency over a wide range of concentrations,
practicability, and wide selection of the sorbent materials. In the latter
context, activated carbons and crystalline porous framework materials
(i.e., MOFs and COFs) have proven to be excellent adsorbents with
remarkably high adsorption capacities and fast kinetics [22–24]; how­
ever their practical applications are greatly hampered by the costly,
tedious, and time-consuming synthesis methods on a large scale. To
realize an economical and sustainable adsorption system in industrial
wastewater treatment, the use of naturally derived materials is highly
desired. Polysaccharides, such as alginates, are especially appealing for
2
Chemical Engineering Journal 452 (2023) 139261
the sequestration of heavy metal ions because they are abundantly
available at low cost and contain ubiquitous metal-scavenging func­
tionalities, such as carboxyl and hydroxyl within the backbone chain of
the polymer. In addition, alginate-based materials can be easily fabri­
cated as free-standing structures, such as beads, films, and sponges via
ionic cross-linking with divalent cations (e.g., Ba, Mg, and Ca), thus
showing advantages over powdery adsorbents (e.g., activated carbons
and MOFs/COFs) in terms of handling, separation, and reuse. However,
the sorption performance of pristine alginate and other polysaccharide-
based materials is generally inferior to those of advanced adsorbents,
mainly due to their low surface areas and rigid nonporous structures. For
example, an alginate extraction product from brown seaweed showed
the Langmuir maximum adsorption capacity of 21.4 mg/g for Cr6+ at pH
2 [25]. In another work by Mohammed et al. [26], Sargassum-derived
calcium alginate thin films were utilized to remove Cu2+ ions from
aqueous solution, affording only an equilibrium uptake capacity of 3.5
mg g− 1. Lagoa and Rodrigues also obtained similar Cu2+ uptake by Ca
alginate gel beads [27]. In addition to low adsorption capacity, these
sorbents also suffer from long equilibration times, owing to the slow
diffusion of metal ions within the nonporous interior of the material,
making their use inefficient in practical wastewater treatment processes.
Furthermore, the relatively poor stability and weak mechanical strength
of ionically cross-linked alginates represent another key issue that needs
to be addressed toward their practical utility in liquid separations.
The incorporation of inorganic lamellar materials, such as clays and
clay minerals into the cross-linked alginate network offers an attractive
strategy to address the above issues, and thus improve the mechanical
and sorptive properties of alginate-based adsorbents. Recent studies
have shown that the attractive interactions between clay lamellae and
alginate chains act as additional cross-links and reinforcing points to
improve the overall mechanical properties of the resultant alginate
composites, which have found applications in the controlled release
systems [28], load-bearing materials [29], and wastewater remediation
[30,31]. Bentonites represent one of the most important sources of
swelling clays in soils and sediments that play an important role in the
nuclear waste management, subsurface containment barriers, and the
cycling of trace elements [32–34]. Moreover, this natural clay exhibits a
large specific surface area, high cation exchange capacity (CEC), good
thermal and chemical stability, and abundant edge hydroxyl groups (i.
e., Si–OH and Al–OH), which can facilitate the formation of dense
hydrogen bond networks within the composite matrix. While there have
been several reports on the fabrication of clay-alginate composites,
achieving high levels of exfoliation and dispersion of clay particles in the
host polymer matrix at relatively high loadings remains a great chal­
lenge. In the previously reported bentonite-alginate composite beads
[28], the good dispersibility of the clay particles in the Ca alginate
matrix was achieved at relatively low loadings (≤5 wt%), while high
bentonite loadings above 10 wt% result in the aggregation of the clay
platelets. Another typical strategy to prepare alginate-clay composites
involves pre-exfoliation of clay tactoids via sonication treatment
[29,35]. This approach, however, can be tedious and time-consuming
since it requires multiple purification steps to obtain appreciable
yields of exfoliated clay sheets.
The exfoliation of the clay layers can also be achieved through the
expansion of the interlayer gallery by organic modification using sur­
factants. In this regard, the enlarged clay interlayers and the presence of
intercalated surfactant molecules promote the penetration of polymer
chains into the interlayer space, leading to efficient exfoliation of the
clay layers. Moreover, the incorporation of surfactant into the clay
gallery has been shown to notably enhance the sorption capacity toward
various heavy metal ions [36–38], further emphasizing the merits of
organic modification. Using plant-based surfactants, such as saponin in
the organic modification of clays offers several advantages over the
synthetic counterparts including renewability, biodegradability, low
toxicity, and environmental friendliness. Saponin molecules possess
hydrophilic sugar moiety and hydrophobic steroid/triterpenoid
S.P. Santoso et al.
backbone [39], in which the former may provide additional sites to
increase metal binding. Moreover, the ability of saponins to produce
stable foams in aqueous solutions upon aeration is expected to benefit
the formation of large pores (i.e., meso- and/or macropores) in the
sorbent, which can facilitate the access and diffusion of metal ions into
the internal surface sites.
In earlier work, our group has developed cellulose-based composite
hydrogels containing homoionic Na-bentonite particles by cross-linking
with epichlorohydrin in an alkali/urea aqueous system, which showed
potential applications in dyeing wastewater treatment and soilless plant
growth [40]. Hybrid Ca alginate and organo-montmorillonite compos­
ites have been employed as adsorbents for the removal of anionic
organic dyes [41] and perchlorate (ClO−4 )/strontium (Sr2+) ions [42]
from aqueous solutions. However, in these previous reports, the resul­
tant composites produced an intercalated structure and the clay particles
were not uniformly distributed within the alginate matrix, leading to
increased aggregation at higher loadings. Moreover, using the radiation-
induced polymerization method [41] to produce intercalated
montmorillonite-alginate composites requires specialized equipment
and highly trained personnel for safe handling of the radioactive source,
which may limit its broad applicability. To the best of our knowledge,
the formation of exfoliated organoclay-alginate composites using a
facile synthetic method has yet to be demonstrated. Herein, we present a
three-dimensional (3D) porous sponge-like Ca alginate composite
incorporating exfoliated organobentonite particles (denoted as CRAB
throughout this study) prepared by saponin-assisted foaming, external
ionic gelation, and freeze-drying processes as an efficient heavy metal
sorbent for Cu2+ and Cr6+ ions. The introduction of macroporosity in the
CRAB sponges by a simple surfactant-foaming technique contributes to
overcoming the intrinsic kinetic limitation observed in the conventional
nonporous Ca alginate particles, while the presence of exfoliated orga­
noclays could enhance the metal uptake capacity of the composite ma­
terial. Detailed structural and surface characterizations of the pristine Ca
alginate and CRAB sorbents were carried out by a variety of techniques,
including Fourier transform infrared (FTIR) spectroscopy, X-ray
diffraction (XRD), scanning electron microscopy (SEM), and nitrogen
sorption. The adsorption characteristics of Cu(II) and Cr(VI) on the as-
prepared CRAB sponges were examined under various temperatures,
pH, ionic strengths, and electrolyte species. Moreover, the kinetics of the
metal ion uptake in the composite sponges are described in detail on the
basis of various kinetic models. To this end, the practical feasibility of
using CRAB sponges for removing Cu2+ and Cr6+ ions from real world
water samples was assessed, along with the potential use of acidic waste
regeneration solution containing copper ions in homogeneous catalysis
of 4-nitrophenol to 4-aminophenol, which may pave the way toward the
development of sustainable tandem adsorption-catalytic systems for
water decontamination.
2. Experimental
2.1. Materials
Sodium alginate from marine algae (M/G ratio of 1.56) was obtained
from Sigma-Aldrich and used as the starting material for preparing
composite sponges. Calcium bentonite was collected from a local mining
site in Pacitan, East Java, and subsequently pulverized to pass through a
− 180/+200 mesh screen. The chemical composition of powdered clay
obtained through X-ray fluorescence (XRF) analysis is given in Supple­
mentary Table S1. The montmorillonite content of the clay was found to
be 75.7 wt% by the methylene blue test [43]. Other mineral impurities,
such as quartz, feldspar, and mica were present in trace amounts of 1.9,
0.2, and 0.5 wt%, respectively based on the selective dissolution method
of Kiely and Jackson [44]. Acid activation of bentonite was carried out
by suspending the clay powder (5 g) in 200 mL of a 2 M aqueous H2SO4
solution under stirring at room temperature overnight following the
procedure reported by Belver et al. [45] with slight modifications.
3
Chemical Engineering Journal 452 (2023) 139261
Rarasaponin was Soxhlet extracted from the dried pericarps of local
soapberry fruits (Sapindus rarak) according to the procedure described in
our earlier study [46]. The molecular structure of this natural surfactant
is given in Fig. S1. Calcium chloride dihydrate (CaCl2⋅2H2O, ≥99.5 %),
cupric nitrate trihydrate (Cu(NO3)2⋅3H2O, >98 %), potassium dichro­
mate (K2Cr2O7, ≥99 %), anhydrous methanol (99.8 %), and sulfuric acid
(H2SO4, 95–98 wt%) were purchased from Brataco Chemical Co., ltd.
(Surabaya, Indonesia) and used directly without further purification. All
aqueous solutions were prepared using deionized water with a resistivity
of 18.2 MΩ cm from the Millipore Milli-Q purification system.
2.2. Preparation of rarasaponin–alginate–bentonite composite (CRAB)
sponges
The CRAB sponges were prepared by an external gelation method in
an aqueous CaCl2 solution. Briefly, 1 g of acid-activated bentonite (AB)
powder was homogeneously dispersed in 50 mL of aqueous rarasaponin
solution (0.2 wt%) via sonication and the mixture was heated in a do­
mestic microwave oven (National model NN-S327WF) at 700 W for 3
min. Subsequently, 50 mL of 2 wt% aqueous sodium alginate solution
was added to the rarasaponin-AB mixture and stirred for 1 h at 70 ◦ C,
followed by stirring overnight at room temperature. The alginate-
rarasaponin-bentonite mixture was foamed using a commercial hand­
held milk frother (PowerLix) and then gelled by the addition of 1.5 M
aqueous CaCl2 solution. The resultant bulk foams were cut into 1 cm3
blocks with a razor blade. Finally, the products were thoroughly washed
using distilled water and freeze-dried. Ca(II)-cross-linked alginate (Ca
alginate) sponges were also synthesized following the same procedure as
above, but without adding AB and rarasaponin. Rarasaponin surfactant-
modified organobentonite (RSOB) was prepared via microwave irradi­
ation of rarasaponin-AB aqueous suspension under the same conditions
as described above and followed by washing and drying in an oven for 6
h.
2.3. Materials characterization
SEM images of the as-prepared CRAB sponges were obtained using a
Zeiss Supra 55 field emission SEM operating at 10 kV. For cross-sectional
imaging, the dried sponges were immersed in liquid nitrogen for 30 s
and then cut with a razor blade. All the samples were sputter coated with
gold using a Pelco SC-6 sputter coater to minimize charging effects on
the SEM images. Elemental mapping analysis was performed using an
Oxford INCA energy dispersive X-ray spectrometer (EDS) system
attached to the SEM instrument. FTIR spectra were collected in trans­
mission mode using a Jasco FT/IR-4600 spectrometer equipped with a
TGS detector from 4000 to 400 cm− 1 by accumulating 128 scans at 8
cm− 1 resolution. The powdered samples (~1 mg) were mixed with 200
mg of dry pulverized KBr (spectroscopic grade), pressed into discs, and
then mounted on the specimen holder for analysis. XRD patterns were
acquired on a Bruker D2 Phaser diffractometer equipped with a Lynxeye
detector and Cu Kα X-ray source (λ = 1.5418 Å) operating at 30 kV and
10 mA in the 5-50◦ 2θ range using a step size of 0.05◦ and an acquisition
time of 1 s/step. The textural characteristics of the composites were
determined by N2 adsorption and desorption at 77 K using a Micro­
meritics ASAP 2020 instrument. Samples were degassed at 150 ◦ C under
vacuum for 16 h before measurement. The Brunauer-Emmett-Teller
specific surface area (SBET) was calculated using the adsorption branch
of the isotherm in the relative pressure (P/P0) range from 0.05 to 0.35,
and the pore size distribution (PSD) was evaluated from the desorption
isotherm curve with the Barrett-Joyner-Halenda (BJH) method. The
pHpzc (pzc = point of zero charge) of the sorbent materials was deter­
mined by the pH drift method [47], whose values are 3.22, 3.19, and
3.18 for AB, RSOB, and CRAB, respectively. The equilibrium swelling
degree of the samples was determined gravimetrically according to the
procedure described elsewhere (see Supplementary Text S1 for details),
and the results were expressed as mean ± standard deviation (SD) from
S.P. Santoso et al. Chemical Engineering Journal 452 (2023) 139261

triplicate experiments.
(C0 − Ct )
qt = ×V (2)
m
2.4. Equilibrium and kinetic sorption experiments
where C0 and Ct are the initial and time-dependent concentrations of
The synthetic wastewater solution containing single metal ions was metal ions (mg L-1), respectively. The distribution coefficient value (Kd,
prepared by dissolving one gram of metal precursors (CuSO4⋅5H2O or mL/g), which serves as a metric for assessing the affinity of a sorbent
K2Cr2O7) in 1 L of DI water and poured into a series of 150 mL glass- material toward heavy metals, can be calculated using the following
stoppered conical flasks. Different amounts of the adsorbent (0.1–5 g) equation:
were added to each flask. The mixture was incubated in a Memmert
thermostatic water bath under gentle shaking for 8 h to reach equilib­ Kd =
qe (C0 − Ce ) V
→ × (3)
rium. During the equilibrium sorption experiments, the bath tempera­ Ce Ce m
ture was maintained at 30, 40, and 50 ◦ C. After 8 h, the solid was
separated from the mixture and the residual metal ion concentrations in where parameters qe and Ce have the same meaning as defined earlier in
the solution were measured by a flame atomic absorption spectropho­ Eq. (1).
tometer (FAAS, Shimadzu AA-6200) equipped with an ASC-6100F
autosampler at the specific analytical wavelength (i.e., 324.7 nm for 3. Results and discussion
Cu and 357.9 nm for Cr). The equilibrium uptake capacity of metal ions
(qe, mg g− 1) was determined by Eq. (1): 3.1. Characterization of the adsorbent materials

(C0 − Ce ) The surface functional groups of AB, RSOB, and CRAB sorbents are
qe = ×V (1)
m evaluated by FTIR spectroscopy, and their corresponding spectra are
shown in Fig. 1a. The AB sample shows a strong and broad absorption
where C0 and Ce are the initial and equilibrium concentrations of metal
band corresponding to the stretching vibration of hydroxyl groups co­
ions in the solution (mg L-1), V is the volume of solution (L), and m is the
ordinated to the octahedral cations (Al–OH) in the 3200–3600 cm− 1
mass of adsorbent (g).
region, as well as Si–O–Si asymmetric and terminal Si–O stretching
To investigate the effect of the initial pH value on the percent
modes at 1082 and 995 cm− 1, respectively. A shoulder band around
removal of the metals, 0.5 g of the sorbent was added to 100 mL of 200
~1120 cm− 1 is assigned to the longitudinal stretching vibration of the
mg/L Cu(II) or Cr(VI) solutions at different pH values (1–9) and the
Si–O bond. The bands around 830 and 760 cm− 1 correspond to the
mixture was equilibrated in a 30 ◦ C shaking water bath for 8 h. For the
Al–Mg–OH deformation mode and Si–O stretching groups of quartz,
adsorption kinetic studies, a known amount of sorbent material (0.8–1.0
respectively [48,49]. In addition, several weak bands observed in the
g) was added into conical flasks containing 100 mL of Cu(II) or Cr(VI)
700–400 cm− 1 region can be assigned to the Si–O–Si symmetric
solutions with known concentrations. The flasks were then placed in a
stretching (668 cm− 1) and the Si–O bending vibrations of Si–O–Al (528
shaking water bath at 30 ◦ C and aliquots of the metal solution were
cm− 1) and Si–O–Si bridges (486 cm− 1). Compared to the IR spectrum of
periodically taken for FAAS measurements to determine the residual
the pristine clay (not shown here), the relative intensities of the octa­
metal content. The amount of metal adsorbed at a certain time (qt, mg
hedral OH stretching and Al–Mg–OH vibration bands for AB slightly
g− 1) was calculated according to Eq. (2):
decrease, while Si–O–Al bending at 528 cm− 1 remains relatively un­
changed. This suggests that the inherent layered structure of clay was

Fig. 1. Characterizations of the AB, RSOB, and CRAB sorbents. (a) FTIR spectra. The right-hand image is the zoom-in spectra showing the frequency shifts of the Si–O
stretching and Al–Mg–OH deformation bands for AB and CRAB samples. (b) XRD patterns along with an enlarged view of the 4-10◦ 2θ angle region. The notations pG
and pM in the XRD pattern of sodium alginate represent poly-α-L-guluronic acid and poly-β-D-mannuronic acid, respectively. (c) N2 adsorption (solid circles) and
desorption (open circles) isotherms at 77 K of CRAB sponge and the corresponding PSD curve (inset) derived from the adsorption branch by the BJH method. (d) SEM
image of CRAB along with EDX elemental mapping of Si (cyan), Al (magenta), Mg (orange), C (red), O (green), and Ca (yellow). The orange and yellow arrows point
toward morphological wrinkles of exfoliated lamellar clays and open pores in the composite sponges. Inset shows the digital photo of bulk CRAB in a free-standing
sponge-like structure with a lateral size of ~1.5 cm. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

4
S.P. Santoso et al.
retained after acidic activation, in agreement with previous studies
[48,49]. Such a relatively mild acid activation process affords a higher
surface area and porosity of AB clay as a result of partial leaching of the
octahedral cations, such as Mg, Fe, and Al [48]. Moreover, the presence
of H+ ions in the clay interlayer can facilitate the intercalation of rar­
asaponin molecules through hydrogen bonding interactions with the
COO− groups on the triterpene moiety.
The FTIR spectrum of CRAB shows the presence of a broad O–H
stretching band centered at 3450 cm− 1, asymmetric (νas) and symmetric
(νs) COO− stretching (1624 and 1462 cm− 1), C–O stretch and OH
deformation (1381 cm− 1), asymmetric C–O–C stretching (1076 cm− 1),
and O–H bending (600 cm− 1). In addition to these vibrational modes,
two absorption bands corresponding to Si–O stretching vibration of
silanol group and Al–Mg–OH deformation were found at 972 and 845
cm− 1, thus confirming the successful incorporation of RSOB particles
into the cross-linked alginate matrix. It was further noticed that these
two bands are red and blue-shifted compared to AB, respectively (see the
magnified spectra), suggesting the intermolecular interactions between
alginate chains and the siloxane and edge surfaces of RSOB through
hydrogen bonding and electrostatic forces. Another support for this
interaction is found by the significant wavenumber shifts of the νas and νs
COO− bands (1624 and 1462 cm− 1, respectively) for CRAB compared to
the reported values of ~1590–1598 and ~1411–1419 cm− 1 for pristine
Ca alginate [50,51]. Moreover, alginates could interact with the inter­
calated rarasaponin molecules through electrostatic attraction between
hydroxyl and oxygen groups of the sugar moieties, which facilitates
penetration of this polymer chain into the clay gallery spacing to pro­
duce an exfoliated structure. The presence of exfoliated clay sheets in
aqueous alginate solution can electrostatically interact with the COO−
groups of the M blocks on different alginate chains, forming additional
cross-links that lead to a denser network structure of the resulting
composite. Accordingly, the as-prepared CRAB sponges exhibited a
lower equilibrium swelling ratio than the pristine Ca alginate (Fig. S2).
Similar results have been observed in some previous studies [52,53].
The intercalation and exfoliation phenomena of clay layers in the CRAB
matrix are also supported by the XRD results presented below.
Fig. 1b shows the XRD patterns of the sorbent materials. As can be
seen from the figure, all the samples exhibit a pattern similar to that of
AB clay. A strong and sharp Bragg reflection at 2θ = 6.12◦ in the XRD
pattern of AB can be assigned to the basal plane spacing (d001) of the
montmorillonite platelets, which is calculated to be 1.44 nm using the
Bragg equation. In addition, the reflection peaks at 2θ = 20.18◦ , 22.24◦ ,
26.93◦ , and 36.21◦ correspond to the montmorillonite (M) and non-clay
mineral phases present in the clay sample, such as quartz (Q) and feld­
spars (F). A noticeable shift of the d001 reflection to a lower 2θ of 5.62◦
was observed for RSOB, indicating an expansion of the clay interlayer
spacing upon intercalation of rarasaponin. The increased d spacing
(1.44–1.57 nm) of RSOB may suggest that the intercalated rarasaponin
molecules adopt a monomolecular configuration with the hydrophobic
aglycone backbone aligned parallel to the basal siloxane surface of the
clay. Meanwhile, the XRD pattern of CRAB revealed a weak and nearly
featureless basal reflection, suggesting an exfoliated (or delaminated)
structure of lamellar clays. Similar observations have been reported for
other exfoliated clay-polymer nanocomposites, such as star polystyrene
(PS5)-Cloisite clay [54], poly(methyl methacrylate)-metallocene inter­
calated montmorillonite [55], and poly(acrylic acid)-Lucentite clay
[56]. The formation of ionically cross-linked alginate networks in the
CRAB sponge was confirmed by the absence of Bragg reflections corre­
sponding to the poly-α-L-guluronic acid (2θ = 13.7◦ ) and poly-β-D-
mannuronic acid (2θ = 21.8◦ ) residues [57]. Moreover, the decreased
reflection intensities for the mineral phases at 2θ = 20.18◦ , 22.24◦ , and
26.98◦ further imply a relatively good dispersion state of the clay
lamellar particles in the CRAB matrix.
The adsorption–desorption isotherms of N2 at 77 K for CRAB sponge
(Fig. 1c) revealed a type IV shape with a type H3 hysteresis loop ac­
cording to IUPAC classification [58], which is characteristic of a
5
Chemical Engineering Journal 452 (2023) 139261
mesoporous material with an open pore structure and wide pore size
distribution. The observed mesopores in the resultant composite sponge
may be originated from the randomly oriented, house-of-cards structure
of exfoliated lamellar clays, consistent with the observed hysteresis
behaviors of other reported 2D nanosheets forming a similar stacking
structure [59,60]. Meanwhile, the steep N2 uptake at high relative
pressure (P/P0 > 0.9) region can be attributed to the capillary conden­
sation phenomenon in the large mesopores and macropores [61]. The
concurrent presence of meso- and macropores in the CRAB sponge was
further evidenced by the BJH-derived PSD curve (see inset), showing a
bimodal pore size distribution composed of 18.2 and 83.4 nm diameter
pores. The BET surface area (SBET) and total pore volume (VT) of CRAB
were found to be 17.5 m2/g and 0.05 cm3 g− 1, respectively. Compared to
the AB clay (SBET = 92.9 m2/g and VT = 0.12 cm3 g− 1), the lower SBET
and VT values for the composite sponge could be ascribed to the inter­
particle pore blocking of the house-of-cards arrangement of exfoliated
clay platelets by rarasaponin molecules and uncross-linked alginate
chains. The proportion of micropores in the CRAB sponge is relatively
small, as reflected by the negligible N2 adsorption at low relative pres­
sures (P/P0 < 0.05) and also supported by the PSD of the material.
Fig. 1d shows the top-view SEM image of the CRAB sponge, which
reveals a fine wrinkle texture of exfoliated clays over the composite
surface. In addition, irregular and large pores with diameters of 50–80
nm (measured by ImageJ software) were visible on the composite
sponge surface, in good agreement with the BJH PSD result shown in
Fig. 1c. These macropores could be attributed to the air bubbles formed
during the foaming process of the alginate-RSOB aqueous mixture,
which is entrapped in the composite matrix upon Ca-induced gelation
and subsequently removed during the freeze-drying process. The inte­
rior porous structure of the composites was also evident from the cross-
sectional SEM image (Fig. S3), which showed a 3D interconnected meso/
macroporous network. The EDX mapping results provide visual evi­
dence for the homogeneous distribution of Si, Al, and Mg elements,
implying a good dispersion of exfoliated clay platelets in a cross-linked
alginate network. Meanwhile, the detected Ca element was attributed to
the ionic cross-linking of alginates with Ca(II) ions in an egg-box fashion,
as well as adsorption of this cation onto the negatively charged clay
surface (see Scheme 1). To further show the formation of exfoliated clay-
alginate composites, we examined the morphology of the solid product
recovered after mixing aqueous sodium alginate solution with an
aqueous dispersion of RSOB at 70 ◦ C with SEM. As can be seen from
Fig. S4a, the resultant RSOB/alginate composite is composed of lamellar
or plate-like particles that are randomly stacked forming a house-of-
cards structure, further suggesting the presence of exfoliated organo­
clay platelets. Unlike the previously reported clay/Ca alginate interca­
lated composites [28,35,41,42], the present strategy involving a pre-
intercalation step of AB clay with rarasaponin molecules and the sub­
sequent penetration of alginate chains prior to external gelation resulted
in the formation of exfoliated clay platelets that have intimate in­
teractions with alginate chains (Scheme 1).
3.2. Metal adsorption studies: Effects of pH and ionic strength on the
removal efficiency
The pH is an important parameter determining the speciation of
adsorbate molecules in an aqueous solution and accordingly their
adsorption efficiency and binding interactions with charged sorbent
surface. The removal efficiency of AB, RSOB, and CRAB sorbents toward
Cu2+ and Cr6+ ions in the pH range of 1 to 10 is shown in Fig. 2. Note
that for the sorption of Cu2+ ions, experimental investigations of the pH-
dependent adsorption behavior were only carried out across the pH
range of 1–7, due to the enhanced formation of Cu(OH)2 in alkaline
solutions. The pH value corresponding to the formation of Cu(OH)2
under the present experimental conditions was found to be 6.15 (see
Supplementary Text S2 for details). For all the sorbent materials, the
results showed that the sorption efficiency of Cu2+ increased gradually
S.P. Santoso et al.
Scheme 1. Graphical illustration of the cross-linked alginate network in (a)
pristine Ca alginate (egg-box model) and (b) CRAB sponges containing exfoli­
ated clay platelets. Numbers 1–7 in the figure are as follows: 1: Na+ ions that
remain in the gel fluid to balance the negative charges on the unoccupied
carboxylate (COO− ) groups, 2: Ca2+ ions tightly bound to two COO− groups in
two parallel-aligned G residues (i.e., cross-linking point); 3: free COO− groups,
4: G residue with deprotonated COO− groups; 5: Coulombic interactions be­
tween COO− groups of M/G residues and the positively charged edge sites of
clay platelets; 6: Ca2+ ions electrostatically adsorbed on the negatively charged
clay basal surface; 7: Coulombic interactions between Ca2+ ions and basal
surfaces of clays; and 8: face-to-edge interactions between exfoliated
clay platelets.
with increasing pH until pH 5 and then remained nearly constant across
the pH range of 5–7 (Fig. 2a). The equilibrium sorption capacities at pH
5 for AB, RSOB, and CRAB were found to be 22.9, 29.5, and 38.5 mg/g,
respectively, with the latter sorbent demonstrating a higher removal
capacity and Kd value than most of the reported biopolymer-based
materials and composites shown in Table 1 [62–74]. As mentioned
above, the concurrent precipitation of Cu(OH)2 also contributes to
higher removal efficiency at pH values above 6, and thus the initial pH of
CuSO4 solution was set at 5 for the remainder of this study. From an
initial 200 ppm, the CRAB sponge achieved ~98 % removal efficiency to
yield a final Cu2+ concentration of ~5 ppm within 8 h contact time.
The increased uptake capacity over the pH range of 1 to 4 can be
explained by the favorable electrostatic interactions between Cu2+ ions
Fig. 2. Effect of pH on the uptake capacity (qe) of CRAB for (a) Cu2+ and (b) Cr6+ (C0 = 200 ppm; batch factor (V/m) = 200 mL/g). Equilibrium uptake amounts
(filled bars) and the Kd values (hashed bars) of CRAB sponge for (c) Cu2+ and (d) Cr6+ at the optimal pH and varying ionic strengths. The ionic radii and the standard
molar Gibbs free energies of hydration for the investigated cations and anions are given in Table S2.
6
Chemical Engineering Journal 452 (2023) 139261
and negatively charged sorbent surface at pH values greater than the
pHpzc. In this regard, the negative surface charge of CRAB arises from the
deprotonated hydroxyl and carboxyl groups of mannuronic (pKa = 3.38)
and guluronic acids (pKa = 3.65) in the cross-linked alginate chains
[75], as well as from deprotonation of the edge hydroxyl groups of the
embedded clay particles. The binding of Cu2+ ions to the COO− groups is
also supported by FTIR analysis shown in Fig. S5. As can be seen, the
separation of the asymmetric and symmetric COO− stretching bands is
84.9 cm− 1 (Δ < Δionic), suggesting the bidentate coordination mode of
carboxylate groups with Cu2+ ions [51,76]. In the case of AB and RSOB
materials, the sorption of Cu2+ occurs mainly via electrostatic in­
teractions with the negatively charged edge surfaces associated with the
silanol (≡Si–OH, pKa ~ [77]) and aluminol (≡Al–OH, pKa ~3.75 [77]).
At lower pH < 4, the net positive charge on the sorbent surface results in
an electrostatic repulsion with metal cations, and consequently, no
significant Cu2+ uptake was observed. Moreover, the excess protons at
low pH can compete with metal ions for the binding sites on the sorbent,
leading to inefficient removal. The enhanced sorption capacities of
RSOB and CRAB toward Cu2+ compared to that of AB can be attributed
to the greater availability of metal ion-binding sites originating from
anionic carboxylate (− COO− ) and hydroxyl groups present in the rar­
asaponin and alginate moieties.
The pH-dependent sorption of Cr6+ demonstrated that the metal
uptake proceeds more efficiently under acidic conditions (pH 2–4) and
reached a maximum at pH 3 (Fig. 2b). This result can be explained by
considering the chemical speciation of Cr6+ oxoanions in an aqueous
solution (Fig. S6). In both acidic and near-neutral aqueous solutions (pH
2–6) with low Cr6+ concentrations (<30 mM), Cr6+ exists predomi­
nantly as hydrogen chromate (HCrO−4 ), while the chromate anion
(CrO2−
4 ) is the dominant and most stable form at pH values above 8
[78,79]. Thus, the maximum Cr6+ uptake at pH 3 was attributed to the
electrostatic interaction between HCrO−4 and the protonated sites of the
sorbent, namely –CO2H+ 2 groups of alginate and ≡M–OH2 (M = Al and
+
Si) groups of clay. The formation of M–OH+ 2 edge groups of clay platelets
under the present experimental conditions (pH = 3) is in good agree­
ment with the pHpzc value of 4.0 ± 0.2 for montmorillonite edge surface
reported by Pecini and Avena [80]. Moreover, a pH value of 3 corre­
sponds closely to the actual acidic conditions of wastewater generated
S.P. Santoso et al. Chemical Engineering Journal 452 (2023) 139261

Table 1
Comparison of the equilibrium uptake capacities (qe), removal efficiency, and the distribution coefficients (Kd) of various adsorbents toward Cu2+ and Cr6+.
Metal Adsorbents pH C0 Removal qe Kd Ref
Ions (ppm) (%) (mg/g) (mL/g)

Cu2+ CRAB sponge 5 200 97.5 38.5 7.8 × 103 This work
Fe3O4/Ca-alginate composite 5 24.2 99 63 n.a. [62]
CS/AOX composite beadsa 4.9 444.5 61.3 54.5 316.9 [63]
Porous PAM/CA beadsb 5 100 50.2 50.2 1.0 × 103 [64]
Kaolin/CA 5 40 78.7 31.5 3.7 × 103 [65]
CHBc 4 200 66.7 20.0 300 [66]
GN2d 5 65 6.5 10.6 174.7 [67]
Chitosan/heulandite/Fe3O4 5 45.1 93.1 8.4 2.7 × 103 [68]
Fe3O4-chitosan beads 5 50 15.6 15.6 369.7 [69]
ECXCe 5 100 13.2 13.2 152.1 [70]
PVA/CMC hydrogelf 1.6 100 n.a. 5.5 n.a. [71]
Compost-derived biochar 5 20 94.7 3.8 3.6 × 103 [72]
EVA-C nanocompositeg 5 10 n.a. 0.35 n.a. [73]
D-N activated carbonh 4.7 7980 n.a. 27.3 n.a. [74]
Cr6+ CRAB sponge 3 200 94.7 37.2 3.5 × 103 This work
Modified halloysite nanotubes 5 100 96.8 32.3 1.0 × 104 [82]
c-DAC nanofibersi 6 100 15.6 31.2 369.7 [83]
Corn stalk biochar 2 588.4 23.6 27.8 61.7 [84]
Polyaniline/SiO2 composite 4.2 50 88 22.0 3.7 × 103 [85]
MOR-1-HAj 3 21.6 97.5 21.1 3.9 × 104 [86]
B-Al nanocompositek 6 10 99.6 16.6 2.8 × 105 [87]
mMOXl 6 5 77.3 3.9 3.4 × 103 [88]
ATP/MNS/GNS compositem 3 5 94 2.97 8.8 × 103 [89]
Cellulose-NaMMT composite 5 20 99.5 1.0 1.0 × 104 [90]
Polyacrylamide-grafted clay 2 25 90.1 1.13 456.6 [91]
Chitosan 4 0.5 94.7 4.74 1.8 × 105 [92]
a
Chelating composite beads based on amidoximated potato starch (AOX) particles embedded in cross-linked chitosan matrix.
b
Polyacrylamide network interpenetrated in Ca2+-alginate network decorated with pore-forming PEG.
c
Chitosan immobilized on bentonite.
d
Aminopropyl-functionalized silica gel.
e
Epichlorohydrin cross-linked xanthate chitosan.
f
Poly(vinyl alcohol) and carboxymethyl cellulose composite hydrogels.
g
Ethylene vinyl acetate-clinoptilolite.
h
Ammonia-treated commercial activated carbon (Carbotech) at 1170 K.
i
Cationic dialdehyde cellulose nanofibers.
j
Anion exchange composite based on UiO-66 type metal organic resin-1 and alginic acid.
k
Amorphous aluminum supported on bentonite clay.
l
Magnetite-manganese oxide alginate xerogel.
m
Calcined attapulgite clay/Macadamia nutshells/groundnut shells composite. n.a.: not available.

from the tannery (pH = 3–4) and electroplating (pH = 2–3) operations
[6,8,81], which may suggest the practical feasibility of CRAB sponge for
treating such chromium-bearing effluents. In strongly acidic conditions
(pH ≤ 1) where Cr6+ mainly exists in the form of H2CrO4, the sorption
process is less efficient than that at pH 3, due to a weak binding affinity
of this neutral species toward the protonated sorbent surface. On the
other hand, in the pH range of 4–10 (pH > pHpzc), the Cr6+ uptake is
retarded by the repulsive solute-sorbent interaction and by the presence
of competing OH− ions, thus leading to a decline in the removal effi­
ciency. The equilibrium removal capacity of 37.5 mg/g afforded by
CRAB sponge at pH is higher than previously reported chromium ad­
sorbents including benchmark commercial activated carbon [82–92],
indicating the great potential of this cheap and sustainable material for
efficient sequestration of toxic Cr6+ oxoanions.
The uptake capacity of CRAB sponge for Cu2+ and Cr6+ under various
ionic strengths was also examined to gain insight into the outer- or
inner-sphere metal interactions, and the results are presented in Fig. 2c
and d. For Cu2+, the adsorptive capacity is slightly declined in the
presence of NaNO3 as a background electrolyte with Na+/Cu2+ molar
ratios of 6:1 (5 mM), 12.1:1 (10 mM), and 24.2:1 (20 mM), yielding the
equilibrium uptake capacities of 37.1, 35.4, and 32.9 mg/g, respec­
tively. The adverse effect of ionic strength on the equilibrium uptake
capacity can be attributed to the competition between Cu2+ and Na+
ions for adsorption sites on the CRAB surface, which becomes more
pronounced at higher electrolyte concentrations. A markedly lower
Cu2+ uptake (27.1 mg/g) was observed in the presence of 10 mM Ca
(NO3)2 (~12-fold molar excess of Ca2+ over Cu2+). According to the
Pearson’s hard/soft acids/bases (HSAB) principle [93], hard divalent
metal cations, such as Ca2+ can form a stronger electrostatic interaction
with carboxylate groups (a hard base) than the monovalent Na+, thus
contributing to greater sorption competition with Cu2+. The effect of
coexisting NO−3 anions on the Cu2+ sorption capacity is considered
insignificant since these ions are electrostatically repelled by the nega­
tively charged CRAB surface at pH 5. Meanwhile, the Cr6+ uptake was
not significantly affected by the presence of NaNO3 background con­
centrations in the range of 5–20 mM (NO−3 /HCrO−4 molar ratios of
7.4:1–29.4:1), where the qe values slightly decreased from 37.2 to 30.8
mg/g (Fig. 2d). This result indicates that NO−3 only weakly competes
with HCrO−4 ions for binding sites on the CRAB surface, considering that
this monovalent anion has a larger hydrated radius (0.335 nm) and
Gibbs free energy of hydration (ΔhydG = -300 kJ mol− 1) than the target
oxoanions (HCrO−4 ). Similarly, no appreciable decrease in the Cr6+ up­
take capacity was observed in the presence of 10 mM Cl− . On the other
hand, sulfate anion (SO2−
4 , hydrated radius = 0.258 nm) competes more
strongly with Cr6+ oxyanions, leading to a marked decrease in the
removal capacity. Similar observations have been reported in other
studies [83,92]. The interference of coexisting Na+ ions in the Cr6+
uptake can be ruled out, considering that this cation is expected to be
repelled from the positively charged CRAB surface at pH 3.

7
S.P. Santoso et al.
3.3. Equilibrium and kinetic studies
3.3.1. Adsorption isotherms
Adsorption isotherms provide crucial information on the equilibrium
distribution of solute molecules between the solid and liquid phases at a
constant temperature, which is essential for designing and optimizing
sorption-based wastewater treatment systems. The equilibrium data for
Cu2+ and Cr6+ uptake on AB, RSOB, and CRAB sorbents at 30, 40, and
50 ◦ C, along with the Langmuir and Freundlich isotherm fits are shown
in Fig. 3. In the single-site (classic) Langmuir isotherm model, the
sorption process can be viewed as a monolayer coverage of the adsorbate
molecules on the solid surface containing a finite number of identical
binding sites [94]. This model further assumes in accordance with the
monolayer theory that each adsorption site can be occupied by only one
adsorbate molecule, and there are no lateral interactions between
adsorbed species. On the other hand, Freundlich isotherm describes a
multilayer adsorption phenomenon of adsorbate molecules on hetero­
geneous solid surfaces without a saturation limit at high concentrations
[95]. The mathematical expressions of Langmuir and Freundlich iso­
therms are shown in Eqs. (5) and (6), respectively.
KL Ce
qe = qmax (5)
1 + KL Ce
qe = KF Ce1/n (6)
In Eqs. (5) and (6), Ce (mg/L) and qe (mg/g) denote the equilibrium
solute concentration in the bulk solution and the equilibrium uptake
capacity of the sorbent, respectively. The empirical parameters qmax
(mg/g) and KL (L/mg) in the Langmuir model specify the theoretical
maximum sorption capacity and a constant characterizing the sol­
ute–surface affinity. Similarly, the adsorption capacity in the Freundlich
model is defined by KF ((mg/g)⋅(mg/L)–n) and n is the dimensionless
parameter describing the adsorbent surface heterogeneity whose value
falls between 0 and 1 (high n values approaching unity indicate a more
homogeneous system and vice versa). Results for the fit parameters
Fig. 3. Adsorption isotherms for the sorption of Cu2+ (top row) and Cr6+ (bottom row) by AB (left), RSOB (middle), and CRAB sponge (right) at various temper­
atures. The circle and square symbols represent the experimental data, while solid and dotted lines are nonlinear fits of the Langmuir and Freundlich models.
8
Chemical Engineering Journal 452 (2023) 139261
obtained from nonlinear least-squares fitting analysis of the qe vs Ce data
using SigmaPlot version 12.5 software are given in Table 2.
As can be seen from Fig. 3, the Freundlich model provides better
agreement with adsorption equilibrium data than the Langmuir model,
which is also reflected by higher goodness-of-fit (R2) values. The fit
parameter 1/n showed values less than unity (or approaching zero) for
all investigated systems, characterizing adsorption on energetically
heterogeneous surfaces. The lower 1/n values observed in the CRAB
sponge suggest a higher degree of adsorbent surface heterogeneity.
Meanwhile, the fit parameter KF demonstrated that the CRAB sponge
exhibited the highest uptake capacity for both metal ions (i.e., 13.4 mg
of Cu2+/g and 17.4 mg of Cr6+/g) among all the investigated sorbents.
Moreover, an enhanced metal uptake capacity of the composite sorbent
was observed as the temperature increased. This result suggests that the
Cu2+ and Cr6+ sorption onto CRAB sponges are endothermic and
chemical in nature. To further corroborate the chemical adsorption
nature of the metal ions, the mean free energy of adsorption (E) was
determined by fitting the equilibrium data with Dubinin–Radushkevich
isotherm model (Fig. S7). According to this model, the E values for the
sorption systems are in the range of 8–16 kJ mol− 1, thus confirming the
chemisorption nature of Cu2+ and Cr6+ binding on CRAB via Cu–OOH
and Cr– interactions, respectively.
Typically, adsorbent materials with exceptional heavy metal
removal performance exhibit Kd values ranging from ~104 to 105 mL/g
[22]. The Kd values of the CRAB sponge are calculated to be 6.0 × 103
and 3.5 × 103 mL/g for Cu2+ and Cr6+, respectively (Table 1). For Cu2+,
the present composite sponge exhibited an order of magnitude higher
affinity than previously reported polysaccharide-based composite ad­
sorbents, such as kaolin/Ca alginate (Kd = 3.7 × 103 mL/g [65]), chi­
tosan/clay/Fe3O4 (Kd = 2.7 × 103 mL/g [68]), Fe3O4– chitosan (Kd =
369.7 mL/g [69]), and chitosan–bentonite (Kd = 300 mL/g [66]). We
also examined the adsorption performance of CRAB at lower initial Cu2+
concentrations. As shown in Fig. S8a, the removal efficiencies remain
higher than 98 % over a concentration range of 10–100 ppm, with Kd
values greater than 104 mL/g. For comparison, pristine Ca alginate
S.P. Santoso et al. Chemical Engineering Journal 452 (2023) 139261

Fig. 4. Adsorption kinetics of Cu2+ (top row) and Cr6+ (bottom row) onto AB (left), RSOB (middle), and CRAB (right) sorbents at various initial concentrations.
Experimental data are represented by circle and square symbols, while the nonlinear regression fits for PFO, PSO, and Elovich kinetic models are shown as solid,
dotted, and dashed lines, respectively.

Table 2
The fitted values of Langmuir and Freundlich isotherm model parameters for Cu2+ and Cr6+ ions.
Sorption System T (◦ C) Langmuir Parameters Freundlich Parameters

qmax KL RL* R2 KF 1/n R2

(mg/g) (L/g) ((mg/g)⋅(mg/L)-n)

Cu2+− AB 30 231.83 1.4 0.42 0.985 1.75 0.64 0.985

40 277.52 2.0 0.33 0.947 2.96 0.62 0.978
50 314.93 2.4 0.29 0.957 3.72 0.62 0.981
Cu2+− RSOB 30 222.77 2.9 0.26 0.986 4.34 0.55 0.987
40 385.41 1.8 0.36 0.961 5.68 0.58 0.977
50 325.04 4.2 0.19 0.962 6.81 0.57 0.971
Cu2+− CRAB 30 193.56 8.8 0.10 0.945 13.44 0.40 0.974
40 339.43 4.1 0.20 0.913 14.17 0.44 0.975
50 317.60 7.3 0.12 0.913 15.38 0.38 0.986
Cr6+− AB 30 166.15 1.7 0.37 0.951 1.99 0.58 0.952
40 214.29 2.2 0.31 0.987 2.94 0.58 0.982
50 199.65 4.1 0.20 0.975 5.35 0.49 0.992
Cr6+− RSOB 30 162.40 3.0 0.25 0.923 4.30 0.50 0.962
40 186.59 4.0 0.20 0.952 6.02 0.49 0.991
50 207.28 5.7 0.15 0.974 8.57 0.47 0.995
Cr6+− CRAB 30 131.56 14.1 0.07 0.927 17.42 0.31 0.980
40 159.34 14.7 0.06 0.952 20.31 0.31 0.972
50 175.44 16.1 0.06 0.955 22.38 0.32 0.975

*RL (the equilibrium parameter) values were calculated from the mathematical equation RL = 1/(1 + bC0) [97] using C0 = 1000 ppm and the adsorption process is
categorized as follows: favorable (0 < RL < 1); unfavorable (RL > 1); linear (RL = 1); and irreversible (RL = 0).

showed only 73–81 % removal and much smaller Kd values of < 103 mL/
g (Fig. S8b), even though this material had a swelling capacity higher
than that of CRAB (Fig. S2). This might suggest that the increase in the
free volume within the network upon swelling is not a decisive factor in
determining metal uptake capacity, given that the size of hydrated metal
ions (i.e., 0.419 nm for Cu2+) is much smaller than the meso- and mac­
ropores of the sorbent and thus, the contribution of steric effect can be
considered to be negligible. Moreover, the presence of exfoliated orga­
noclay platelets in CRAB may induce additional interactions with metal
ions, leading to enhanced capacity. Furthermore, for the typical Cu2+
concentrations in wastewater streams from electroplating (2–40 ppm)
and tanning (2–100 ppm) industries, the composite sorbent can reduce
these values to < 0.5 ppm, which is below the maximum contaminant
limit of 1.3 ppm recommended by the US EPA for drinking water.

9
S.P. Santoso et al.
For Cr6+, the Kd value of CRAB sponge is comparable to those of
polyaniline/SiO2 composite (Kd = 3.7 × 103 mL/g [84]) and
Fe3O4–MnO2 alginate xerogel (known as mMOX, Kd = 3.4 × 103 mL/g
[87]), while affording higher removal efficiency and capacity. Metal-
organic resin–alginic acid composite (MOR-1–HA), amorphous
aluminum supported on bentonite (B-Al), and powdered activated car­
bon all displayed Kd values that are 1–2 orders of magnitude higher than
the CRAB sponge. However, it is important to note that such remarkably
high Kd values of those sorbent materials were recorded at low con­
centration conditions. Accordingly, we conducted batch removal ex­
periments using Cr6+ solution with lower initial concentrations (10–100
ppm), and the results are presented in Fig. S8c. It can be seen that the
composite sponge achieved > 99 % removal efficiency and yielded Kd
values of 7.1 × 104 and 2.6 × 104 mL/g at initial concentrations of 10
and 50 ppm, respectively, while the pristine Ca alginate showed only
~60 and ~54 % removal, and Kd values of 2.9 × 102 and 2.3 × 102 mL/
g. Moreover, the reduced concentration of 28 ppb (from 10 ppm) meets
the U.S. EPA-mandated drinkable water standard for total chromium
(100 ppb), further suggesting the potential of CRAB sponge for water
treatment of streams. The above-mentioned MOR-1–HA, B-Al, and
activated carbon sorbents suffer from several drawbacks that hamper its
widespread use in practical wastewater treatment, such as high pro­
duction and regeneration costs for the carbons [96]. Bentonite clay-
supported amorphous aluminum (B-Al) composites exhibit lower up­
take capacities, and their preparation methods involve multiple tedious
and time-consuming processes, in addition to the use of toxic organic
solvents (e.g., N,N-dimethylformamide in the case of MOR-1). On the
other hand, the as-prepared CRAB hydrogel is produced using a simple
and greener approach from cheap and abundant starting materials (i.e.,
alginate, bentonite clay, and plant-based saponin), which provide an
economical and sustainability advantage for the up-scaled production
process and practical operation.
3.3.2. Adsorption kinetics study
Analysis of the adsorption kinetics is carried out to gain insights into
the removal mechanisms and the rate-limiting step for heavy metal
uptake by the investigated sorbent materials. The pseudo-first-order
(PFO), pseudo-second-order (PSO), Elovich, and Weber-Morris intra­
particle diffusion (IPD) models (eqs 7–10) were employed to correlate
the sorption kinetics of Cu2+ and Cr6+ ions in single systems [98].
q(t) = qe (1 − exp(− k1 t)) (7)
k2 q2e t
q(t) = (8)
1 + k2 qe t
q(t) = (1/β)ln(1 + αβt) (9)
q(t) = Kid (t)0.5 + Ci (10)
where k1 (min− 1) and k2 (g mg− 1 min− 1) are the PFO and PSO rate
constants, respectively and qe (mg g− 1) is the equilibrium adsorption
capacity value. The rate constant parameters k1 and k2 can also be
viewed as a time-scaling factor that reflects how fast a sorption system
reaches an equilibrium state and is dependent on the initial solute
concentration [98]. The empirical constants α and β in the Elovich
equation (eq (9)) correspond to the adsorption (mg g− 1 min− 1) and
desorption (g mg− 1) rate constants, respectively. Meanwhile, the Kid and
C parameters in the IPD model denote the diffusion rate constant (mg L-1
min− 1/2) and a constant related to the apparent thickness of the film
boundary layer, respectively. The nonlinear least-squares fits of the PFO,
PSO, and Elovich kinetic models to the experimental data are shown in
Fig. 4 and the fitted kinetic parameters (i.e., k1, k2, qe, α, and β) are
summarized in Tables 3 and 4.
Judging from R2 values in Table 3, both PFO and PSO models are able
to fit the kinetic data satisfactorily, although the former yields an overall
10
Chemical Engineering Journal 452 (2023) 139261
better fit for all initial solute concentrations (C0) investigated (see the
residual plots in Figs. S9 and S10). Moreover, the fitted qe parameter of
the PFO model is much closer to the experimental values (qe,exp) than the
PSO model. As shown in Fig. 4, the CRAB sponge displayed faster uptake
kinetics of Cu2+ and Cr6+ than AB and RSOB, due to the enhanced
diffusion of metal ions within the meso-macropore network and the
greater number of binding sites on the adsorbent surface. SEM cross-
sectional analysis of CRAB after adsorption of Cu2+ and Cr6+ revealed
that the metal ions were uniformly distributed on the interior surface of
the sorbent (Fig. S11). The k1 values for the sorption systems at different
initial concentrations follow the order CRAB > RSOB > AB, in good
agreement with experimental observations. In this context, the increase
in the Cu2+ and Cr6+ concentrations from 100 to 1000 mg/L decreases k1
and k2 values, which could be ascribed to the longer time needed to
reach equilibrium. Compared with other alginate-based composite sor­
bents, the CRAB sponge exhibits faster adsorption equilibration
(Fig. S12), which could be ascribed to abundant meso and macroporous
networks that allow efficient molecular diffusion of metal ions into the
interior surface sites of the sorbent.
The kinetics of Cu2+ and Cr6+ sorption was further analyzed by the
Elovich equation to evaluate the contribution of the diffusion-controlled
process and the initial adsorption rate. However, before interpreting the
physical meaning of the Elovich parameters (i.e., α and β), it should be
noted that this rate equation provides a better fit to the adsorption data
when the system remains far from equilibrium [98]. As can be seen in
Fig. 4, most of the kinetic data points at the near-equilibrium regime do
not fit well to the model regression line, in agreement with the above
statement. The fit parameter α, which can be treated as the initial
adsorption rate, indicates that the CRAB sponges exhibited the fastest
Cu2+ and Cr6+ removal, consistent with the PFO rate constants reported
in Table 3 Table S3. The α values were found to increase with initial
concentration (Table 4), which could be ascribed to the larger driving
force for mass transport of solute molecules from the bulk aqueous so­
lution to the sorbent surface. The adsorption characteristics of Cu2+ and
Cr6+ on the sorbent surfaces were further assessed by the approaching
equilibrium factor (RE) of the dimensionless Elovich equation [99] and
the curve fitting results are shown in Fig. S13. As shown in Table 4, the
RE values for Cu2+ and Cr6+ uptake on the sorbent are typically in the
range of 0.1–0.3, which correspond to the Zone II of mildly rising
adsorption curves. Lower RE values for Cu2+− CRAB and Cr6+− CRAB
systems indicate faster uptake kinetics to reach equilibrium than AB and
RSOB sorbents.
To investigate the rate-limiting step in the overall sorption process,
the kinetic data were analyzed with IPD model. As shown in Fig. S14, the
IPD plots for Cu2+ sorption (100 ppm initial concentration) onto all
sorbents reveal two linear regions with different slopes. The first linear
region with a steeper slope and negative y-axis intercept could be
attributed to the film diffusion of the hydrated metal ions on the external
surface and internal macropore surface of the sorbent particles. As
shown in Table 5, the value of the intercept (C1) for Cu2+ uptake on
CRAB is more negative than those for AB and RSOB, which is ascribed to
the internal film diffusion resistance in macropores [100]. The diffusion
rate constant for the first step (K1) follows the order of CRAB > RSOB >
AB, indicating that the presence of macropores enables faster ion uptake.
Meanwhile, the second linear portion of the plot corresponds to the
surface diffusion of Cu2+ ions in the micropores for AB and RSOB,
whereas in the case of CRAB, it represents the adsorption equilibrium
state. The rate constant values obtained for this step (K2) are much
smaller than those for the film diffusion (K1), which can be ascribed to
slow diffusion and sorption of metal ions onto internal sites through
micropores. Similar behavior was observed for Cr6+ uptake (Fig. S15).
For Cu2+ and Cr6+ at 1000 ppm concentration, the IPD plots for AB and
RSOB show three linear regions. The linear portion observed during the
first 20 min can be ascribed to the external film diffusion of metal ions
on the exterior surface of the sorbent. The second and third linear seg­
ments represent mesopore and micropore diffusion within the clay
S.P. Santoso et al. Chemical Engineering Journal 452 (2023) 139261

Table 3
Fitted pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic parameters for adsorption kinetics of Cu2+ and Cr6+ onto AB, RSOB, and CRAB.
C0 qe,exp† PFO PSO
(ppm) (mg/g)
k1 £ 10-2 qe R2 SSE‡ k2 £ 10-2 qe R2 SSE
(1/min) (mg/g) (g/mg⋅min) (mg/g)

Cu2þ-AB
100 6.36 1.51 6.43 0.993 0.094 0.18 8.16 0.997 0.122
300 17.61 1.39 17.85 0.998 0.234 0.06 23.05 0.998 0.271
500 26.29 1.24 27.02 0.996 0.432 0.03 35.54 0.992 0.413
1000 46.75 0.98 50.27 0.995 0.730 0.01 69.65 0.998 0.849
Cu2þ-RSOB
100 7.94 1.63 7.96 0.997 0.103 0.16 9.97 0.997 0.170
300 23.16 1.51 23.65 0.996 0.367 0.05 30.24 0.993 0.757
500 35.76 1.36 36.97 0.991 0.425 0.03 48.22 0.995 1.027
1000 68.14 1.02 73.64 0.988 1.130 0.008 102.20 0.994 1.901
Cu2þ-CRAB
100 10.28 2.80 10.43 0.997 0.232 0.27 12.15 0.978 0.591
300 32.18 2.69 31.87 0.998 0.574 0.08 37.22 0.994 0.885
500 45.74 2.53 45.64 0.996 0.734 0.06 53.50 0.994 1.371
1000 97.37 2.25 98.31 0.988 1.383 0.02 117.64 0.988 4.082
Cr6þ-AB
100 5.94 1.64 6.01 0.997 0.070 0.21 7.55 0.995 0.164
300 16.15 1.49 16.83 0.995 0.114 0.07 20.91 0.997 0.317
500 24.41 1.33 24.85 0.991 0.261 0.04 32.31 0.988 0.356
1000 40.38 1.07 42.94 0.996 0.419 0.02 57.74 0.996 0.420
Cr6þ-RSOB
100 7.75 1.98 7.78 0.998 0.131 0.22 9.50 0.991 0.290
300 22.11 1.79 22.32 0.996 0.373 0.07 27.42 0.994 0.628
500 33.87 1.65 33.92 0.998 0.537 0.04 42.21 0.998 0.556
1000 58.82 1.36 60.14 0.994 0.523 0.02 78.00 0.998 1.055
Cr6þ-CRAB
100 10.28 3.61 10.19 0.996 0.244 0.41 11.50 0.993 0.314
300 28.45 3.43 28.19 0.997 0.564 0.13 32.13 0.990 1.047
500 45.27 3.18 45.49 0.993 0.674 0.08 52.12 0.992 1.539
1000 91.22 2.87 90.87 0.998 1.362 0.03 105.23 0.994 3.397

The best model fits are indicated in bold.

†
Values are taken at the longest time point examined.
‡
SSE: sum of the squared errors.

particles. However, the IPD plot for the CRAB sponge only showed two
Table 4 linear regimes. This could be plausibly ascribed to the higher density of
Elovich kinetic parameters for the sorption of Cu2+ and Cr6+ onto AB, RSOB, and
metal binding groups on the external sponge surface such that the
CRAB.
external sorption and internal film diffusion in macropores could coin­
Sorption C0 α (mg/ β (g/ RE† R2 SSE cide [83]. Based upon these results, it can be implied that the kinetics of
System (ppm) g⋅min) mg)
Cu2+ and Cr6+ uptake on CRAB is controlled by film diffusion and sur­
Cu2+-AB 100 0.16 0.45 0.257 0.991 0.231 face adsorption to some degree.
300 0.38 0.15 0.257 0.993 0.549
500 0.49 0.10 0.254 0.985 0.669
1000 0.64 0.05 0.246 0.986 1.148 3.4. Reusability and performance of CRAB sponges in real-world samples
Cu2+-RSOB 100 0.22 0.38 0.252 0.988 0.323
300 0.55 0.12 0.268 0.982 1.208 Apart from the high sorption capacity and fast kinetics, the successful
500 0.74 0.07 0.267 0.986 1.642
implementation of the sorption process in industrial operation also relies
1000 0.96 0.03 0.270 0.990 2.648
Cu2+-CRAB 100 0.69 0.37 0.247 0.940 0.980 on the efficient regeneration and reuse of the sorbent material. In this
300 2.03 0.12 0.239 0.970 2.063 regard, the reusability of CRAB was evaluated for four cycles of sorption
500 2.69 0.08 0.240 0.971 2.883 and regeneration using 1 M aqueous HCl solution. As can be seen from
1000 4.44 0.04 0.254 0.964 7.111 Fig. S16, a slight decrease (<5%) in the percent removal of Cu2+ ions
Cr6+-AB 100 0.16 0.49 0.261 0.984 0.290
was observed for CRAB sponges after the fourth adsorption–desorption
300 0.38 0.17 0.259 0.989 0.625
500 0.50 0.11 0.256 0.994 0.722 run, suggesting its excellent reusability performance. For comparison,
1000 0.61 0.06 0.257 0.997 0.815 the pristine Ca alginate sponges showed an appreciable loss in the
Cr6+-RSOB 100 0.28 0.42 0.259 0.972 0.497 sorption efficiency after each regeneration cycle. This result could be
300 0.71 0.14 0.251 0.983 1.083
attributed to the decreased number of cation (Ca2+) exchange sites, due
500 0.96 0.09 0.250 0.991 1.204
1000 1.23 0.04 0.259 0.992 2.005
to the structural transformation of calcium alginate from ionic to acid
Cr6+-CRAB 100 1.23 0.44 0.212 0.959 0.743 gel after being immersed in an acidic solution at pH < 3 [101,102].
300 2.82 0.15 0.223 0.953 2.260 However, this phenomenon was minimized in the CRAB sponge, which
500 4.07 0.09 0.225 0.959 3.373 might suggest that the presence of exfoliated clay platelets could help
1000 6.67 0.04 0.232 0.961 6.703
stabilize and prevent the alginate network. We also hypothesized that
†
Approaching equilibrium factor, determined by nonlinear least-squares the acidic waste regeneration solution containing Cu2+ ions could be
fitting of the plot of (qt/qref) vs (t/tref), as described in ref 98. All the adsorp­ employed as a homogeneous catalytic system for realizing a tandem
tion systems exhibit a “mildly rising” kinetic behavior (0.1 < RE < 0.3). adsorption-catalysis strategy. To test this hypothesis, the reduction of 4-
nitrophenol (4-NP) to 4-aminophenol (4-AP) by borohydride was
adopted as a model catalytic reaction. As shown in Fig. S17, the waste

11
S.P. Santoso et al. Chemical Engineering Journal 452 (2023) 139261

Table 5
Kinetic parameters of the IPD model for Cu2+ and Cr6+ uptake onto AB, RSOB, and CRAB.
Sorption System C0 Step 1 Step 2 Step 3
(ppm)
K1 C1 R2 K2 C2 R2 K3 C3 R2
2+
Cu -AB 100 0.59 − 0.84 0.997 0.17 3.62 0.977 – – –
Cu2+-RSOB 0.75 − 0.98 0.998 0.19 4.86 0.992 – – –
Cu2+-CRAB 1.32 − 1.69 0.994 0.04 9.67 0.941 – – –
Cr6+-AB 100 0.59 − 0.91 0.997 0.12 3.99 0.975 – – –
Cr6+-RSOB 0.83 − 1.18 0.990 0.11 5.95 0.968 – – –
Cr6+-CRAB 1.12 0.04 0.980 0.05 9.52 0.963 – – –
Cu2+-AB 1000 4.16 − 10.32 0.997 1.87 16.21 0.997 2.66 − 2.40 0.999
Cu2+-RSOB 6.75 − 18.95 0.997 2.28 31.13 0.988 3.89 − 5.40 0.991
Cu2+-CRAB 10.68 − 12.80 0.988 0.56 88.48 0.951 – – –
Cr6+-AB 1000 3.37 − 6.45 0.997 1.38 17.78 0.994 2.27 − 2.15 1.000
Cr6+-RSOB 5.10 − 7.22 0.991 1.18 39.52 0.995 2.71 − 0.88 1.000
Cr6+-CRAB 10.44 − 7.53 0.987 0.88 77.38 0.897 – – –

regeneration solution with ~3.1 mM Cu2+ ions (pH 1.98) could catalyze
the complete reduction of 4-NP within 3 min, affording a pseudo-first-
order rate constant of 0.57 min− 1. For comparison, no noticeable color
change was observed in the yellow solution of 4-nitrophenolate ions
after several hours, indicating negligible catalytic activity in the pres­
ence of NaBH4, while a slower reduction rate (0.12 min− 1) was observed
upon the addition of HCl solution (Fig. S17c). This result may thus
suggest the synergy between Cu2+ ions and protons in the catalytic
reduction of 4-NP. For Cr6+, the CRAB sorbent demonstrated a lower
regeneration efficiency, whereas the percent removal decreased from an
initial 97.1 % to 86.4 % at the end of the fourth cycle (Fig. S18a). This
could be ascribed to the presence of Cr3+ that occupies the sorption sites
and could not be completely desorbed from the sorbent surface, thus
hindering Cr6+ uptake in the subsequent cycle. Again, compared to its
pristine counterpart, the CRAB sorbent exhibited superior reusability
and 86 % retention in the removal efficiency after four sorption-
regeneration cycles compares favorably with those of other reported
alginate composites (Fig. S18b).

Fig. 5. Removal of Cu2+ and Cr6+ ions from real-

world water samples. (a, b) The river water was
spiked with Cu2+ ions at 10 ppm and the metal ion
concentration after treatment with CRAB at various
time points. The dotted line represents the U.S. EPA
copper limit in drinking water. (c, d) The river water
was spiked with Cr6+ ions at 10 ppm and the con­
centration–time profiles of metal ions were treated
with the composite at pH 3 and 6.5. The inset in (d)
shows a zoom-in of the low concentration region. (e,
f) The river water was spiked with ~20 ppm of mixed
Cu2+ and Cr6+ (10 ppm each) without pH adjustment
and the concentration profiles of each metal ion at
different time points following treatment with the
composite.

12
S.P. Santoso et al.
To further evaluate the potential of the CRAB sponge for actual water
decontamination application, we conducted batch removal experiments
using river water and a wastewater sample collected from an electro­
plating facility in Surabaya, East Java. The physicochemical properties
of these water samples are given in Table S4. Given the low concen­
trations of Cu2+ and Cr6+ ions in river water (i.e., ~4.5 and ~27 ppb,
respectively), the water was spiked with either ~10 ppm of Cu2+ and
Cr6+ and the concentrations of metal ions before and after treatment
with CRAB sponge were analyzed by AAS (Tables S5 and S6). The
adsorption experiments were performed under the respective optimum
pH values for each metal ion and the original pH of collected river water
samples to simulate actual natural water conditions. For the copper-
spiked river water, the results showed that the composite material
could lower the Cu2+ concentration from 10.17 ppm to drinkable levels
of <1.3 ppm (92 % removal) within 20–30 min and 99 % removal was
achieved after 6 h contact time (Fig. 5b). A similar result was observed
for removal experiments at pH 5. For Cr6+ originally present in the water
sample, the residual concentration of this anion after treatment with
CRAB was found to be below the detection limit of the AAS instrument
(2 ppb). Based on this result, one can expect that the percent removal of
Cr6+ in spiked water samples is >93 % at both pH values (Table S5). The
Kd value of CRAB for Cu2+ in spiked river water reached 2.0 × 104 mL/g,
demonstrating a good uptake ability of the composite sponges for
removing ions in the presence of various competing ions from actual
water samples. For Cr6+-spiked river water samples, ~86 % removal was
achieved at pH 6.5 within 6 h, yielding a final concentration of 1.44 ppm
and Kd value of 1.21 × 103 mL/g (Table S6). At pH 3, the removal
reached 99.2 %, reducing Cr6+ concentration from an initial ~10 ppm to
drinkable levels (<100 ppb) within 40 min (Fig. 5d).
Apart from Cr6+ uptake, we also observed a marked decrease in Mg2+
and Ca2+ concentrations (Fig. 5c), indicating that these divalent metal
ions are involved in Cr6+ binding to the CRAB surface. This result is not
particularly surprising, given that Mg2+ and Ca2+ can act as cation
bridges between HCrO−4 ions (the most predominant species at pH 6.5,
see Fig. S19) and the negatively charged carboxylate groups on the
sorbent surface [103]. It is also important to note that the formation of
Ca2+ cations can form a precipitate with CrO2− 4 anions, however, such
conditions can be neglected under our experimental conditions (see
Supplementary Text S3 for details). The as-prepared CRAB sponges were
also used to treat river water spiked with ~20 ppm of mixed Cu2+ and
Cr6+ ions, as well as electroplating wastewater (Fig. 5e,f and Tables S7
and S8). The results demonstrated that the composite was capable of
reducing Cu2+ concentration in river water to the drinkable level of
~1.2 ppm (88.6 % removal), while less efficient removal (72.6 %) was
observed for Cr6+ ions. The ability of the CRAB sponges to sequester
more copper ions could be attributed to the favorable electrostatic in­
teractions of this cation with the carboxylate groups of the sorbent under
near-neutral pH conditions of river water.
4. Conclusions
In summary, we have demonstrated a facile preparation of alginate-
based composite sponges containing exfoliated organoclay platelets
(CRAB) via Ca2+-induced gelation of an aqueous mixture of alginate, AB
clay, and rarasaponin surfactant. All these starting materials are readily
provided by nature, thus making the preparation of the present com­
posite sorbent industrially and economically attractive. The presence of
rarasaponin in the alginate-clay aqueous mixture played a dual role in
facilitating: (i) the penetration of alginate chains into clay interlayers
that lead to efficient exfoliation and well dispersion of organoclay in the
polymer matrix, and (ii) formation of stable foams in bulk solution
during foaming, which contributes to the formation of macropores. The
macro-mesoporous network structure of CRAB sponges, together with
the readily accessible metal-binding sites within the interior of the
sorbent resulted in fast and efficient removal of Cu2+ and Cr6+ ions from
aqueous solutions. Batch removal experiments at the optimum pH
13
Chemical Engineering Journal 452 (2023) 139261
demonstrated that the CRAB sponges were able to remove ~99.5 and
~99.7 % of Cu2+ and Cr6+ ions in a 10 ppm solution within 20–30 min,
respectively, bringing their final concentrations below the permissible
U.S. EPA limits for drinking water. Moreover, the removal performance
of this porous alginate-organoclay composite in terms of both uptake
capacity and Kd value is superior to those of other reported alginate-
based composites. Adsorption isotherm studies at various tempera­
tures revealed the endothermic and chemical nature of Cu2+ and Cr6+
uptake on CRAB with mean free energies of adsorption ranging from
12.6 to 13.8 kJ mol− 1 and from 10.8 to 11.5 kJ mol− 1, respectively. The
Freundlich isotherm model was found to best describe the equilibrium
adsorption data. Detailed kinetic analysis of Cu2+ and Cr6+ uptake by
the composite sponge shows that the sorption process is controlled by
film diffusion on the external adsorbent and internal macropore sur­
faces. When applied to real world water samples, the CRAB sponges
display satisfactory performance, showing 99 and 88% removal for Cu2+
and Cr6+ in spiked river water samples with the interference of Na, K,
Ca, and Mg, respectively. Given the demonstrated ease of preparation,
sustainable material resources, and combined with excellent sorption
performance and good reusability, the as-prepared CRAB sponges could
become a compelling candidate for efficient and cost-effective seques­
tration of copper and chromium ions in water and wastewater. It is also
envisioned that the practical utility of CRAB sponges in water and
wastewater treatment can be easily extended to other hard and
borderline Lewis metal ions (e.g., arsenic, cesium, and lead), as well as
cationic and anionic organic pollutants. Further investigations on the
mechanical properties and the sorption performance of the composite
sponges in a flowing (column) system will be an important research
direction to realize their practical use in industrial wastewater treatment
operations.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
The authors gratefully acknowledge financial support from The
Ministry of Education, Culture, Research, and Technology (Kementerian
Pendidikan Dan Kebudayaan, Riset Dan Teknologi), with contrat num­
ber 003/SP2H/PT-L/LL7/2022, 260D/WM01.5/N/2022.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2022.139261.
References
[1] M. Okumura, E. Naya, M. Harima, S. Murakami, S. Miyamoto, Contact material
for vacuum circuit breaker. US Patent US4677264A.
[2] S.V. Dobatkin, J. Gubicza, D.V. Shangina, N.R. Bochvar, N.Y. Tabachkova, High
strength and good electrical conductivity in Cu− Cr alloys processed by severe
plastic deformation, Mater. Lett. 153 (2015) 5–9.
[3] G. Stando, P.-M. Hannula, B. Kumanek, M. Lundström, D. Janas, Copper recovery
from industrial wastewater – Synergistic electrodeposition onto nanocarbon
materials, Water Res. Ind. 26 (2021), 100156.
[4] S.H. Jordanov, M. Maletić, A. Dimitrov, D. Slavkov, P. Paunović, Waste waters
from copper ores mining/flotation in ‘Bučbim’ mine: characterization and
remediation, Desalination 213 (2007) 65–71.
[5] N. Adhoum, L. Monser, N. Bellakhal, J.-E. Belgaied, Treatment of electroplating
wastewater containing Cu2+, Zn2+ and Cr(VI) by electrocoagulation, J. Hazard.
Mater. 112 (2004) 207–213.
S.P. Santoso et al.
[6] A. Agrawal, V. Kumar, B.D. Pandey, Remediation options for the treatment of
electroplating and leather tanning effluent containing chromium–A review,
Mineral Process. Extract. Metall. Rev. 27 (2006) 99–130.
[7] S.T.H. Rao, N.K. Papathoti, R. Gundeboina, Y.K. Mohamed, G.R. Mudhole, H. Bee,
Hexavalent chromium reduction from pollutant samples by Achromobacter
xylosoxidans SHB 204 and its kinetics study, Indian J. Microbiol. 57 (2017)
292–298.
[8] F.A. Dawodu, B.M. Akpan, K.G. Akpomie, Sequestered capture and desorption of
hexavalent chromium from solution and textile wastewater onto low cost Heinsia
crinita seed coat biomass, Appl. Water Sci. 10 (2020) 32.
[9] J.A.S. Costa, V.C. Costa, E.R. Pereira-Filho, C.M. Paranhos, Removal of Cr(VI)
from wastewater of the tannery industry by functionalized mesoporous material,
Silicon 12 (2020) 1895–1903.
[10] A.W. Lothongkum, Y. Khemglad, N. Usomboon, U. Pancharoen, Selective
recovery of nickel ions from wastewater of stainless steel industry via HFSLM,
J. Alloy. Comp. 476 (2009) 940–949.
[11] A.A. Taylor, J.S. Tsuji, M.R. Garry, M.E. McArdle, W.L. Goodfellow Jr., W.
J. Adams, C.A. Menzie, Critical review of exposure and effects: Implications for
setting regulatory health criteria for ingested copper, Environ. Manage. 65 (2020)
131–159.
[12] B. Chen, J. Xiong, J.-H. Ding, B.-F. Yuan, Y.Q. Feng, Analysis of the effects of Cr
(VI) exposure on mRNA modifications, Chem. Res. Toxicol. 32 (2019)
2078–2085.
[13] A. Zhitkovich, Chromium in drinking water: Sources, metabolism, and cancer
risks, Chem. Res. Toxicol. 24 (2011) 1617–1629.
[14] United States Environmental Protection Agency. National Primary Drinking
Water Regulations. https://www.epa.gov/ground-water-and-drinking-water/
national-primary-drinking-water-regulations#Inorganic (accessed 22 July 2022).
[15] X. Wei, X. Kong, S. Wang, H. Xiang, J. Wang, J. Chen, Removal of heavy metals
from electroplating wastewater by thin-film composite nanofiltration hollow-
fiber membranes, Ind. Eng. Chem. Res. 52 (2013) 17583–17590.
[16] C. Liu, T. Wu, P.-C. Hsu, J. Xie, J. Zhao, K. Liu, J. Sun, J. Xu, J. Tang, Z. Ye, D. Lin,
Y. Cui, Direct/alternating current electrochemical method for removing and
recovering heavy metal from water using graphene oxide electrode, ACS Nano 13
(2019) 6431–6437.
[17] C.H. Yun, R. Prasad, A.K. Guha, K.K. Sirkar, Hollow fiber solvent extraction
removal of toxic heavy metals from aqueous waste streams, Ind. Eng. Chem. Res.
32 (1993) 1186–1195.
[18] M. Gharabaghi, M. Irannajad, A.R. Azadmehr, Selective sulphide precipitation of
heavy metals from acidic polymetallic aqueous solution by thioacetamide, Ind.
Eng. Chem. Res. 51 (2012) 954–963.
[19] T. Kikuchi, S. Tanaka, Biological removal and recovery of toxic heavy metals in
water environment, Crit. Rev. Environ. Sci. Technol. 42 (2012) 1007–1057.
[20] S. Muthusaravanan, N. Sivarajasekar, J.S. Vivek, T. Paramasivan, M.u. Naushad,
J. Prakashmaran, V. Gayathri, O.K. Al-Duaij, Phytoremediation of heavy metals:
mechanisms, methods and enhancements, Environ. Chem. Lett. 16 (2018)
1339–1359.
[21] A. Kurniawan, A.N. Kosasih, J. Febrianto, Y.-H. Ju, J. Sunarso, N. Indraswati,
S. Ismadji, Evaluation of cassava peel waste as lowcost biosorbent for Ni-sorption:
Equilibrium, kinetics, thermodynamics and mechanism, Chem. Eng. J. 172
(2011) 158–166.
[22] D.T. Sun, L. Peng, W.S. Reeder, S.M. Moosavi, D. Tiana, D.K. Britt, E. Oveisi, W.
L. Queen, Rapid, selective heavy metal removal from water by a metal− organic
framework/polydopamine composite, ACS Cent. Sci. 4 (2018) 349–356.
[23] A.R. Bagheri, N. Aramesh, F. Sher, M. Bilal, Covalent organic frameworks as
robust materials for mitigation of environmental pollutants, Chemosphere 270
(2021), 129523.
[24] T. Rasheed, N. Ahmad, S. Nawaz, F. Sher, Photocatalytic and adsorptive
remediation of hazardous environmental pollutants by hybrid nanocomposites,
Case Stud. Chem. Environ. Eng. 2 (2020), 100037.
[25] C. Bertagnolli, A. Uhart, J.C. Dupin, M.G.C. da Silva, E. Guibal, J. Desbrieres,
Biosorption of chromium by alginate extraction products from Sargassum
filipendula: Investigation of adsorption mechanisms using X-ray photoelectron
spectroscopy analysis, Bioresour. Technol. 164 (2014) 264–269.
[26] C. Mohammed, S. Mahabir, K. Mohammed, N. John, K.-Y. Lee, K. Ward, Calcium
alginate thin films derived from Sargassum natans for the selective adsorption of
Cd2+, Cu2+, and Pb2+ ions, Ind. Eng. Chem. Res. 58 (2019) 1417–1425.
[27] R. Lagoa, J.R. Rodrigues, Kinetic analysis of metal uptake by dry and gel alginate
particles, Biochem. Eng. J. 46 (2009) 320–326.
[28] H. Zhang, Y. Shi, X. Xu, M. Zhang, L. Ma, Structure regulation of bentonite
nanocomposites for controlled release of imidacloprid, ACS Omega 5 (2020)
10068–10076.
[29] X. Su, B. Chen, Transparent, UV-proof and mechanically strong montmorillonite/
alginate/Ca2+ nanocomposite hydrogel films with solvent sensitivity, Appl. Clay
Sci. 165 (2018) 223–233.
[30] A.A. Edathil, P. Pal, F. Banat, Alginate clay hybrid composite adsorbents for the
reclamation of industrial lean methyldiethanolamine solutions, Appl. Clay Sci.
156 (2018) 213–223.
[31] Y. Zvulunov, A. Radian, Alginate composites reinforced with polyelectrolytes and
clay for improved adsorption and bioremediation of formaldehyde from water,
ACS EST Water 1 (2021) 1837–1848.
[32] N. Matschiavelli, S. Kluge, C. Podlech, D. Standhaft, G. Grathoff, A. Ikeda-Ohno,
L.N. Warr, A. Chukharkina, T. Arnold, A. Cherkouk, The year-long development
of microorganisms in uncompacted Bavarian bentonite slurries at 30 and 60 ◦ C,
Environ. Sci. Technol. 53 (10514–1) (2019) 0524.
14
Chemical Engineering Journal 452 (2023) 139261
[33] R.W. Gullick, W.J. Weber, Evaluation of shale and organoclays as sorbent
additives for low-permeability soil containment barriers, Environ. Sci. Technol.
35 (2001) 1523–1530.
[34] W. Ling, Q. Shen, Y. Gao, X. Gu, Z. Yang, Use of bentonite to control the release of
copper from contaminated soils, Aust. J. Soil Res. 45 (2007) 618–623.
[35] R. da Silva Fernandes, M.R. de Moura, G.M. Glenn, F.A. Aouada, Thermal,
microstructural, and spectroscopic analysis of Ca2+ alginate/clay nanocomposite
hydrogel beads, J. Mol. Liq. 265 (2018) 327–336.
[36] P. Stathi, K. Litina, D. Gournis, T.S. Giannopoulos, Y. Deligiannakis,
Physicochemical study of novel organoclays as heavy metal ion adsorbents for
environmental remediation, J. Colloid Interface Sci. 316 (2007) 298–309.
[37] K. Tohdee, L. Kaewsichan, Asadullah. Enhancement of adsorption efficiency of
heavy metal Cu(II) and Zn(II) onto cationic surfactant modified bentonite.
J. Environ. Chem. Eng. 2018, 6, 2821–2828.
[38] S. Mao, M. Gao, Functional organoclays for removal of heavy metal ions from
water: A review, J. Mol. Liq. 334 (2021), 116143.
[39] O. Güçlü-Ustündağ, G. Mazza, Saponins: properties, applications and processing,
Crit. Rev. Food Sci. Nutr. 47 (2007) 231–258.
[40] S.P. Santoso, A. Kurniawan, F.E. Soetaredjo, K.-C. Cheng, J.N. Putro, S. Ismadji,
Y.-H. Ju, Eco-friendly cellulose− bentonite porous composite hydrogels for
adsorptive removal of azo dye and soilless culture, Cellulose 26 (2019)
3339–3358.
[41] M.F.A. Taleb, D.E. Hegazy, S.A. Ismail, Radiation synthesis, characterization and
dye adsorption of alginate-organophilic montmorrilonite nanocomposite,
Carbohydr. Polym. 87 (2012) 2263–2269.
[42] W. Luo, Q. Huang, P. Antwi, B. Guo, K. Sasaki, Synergistic effect of ClO−4 and Sr2+
adsorption on alginate-encapsulated organo-montmorillonite beads: Implication
for radionuclide immobilization, J. Colloid Interface Sci. 560 (2020) 338–348.
[43] American Society for Testing and Materials, Standard Test Method for Methylene
Blue Index of Clay (C837–09), ASTM International, 2014.
[44] C.A. Alexiades, M.L. Jackson, Quantitative clay mineralogical analysis of soils and
sediments, Clays Clay Minerals 14 (1966) 35–52.
[45] C. Belver, M.A.B. Muňoz, M.A. Vicente, Chemical activation of a kaolinite under
acid and alkaline conditions, Chem. Mater. 14 (2002) 2033–2043.
[46] S.P. Santoso, A.E. Angkawijaya, M. Yuliana, V. Bundjaja, F.E. Soetaredjo,
S. Ismadji, A.W. Go, P.L. Tran-Nguyen, A. Kurniawan, Y.-H. Ju, Saponin-
intercalated organoclays for adsorptive removal of β-carotene: Equilibrium,
reusability, and phytotoxicity assessment, J. Taiwan Inst. Chem. Eng. 117 (2020)
198–208.
[47] Q. Liu, L.-B. Zhong, Q.-B. Zhao, C. Frear, Y.-M. Zheng, Synthesis of Fe3O4/
polyacrylonitrile composite electrospun nanofiber mat for effective adsorption of
tetracycline, ACS Appl. Mater. Interfaces 7 (2015) 14573–14583.
[48] A. Steudel, L.F. Batenburg, H.R. Fischer, P.G. Weidler, K. Emmerich, Alteration of
swelling clay minerals by acid activation, Appl. Clay Sci. 44 (2009) 105–115.
[49] W. Yu, P. Wang, C. Zhou, H. Zhao, D. Tong, H. Zhang, H. Yang, S. Ji, H. Wang,
Acid-activated and WOx-loaded montmorrilonite catalysts and their catalytic
behaviors in glycerol dehydration, Chin. J. Catal. 38 (2017) 1087–1100.
[50] G. Lawrie, I. Keen, B. Drew, A. Chandler-Temple, L. Rintoul, P. Fredericks,
L. Grøndahl, Interactions between alginate and chitosan biopolymers
characterized using FTIR and XPS, Biomacromolecules 8 (2007) 2533–2541.
[51] S.K. Papageorgiou, E.P. Kouvelos, E.P. Favvas, A.A. Sapalidis, G.E. Romanos, F.
K. Katsaros, Metal− carboxylate interactions in metal− alginate complexes studied
with FTIR spectroscopy, Carbohydr. Res. 345 (2010) 469–473.
[52] A. Heydari, H. Sheibani, Fabrication of poly(β-cyclodextrin-co-citric acid)/
bentonite clay nanocomposite hydrogel: thermal and absorption properties, RSC
Adv. 5 (2015) 82438–82449.
[53] G. Al, G. Güçlü, T.B. Iyim, S. Emik, S. Özgümüş, Synthesis and properties of
starch-graft-acrylic acid/Na-montmorrilonite superabsorbent nanocomposite
hydrogels, J. Appl. Polym. Sci. 109 (2008) 16–22.
[54] D.R. Robello, N. Yamaguchi, T. Blanton, C. Barnes, Spontaneous formation of an
exfoliated polystyrene− clay nanocomposite using a star-shaped polymer, J. Am.
Chem. Soc. 126 (2004) 8118–8119.
[55] W.R. Mariott, E.-Y.-X. Chen, Stereochemically controlled PMMA-exfoliated
silicate nanocomposites using intergallery-anchored metallocenium cations,
J. Am. Chem. Soc. 125 (2003) 15726–15727.
[56] N.H. Tran, M.A. Wilson, A.S. Milev, G.R. Dennis, A.L. McCutcheon, G.S.
K. Kannangara, R.N. Lamb, Structural− chemical evolution within exfoliated
clays, Langmuir 22 (2006) 6696–6700.
[57] L. Li, Y. Fang, R. Vreeker, I. Appelqvist, E. Mendes, Reexamining the egg-box
model in calcium–alginate gels with X-ray diffraction, Biomacromolecules 8
(2007) 464–468.
[58] M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso,
J. Rouquerol, K.S.W. Sing, Physisorption of gases, with special reference to the
evaluation of surface area and pore size distribution, Pure Appl. Chem. 87 (2015)
1051–1069.
[59] J.L. Gunjakar, T.W. Kim, H.N. Kim, I.Y. Kim, S.-J. Hwang, Mesoporous layer-by-
layer ordered nanohybrids of layered double hydroxide and layered metal oxide:
Highly active visible light photocatalysts with improved chemical stability, J. Am.
Chem. Soc. 133 (2011) 14998–15007.
[60] J. Seo, X. Jin, M. Kim, I.Y. Kim, Y.K. Jo, S. Bera, N.-S. Lee, W.I. Lee, H. Kim, S.-
J. Hwang, Exfoliated metal oxide nanosheets as effective and applicable
substrates for atomically dispersed metal nanoparticles with tailorable
functionalities, Adv. Mater. Interf. 3 (2016) 1600661.
[61] Y.H. Tan, J.A. Davis, K. Fujikawa, N.V. Ganesh, A.V. Demchenko, K.J. Stine,
Surface area and pore size characteristics of nanoporous gold subjected to
thermal, mechanical, or surface modification studied using gas adsorption
S.P. Santoso et al.
isotherms, cyclic voltammetry, thermogravimetric analysis, and scanning
electron microscopy, J. Mater. Chem. 22 (2012) 6733–6745.
[62] S.-F. Lim, Y.-M. Zheng, S.-W. Zou, J.P. Chen, Characterization of copper
adsorption onto an alginate encapsulated magnetic sorbent by a combined FT-IR,
XPS, and mathematical modeling study, Environ. Sci. Technol. 42 (2008)
2551–2556.
[63] E.S. Dragan, D.F.A. Loghin, A.I. Cocarta, Efficient sorption of Cu2+ by composite
chelating sorbents based on potato starch-graft-polyamidoxime embedded in
chitosan beads, ACS Appl. Mater. Interfaces 6 (2014) 16577–16592.
[64] H. Luo, Y. Liu, H. Lu, Q. Fang, H. Rong, Efficient adsorption of tetracycline from
aqueous solutions by modified alginate beads after removal of Cu(II) ions, ACS
Omega 6 (2021) 6240–6251.
[65] Y. Li, B. Xia, Q. Zhao, F. Liu, P. Zhang, Q. Du, D. Wang, D. Li, Z. Wang, Y. Xia,
Removal of copper ions from aqueous solution by calcium alginate immobilized
kaolin, J. Environ. Sci. 23 (2011) 404–411.
[66] C.M. Futalan, C.-C. Kan, M.L. Dalida, K.-J. Hsien, C. Pascua, M.-W. Wan,
Comparative and competitive adsorption of copper, lead, and nickel using
chitosan immobilized on bentonite, Carbohydr. Polym. 83 (2011) 528–536.
[67] V. Manu, H.M. Mody, H.C. Bajaj, R.V. Jasra, Adsorption of Cu2+ on amino
functionalized silica gel with different loading, Ind. Eng. Chem. Res. 48 (2009)
8954–8960.
[68] D.-W. Cho, B.-H. Jeon, C.-M. Chon, Y. Kim, F.W. Schwartz, E.-S. Lee, H. Song,
A novel chitosan/clay/magnetite composite for adsorption of Cu(II) and As(V),
Chem. Eng. J. 200–202 (2012) 654–662.
[69] W. Jiang, W. Wang, B. Pan, Q. Zhang, W. Zhang, L. Lv, Facile fabrication of
magnetic chitosan beads of fast kinetics and high capacity for copper removal,
ACS Appl. Mater. Interfaces 6 (2014) 3421–3426.
[70] B. Kannamba, K.L. Reddy, B.V. AppaRao, Removal of Cu(II) from aqueous
solutions using chemically modified chitosan, J. Hazard. Mater. 175 (2010)
939–948.
[71] L.-Y. Wang, M.-J. Wang, Removal of heavy metal ions by poly(vinyl alcohol) and
carboxymethyl cellulose composite hydrogels prepared by a freeze− thaw
method, ACS Sustainable Chem. Eng. 175 (2010) 939–948.
[72] F.-M. Pellera, A. Giannis, D. Kalderis, K. Anastasiadou, R. Stegmann, J.-Y. Wang,
E. Gidarakos, Adsorption of Cu(II) ions from aqueous solutions on biochars
prepared from agricultural by-products, J. Environ. Manage. 96 (2012) 35–42.
[73] T.S. Mthombo, A.K. Mishra, S.B. Mishra, B.B. Mamba, The adsorption behavior of
Cu(II), Pb(II), and Co(II) of ethylene vinyl acetate-clinoptilolite nanocomposites,
J. Appl. Polym. Sci. 121 (2011) 3414–3424.
[74] S. Biniak, M. Pakula, G.S. Szymański, A. Świątkowski, Effect of activated carbon
surface oxygen- and/or nitrogen-containing groups on adsorption of copper(II)
ions from aqueous solution, Langmuir 15 (1999) 6117–6122.
[75] A. Haug, Dissociation of alginic acid, Acta Chem. Scand. 15 (1961) 950–952.
[76] Y. Lu, J.D. Miller, Carboxyl stretching vibrations of spontaneously adsorbed and
LB-transferred calcium carboxylates as determined by FTIR internal reflection
spectroscopy, J. Colloid Interface Sci. 256 (2002) 41–52.
[77] C. Tournassat, J.A. Davis, C. Chiaberge, S. Grangeon, I.C. Bourg, Modeling the
acid− base properties of montmorillonite edge surfaces, Environ. Sci. Technol. 50
(2016) 13436–13445.
[78] C.F. Baes Jr., R.E. Mesmer, The Hydrolysis of Cations, John Wiley & Sons, New
York, 1976.
[79] B.M. Weckhuysen, I.E. Wachs, R.A. Schoonheydt, Surface chemistry and
spectroscopy of chromium in inorganic oxides, Chem. Rev. 96 (1996) 3327–3349.
[80] E.M. Pecini, M.J. Avena, Measuring the isoelectric point of the edges of clay
mineral particles: The case of montmorillonite, Langmuir 29 (2013)
14926–14934.
[81] R. Aravindhan, B. Madhan, J.R. Rao, B.U. Nair, T. Ramasami, Bioaccumulation of
chromium from tannery wastewater: An approach for chrome recovery and reuse,
Environ. Sci. Technol. 38 (2004) 300–306.
[82] P. Luo, J.-S. Zhang, B. Zhang, J.-H. Wang, Y.-F. Zhao, J.-D. Liu, Preparation and
characterization of silane coupling agent modified halloysite for Cr(VI) removal,
Ind. Eng. Chem. Res. 50 (2011) 10246–10252.
15
Chemical Engineering Journal 452 (2023) 139261
[83] X. Huang, G. Dognani, P. Hadi, M. Yang, A.E. Job, B.S. Hsiao, Cationic dialdehyde
nanocellulose from sugarcane bagasse for efficient chromium(VI) removal, ACS
Sustainable Chem. Eng. 8 (2020) 4734–4744.
[84] X. Guo, A. Liu, J. Lu, X. Niu, M. Jiang, Y. Ma, X. Liu, M. Li, Adsorption mechanism
of hexavalent chromium on biochar: Kinetic, thermodynamic, and
characterization studies, ACS Omega 5 (2020) 27323–27331.
[85] R. Karthik, S. Meenakshi, Removal of hexavalent chromium ions using
polyaniline/silica gel composite, J. Water Process Eng. 1 (2014) 37–45.
[86] S. Rapti, A. Pournara, D. Sarma, I.T. Papadas, G.S. Armatas, A.C. Tsipis,
T. Lazarides, M.G. Kanatzidis, M.J. Manos, Selective capture of hexavalent
chromium from an anion-exchange column of metal organic resin− alginic acid
composite, Chem. Sci. 7 (2016) 2427–2436.
[87] N. Khandelwal, N. Singh, E. Tiwari, G.K. Darbha, Novel synthesis of a clay
supported amorphous aluminum nanocomposite and its application in removal of
hexavalent chromium from aqueous solutions, RSC Adv. 9 (2019) 11160–11169.
[88] A. Kumar, S. Prasad, P.N. Saxena, N.G. Ansari, D.K. Patel, Synthesis of an
alginate-based Fe3O4− MnO2 xerogel and its application for the concurrent
elimination of Cr(VI) and Cd(II) from aqueous solution, ACS Omega 6 (2021)
3931–3945.
[89] M.C. Qhubu, L.G. Mgidlana, L.M. Madikizela, V.E. Pakade, Preparation,
characterization and application of activated clay biochar composite for removal
of Cr(VI) in water: Isotherms, kinetics and thermodynamics, Mater. Chem. Phys.
260 (2021), 124165.
[90] A.S.K. Kumar, S. Kalidhasan, V. Rajesh, N. Rajesh, Application of cellulose-clay
composite biosorbent toward the effective adsorption and removal of chromium
from industrial wastewater, Ind. Eng. Chem. Res. 51 (2012) 58–69.
[91] A.-E.-A. Sallam, M.S. Al-Zahrani, M.I. Al-Wabel, A.S. Al-Farraj, A.R.A. Usman,
Removal of Cr(VI) and toxic ions from aqueous solutions and tannery wastewater
using polymer-clay composites, Sustainability 2017 (1993) 9.
[92] C. Jung, J. Heo, J. Han, N. Her, S.-J. Lee, J. Oh, J. Ryu, Y. Yoon, Hexavalent
chromium removal by various adsorbents: Powdered activated carbon, chitosan,
and single/multi-walled carbon nanotubes, Sep. Purif. Technol. 106 (2013)
63–71.
[93] R.G. Pearson, Hard and soft acids and bases, J. Am. Chem. Soc. 85 (1963)
3533–3539.
[94] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and
platinum, J. Am. Chem. Soc. 40 (1918) 1361–1403.
[95] H. Freundlich, Over the adsorption in solution, J. Phys. Chem. 57 (1906)
385–470.
[96] G.G. Stavropoulos, A.A. Zabaniotou, Minimizing activated carbons production
cost, Fuel Process. Technol. 90 (2009) 952–957.
[97] T.W. Weber, R.K. Chakravorti, Pore and solid diffusion models for fixed-bed
adsorbers, AIChE J. 20 (1974) 228–238.
[98] W. Plazinski, W. Rudzinski, A. Plazinska, Theoretical models of sorption kinetics
including a surface reaction mechanism: A review, Adv. Colloid Interface Sci. 152
(2009) 2–13.
[99] F.-C. Wu, R.-L. Tseng, R.-S. Juang, Characteristics of Elovich equation used for the
analysis of adsorption kinetics in dye-chitosan systems, Chem. Eng. J. 150 (2009)
366–373.
[100] Q. Zhu, G.D. Moggridge, C. D’Agostino, Adsorption of pyridine from aqueous
solutions by polymeric adsorbents MN 200 and MN 500. Part 2: Kinetics and
diffusion analysis, Chem. Eng. J. 306 (2016) 1223–1233.
[101] I.T. Norton, W.J. Frith, S. Ablett, Fluid gels, mixed fluid gels and satiety, Food
Hydrocolloids 20 (2006) 229–239.
[102] M. Urbanova, M. Pavelkova, J. Czernek, K. Kubova, J. Vyslouzil, A. Pechova,
D. Molinkova, J. Vyslouzil, D. Vetchy, J. Brus, Interaction pathways and
structure− chemical transformations of alginate gels in physiological
environments, Biomacromolecules 20 (2019) 4158–4170.
[103] S. Barnie, J. Zhang, H. Wang, H. Yin, H. Chen, The influence of pH, co-existing
ions, ionic strength, and temperature on the adsorption and reduction of
hexavalent chromium by undissolved humic acid, Chemosphere 212 (2018)
209–218.