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Article

Cite This: ACS Omega 2018, 3, 13045−13054 http://pubs.acs.org/journal/acsodf

Graphene Oxide−Chitosan Composite Material for Treatment of a

Model Dye Effluent
Mina Sabzevari,† Duncan E. Cree,† and Lee D. Wilson*,‡
†
Department of Mechanical Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, Saskatchewan S7N 5A9, Canada
‡
Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, Saskatchewan S7N 5C9, Canada
*
S Supporting Information

ABSTRACT: Graphene oxide (GO) was cross-linked with chitosan

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to yield a composite (GO-LCTS) with variable morphology,

enhanced surface area, and notably high methylene blue (MB)
adsorption capacity. The materials were structurally characterized
using thermogravimetric analysis and spectroscopic methods (X-ray
Downloaded via 5.188.219.231 on October 11, 2018 at 19:15:46 (UTC).

diffraction, Fourier transform infrared spectroscopy, Raman spectros-

copy, and 13C solid-state NMR) to support that cross-linking occurs
between the amine groups of chitosan and the −COOH groups of
GO. Equilibrium swelling studies provide support for the enhanced
structural stability of GO-cross-linked materials over the synthetic
precursors. Scanning electron microscopy studies reveal the enhanced
surface area and variable morphology of the cross-linked GO
materials, along with equilibrium and kinetic uptake results with
MB dye in aqueous media, revealing greater uptake of GO-LCTS
composites over pristine GO. The monolayer uptake capacity (Qm; mg g−1) with MB reveals twofold variation for Qm, where
GO-LCTS (402.6 mg g−1) > GO (286.9 mg g−1). The kinetic uptake profiles of MB follow a pseudo-second-order trend, where
the GO composite shows more rapid uptake over GO. This study reveals that the sorption properties of GO are markedly
improved upon formation of a GO−chitosan composite. The facile cross-linking strategy of GO reveals that its physicochemical
properties are tunable and versatile for a wider field of application for contaminant removal, especially over multiple
adsorption−desorption cycles when compared against pristine GO in its highly dispersed nanoparticle form.

1. INTRODUCTION has a low aqueous solubility, GO is highly dispersible in water

The development of advanced materials for the controlled
removal of dyes and organic contaminants from effluent
originating from printing, food, textile, paper, and pharma-
ceutical industries1,2 is an active area of research. Many dye
species are known to be carcinogenic and can affect water
quality, as shown by undesirable human and ecosystem health
effects.3 Adsorption-based removal is an efficient process for
the capture of dyes and contaminants from wastewater
systems. Solid phase adsorbents represent an effective
remediation strategy because of their technical simplicity,
high efficiency, low cost, and potential reuse of the
adsorbent.4,5 Therefore, continued effort is required for the
development of an efficient, novel, and cost-effective solid
adsorbent material.
Recently, graphene- and graphene oxide (GO)-based
materials have been studied for applications in adsorption
and water treatment.6,7 In particular, GO has emerged over the
past decade as a next-generation material for wastewater
treatment because of its low-cost production, large surface
area, and strong interaction with a wide range of anionic,
cationic, or neutral dyes in aqueous media.8,9 Graphene is
comprised of sp2-hybridized carbon atoms arranged in a two-
dimensional honeycomb lattice. In contrast to graphene, which
and organic solvents because of the presence of polar
functional groups and high surface area.9 The highly negative
charge density of GO in aqueous solutions provides effective
adsorption sites for cationic dyes,6 such as methylene blue
(MB) and serves as a material for gas capture (e.g., N2 and
CO2) applications.10,11 Although GO is a promising material as
an adsorbent, efficient recovery is problematic because of its
tendency of forming stable colloids that hinder phase
separation. However, the use of polymers to immobilize GO
offers an opportunity to produce composite materials with
unique properties for solid phase separation and adsorption.
Fabrication of framework structures from individual GO
sheets was studied using physical and chemical interactions to
yield GO self-assembled films, hydrogels, and aerogels.12,13
However, produced GO frameworks have limited applications
in wastewater treatment because of scalability as a result of
repulsive hydration forces between GO layers that result in
electrostatic separation.14 Therefore, the development of stable
interconnected GO frameworks is one strategy for the
Received: August 2, 2018
Accepted: September 21, 2018
Published: October 11, 2018

© 2018 American Chemical Society 13045 DOI: 10.1021/acsomega.8b01871

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Figure 1. Synthetic procedure for cross-linked GO-LCTS composite materials.
successful application of these materials in wastewater
treatment. Previous works reveal that cross-linking and other
forms of synthetic modification of GO sheets can improve the
sorption properties, as shown by the variation in methylene
blue uptake (cf. Table S1, Supporting Information).15,16 The
resulting material would offer higher sorption capacity
compared to pure GO because of the increased available
adsorption sites as well as improved stability and mechanical
structure for producing thin films.17,18
GO framework structures can be achieved by cross-linking
GO sheets through noncovalent or covalent bonds by using
biopolymers as cross-linkers.15,19 Chitosan (CTS) is among a
group of abundant renewable biopolymers20 that has been
used as an adsorbent for removal of organic dyes from aqueous
solution because of the presence of active adsorption sites
(hydroxyl and amino groups).21 CTS can undergo an
amidation reaction with the carboxyl groups of GO to form
a homogenous and well-dispersed GO composite.22,23 On the
basis of the foregoing considerations, a key objective of this
study was to develop a facile method for the preparation of a
GO composite by cross-linking GO with CTS to obtain a
material with improved physicochemical properties for
sorption-based applications. To this end, spectroscopic
methods [Fourier transform infrared spectroscopy (FTIR),
Raman spectroscopy, and 13C nuclear magnetic resonance
(NMR)] were used to characterize the structure and
composition of cross-linked GO composites. Also, thermogra-
vimetric analysis (TGA) and scanning electron microscopy
(SEM) were used to analyze the thermal stability and surface
morphology of the GO composites. The adsorption properties
were evaluated under equilibrium and kinetic conditions using
MB in aqueous solution. It will be shown that this study
contributes significantly to the field of sustainable GO
composites through the development of a suitable adsorbent
for contaminant removal with tunable properties that exceed
those of GO alone, and also can be reused for multiple cycles
of adsorption−desorption. Also, this study advances the field of
GO composites by use of a facile cross-linking methodology
that is low cost and ecofriendly, where the structure of the
composites are supported by several complementary methods.
2. EXPERIMENTAL SECTION
2.1. Materials. Low molecular weight CTS (LCTS) (Mw =
950 000 Da, 75−85% deacetylation), sodium nitrite (NaNO3),
potassium permanganate (KMnO4), sulfuric acid (98%, ACS
grade), MB (high purity, biological stain), and hydrogen
peroxide (30 v/v %) used in this study were obtained from
Sigma-Aldrich Canada Ltd. HPLC-grade methanol was
obtained from Fisher Scientific, NJ, USA. Filter paper
(Ahlstrom grade 613, 7.5 cm) and graphite flakes, natural,
325 mesh, 99.8% (metals basis) were obtained from Alfa Aesar
Thermo Fisher Scientific and further purified by Soxhlet
extraction for 24 h using HPLC-grade methanol, followed by
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drying in a vacuum oven at 60 °C for 12 h to remove
impurities.
2.2. Synthesis of GO. GO was synthesized from graphite
flakes using the modified Hummer’s method.24 Briefly, 100 mL
concentrated H2SO4 was added into a 500 mL flask filled with
4 g of graphite in an ice bath, followed by the addition of 2 g of
NaNO3, and stirred for 4 h. Then, 12 g of KMnO4 was
gradually added while the mixture was stirred for 2 h. The ice
bath was removed, and the system was heated at 35 °C for
another 30 min. Subsequently, 240 mL of distilled water was
slowly added to the system, which caused a temperature rise to
90 °C, and continued to stir for another 30 min. Then, 160 mL
of water and 30 v/v % H2O2 were added to terminate the
reaction. The solution was stirred overnight and purified using
multiple washings with Millipore water, HCl (30%), and
ethanol until it reached neutrality (pH 7). After multiple
washings, the solid GO was vacuum-dried at 40 °C to obtain
dried GO powder.
2.3. Preparation of GO−CTS Cross-Linked Composite.
The composite materials (GO-LCTS) were prepared by
making the GO solution with a concentration of 3 mg/mL.
LCTS solution was produced by dissolving 5 g of LCTS in 500
mL of 1 v/v % glacial acetic acid with stirring. The resulting
LCTS solution (1 v/v %) was added drop-wise to the GO
solution with continuous stirring for about 4 h. The mixture
was neutralized to pH ≈ 7 using 1 M NaOH followed by
stirring for 12 h. Herein, several cross-linked GO samples were
prepared with variable precursor weight ratios. The results
reported herein are focused on GO-LCTS with 1:0.3 (w/w)
ratio because this condition affords a minimum amount of
cross-linker level to stabilize the GO-LCTS composite. The
solution was washed with Millipore water followed by pouring
onto a glass surface and dried at ambient conditions for 48 h to
obtain the GO-LCTS films with an average thickness ranging
from 20 to 60 μm. An outline of the experimental sequence is
shown in Figure 1.
2.4. Characterization. 2.4.1. Surface Charge (ζ Potential)
Measurement. The ζ potential of the GO solutions (0.01 w/v
%) were measured at various pH values (4−12) using a
Zetasizer Nano ZS (Nano ZS90, Malvern, UK), before and
after cross-linking. All samples were diluted to 0.01 w/v % and
measured in Milli-Q water at different pH.
2.4.2. Scanning Electron Microscopy. The surface
morphology and surface topography of non-cross-linked and
cross-linked composite materials were studied using SEM
(Hitachi model SU8010). SEM images of samples were
collected under an accelerating voltage (5 kV).
2.4.3. FTIR Spectroscopy. A Bio-Rad FTS-40 IR spec-
trophotometer was used to obtain the IR spectra of the
composite materials. The sample powder was mixed with pure
spectroscopic-grade KBr (weight ratio: 1:10). The FTIR
spectra were obtained in reflectance mode with a resolution
of 4 cm−1 over a spectral range of 400−4000 cm−1.
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Figure 2. ζ Potential for GO at variable pH and GO-LCTS composite. The right-hand panel corresponds to solution conditions at ambient pH and
295 K.
2.4.4. Raman Spectroscopy. The Raman spectra of pure
GO and cross-linked GO-LCTS samples were obtained to
monitor changes in the degree of order−disorder of the GO
structure after cross-linking using a Renishaw Raman
spectrophotometer equipped with an inVia reflex optical
microscope and a laser excitation wavelength of 514.5 nm
over the spectral range 3700−5000 cm−1.
2.4.5. 13C Solid-State NMR. The 13C solid NMR spectra of
GO and GO-LCTS composite material were obtained using a
Bruker AVANCE III HD spectrometer equipped with a 4 mm
DOTY cross-polarization with magic angle spinning (CP/
MAS). Spectra were acquired using CP/MAS using a solid
probe operating at 125.77 MHz (1H spectral frequency at
500.23 MHz). The 13C CP/MAS NMR spectra were acquired
using a contact time of 0.75 ms, MAS at 10 kHz, and 1H 90°
pulse of 3.5 μs, with a ramp pulse on the 1H channel. All
spectral data were recorded using 71 kHz SPINAL-64
decoupling during acquisition with external reference to
adamantane at δ = 38.48 ppm.
2.4.6. X-ray Diffraction. The X-ray diffraction (XRD)
patterns of GO and cross-linked composite materials were
obtained using a PANalytical Empyrean powder X-ray
diffractometer equipped with a Co source and X’Celerator
detector. The powdered samples were placed in a horizontal
mode and mounted for the test. The PXRD patterns were
measured in continuous mode over a range of 5−60° 2θ, with
a scan speed of 335 ms/step (3°/min).
2.4.7. Thermogravimetric Analysis. Thermal stability and
decomposition temperature of the materials were measured
using a TA Instruments Q50000IR TGA system, which was
operated from 23 to 500 °C with a heating rate of 5 °C min−1
under a nitrogen atmosphere.
2.4.8. Equilibrium Swelling Properties. The swelling
properties and water uptake of the GO-LCTS composites
and the precursors (graphite, LCTS, and GO) were evaluated
by immersing 50 mg of the material in 12 mL Millipore water
as the solvent and equilibrated in a horizontal shaker for ∼24
h.25 The weight of swollen samples (Ws) was determined by
weighing hydrated samples after removing excess surface water
with filter paper. By drying the hydrated samples in an oven at
60 °C, the dry weight (Wd) was obtained and the water
swelling (Sw) was calculated using eq 1 as below
Ws − Wd
Sw (%) = × 100
Wd
Article
2.5. Sorption Studies of GO-LCTS Composite.
2.5.1. MB Sorption of GO-LCTS Composite. The equilibrium
MB uptake capacity of GO and GO-LCTS composites was
evaluated by batch mode using fixed amounts of adsorbent in
sealed glass vials. The adsorption isotherms obtained by such
batch mode conditions used a dosage of 5 mg adsorbent with 7
mL MB solution (pH = 7) at variable initial MB (100−1000
μM). Samples were mixed on a horizontal shaker (SCILOGEX
SK-O330-Pro) for 24 h to ensure equilibrium. A 1 mM stock
solution of MB in water was prepared, and other solutions
were obtained by appropriate dilution. Absorption measure-
ments were carried out at λ = 664 nm, and a linear calibration
curve for MB absorbance at variable concentration was
obtained with a slope of 0.0615 = Abs664nm/[MB]. After 24
h shaking to achieve equilibrium, the sample powders were
separated from the solution by centrifugation and the residual
(MB) was measured using UV−vis spectroscopy (Varian Cary
100 Scan UV−vis spectrophotometer). The equilibrium uptake
of MB was calculated using eq 2.
C0 − Ce
Qe = ×m
V (2)
−1
where Qe (mg g ) is the MB adsorbed per unit mass of
adsorbent, C0 (mM) is the initial dye concentration, Ce (mM)
is the residual amount of MB, V (L) is the volume of the MB
solution, and m (g) is the weight of the adsorbent.
The GO composite was tested for its regeneration properties
over several adsorption−desorption cycles with MB, as
described in further detail in the Supporting Information.
2.5.2. Kinetic Uptake Studies of MB. Kinetic adsorption
studies of GO samples cross-linked with LCTS toward MB as
the dye probe in aqueous solution to estimate the sorption
capacity of GO before and after cross-linking with LCTS.
Kinetic isotherm profiles were obtained by plotting Qt versus t
using a one-pot method described elsewhere to account for
adsorption processes of nanomaterial sorbents.26 In brief, ca.
100 mg of a powdered sample was placed into a folded filter
paper with both ends sealed before adding to the MB solution,
where it should be noted that the adsorption of MB by the
filter paper was deemed to be negligible overall.27 The sealed
filter paper was immersed in a fixed volume (250 mL) of an
aqueous 5 μM MB solution. Aliquots of MB solution were
pipetted (3 mL) at variable time intervals and further
quantified via UV−vis spectrophotometry (Varian Cary 100
Scan UV−vis spectrophotometer). It is worth mentioning that
(1) the filter paper used in our experiment provides reliable results
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Figure 3. SEM micrographs of carbonaceous materials (GO, graphite) and the GO-composite material: (a) graphite, (b) GO, and (c) GO-LCTS.
Figure 4. FTIR (a) and Raman spectra (b) of the precursors and GO-LCTS.
because of the fast diffusion processes and negligible
adsorption throughout the experiment.27 The MB adsorption
capacity at variable times for the GO and GO-LCTS materials
was calculated using eq 3
C0 − Ct
Qt = ×V
m (3)
where C0 and Ct are the concentration values of MB initially
and at variable time (t), respectively; V is the solution volume;
and m is the weight of the adsorbent. The adsorption kinetics
can be described by the pseudo-first-order and the pseudo-
second-order (PSO) model to evaluate parameters of the
isotherm. In this study, the best-fit results were obtained by
PSO model as given in eq 4
Q e 2 k 2t
Qt =
1 + k2 t Q e (4)
−1
where Qt is the amount of solute adsorbed at time t (mg g ),
Qe is the amount of solute adsorbed at a pseudo-equilibrium
(mg g−1) condition, and k2 is the rate constant according to the
PSO adsorption model. The kinetic sorption parameters that
were deduced from the PSO model in this study provide a
comparison of sorption characteristics of GO and its cross-
linked form with LCTS.
3. RESULTS AND DISCUSSION
3.1. Surface Charge Material Characterization. The
point of zero charge of GO at different pH conditions is an
important indicator of the nature of adsorptive interactions
because the surface charge of the adsorbent phase (GO and
GO-LCTS composite) is likely to affect the adsorption
capacity of MB. As shown in Figure 2, the ζ potential of the
GO materials was highly negative, and this charge decreases
continuously with increasing pH from 4 to 10, and is
consistent with previous literature.28 This negative charge is
primarily because of the introduction of various functional
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groups (such as −OH and COOH) on the GO surface, which
form during the oxidation of graphite. Such groups become
ionized at higher pH and result in enhanced negative charge.7
Therefore, it is expected that GO and its modified forms will
display favorable affinity with cationic species, especially over
the pH range 6−12. GO forms a stable suspension in aqueous
solution in the pH range 6−12 because its ζ potential is below
−30 mV. Accordingly, particles with ζ potential lower than
−30 mV are strong enough to maintain a stable colloidal
solution because of repulsive forces between them.29 There-
fore, it would be appropriate to run the cross-linking
experiment at any pH above 6. The ζ-potential measurement
of GO-LCTS composite further supports the formation of the
GO-LCTS composite. The ζ potential of GO was −37.5 mV
prior to cross-linking with LCTS, whereas the surface charge of
the composite was −2.5 mV.
3.2. SEM Results. Figure 3 shows SEM micrographs for
GO and its cross-linked form (GO-LCTS). The SEM images
depict the graphite starting material and the synthesized GO,
further revealing the layered structure of these materials. By
comparison, the cross-linked GO composites have wrinkled
edges with irregular shapes of dense interconnected layers. The
micrographs reveal that cross-linking of GO alters its regular
layered morphology and surface roughness according to the
cross-linker type. The SEM results indicate that the composites
possess higher surface roughness and porosity when compared
with pristine graphite or GO. These variations in morphology
and textural properties provide support for unique product
morphology that occurs upon formation of a cross-linked
composite between GO and LCTS.
3.3. FTIR and Raman Spectral Characterization. IR
spectroscopy was used to monitor the changes in surface
functional groups upon the formation of GO from graphite and
the structural characterization of the GO-LCTS composite.
The FTIR spectra of the cross-linked composite material and
its precursors (GO and LCTS) are shown in Figure 4a.
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First, the GO preparation was characterized by identifying
the characteristic IR bands for −OH stretching at ∼3200−
3700 cm−1, carbonyl groups (CO) at ca. 1680−1730 cm−1,
CC groups at ca. 1550−1650 cm−1, and epoxy groups at ca.
1230−1350 cm−1. For the IR spectrum of LCTS, characteristic
bands are centered at 1152 and 895 cm−1, corresponding to
signatures assigned to a glucopyranose ring unit, whereas the
CO stretching vibration of amide I (NHCO) and amide II
(N−H) bending of NH2 is observed at 1650 and 1590 cm−1,
respectively. The presence of the band of both precursors (GO
and LCTS) is supported by the similar spectral features of
cross-linked composite materials. A noteworthy observation for
the cross-linked GO composites includes the absence of some
bands or changes of intensity when compared to similar IR
bands for the unmodified GO. For instance, the LCTS
glucopyranose band at 895 cm−1 was not observed in GO-
LCTS. The formation of an amide linkage between GO and
LCTS can be demonstrated by the absence of GO peaks at
1730 cm−1, attributed to CO in the −COOH moiety of GO,
where a greater IR intensity of the amide II band at 1595 cm−1
is observed for cross-linked GO composites. This provides
support for the formation of a linkage between GO and LCTS
as the linker, in agreement with previous reports.30
The Raman spectrum in Figure 4b for GO consists mainly of
D- and G-band signatures at 1350 and 1580 cm−1. The G band
is characteristic of sp2-hybridized carbon networks of graphene
sheets, whereas the D-band results because of structural
imperfections created by the attachment of oxygen-based
functional groups on the carbon basal plane and its partially
disordered structure.31 In contrast to GO, graphite has an
almost insignificant D band because of its highly crystalline
structure. However, the intensity of this Raman band
increased, and it became broader upon cross-linking. Various
studies report that the removal of functional groups from the
GO structure results in a greater D/G intensity ratio because of
the onset of defects after reduction and also in self-assembly of
the GO composites.32,33 In this study, cross-linking of GO led
to changes in the D/G intensity ratio, from 0.98 in GO to 1.26
in the cross-linked GO composite. This change in the D/G
signal intensity ratio can be attributed to disruption of the GO
layered structure upon cross-linking with CTS.
3.4. 13C Solid NMR Spectral Characterization. The
spectra for pristine GO (Figure 5) present 13C NMR lines for
epoxide groups (∼60 ppm), −C−OH groups (∼70 ppm), and
graphenic group (∼130 ppm), in agreement with a previous
report.34 The spectral differences between the cross-linked GO
materials with GO relate to the broadening and 13C spectral
Figure 5. Normalized 13C solid NMR spectra of GO and GO-based
cross-linked composites.
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shift variation for the C−OH groups (∼70 ppm) of GO, along
with new spectral signatures ca. 30 and 100 ppm assigned to
the glucosamine and acetylated forms of the co-monomers of
LCTS. The upfield signatures (ca. 20−80 ppm) for GO relate
to the alkyl and alkenic groups. In addition, the appearance of
downfield signatures at ca. 170−180 ppm relate to the
presence of carbonyl (acetyl/amide groups of LCTS and
−COOH groups of GO). The two 13C carbonyl signatures for
the GO-LCTS composite is related to the presence of at least
two carbonyl groups, one for the acetyl or amide groups. The
NMR results support that cross-linking has occurred, in
agreement with FTIR bands at 1655 and 1595 cm−1. The
above results are in general agreement with 13C NMR results
reported by Mahaninia and Wilson35 for unmodified and cross-
linked CTS with different bifunctional linker systems. The
results presented herein provide an example of the first
reported solid NMR spectral results for this type of GO
composite material (Figure 5).
3.5. XRD Structural Characterization. XRD character-
ization (Figure 6a) of GO (after oxidation of graphite) and
GO-LCTS (after cross-linking of GO with LCTS) was used to
evaluate the structure of each of the samples, as well as monitor
changes in the interlayer spacing of GO after cross-linking. The
XRD pattern of graphite shows a sharp characteristic peak at
2θ = 31.5°. After the introduction of oxygen functional groups
to the structure of graphite, the graphitic peak shifts to 2θ =
12.5°, related to the interlayer distance of 0.72 nm between
GO sheets.36
Also, the XRD pattern of pure LCTS powder displays two
broad peaks at 2θ = 9.5° and 22.5°, related to the amorphous
hydrated and anhydrous structure of LCTS, respectively.37 In
comparison to the GO and LCTS patterns, cross-linked GO-
LCTS shows shifting of the sharp XRD line of GO at 12.5° to a
lower 2θ (10.2°) value with an absence of broad LCTS peaks.
These changes indicate the exfoliation of LCTS into the GO
sheets38 and an increase in the interplanar distance (0.72−0.87
nm) between GO sheets by the introduction of LCTS.
Although the broadening peak in the XRD pattern of GO-
LCTS suggests slightly lower crystallinity of the GO-LCTS,
shifting of the peak to lower wavenumbers indicates an
increase in interlayer distance of GO sheets by 0.15 nm upon
cross-linking with LCTS. This indicates that LCTS chains are
well introduced and strongly bonded to the oxygen functional
groups of GO, while maintaining the stacked structure of GO
sheets in the material.23,39 The higher crystallinity of the
graphite and GO sheets agrees with the layered cross-sectional
morphology observed in SEM images (Figure 3a,b), as
compared to the slightly separated layered cross-section
morphology of the GO-LCTS composite (Figure 3c). The
results for GO and GO-LCTS composites suggest that cross-
linking of the GO sheets is a critical technique to tune GO-
based material properties, including morphology, degree of
crystallinity, and interlayer distance between corresponding
GO sheets.
3.6. Thermal Stability Properties. The TGA results for
the cross-linked GO composite are shown in Figure 6b, where
a sharp thermal decomposition occurs starting near 120 °C for
GO, which results in a total weight loss event for the material.
The cross-linked GO-LCTS material does not show a
comparable thermal event, however; two key thermal events
appear at ca. 155 and 250 °C with a weight loss of 15.6 and
35.4%, respectively. These thermal events for the GO
composite relate to loss of adsorbed or free water and
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Figure 6. XRD patterns (a) and TGA curves (b) of GO, precursors (graphite, LCTS), and GO-LCTS composite.
decomposition of GO oxygen functionalities and the LCTS
backbone that yields degradation of the GO-LCTS framework
structure. The TGA results confirm that the GO-LCTS
structure has greater stability over GO as shown by its stability
upon heating to the upper-temperature limit (500 °C).
3.7. Solvent Swelling and Dye Sorption Properties.
Equilibrium swelling properties of GO-LCTS composite and
the precursors are listed in Table 1. The results indicate that
Table 1. Water Swelling Properties of the GO-LCTS
Composite and Precursors (Graphite and GO)
material swelling (%)
graphite 510
LCTS 345
GO 9745
GO-LCTS 6500
graphite and LCTS have the least swelling, whereas GO and
the cross-linked GO composite (GO-LCTS) display greater
swelling in water. The GO-LCTS composite has reduced
swelling relative to pristine GO that may relate to the fewer
ionic sites (−COOH) as a result of amide bond formation
because of cross-linking, in agreement with the IR and NMR
spectral results above.
The greater swelling of GO is attributed to its highly
hydrophilic nature imparted by its polar functional groups
(e.g., −OH, −COOH, etc.). By contrast, cross-linking of GO
with LCTS decreases the overall hydrophilic character of the
Figure 7. (A) Isotherm sorption results for MB with GO and GO-LCTS sorbents, and (B) decolorization of MB before and after the sorption
process with GO-LCTS.
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composite that may alter water infiltration and hydration
properties of the system. The denser arrangement of the GO-
LCTS 3D framework (according to SEM results) is expected
to contribute steric hydration effects that differ from the 2D
nature of GO because of the greater abundance and
accessibility of polar functional groups in pristine GO.
Differences in the hydrophilic character and network structure
of GO-LCTS and GO provide an account for the water
swelling properties of these materials.
3.7.1. Equilibrium Dye Uptake of MB. The MB sorption
behavior of the GO and GO-LCTS adsorbents in aqueous
solution was analyzed by fitting the adsorption isotherm results
for uptake of MB at variable concentration by various models
(Langmuir, Freundlich, and Sips isotherms). The Langmuir
model (eq 5) describes monolayer sorption for the adsorbate−
adsorbent system. By comparison, Freundlich and Sips models
describe the relationship for adsorbent−adsorbate systems
with variable adsorption sites (eqs 6 and 7). The Sips model
accounts for Langmuir and Freundlich behavior, where the
maximum adsorption capacity of the adsorbate (Qm) onto the
adsorbent surface can be estimated.
K1Ce
Qe = Qm
1 + K1Ce (5)
Q e = K f Ce1/ nf (6)
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Q m K sCe ns
Qe = ns
1 + K sCe
In eq 5, Qe is the equilibrium uptake of dye per unit mass of
adsorbent, Ce is the residual equilibrium concentration of dye,
and K1 is the Langmuir adsorption affinity constant. In eq 6, Kf
is the Freundlich adsorption capacity constant and nf relates to
the intensity of adsorption, where 1/nf < 1.0 represents highly
favorable adsorption, whereas 1/nf > 2 denotes unfavorable
adsorption process, where 1/nf < 1 obtained for both GO and
GO-LCTS materials showed favorable adsorption for these
adsorbents. In eq 7, Ks is the Sips adsorption constant that
relates to the adsorption energy, and ns indicates surface
heterogeneity of the sorbent, where Ce is defined as in eq 5.
The adsorption isotherms for MB onto GO and GO-LCTS
are shown in Figure 7, where the best-fit sorption parameters
obtained by the Sips model are listed in Table 2, where
Table 2. Isotherm Parameters for MB Adsorption with GO
and GO-LCTS Sorbent Materials at 295 K
sorbent material
adsorbate parameter GO GO-LCTS
MB Qm (mg g−1) 286.9 402.6
Ks (L mg−1) 0.028 0.111
ns 0.90 0.96
R2 0.960 0.972
favorable correlation coefficients (R2) are obtained (R2 ≈
0.960−0.972). The MB adsorption results for GO and GO-
LCTS material adopt behavior described by monolayer
adsorption onto homogeneous adsorption sites. The latter is
supported by values of ns near unity (ns = 0.96) for the surface
cross-linked GO (GO-LCTS). The maximum adsorption
capacity (Qm) of MB, according to the Sips model for GO-
LCTS (Qm = 402.6 mg g−1) exceeds that for pristine GO (Qm
= 286.9 mg g−1) and LCTS (Qm = 12.0 mg g−1; data not
shown here). The adsorption capacity of MB by GO-LCTS
reported here is notably higher than a number of reported
values for other graphene-based adsorbents (cf. Table S1;
Supporting Information).
The Qm value for cross-linked GO increased by 115 mg g−1
compared to unmodified GO, reflecting the enhanced
adsorption properties of the composite. The superior Qm
values may relate to several factors: (i) alteration of the
surface functional groups of GO-LCTS provides additional
adsorption sites that favor adsorption, and (ii) cross-linking of
GO with LCTS contributes cooperative sorbent−MB dye
interactions because of changes in the macromolecular
structure, along with alteration of the hydrophile−lipophile
balance of the composite over GO. It should be noted that
pristine LCTS has negligible uptake of MB, whereas the GO-
LCTS material has notably higher uptake of MB. There is a
strong binding interaction between MB (cationic dye) and the
GO-based materials because of the presence of polar/charged
functional groups with Lewis base character on the surface of
these materials. MB shows a favorable binding with GO,
whereas the GO cross-linked material shows much greater
uptake of MB after cross-linking with LCTS. The higher
adsorption capacity of GO-LCTS is attributed to its composite
structure, which serves to disperse GO and prevent its
aggregation in aqueous media. The favorable dispersion of
GO through the composite lends to its large surface area and
Article
microporous structure that is critical for adsorption applica-
tions.23 The interconnected network structure and higher
(7)
interlayer distance between GO sheets in the GO-LCTS
composite (as shown in XRD result Figure 6a) allow adsorbate
molecules (MB) to diffuse into the active sites of GO-LCTS.23
Additionally, both GO and LCTS are known to remove dyes
via electrostatic interactions.40,41 Therefore, the combined
effect of these precursors contribute excellent sorption
properties that enhance the overall sorption capacity of the
GO-LCTS composite.
The high removal efficiency of cross-linked GO samples is
evidenced by Figure 7b. At an initial MB dye concentration
from 100 to 1000 μM, variable decolorization occurs after the
adsorption process relative to the initially turbid colored
solutions prior to adsorption.
3.7.2. Kinetic Dye Uptake of MB. The kinetic uptake
performance of GO and GO-LCTS materials are shown in
Figure 8, where the MB adsorption capacity increased quickly
Figure 8. Kinetic uptake profile of MB with GO and GO cross-linked
composite material, where the solid lines represent the best fit by the
PSO model (see eq 4).
for both GO and GO-LCTS sorbent materials in the first 50
min and decreased slowly thereafter. The rapid MB uptake is
contributed by the negatively charged adsorption sites
accessible on the sorbent surface. By contrast, the slower
uptake is because of the greater adsorption site occupancy as
the surface sites become more saturated with MB at later stages
of the isotherm profile. Consequently, preliminary MB
adsorption may avoid the diffusion of further species onto
the dense GO-LCTS structure, resulting in longer equilibrium
times.
Table 3 represents the kinetic adsorption parameters for
sorbent materials with MB over a 250 min interval, in which
Table 3. PSO Kinetic Model Values for GO-Based Materials
at 295 K
sorbent material Qm (μmol/g) k2 (g/μmol min) R2
GO-LCTS 5.10 0.019 0.987
GO 4.17 0.004 0.996
the PSO kinetic model provided reasonable fitting results
based on favorable correlation coefficients (R2), where R2 ≈
0.987−0.996. According to the obtained kinetic parameters (k2
and Qe), the GO-LCTS material has greater uptake over
pristine GO based on the kinetic profiles. The value of Qe
(μmol g−1) and the PSO rate constant values (k2; g/μmol min)
13051 DOI: 10.1021/acsomega.8b01871
ACS Omega 2018, 3, 13045−13054
ACS Omega
for the sorbent materials increased after cross-linking: GO
(4.17 μmol g−1) < GO-LTS (5.10 μmol g−1), and GO (0.004
g/μmol min) < GO-LCTS (0.019 g/μmol min), respectively.
These trends in uptake are consistent with the results for the
TGA and spectral characterization (FTIR, 13C NMR, and
Raman) for the GO-LCTS material. Also, a previous report17
indicates that the intraparticle diffusion and external diffusion
play an important role in the adsorption kinetics.42 It has been
previously reported that the structure of monolith aerogels
containing CTS is affected by the addition of GO. This leads
to considerable changes in the morphological characteristics of
both CTS and GO43 that parallel observations noted in the
SEM results for GO-LCTS in Figure 3. Changes in the
macromolecular structure of GO and its composite form are
evidenced according to the change in surface area upon
swelling, sorption, and storage capacity,43 as similarly noted in
the case of water swelling or strong interactions with gaseous
species.44 Additionally, cross-linking GO with LCTS facilitated
the nano-dispersion of components that yield more surface
active sites for adsorption that enhance the adsorption capacity
of GO-LCTS, as outlined below(cf. Figure 8).
The greater kinetic uptake of the composite material
provides support that cooperative effects occur because of
amide bond formation between GO and LCTS that may yield
secondary adsorption sites for MB adsorption. Also, there are
more active adsorption sites according to the increasing Qe
values as the GO becomes cross-linked with LCTS. The
decreasing kinetic trend of all sorbent materials also suggest
that diffusion of MB through the pore network of the sorbent
materials decreased with increasing contact time between
sorbent where MB, along with a decreasing number of available
adsorption sites over the kinetic profile as time increases.
4. CONCLUSIONS
GO and its cross-linked composites were synthesized by cross-
linking LCTS and GO to yield a framework material. The
materials were systematically characterized by several comple-
mentary methods to affirm the structure of the GO-LCTS
composite, where MB removal efficacy was used to study the
adsorption properties of the materials at equilibrium and
kinetic conditions. The FTIR and 13C NMR spectra are
reported for the first time for GO-LTCS composites that
provide support for the formation of amide linkages and a
unique framework structure relative to the 2D layered structure
of GO. The greater surface roughness of the GO cross-linked
composite parallels the variable morphology revealed by SEM
that is also supported by the concomitant changes in thermal
stability revealed by TGA results. The GO composite displays
improved adsorbent properties over GO that are suitable for
wastewater decontamination, as shown by its effective MB
removal at equilibrium and kinetic conditions. The monolayer
adsorption capacity (Qm) of the GO-LCTS material with MB
was 402.6 mg g−1, which far exceeds that of pristine GO and
CTS. The development GO-based composites derived via
biopolymer cross-linking display enhanced adsorption proper-
ties with improved stability for reuse in multiple adsorption−
desorption processes. This strategy extends the field of
application of GO due to the facile nature and versatility of
the cross-linking approach for tuning the structure of GO,
along with the unique adsorption properties of cross-linked
GO−CTS. This work demonstrates the potential utility of
GO−CTS composites as versatile candidates in solid phase
13052
Article
extraction for potential applications in wastewater decontami-
nation, advanced nanomedicine, and drug delivery.45−48
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsome-
ga.8b01871.
Additional description of composite regeneration
properties for the uptake of MB and tabular comparison
of literature values of adsorption properties of composite
materials with MB (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: lee.wilson@usask.ca Phone: +1-306-966-2961. Fax:
+1-306-966-4730.
ORCID
Lee D. Wilson: 0000-0002-0688-3102
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful for the support of the Natural
Sciences and Engineering Research Council of Canada
(NSERC) Discovery Grant (418729-2012 RGPIN and
RGPIN 2016-06197) for the financial support of this study.
Support and expert technical assistance from Leila Dehabadi
for acquiring IR/13C solids NMR spectra and TGA profiles are
greatly appreciated.
■ ABBREVIATIONS AND NOMENCLATURE
GO, graphene oxide; LCTS, low molecular weight chitosan;
MW, molecular weight; MB, methylene blue
■
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13054 DOI: 10.1021/acsomega.8b01871

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