Carbohydrate Polymers 234 (2020) 115890

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Adsorption of copper ions onto chitosan/poly(vinyl alcohol) beads T

functionalized with poly(ethylene glycol)
Dimitrios G. Trikkaliotis, Achilleas K. Christoforidis, Athanasios C. Mitropoulos, George Z. Kyzas*
Department of Chemistry, International Hellenic University, Kavala, Greece

A R T I C LE I N FO A B S T R A C T

Keywords: A novel adsorbent material composed of chitosan (Cs), polyvinyl alcohol (PVA) and polyethylene glycol (PEG)
Chitosan was prepared in hydrogel bead form to efficiently remove copper ions from aqueous solutions. The properties of
Poly(vinyl alcohol) the composite were characterized by scanning electronic microscopy (SEM), X-ray diffraction (XRD), energy
Poly(ethylene glycol) dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM) and Fourier transform infrared spectro-
Adsorption
scopy (FTIR). The adsorption behavior of Cu(II) onto Cs/PVA/PEG beads was studied as a function of solution
Copper ions
EDS
pH, temperature and contact time. The maximum adsorption was observed equal to 99.99 % for initial copper
XRD ion concentration of 25 mg/L at pH 5, temperature 45 °C, 5 h as contact time and 1 g/L of adsorbent dose.
FTIR Langmuir isotherm and pseudo-second kinetic model fitted the experimental data sufficiently. Thermodynamic
studies indicated that the process was spontaneous and endothermic. Cs/PVA/PEG beads can act as an effective
adsorbent for the removal of Cu(II) from aqueous solution.

1. Introduction
A major public and environmental issue is the presence of heavy
metals (Cu, Ni, Zn, Pb, Cr, Cd, Co, As, Fe) in industrial effluents
(Altinisik & Yurdakoc, 2015; Anitha, Kumar, & Kumar, 2014). Toxicity,
non-biodegradation, bioaccumulation, biotransportation, carcinogen-
esis and quick spread to large area due to high mobility are the main
characteristics of heavy metals (Behbahani et al., 2014; Chen, Zhou,
Zhang, You, & Xu, 2016; Musico, Santos, Dalida, & Rodrigues, 2013; Yu,
Zhuang, Song, & Wang, 2015; Zarghami, Mohammadi, &
Kazemimoghadam, 2015). Manufacturing industries such as metal
plating, batteries, textiles, dyes, alloys and mining operations are the
common heavy metal sources. Copper, an essential nutrient in trace
amounts, is related with brain, liver, respiratory and nervous system
diseases especially for children (Duru, Ege, & Kamali, 2016; Ngah,
Kamari, & Koay, 2004; Yi et al., 2018). The maximum industrial ef-
fluent discharge for copper is 1.3 mg/L, while the concentration for
drinking water must be less than 2 mg/L (Al-Saydeh, Naas, & Zaidi,
2017; El-Araby, Ibrahim, Mangood, & Rahman, 2017).
Indicative conventional methods for the removal of heavy metal
ions from polluted water are ion exchange, nanomaterials applications
(Mir, Salavati-Niasari, & Davar, 2012; Safardoust-Hojaghan & Salavati-
Niasari, 2017; Zinatloo-Ajabshir & Salavati-Niasari, 2015), membrane
filtration, reverse osmosis, flotation, sedimentation and adsorption
where the latter is preferred due to simplicity, effectiveness, fast re-
sponse, no secondary pollutants such as toxic sludge, and lower costs in
the whole process of preparation (Lu, Wu, Li, Liu, & Wang, 2014; Tan,
Hu, & Bi, 2016). Generally speaking, adsorption is the physicochemical
process that involves the collection of soluble substances in liquid phase
to a suitable interface; therefore, development of novel and effective
adsorbents has been emerged as hotspot in wastewater treatment (Al-
Saydeh et al., 2017; Kyzas, Deliyanni, & Matis, 2013). Fast adsorption
and high capacity, derived from high specific surface area and plethora
of adsorption sites, are the main challenges for an efficient adsorbent
(Li et al., 2013; Perez, Nadres, Nguyen, Dalida, & Rodrigues, 2017; Tan
et al., 2015). Materials science, chemistry, environmental science and
nanotechnology have assisted in producing various novel adsorbents.
Traditional adsorbents include silica, resins, activated carbon and
zeolites but either the low adsorption capacity or the expensiveness is
their main disadvantage (Dorabei, Ferdowsi, Barzin, & Tadjarodi, 2016;
Sherlala, Raman, Bello, & Asghar, 2018; Yang, Yang, & Huang, 2017).
A recent trend for accumulation and removal of precious and heavy
metals from solutions is the use of adsorbents of biological origin
functionalized with biodegradable polymers. Hydrogels are three-di-
mensional cross-linked polymers that can swell but do not dissolve in
aqueous media (Dai, Huang, & Huang, 2018; Jin & Bai, 2002;
Mahdavinia, Soleymani, Etemadi, Sabzi, & Atlasi, 2018). Polymer
blends have enhanced properties than their individual components

⁎
Corresponding author.
E-mail address: kyzas@chem.ihu.gr (G.Z. Kyzas).

https://doi.org/10.1016/j.carbpol.2020.115890
Received 30 September 2019; Received in revised form 11 January 2020; Accepted 16 January 2020
Available online 18 January 2020
0144-8617/ © 2020 Elsevier Ltd. All rights reserved.
D.G. Trikkaliotis, et al.
(synergistic effect) possessing advantages such as low(er) cost, en-
hanced mechanical and chemical properties, improved porosity and
high(er) efficiency of metal ion removal (Anitha et al., 2014; Ngah
et al., 2004).
Chitosan (Cs) ((C6H11NO4)n) is the derivative of N-deacetylation of
chitin ((C8H13NO5)n) which is present in the shells of the crustaceans.
This positively charged natural linear polysaccharide gained im-
portance in environmental biotechnology due to non-toxicity, bio-
compatibility, biodegradability and possession of (i) amino-acetamido
groups, (ii) primary hydroxyl groups, and (iii) secondary hydroxyl
groups located at C-2, C-3 and C-6 positions, respectively, which are
suitable for adsorption applications (Kasaai, Arul, & Charlet, 2000;
Kyzas, Deliyanni et al., 2013; Rupiasih, Sumadiyasa, Suyanto, &
Windary, 2017; Salehi, Bakhtiari, & Askari, 2016; Terzopoulou, Kyzas,
& Bikiaris, 2015). On the other hand, chitosan swells and disintegrates
in acidic media due to the protonation of amino-groups, therefore its
cross-linking is inevitable (Filipkowska, Zadrozna, Jozwiak, Szymczyk,
& Nierobisz, 2016; Fu et al., 2012; Kyzas, Travlou, & Deliyanni, 2013).
Chitosan is considered to be an excellent metal-ligand binding agent
and can easily form stable complexes with many metal ions due to (i) its
abundancy of hydroxyl (−OH) and amino (-NH2) groups on its chain
backbone (Wu, Cheng, Li, & Yang, 2019), and the general hydro-
philicity and metal location of the polymer functional groups and their
concerted chelating binding action that can be directed at the metal
cations (Ren et al., 2019).
Poly(vinyl alcohol) (PVA) ((C2H4O)n), a derivative of polyvinyl
acetate, is a low-price, non-toxic, water-soluble, semi-crystalline syn-
thetic polymer with a massive number of hydroxyl groups suitable for
reactions with many type of functional groups. Also, when PVA is fully
hydrolyzed, the whole composite is non-ionic (Jang & Lee, 2016; Puyol
et al., 2015). So, blending PVA with chitosan increases the number of
−OH groups on the chitosan chain.
Poly(ethylene glycol) (PEG) (H(OCH2CH2)nOH) is a cost-effective
non-ionic synthetic polymer which enhances the composite’s dis-
persivity and pore capacity. This organic porogen generates macro-
porous networks when blended with chitosan by selective dissolution
from the polymeric matrix into the solution. The porous and coarse
structure of an adsorbent increases its active surface area and promotes
the diffusion of the adsorbate into the hydrogels (Gupta et al., 2015;
Mahdavinia et al., 2018; Zhang, Servos, & Liu, 2012).
In this study, a Cs/PVA/PEG blend in bead form was used as novel
adsorbent for Cu(II) ions removal from aqueous solutions. The selection
of copper ions as model pollutant in the present work (to initially set a
basis of research of heavy metals ions removal by the produced mate-
rial) is based on the fact that Cu2+ can be found in high concentrations
because it is usually used in many industrial sectors like metal finishing,
electroplating, plastics, and etching. It is recognized as one of the most
widespread heavy metal contaminants in the environment. Water
contaminated with copper must be treated before being discharged into
the environment because of its toxic properties, even at low con-
centrations. The influence of pH, temperature, contact time and initial
copper ion concentration were studied. Adsorption data were fitted by
Langmuir, Freundlich, Langmuir-Freunldich, Temkin, Redlich, and
Dubinin-Radushkevic isotherm models. Pseudo-1st, pseudo-2nd order
and intra-particle diffusion model were applied to analyze the adsorp-
tion kinetic mechanism of Cu(II) onto the beads. Thermodynamic
parameters were also calculated, estimating the important parameters
of free energy, enthalpy, and entropy change. The composite’s mor-
phology and properties were evaluated by SEM, XRD, EDS, AFM and
FTIR characterization techniques.
2. Materials and methods
2.1. Materials
The reagents were used as received. Chitosan (abbreviated hereafter
2
Carbohydrate Polymers 234 (2020) 115890
as Cs, 310−375 kDa, DDA > 75 %), poly(vinyl alcohol) (denoted as
PVA, MW 13000–23000, 87-89 % hydrolyzed), poly(ethylene glycol)
(abbreviated as PEG, MW 2050), glutaraldehyde (abbreviated as GLA,
50 % in H2O) and sodium tripolyphosphate (abbreviated as TPP, 98 %)
were purchased from Sigma-Aldrich.
2.2. Synthesis of adsorbent
Chitosan as polymeric matrix presents some potentially limiting
disadvantages regarding its structural properties. The solubility beha-
vior of chitosan causes some problems, because can only be dissolved in
few diluted acids due to intra- and inter-molecular bonding interactions
(i.e. hydrogen bonds). Also, the relatively weak mechanical strength
and (weak, too) 3D-structural stability of solute CS in a number of
solvents limits its applicability. But, against this background, the gen-
eral groups of these modified macrocyclic materials are cyclodextrins,
glutaraldehydes, maleic anhydrides, caprolactones and polylactides
(Ren et al., 2019).
The Cs/PVA/PEG blend (1:1:1) was stirred at 50 °C to form homo-
genous solution. Although the physical H-bonding in Cs/PVA blends
results to network with thermal stability and reduced solubility in
acidic solutions, suitable cross-linking leads to highly insoluble com-
posites (Abdeen, Mohammad, & Mahmoud, 2015; Casey & Wilson,
2015; Li et al., 2015; Zarghami, Tofighy, & Mohammadi, 2014). GLA
and TPP were the cross-linking agents and their concentrations were
selected in relation to Cs amino groups (Filipkowska et al., 2016). The
aim is to prepare a material that presented high adsorption capacity,
which means to have free functional groups (able to bind the copper
ions) as well as high durability which means it has to be strongly cross-
linked with reagents (i.e. GLA and TPP) so as to render the extreme
conditions of effluents. The latter means that the addition of GLA will
immediately bind the free functional groups of chitosan. So, it was
mandatory to find a balance (optimum ratio) between the added
quantity of cross-linker over the whole quantity of the final material.
This was the reason that the we followed the suggestion of Filipkowska
et al. (Filipkowska et al., 2016) for the bare minimum amount of GLA
and TPP as the degree of deacetylation is in close proximity. So, chit-
osan cross-linked with a homobifunctional aldehyde (GLA) is described
by a simplified imine formation with primary amines originating from
chitosan. Considering this mechanism, the theoretical stoichiometric
ratio for a complete conversion would be 0.5 mol GLA per 1.0 mol of
primary amine. The amount of primary amines is calculated (Eq. (1)) by
using the degree of deacetylation (DD), and the molecular weight of
glucosamine is used as the structural repeating unit (SRU) (Riegger,
Baurer, Mirzayeva, Tovar, & Bach, 2018).
m DD
n(primary amine) = ⎛ CS ⎞⋅
⎜ ⎟
⎝ mSRU ⎠ 100 (1)
Then, the mixture was added dropwise to double-distilled water and
left for 24 h in gentle stirring at room temperature. The hydrogel beads
were washed with deionized water several times till the removal of the
residual reagents and dried at 40 °C. Evaporation of the solvent turns
the bead’s white color to yellow (Supporting information, Fig. SI1). The
latter can be explained taking onto consideration that as the water
content decreases during drying process, the water molecules are less
and finally the color becomes more intense. Generally, the color change
is a poly-parametric condition. A broad variety of reactions products
are formed. The results of several studies show that it is likely for GLA
molecules not only to react exclusively with the primary amines ori-
ginated from chitosan, but also with itself. The characteristic orange/
red/brown color of GLA-chitosans is attributed to the complex pro-
cesses during the reaction of GLA with primary amines, leading to its
oligomerization, rearrangements, and/or its cyclization, resulting to
irregular products (i.e. aromatic/heterocyclic structures) (Riegger et al.,
2018). Another possible factor for this color change is presence of
D.G. Trikkaliotis, et al.
unsaturated imines or enol products (Nematidil, Sadeghi, Nezami, &
Sadeghi, 2019).
A special discussion can be done for the reason of selecting at least
two different cross-linking agents. Chitosan presents high swelling de-
gree in aqueous solutions. Especially in a powdered form, swells con-
siderably and crumble easily, thus not behaving ideally in packed-
column configurations common to pump-and-treat adsorption pro-
cesses, usually leading to plugging of the column. For pure chitosan
swelling degrees as high as 2000 % have been reported (Goycoolea
et al., 2007). In order to overcome this problem chitosan could be cross-
linked either covalently, by glutaraldehyde (GLA) (Rinaudo, 2008) or
ionically, by a polyanion such as tripolyphosphate (TPP) (Janes, Calvo,
& Alonso, 2001). In the first case, a solid matrix is produced which
should be ground to generate chitosan particles, but still presenting
high swelling degree e.g higher than 600 %, especially in an acidic
environment (Yao, Peng, Feng, & He, 1994). In the second case, micro-
or nanoparticles can be formed but with reduced stability in acidic
environment, despite their low swelling degree as low as 50 % (Lee, Mi,
Shen, & Shyu, 2001). In order to produce directly chitosan micro-
spheres several methods have been developed by employing glutar-
aldehyde, formaldehyde or genipin (Sinha et al., 2004). However, in
these methods chitosan microspheres are prepared mainly through w/o
emulsion procedure, which is complicated since liquid paraffin and
surfactants should be added (Jameela & Jayakrishnan, 1995). Another
way to produce directly chitosan microspheres is by dual cross-linking
with TPP and GLA (Durkut, Elçin, & Elçin, 2006; Wang et al., 2006). In
this case microspheres are formed in two stages by adding in the first
stage TPP and in the second GLA.
2.3. Characterization techniques
As a standard routine, any newly synthesized composite requires
characterization in order to confirm its successful production. The
morphology of the hydrogel beads was characterized using a JEOL
JSM6390LV scanning electron microscope (SEM). Prior to analysis, the
dried beads were coated with a thin layer of gold using a Quorum 150 T
ES sputter coater to ensure the samples’ surface conductivity, to prevent
electrostatic charging, and to protect them from the energy beam of the
instrument (Gu, Yang, Hu, Hu, & Wang, 2015; Perez et al., 2017).
Characterization of the topography performed with a BRUKER Innova
atomic force microscope (AFM). Crystallinity was detected by a
BRUKER D8 FOCUS X-ray diffractometer (XRD) equipped with a CuKα
radiation (λ = 0.154 nm) under normal laboratory conditions, and the
elemental analysis (EDS) was determined by a BRUKER-AXS XFlash
detector attached to the SEM. The surface chemistry and bonding in-
teractions of the adsorbent as well as the chitosan’s degree of deace-
tylation (DDA) were evaluated by a Perkin-Elmer Frontier attenuated
total reflectance Fourier transform infrared spectrometer (ATR-FTIR,
ZnSe) at a nominal resolution of 2 cm−1. A Hitachi U-2900 UV–vis
spectrophotometer was used to evaluate the equilibrium concentration
of Cu(II).
2.4. Adsorption studies
A stock solution of Cu(II) ions (1 g/L) was prepared by dissolving
3.66 g Cu(NO3)2·2.5H2O(Sigma-Aldrich) in 1-L double distilled water.
The desired concentrations of working solutions prepared by serial di-
lution, and the pH adjusted to the required value with HCl and NaOH
ranged from 1 to 0.01 mol/L. The experiments were conducted into a
temperature-controlled shaking water bath (GFL 1083, Germany) at
125 rpm into 50 mL beakers. 9 mL of suspension were collected and
1 mL NH3 was added for the UV–vis analysis of the residual copper
concentration at λmax=612 nm (Supporting information, Fig. SI2). The
divalent copper cation, Cu2+, forms a coordinate covalent complex
with ammonia, as: Cu(NH3)42+. This complex species absorbs strongly
in the visible region of the EMR spectrum from 550−650 nm. The
3
Carbohydrate Polymers 234 (2020) 115890
wavelength of maximum absorption lies between 600−620 nm, nom-
inally at 610 nm. However, the strongly absorbing species is formed
only in an excess of the complexing agent, NH3. If an excess of am-
monia is not present in the solution, non-absorbing complexes may be
formed instead of the tetraamminecopper(II) species, and the Beer’s
Law relationships will not be observed. Each experiment was carried
out in triplicate and the means of the data were used for results and
discussion. The amount of the adsorbed metal ion at equilibrium and
the removal (%) were calculated using the following equations (Eqs.
(2),(3)):
V
Qe = (C0 − Ce ) ⎛ ⎞
⎝m⎠ (2)
C − Ce ⎞
R(%) = ⎛ 0
⎜ ⋅100%
⎟
⎝ C0 ⎠ (3)
where qe (mg/g) is the adsorbent’s capacity, V (L) is the solution vo-
lume, m (g) is the mass of the adsorbent, C0 and Ce (mg/L) are the
initial and equilibrium concentration of metal ions.
3. Results and discussion
3.1. Characterizations
3.1.1. SEM
The beads’ diameter was found ∼665 μm (Fig. 1a) and a rough
morphology with striated and shrunk surface was observed (Salehi
et al., 2013; Vatanpour, Salehi, Sahebjamee, & Ashrafi, 2020) (Fig. 1b).
The thickness of the surface was ∼20 μm (Fig. 1c,d). The characteristic
squamous structure of Cs was visible as well as the plenty black holes,
which are related to PVA and PEG macroporous effect (Supporting in-
formation, Fig. SI3a). The mazy internal porosity (Supporting in-
formation, Fig. SI3b) was penetrated by large pores with irregular
density and size (Supporting information, Fig. SI2c). The beads retain
the morphological characteristics after the Cu(II) adsorption, but pre-
sent a decrease in diameter ∼3.6 % and cracking (Supporting in-
formation, Fig. SI3d), which may be attributed to the adsorption con-
ditions (pH, agitation, temperature).
3.1.2. EDX
EDS, which covers a depth range of several microns below the
surface (Chen et al., 2017), provided evidence of the presence of cer-
tain/fundamental elements of Cs/PVA/PEG beads as well as of the
adsorbed copper (Fig. 2). Moreover, mapping the surface and the nu-
cleus of the beads indicated the homogenous ion adsorption due to the
porosity (Supporting information, Fig. SI4).
3.1.3. AFM
The effective external surface area is directly associated to rough-
ness, resulting to higher adsorption rate and capacity (Koushkbaghi
et al., 2018; Salehi et al., 2013). Although the roughness of the external
surface was an obstacle for AFM measurements due to the combined
topography of Cs and PVA (Chibowski, Paszkiewicz, & Wisniewska,
2002; Wiśniewska, Chibowski, & Urban, 2011), the internals of the
beads provided useful information before and after the Cu(II) adsorp-
tion (Fig. 3). The roughness before the adsorption was Ra = 39 nm
while after the adsorption was Ra = 65 nm. A large pore with width
∼2.68 μm was also identified, in well agreement with SEM (Supporting
information, Fig. SI2c).
3.1.4. XRD
The XRD patterns of Cs, PVA and PEG are presented to Figs. SI5-SI7
(Supporting information), respectively. The XRD diffractograms of the
hydrogel beads (cross-linked polymers) before and after the adsorption
of copper ions are presented to Fig. 4. The intermolecular hydrogen
bonding between −OH of PVA and PEG and −OH or NH2 of Cs result
D.G. Trikkaliotis, et al.
Fig. 1. Morphology of Cs/PVA/PEG beads; (a) overview and diameter, (b) external and internal morphology, (c) surface thickness.
to low crystallinity (20.5 %), while the crystallinity enhancement (22
%) after the Cu(II) adsorption indicates the adsorptive behavior of the
composite and the less crystal plane distance (Feng et al., 2013; Habiba,
Islam, Siddique, Afifi, & Ang, 2016; Rajeswari, Amalraj, & Pius, 2016;
Zhao et al., 2019). The peak at 2θ = 12° can be related with Cs (re-
maining chitin) and its strong hydrogen bonding between hydroxyl and
amino-groups, and the amorphous diffraction peaks in the 19–25 region
are indicative of the reduction of semi-crystalline sections in Cs-PVA-
PEG blends. Moreover, the broad peaks in the 39–49 region could be
related with PVA-PEG crystallinity reduction (Anitha et al., 2014; Kolhe
& Kannan, 2003; Kyzas, Bikiaris, & Deliyanni, 2014; Liu et al., 2014;
Mahdavinia et al., 2018).
3.1.5. FTIR
Changes in molecular vibrations such as bond breaking-and-making
were investigated with infrared spectroscopy. The initial beam at-
tenuates due to absorption from the sample, and a transmission spec-
trum is recorded. The deacetylated chitin (Cs) was subjected to infrared
spectroscopy to define the degree of deacetylation (DDA). DDA in-
dicates the extend of transformation of N-acetyl-D-glucosamine to D-
glucosamine units. The degradation rate of Cs decreases as the DDA
increases. Absorbance ratios of various spectral bands have been used
for the DDA calculation. The band ratio of amide group A1652 to hy-
droxyl group A3355 was selected for the calculation, where A is the
absolute height of the absorption band at air atmosphere. This ratio
tends to zero for a completely deacetylated Cs (Biskup, Jarosinska,
Rokita, Ulanski, & Rosiak, 2012; Habiba, Afifi, Salleh, & Ang, 2017;
Heidari et al., 2018; Mojet, Ebbesen, & Lefferts, 2010; Sabnis & Block,
1997; Zawadzki & Kaczmarek, 2010). The DDA of Cs was calculated
∼79.44 %.
FTIR analysis of Cs, PVA, PEG, Cs/PVA/PEG blend and of the cross-
linked beads is presented to Figs. SI8-SI12 (Supporting information),
respectively. At first, it is mandatory to mention about the way of
binding PVA to Cs backbone. The addition of PVA to Cs results to the
4
Carbohydrate Polymers 234 (2020) 115890
increase of the hydroxyl groups and the −OH band shift from 3221 to
3268 cm−1. Also, there is increase of −CH groups (2923, 1248 and
838 cm−1) and appearance of the carbonyl groups at 1735 cm−1. So,
the bonding mechanism mainly involves the hydroxyl groups of PVA
and the hydroxyl (majorly) and also amino groups of Cs as the char-
acteristic NeH band at 1535 cm−1 reduces and shifts to 1550 cm−1.
Then after PEG functionalization to the prepared Cs/PVA composite,
the presence of PEG to the composite is underlined by the CeC char-
acteristic peak at 842 cm−1 and the CeH wagging band at 1341 cm−1.
The bonding mechanism (Cs/PVA with PEG) mainly involves the end-
chain hydroxyl groups of PEG and the NeH groups of Cs/PVA which
reduce and shift from 3269 to 3263 cm−1.
The beads before and after the Cu2+ adsorption were assessed
(Fig. 5b). Spectra comparison of the composites before and after copper
ions adsortpion revealed the active sites. The major variations were
observed to hydroxyl bands (centered to 3249 cm−1), CeH stretching
groups (2943 cm−1 and 2880 cm−1), C]O bands (1724 cm−1), CH2
scissoring vibrations (1431 cm−1), CeH stretch from –NHCOCH3 group
and –C–N (1377 and 1320 cm−1), CeH wagging and P]O stretching
vibrations (1227 cm−1), and CH2 rocking vibrations (891 cm−1). The
band at 892 cm−1 belongs to β-glycosidic linkage between the sugar
units (Bao et al., 2019). Minor variations were noticed at C]O of pri-
mary amino (1635 cm−1), NeH bending of amide II (1536 cm−1), CeO
stretching modes (1155 and 1059 cm−1), and CeOeC stretching vi-
bration (1030 cm−1) of glucose circle (Ali, Rajendran, & Joshi, 2011;
Gacchi & Hungund, 2018; Shameli et al., 2012; Vrandecic, Erceg, Jakic,
& Klaric, 2010; Zidan, Abdelrazek, Abdelghany, & Tarabiah, 2019).
Since NH2 is a Lewis base (donate lone pair electrons) and Cu acts as a
Lewis acid (electrons acceptor) coordination is possible by electron
transfer (Abdeen et al., 2015; Karaer & Kaya, 2017; Liu et al., 2014).
Also, the cross-linking of chitosan with GLA is demonstrated from a
peak at ∼1600 cm−1, belonging to the imine C]N bond, formed be-
tween the amine residues of chitosan and the aldehyde terminals of the
Glu. The disappearance of the imines band (C]N) at 1633 cm−1 is due
D.G. Trikkaliotis, et al.
Fig. 2. Elemental percent analysis of the Cs/PVA/PEG beads: (a) before Cu(II) adsorption; (b) after Cu(II) adsorption.
to the poly condensation reactions (Nematidil et al., 2019; Zhang, Li,
Mao, & He, 2019).
3.2. Adsorption evaluation
3.2.1. Effect of pH on Cu(II) adsorption
The effect of pH on the adsorption of Cu(II) onto the Cs/PVA/PEG
beads was studied within the range of 2–5 ( ± 0.05); as the acidity of
the solution is one of the key-affecting factors of metal ions adsorption
resulting in protonation/deprotonation of the adsorbent’s functional
groups (Chaipuang et al., 2018; Dorabei et al., 2016; Liu et al., 2010;
Luo et al., 2014; Yang et al., 2017). The point of zero charge (PZC),
which determines the pH at which the net total particle charge is zero
(Shahzad et al., 2017; Sherlala et al., 2018), was found equal to 3.5
(Supporting information, Fig. SI13a). Therefore, at pH higher than 3.5
the hydrogel surface was negatively charged resulting to higher ad-
sorption of the positively charged copper ions. The maximum removal
of Cu(II) was obtained at pH 5 for 1 g/L of adsorbent dose (Supporting
information, Fig. SI13b). At low pH values the concentration of H+ is
high, leading to competition with Cu(II) to attach with the functional
5
Carbohydrate Polymers 234 (2020) 115890
groups. On the contrary, increment of pH increase the number of ne-
gatively charged active sites boosting the copper adsorption. Mean-
while, precipitation of Cu(II) ions as Cu(OH)2 occurs for pH > 6
(Anitha, Kumar, Kumar, Sriram, & Ahmed, 2016; Dorabei et al., 2016;
Vatanpour et al., 2020). At this point, it is worth to mention that the pH
of industrial wastewater is around 5 (Sun & Ma, 2016).
3.2.2. Effect of contact time on Cu(II) adsorption
The effect of contact time on equilibrium was investigated by car-
rying out adsorption experiments with the following conditions
(m = 0.03 g, V = 30 mL, T =45 °C, N = 125 rpm, pH = 5, t = 0−24 h,
C0 = 50, 100, 150 mg/L).
The effect of contact time on the adsorption of Cu(II) onto the Cs/
PVA/PEG beads was studied, and as it can be seen (Supporting in-
formation, Fig. SI13c) the adsorption capacity shows a sharp increase
during the beginning due to the highly available active sites (external
surface adsorption). Then, as the active sites are filled up there is a slow
increase till the equilibrium state (intraparticle diffusion) (El-Araby
et al., 2017; Lahiji, Keshtkar, & Moosavian, 2018; Sherlala et al.,
2018).Therefore, the optimum contact time was set at 300 min.
D.G. Trikkaliotis, et al. Carbohydrate Polymers 234 (2020) 115890

Fig. 3. The beads internal roughness (a) before Cu(II) adsorption ; (b) after Cu(II) adsorption. Profile analysis indicated a large pore (∼2.68 μm) on the top right
corner (a).

3.2.3. Adsorption isotherms
The effect of initial copper concentration on equilibrium was in-
vestigated by carrying out adsorption experiments with the following
conditions (m = 0.03 g, V = 30 mL, T = 25, 35, 45 °C, N = 125 rpm,
pH = 5, t =24 h, C0 = 10−200 mg/L).
The distribution of the adsorbate species between liquid and ad-
sorbent is described by mathematical models. There are several iso-
therm models to investigate the equilibrium of the system and to define
the capacity of the adsorbent. Usually, Langmuir or Freundlich model
describe accurately the system in the case of two parameters. Langmuir
model assumes monolayer adsorption onto homogenous surface where
the binding sites have equal affinity and energy, and there is no
transmigration or interaction between the molecules. Hence, it can
reach saturation (Eq. (4)). The Freundlich model assumes multilayer
adsorption on heterogeneous surface and the amount of adsorbed ad-
sorbate increases infinitely with an increase in concentration (Eq. (5))
(Liu et al., 2010; Lujaniene et al., 2017; Yi et al., 2018).
Q max KL Ce
Qe =
1 + KL Ce (4)
Qe = KF Ce1/ n (5)
where Qe (mg/g) is the equilibrium concentration in the solid phase;

Fig. 4. XRD patterns of the beads before (black) and after Cu(II) adsorption (red). (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article).

6
D.G. Trikkaliotis, et al.
Fig. 5. (a) FTIIR spectra of Cs (black line), Cs/PVA (blue line), Cs/PVA/PEG (red line); (b) FTIIR spectra of Cs/PVA/PEG before (red line) and after copper ions
adsorption (green line); (c) Cs/PVA/PEG structure and possible interactions with Cu2+. (For interpretation of the references to colour in this figure legend, the reader
is referred to the web version of this article).
Qmax (mg/g) is the maximum amount of adsorption; KL (L/mg) is the
Langmuir adsorption equilibrium constant representing the enthalpy of
adsorption; KF (mg1−1/nL1/n/g) is the Freundlich constant representing
the adsorption capacity and n (-) is the constant depicting the adsorp-
tion intensity.
The separation factor from the Langmuir isotherm equation is given
as follows:
1
RL =
1 + KL C0
where the factor RL(-) provides data about the nature of adsorption;
irreversible if RL = 0, favourable if 0 < RL < 1, linear if RL = 1, and
unfavourable if RL > 1.
Regarding the significance of n; adsorption is linear if n = 1, che-
mical process if n > 1, and physical process if n < 1.
The Langmuir isotherm model fitted the adsorption equilibrium
data better than that Freundlich’s, revealing homogenous distribution
Carbohydrate Polymers 234 (2020) 115890
of the beads’ active sites and uniform interactions with the copper ions
(Fig. 6a–c).The high KL values indicated the strong adsorption strength
(El-Araby et al., 2017; Yu et al., 2013).
Redlich-Peterson (Eq. (7)) and Langmuir-Freundlich (L-F) (Eq. (8))
isotherm models are also applied to obtain meaningful results. Their
constants and correlation coefficients in single system are presented to
Table 1. Redlich’s model value g reflects the suitability among the
Langmuir and Freundlich models (when g tends to 1 the system is well-
described by the Langmuir model and when it tends to 0 by the
(6)
Freundlich model). Also, the supreme fit of Redlich’s model
(R2 > 0.985) suggests that monolayer adsorption might not be the sole
occurring phenomenon (Debnath, Parashar, & Pillay, 2017; Duru et al.,
2016). Similarly, the L-F model trends to Langmuir when the hetero-
geneity parameter b is set to unity (Kyzas, Bikiaris, Seredych, Bandosz,
& Deliyanni, 2014; Kyzas, Lazaridis, & Mitropoulos, 2012).
The suitability of Dubinin-Radushkevich (D-R) model is also
checked, a direct temperature-dependent method to distinguish physi-
7
D.G. Trikkaliotis, et al. Carbohydrate Polymers 234 (2020) 115890

Fig. 6. Fitting of isotherm models for (a) 25 °C, (b) 35 °C, and (c) 45 °C. Adsorption kinetics of Cu(II) onto Cs/PVA/PEG beads evaluated by pseudo-first and pseudo-
second order models (d), and intra-particle diffusion model (e). Inset: multi-linearity to specify the deviation from the origin and the rate-controlling steps.

Table 1 and chemi- sorption through the mean free energy for heterogeneous
Characteristic values of the fitted isotherm models.a surfaces (Eq. (9)). When E < 8 kJ/mol, the process is physical in
Parametersb 25 °C 35 °C 45 °C
nature (Dada, Olalekan, Olatunya, & Dada, 2012; Inam, Etim, Akpabio,
& Umoren, 2017; Yang et al., 2016).
Langmuir Temkin model is also tested (Eq. (10)) that takes into account the
R2 0.982 0.984 0.989 heterogeneity of the surface (Ghogomu, Noufame, Ketcha, & Ndi, 2013;
Qmax 38.679 42.217 44.046
KL 4.372 3.713 3.665
Inam et al., 2017):
RL 0.001 – 0.022 0.001 – 0.026 0.001 – 0.027 AC e
Freundlich Qe =
1 + BCeg (7)
R2 0.908 0.905 0.879
n 8.268 7.896 8.225
KF 23.68 25.36 26.79 Qmax KLF Ce1/ b
Qe =
Langmuir-Freundlich 1 + KL Ce1/ b (8)
R2 0.981 0.986 0.987
Qmax 39.832 43.707 43.835 2 1⎞ 1
b 1.385 1.371 0.933 Qe = Qmax e−kDR ε with ε = RT ln ⎛1 +
⎜ and E =
⎟

KLF 2.436 2.149 4.172 ⎝ Ce⎠ 2kDR (9)

Redlich-Peterson
R2 RT ⎞ RT
0.985 0.991 0.989 Qe = ⎛ ⎜ ln (AT Ce ) and ET =
⎟

g 0.972 0.967 0.984 ⎝ bT ⎠ bT (10)

A 193.89 185.43 176.00
B 5.572 4.966 4.238 where A (L/mg) and B (L/mg) are constants and 0 < g < 1, KLF (L/
Dubinin-Radushkevic mg)1/b is constant and b (-) is the heterogeneity constant, KDR (mol2/
R2 0.325 0.956 0.972
kJ2) is the activity coefficient and ε (J/mol) is the Polanyi potential
Qmax 39.188 41.46 43.127
E 0.787 3.709 3.744 while E (kJ/mol) is the mean free energy, bT (-) is constant and AT (L/g)
KDR 8.0 × 10−7 3.6 × 10−8 3.6 × 10−8 is the equilibrium binding constant while ET (J/mol) is related to the
Temkin heat of adsorption.
R2 0.947 0.948 0.922 An increase ∼14 % in adsorption capacity was observed when the
AT 528.5 359.4 480.0
temperature increased from 298 to 318 K (Supporting information, Fig.
bT 651.0 590.2 605.3
ET 3.806 4.338 4.368 SI14). It could be attributed to the rise of functional groups caused by
breaking some of the bonds near the edge of the active surface sites of
a
pH = 5, V = 30 mL, m = 30 mg, 125rpm. the adsorbent. It might also be attributed to the increased penetration
b
The units of the parameters are given in the text. of copper ions inside the micropores and cavities, as well as to the
creation of new active sites (Travlou, Kyzas, Lazaridis, & Deliyanni,
2013). RL values revealed the favorability of the process, and the

8
D.G. Trikkaliotis, et al. Carbohydrate Polymers 234 (2020) 115890

proportional erection of KF with temperature supported the capacity
enhancement. Parameter n indicated the strong adsorption of Cu(II)
onto the hydrogel as it lies in the range 2–10, indicating chemisorption
(Chen et al., 2016; Li et al., 2013; Lujaniene et al., 2017; Zarghami
et al., 2014).
The different Qmax obtained from Langmuir, L-F and D-R models
should be attributed to the different definition of maximum capacity of
the models (El-Araby et al., 2017). The positive values of the heat of
adsorption (3.80 < ET < 4.37 J/mol) revealed that the process was
endothermic (Ghogomu et al., 2013; Inam et al., 2017); but they were
lower than 40 kJ/mol suggesting ion exchange, a physical phenomenon
(II) from the bulk solution to the external surface of the beads (film
diffusion), (ii) movement of Cu(II) into the internals of the beads (in-
traparticle diffusion), and (iii) adsorption of Cu(II) onto the interior
pores of the beads (adsorption). Lagergen pseudo-first order model (Eq.
(11)), Ho-Mckay pseudo-second order model (Eq. (12)) and Weber-
Morris intraparticle model (Eq. (13)) were employed to get a good
understanding of the process dynamics and predict the adsorption rate:
Ct = C0 − (C0 − Ce )(1 − e−k1 t ) (11)
1 ⎞
Ct = C0 − (C0 − Ce ) ⎛1 −
⎜ ⎟

⎝ 1 + k2 t ⎠ (12)
that lies closer to physisorption (< 80 kJ/mol) (Ghogomu et al., 2013;
Inglezakis & Zorpas, 2012). Moreover, Temkin isotherm is used to
Qt = kidt 0.5 + c (13)
evaluate the reduction in the adsorption heat. The model assumes that
the sorption heat of all molecules in a layer would decrease linearly. By where k1, k2 (min−1) and kid (mg g−1 min-1/2) are the rate constants for
using Dubinin-Radushkevich isotherm, the nature of adsorption (che- pseudo-first order, pseudo-second order and intraparticle kinetic model,
misorption or physisorption) could be understood. If E < 8 kJ/mol, the respectively. C0, Ct and Ce (mg/L) are the initial, transient and equili-
adsorption would be performed through weak van der Waals forces and brium concentrations of Cu(II) in the aqueous solution, respectively. Qt
a physical adsorption nature is observed. Otherwise, if 8 < E < 16 is the amount adsorbed at time t (mg/g) and c is the intercept (mg/g)
(kJ/mol), the adsorption would be performed through ion-exchange that describes the thickness of the boundary/external layer.
mechanism, while for values higher than 16 kJ/mol, the adsorption Correlation coefficients (R2) and the negligible differences between
process is considered to be controlled by a particle diffusion mechanism the calculated and the experimental capacities suggest that the pseudo-
(Sahebjamee, Soltanieh, Mousavi, & Heydarinasab, 2019). Table2 in- second order is the predominant kinetic model for Cu(II) removal by
cludes adsorbents for Cu(II) removal along with the synthesized Cs/ Cs/PVA/PEG hydrogel beads at all initial concentrations (Fig. 6d–e,
PVA/PEG micro-beads. Further increase to the capacity is obtainable, Table3). The c values from the intra-particle diffusion model reveal
and some proposals about that and suggestions are mentioned below. both the strong effect of the boundary layer and the film diffusion effect
in the process (Debnath et al., 2017; Ghogomu et al., 2013; Gupta et al.,
2015; Yu et al., 2013). Multi-linearity of the plots revealed that more
3.2.4. Adsorption kinetics than one step occurred during the process (inset of Fig. 6e). The first
The adsorption mechanism is associated with the rate-limiting step part corresponds to film diffusion and the second to intra-particle dif-
(s) in an adsorption process (Anastopoulos & Kyzas, 2016; Kyzas, fusion into the pores. According to a pseudo-second order model as-
Deliyanni et al., 2013; Ngah et al., 2004). The adsorption of Cu(II) onto sumption the rate-determining step may be chemical sorption (chemi-
the Cs/PVA/PEG hydrogel beads may be controlled either by one step sorption), relating valence forces through sharing or exchange of
or could be a combination of several steps such as (i) movement of Cu electrons between metal ions and active sites (Jamnongkan &
Singcharoen, 2016; Salehi et al., 2013; Yi et al., 2018; Yu et al., 2017;
Table 2 Zarghami et al., 2015).
Adsorption capacities of materials used in Cu(II) adsorption (Al-Saydeh et al., It would be unfair to discard all the collected data from Freundlich,
2017; Duru et al., 2016; Tan et al., 2015).
L-F, D-R and Temkin isotherm models, especially after the supreme
Type of Adsorbent Solution pH Uptake (mg/g) fitting of Redlich model, as well as to ignore the suggestions from
pseudo-first and intra-particle kinetic models; but as Levenspiel said in
Granular activated carbon 3 0.79
his Chemical Reaction Engineering book in 1972 “…if we choose a model
Chlorella vulgaris 4-5 1.52
Scolecite 6 4.2 we must accept its rate equation, and vice versa. If a model corresponds
Amino-SiO2/GO 5.5 5.85-6.15 closely to what really takes place, then its rate expression will closely predict
Oligotrophic peat 5 6.41 and describe the actual kinetics; if a model widely differs from reality, then
Date pits 5.8 7.4
the kinetic expressions will be useless…” (Inglezakis & Zorpas, 2012).
Amino-PAA/Fe3O4 5 12.0
Graphene oxide/Fe3O4 5.3 18.26
Eutrophic peat 5 19.56 3.2.5. Adsorption thermodynamics
Waste slurry 3 20.97 Calculations of the thermodynamic parameters require two or more
Activated carbon from Ceibapentandra hulls 6 21.0
PD/GO composites 6 24.4
temperatures (Anastopoulos & Kyzas, 2016). The temperature effect on
MWCNT 5 24.5 the adsorption of Cu(II) onto Cs/PVA/PEG hydrogel beads was studied
GO/CS aerogel 6 25.4 at 298, 308 and 318 K at pH 5 for 5 h of contact time at 125 rpm. The
Activated carbon from pecan shells 4.8 31.7 results showed that the adsorption capacity of Cu(II) increased with
GO/PAMAM 4.5-5.6 38.4-68.68
temperature increment, indicating an endothermic in nature process.
Steel-making-by-product 6 40.0
S-MWCNTs 5 43.2 The thermodynamic equilibrium constant Kc (-) was calculated by
Valonia tannin resin 5 44.0 equation:
Iron oxide coated eggshell powder 6 44.0
Cs/PVA/PEG micro-beads 5 44.05 Cs
Kc =
Graphene oxide 5 45.2–46.6 Ce (14)
Kaolinite/Fe (NP) 6 49.0
CSGO 5 53.69 where Cs (mg/L) is the amount adsorbed on solid at equilibrium.
Rose waste biomass 5 56.0 Gibbs free energy change (ΔG0), enthalpy change (ΔH0) and entropy
Ag(NP)/Activated Carbon 4.7 60 change (ΔG0) were calculated using the following equations:
Chitosan crosslinked (EPI) 5 62.4
SMGO 4.7 62.73 ΔS0 ΔH0
GO/CS hydrogels 5.1 70 ln(K c) = −
R RT (15)
GO membranes 5.8 72.6
Chitosan 4.5-5 85-88.43
ΔG0 = −RTln(K c) (16)

9
D.G. Trikkaliotis, et al. Carbohydrate Polymers 234 (2020) 115890

Table 3
Kinetic parameters for the adsorption of copper ions in aqueous solutions onto the Cs/PVA/PEG composite hydrogel beads.a
C0 Exp. Qe Pseudo-first order Pseudo-second order Intraparticle diffusion
(mg/L) (mg/g)
2 2
K1 Qe R K2 Qe R Kid C R2
(min−1) (mg/g) (min−1) (mg/g) (mg/g min0.5) (mg/g)

50 40.30 0.094 35.81 0.996 0.199 37.25 0.998 8.912 4.50 0.888
100 44.54 0.080 41.16 0.927 0.129 43.74 0.960 10.59 3.86 0.935
150 44.49 0.089 42.33 0.940 0.157 44.57 0.966 10.76 4.54 0.916

a
pH = 5, V = 30 mL, m = 30 mg, 125 rpm.

Table 4 rare. Adsorption can be either physical or chemical, depending on the

Thermodynamic parameters for the adsorption of copper ions in aqueous so- forces/interactions of adsorbate and adsorbent. Physical adsorption is
lutions onto the Cs/PVA/PEG micro-beads.a dominated by van der Waals force while chemisorption involves the
C0 T Qe Kc ΔG0 ΔH0 ΔS0 Removal formation of new, ionic or covalent bonds. For example, during ligand
(mg/L) (K) (mg/L) (-) (kJ/mol) (kJ/mol) (kJ/mol K) (%) exchange processes. However, the majority of studies present data
about the synergetic phenomenon of physical process (A%) and che-
10 298 9.90 99 −11.39 90.64 0.341 100
mical process (B%). In general, B is higher than A (B > A), but also “A”
308 9.95 199 −13.56 100
318 9.99 999 −18.26 100 still exists. Identification of type of adsorption can be done by isotherm
40 298 34.46 6.22 −4.53 53.03 0.193 86 analysis if both Freundlich and Langmuir fitted well for the process then
308 36.47 10.33 −5.98 91 it can be said that the adsorption is neither only physical nor only
318 38.40 24 −8.40 96 chemical but the combination of both. Also, some assumptions are
50 298 37.04 2.86 −2.6 14.86 0.059 74
(Adamson & Gast, 1997): (i) if desorption is more using only distilled
308 40.03 4.02 −3.56 80
318 40.30 4.15 −3.77 81 water without any chemical reagent, it can be physisorption; (ii) if
75 298 36.96 0.97 0.07 9.99 0.033 49 desorption is more by use of any eluent, it could be chemisorption; (iii)
308 39.81 1.13 −0.32 53 if the rate of reaction follows pseudo-second order model, it could be
318 41.69 1.25 −0.59 56
chemisorption; (iv) if new crystals are observed after adsorption
100 298 41.62 0.71 0.84 4.71 0.013 42
308 43.73 0.78 0.65 44 through XRD, then it is chemisorption; (v) if there is not much influence
318 44.54 0.8 0.58 45 of variation in pH is observed in sorption, then it could be physisorp-
150 298 38.92 0.35 2.6 7.33 0.016 26 tion; (vi) if the rate of sorption is very rapid in the initial few minutes of
308 42.88 0.4 2.34 29 sorption, then chemisorption might be involved. All above are hy-
318 44.49 0.42 2.28 30
pothetical assumptions that may be helped to ssify the process. In the
200 298 39.86 0.25 3.45 7.68 0.014 20
308 44.88 0.29 3.18 22 present work, although too many functional groups exist in adsorbent
318 46.41 0.3 3.16 23 and chemi-sorption can be easily observed with strong electrostatic
interaction between adsorbent and adsorbate (between functional
a
pH = 5, V = 30 mL, m = 30 mg, 125 rpm. groups of Cs/PVA/PEG and copper ions), there are also findings based
on isotherm model that indicate that the process majorly is dominated
ΔG0 = ΔH0 − TΔS0 (17)
by physical nature/process (not solely). For example, the mean free
where T is the absolute temperature (K) and R the universal gas con- energy (E) is lower than 8 kJ/mol in D-R model, the heat of adsorption
stant (8.314 J/(mol K)). The values of ΔH° and ΔS° can be calculated (ET) is lower than 80 kJ/mol in Temkin model, also ΔH° is lower than
from the slope and intercept of the plot ln(Kc) vs 1/T, respectively (Fig. 20 kJ/mol. All above lead to the conclusion of “A > B” scenario.
SI15, Table 4). The negative values of ΔG° reveal the spontaneous
nature and feasibility of the adsorption process of Cu(II) onto the beads.
The higher the negative values, the more the favorable conditions for 4. Conclusions and perspectives
the ion adsorption (Anastopoulos & Kyzas, 2016; Li et al., 2015; Salehi
et al., 2013). In case of high initial copper ion concentrations This study highlighted the potential of Cs/PVA/PEG micro-beads to
(C0 > 100 mg/L) the free energy is positive presenting non-spontaneous adsorb copper ions from aqueous solutions. Some basic findings are
behavior. When copper ions are about to be adsorbed they lose part of listed below:
their hydration sheath. The positive ΔH° values confirm that the process
is endothermic in nature. According to literature, when ΔH° > 40 kJ/ (i) The adsorbent showed efficiency 99.99 % for initial copper ion
mol the process is chemisorption and when ΔH° < 20 kJ/mol is physi- concentration of 25 mg/L.
sorption. The positive ΔS° values indicate increased randomness at the (ii) The process was spontaneous and endothermic.
solid-solution interface during the adsorption processes. The adsorbate (iii) Experimental data are well-described by Langmuir and pseudo-
species displace the adsorbed water molecules and the latter gain more second order models.
translational entropy than is lost by the former, resulting to prevalence (iv) The maximum adsorption capacity was about 45 mg/g.
of randomness in the system (Abdeen et al., 2015; Kyzas et al., 2012;
Vatanpour et al., 2020). This promising for industrial wastewater cleanup adsorbent could
Percent removal, ΔH° and ΔS° showed a decrease at higher Cu(II) further improve its capacity through the following actions: (i) further
initial concentration. This effect might be attributed to the energetic deacetylation of chitosan; (ii) lyophilization (freeze-drying) of the hy-
heterogeneity of the surface. At low C0, and therefore at low Qe, the drogel to get aerogel; (iii) conduct adsorption experiments at pH
adsorption sites with the highest affinity for copper ions are firstly 5.85 ± 0.1; (iv) incorporation of swelling and regeneration data as
occupied. Then, with increasing Qe, the remaining sites with lower af- well as simulations in columns (fixed-bed) would provide a spherical
finity are progressively occupied (Kyzas et al., 2012). description of the sorbent.
It is fact that adsorption process is a very complicated process be-
cause the clear existence of physical-sorption or chemical-sorption is

10
D.G. Trikkaliotis, et al.
Funding
This research received no external funding.
CRediT authorship contribution statement
Dimitrios G. Trikkaliotis: Methodology, Data curation, Writing -
original draft. Achilleas K. Christoforidis: Methodology, Writing -
original draft. Athanasios C. Mitropoulos: Methodology, Writing -
review & editing. George Z. Kyzas: Supervision, Methodology, Writing
- review & editing.
Declaration of Competing Interest
The authors declare no conflict of interest.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.carbpol.2020.115890.
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