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Accepted Manuscript

Evaluation of the potential cationic dye removal using adsorption on graphene

and carbon nanotubes

Akbar Elsagh, Omid Moradi, Ali Fakhri, Fahime Najafi, Reza Alizadeh, Vahid
Haddadi

PII: S1878-5352(13)00383-3
DOI: http://dx.doi.org/10.1016/j.arabjc.2013.11.013
Reference: ARABJC 1163

To appear in: Arabian Journal of Chemistry

Received Date: 12 February 2013

Accepted Date: 16 November 2013

Please cite this article as: A. Elsagh, O. Moradi, A. Fakhri, F. Najafi, R. Alizadeh, V. Haddadi, Evaluation of the
potential cationic dye removal using adsorption on graphene and carbon nanotubes, Arabian Journal of
Chemistry (2013), doi: http://dx.doi.org/10.1016/j.arabjc.2013.11.013

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 Evaluation of the potential cationic dye removal using adsorption
on graphene and carbon nanotubes

Akbar Elsagh 1,*, Omid Moradi2,**, Ali Fakhri2 , Fahime Najafi3, Reza Alizadeh4 and Vahid
Haddadi5
1
Faculty of Chemistry, Department of Chemistry, North Tehran Branch, Islamic Azad
University, Iran, P.O. Box: 1913674711-Tehran-Iran
2
Department of Chemistry, Shahre-Qods Branch, Islamic Azad University, Shahre-Qods, Iran
3
Department of Chemistry, Roudehen Branch, Islamic Azad University, Roudehen, Iran
4
Faculty Engineering Khatam Alanbia University of Technology, Iran
5
Department of Chemistry, Islamshahr Branch, Islamic Azad University, Islamshahr, Iran

Abstract

We are employed in the present study single-walled carbon nanotube (SWCNTs),

carboxylate group functionalized single-walled carbon nanotube (SWCNT-COOH), Graphene
(G) and Graphene oxide (GO) as alternative adsorbents for removal of cationic dye Basic Red
46 (BR 46), from aqueous solution. Various physico-chemical parameters were studied such
as electrical conductively behaviors, contact time, solution pH, and dye concentration. The
experimental results show that SWCNTs, SWCNT-COOH, G and GO are promising adsorbents
for removing BR 46. The adsorption equilibrium data were analyzed using various
adsorption isotherms, and the results have shown that adsorption behavior of BR 46 could
be described reasonably well by Langmuir isotherm. Results showed that removal of BR 46
increased with increasing initial dye concentration, contact time and pH. Adsorption kinetics
data were modeled using the pseudo-first and pseudo-second order, and intra-particle
diffusion models. Results show that the pseudo-first order kinetic model for SWCNTs,
SWCNT-COOH and the pseudo-second order for G and GO was found to correlate the
experimental data well.

Key words: Adsorption, Basic Red 46 removal, Isotherms, Kinetic models

* email:akbarelsagh@yahoo.com
** o.moradi@shahryaiu.ac.ir, moradi.omid@gmail.com

1
Introduction

Effluents from the textile industry contain various kinds of synthetic dyestuffs, and
there has been increasing scientific interest in regard to decolorization of these effluents in
the last few decades (Karadag et al., 2007). Removing color from wastes is often more
important than other colorless organic substances, because the presence sence of small
amounts of dyes (below 1 ppm) is clearly visible and influences the water environment
considerably (Daneshvar et al., 2003). Many industries, such as plastics, textile, paper and
printing use dyes in order to color their products. Most of dye wastes are toxic and even
carcinogenic and this poses a serious hazard to aquatic living organisms.

Physical, chemical and biological processes are the principles used in treating dyes in
effluent wastewater (Barragán et al., 2007; Habib et al., 2013). Methods used to treat
wastewater containing dye include coagulation-flocculation (Rahbar et al., 2006) and
advanced oxidation process (Ai et al., 2010). However, these methods are expensive and
present operational problems such as development of toxic intermediates, lower removal
efficiency, and higher specificity for a group of dyes, among others (Pelekani et al., 2000, Jin
et al., 2008). Adsorption is the most versatile and widely used method of water treatment
because of its low cost, ease of operation, and efficiency in treatment (Najafi et al, 2013;
Saadi et al., 2013).

Adsorption is the transfer of a constituent in a liquid phase to a solid phase. The

adsorbent refers to the solid, liquid, or gas phase on where the adsorbate accumulates. The
substance that is being removed from the liquid phase is known as the adsorbate (Metcalf
et al., 2004). Adsorption processes are the most effective in dye removal compared to other
methods of wastewater treatment (Rajamohan, 2009). In industrial processes, adsorption is
a crucial step in downstream processing. The behavior of a fixed-bed adsorption column and
the adsorption breakthrough analysis can be done using mathematical models. The
breakthrough point is important to determine the stopping time of the adsorption
operation. This is because the operating time of the adsorption system affects the
effectiveness of adsorption by the column (Gupta et al., 2009).
Graphene is considered as the mother element of some carbon allotropes, which is a
basic building block for graphitic materials of all other dimensionalities, and can be
converted into fullerenes, carbon nanotube (CNT) (Sedaghatet, 2013), or 3D graphite via
wrapping, rolling, or stacking, respectively (Singh et al., 2011). Because of its unique
nanostructure, graphene has many novel properties, such as high surface area, excellent
electrical conductivity and electron mobility at room temperature, and has unique thermal
and mechanical properties (Choi et al., 2010). Graphene oxide (GO) is similar to graphene,
but presents oxygen-containing functional groups (Dreyer et al., 2010; Zhu et al., 2012; Kim
et al., 2012). In comparison with classical adsorbents such as activated carbon and clay,
CNTs is more attractive because of its favorable physicochemical stability, high selectivity,

2
and structural diversity. Extensive experiments have been conducted on the adsorption of
inorganic or organic contaminants on CNTs such as Zn2+ (Lu et al., 2006), Cd2+ (Li et al.,
2003), Pb2+ (Kabbashi et al., 2009), Cu2+ (Wu et al., 2007), Cr6+ (Di et al., 2006), fluoride (Li et
al., 2003) and dioxin (Long et al. 2001). Therefore, CNTs might be ideal sorbents for the
removal of dyes from water.
Therefore, the present objective of this study is to evaluate the Basic red 46 removal
potential and adsorption ability of dye using SWCNTs, SWCNT-COOH, G and GO was
investigated. Finally, the rates and mechanism of the adsorption process were investigated.
The objective of this study is to investigate the effect of Basic red 46 on contact time, initial
concentration, pH and temperature on the adsorption process. Various kinetic evaluations
have been used to describe the adsorption process. Here we attempted to apply pseudo
first-order rate equation and pseudo second-order and intraparticle diffusion model for the
adsorbent phase concentration.

Experimental methods

Chemicals and reagents

SWCNTs and SWCNT-COOH were purchased from NanoAmor Nanostructured & Amorphous
Materials, Inc, USA. SWCNTs (Armchair (6,6), Young's Modulus (0.94T TPa), Tensile strength
(GPa 126.2T), purity, > 95; diameter 1-2 nm; length, 5-30 nm; surface area, ~ 400 m2/g; and
manufacturing method, catalytic chemical vapor deposition (CVD)) and SWCNT-COOH
(content of COOH, 6 wt%; with purity > 95%; average diameter 1-2 nm; length 5-30 nm and
SSA ~400 m2/g). Purified natural graphene (Monolayer graphene film) was purchased from
Sigma–Aldrich Inc. The BR 46 is from the commercial manufacturing company DyStar Co.
(Germany). The structure of the dye is given in Fig. 1.

Fig. 1. Molecular structure of BR 46

Batch adsorption experiments

Tests were carried out with the removal in 100 mL conical flasks containing 20 mL BR 12 and
BR 46 solutions in a water, bath to elucidate the values of the tests parameters including
solution pH (2–9), dye concentration (20–80 mg/ L), temperature (20– 40 °C), contact time
(0–90 min) and amount of each adsorbents SWCNTs, SWCNT-COOH, G and GO as adsorbent
were equal 0.05 g. After each removal condition experiments, the samples were centrifuged
(2000 rpm, 20 min) for separation adsorbents from dye solutions and the residual dye
molecules concentration in solution were analyzed by a UV–Vis spectrophotometer at 530
nm for BR 46. The kinetic and thermodynamic studies were performed by determining
removal conditions. The removal efficiency and adsorption by solid surface as adsorbents, q
(mg/g) capacity were calculated with the following equations (Tadjarodi et al., 2013):

( Ci − C f )V
qe =
W (1)

3
where qe is the concentration of the adsorbed solute, BR 46 (mg/g adsorbent); Ci and Cf are
the initial and final (equilibrium) concentrations of the solute in solution (mg/ L); V (L) is the
volume of the solution and W (g) is the mass of the adsorbent.

Preparation Graphene oxide (GO)

GO was obtained following a modified Hummers–Offeman method (Zhou et al., 2011).

Briefly, graphene (2.0 g), sodium nitrate (1.0 g), concentrated sulfuric acid (98%, 50 mL), and
potassium permanganate (6.0 g) were consistently mixed in an ice bath for 2 h, with the
mixture gradually becoming pasty and black-greenish. Next, the mixture was placed in a 35
0
C water bath and kept at that temperature for 60 min, followed by the slow addition of
distilled water (100 mL) to keep the solution from effervescing; the resulting solution was
placed at well below 100 0C for 3 h. With progression of the reaction, the color turned a
little yellowish. After further treatment with H2O2 (5%, 100 mL), the filtered cake was
washed with distilled water several times until its supernatant was without SO42−, as tested
using barium chloride (0.1 mM). Then the cake was dispersed in water for further ultra-
sonication for 1 h. Of note, for facilitating the following experiments, we selected solutions
with GO centrifuged at speeds ranging from 2500 to 5000 rpm. GO-based samples were
characterized using various techniques such as Fourier transform infrared spectrum (FT-IR).

Results and discussion

Characterization of graphene (G) and graphene oxide (GO) surfaces

Electrical conductively behavior of graphene was measured 0.005 S/m and for graphene
oxide was 0.14 S/m by conductive-meter in aqueous solution at 25 0C. This results indicated
was electrical conductively behavior of graphene improved by oxidation of graphene. The
FTIR pattern of graphene has a characteristic peak at 1610 cm-1 due to the aromatic C=C
skeletal vibrations are shown in Fig. 2.a. The FTIR pattern of GO, which is shown in Fig. 2.b,
reveals the presence of the oxygen-containing functional groups. The peaks at 1071, 1380,
1630 correspond to C- O- C stretching vibrations, C-OH stretching, C-C stretching mode of
the sp2 carbon skeletal network, respectively, while peaks located at 1730 and 3440 cm−1
correspond to C-O stretching vibrations of the COOH groups and O-H stretching vibration,
respectively (Fan et al., 2013).

Fig. 2. Fourier transform infrared spectrum (FT-IR) for pristine graphene (a) and oxidized
graphene (b)

Effect of contact time and dye concentration

The effect of contact time on the adsorption of BR 46 by SWCNTs, SWCNT-COOH, G and GO

surfaces as adsorbents was shown in Fig. 3. The experiments were carried out at 60 mg/ L
initial dye for and concentration with 0.05 g adsorbent mass for adsorbent surfaces at

4
temperatures 25 °C. The amount of each dye adsorbed increased with increase in contact
time and reached equilibrium after 80 min for SWCNTs, SWCNT-COOH and 90 min for G and
GO.

Fig. 3. Effect of contact time on the adsorption of BR 46 by SWCNTs, SWCNT-COOH, G and

GO surfaces, (temperature: 298 K, mass each of adsorbent: 0.05 g and pH 9).

Effect of initial concentration on BR 46 adsorption by SWCNTs, SWCNT-COOH, G and GO as

adsorbent surfaces is shown Fig. 4. Furthermore, the amount adsorption dye is increased
with the increase in initial dye concentration. It is because of the fact at higher
concentration, the ratio of the initial number of dye molecules to the available surface area
is high subsequently the fractional adsorption becomes independent of initial
concentration. However, at high concentration the available sites of adsorption becomes
more and hence the adsorption of dye depends upon concentration (Al-Rashed and Al-Gaid
2012).

Fig. 4. Effect of initial BR 46 concentration on adsorption of BR 46 by SWCNTs, SWCNT-

COOH, G and GO surfaces, mass each of adsorbents = 0.05 g, initial pH 9 and Temperature
298 K.

Effect of pH

The pH is one of the most important factors controlling the adsorption of dyes onto
suspended particles, because both adsorbed molecules and adsorbent particles may have
functional groups which are affected by the concentration of hydrogen ions (H+) in the
solution and which are involved in the molecular adsorption process at the active sites of
adsorbent. The pH of the dye solution affects not only the surface charge of the SWCNTs,
SWCNT-COOH, G and GO surfaces adsorbents, the degree of ionization of the materials and
the dissociation of functional groups on the active sites of the adsorbents surface, but also
the structure of the dye molecule (Lin and Leu 2008). The results of the pH studies at
different pH values are shown in Fig. 5. Adsorption capacity of the BR 46 increased with
increasing pH and reached a maximum level at the pH of 9.0. Similar pH trends were also
reported by other researchers (Nadi et al., 2009). The lower adsorption of BR 46 by surfaces
adsorbents at low pH values may be explained by the competition of excess H+ ions with the
dye cation for active adsorption sites (Batzias and Sidiras 2007). However, it did not explain
the slight decrease of the dyes by both surfaces adsorption at higher pH values.

Fig. 5. Effect of initial pH of solution on adsorption of BR 46 by SWCNTs, SWCNT-COOH, G

and GO surfaces, mass each of adsorbents = 0.05 g, initial pH 9, and Temperature 298 K.

Adsorption isotherms

5
 From the various isotherm equations that may be used to analyze adsorption data in
aqueous phase, the Langmuir (Najafi et al, 2013; Ayad and El-Nasr 2012)—the theoretical
equilibrium isotherm and the Freundlich (Najafi et al, 2013; Moradi et al., 2012)—the
empirical equilibrium isotherm are the most common models. The linear forms of these
equations are displayed as equation (2) (Langmuir) and (3) (Freundlich):

= + (2)

(3)
where qm (mg g−1) is the maximum adsorption capacity, qe (mg g−1) is the amount of
adsorbed 4C2NP, Ce (mg L−1) is the equilibrium BR46 concentration, KF and n are the
Freundlich constants, and KL (L mg−1) is the Langmuir constant. The Langmuir and Freundlich
parameters, along with the coefficients of determination (r2) of the linear plots, are
presented in Table 1. Adsorption of BR46 on SWCNTs, SWCNT-COOH, G and GO surfaces can
be fitted by Langmuir model.

Table 1 Isotherm constants for the adsorption of BR 46 by adsorbents

Kinetics study

The adsorption process on a porous adsorbent in a stirring chamber generally

involves several transport stages (Weirich et al., 2002, Ravindran et al., 1999); external
diffusion, internal diffusion, and actual adsorption. Although many theoretical model
equations have been proposed to describe the adsorption kinetics based on mass balance,
pore diffusion rate, and initial/boundary conditions, these equations are not only
complicated and impractical in industry, but also require detailed data such as the
characteristics of adsorbate and adsorbent. The conformity between experimental data and
the model predicted values was expressed by the correlation coefficient (r2, values close or
equal to 1). A relatively high r2 value indicates that the model successfully describes the
kinetics of BR46 adsorption.

Pseudo Firs-order Model

The sorption kinetics may be described by a pseudo first order equation (Hossain et
al., 2005; Özacar, 2003; Robati, 2013; Ho et al., 2001). The linear form equation is the
following:

log(qe − qt) = log(qe) − k1t (4)

where qe and qt are amounts of dye adsorbed at equilibrium and at time (mg/g),
respectively, and is the equilibrium rate constant of pseudo first-order adsorption, (1/min).

6
Fig. 6 shows a plot of linearization form of pseudo first-order model. The slopes and
intercepts of plots of versus were used to determine the pseudo first-order constant and
equilibrium adsorption density. However, the experimental data deviated considerably from
the theoretical data. A comparison of the results with the correlation coefficients is shown
in Table 2. The correlation coefficients for the pseudo first order kinetic model obtained at
all the studies concentrations were high for SWCNTs, SWCNT-COOH. This suggests that this
adsorption system is a pseudo first-order reaction.

Fig. 6. Plot of the Pseudo first-order kinetics for adsorption of BR46

Pseudo Second-order Model

The adsorption kinetics may also be described by a pseudo second-order equation

(Özacar, 2003; Robati, 2013; Ho et al., 2001). The linear form equation is the following:

‫ݐ‬/‫ = ݍ‬1/݇2‫݁ݍ‬2 + t/‫݁ݍ‬ (5)

where k2 is the equilibrium rate constant of pseudo second-order adsorption (g/mg.min).

The slopes and intercepts of plots t / q versus t were used to calculate the pseudo second-
order rate constants k2 and qe. The straight lines in plot of t / q versus t (Fig. 8) show good
agreement of experimental data with the pseudo second-order kinetic model for different
initial dye concentrations. Table 2 lists the computed results obtained from the pseudo
second-order kinetic model. These indicate that the adsorption system studied belongs to
the second order kinetic model.

Fig. 7. Plot of the Pseudo second-order kinetics for adsorption of BR46

The Intra-particle Diffusion Model

The intra-particle diffusion model is expressed as (Moradi et al., 2001, Moradi et al.,
2013):

q = ki t 1/2 + C (6)

where C is the intercept and ki is the intra-particle diffusion rate constant (mg/g h0.5), which
can be evaluated from the slope of the linear plot of q versus t1/2. Fig. 8 shows a plot of the
linearized form of the intra-particle diffusion model.
As can be seen from these figures, the pseudo first-order kinetic model provides the
best correlation for all of the adsorption process, whereas the other models fits the
experimental data well not for initial periods of the adsorption process only. Hence it was
concluded that the pseudo second-first kinetic model was found to be rate limiting.

Fig. 8. Plot of the Intra-particle diffusion model for adsorption of BR46

7
Table 2 Comparison of the kinetic models for adsorption of BR46

Conclusions

Single-walled carbon nanotube (SWCNTs), carboxylate group functionalized single-walled

carbon nanotube (SWCNT-COOH), Graphene (G) and Graphene oxide (GO) can be used as
effective adsorbents for removing Basic red 46 from contaminated water sources. Increasing
the temperature decreased the BR46 adsorption rate but the maximum adsorption capacity
was similar. The adsorption isotherms are fitted by Langmuir equation. The pseudo first-
order kinetic model for SWCNTs, SWCNT-COOH and the pseudo second-order kinetic model
for G and GO accurately described the adsorption kinetics. The adsorption mechanism was
found to be physic-sorption and the rate-limiting step was mainly surface adsorption.

Acknowledgements

This project was financial support by the Islamic Azad University, North Tehran Branch, of
Iran.

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11
Fig. 1

Fig. 2

12
 50

45 BR 46 on G
40
BR 46 on GO
35

30
q (mg/g)

25

20

15

10

0
0 10 20 30 40 50 60 70 80 90 100
Tim e (m in)

Fig. 3

13
 60
BR 46 on G
50
BR 46 on GO

40
q (mg/g)

30

20

10

0
0 10 20 30 40 50 60 70 80 90
Initial concentration (mg/L)

Fig. 4

14
 50
45 BR46 on GO

40 BR 46 on GO
35
q (mg/g)

30
25
20
15
10
5
0
0 2 4 6 8 10

pH

Fig. 5

15
 0

-0.5

-1

-1.5

-2
ln(qe-q)

-2.5

-3

-3.5

-4 BR 46 on G
BR 46 GO
-4.5 Linear (BR 46 on G)
Linear (BR 46 GO)
-5
0 20 40 60 80 100
tim e (m in)

Fig. 6

16
 30
BR 46 on G
25
BR 46 on GO
20
t/q

15

10

0
0 20 40 60 80 100
Tim e (m in)

Fig. 7

17
 50

45 BR 46 on G
40 BR 46 on GO
35
30
q (mg/g)

25
20
15
10

5
0
0 2 4 6 8 10
√t

Fig. 8

18
 Table 1

Isotherm Langmuir Freundlich

qm(mg/g) KL(L/mg) r2 KF 1/n r2

SWCNTs 38.35 1.71 0.942 16.12 0.233 0.912

SWCNT-COOH 49.45 1.57 0.955 15.11 0.458 0.931

G 30.52 2.24 0.972 18.23 0.184 0.927

GO 55.57 1.25 0.984 14.21 0.519 0.939

Table 2

Kinetic model SWCNTs SWCNT-COOH G GO

Pseudo-first-order

qe (mg/g) 137.52 126.64 0.0075 0.3624

k1 (1/min) 0.0076 0.0105 0.0027 0.0252

R2 0.9978 0.9973 0.9929 0.9960

Pseudo-second-order

qe (mg/g) 149.25 227.27 3.194 50.00

k2 (g /mg min) 0.0004 0.0009 2.4449 0.0740

R2 0.9909 0.9901 1.0000 1.0000

Intra particle diffusion

Ki (mg/g min0.5) 13.464 15.254 0.3844 5.1805

C (mg/g ) 6.3588 27.312 0.3715 2.6327

R2 0.9954 0.9970 0.9789 0.9939

19

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