Cellulose

https://doi.org/10.1007/s10570-018-1972-3 (0123456789().,-volV)
(0123456789().,-volV)

ORIGINAL PAPER

Aqueous hardness removal by anionic functionalized

electrospun cellulose nanofibers
Muhammad Muqeet . Abdul Khalique . Umair Ahmed Qureshi .
Rasool Bux Mahar . Farooq Ahmed . Zeeshan Khatri . Ick Soo Kim .
Khan Muhammad Brohi

Received: 13 March 2018 / Accepted: 1 August 2018

Ó Springer Nature B.V. 2018

Abstract Herein we examine the adsorption behav-
ior of anionic-cellulose nanofibers (a-CNFs) having a
carboxymethyl group concentration of 1.14 mmol/g
of nanofibers. The effects of key parameters governing
the efficiency of the adsorption process in the batch
mode were investigated. Electrospinning was
employed to fabricate cellulose acetate nanofibers
(CANFs). The fabricated nanofibers were then
deacetylated to convert them into CNFs that were
subsequently anionized by a pad-batch process. The
a-CNF web was characterized through scanning
electron microscopy (SEM), thermogravimetric anal-
ysis, and IR spectroscopy. SEM revealed
315 ± 10 nm average nanofiber diameters in the
a-CNF web. Moreover, zeta-potential measurements
revealed isoelectric point at ca. pH 4. The Freundlich
isotherm and the Pseudo-second-order kinetic models
fit the adsorption data well. Also, the Langmuir
adsorption capacities of a-CNFs for Ca2? and Mg2?
were 57.66 and 65.55 mg/g, respectively.

Electronic supplementary material The online version of

this article (https://doi.org/10.1007/s10570-018-1972-3) con-
tains supplementary material, which is available to authorized
users.

M. Muqeet  R. B. Mahar (&) K. M. Brohi

US-Pakistan Center for Advanced Studies in Water, Institute of Environmental Engineering and Management,
Mehran University of Engineering and Technology, Mehran University of Engineering and Technology,
Jamshoro 76060, Pakistan Jamshoro 76062, Pakistan
e-mail: rbmahar.uspcasw@faculty.muet.edu.pk

A. Khalique  U. A. Qureshi  F. Ahmed  Z. Khatri (&)

Centre of Excellence in Nanotechnology and Materials,
Mehran University of Engineering and Technology,
Jamshoro 76060, Pakistan
e-mail: zeeshan.khatri@faculty.muet.edu.pk

Z. Khatri  I. S. Kim (&)

Nano Fusion Technology Research Lab, Division of
Frontier Fibers, Institute for Fiber Engineering (IFES),
Interdisciplinary Cluster for Cutting Edge Research
(ICCER), Shinshu University, 3-15-1, Tokida, Ueda,
Nagano 386-8567, Japan
e-mail: kim@shinshu-u.ac.jp

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Graphical abstract
Keywords Cellulose nanofiber  Adsorption 
Electrospinning  Water hardness
Introduction
Aqueous hardness, a most critical parameter, is
directly and indirectly responsible for problems in
both industries and residences. It produces a hard scale
in piping, valves and pumping devices, eventually,
causing material deterioration. Furthermore, the main
problem, associated with scaling is the reduction of
heat transfer rate in heat exchange devices such as,
boilers, evaporators, cooling towers and condensers.
Apart from industrial applications, hard water causes
increased detergent consumption in residential appli-
cations (Racho and Namseethan 2017).
The major constituents (Ca2? and Mg2?) respon-
sible for aqueous hardness, originate in water from
seepage, sedimentary rocks (e.g., chalk and limestone)
and run-off from soils. Moreover, some other polyva-
lent ions such as iron, zinc, manganese, barium
aluminum and strontium also contribute slightly to
the total hardness and these originate from different
sources of industrial effluents.
The removal of Ca2? and Mg2? ions from water is
achieved commercially by employing different meth-
ods, for example, Ion-exchange (Comstock and Boyer
2014), lime-soda softening (Franco et al. 2017),
123
Cellulose
adsorption (Rolence et al. 2014), electrocoagulation
(Malakootian et al. 2010) and reverse osmosis/nanofil-
tration (Ahn and Han 2017). The ion-exchange
method involves extensive regeneration of synthetic
polymers with either HCl or NaOH. Consequently, it
produces toxic waste water upon regeneration. The
lime-soda softening process is now outdated due to
high pre-and-post treatment requirements. The reverse
osmosis/nanofiltration, pressure driven separation
methods have a high cost in terms of pressure energy
and pre-treatment of feed water. Finally, adsorption is
now receiving attention; owing to its simplicity, cost
effectiveness, and this mode of separation does not
have any environmental footprints after process com-
pletion (Chen 2015; Sehaqui et al. 2016a). Therefore,
a great deal of attention is now being focused on the
development of efficient, cost effective and readily
available sorbent for the removal of dissolved con-
taminants from aqueous solutions.
Several materials have already been tested for the
removal of aqueous hardness-causing metal ions, such
as, sugar cane bagasse (Júnior et al. 2017), modified
cellulose (Karnitz et al. 2007), modified pumice
(Sepehr et al. 2013), Glycidyl methacrylate–divinyl-
benzene (Atia et al. 2005), methyl methacrylate-Na-
Y-Zeolite (Elwakeel et al. 2017), poly p-phenylene-
diamine-thiourea-formaldehyde (Elwakeel and Al-
Bogami 2018), activated carbon (Amosa 2016) and
coconut shell (Rolence et al. 2014). All materials are
either limited due to their low adsorption capacity or
Cellulose
high equilibrium time and cost. Among these, elec-
trospun CNFs, due to biocompatibility, high surface to
volume ratio, natural abundance, outstanding stiff-
ness, and cost-effectiveness are the promising choice
for the adsorption of dissolved constituents present in
natural waters (Gopiraman et al. 2015; Khatri et al.
2012; Sehaqui et al. 2015a; Qureshi et al. 2017a).
Normally, cellulose-based adsorbents, micro or nano
fibrils are prepared by tedious extraction procedures
from natural biomass followed by their surface
treatments. Such treatment conditions impair their
practical applications as most of the constituents are
difficult to remove from natural biomass in order to
achieve pure cellulose. We, therefore, have tried to
follow a simple and quick way to obtain cellulose from
cellulose acetate through alkaline treatment and
subsequent surface modification to achieve an adsor-
bent capable of removing cations from the water.
A few approaches have already addressed the
fabrication procedure of the nanofibers, such as phase
inversion (Ahmed et al. 2015a), drawing (Suzuki et al.
2014), self-assembly (Tao and Desai 2007), templet
synthesis, electrospinning (Mahar et al. 2017; Qureshi
et al. 2017b), and most recent 3D-printing (Chou et al.
2017; Li et al. 2017). Amongst them, electrospinning
is an emerging technique having the capability of
producing, from a variety of polymers, bead-free
nanofibers with controllable morphology and in
diameters ranging micro-to-nano size (Khatri et al.
2012; Gopiraman et al. 2015; Rajesh et al. 2017).
In the present study, anionic-cellulose nanofibers
(a-CNFs) with sodium carboxymethyl groups have
been synthesized via pad-batch process followed by
electrospinning and deacetylation. To the best of our
knowledge, this is the first time, wherein a-CNFs
fabricated via electrospinning is addressing the
adsorption of water hardness-causing constituents.
Further, adsorption isotherm and kinetic modeling is
also an important part of this study along with
nanofiber characterization by different instrumental
techniques; such as, SEM, FTIR, TGA, BET surface
area and porosity analyzer and zeta-potential
measurements.
Experimental
Materials and reagents
Cellulose acetate (39.8% acetyl content having aver-
age molecular wt. 30,000 Dalton) was obtained from
Sigma Aldrich, Japan and used as received. N,N di-
methyl formamide (DMF) and acetone were also
purchased from Sigma Aldrich, Japan. NaOH and HCl
were used for pH adjustments. Sodium chloro acetate
was purchased from Wako Pure Chemical Industries
Ltd., Japan. Calcium chloride and magnesium sulfate
were received from Merck, Germany.
Nanofiber preparation
Cellulose acetate nanofibers (CANFs) were fabricated
through the procedure reported in our previous
literature with a little modification (Muqeet et al.
2017). Briefly, 17% (w/w) cellulose acetate in 2:1
(acetone:DMF) was prepared followed by stirring at
room temperature for 10 h in an air tight glass bottle.
The polymer was then supplied to 3-mL plastic
syringes attached to the capillary tip having the inner
diameter of 0.6-mm. The syringes were placed at an
angle of 10° from the abscissa. A pure copper wire was
connected to the positive terminal dipped into the CA
solution and a negative terminal was attached to the
grounded metallic collector (RMC) rotating at the
speed of ca. 15-rpm. A high DC voltage (13-kV) was
applied to the electrode and the tip-to-collector
distance was adjusted to 10 cm. The fabricated
CANFs were deposited continuously over a RMC
wrapped with aluminum foil to obtain ca. 60–70-lm
thick nanofiber web. After the electrospinning, The
CANF web was peeled out and subjected to drying at
room temperature (for ca. 24-h) to remove residual
solvents. Additionally, the parameters are also shown
in the tabulated form for the easiness of the reader, as
shown in Table 1.
The resultant CANFs were subjected to the 0.05 M
NaOH solution for deacetylation to convert them into
CNFs. The alkali treated CNFs were steeped in
aqueous solution of 1 M sodium chloroacetate for
5-min (Gopiraman et al. 2015). Finally, the 100% wet
nanofibers were packed into the air tight polyethylene
bag for 1 h at room temperature for the completion of
the reaction. After the anionization, the nanofibers
were washed thoroughly with DI water and dried at
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Table 1 Optimized conditions for electrospinning of cellulose acetate nanofibers
Solution Ambient cond.
Polymer Solvents Conc. Temp. Humidity
(%) (°C) (%)
Cellulose acetate DMF/acetone (1:2) 17 23 ± 2 40 ± 5
room temperature for 24-h. The graphical depiction of
the whole process was presented in Fig. S1 (refer
supplementary material, S1).
Nanofiber characterization
To examine the morphology, nanofibers were ana-
lyzed using a scanning electron microscopy (SEM,
Hitachi S-4800). Prior to examination, nanofibers
were sputter-coated (BAL-TEC AG, Balzers, Liecht-
enstein) with gold (ca. 10-nm thick). The SEM images
were generated under an accelerating voltage of 5-kV
with a working distance of 4.0-mm. The average
thickness of fabricated and modified nanofiber webs
was measured using digital micrometer (MCD130-25)
having measuring sensitivity of 1-lm. The thermal
stability of CNFs and a-CNFs as a function of
increasing temperature was investigated at a constant
heating rate of 15 °C/min (before and after reaching
iso-thermal conditions i.e., 102 °C for 30-min). The
thermograms were obtained using SDT-Q600 thermal
gravimetric analyzer (TA-Instruments) under a pure
nitrogen (gas) flow rate of 40-mL/min from 25 to
500 °C.
It is important to determine net charges on the
surfaces of CNFs and a-CNFs; therefore, zeta-poten-
tial measurements were performed for CNFs and
a-CNFs using Zetasizer NanoZS instrument (Malvern,
U.K.). For the analysis of samples, a suspension of 0.1
wt% was prepared in DI water. Further, the car-
boxymethyl groups grafted on the a-CNFs were
determined by the acid–base titration method, which
was discussed in the supplementary information (refer
supplementary material, S2).
Conformity of deacetylation and anionization was
analyzed using two independent techniques i.e., DMF
solubility test and FTIR. The qualitative test was
performed to examine the conversion of CANFs into
CNFs (deacetylation). In the examination the CANF
web (5 9 5 cm) and CNF web (5 9 5 cm) were
123
Cellulose
Electrospinning parameters
App. voltage (kV) Tip-to- Syringe angle RMC
collector from x-axis (°) speed
distance (cm) (rpm)
13 10 10 15
subjected to DMF separately. As DMF is a good
solvent for CA, therefore, the cellulose cannot be
dissolved in this solvent. Similarly, the deacetylation
and the success of chemical reactions were examined
using Fourier transform infrared (FTIR) spectroscopy
(Shimadzu IR Prestige-21) at ATR (attenuated-total-
reflectance) mode in the range of wavenumbers from
4000 to 500 cm-1.
Adsorption experiment
A sequence of experiments was performed to obtain
adsorption data for kinetic and isotherm modeling. In
all experiments, 15-mL solution was shaken at a
temperature ca. 25 °C at 200 rpm using 20-mg of
nanofibers in each batch. The calcium and magnesium
solutions were prepared in DI water with pH adjust-
ments performed through the addition of either 0.5 M
HCl or NaOH. For kinetics, adsorption experiments
were systematically performed as a function of several
shaking times (10, 20, 30, 40, 50, 60, and 120 min) for
both Ca2? and Mg2?. Adsorption experiments were
also performed as a function of initial concentrations
(25, 50, 75, 100, 200, and 400 mg/L) and pH of the
solutions (ca. 4, 5, 6, 7, 8, 9, 10). The % adsorption
efficiency was calculated using Eq. 1.
ðCo  Cf Þ
Adsorption efficiency ð%Þ ¼ 100 ð1Þ
Co
where Co and Cf represented the initial and residual
concentrations of Ca2? or Mg2? ions in mg/L. Also,
adsorption capacity at equilibrium (denoted by qe) was
calculated in mg/g through the Eq. 2.
ðCo  Ce Þ
qe ¼ m ð2Þ
V
where m is the mass of nanofibers measured in gram
(g) and V is the solution volume in (L). All experi-
ments were performed in triplicate and the mean
values were provided in the current work. An error
Cellulose

analysis was also established to compare the validity measured thickness of the nanofiber web was seen to
of kinetic and isotherm models using the following decrease up-to 11%.
equation: The conversion of CANFs into CNFs can be
detected through DMF solubility test (Ahmed et al.
X
n
SSE ¼ ðqcal  qexp Þ2 ð3Þ 2017; Muqeet et al. 2017). In the DMF solubility test
n¼1 we observed the rapid dissolution of CANF web when
subjected to DMF, however, cellulose did not dissolve
where qcal and qexp are the calculated and experimental
in DMF; which shows the conversion of CANFs into
adsorption capacities of a-CNFs.
CNFs. Further, success of chemical modifications
The used nanofibers, after the adsorption were
(deacetylation and anionization) was also confirmed
separated by the simple filtration using 0.45-micron
by FTIR in ATR mode (Fig. 2). Three exhaustive
polypropylene filter paper. The percentage removal of
peaks at 1740, 1377 and 1220 cm-1 were detected in
both Ca2? and Mg2? ions was determined by Flame
the spectra recorded for CANF. These peaks con-
atomic absorption spectrometer (Aurora-Al 1200).
firmed the stretching vibration of C=O, C–CH3 and C–
The resultant absorption reading was compared with
O–C functional groups, respectively (Khatri et al.
the stable calibration curve having R2 = 0.999. All the
2013). After deacetylation of CANF, a broad peak
experiments were conducted three times and standard
appeared at 3000–3400 cm-1 (Pan et al. 2018);
deviations were calculated.
simultaneously, a strong carbonyl absorption peak at
ca. 1740 cm-1 was found to disappear completely.
Finally, the characteristic peaks at ca. 1590 cm-1 and
Results and discussion
1400 cm-1 correspond to C=C–O and C–CH2 respec-
tively, represented the occurrence of sodium car-
Nanofiber characterization
boxymethyl groups (Lawal et al. 2011).
The surface charges information of CNFs and
The SEM images of the surfaces of the CANFs, CNFs
a-CNFs at various pH values was obtained by f—
and a-CNFs with their diameter distribution (among
potential measurements. The CNFs, as shown in
ca. 50 nanofibers) were observed in Fig. 1a–f. The
Fig. 3, represented the negative and pH dependent
SEM images showed smooth, continuous, and bead-
zeta-potential values. On the other hand, the surface
free morphology. The CANFs having average nano-
charge reversal at low pH values and high pH
fiber diameter ca. 330-nm decreased to 290-nm upon
dependency of a-CNFs were observed. Potential
deacetylation. The potential reason might be the
values revealed the isoelectric point at low pH (the
removal of the acetyl groups during the conversion
pH value ca. 4) for a-CNFs (Sehaqui et al. 2015b). The
of CANF to CNFs (Deng et al. 2013; Ahmed et al.
presence of dual (positive and negative) surface
2015a, b). Khatri et al. (2012) reported another reason
charges onto a-CNFs at acidic and alkaline pH values
for the decrease in diameter i.e., nanofibers shrinkage
are representing the surface neutralization at low pH
when it is subjected to alkali media (NaOH or KOH).
values. Another reason for the positive f—potential at
Additionally, nanofiber surface roughness was also
low pH might be the dissociation of hydroxyl groups
observed due to interaction with NaOH used for the
(Liu et al. 2014). Further quantitative analysis of
deacetylation (Khatri et al. 2013; Gopiraman et al.
carboxymethyl groups revealed 1.14 mmol/g (refer
2016). Remarkably, nanofibers regain their original
supplementary information S2).
average diameter up-to 315-nm owing to subsequent
The TGA analysis provides evidence that both
anionization (Sehaqui et al. 2014). Gopiraman et al.
CNFs and a-CNFs start to degrade at the temperature
(2015) reported the presence of carboxymethyl groups
greater than 300 °C. Initially, weight loss in both
(–CH2COOH) as the main reason of increasing in
samples was 3–7% up-to isothermal condition (i.e.,
nanofiber diameter.
102 °C for 30 min) due to release of substantial
On the other hand, the thickness of CANF and CNF
amount of moisture, which was already present in both
webs were measured to investigate the other morpho-
CNFs and a-CNFs (Qureshi et al. 2016). On the other
logical changes occurred owing to deacetylation. The
hand, it was observed from TGA results that, CNFs
lost ca. 88% of its original weight in the range from

123

Fig. 1 SEM images along
with histogram a, b CANFs,
c, d CNFs, and e, f a-CNFs
200 to 400 °C due to molecular disintegration into a
great number of char and volatile matters (Sehaqui
et al. 2016b). The characteristic peak appeared at ca.
350 °C (refer Fig. 4a), was mainly attributed to
cellulose. However, in case of a-CNFs, the main
degradation peak appeared at 405 °C. It was very
interesting to recognize that, a-CNFs become more
thermally stable over anionization. The potential
reason might be the presence of sodium metal ion in
grafted functional groups providing shielding effect
(Gopiraman et al. 2015). Concludingly, a-CNFs can be
used at a temperature up-to 405 °C.
123
Cellulose
It is evident from the BET surface area and porosity
analysis that CNFs and a-CNFs contain BET surface
areas of 15.20 m2/g and 4.94 m2/g respectively. In
case of a-CNFs, the decrease in the BET surface area
reflected the increase in diameter of a-CNFs in
comparison with CNFs. Another crucial reason for
low surface was the pores blockage due to the
penetration of carboxymethyl groups. Explanatory,
penetrated carboxymethyl groups do not allow nitro-
gen molecules (N2) to enter in the available pores,
which consequently reduces the BET surface area
(Sehaqui et al. 2016a).
Cellulose
Fig. 2 FTIR spectra depicting CANFs, CNFs and a-CNFs
Fig. 3 Zeta potential measurements of CNFs and a-CNFs at
different pH values
Adsorption study
In the preliminary study, a separate set of adsorption
experiments was performed to compare the effects of
anionization. Briefly, CNFs and a-CNFs were used as
Fig. 4 TGA thermograms with differential curves a CNFs, and b a-CNFs
an adsorbent separately. The adsorption parameters
are shown in the caption of Fig. 5.
The experimental results, depicted in Fig. 5, repre-
senting the improved adsorption efficiency of a-CNFs
as compare to CNFs. The possible reason for the
improved adsorption capacity is the presence of
grafted carboxymethyl groups on a-CNFs that also
renders negative charge on CNFs as reported in the
literature (Gopiraman et al. 2015).
Effect of pH
It is important to study the effect of pH on the
adsorption of Ca2? and Mg2? ions owing to possible
effects on the degree of ionization of surface charges.
The removal percentages obtained by the adsorption
of Ca2? and Mg2? ions over a-CNFs at pH values
ranging ca. 4–10. Based on results as depicted in
Fig. 6, higher removal efficiency of a-CNFs for Ca2?
and Mg2? was achieved at neutral and basic pH values
as compare to acidic pH values. These results also in
agreement with zeta potential measurement for the
sorbent (refer ‘‘Nanofiber characterization’’). The
potential reasons responsible for adsorption can be
the electrostatic interactions between sorbent and
metal ions along with complexation (Mo et al. 2018).
The adsorption data revealed the lower removal
percentages at acidic pH values; this can be attributed
to the competition between metal ions and H? ions
originated due to the addition of 0.1 M HCL to reduce
pH of the solution. Sepehr et al. (2013), reported
another reason i.e., protonation of functional groups
grafted on a-CNFs. On the other side, at basic pH
values (i.e., ca. 9 and 10) a slight decrease in removal
123
 Cellulose

100 isotherm models (Supplementary material S1,

CNF Fig. S2).
80 The Langmuir isotherm model assumes uniform
a-CNF
energies of adsorption onto the surface and no
transmigration of adsorbate in the plane of the surface.
Removal, %

60
The non-linear equation for the Langmuir isotherm
may be expressed as:
40
qm KL Ce
qe ¼ ð4Þ
1 þ KL Ce
20
where qe is the adsorption at equilibrium (mg/g), qm
represented the maximum adsorption capacity (mg/g),
0
Ce represented the solute concentration at equilibrium
Ca2+ Mg2+
(mg/L), and KL is the constant related to the free
energy of adsorption (L/mg).
Fig. 5 Comparative adsorption using CNFs and a-CNFs (mass
of nanofibers: 20-mg; solution volume: 15-mL; shaking time: Another well-known adsorption model namely
60-min; initial concentration: 25-mg/L) Freundlich isotherm was used to describe the multi-
layer adsorption over a heterogenous active site of
100 nanofibers. The empirical equation can be expressed
Ca
as:
Mg
80 1
qe ¼ KF CneF ð5Þ
Removal, %

60 where KF represented the relative adsorption-capacity

40
20
0 adsorption isotherm model may be expressed by a
4 5 6 7 8 9 10
pH
Fig. 6 Plot of calcium and magnesium removal percentages at
different pH values (mass of sorbent, 20-mg; contact time,
60-min; initial concentration, 25-mg/L)
percentages was observed for both metal ions which is
associated with the formation of metal hydroxide.
Adsorption isotherm
As the concentration of Ca2? and Mg2? ions present in
water varies, depending on the geo-chemical nature of
aquifer, it is important to examine the adsorption
capacity of a-CNFs as a function of initial concentra-
tion of Ca2? and Mg2? ions present in the solution.
The theoretical adsorption capacity of a-CNFs was
determined using non-linear Langmuir and Freundlich
measured in mg/g and the 1/nF indicates the surface
heterogeneity; the smaller the value of 1/n, the greater
the availability of heterogeneous active sites and the
adsorption mechanism would preferably be physical in
nature (Qureshi et al. 2017a, b).
The important characteristic term of Langmuir
dimensionless factor RL, which is calculated by:
1
RL ¼ ð6Þ
1 þ KL Co
where Co represents the initial concentration of either
Ca2? or Mg2?, and RL represents the type of isotherm,
which can be linear (RL = 1), favorable (0 \ RL \ 1),
irreversible (RL = 0), or finally, unfavorable (RL [ 1).
The values of the RL were calculated for various initial
sorbate concentrations and were found between 0 and
1 (0.8–0.2 for calcium and 0.16–0.012 for magne-
sium). This is representing a promising adsorption
process, as further confirmed from the values of the
Freundlich adsorption factor (1/n) which were in the
range of 0–1 (Subramaniam et al. 2017; Sogut and
Caliskana 2017).
In the Table 2, the correlation coefficient along
with the sum of error squared imply that the

123
Cellulose
Table 2 Parameters for the Langmuir and Freundlich isotherm
Exp Langmuir
qmax (exp) RL qmax (cal) KL
(mg g-1) (mg g-1) (L mg-1)
Ca2? 65.38 0.8–0.2 57.66 0.78
Mg2? 77.43 0.16–0.012 65.55 0.93
Freundlich isotherm is more suitable for the adsorp-
tion of both calcium and magnesium ions. It indicates
the heterogeneous active sites available for targeted
pollutants (Madaeni and Salehi 2009).
Adsorption kinetics
For the practical implementations, it is necessary to
investigate the rate at which sorption takes place.
Particularly at batch mode, it becomes utmost impor-
tant to model the sorption rate-data obtained under
varied parameters. For example, the adsorption kinetic
modeling was performed by using data obtained as a
function of contact time ranging from 10 to 120 min.
Other parameters, such as, pH (ca. 7), mass of
adsorbent (20 ± 0.2 mg), initial concentration of
solution (25-mg/L) were fixed for the entire kinetic
experiment. From the adsorption rate data, it was
perceived that, after 60-min, adsorption progressed at
the lower rate or even no significant removal was
observed. This might be due to the unavailability of
active sites on the surface of a-CNFs (Qureshi et al.
2017b).
The Lagergren’s first-order kinetic model was
initiated on the assumption that, the single ion can
occupy only one adsorptive site available onto the
sorbent surface (Haider et al. 2015). However, for the
sorption of divalent metal ions, Ho proposed a second-
order kinetic model with the assumption that one
adsorbate occupies two active sorption sites available
onto the sorbent surface (Ho 1995). The equations for
the Pseudo-first-order (PFO, Eq. 7) and Pseudo-
second-order (PSO, Eq. 8) can be expressed as:
lnðqe  qt Þ ¼ lnqe  k1 t ð7Þ
t 1 t an adsorbent. Hence the resultant a-CNFs has revealed
¼ 2
þ ð8Þ
qt k 2 qe qe
Freundlich
2
R SSE Kf 1/n R2 SSE
(mg g-1)
0.98 0.30 1.589 0.629 0.99 0.15
0.98 0.33 2.796 0.556 0.99 0.20
where qt and qe represented the adsorption at the time t
and the equilibrium respectively. K1 and K2 are rate
constants for PFO and PFO respectively.
Both PFO and PSO kinetic models do not define the
diffusion phenomenon occurs in the solid–liquid
adsorption system. Therefore, the adsorption rate-data
was further fitted to the intra-particle diffusion (IPD)
kinetic model. Here, the plot was constructed against
qt versus t1/2 to explain the process of diffusion (refer
supplementary information S1, Fig. S4).
The derived parameters obtained by fitting adsorp-
tion rate-data into PFO and PSO kinetic models were
presented in Table 3. Values as depicted in Table 3,
revealed that, the adsorption data followed the PSO
kinetic model suggested by the higher value of R2 and
the lower SSE values. It can be suggested from the
derived values that, adsorption is taking place at the
rate of 0.00036 and 0.00052 mg g-1min-1 for Ca2?
and Mg2? respectively, and both sorbates individually
occupy two active sites. Another finding can be
concluded to further explain the adsorption behavior
is the dual mechanism i.e., chemisorption and
physisorption as suggested by PSO kinetic model
(Qureshi et al. 2017b).
Comparative study
The related studies were compiled to compare the
main features i.e. saturation time and adsorption
capacities of CNFs and a-CNFs (refer Table 4). It is
apprised from the compiled results that a-CNFs has
shown the higher adsorption capacities towards the
same targeted ions as compare to other adsorbents
used for the same purpose. Besides, the saturation time
is an important factor for practical implementation of
the lowest saturation time among others as compiled in
Table 4.
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 Cellulose

Table 3 The Pseudo-first-order and Pseudo-second-order adsorption kinetic parameters

Eq. qe, (exp) ± SD Pseudo-first-order Pseudo-second-order
mg g-1 2
K1 qe, (cal) R SSE K2 qe, (cal) R2 SSE
(min-1) (mg g-1) (mg g-1 min-1) (mg g-1)

Ca2? 65.38 ± 17.2 0.0397 37.71 0.93 0.18 0.00036 90.9 0.99 0.06
Mg2? 77.43 ± 19.5 0.118 401.4 0.85 0.20 0.00052 100 0.99 0.12

Table 4 Comparison of a-CNFs with other adsorbents

Sorbent pH qmax Saturation time (min) References
(mg g-1)
Ca2? Mg2? Ca2? Mg2?

CNFs ca. 7 42.5 55.4 – –

a-CNFs 65.38 77.43 60 60 This study
(*RN-COOH) ca. 6.7 40 21.89 – –
(RN-COONa) 36.0 19.46 100 100 Atia et al. (2005)
Natural pumice 57.27 44.53 – –
Modified pumice 6.8 62.34 56.11 150 180 Sepehr et al. (2013)
Sugar cane bagasse 13.5 15.6 – –
Modified sugarcane bagasse 10 46.1 54.1 240 240 Júnior et al. (2017)
Chemically modified cellulose (EMC) 5.5 15.6 46.1 120 120 Júnior et al. (2017)
Coconut shell activated carbon 7 48.5 55.88 1440 1440 Rolence et al. (2014)
*RN = amino-resins

Reusability
100

Keeping in mind a critical factor i.e. disposal of used Ca2+

Mg2+
Adsorption/desorption, %

sorbent to minimize the environmental degradation; 80 Cycle 1

recycling of saturated nanofibers was attempted. The
Desorption

20-mg sorbent was shaken in 15-mL Ca2? and Mg2?

Desorption

60 Cycle 2
solution separately, having concentration of 400 mg/L
Cycle 3
for 60-min. The fully-saturated nanofibers were air
40
dried and rinsed in 0.1 M NaOH solution for 2 h at
room temperature to strip out the Ca2? and Mg2? ions.
Finally, nanofibers were separated and thoroughly 20
washed using DI water and dried at 60 °C. The
adsorption–desorption cycle for used nanofibers was 0
repeated trice followed by the same procedure, as No. of cycle
shown in Fig. 7.
Fig. 7 Plot of a-CNFs reusability data for calcium and
magnesium

123
Cellulose
Conclusion
In this study adsorption behavior of anionic function-
alized electrospun cellulose nanofibers were exam-
ined. The grafting of carboxymethyl groups
(1.14 mmol/g) was achieved by the pad-batch process.
It is stated that, the same carboxymethyl groups are
mainly responsible for the improved adsorption
capacities of a-CNFs, studied at batch mode. The
Langmuir adsorption capacities for calcium and
magnesium were calculated as 65.38 and 77.43 mg
of either Ca2? or Mg2?/g of a-CNFs, respectively.
a-CNFs having 315 ± 20 nm average nanofiber diam-
eter and 0.865 m2/g BET surface area and it has shown
excellent thermal stability. Other approaches for the
modification of CNFs or tested the same material for
other positively charged contaminants may lead to a
sustainable solution for water de-contamination.
Acknowledgments Authors are thankful to the Mehran
University of Engineering and Technology Jamshoro and
Shinshu University Japan for their kind support.
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