Accepted Manuscript

Graphite oxide/chitosan composite for reactive dye removal

Nikolina E. Travlou, George Z. Kyzas, Nikolaos K. Lazaridis, Eleni A.

Deliyanni

PII: S1385-8947(12)01637-3
DOI: http://dx.doi.org/10.1016/j.cej.2012.12.008
Reference: CEJ 10142

To appear in: Chemical Engineering Journal

Received Date: 18 October 2012

Revised Date: 2 December 2012
Accepted Date: 3 December 2012

Please cite this article as: N.E. Travlou, G.Z. Kyzas, N.K. Lazaridis, E.A. Deliyanni, Graphite oxide/chitosan
composite for reactive dye removal, Chemical Engineering Journal (2012), doi: http://dx.doi.org/10.1016/j.cej.
2012.12.008

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Graphite oxide/chitosan composite for reactive dye removal

Nikolina E. Travlou, George Z. Kyzas, Nikolaos K. Lazaridis, Eleni A. Deliyanni∗

Division of Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR–541

24 Thessaloniki, Greece

∗
Corresponding author. Tel.: +30 2310 997808; fax: +30 2310 997859. E–mail address:

lenadj@chem.auth.gr (E.A. Deliyanni).

1
ABSTRACT

In the current work a novel composite material consisted of cross–linked chitosan (Ch) and graphite oxide

(GO) (and not graphene oxide, as numerous studies deal with) was prepared for the removal of Reactive

Black 5 dye. After synthesis, the full characterization with various techniques (SEM/EDAX, FTIR, XRD,

DTA, DTG, TGA) was achieved revealing many possible interactions/forces of dye–composite system.

Through the latter interactions, the possible adsorption mechanism was elucidated and explained. Also, the

adsorption evaluation of the composite material presented high adsorption capacity (277 mg/g at 25 oC).

Equilibrium experiments are also performed studying the effect of pH on adsorption (optimum 2) and

desorption (optimum 12), initial dye concentration, contact time (pseudo–first, –second order equations and

a generalized fractal kinetic model), temperature (isotherms at 25, 45 and 65 oC fitted to Langmuir,

Freundlich, Langmuir–Freundlich model) and ionic strength. A full thermodynamic evaluation was carried

out, calculating the parameters of enthalpy, free energy and entropy ( H0, G0, and S0). The adsorption

behavior of the composite material was also compared with the respective of its components (GO and Ch).

Keywords: Graphite oxide/chitosan composite; Reactive Black 5; Characterization; Adsorption;

Interactions

2
1. Introduction

Nowadays, one of the most promising adsorption methods for the removal of dyes is the application

of chitosan. Chitosan is synthesized from chitin, which is the second most abundant polymeric material in

nature after cellulose [1]. Chitin can be easily extracted from crustacean shell such as crabs, fungi, prawns,

insects and other crustaceans [1]. Chitosan can be used as an adsorbent to remove cationic and/or anionic

dyes due to the simultaneous presence of amino and hydroxyl groups, which can serve as active/adsorption

sites [2]. The performance of chitosan as adsorbent can be improved by (i) the use of cross–linking

reagents, which stabilize chitosan in acid solutions and enhance its mechanical properties and (ii)

derivatization with grafting functional groups onto the chitosan backbone, which improve its adsorption

capacity [3].

Recently, chitosan composites have been developed to adsorb dyes from wastewaters [4,5].

Different kinds of substances have been used to form composite with chitosan such as graphene oxide and

magnetite. These composites have been affirmed to present better adsorption capacity and resistance to

acidic environment. Some works in literature dealt with highlights of the application of chitosan composites

as adsorbents, including synthesis, mechanisms and other factors, which can affect its adsorption capacity

[4,5].

Graphite–like nanoplatelets have recently attracted attention as viable and inexpensive filler in

composite materials. These excellent properties may be relevant at the nanoscale, if graphite can be

exfoliated into thin nanoplatelets, and even down to the single graphene sheet level [6]. Graphene and

graphene oxide have been used as effective adsorbent toward anionic and cationic dyes [7].

Graphite oxide (GO), a precursor in the formation of graphene layers, has been studied as an

adsorbent and its ability to remove cationic dyes has been demonstrated [8,9]. From a structural point of

view, GO is a highly–oxidized planar material containing 25–33% oxygen with good adsorption between

layers. It is characterized to be a lamellar solid and can be easily prepared by chemical modification.

Generally, GO can be synthesized by oxidation of graphite with strong oxidizing agents such as potassium

3
chlorate, permaganate, bichromate and chlorine dioxides. The strong oxidation makes GO to have multiple

oxygen–containing functional groups (as for example carboxyl, hydroxyl, epoxy) and could consequently

be covalently attached to its layers. Moreover, the spatial distribution of functional groups on the carbon

skeleton is also diverse. The epoxy and hydroxyl groups are near each other, and the carboxyl is possibly

situated at the edges of GO. These oxygen functionalities make GO extensively disperse in water, because

the functionalities are hydrophilic, thus stabilizing it to be easily [10].

The novelty of the current work is the synthesis of the new composite material graphite oxide –

chitosan (GO–Ch), consisted of cross–linked chitosan (Ch) and graphite oxide (GO). The composite

prepared was applied for the removal of the Reactive Black 5, given the lack of literature of a GO/chitosan

material as reactive dye adsorbent. Reactive Black 5 dye has been used in the textile industries for the

dying of cotton, woollen and nylon fabrics worldwide. It is reported to be toxic and cause allergic reactions

of respiratory tract [11]. After synthesis, the characterization with various techniques (SEM/EDAX, FTIR,

XRD, DTA, TGA) was performed revealing many possible interactions of dye–composite system. Through

the latter interactions, the possible adsorption mechanism was elucidated and explained. The influence of

solution pH, initial dye concentration, contact time, temperature and ionic strength was performed in batch

mode.

2. Materials and methods

2.1. Materials

Chitosan of high molecular weight was purchased by Sigma–Aldrich and purified by extraction with

acetone in a Soxhlet apparatus for 24 h. Then, its drying was carried out under vacuum at 20 oC. Its average

molecular weight was estimated at 3.55×105 g/mol and the degree of deacetylation was 82 wt% [12]. The

cross–linking agent used was glutaraldehyde (GLA), which was obtained from Sigma–Aldrich (50 wt% in

water). All solvents were of analytical grade.

A commercial reactive dye (anionic and anthraquinonic) was used as target molecule for dye

4
adsorption experiments. The reactive dye, C.I. Reactive Black 5 – 20505 (abbreviated hereafter as RB5,

supplied by Kahafix), presents the following characteristics: C26H21N5Na4O19S6, MW=991.82 g/mol,

λmax=603 nm, purity=55% w/w. The dye purity was taken into account for all calculations. The chemical

structure of the dye used is given in Fig. 1.

2.2. Synthesis of adsorbents

Three adsorbent materials were prepared: (i) cross–linked chitosan powder (Ch); (ii) graphite oxide

(GO), and (iii) graphite oxide/cross–linked chitosan composite (GO–Ch).

Ch was prepared in the same manner as in a previously published work [13]. Briefly, 5 g of chitosan

powder was dissolved into acetic acid solution (2% v/v) with the use of a magnetic stirrer suspended in an

0.05 mol/L aqueous solution of cross–linker GLA (approximately 2:1 GLA aldehyde groups (–CHO) per

initial chitosan amine groups (–NH2)). The reactions were carried out at ambient temperature for 24 h and

the cross–linking mechanism is presented in Supplementary Data (Fig. SI1). Extensive rinsing of the

granulated chitosan particles with hot deionized water ensured the removal of any unreacted GLA reagent.

GO was similarly prepared according to a simplified Hummers method [14], following which

commercial graphite powder (10 g) was stirred in concentrated sulfuric acid (230 mL, 0 oC). Then,

potassium permanganate (30 g) was slowly added to the suspension. The rate of addition was controlled to

prevent the rapid rise in the temperature of the suspension that should be less than 20 oC. The reaction

mixture was then cooled to 2 °C. After removal of the ice–bath, the mixture was stirred at room

temperature for 30 min. Distilled water (230 mL) was slowly added to the reaction vessel, keeping the

temperature less than 98 oC. The diluted suspension was stirred for an additional 15 min, was further

diluted with 1.4 L of distilled water and then 100 mL of a 30 wt% solution of hydrogen peroxide was

added. The mixture was left overnight. The GO particles settled at the bottom were separated from the

excess liquid by decantation. The remaining suspension was transferred to dialysis tubes (Sigma Co.).

Dialysis was carried out until no precipitate of BaSO4 was detected by addition of an aqueous solution of

5
BaCl2. Then, the wet form of graphite oxide was separated by centrifugation. The gel–like material was

freeze dried and a fine dark brown powder of the initial graphite oxide was obtained.

For the preparation of the novel GO–Ch composite [8,9], chitosan solution (2% w/v) was prepared

by dissolving 0.4 g of powder chitosan into 20 mL of acetic acid solution (2% v/v) under ultrasonic stirring

for 2 h at room temperature. Also, 3 mL of GLA (50 wt% in water) were added to cross–linked chitosan.

Then, 0.3 g of GO were added in the solution prepared and the mixed system was stirred continuously for

90 min in a water bath at 50 oC. The pH of the reaction system was adjusted to 9–10 with micro–additions

of NaOH (0.1 mol/L) and kept in the water bath for further 60 min at 80 oC. Black products were washed

with ethanol and distilled water in turn until the pH was reached about 7 and dried in a vacuum oven at 50
o
C. The final product was the composite of graphite oxide/cross–linked chitosan (GO–Ch). All prepared

products (GO, Ch, and GO–Ch) were ground to fine powders, with size after sieving 75–125 µm.

2.3. Characterization techniques

Scanning electron microscopy (SEM) images were performed at Zeiss Supra 55 VP. The

accelerating voltage was 15.00 kV and the scanning was performed in situ on a sample powder. EDAX

analysis was done at magnification 10 K and led to the maps of elements and elemental analysis. The FTIR

spectra of the samples were taken with a PerkinElmer–2000 FTIR spectrometer using KBr disks prepared

by mixing 0.5% of finely ground carbon sample in KBr. Pellet made of pure KBr was used as the reference

sample for background measurements. The spectra were recorded from 4000 to 400 cm–1 at a resolution of

4 cm–1. The spectra presented are baseline corrected and converted to the transmittance mode. Also,

thermal analysis was carried out using a TA Instrument thermal analyzer (SDT). The instrument had the

following settings: (i) heating rate of 10 K/min, and (ii) flow rate of nitrogen atmosphere equal to 100

mL/min. Approximately 25 mg of sample was used for each measurement. Moreover, X–ray powder

diffraction (XRD) patterns were recorded on a Philips PW1820 diffractometer with a Cu Kα radiation for

crystalline phase identification. The sample was scanned from 20 to 80o.

6
2.4. Adsorption–desorption experiments

For the pH–effect experiments, 0.02 g of adsorbent was mixed with 20 mL of dye solution (the

initial dye concentration was 250 mg/L). The suspensions were shaken for 24 h (pH=2–12; ionic

strength=0.001 mol/L; agitation rate=160 rpm) into a water bath to control the temperature at 25 °C (Julabo

SW–21C). The optimum pH found (for performing the next adsorption experiments) was pH=2 for RB5.

To study the effect of contact time on dye adsorption, kinetic experiments were performed by

mixing 0.02 g of adsorbent with 20 mL of dye solution (the initial dye concentration was 250 mg/L). The

suspensions were shaken for 24 h at the optimum pH (found from experiments for the effect of adsorption

pH) in water bath at 25 °C (ionic strength=0.001 mol/L; agitation rate=160 rpm). Samples were collected at

fixed intervals (5–45 min, 1–24 h). Pseudo–first [15], –second order equations [16] and Brouers–Sotolongo

model (BS) [17,18] were selected to fit the experimental kinetic data. The BS model generalized fractal

kinetic equation was developed in order to come with a universal function for the kinetics of complex

systems characterized by stretched exponential and/or power law behaviors. This kinetic function unifies

and generalizes previous theoretical attempts to describe what has been called “fractal kinetic”. The kinetic

equations are given in Table 1.

The effect of initial dye concentration on equilibrium was realized by mixing 0.02 g of adsorbents

with 20 mL of dye solutions with varying initial dye concentrations (0–1000 mg/L). The suspensions were

shaken for 24 h at pH=2 in water bath at 25, 45, and 65 °C (ionic strength=0.001 mol/L; agitation rate=160

rpm). The equilibrium data resulted were fitted to the Langmuir [19], Freundlich [20] and Langmuir–

Freundlich (L–F) isotherm models [21]. The amount of total dye uptake at equilibrium Qe (mg/g) was

calculated using the mass balance equation (Eq. (1)):

(C0 − Ce )V
Qe = (1)
m

where C0, Ce (mg/L) are the initial and equilibrium concentrations of dye in the aqueous solution; m (g) is

the mass of adsorbent; V (L) the volume of the solution.

7
 Another important parameter of adsorption is the ionic strength. Its effect on adsorption was studied

performing experiments with various values of ionic strength (0.001, 0.1, and 1 mol/L NaCl). The other

parameters of adsorption were kept constant (pH=2; 0.02 g of adsorbent; 20 mL of solution volume; 250

mg/L initial dye concentration; 25 °C; 160 rpm; 24 h contact time).

Completing adsorption experiments with 250 mg/L of dye solution at 25 °C and pH=2, the dye–

loaded adsorbent material was collected and filtered, using fixed pore–sized membranes (0.50 µm).
m). A small

fraction of the dye (1–2 %) and adsorbent (1%) were retained on the filter membrane; these small variations

due to filtration were neglected. To determine the optimum desorption pH value of the dye–loaded

sorbents, experiments were carried out by mixing the collected, after adsorption, amount of dye–loaded

materials (0.02 g) with 20 mL (same volume as in the adsorption step) of deionized water as eluant over a

pH range between 2 and 12 (pH–adjustment with addition of acid (HNO3) or base (NaOH)), at 25 °C for 24

h (agitation rate=160 rpm).

All experiments were repeated 4 times. Therefore, the experimental points presented in adsorption

and desorption figures are the average values of 4 repetitions.

2.5. Dye analysis

The residual dye, i.e. that remaining in solution after the application of solid/liquid separation of

suspended solids using 50 μm pore size filtration membrane, was analyzed spectrophotometrically by

monitoring the absorbance of the dyes using UV–Vis spectrophotometer (model U–2000, Hitachi). Before

the adsorption experiments, the effect of pH over the calibration curves of dye was studied, but no

significant deviation was observed (data non shown).

3. Results and Discussion

3.1. Characterization and dye–adsorbent interactions

The XRD patterns of Ch, GO, and GO–Ch composite are presented in Fig. 2, while the X–ray

8
diffraction patterns of pristine graphite and GO (for comparison) are shown in the inset of Fig. 2. Observing

the patterns of inset, the d002 peaks reflect the changes in the nature of graphite by introduction of chemical

groups to the graphene layers. The d002=3.36 Å diffraction peak of natural graphite occurs near the location

where 2θ=26o; it can be seen from the pattern that the peak is sharp and high, showing high crystallinity

and degree of order. In the spectrogram of GO, the diffraction peak (002) of graphite crystal disappears,

indicating that the graphite had been completely oxidized. In its place, the diffraction peak (002) of GO

occurs. The characteristic XRD peak of GO appeared at 2θ=10.9o [22]. It can be seen that the interlayer

distance between the carbon layers as determined by Bragg’s law, is increased clearly from 3.36 Å for

graphite to 8.11 Å for graphite oxide. This is caused by the large amount of polar groups generated between

the layers of graphite during oxidation [23,24], in which the oxygen and carbon atoms are covalently

bonded, leading to an increase in the graphite’s crystal lattice length along axis c. Also, the existence of the

polar groups causes very strong hydroscopicity of GO, as well. As a result, the water molecules entering

into the space between the layers are bonded with the oxygen atoms of the groups through hydrogen bonds,

further enlarging the interlayer distance [25]. On the other hand, the elemental analysis of GO evaluated

using energy dispersive X–ray analysis (EDX), showed that GO had a composition of 48% carbon and

49.5% oxygen (w/w). In addition, 1.5% (w/w) of sulfur is also presented, which is a consequence of

sulfuric acid treatment. Sulfones are also introduced to graphene sheets or residual sulfuric acid is

intercalated between layers. This may also result in defects in the graphene sheets, reflected in the greater

d002 that graphite.

The XRD patterns of Ch, GO, and GO–Ch composite are presented in Fig. 2. Both the patterns of

Ch and GO–Ch exhibited a broad peak at 2θ=20.2o due to the amorphous state of chitosan, indicating that

the amorphous–like structure of Ch was not changed by the addition of GO in the composite material.

Moreover, the feature of GO is still visible at 2θ=10.9o in the XRD pattern of the composite, which

indicates the presence of the two phases in this material. Considering similarly the Bragg’s law, the

interlayer distance of the composite’s component was found to remain 8.11 Å. However, according to

9
Scherrer’s equation, the number of layers were found to decrease from 7.5 for GO to 3.7 for GO–Ch. That

decrease may be the apparent result of the decrease of the average size of the crystallite of the GO–Ch

composite, from 61 Å for the GO to 29 Å for the GO–Ch composite, calculated using the Debye–Scherrer

equation [26].

The insertion pathway of aliphatic amines via the nucleophilic substitution reactions on the epoxy

groups of GO induces changes in the basal spacing of GO respective to their chain length [27]. On the other

hand, the introduction of large organic ammonium ions also resulted in changes in the basal spacing or/and

exfoliation of layered structure [28]. Taking these into account, as well as the XRD results it is concluded

that a significant part of the graphite oxide did not exfoliated/reduced on reacting with chitosan having as

result an increased heterogeneity of the composite material.

Changes are also obvious in the SEM images of GO and GO–Ch and presented in Fig. 3. The GO

presents the sheet–like structure (Fig. 3a), while after the combination with Ch a rougher surface is

presented (Fig. 3b), revealing that Ch had been assembled on the surface of GO layers with a high density

[8].

Differences in the chemistry of the surfaces have been also seen on differential thermal gravimetric

(DTG) curves measured in nitrogen (Fig. 4). The peaks represent weight loss at the specific temperature

range and the area under the peaks is related to the extent of that weight loss. The first peak centered at

about 80–100 oC for all under examination samples, in correlation to the endothermic effect on the

differential thermal analysis (DTA) curves presented in Fig. 5 can be linked to weight loss due to the

evaporation of physically adsorbed water. In the case of the GO–Ch composite, that peak presented a

maxima at 100 oC, while the second peak presented between 200–250 oC is related to decomposition of

epoxy and carboxylic groups, with latter being more stable [23], that are associated with the exfoliation of

graphene layers, which is represented by exothermic peaks on the differential thermal analysis (DTA) curve

presented in Fig. 5. The shoulder observed between 250–300 oC for the GO represents decomposition of

sulfones or removal of residual sulfuric acid.

10
 The TGA of Ch, GO and GO–Ch were conducted in nitrogen atmosphere and the curves are shown

in the inset of Fig. 4. GO shows ~20% mass loss below 200 °C, resulting from the evaporation of adsorbed

water and a rapid 26% mass loss from 200 to 250 °C owing to the removal of the oxygen–containing

functional groups. It then displays a gradual mass loss above 250 °C, which is due to the further removal of

functional groups. The mass loss of GO–Ch composite is obviously lower than that of GO, especially the

mass loss at 200 °C (~7%), which demonstrates a gradual decrease in the amount of oxygen–containing

functional groups. Meanwhile, higher mass losses are found in GO–Ch at 400 °C caused by the

decomposition of Ch [29]; this indicates that Ch has been adsorbed onto the GO nanosheets.

As seen from the graphs, there is a significant difference in thermal behavior between the GO–Ch

composite and the separate GO and Ch samples. On the DTG curve of this sample, two peaks with maxima

at 150 and 250 °C are presented. Because the first peak is associated with an exotherm on DTA curves (Fig.

5), it is related to the decomposition of surface functional groups, accompanied by some degree of

exfoliation of the graphene layers [30]. This decomposition occurs at lower temperature than that in the

case of pure GO. The second peak, which is linked to an exotherm, represents the degradation of chitosan

[31]. The fact that this peak appears at higher temperature than for the pure chitosan (Ch) suggested an

increase in the numbers of primary amino groups after combined to GO [32].

FTIR spectra (Fig. 6) revealed the obvious differences in the chemical features of the raw materials,

as well as for the composite one. In the spectrum of GO (spectrum A), carboxyl groups are observed as

bands at 1050–1100 and 1665–1760 cm–1, whereas the band at ~1600 cm–1 is attributed to the presence of

epoxy groups [23] and to C=C stretching mode of the sp2 carbon skeletal network. The peak at 1380 cm–1,

as well as the broad band between 2200 and 3800 cm–1 correspond to O–H groups (C–OH stretching),

which are either attached to carbons or represent adsorbed water. The band at 1055 cm–1 can be also

attributed to epoxy groups. On the spectrum a vibration at 1220 cm–1 is visible, which may be arise from

S=O asymmetric stretching vibrations in sulfones or sulfates present after graphite oxidation and/or

vibrations of C–O in epoxy groups [23,24]. The pattern of cross–linked chitosan (spectrum C) has a strong

11
peak around 3400 cm–1 due to the stretching vibration of O–H, the extension vibration of N–H and the

inter–hydrogen bonds of the polysaccharide [33], while two characteristic bands centered at 1636 and 1597

cm–1 can be attributed to the C=O stretching vibration of NHCO (amide I) and the N–H bending of NH2,

respectively [13]. On the spectrum of GO–Ch composite (spectrum E), the intensity of the peaks at 3417

(νO–H) and 1075 (νC–O) cm–1 increased compared to GO (spectrum A), which is due to the –OH groups from

the adsorbed chitosan. The peak at 1730 cm–1 (attributed to carboxylic groups) disappeared, proving that

carboxylic groups reacted with chitosan during the preparation of the composite, while it can be distinctly

observed that the intensity of NH2 absorbance band has increased compared to the intensity of the amino

group NHCO (amide I). Since chitosan has –NH2 groups on its macromolecular chains, these functional

groups can form hydrogen bonds and/or electrostatic interactions with the residual oxygen–containing

groups of GO. The amino groups of chitosan can react with oxygen–containing functional groups of GO in

the following ways: (i) after hydrogen–bonding interactions between the amino groups and the oxygen–

containing functional groups of GO (G–OH…H2N–R) (Eq. (2a)); (ii) after protonation of the amine by the

weakly acidic sites of the GO layers (–COO–+H3N–R) with amides and amine carboxylate salts as reactions

products (Eq. (2b)), and (iii) after nucleophilic substitution reactions on the epoxy groups of GO (Eq. (2c))

[27]:

H O H O
NH + C RGO N C + H2O
RCh HO RCh RGO (2a)

H O H O
NH + C RGO NH2+O C
RCh HO RCh RGO (2b)

H H
O H+ O RChNH2-H RChNH2 C C OH
RChNH2 C C OH
(2c)

where RCh is the residual part of Ch (especially its amino groups), and RGO is the respective part of GO

(especially its carboxyl groups).

12
 Concerning the spectra of the GO–Ch composite (spectrum E), it is concluded that carboxyl groups

of GO reacted with –NH2 groups of chitosan to form amides (band at 1636 cm–1) and carboxyl groups

(band at ~1400 cm–1), in line with the amine nucleophilic attack on the epoxy groups of GO, which leads to

the amino (band increase at 1597 cm–1) and hydroxyl (band at 1027 cm–1) formation.

In Fig. 6, the spectra of adsorbents after dye adsorption are presented. For GO, the shift of the band

(spectrum B) is indicative that the binding of dye molecules is predominant based on the π–π interaction

between the aromatic ring of the dye and the GO basal planes. For Ch and GO–Ch composite as well, the

driving forces for reactive dye adsorption could be given by the following equations [34]:

⎯⎯
→ R − NH 3+
R − NH 2 + H + ←⎯
⎯ (3)

Dye − SO3 Na ⎯⎯⎯

H2O
→ Dye − SO3− + Na + (4)

⎯⎯
→ R − NH 3+ − O3S − Dye
R − NH 3+ + Dye − SO3− ←⎯
⎯ (5)

where R is the alkyl group originated from Ch or GO–Ch.

The aforementioned interactions between dye molecules and (i) Ch, (ii) GO–Ch, was affirmed by the

diminishing of the amine peak at 1590 cm–1 after comparison of the spectra for initial and after dye

adsorption samples (spectrum D; spectrum F) confirming the binding of the dye molecule to amino groups

according to Eq. (5). The interaction between RB5 and Ch was also affirmed by the shift of the carbonyl

peak. In particular, the amide–carbonyl peak of Ch was shifted from 1659 to 1652 cm–1. For the GO–Ch

composite, the contribution of GO to dye adsorption can be attributed to the π–π dispersion interaction

between the aromatic ring of the dye and the GO basal planes. Due to the binding of carboxyl groups to

chitosan, these interactions expected to be stronger.

3.2. Effect of pH on adsorption

Fig. 7 shows the effect of initial pH on the adsorption of RB5 onto adsorbents, which is nearly

explained by the interactions described above. The optimum pH found for all adsorbents tested was

13
acidic (pH=2). This fact is explained by Eq. (5), where the main interaction is the electrostatic force

between amino groups of Ch or Ch–GO and dye. At pH=2, the removal of RB5 was 86, 75, 54% for GO–

Ch, Ch, and GO, respectively. Increasing the pH of the solution, it is absolutely normal the weakening of

forces and consequently the reduction of attraction/interaction between dye molecules and adsorbent. So, at

alkaline conditions (pH=12), the dye removal was 36, 11, 32% for GO–Ch, Ch, and GO, respectively. GO

has not been affected so much from the change of pH (from 54 at pH=2 to 32% at pH=12), which attributed

to the existence of π–π interactions as the main forces between GO and RB5, and not the electrostatic bonds

between positively charged amino groups and negatively sulfonate groups of dye. In general, the pH–

behavior observed was the expectable based on considerations of 3.1 section. Fig. 7 also shows the changes

of the solution pH during the course of an adsorption experiment.

3.3. Kinetics

The effect of contact time on adsorption is depicted in Fig. 8. The kinetic curves of Ch and GO

obtained were qualitatively same as those in many papers [35]. The instantaneous dye adsorption (0–1 h),

governed by fast external diffusion and mainly surface adsorption, was followed by a milder and gradual

ascend (1–3 h), resulting in an equilibrium state plateau from 3 to 24 h. However, the kinetic behavior of

GO–Ch composite is slightly different. The kinetic rate seemed to be slower than that of GO and Ch. The

first stages lasted approximately 3 h, while the gradual equilibrium reached 15 h. The equilibrium is

observed to be completed after 18 h. This different behavior may be due to the co–existence on the surface

of GO–Ch different active adsorption sites (amino or carboxyl groups), which maybe act competitively.

Also, a possibility of pore diffusion can be posed, given the complicated form (network) of GO–Ch

composite.

Three kinetic models, pseudo–first, –second and Brouers–Sotolongo fractal kinetic, were selected to

fit the experimental kinetic data. The identification of the kinetic model, which best fitted the results has

been performed by non–linear regression and employing experimental Qe values determined independently

(equilibrium data). Table 1 presents the kinetic parameters resulted by fitting the models to the
14
experimental data. According to the correlation coefficients (R2) exported, the best fitting was for the

Brouers–Sotolongo fractal kinetic model (R2~0.999). This could be attributed to the additional parameters n

and a, which serve as extra degrees of freedom to make the BS model more flexible.

3.4. Isotherms – thermodynamics

Fig. 9 presents the effect of initial dye concentration on adsorption of RB5. The experimental results

were fitted to Langmuir, Freundlich and L–F models. Table 2 reports the maximum adsorption capacities

(Qmax) and the other isothermal parameters resulted from the fitting. The correlation coefficients (R2>0.990)

showed that the L–F model results in better fitting (closer prediction of the isotherm to the experimental

data). The Qmax at 25 oC was 205, 224, and 277 mg/g (pH=2) for GO, Ch, and GO–Ch, respectively.

Furthermore, the dye uptake was influenced by the initial dye concentration (with constant adsorbent’s

dosage). The equilibrium is intense and continues rapidly at low initial dye concentrations. So, there is

possibility for monolayer coverage of dye molecules at the outer interface of adsorbents. Increasing the

initial dye concentrations, the available adsorption sites become lower and subsequently the adsorption

depends on the initial concentration of dye. In the case of GO–Ch, the latter phenomenon is more intense,

owing to the combination of two structurally different parts, as Ch and GO are.

The effect of temperature on equilibrium is presented in Table 2. Increasing the temperature from

25 to 65 oC, an increase of the Qmax is observed. As the majority of the chitosan–based and graphite–like

materials [6,7,22,29,35], this increase is caused by the enhancement of the number of adsorption sites; the

latter is due to the weakening and/or breaking of many structural bonds of network, existed near the edge of

the active surface sites of materials. Another, possible explanation is the increase of diffusion (especially

that of pores), which helps the penetration of dye molecules inside the structure of materials. Also, some

works revealed the role of the formation of new active adsorption sites at high temperatures [35]. In

addition, the parameter RL (dimensionless), which is called equilibrium parameter, is calculated according

to Eq. (6) [36] in order to identify whether an adsorption system is favorable or unfavorable.

15
 1
RL = (6)
1+K L C0

where KL (L/mg) is the Langmuir adsorption equilibrium constant.

The range of RL values (Table 2) was calculated for all initial dye concentrations, beginning from

the lowest (C0=20 mg/L) and ending to the highest (C0=1000 mg/L). It is obvious that, the adsorption

process under the studied conditions was favorable (0<RL<1) [36].

Table 3 presents the adsorption capacities of various adsorbents for Reactive Black 5 [37-44]. The

composite material exhibits a significant high capacity, higher than its components, which indicates an

effective combination of chitosan and graphite oxide.

Furthermore, Table 4 presents the thermodynamic parameters resulted from the experimental data

of isotherms at three different temperatures, calculating the respective parameters ( G0, H0, S0). The Gibbs

free energy change ( G0, kJ/mol) of the adsorption process is expressed by the Van’t Hoff equation (Eq.

(7)) [45], with the previous calculation of the equilibrium constant (Kc) (Eq. (8)):

ΔG 0 = − R T ln ( K c ) (7)

Cs
Kc = (8)
Ce

where Cs (mg/L) is the amount adsorbed on solid at equilibrium and R (=8.314 J/mol K) is the universal gas

constant.

The change in entropy ( S0, kJ/mol K) and the heat of adsorption ( H0, kJ/mol) at a constant temperature T

(K) can be calculated from Eq. (9):

ΔG 0 = ΔH0 − T ΔS0 (9)

From Eqs. (7)–(9):

⎛ ΔH0 ⎞ 1 ΔS0
ln(Kc ) = ⎜ − ⎟ + (10)
⎜ R ⎟T R
⎝ ⎠

The values of H0 and S0 were calculated from the slop and intercept of the plot between ln(Kc) versus 1/T.

16
 The negative values of ΔG0 showed that the adsorption of RB5 onto all adsorbents used was
0
spontaneous. The positive values of of adsorption indicated an endothermic nature. The latter can be

further explained as a result of the desorption of water molecules, which were previously adsorbed onto the

dye molecule and the adsorption of dye molecules onto the surface of adsorbent material. The positive

values of S0 demonstrated the increased randomness at the solid/liquid interface. The water coordinated

molecules are displaced by dye molecules and consequently gain more translational entropy than is lost by

dye molecules (this occurs during adsorption); the latter results in increased randomness in the dye–

adsorbent interaction [46].

3.5. Ionic strength

In dyeing technology many additives used, such as salts and surfactants can either accelerate or

retard dye adsorption processes. Sodium chloride, which is often used as a stimulator in dyeing processes

can act in dual mode: (i) it may screen the electrostatic interaction of opposite charges in adsorbents and the

dye molecules, and an increase in salt concentration could decrease the amount of dye adsorbed, (ii) it may

enhance the degree of dissociation of the dye molecules and facilitate the amount of pollutant adsorbed

[35]. So, the ionic strength is another important factor in the dye adsorption process. Fig. 10 presents the

effect of ionic strength on dye adsorption. The behavior of materials containing cross–linked chitosan (Ch

and GO–Ch) showed the same behavior. Increasing the concentration of NaCl from 0.001 to 1 mol/L in dye

solution, a strong augmentation of adsorption capacity is observed reaching ~70 mg/g for Ch and 80 mg/g

for the GO–Ch composite. On the contrary, a deep decrease was observed for GO increasing the salinity

(reduction ~70 mg/g). In the case of GO the excess of ions acted competitively with the charged parts of

dye for the adsorption onto surface of material reducing the electrostatic interactions/forces, while for

chitosan–based materials (Ch, GO–Ch), the adsorption is mainly based on coulombic/electrostatic bonds

which overcome the ions from salts and be sub–helped from the dissociation of dye molecules.

17
3.6. Desorption

The opposite phenomenon of adsorption is called desorption and has a great impact on

decolorization technology. Given the recent industrial trend for regeneration and consequently reuse of

adsorbents, desorption plays an important role for the selection (as adsorbent) of a material. So, a material,

which can easily desorb, is valuable. In this way, the experiments for the pH effect on desorption revealed

that the optimum desorption pH value was alkaline. At pH=12 the desorption of RB5 was 95, 95, and 80%

for GO–Ch, Ch, and GO, respectively. Decreasing the pH of the eluant, desorption reduces. In many dye–

adsorbent systems, desorption phenomenon is just the reverse of that of adsorption. For example, if the

optimum adsorption conditions are alkaline, the optimum desorption ones are acidic, and vice versa.

However, this is does not ever occur, since dye adsorption is more complex phenomenon, based on a

combination of interactions, and not only the classic electrostatic forces (e.g. hydrogen bonding, π–π

interactions, covalent bonding, diffusion phenomena, random dye bindings etc).

4. Conclusions

A graphite oxide/chitosan composite (GO–Ch) was prepared in order to remove Reactive Black 5

dye from aqueous solutions. The GO presented the sheet–like structure, while after the combination with

Ch a rougher surface was presented in GO–Ch, revealing that Ch had been assembled on the surface of GO

layers with a high density. The amorphous–like structure of Ch was not changed by the addition of GO in

the composite material as observed from XRD patterns. According to the same technique, it is concluded

that a significant part of the GO did not exfoliated/reduced on reacting with Ch resulting in an increased

heterogeneity of the GO–Ch composite. A deeper characterization of the prepared composite was also

achieved with other techniques as TGA, DTG, DTA. The interactions between dye and materials are

determined with FTIR spectroscopy, leading to conclusions about the adsorption mechanism of dye onto

composite. The amino groups of chitosan can react with oxygen–containing functional groups of GO in the

following ways: (i) after hydrogen–bonding interactions between the amine molecules and the oxygen–

18
containing functional groups of GO (G–OH…H2N–R); (ii) after protonation of the amine by the weakly

acidic sites of the GO layers (–COO–+H3N–R) with amides and amine carboxylate salts as reactions

products, and (iii) after nucleophilic substitution reactions on the epoxy groups of GO. In the field of

adsorption evaluation of the material prepared, the optimum pH found after adsorption experiments was

pH=2. The equilibrium data were fitted to the Langmuir, Freundlich and L–F model, while the calculated

Qmax for the composite material at 25 oC was 277 mg/g (pH=2). The positive values of H0 suggest the

endothermic nature of the process, while the negative values of G0 suggest that the process is spontaneous

(positive values of S0 confirmed the increased randomness at the solid/liquid interface). Kinetic data were

fitted to the pseudo–first, –second order equations and Brouers–Sotolongo model and the optimum pH for

dye desorption was 12.

Appendix. Supplementary Data

The Supplementary Information section includes: (i) Fig. SI2, which illustrates the cross–linking

mechanism of chitosan; (ii) Fig. SI1, which demonstrates the differences in FTIR spectra of pure (non

cross–linked) and cross–linked chitosan (Ch).

19
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23
24
Figure List

Fig. 1. Chemical structure of C.I. Reactive Black 5 (RB5).

Fig. 2. X–ray diffraction (XRD) patterns of Ch, GO, and GO–Ch (Inset: XRD patterns of
graphite and GO).

Fig. 3. SEM image of (a) GO and (b) GO–Ch composite.

Fig. 4 Differential thermogravimetry (DTG) curves in nitrogen (Inset: Thermogravimetric

analysis (TGA) of Ch, GO and GO–Ch in nitrogen).

Fig. 5. Differential thermal analysis (DTA) curves in nitrogen.

Fig. 6. FT–IR spectra of adsorbents before and after adsorption of RB5: (A) GO; (B) dye–
loaded GO; (C) Ch; (D) dye–loaded Ch; (E) GO–Ch; (F) dye loaded GO–Ch.

Fig. 7. Effect of initial pH on adsorption of RB5 onto Ch, GO, and GO–Ch (pH=2–12; 250
mg/L dye concentration; 1 g/L adsorbent; T=25 °C; 160 rpm; 0.001 mol/L NaCl; 24 h
contact).

Fig. 8. Effect of contact time on adsorption RB5 onto Ch, GO, and GO–Ch (pH=2; 250 mg/L
initial dye concentration; 1 g/L adsorbent; T=25 °C; 160 rpm; 0.001 mol/L NaCl; 0–24
h contact), fitted to (a) pseudo–first order, (b) pseudo–second order, and (c) Elovich
equation.
Fig. 9. Effect of initial dye concentration on adsorption of RB5 onto Ch, GO, and GO–Ch
(pH=2; 0–1000 mg/L dye concentration; 1 g/L adsorbent; T=25, 45, 65 °C; 160 rpm;
0.001 mol/L NaCl; 24 h contact).
Fig. 10. Effect of ionic strength on adsorption RB5 onto Ch, GO, and GO–Ch (pH=2; 250 mg/L
initial dye concentration; 1 g/L adsorbent; T=25 °C; 160 rpm; 0.001, 0.1 and 1 mol/L
NaCl; 24 h contact).

25
FIGURE CAPTIONS

NH2 OH O H2 H
H2 H2 O 2
NaO3SO C C S N N N N S C C OSO3Na
O O

HO3S SO3H

Fig. 1. Chemical structure of C.I. Reactive Black 5 (RB5).

26
 1400

Graphite
1200
Intensity (counds/sec)

1000

800 GO

600 GO-Ch 10 20 30 40 50
2θ (deg)
400

200
Ch GO
5 10 15 20 25 30 35 40 45 50
2θ (deg)

Fig. 2. X–ray diffraction (XRD) patterns of Ch, GO, and GO–Ch (Inset: XRD patterns of graphite and
GO).

27
 (a) (b)

Fig. 3. SEM image of (a) GO and (b) GO–Ch composite.

28
 0.9 100

90
0.8
Weight loss derivative (%/ C)
80
7%
o

Weight (%)
70
0.7 26% 28% 40%
60 Ch
50
0.6 40

30 GO-Ch
0.5 GO-Ch 20
GO
0 200 400 600 800

0.4 GO o
Temperature ( C)

0.3

0.2 Ch
0.1

0.0
0 50 100 150 200 250 300 350 400 450 500
o
Temperature ( C)

Fig. 4. Differential thermogravimetry (DTG) curves in nitrogen (Inset: Thermogravimetric analysis (TGA)

of Ch, GO and GO–Ch in nitrogen).

29
 4

3
Temperature Difference ( C)
o
2

1 GO-Ch

0
Ch
-1

-2
GO-Ch
-3

-4
0 100 200 300 400 500 600 700 800 900
o
Temperature ( C)

Fig. 5. Differential thermal analysis (DTA) curves in nitrogen.

30
 A

Transmitance (%) B

3500 3000 2500 2000 1500 1000

-1
Wavenumber (cm )

Fig. 6. FT–IR spectra of adsorbents before and after adsorption of RB5: (A) GO; (B) dye–loaded GO; (C)
Ch; (D) dye–loaded Ch; (E) GO–Ch; (F) dye loaded GO–Ch.

31
 100 14
Ch GO GO-Ch
90
12
80
70 10
Adsorption (%)

60
8

pH,fin
50
6
40
30 4
20
2
10
0 0
0 2 4 6 8 10 12 14
pH,in

Fig. 7. Effect of initial pH on adsorption of RB5 onto Ch, GO, and GO–Ch (pH=2–12; 250 mg/L dye
concentration; 1 g/L adsorbent; T=25 °C; 160 rpm; 0.001 mol/L NaCl; 24 h contact).

32
 250
225
200
175
150
Qt (mg/g)

125
100
75
50
Ch
25 GO
GO-Ch
0
0 4 8 12 16 20 24 28
t (h)

Fig. 8. Effect of contact time on adsorption RB5 onto Ch, GO, and GO–Ch (pH=2; 250 mg/L initial dye
concentration; 1 g/L adsorbent; T=25 °C; 160 rpm; 0.001 mol/L NaCl; 0–24 h contact).

33
 350
Ch
300 GO
GO-Ch
Qe (mg/g) 250

200

150

100

50

0
0 50 100 150 200 250 300
Ce (mg/L)

Fig. 9. Effect of initial dye concentration on adsorption of RB5 onto Ch, GO, and GO–Ch (pH=2; 0–1000
mg/L dye concentration; 1 g/L adsorbent; T=25 °C; 160 rpm; 0.001 mol/L NaCl; 24 h contact).

34
 320 Ch GO GO-Ch
300
280
Qe (mg/g) 260
240
220
200
180
160
140
120
100
0.001 0.01 0.1 1
NaCl (mol/L)

Fig. 10. Effect of ionic strength on adsorption capacity of Ch, GO, and GO–Ch (pH=2; 250 mg/L initial
dye concentration; 1 g/L adsorbent; T=25 °C; 160 rpm; 0.001, 0.01, 0.1 and 1 mol/L NaCl; 24 h contact).

35
Table 1
Kinetic constants for the adsorption of RB5 onto Ch, GO, and GO–Ch.

Pseudo–first order model Pseudo–second order model Brouers–Sotolongo model

⎡ ⎛ ⎞⎤ 1/ ( n −1)
Q t = Q e (1 − e − k1t ) Q t ( n,a ) = Qe ⎡1 − (1 + Qe n −1 ( n − 1) k n,a t a )
1 ⎤
Q t = Qe ⎢1 − ⎜ ⎟⎥
⎣ ⎝ 1 + Qe k 2 t ⎠ ⎦ ⎣⎢ ⎦⎥

k1 R2 k2 R2 n a kn,a R2
Adsorbent min–1 min–1(mg/g)–1 min–a(mg/g)1–n
Ch 0.987 0.983 0.010 0.943 1.462 1.253 0.213 0.999
GO 2.067 0.512 0.049 0.421 1.197 0.959 0.517 0.966
GO–Ch 0.765 0.979 0.006 0.988 1.899 1.188 0.011 0.988
k,, k2, kn,a are the rate constants for the pseudo–first, pseudo –second order and Brouers–Sotolongo kinetic models, respectively; n is the fractional
reaction order of Brouers–Sotolongo model; a “fractal time” parameter of Brouers–Sotolongo model.

36
Table 2
Equilibrium parameters for the adsorption of RB5 onto Ch, GO and GO–Ch at 25, 45, and 65 oC.
Langmuir equation Freundlich equation Langmuir–Freundlich (L–F) equation

Qmax ( K LFCe )
b
Q max K L Ce 1/n
Qe = Q e = K FC Qe =
1+ ( K LFCe )
e b
1+K L Ce

T Qmax KL RL R2 KF n R2 Qmax KLF b R2

Adsorbent (oC) (mg/g) (L/mg) mg1–1/n L1/n g–1 mg/g (L/mg)1/b
Ch 25 224 0.067 0.015<RL<0.427 0.984 60.01 3.49 0.936 299 0.049 1.31 0.992
45 284 0.057 0.017<RL<0.467 0.985 58.67 3.06 0.962 325 0.033 1.39 0.995
65 345 0.060 0.016<RL<0.455 0.980 64.59 2.97 0.963 388 0.030 1.45 0.993
GO 25 205 0.064 0.015<RL<0.439 0.931 19.85 2.54 0.984 221 0.022 0.67 0.984
45 269 0.018 0.053<RL<0.735 0.976 24.08 2.39 0.992 286 0.018 0.64 0.992
65 275 0.018 0.053<RL<0.735 0.926 52.99 3.29 0.993 299 0.014 0.58 0.993
GO–Ch 25 277 0.081 0.012<RL<0.382 0.975 62.02 3.32 0.977 325 0.029 1.76 0.986
45 377 0.065 0.015<RL<0.435 0.983 62.12 2.74 0.991 441 0.048 1.50 0.994
65 425 0.098 0.010<RL<0.338 0.986 93.43 3.07 0.983 521 0.016 1.70 0.999
Qe (mg/g) is the equilibrium dye concentration in the solid phase; Qmax (mg/g) is the maximum amount of adsorption; KL (L/mg) is the Langmuir adsorption
1–1/n 1/n
equilibrium constant; KF (mg L /g) is the Freundlich constant representing the adsorption capacity, n (dimensionless) is the constant depicting the adsorption
1/b
intensity, KLF (L/mg) is the Langmuir–Freundlich constant, and b (dimensionless) is the Langmuir–Freundlich heterogeneity constant.

37
Table 3
Comparative table presenting the maximum adsorption capacities of different
materials after adsorption of RB5.
Adsorbent Qmax (mg/g) Reference
Protonated chitosan 550 [37]
Glycidyl methacrylate resin 484 [38]
BACX6 473 [39]
BACX2 286 [39]
Graphite oxide/chitosan composite 277 This study
Chitosan 224 This study
Graphite Oxide 205 This study
F400 198 [39]
Bone char 160 [39]
Sepiolite 121 [40]
Aspergillus foetidus biomass 92 [41]
Modified zeolites 61 [42]
Activated Carbon 59 [43]
Fly Ash 8 [43]
Sunflower seed shells 1 [44]

38
Table 4
Thermodynamic parameters for the adsorption of RB5 onto GO, Ch, and GO–Ch.
C0 T Qe Kc G0 H0 S0
Adsorbent (mg/L) (K) (mg/g) (kJ/mol) (kJ/mol) (kJ/mol K)
Ch 20 298 18.97 18.49 –7.23
318 19.00 19.00 –7.78 +5.35 +0.042
338 19.20 24.00 –8.93
80 298 76.92 24.99 –7.97
318 77.25 28.09 –8.82 +8.67 +0.056
338 77.95 37.99 –10.22
300 298 240.49 4.04 –3.46
318 250.75 5.09 –4.30 +10.53 +0.047
338 261.01 6.69 –5.34
GO 20 298 19.67 59.61 –10.13
318 19.72 70.43 –11.25 +10.53 +0.069
338 19.80 99.00 –12.91
80 298 60.61 3.12 –2.82
318 65.14 4.39 –3.91 +53.40 +0.186
338 78.13 41.81 –10.49
300 298 139.07 0.86 0.36
318 175.04 1.40 –0.89 +21.98 +0.072
338 213.73 2.48 –2.55
GO–Ch 20 298 19.72 65.67 –10.37
318 19.81 99.00 –12.15 +37.29 +0.159
338 19.95 399.00 –16.83
80 298 75.57 17.06 –7.03
318 77.05 26.12 –8.63 +22.76 +0.100
338 78.46 50.95 –11.05
300 298 227.11 3.11 –2.81
318 261.15 6.50 –4.95 +27.41 +0.102
338 275.98 11.50 –6.86

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Highlights

• Graphite oxide/chitosan as reactive dye adsorbent

• Characterization with FTIR, SEM, XRD, DTA, DTG, TGA

• Adsorption evaluation of pH, isotherms, kinetics, ionic strength, desorption

• Adsorption mechanism and explanation of interactions in dye-composite system

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