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ORIGINAL PAPER
Abstract Herein we examine the adsorption behav- a-CNF web was characterized through scanning
ior of anionic-cellulose nanofibers (a-CNFs) having a electron microscopy (SEM), thermogravimetric anal-
carboxymethyl group concentration of 1.14 mmol/g ysis, and IR spectroscopy. SEM revealed
of nanofibers. The effects of key parameters governing 315 ± 10 nm average nanofiber diameters in the
the efficiency of the adsorption process in the batch a-CNF web. Moreover, zeta-potential measurements
mode were investigated. Electrospinning was revealed isoelectric point at ca. pH 4. The Freundlich
employed to fabricate cellulose acetate nanofibers isotherm and the Pseudo-second-order kinetic models
(CANFs). The fabricated nanofibers were then fit the adsorption data well. Also, the Langmuir
deacetylated to convert them into CNFs that were adsorption capacities of a-CNFs for Ca2? and Mg2?
subsequently anionized by a pad-batch process. The were 57.66 and 65.55 mg/g, respectively.
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Cellulose
Graphical abstract
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Cellulose
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Cellulose
room temperature for 24-h. The graphical depiction of subjected to DMF separately. As DMF is a good
the whole process was presented in Fig. S1 (refer solvent for CA, therefore, the cellulose cannot be
supplementary material, S1). dissolved in this solvent. Similarly, the deacetylation
and the success of chemical reactions were examined
Nanofiber characterization using Fourier transform infrared (FTIR) spectroscopy
(Shimadzu IR Prestige-21) at ATR (attenuated-total-
To examine the morphology, nanofibers were ana- reflectance) mode in the range of wavenumbers from
lyzed using a scanning electron microscopy (SEM, 4000 to 500 cm-1.
Hitachi S-4800). Prior to examination, nanofibers
were sputter-coated (BAL-TEC AG, Balzers, Liecht- Adsorption experiment
enstein) with gold (ca. 10-nm thick). The SEM images
were generated under an accelerating voltage of 5-kV A sequence of experiments was performed to obtain
with a working distance of 4.0-mm. The average adsorption data for kinetic and isotherm modeling. In
thickness of fabricated and modified nanofiber webs all experiments, 15-mL solution was shaken at a
was measured using digital micrometer (MCD130-25) temperature ca. 25 °C at 200 rpm using 20-mg of
having measuring sensitivity of 1-lm. The thermal nanofibers in each batch. The calcium and magnesium
stability of CNFs and a-CNFs as a function of solutions were prepared in DI water with pH adjust-
increasing temperature was investigated at a constant ments performed through the addition of either 0.5 M
heating rate of 15 °C/min (before and after reaching HCl or NaOH. For kinetics, adsorption experiments
iso-thermal conditions i.e., 102 °C for 30-min). The were systematically performed as a function of several
thermograms were obtained using SDT-Q600 thermal shaking times (10, 20, 30, 40, 50, 60, and 120 min) for
gravimetric analyzer (TA-Instruments) under a pure both Ca2? and Mg2?. Adsorption experiments were
nitrogen (gas) flow rate of 40-mL/min from 25 to also performed as a function of initial concentrations
500 °C. (25, 50, 75, 100, 200, and 400 mg/L) and pH of the
It is important to determine net charges on the solutions (ca. 4, 5, 6, 7, 8, 9, 10). The % adsorption
surfaces of CNFs and a-CNFs; therefore, zeta-poten- efficiency was calculated using Eq. 1.
tial measurements were performed for CNFs and
ðCo Cf Þ
a-CNFs using Zetasizer NanoZS instrument (Malvern, Adsorption efficiency ð%Þ ¼ 100 ð1Þ
Co
U.K.). For the analysis of samples, a suspension of 0.1
wt% was prepared in DI water. Further, the car- where Co and Cf represented the initial and residual
boxymethyl groups grafted on the a-CNFs were concentrations of Ca2? or Mg2? ions in mg/L. Also,
determined by the acid–base titration method, which adsorption capacity at equilibrium (denoted by qe) was
was discussed in the supplementary information (refer calculated in mg/g through the Eq. 2.
supplementary material, S2).
ðCo Ce Þ
Conformity of deacetylation and anionization was qe ¼ m ð2Þ
analyzed using two independent techniques i.e., DMF V
solubility test and FTIR. The qualitative test was where m is the mass of nanofibers measured in gram
performed to examine the conversion of CANFs into (g) and V is the solution volume in (L). All experi-
CNFs (deacetylation). In the examination the CANF ments were performed in triplicate and the mean
web (5 9 5 cm) and CNF web (5 9 5 cm) were values were provided in the current work. An error
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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
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Cellulose
200 to 400 °C due to molecular disintegration into a It is evident from the BET surface area and porosity
great number of char and volatile matters (Sehaqui analysis that CNFs and a-CNFs contain BET surface
et al. 2016b). The characteristic peak appeared at ca. areas of 15.20 m2/g and 4.94 m2/g respectively. In
350 °C (refer Fig. 4a), was mainly attributed to case of a-CNFs, the decrease in the BET surface area
cellulose. However, in case of a-CNFs, the main reflected the increase in diameter of a-CNFs in
degradation peak appeared at 405 °C. It was very comparison with CNFs. Another crucial reason for
interesting to recognize that, a-CNFs become more low surface was the pores blockage due to the
thermally stable over anionization. The potential penetration of carboxymethyl groups. Explanatory,
reason might be the presence of sodium metal ion in penetrated carboxymethyl groups do not allow nitro-
grafted functional groups providing shielding effect gen molecules (N2) to enter in the available pores,
(Gopiraman et al. 2015). Concludingly, a-CNFs can be which consequently reduces the BET surface area
used at a temperature up-to 405 °C. (Sehaqui et al. 2016a).
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Cellulose
Effect of pH
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Cellulose
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, %
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Cellulose
Ca2? 65.38 0.8–0.2 57.66 0.78 0.98 0.30 1.589 0.629 0.99 0.15
Mg2? 77.43 0.16–0.012 65.55 0.93 0.98 0.33 2.796 0.556 0.99 0.20
Freundlich isotherm is more suitable for the adsorp- where qt and qe represented the adsorption at the time t
tion of both calcium and magnesium ions. It indicates and the equilibrium respectively. K1 and K2 are rate
the heterogeneous active sites available for targeted constants for PFO and PFO respectively.
pollutants (Madaeni and Salehi 2009). Both PFO and PSO kinetic models do not define the
diffusion phenomenon occurs in the solid–liquid
Adsorption kinetics adsorption system. Therefore, the adsorption rate-data
was further fitted to the intra-particle diffusion (IPD)
For the practical implementations, it is necessary to kinetic model. Here, the plot was constructed against
investigate the rate at which sorption takes place. qt versus t1/2 to explain the process of diffusion (refer
Particularly at batch mode, it becomes utmost impor- supplementary information S1, Fig. S4).
tant to model the sorption rate-data obtained under The derived parameters obtained by fitting adsorp-
varied parameters. For example, the adsorption kinetic tion rate-data into PFO and PSO kinetic models were
modeling was performed by using data obtained as a presented in Table 3. Values as depicted in Table 3,
function of contact time ranging from 10 to 120 min. revealed that, the adsorption data followed the PSO
Other parameters, such as, pH (ca. 7), mass of kinetic model suggested by the higher value of R2 and
adsorbent (20 ± 0.2 mg), initial concentration of the lower SSE values. It can be suggested from the
solution (25-mg/L) were fixed for the entire kinetic derived values that, adsorption is taking place at the
experiment. From the adsorption rate data, it was rate of 0.00036 and 0.00052 mg g-1min-1 for Ca2?
perceived that, after 60-min, adsorption progressed at and Mg2? respectively, and both sorbates individually
the lower rate or even no significant removal was occupy two active sites. Another finding can be
observed. This might be due to the unavailability of concluded to further explain the adsorption behavior
active sites on the surface of a-CNFs (Qureshi et al. is the dual mechanism i.e., chemisorption and
2017b). physisorption as suggested by PSO kinetic model
The Lagergren’s first-order kinetic model was (Qureshi et al. 2017b).
initiated on the assumption that, the single ion can
occupy only one adsorptive site available onto the Comparative study
sorbent surface (Haider et al. 2015). However, for the
sorption of divalent metal ions, Ho proposed a second- The related studies were compiled to compare the
order kinetic model with the assumption that one main features i.e. saturation time and adsorption
adsorbate occupies two active sorption sites available capacities of CNFs and a-CNFs (refer Table 4). It is
onto the sorbent surface (Ho 1995). The equations for apprised from the compiled results that a-CNFs has
the Pseudo-first-order (PFO, Eq. 7) and Pseudo- shown the higher adsorption capacities towards the
second-order (PSO, Eq. 8) can be expressed as: same targeted ions as compare to other adsorbents
lnðqe qt Þ ¼ lnqe k1 t ð7Þ used for the same purpose. Besides, the saturation time
is an important factor for practical implementation of
t 1 t an adsorbent. Hence the resultant a-CNFs has revealed
¼ 2
þ ð8Þ
qt k 2 qe qe the lowest saturation time among others as compiled in
Table 4.
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Cellulose
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
Reusability
100
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
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