Article

Cite This: Ind. Eng. Chem. Res. 2017, 56, 14078-14088 pubs.acs.org/IECR

Cationization of Cellulose Nanofibers for the Removal of Sulfate Ions

from Aqueous Solutions
Muhammad Muqeet,† Hammad Malik,† Rasool Bux Mahar,*,† Farooq Ahmed,‡ Zeeshan Khatri,‡
and Krista Carlson§
†
U.S.-Pakistan Center for Advanced Studies in Water and ‡Nanomaterials Research Laboratory, Textile Engineering Department,
Mehran University of Engineering and Technology, Jamshoro 76060, Pakistan
§
Department of Metallurgical Engineering, University of Utah, Salt Lake City, Utah 84112, United States
*
S Supporting Information
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ABSTRACT: In this study, the adsorption properties of

cationized cellulose nanofibers (c-CNF) were examined for
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the removal of sulfate (SO42−) ions from aqueous solutions

under diverse experimental conditions. Nanofiber mats were
fabricated through electrospinning and cationized with 3-
chloro-2-hydroxypropyl trimethylammonium chloride
(CHTAC). The resultant c-CNF with an ammonium content
of 0.134 mmol/g showed the maximum adsorption capacity of
24.5 mg of SO42− per gram of sorbent using a Langmuir
isotherm model. A pseudo-second-order (PSO) kinetic model
was fitted to the adsorption rate data, showing a higher
adsorption rate of 0.0022 mg g−1 min−1. Scanning electron
microscopy (SEM) micrographs revealed the average fiber
diameter to be 280 ± 10 nm, and a BET surface area of 5.04
m2/g was obtained with a BET surface area and porosity analyzer. Fourier transform infrared (FTIR) spectroscopy confirmed the
conversion of cellulose acetate (CA) to cellulose and its subsequent cationization. Furthermore, the consequences of
cationization were evaluated by zeta potential measurements and thermogravimetric analysis (TGA).

1. INTRODUCTION biodegradable, and inexpensive sorbent is considered to be a

Sulfate contamination in surface water is a major concern in
both residential and industrial water supplies. When sulfate-
contaminated water is used for residential applications (e.g.,
drinking water), ingestion can lead to dehydration, gastro-
intestinal irritation, and laxative effects if the concentration
becomes greater than the permissible limit (i.e., 250 mg/L).1
Increasing sulfate levels in water provide a strong indication of
the acidification of bodies of water owing to water pollution,
which also causes health concerns.2 The use of sulfate-laden
water in industrial applications can produce hard scale in heat
exchangers, which ultimately decreases the heat-transfer rate.
Additionally, SO42− ions are corrosive in nature, which can lead
to material deterioration. The presence of sulfate ions in water
is primarily a result of chemical weathering, wide industrial
application of sulfuric acid, and acidic deposition due to the use
of coal and subsequent oxidation of minerals that contain
sulfur.3,4
Current methods and materials for the removal of sulfate
ions from water tend to be limited for different reasons or
costly. For example, biological and ion-exchange treatments are
costly, whereas chemical precipitation methods produce sludge,
which requires secondary treatment.5 Membrane filtration
(mostly reverse osmosis) is highly effective, but it has high
energy consumption.6 In contrast, adsorption with an effective,
feasible solution for the removal of ions from aqueous
solutions.7
Zirconium-loaded sorbents are considered to be an effective
choice for sulfate removal, but there are issues due to the cost
of zirconium metal.5 Cellulose has been reported extensively as
a sorbent for aqueous pollutants because of its low cost, as well
as its sustainable and ecofriendly nature.8 Past sulfate
adsorption studies have reported different materials such as
coir pitch carbon,9 modified raw straw,5 sugar cane bagasse
cellulose,10 surfactant-modified palygorskite,3 carbon residue
from biomass gasification,11 cationic cellulose nanofibers from
waste pulp residues,12 and a poly(vinyl chloride) (PVC)−
zeolite nanoparticle−surfactant anion-exchange membrane.4
These materials have limitations in terms of extended
adsorption times required for the removal of sulfate ions,
preparation method, or material costs.
The use of electrospun cationized cellulose nanofibers (c-
CNF) provides benefits over other absorption methods, as the
fabrication process is easy, scalable, and cost-effective.13,14 On
Received: September 8, 2017
Revised: October 30, 2017
Accepted: November 4, 2017
Published: November 5, 2017

© 2017 American Chemical Society 14078 DOI: 10.1021/acs.iecr.7b03739

Ind. Eng. Chem. Res. 2017, 56, 14078−14088
Industrial & Engineering Chemistry Research
Figure 1. Schematic showing the route for the synthesis of cationic cellulose nanofiber sorbent.
the other hand, the remarkable performance of c-CNF within a
possibly shorter equilibrium time (i.e., 75 min) might become
meaningful in industrial applications as it would save operating
time compared to other effective adsorbents.15 Additionally, the
fabrication process produces mats, which intrinsically immo-
bilizes the fibers, thereby enabling them to be reused.
Immobilization is a critical challenge to the implementation
of nanostructured materials in practical applications, as any
sorbent medium needs to be easily separated from aqueous
solutions after use. An immobilized matrix also enables the
potential for reuse, which is important from environmental and
economic perspectives.16,17
Several methods have been reported for the fabrication of
polymeric nanofibers, such as drawing,18 template synthesis,19
self-assembly,20 phase inversion,21 and electrospinning.22
Among these methods, electrospinning is emerging as a
reliable, scalable, and simple technique, because it produces
smooth and continuous nanofibers with controllable physical
properties from a variety of polymeric solutions.22,23
This work aimed to introduce an efficient, cost-effective, and
ecofriendly material for the removal of sulfate ions by the
adsorption technique. Kinetic and isotherm modeling of
experimental sorption data as a function of time and initial
concentration was performed to predict the adsorption
mechanism and capacity. On the other hand, several
instrumental techniques were employed to characterize the
sorbent, including scanning electron microscopy (SEM),
Brunauer−Emmett−Teller (BET) analysis, Fourier transform
infrared (FTIR) spectroscopy, thermogravimetric analysis
(TGA), and zeta potential measurements.
2. EXPERIMENTAL SECTION
2.1. Materials and Reagents. Cellulose acetate (CA, 39.8
wt % acetyl content and 30 kDa average molecular weight) was
obtained from Sigma-Aldrich Japan. N,N-Dimethylformamide
(DMF) and acetone were used as solvents. The cationizing
agent, 3-chloro-2-hydroxypropyl trimethylammonium chloride
(CHTAC; average molecular weight 188.1 g/mol, 69 wt %
concentration), was obtained from Sigma-Aldrich Japan. C.I.
Acid Blue 117 dye (molecular weight = 594.5 g/mol, λmax = 580
14079
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nm) was received from Archroma Pakistan Ltd. To adjust the
pH for adsorption experiments, 0.1 M HCl or NaOH was used.
2.2. Preparation of c-CNF Sorbent. CA solution (17 wt
%) was prepared in 2:1 acetone/DMF and filled in a plastic
syringe as reported in the literature.23 Briefly, a high-voltage
power supply (HV35P OV, FNM Co. Ltd.) was used under an
electric field of 14 kV to overcome surface tension forces with a
10-cm tip-to-collector distance. Nanofibers discharged from the
syringe tip having an internal diameter of 0.6 mm were
collected on a grounded rotating metallic collector (RMC)
wrapped in aluminum foil. The speed of the RMC was
controlled at about 12 rpm. The jet was elongated and dried
before it touched the collector, where it formed a ca. 50−70-
μm-thick well-connected mat of nanofibers.
The fabricated web of cellulose acetate nanofibers (CANF)
was deacetylated in 0.05 M NaOH aqueous solution for 30 h to
convert them into cellulose nanofibers (CNF). The sample was
air-dried and completely washed with deionized (DI) water to
remove unfixed −OH− groups.23−26 To prepare c-CNF, the
dried CNF web was again treated with 0.35 M NaOH (first
bath) and 1 M CHTAC (second bath) in a two-bath pad-batch
process.24,25 The complete reaction occurred in two steps: (1)
CHTAC was immediately converted into epoxy trimethylam-
monium chloride (EPTAC), which (2) subsequently reacted
with cellulose to form cationic cellulose.25 The two sequential
baths were 100% wet-on-wet. After the second bath, the sample
was left in an airtight pot at room temperature for 24 h to allow
ionic cross-linking to occur, and afterward, it was thoroughly
washed with DI water. A graphical depiction of this preparation
process is provided in Figure 1.
2.3. Characterization. Scanning electron microscopy
(SEM) was employed to examine the morphology of the
electrospun nanofibers. Samples were sputter-coated (BAL-
TEC AG, Balzers, Liechtenstein) with a 10-nm layer of gold
and imaged using a Helios NanoLab scanning electron
microscope at an accelerating voltage of 3 kV and a working
distance of 4.2 mm. The specific surface areas of the CNF and
c-CNF mats were analyzed using a BET surface area and
porosity analyzer (Micromeritics ASAP-2020), and the pore
size distribution was determined by nitrogen (N2) adsorption−
desorption isotherm. Both samples were degassed individually
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Industrial & Engineering Chemistry Research
Figure 2. (a−f) SEM micrographs and (b,d,f insets) histograms of (a,b) CANF, (c,d) CNF, and (e,f) c-CNF.
before analysis for 6 h at 90 °C to remove moisture from the
sample tube.
The success of the reaction and chemical modification was
determined using a Fourier transform infrared (FTIR)
spectrometer (Nilcolet iS50, Thermo Scientific) in attenu-
ated-total-reflectance (ATR) mode in the range of wave-
numbers from 4000 to 400 cm−1. Another qualitative test was
also employed in this study in which the conversion of CANF
to CNF was examined through the DMF solubility test as
discussed in the literature.27 DMF is a good solvent for
cellulose acetate, but cellulose cannot be dissolved in this
solvent.
The thermal stability of CNF and c-CNF was studied to
determine the changes in chemical and physical properties as a
function of increasing temperature at a constant heating rate of
10 °C/min, before and after reaching isothermal conditions
(i.e., 105 °C for 20 min). The data were obtained using an
SDT-Q600 thermogravimetric analyzer (TA Instruments)
under a nitrogen flow rate of 50 mL/min from 30 to 500 °C.
The degree of cationization was determined by an analytical
method in which Acid Blue 117 dye (molecular weight = 594.5
g/mol), which contains sulfonate groups, was adsorbed using
CNF and c-CNF at equilibrium conditions (shown in Figure
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S1, Supporting Information). The residual dye concentration
was determined by UV/vis/NIR (UV-3600, Shimadzu) spec-
troscopy at λmax = 580 nm. Zeta potential measurements of
CNF and c-CNF were performed at different pH values using a
Zetasizer NanoZS instrument (Malvern, U.K.). For sample
analysis, a suspension of ca. 0.1 wt % was prepared in DI water.
2.4. Adsorption Studies. A series of preliminary experi-
ments were performed for isotherm and kinetic modeling to
predict the adsorption mechanism and understand the
adsorption behavior. In all experiments, 20 mL of aqueous
solution was shaken (Lab-line Industries, Inc.) at 200 rpm at ca.
23 °C. Adsorption kinetic experiments were carried out by
following the batch adsorption method for various contact
times (15, 30, 45, 60, 75, 90, 105, 120, 135, and 150 min). The
sulfate solution was synthesized in DI water with pH
adjustments performed through the addition of either 0.1 M
NaOH or HCl.28 Adsorption studies were also carried out as a
function of pH (at values of ca. 5, 6, 7, 8, and 9) and initial
concentration of SO42− ions (at values of 25, 50, 100, 150, 200,
250, and 300 mg/L).
The percentage sulfate removal was determined by analyzing
the initial and residual SO42− ion concentrations in water by
UV/vis/NIR (UV-3600, Shimadzu) spectroscopy to measure
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the absorbance of the aqueous solution (filtrate) at a fixed
wavelength (λ max = 420 nm) and then applying the
turbidimetric method.3 In the turbidimetric method, residual
sulfate ions are precipitated in an acetic acid medium with
barium chloride (BaCl2) to produce barium sulfate (BaSO4)
crystals.29 The light absorbance of the barium sulfate
suspension was measured, and the sulfate concentration was
determined by comparison of the turbidity reading with a stable
calibration curve having R2 = 0.999. On the other hand, the
chloride concentration was critically investigated using the
silver nitrate (AgNO3) titration method to understand the ion-
exchange phenomenon.30
3. RESULTS AND DISCUSSION
3.1. Sorbent Characterization. Physical examination of all
of the fibers is important in the investigation of the effects of
the process parameters and external conditions on the
morphology during electrospinning and chemical modification.
Figure 2 shows SEM micrographs of CANF, CNF, and finally
prepared c-CNF in which the nanofibers appear to be
continuous and to exhibit a bead-free morphology. The
diameter of the originally fabricated cellulose acetate nanofibers
(CANF) ranged from 75 to 650 nm (average diameter = 280 ±
10 nm), and no significant change was observed in the fiber
appearance or in the diameter of the fibers after deacetylation
and cationization. However, slight changes appeared after
deacetylation in terms of the fiber diameter and surface
roughness. The fiber diameter decreased slightly, and the
micrographs show a rough surface, but, again, the fibers
retained their surface smoothness after cationization.
The BET surface areas of CNF and c-CNF are reported in
Table 1. A decrease in the surface area occurred after the
Table 1. BET Surface Areas, Pore Volumes, And Zeta
Potentials of the Sorbents at Neutral pH and Ammonium
Content in c-CNF
zeta
BET surface pore volume potential ammonium
sorbent area (m2/g) (cm3/g) (mV) content (mmol/g)
CNF 15.20 0.0230 −26.4 − section S1). In addition, surface charge information was
c-CNF 5.04 0.0017 39.1 0.134
cationization of CNF. One potential reason for this decrease is
CHTAC agglomeration owing to interparticle hydrophobic
interactions,31 which could result in pore blockage and hinder
the accessibility of nitrogen during testing.8 Evidence for this
blockage is also shown in the reduction of the cumulative pore
volume from 0.0230 cm3/g for CNF to 0.0017 cm3/g for c-
CNF.
The DMF solubility tests qualitatively confirmed the
conversion of CANF to CNF, as CNF did not dissolve upon
contact with DMF, indicating the complete removal of the
acetyl group. This conversion was also confirmed by the ATR-
FTIR spectra (Figure 3), which also showed the subsequent
cationization of CNF to c-CNF. Figure 3a shows three intense
peaks matching the stretching vibrations of CO, CCH3,
and COC at 1748, 1370, and 1235 cm−1, respectively.13
After deacetylation of CANF to CNF (Figure 3b), the carbonyl
absorption peak at 1748 cm−1 disappeared, and the OH
stretching peak at 3400 cm−1 broadened.32,33 According to
Ahmed et al.,27 this broader OH stretching peak confirms the
complete conversion of cellulose acetate into cellulose. After
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Figure 3. FTIR spectra of (a) CANF, (b) CNF, and (c) c-CNF.
functionalization, the c-CNF spectrum (Figure 3c) shows a
noticeable new peak at about 1450 cm−1, indicative of CN,
which is attributed to the presence of quaternary ammonium
groups.23
The TGA thermograms (Figure 4a,b) provide evidence that
CNF and c-CNF start to degrade at temperatures greater than
200 °C. The first weight loss in both samples was about 3−5%
up to isothermal conditions (i.e., 105 °C for 20 min) owing to
the release of significant amounts of moisture present in both
CNF and c-CNF.34 CNF lost ca. 92% of its weight in the range
from 220 to 480 °C owing to molecular disintegration into a
great number of volatiles and char. The thermogram for CNF
in Figure 4a shows the main degradation peak at ca. 345 °C.
This degradation peak was mainly attributed to cellulose. The
thermogram in Figure 4b, on the other hand, shows other
degradation peaks at ca. 220 and 280 °C that can be associated
with the structural heterogeneity of c-CNF.12 The thermal
degradation analysis indicates that c-CNF can be used at
temperatures up to 220 °C.
The ammonium content (0.134 mmol/g) in c-CNF was
determined by an analytical method (Supporting Information,
determined by zeta potential analysis. In Figure 4c, a shift of
the zeta potential from negative to positive can be seen. A
negative zeta potential corresponds to a negatively charged
surface and vice versa. CNF presents a negative zeta potential
throughout the analysis range, with values ranging from −26.4
to −10 mV, and its charge values are significantly dependent on
the pH of the CNF suspension. The values of the CNF zeta
potential over a wide range of pH are attributed to the
negatively charged surface groups (i.e., hydroxyl groups). On
the other hand, the results revealed a positive zeta potential for
c-CNF with values ranging from 31.9 to 39.3 mV, as expected
because of the presence of quaternary ammonium functional
groups.35 These results agree with the presence of positively
charged ammonium groups on the surface of c-CNF.
3.2. Comparative Sorption Study. Before selecting a
sorbent, one must consider different factors such as
effectiveness, capital costs, design simplicity, flexibility. and
ease of separation after adsorption. Adsorption data collected
on c-CNF were compared with previously reported data
(Table. 2) obtained for different sorbent materials such as rice
straw,5 palygorskite,3 zirconium-loaded sugar cane bagasse
cellulose,10 carbon residue from biomass gasification,11 coir
pitch carbon,9 and c-CNF obtained from pulp residue.12 A mat
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Figure 4. (a,b) TGA thermograms with differential curves of (a) CNF and (b) c-CNF. (c) Zeta potentials of CNF and c-CNF at different pH values.

Table 2. Adsorption Data for the c-CNF Membranea

material adsorption capacity (mg/g) pH equilibrium time (min) ref
c-CNF 24.5 6.8 75 present study
cellulose nanofibers from waste pulp 52.0 (modified) 7.7 ∼720 (overnight) 12
carbon residue from biomass gasification 7.59 (activated carbon) 2 1440 11
19.5 (modified CR) 4
rice straw 11.68 (raw) 6.4 120 5
74.76 (modified)
palygorskite 0.324 (natural) 360 3
0.324 (acid-activated) −
3.240 (surfactant-modified) 4
sugar cane bagasse cellulose 57.5 (zirconium-loaded) 10 5 10
coir pitch carbon 0.06 (no ZnCl2) − 30 9
4.9 (ZnCl2-activated) 4
a
Additional data from other studies included for comparison.

of entangled fibers is advantageous from the standpoint of use
and reuse because, in practical implementations, it is difficult to
separate free-standing nanostructured materials from aqueous
solutions.43 Although several authors have reported higher
adsorption capacities for other materials and/or preparation
methods compared to the electrospun nanofibers developed in
this work, there are several drawbacks to those materials that
could limit their use in commercial settings, such as extended
adsorption times and high material costs.
3.3. Binding Mechanism of Sulfate Ions. The adsorption
behavior and binding mechanism of sulfate ions on the sorbent
used in this work were explored by comparing the adsorption of
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chloride and sulfate ions using CNF and c-CNF. At a constant
sulfate ion concentration (50 mg/L) and time (75 min), it was
found that electrospun CNF showed 18% removal of sulfate
ions and 11% removal of chloride ions. Similarly, c-CNF
showed 75% and 32% removals of sulfate and chloride ions,
respectively, under the same equilibrium conditions (see Figure
5a). This difference in adsorption was due to the cationic
charge strength of the ammonium groups on c-CNF, and the
prepared c-CNF membrane was found to be more selective
toward divalent sulfate ions.12
Bearing in mind the problem of disposing of used adsorbent
and minimizing environmental pollution due to waste disposal,
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Figure 5. (a) Comparative adsorption removals of sulfate and chloride. (b) Schematic map showing the electrostatic relationship between negatively
charged sulfate ions and positively charged ammonium groups grafted on the surface of cationic cellulose nanofibers.

recycling of saturated c-CNF after the first trial of the PFO model
adsorption test was attempted. For this purpose, saturated c- k1
CNF was regenerated using 0.35 M NaOH (for sulfate log(qe − qt ) = log qe − t
2.303 (1)
desorption), and ca.1−2 mg of fresh c-CNF was added to
make up for the weight lost during adsorption and the fixed PSO model
weight of nanofibers (i.e., 10 mg), as well as stimulating the t 1 t
used materials with new active sites. The experimental = +
qt k 2qe 2 qe (2)
observations showed that the regenerated cellulose nanofibers
were capable of removing 55% of the sulfate ions present in the where qt and qe represent the amounts adsorbed at time t and at
aqueous solution under the optimized conditions (pH 6.8; equilibrium, respectively, and k1 and k2 represent the rate
initial concentration, 50 mg/L; contact time, 75 min). coefficients for the PFO and PSO kinetic models,
3.4. Adsorption Kinetics. It was perceived from the kinetic respectively.44
data that the adsorption was rapid in the first 15 min and Solid−liquid adsorption generally involves film diffusion and
afterward progressed at the comparatively lower rate because of intraparticle diffusion (IPD).36 Neither the PFO nor PSO
kinetic model describes this diffusion phenomenon. Therefore,
the sufficient numbers of vacant active sites available at the
the IPD model (Figure 6d) was constructed to define the
initial times on the surface of sorbent.44 At the 75-min process of diffusion. According to this model, a plot of qt versus
equilibration time, the surface of the sorbent became saturated, t1/2 must be linear and pass through the origin for IPD to be the
and subsequently, the removal efficiency became almost rate-limiting step. In the model developed by Poots, Morris,
constant. This equilibrium time was selected for further and McKay, the initial rate of IPD is calculated by linearization
adsorption studies. of the equation
Pseudo-first-order (PFO; Figure 6b) and pseudo-second-
qt = K it 0.5 + C (3)
order (PSO; Figure 6c) kinetic models describe the adsorption
rate and the factors that influence the rate in the attainment of where Ki represents the IPD rate constant and C is the
equilibrium in a reasonable amount of time.36,37 The equations intercept. The value of C (intercept) gives an idea of the
for these models can be expressed as follows thickness of the boundary layer; that is, the larger the value of
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Figure 6. (a) Plot of sulfate uptake kinetics by c-CNF (pH ∼7; mass of sorbent, 10 mg; initial concentration, 50 mg/L; shaking time range, 15−150
min). (b−d) Fits to (b) pseudo-first-order (PFO), (c) pseudo-second-order (PSO), and (d) intraparticle diffusion (IPD) kinetic models.

Table 3. Kinetic Parameters of Pseudo-First-Order, Pseudo-Second-Order, and Intraparticle Diffusion Rate Equations
pseudo-first-order pseudo-second-order intraparticle diffusion
parameter value parameter value parameter value
−1 −1 −1 −1 −1/2
K1 (min ) 0.0285 K2 (mg g min ) 0.0022 Ki (mg g min ) 1.68
qe (mg/g) 22.98 qe (mg/g) 62.11 C 40.64
R2 0.673 R2 0.995 R2 0.76

C, the greater the boundary layer effect.38 The value of the IPD
rate constant (see Table 3) clearly shows that the boundary
layer has a significant effect on the diffusion mechanism of
sulfate ions uptake by c-CNF.
The results reported in Table 3 provide the values of
constants obtained by kinetic modeling. These results indicate
that the adsorption of sulfate ions follows PSO kinetics,
suggesting the co-occurrence of both physisorption and
chemisorption.39,40 Figure 6d shows that a plot of qt versus
t1/2 is not linear over the whole range of time. Rather, the data
points exhibit a trilinearity of three successive adsorption stages
of mass transport with a decreasing rate. This type of trilinearity
can be attributed to (1) adsorption on the outer surface
associated with boundary layer diffusion, (2) IPD states where
this step is highly involved in the rate control of this
mechanism, and (3) the ultimate equilibrium stage where
14084
IPD starts to become slower because of the low sulfate ion
concentration in the aqueous solution.40
3.5. Adsorption Isotherm. As the concentration of sulfate
ions present in natural water varies depending on location, it is
imperative to investigate the adsorption capacity of the sorbent
at different concentrations. Figure 7 illustrates the adsorption of
sulfate ions as a function of initial concentration. Figure 7a
shows the reduction in adsorption efficiency of c-CNF with
increasing initial concentration of sulfate ions. This reduction
can be attributed to the finite number of active sites available on
c-CNF that were occupied by adsorbed sulfate ions,
subsequently leading to a decrease in sulfate adsorption.
The experimentally derived batch adsorption data were also
correlated with the two most famous adsorption isotherm
models, namely, the Langmuir and Freundlich models, to
determine the adsorption mechanism.7 The equations for the
Langmuir and Freundlich models are given by
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Figure 7. (a) Effects of initial concentration on the adsorption of sulfate ions (pH ∼7; mass of sorbent, 10 mg; shaking time, 75 min; concentration
range, 25−300 mg/L). (b−d) Fits to (b) nonlinear adsorption isotherms, (c) the Langmuir isotherm, and (d) the Freundlich isotherm.

Langmuir model the sorbent (c-CNF) and the concentration of residual solute in
Ce C solution after adsorption.
1
= e + The essential characteristic term of the Langmuir equation
qe qm qmKL (4) can be expressed by RL, which is given by
Freundlich model RL = 1/(1 + KLC0) (6)
1
ln qe = ln Ce + ln KF where RL designates the type of isotherm, which can be linear
n (5)
(RL = 1), irreversible (RL = 0), favorable (0 < RL < 1), or
where qm is the maximum adsorption capacity; Ce is the unfavorable (R L > 1), and C 0 represents the initial
equilibrium solution-phase concentration; KL is the Langmuir concentration of sulfate ions.
constant, which is associated with the adsorption free energy Table 4 shows that the Langmuir model fit the adsorption
and specifies the sorbent−sorbate affinity; KF is the Freundlich isotherm parameters better than the Freundlich model.
constant, which gives the adsorption capacity at unit Moreover, the maximum experimental adsorption value (i.e.,
concentration; and the value of 1/n in the Freundlich
isotherm describes the comparative dissemination of active Table 4. Parameters of the Langmuir and Freundlich
sites: the smaller the value of 1/n, the greater the availability of Adsorption Isotherms for Sulfate (SO42−) Adsorption
heterogeneous active sites and the greater the likelihood that
the adsorption mechanism is physical in nature.15 The Langmuir isotherm Freundlich isotherm
Langmuir adsorption isotherm model assumes that adsorption
constant value constant value
of a monolayer occurs with no interactions between adjacent
adsorbed molecules on identical surface sites and that the same qexp (mg/g) 27.32 1/n 0.229
mechanism is involved for all adsorption.9,45 This contrasts with qm,cal (mg/g) 24.5 Kf (mg/L) 2.076
the Freundlich model, which is an empirical equation and the KL (L/mg) 0.432 R2 0.742
linear form of this isotherm model. This is an empirical RL 0.0076
relationship between the solute (sulfate ion) concentration on R2 0.990

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qexp = 27.32 mg/g) is very close to the calculated value of qm,
the maximum theoretical adsorption value of sulfate ion uptake
for c-CNF. The current results are evidence for the formation
of a monomolecular layer of sulfate ions on the surface of c-
CNF, which also confirms that chemisorption is responsible for
the uptake of sulfate ions.46,47
3.6. pH Effect on Sulfate Adsorption. The pH value of
an aqueous solution has a strong effect on the adsorption
efficiency of a sorbent. Figure 8 displays the sulfate removal
Figure 8. Plot of percentage sulfate removals at different pH values
(initial concentration, 50 mg/L; mass of sorbent, 10 mg; shaking time,
75 min).
percentages obtained using c-CNF. The sulfate adsorption
behavior in near-neutral pH solutions is based on the
interaction of the positively charged ammonium groups with
the negatively charged sulfate ions present in the aqueous
solution.41 A maximum removal of ca. 73% was achieved at pH
7 because of the number of factors employed in the present
adsorption such as hydrogen bonding, electrostatic interactions,
and complexation.43 Another potential reason for this behavior
can also be provided by the Hofmeister effect if the solution
contains nonpolar molecules.48 However, in this study,
adsorption experiments were conducted in synthetically
prepared sulfate solutions.
At lower pH values, the SO42− ions present in aqueous
solution are protonated to form hydrogen sulfate or bisulfate
ions (HSO4−). Consequently, there will be a low force of
attraction between the positively charged surface of the sorbent
and the protonated sulfate ions, resulting in a reduction of the
percentage adsorption.43,46 On the other hand, as the pH is
increased, the concentration of H+ decreases, and at the same
time, the concentration of OH− increases. Thus, OH− and
SO42− coexist with the same electrostatic charges and compete
for the same adsorption sites available on c-CNF. This is the
reason for the ddecrease in the adsorption efficiency with
increasing pH.9,42 In addition, the presence of Na+ ions from
the NaOH titrant could have produced a transmission effect,
which is responsible for a reduction in removal efficiency.35 Still
for lower and higher pH values, the removal percentages of
sulfate ions are greater than 50%. This indicates the influence of
physical adsorption due to hydrogen bonding and the interpore
structure of the nanofibers.
14086
Article
4. CONCLUSIONS
In this study, nanostructured cationic cellulose nanofibers (c-
CNF) with an average diameter of 280 ± 10 nm and an
ammonium content of 0.134 mmol/g were successfully
prepared. The chemical alteration reversed the surface charge
of CNF to positive values and revealed the other thermal
degradation peaks of CHTAC-modified cellulose in TGA
experiments. Owing to the positive charges, c-CNF showed a
promising capability to adsorb negatively charged sulfate ions
through electrostatic interactions and complexation. It was
concluded that the Langmuir model fit the data well, presenting
a high value of R2 = 0.99, and that the experimental adsorption
data followed a pseudo-second-order kinetic model, indicating
the co-occurrence of both physisorption and chemisorption.
The maximum adsorption capacity of c-CNF was determined
to be 24.5 mg of sulfate ions per gram of sorbent.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.7b03739.
Description of the method used to determine the degree
of cationization, UV−vis spectra of Acid Blue 117 dye,
and TGA curve representing the percentage weight loss
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: rbmahar.uspcasw@faculty.muet.edu.pk. Tel.: +92-22-
2772250 ext. 6508.
ORCID
Rasool Bux Mahar: 0000-0002-1966-0397
Zeeshan Khatri: 0000-0001-8779-3805
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors are grateful to the U.S.-Pakistan Center for
Advanced Studies in Water, Mehran University of Engineering
and Technology, Jamshoro, Sindh, Pakistan. for providing
financial support. We also acknowledge the Roger and Dawn
Crus Center for Renewable Energy at the University of Utah,
Salt Lake City, UT, for technical assistance and sample
characterization.
■
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