See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/255764966

Exploring the interesting interaction between

graphene oxide, Aliquat-336 (a room
temperature ionic liquid) and...

Article in RSC Advances · January 2013

DOI: 10.1039/C2RA22627H

CITATIONS READS

32 695

2 authors, including:

SANTHANA KRISHNA Kumar

National Sun Yat-sen University
33 PUBLICATIONS 569 CITATIONS

SEE PROFILE

All content following this page was uploaded by SANTHANA KRISHNA Kumar on 19 March 2014.

The user has requested enhancement of the downloaded file.

RSC Advances

PAPER

Exploring the interesting interaction between graphene

oxide, Aliquat-336 (a room temperature ionic liquid)
Cite this: RSC Advances, 2013, 3,
2697 and chromium(VI) for wastewater treatment
A. Santhana Krishna Kumar and N. Rajesh*

Received 24th October 2012,
Accepted 11th December 2012
DOI: 10.1039/c2ra22627h
www.rsc.org/advances
We report an interesting interaction between exfoliated graphene oxide (EGO), ionic liquid (IL) Aliquat-
336 and hexavalent chromium. Graphene oxide was impregnated with the ionic liquid and the interaction
primarily involves electrostatic affinity between the quaternary ammonium cation and surface hydroxyl
groups in EGO. The IL-EGO combination functions as an effective adsorbent for hexavalent chromium. The
IL-EGO adsorbent acts as a good host in welcoming the incoming guest, hydrochromate anion and several
interesting interactions such as cation–p, electrostatic as well as anion–p could be conceptualized in this
process. The adsorbent features are ably supported by various physico-chemical characterization
techniques and the effect of various analytical parameters affecting the adsorption is examined in detail.
A high Langmuir adsorption capacity of 285.71 mg g21 is augmented by the thermodynamically
favourable adsorption process. Kinetic studies confirm the pseudo second order model and furthermore,
the process could be upgraded by column study to a sample volume of 1200 mL. Effective regeneration of
the adsorbent could be accomplished with ammonium hydroxide and the potential of this novel
adsorbent material has been examined in the total removal of chromium from a tannery effluent sample.

Introduction varying oxidation states. In this context, some carbon based

There is a growing need for an affirmative action to tackle the
environmental pollution due to heavy metal discharge from
various industrial effluents. Chromium pollution is an
important concern that requires effective strategies in devising
an appropriate remediation technology. The concentration of
chromium in natural water1 is in the range 0.1–2.5 mg L21 and
this could increase due to the pollution from dyeing and
electroplating waste effluents. Industrial effluents arising from
tannery2 is one of the sources for the leaching of chromium
into the ground water. The chromium concentration in
tannery water could range between 1500–3000 mg L21 and
conventionally the Cr(III) in the effluent is converted to its
hydroxide prior to disposal. The discharge of Cr(VI) to surface
water3 is restricted to less than 0.05 mg L21 and the US EPA
restricts the limit for total chromium to 0.1 mg L21 in drinking
water.4 Adsorbents ought to be properly tailored for fast and
effective adsorption-desorption kinetics in heavy metal removal
from aqueous solutions. The toxicity of chromium5 has catalyzed
the development of a variety of adsorbent materials. Macrocyclic
polymers,6–9 biopolymer adsorbents,10–14 biomass15,16 and fly
ash17 are well known for their ability to adsorb chromium in
Department of Chemistry, Birla Institute of Technology and Science, Pilani-
Hyderabad Campus, Jawahar Nagar, Shameerpet Mandal, R. R. Dist-500 078 (AP),
India. E-mail: nrajesh05@gmail.com (N. Rajesh); Fax: +91 40 66303998;
Tel: +91 40 66303503
adsorbents18–25 merit citation in view of their low cost and other
advantages such as renewability and good stability. Instead of
reconciling with the traditional adsorbents, focus has shifted
towards the development of newer customized sorbents such as
graphene for environmental remediation. Graphene as a two
dimensional carbon nanomaterial has evoked considerable
interest due to its multifarious applications.26,27 Graphene oxide,
the derivative of graphene could be obtained from graphite
followed by the oxidation of graphene and its interesting
chemistry finds its application as a useful entity in a broad
range of chemical transformations.28 Graphene oxide is endowed
with multiple functional groups such as hydroxyl, carboxylic,
carbonyl and epoxy for effective complexation with metal ions.
Graphene oxide has been utilized for the removal of heavy metal
ions such as copper,29 cadmium and cobalt,30 mercury,31 and
arsenic32 from aqueous solution. Photocatalytic reduction of
Cr(VI) has been reported using TiO2 reduced graphene oxide
composites.33 The utility of graphene oxide has also been
illustrated in the removal of humic acid34 and organic dyes35–37
from aqueous medium. The chemical reduction of Cr(VI) using
EDTA reduced graphene oxide has been reported.38 The effect of
imidazolium based ionic liquids on the exfoliation of graphene
oxide offers interesting insight into the various mechanistic
aspects such as electrostatic, cation-p and hydrogen bonding
interactions.39 Literature reports on the utility of a graphene
oxide–ionic liquid combination for chromium detoxification are

This journal is ß The Royal Society of Chemistry 2013 RSC Adv., 2013, 3, 2697–2709 | 2697
Paper RSC Advances

scarce. We report for the first time the interaction between

Aliquat-336, a room temperature ionic liquid,40 exfoliated
graphene oxide and hexavalent chromium. This IL-EGO novel
adsorbent shows excellent sorption characteristics for Cr(VI) as
substantiated through the comprehensive physico-chemical
characterization techniques, batch adsorption study and column
dynamic upgradation to a large sample volume.

Experimental section
Materials
The quality of reagents was of analytical grade and Milli Q
water (Elix 3) was used in the dilution of aqueous solutions.
Graphite was purchased from Sigma Aldrich. Aliquat-336 was
procured from Spectrochem, India. The other essential Fig. 1 Absorption spectrum of chromium(VI)-diphenylcarbazide complex.
reagents were procured from S.D. fine chemicals, India and
Merck, India respectively. A working solution of 300 mg L21
Cr(VI) for batch adsorption experiments was prepared from
between the initial concentration (C0) of chromium(VI) and the
stock 1000 mg L21 Cr(VI) using potassium dichromate.
equilibrium concentration (Ce) in solution. This is related
Preparation of exfoliated graphene oxide (EGO) from graphite through the expression
The exfoliated graphite (EG) was first prepared by the well ðC0 {Ce ÞV
qe ~ (1)
known procedure reported earlier.41 6 g of graphite powder W
was treated mixture of conc. H2SO4/HNO3 (3 : 1) for 24 h at
ambient environment. The material was washed with Milli Q where V and W are the volume of sample solution (L) the
water, dried and the exfoliation was performed at 800 uC. 1 g of weight (g) of the IL-EGO adsorbent. Spectrophotometric
EG was sonicated with acetone for 1 h. The powdered EG was determination of chromium in the aqueous phase was carried
dried and further oxidation to EGO was carried out based on out using diphenyl carbazide reagent43 which gives a distinct
the Hummers method.35,41,42 The method involves the treat- red-violet color characteristic of chromium (Fig. 1). The uptake
ment of EG with approximately 50 mL of conc. H2SO4 and 6 g of chromium was rapid, quantitative adsorption (99.8 ¡
of KMnO4 as the oxidizing agent maintaining a temperature 0.06%) was attained in 45 min, and this is indicative of the
between 0–5 uC. The temperature of the mixture was raised to relatively fast adsorption kinetics. Retention of chromium was
95 uC followed by treatment with 25 mL of 30% H2O2. The quantitative with 0.2 g of the IL-EGO adsorbent material. The
resulting solid was filtered, washed with 5% HCl and the isotherm studies were performed at 30 uC using varying
filtrate was checked for the presence of sulfate. The EGO was concentrations of chromium(VI) and various empirical models
further washed thoroughly with Milli Q water and dried in a (Table 1) were used to corroborate the experimental data. The
hot air oven at 60 uC for 24 h. equilibrium constant (Kads) of adsorption was found from the
Preparation of adsorbent concentration of the adsorbed chromium in the IL-EGO
2 g of EGO was taken in a round bottom flask followed by the
addition of 13.8 mL of 0.03 mole Aliquat-336 (IL) in acetone
medium and stirred for 8 h. The resulting mixture was washed Table 1 Various isotherms and the relevant expressions
thoroughly with water, filtered and the supernatant was
checked for the presence of chloride with silver nitrate. The Sl. No. Isotherm Equation
solid was washed with water and the IL-EGO adsorbent was
dried in a hot air oven overnight and used for further 1 Langmuir52 Ce 1 Ce
~ z
qe q0 b q0
adsorption studies. Comprehensive characterization of the 2 Freundlich53 1
adsorbent was done using various physico-chemical techni- log qe ~ log KF z log Ce
n
ques to confirm the presence of IL and EGO in the adsorbent. 3 Dubinin–Radushkevich54,55 lnqe = lnqm 2 be2
1
e~RT ln 1z
Batch adsorption experiments Ce
EDR = 1/(2b)20.5
Chromium(VI) at 300 mg L21 level with 0.2 g of the IL-EGO 4 Redlich–Peterson56,57 ACe
qe ~
adsorbent was equilibrated in an incubator shaker ð1zBCe g Þ
(Biotechnics, India) for different time intervals at pH 2.5. ln(AC
 e /qe 2 1) = g ln(Ce) + ln(B)
5 Elovich58,59 qe qe
The aqueous volume was fixed at 25 mL during this study. The ln ~ lnðKE qm Þ{
Ce qm
amount of chromium(VI) adsorbed on the IL-EGO solid 6 Temkin60,61 RT RT
adsorbent at equilibrium (qe) is obtained from the difference qe ~ ln Az ln Ce
b b

2698 | RSC Adv., 2013, 3, 2697–2709 This journal is ß The Royal Society of Chemistry 2013
RSC Advances
adsorbent to that in the solution phase (CIL-EGO/Csolution). The
thermodynamics of adsorption was studied at different
temperatures. The Gibbs free energy change is obtained from
the expression connecting DGo with equilibrium constant as
DGo = 2RT lnK. The slope and intercept of the Van’t Hoff plot
of lnK against the reciprocal of temperature (T) gives the
entropy and enthalpy changes.44
{DH 0 DS 0
ln K~ z (2)
RT R peaks were obtained at 1402 cm21. The C–O–C in epoxide
Physico-chemical characterization
Spectrophotometric determination of chromium was per-
formed with a Jasco V-650 UV visible spectrophotometer using
1 cm matched quartz cuvettes. The FT-IR spectra of EG, EGO
and the IL-EGO adsorbent were recorded using a Jasco-4200
FT-IR spectrometer in the range 500–4000 cm21 by mixing 0.01
g of the samples with 0.1 g of spectroscopy grade KBr. X-ray
diffraction (XRD) patterns were obtained using a Philips
PANalytical X9pert PRO diffractometer using Cu-Ka radiation
(l = 1.54 Å) operating at 40 kV and 30 mA with step size of 0.05.
The energy dispersive spectral analysis (EDS) of the IL-EGO
adsorbent consequent to the adsorption of chromium was
recorded with a JEOL JSM-6390 analyzer. An Elico LI-127 pH
meter supplied by Elico, India was used for pH adjustment.
Results and discussion
FT-IR spectral analysis
The FT-IR spectrum obtained for graphite and EGO were in
accordance with the reported literature.29,62,35,45 The FT-IR
spectrum (Fig. 2) showed characteristic peaks for pure
Fig. 2 FT-IR Spectrum of (A) graphite, (B) exfoliated graphene oxide, (C) ionic
liquid impregnated EGO, (D) after adsorption of chromium(VI) on IL-EGO.
This journal is ß The Royal Society of Chemistry 2013
Paper
graphite corresponding to aromatic C–H stretching at 3152
cm21, CLC stretching at 1672 and 1536 cm21 and C–H
bending at 1401 cm21.32 After oxidation with nitric acid/
sulfuric acid and KMnO4 functional groups such as hydroxyl,
carboxylic acid and epoxy group are introduced characteristic
of graphene oxide. In the case of EGO, the OH group stretching
vibrations were obtained at 3387 cm21. The carbonyl group
(CLO) stretching vibrations were seen at 1745 cm21. The
aromatic CLC stretching 1647 cm21 and C–OH stretching
stretching was observed at 1128 cm21. After impregnation with
ionic liquid two new peaks appeared at 2908 cm21 and 2821
cm21 resulting from the CH2 stretching of the aliphatic chain
in Aliquat 336.45 Furthermore, the hydroxyl group frequency is
shifted to 3214 cm21. The carbonyl group frequency and the
CLC peaks are also shifted to 1724 cm21 and 1671 cm21
respectively. These spectral shifts could be ascribed to
electrostatic interaction of the quaternary ammonium cation
with the OH group and the interaction of the p electrons in the
polarizable aromatic ring manifested as cation–p interaction.
In the pH range 2.5–3.0, the hydroxyl groups in the adsorbent
(IL-EGO) could be protonated and these positively charged
surface hydroxy groups could also interact with the hydro-
chromate anion (HCrO42). After adsorption of chromium two
peaks appeared at 874 cm21 and 770 cm21 characteristic of
CrLO and Cr–O stretching frequencies in the hydrochromate
anion.6,10,46,47
XRD and EDS studies
XRD pattern (Fig. 3) of graphite shows a diffraction peak at 2h
= 26.49u which corresponds to the (002) plane. The oxidation
of graphite to exfoliated graphene oxide results in the
appearance peaks corresponding to 2h = 37.3u and 49.7u
which is due to the creation of the abundant oxygen-contain-
ing functional groups on the surfaces of graphene oxide. These
values are in accordance with the earlier reported litera-
ture.30,36,41 A slight shift in the 2h value to 26.39u with little
broadening is also seen in the XRD pattern of EGO. After
impregnation of ionic liquid in the EGO matrix peak
sharpening occurs corresponding to 2h = 26.76u, 42.7u, 44.8u
and 54.8u respectively. The sharpness in the peak intensity
could be ascribed to a certain degree of crystallinity in the
amorphous IL-EGO adsorbent matrix. The average crystallite
size was obtained using the Debye-Scherrer’s equation (0.9l/b
cosh) where ‘l’ is the wavelength of X-ray and b is the full
width half maximum (FWHM) of the diffraction peak. The
average crystallite size was found to be 12.76 nm. After
adsorption of chromium, we could see an upward spectral
shift corresponding to 26.53u and 45.0u.11 There is a slight
peak broadening as compared to the IL-EGO adsorbent and
this shows that after the adsorption of chromium the
adsorbent matrix is relatively more amorphous. We could also
authenticate the adsorption of chromium from the EDS
spectrum (Fig. 4) along with other elements such as Mn, C,
O and S respectively. The appearance of the peak in the range
5–6 keV is also in agreement with the earlier reported
literature characteristic of chromium.2,7
RSC Adv., 2013, 3, 2697–2709 | 2699
Paper RSC Advances

Fig. 3 XRD patterns: (A) graphite; (B) exfoliated graphene oxide; (C) ionic liquid impregnated EGO; (D) after adsorption of chromium(VI) on IL-EGO.

Interaction of EGO with Aliquat 336, optimum pH and dominant form of Cr(VI) is HCrO426,7,10,50 and increasing the
mechanism of adsorption pH would shift the equilibrium to the CrO422 oxy anion. At pH
less than 2 the dichromate ion, Cr2O722 is the key species6 that
The presence of functional groups in EGO such as COOH, OH
exists in solution. In the present system, the optimum pH for
and CLC is a boon with regard to interactions of the ionic
adsorption of hexavalent chromium on IL-EGO adsorbent was
liquid. The ionic liquid, Aliquat-336, is essentially a long chain
in the range 2.5–3.5. This is a characteristic feature associated
quaternary ammonium halide with a long hydrophobic tail
with the existence of hydrochromate anion as reported by
and the head group contains the positively charged nitrogen
several groups working on the removal of chromium.7,10 The
atom. The trioctylammonium cation would involve in an
effect of pH on the adsorption of chromium is depicted in
electrostatic interaction with the surface hydroxyl and carboxyl
Fig. 5. The trioctylammonium cation is involved in an ion-pair
groups and furthermore, the affinity could also be strength-
electrostatic interaction with the HCrO42 anion11 as well as
ened via the cation–p interaction39,48,49 involving the con-
protonated hydroxyl groups on the surface. The overall
jugated aromatic ring. In an aqueous solution containing
mechanism that could be conceptualized in this adsorption
Cr(VI) ions, the interaction certainly would depend on the pH
process is given in Fig. 6. With increase in pH, the repulsion
of the medium. Hence, aqueous phase pH plays an important
between the negatively charged EGO surface (owing to the
role in the interaction of hexavalent chromium with the ionic
deprotonation of the surface hydroxyl groups) and the
liquid and graphene oxide. A well known fact in several
hydrochromate anion results in a decrease in the percentage
adsorption systems involving chromium is its existence as
adsorption of chromium. Furthermore, the competition from
various oxo anions depending on the pH of the sample
hydroxyl anions for the active sites of the IL-EGO also would
solution. The optimization of pH was studied at an initial
influence the adsorption at higher pH. The pHzpc of the IL-
Cr(VI) concentration of 300 mg L21. In the pH range 2–5, the

2700 | RSC Adv., 2013, 3, 2697–2709 This journal is ß The Royal Society of Chemistry 2013
RSC Advances Paper

Fig. 4 EDS spectrum of the adsorbed Cr(VI) on EGO.

EGO adsorbent was measured using the pH drift method.51

The experiment was carried out at 30 uC by taking 0.10 g of the
IL-EGO adsorbent in 50 mL of the 1 mol L21 sodium chloride.
The initial pH was adjusted using dilute sulfuric acid and
sodium hydroxide. The final pH was recorded after 24 h so as
to ensure the stability and the plot of initial versus final pH was
used to determine the (pHzpc) of the sorbent. The pHzpc of the
IL-EGO adsorbent (Fig. 7) was found to be 3.5. At pH , 3.5, the
surface charge of exfoliated graphene oxide is positive, and
this promotes the adsorption of hexavalent chromium due to
electrostatic attraction. Above pH 3.5, the surface charge of
exfoliated graphene oxide becomes negative with the slow
deprotonation of the surface hydroxy groups leading to
electrostatic repulsion between the hexavalent chromium oxo
anion and the adsorbent surface. The amount of Cr(VI)
adsorbed depends on pH, temperature and the concentration
of the ionic liquid. At low pH, the facile electrostatic
interaction of Aliquat 336 with hexavalent chromium is
Fig. 5 Effect of pH. dominant. Aliquat-336 does play a significant role in the

This journal is ß The Royal Society of Chemistry 2013 RSC Adv., 2013, 3, 2697–2709 | 2701
Paper
Fig. 6 Left. Illustration of interaction between IL and EGO. Right. Illustration of interaction between EGO, IL and chromium(VI).
adsorption of chromium. This is further authenticated from
FT-IR and XRD studies. The adsorption capacity of
chromium(VI) in the absence of Aliquat-336 was found to be
67.52 mg g21 while Aliquat-336 impregnated graphene oxide
provided an enhanced Langmuir adsorption capacity of 285.71
mg g21.
Adsorption isotherms
The various isotherm (Fig. 8A–F) models essentially correlate
the amount of the hexavalent chromium adsorbed at
equilibrium and the concentration in solution. The experi-
mental data were fitted into various adsorption isotherms by
equilibrating varying initial concentrations of hexavalent
chromium (300, 500, 700, 1000, 1500, 2000 mg L21) with a
known weight (0.2 g) of the adsorbent. Even though, Langmuir
and Freundlich isotherms are widely used in adsorption
Fig. 7 Zero point charge (pHzpc) of the IL-EGO adsorbent.
2702 | RSC Adv., 2013, 3, 2697–2709
RSC Advances
studies, various other empirical models (Table 1) also offer
vital insight into the nature of adsorption.52–61 The isotherm
parameters obtained through these models are given in
Table 2. The Langmuir plot of Ce/qe against Ce gives the
corresponding isotherm parameters such as the maximum
adsorption capacity (q0) and the adsorption energy b. A high
adsorption capacity of 285.71 mg g21 reflects the excellent
sorption potential of the IL-EGO adsorbent for chromium(VI).
Furthermore, in this model the separation factor (RL = 1/1 +
bCo) was found to be less than unity which shows the
effectiveness of interaction of the IL-EGO adsorbent with
chromium(VI) oxy anion.62 The intensity of adsorption n and
the adsorption capacity KF are two other vital parameters
which are obtained from the Freundlich isotherm plot of log qe
against log Ce. When 1/n , 1, it corresponds to a normal L-type
Langmuir isotherm,63 while 1/n . 1 reflects a co-operative
sorption.64 As shown in Table 2, the values of 1/n and KF along
with a high regression coefficient of 0.99 indicate the effective
uptake of chromium by the IL-EGO adsorbent in this
adsorption process. The adsorption energy (b), Polanyi
potential (e) and the mean free energy EDR of adsorption are
also given by yet another interesting D-R isotherm model. The
EDR value obtained in this study is characteristic of physical
adsorption involving hexavalent chromium and the IL-EGO
adsorbent. In case of the R-P isotherm, the exponent ‘‘g’’ in the
equation is significant and values close to unity are an
indication of the good fit to the Langmuir model. In the
adsorption of chromium(VI) on the IL-EGO surface, the value
signifies that the experimental data could be correlated based
on the Langmuir model as well. The low binding energy b
obtained in the present study involving the Tempkin isotherm
illustrates the electrostatic interaction65 between the hydro-
chromate anion and the IL-EGO adsorbent. The adherence to
the Freundlich model was also established further from the
individual isotherm data plots of qe against Ce. The L shaped
adsorption isotherms are in agreement with the Giles
categorization66 and the qe values obtained experimentally
This journal is ß The Royal Society of Chemistry 2013
RSC Advances Paper

Fig. 8 A. Freundlich isotherm. B. Langmuir isotherm. C. Dubinin–Radushkevich isotherm. D. Redlich–Peterson isotherm. E. Elovich isotherm. F. Temkin isotherm.

This journal is ß The Royal Society of Chemistry 2013 RSC Adv., 2013, 3, 2697–2709 | 2703
Paper RSC Advances

Table 2 Study of various isotherm models intraparticle rate constant (kint). The Weber-Morris plot
(Fig. 9D) gives a linear fit without passing through the origin
Sl. No Model Isotherm parameters and this is an indication that the adsorption of hexavalent
chromium could involve a boundary layer mechanism too.
1 Freundlich KF (mg121/n g21 L1/n) 28.11
n 2.11 Thermodynamics of adsorption
r2 0.99
2 Langmuir q0 (mg g21) 285.71 The adsorption process is spontaneous and exothermic with
b (L mg21) 0.0423
negative entropy change (Table 4). The Van’t Hoff plot (Fig. 9E)
RL 0.073
r2 0.91 gives the entropy and enthalpy changes accompanying the
3 Redlich Peterson g 0.773 adsorption process. The decreased randomness at the IL-EGO
B (L mg21) 0.11 adsorbent–hydrochromate solution interface is reflected in the DS0
A (L g21) 12.08
r2 0.98 value. The average energy of activation71 was found to be 261.36 kJ
4 Temkin B 49.31 mol21 which also authenticates the exothermicity of the adsorption
A (L mg21) 0.785 process. The negative free energy (DG0) values corroborate the
b (kJ mol21) 0.05
r2 0.88
effectiveness of the electrostatic interaction between HCrO42 and
5 Elovich qm (mg g21) 108.69 the IL-EGO adsorbent surface. Indeed, the free energy of adsorption
KE (L mg21) 0.1883 could arise from the interaction between IL-EGO, HCrO42-IL and
r2 0.83 HCrO42-EGO. The overall free energy of adsorption (DGads) is a result
6 Dubinin Radushkevich qm (mg g21) 123.21
b (mol2 kJ22) 0.835 of this electrostatic force of attraction as well as the cation–p
E (kJ mol21) 0.78 interaction between the positively charged quaternary ammonium
r2 0.61 cation and the polarisable aromatic p electron cloud.48,49

show a good correspondence to the Freundlich type isotherm

DGadsorption = DGIL-EGO + DGHCrO42 2 IL + DGHCrO42 2 EGO (5)
as shown in Fig. 9A. The effective electrostatic interaction
between the hydrochromate anion and the IL-EGO adsorbent
The feasibility of the adsorption process at low temperatures is
is evident from the ascending portion of the curve and the
relatively flat terrains at higher Ce values denote the saturation also evident from the trend in the free energy values. Typically,
of the adsorption sites. the exfoliated graphene oxide would act as a primary host to the
trioctylammonium cation, which in turn functions as a
Adsorption kinetics secondary host to the chromium(VI) solution from the bulk.
The kinetic mechanism that controls the adsorption of Cr(VI) Hence, the enthalpy and entropy of adsorption should also take
on the IL-EGO adsorbent was evaluated using the pseudo first- cognizance of the interaction between the ionic liquid
order, second-order and the intraparticle diffusion models. impregnated graphene oxide and the hydrochromate oxy anion.
These models relate the amount of the Cr(VI) adsorbed at
equilibrium and the respective rate constants at varying DHadsorption = DH(IL-EGO) + DHCr(VI) (6)
equilibration time. The Lageregen first order67 and Ho68
second order expressions given below are extensively used in DSadsorption = DS(IL-EGO) + DSCr(VI) (7)
all adsorption processes to correlate the experimental data
DGadsorption = DHadsorption 2 T(DSIL-EGO + DHCr(VI)) (8)
t 1 t
~ z (3)
qt k2 qe 2 qe Indeed, in an ion-pair mechanism involving electrostatic
interactions, the enthalpy and entropy factors play a signifi-
k1 t cant role.72,73 The ability of the HCrO42 anion to interact with
logðqe {qt Þ~ log qe { (4) the head (positively charged ammonium cation) results in a
2:303
compact and ordered transition state as shown below thereby
leading to a decrease in the entropy.
The kinetic parameters (Table 3) could be acquired from the
relevant plots (Fig. 9B, C) and the higher regression coefficient
attained using the second order kinetics illustrates the
applicability of this model to fit the experimental adsorption
data. In addition, equilibrium adsorption capacity (qe) values
of 37.08 mg g21 and 38.50 mg g21 (experimental and
calculated) concur well with the second order kinetic model.
The transfer of HCrO42 oxy anion from the aqueous phase to
the IL-EGO adsorbent matrix could be governed by pore,
surface or film diffusion processes.69 The kinetics of uptake of
Cr(VI) could also be influenced by intraparticle diffusion and
the classic Weber-Morris70 model (qt = kint!t + C) relates the
amount of hexavalent chromium adsorbed at time t to the

2704 | RSC Adv., 2013, 3, 2697–2709 This journal is ß The Royal Society of Chemistry 2013
RSC Advances Paper

Fig. 9 A. Plot of qe against Ce. B. Pseudo second order kinetics. C. Pseudo first order kinetics. D. Weber-Morris intraparticle diffusion. E. Variation of lnK with
temperature.

This journal is ß The Royal Society of Chemistry 2013 RSC Adv., 2013, 3, 2697–2709 | 2705
Paper
Table 3 Kinetic data associated with the adsorption process
Rate constant Regression
k2/(g mg21 min21) coefficient
0.0159 0.99
As reported earlier73,74 in ion-pair interactions involving
metals like mercury, ions that are multiply charged ions with
high charge density could be categorized as kosmotropic while
singly charged large size ions are chaotropic in nature. Based
on this classification, the hydrochromate anion would be
regarded as chaotropic anion and is poorly solvated. The large
size quaternary ammonium cation is kosmotropic due to its
hydrophobic hydration74 accompanied by an effective and
ordered interaction with the HCrO42 anion leading to negative
entropy change in the adsorption process. The counter ionic
atmosphere can also influence the degree of kosmo/chaotro-
picity. The bulky and large trioctylammonium cation induces a
certain amount of kosmotropicity in the hydrochromate anion.
Hence, we can envisage a sort of symbiotic effect in this
interaction leading to the entrapment of the HCrO42 anion
(guest) as an ion pair with the quaternary ammonium cation
on the EGO surface. A combination of solvation and
electrostatic interactions74,75 govern the overall entropy
change in the adsorption process.
DSads = DSelectrostatic + DSsolvation
Since the quaternary ammonium cation as well as the
hydrochromate anion could also be solvated, this non-bonding
ion–solvent interaction ushered by the electrostatic affinity
reflects the negative entropy in the adsorption of chromium.
Solvation is more favored at a lower temperature range and we
fathom the electrostatic interaction to be the predominant
feature involving the negatively charged hydrochromate anion,
quaternary ammonium cation and the exfoliated graphene
oxide.
Column adsorption study
After getting an insight into the adsorption by batch process,
we decided to test the method for a larger sample volume.
Column studies were carried out by packing a glass column (3
cm diameter, 30 cm length) with 3.0 g of the IL-EGO
adsorbent. With 20 mg L21 Cr(VI) and a flow rate of 8 mL
min21 the adsorption of chromium(VI) was quantitative up to a
sample volume of 1200 mL (Fig. 10). We confirmed the
adsorption by analyzing chromium in the solution phase by
complexing chromium(VI) with diphenylcarbazide. Beyond,
Table 4 Thermodynamics of adsorption
Temperature/(K) DG0/(kJ mol21) DS0/(J mol21 K21) DH0/(kJ mol21)
303 28.88 2183.71 264.01
313 25.89
323 24.1
333 23.4
2706 | RSC Adv., 2013, 3, 2697–2709
RSC Advances
Rate constant Regression Intraparticle rate constant
k1/(min21) coefficient kint/(mg g21 min2K)
0.0913 0.97 1.552
1200 mL, the saturation of the adsorbent bed results in a
lowering of the percentage of chromium retained in the
column. In any adsorption process, the economics of the
entire operation is quite important and in this perspective,
regeneration of the adsorbent is a vital parameter. Hence,
certain prospective reagents were chosen for desorption of
chromium(VI). Ideally, the reagent so chosen should be cost
effective and not damage the adsorbent bed. Some of these
reagents have proved their worth in earlier adsorption studies
involving chromium.6,10,47,76 These include reducing agents
such as sodium sulfite, ascorbic acid, sodium metabisulfite,
sodium nitrite and ascorbic acid as well as reagents such as
sodium hydroxide and ammonium hydroxide which could
elute chromium(VI) by reducing it to the less toxic Cr(III) and
also to the corresponding chromate salts. The desorption
ratio77 is calculated as follows
Desorption ratio(%)~
Concentration of Cr(VI) desorbed into the eluate
|100
Concentration of Cr(VI) adsorbed onto the ILEGO adsorbent
(9)
The percentage of chromium eluted given in Fig. 11
illustrates that 15 mL of 2 mol L21 ammonium hydroxide
was very effective in the desorption of chromium as
ammonium chromate in the eluate. After 12 repetitive cycles,
we observed a decrease in the percentage elution of chro-
mium. A 15 mL elution volume from a large initial sample
volume of 1200 mL ensures a preconcentration factor of 80
which indicates the efficacy in detoxifying chromium from an
industrial effluent.
Fig. 10 Effect of sample volume variation.
This journal is ß The Royal Society of Chemistry 2013
RSC Advances
Fig. 11 Desorption of chromium with various reagents.
Effect of different ions
In any analytical solid phase extraction method, the effects of
different ions that affect the performance efficiency are to be
examined. The ions so chosen should also be representative of
Fig. 12 Scheme illustrating the interaction between chromium(III), exfoliated graphene oxide, and ionic liquid.
This journal is ß The Royal Society of Chemistry 2013
Paper
the real effluent sample. In this perspective, the interfering
effect of ions such as Cd2+ (500 mg L21), Co2+ (500 mg L21),
Zn2+ (500 mg L21), Ni2+ (500 mg L21) Fe2+ (100 mg L21), Pb2+
(500 mg L21), Hg2+ (250 mg L21) and Mn2+ (150 mg L21) were
examined individually in a 250 mL sample volume containing
20 mg L21 hexavalent chromium. The adsorption efficiency of
Cr(VI) was not influenced by Cd2+, Co2+, Zn2+, Ni2+, Pb2+ while
Fe2+ and Mn2+ interfere by reducing the hexavalent chromium
to trivalent state.7 In the case of anionic species, at 250 mg L21
level chloride, sulfate and phosphate caused considerable
reduction in the adsorption of chromium(VI) by competing
with the HCrO42 ion for the active sites in the IL-EGO
adsorbent. Lower oxidation state ions like sulfite and nitrite
would also reduce Cr(VI) thereby decreasing the percentage
retention of chromium(VI) in the adsorbent column.
Testing the adsorbent in a real sample and comparison with
other carbon based sorbents
The vibrant features of the IL-EGO adsorbent material
prompted us to test the applicability of the method in a
tannery waste water sample. In the tannery effluent,
chromium(III) is the major species along with some amount
of Cr(VI) and the associated organic components. Hence, it is
imperative to digest the sample with strong acids such as
nitric acid-sulfuric acid mixture to destroy the organic matter.
The total chromium was then determined by oxidation with
alkaline peroxide7,10 by passing a known volume of the diluted
effluent on the IL-EGO adsorbent column. Dilution takes care
RSC Adv., 2013, 3, 2697–2709 | 2707
Paper
Table 5 Adsorption capacity comparison against other carbon based adsor-
bents
Adsorption
Sl. No. Adsorbent material capacity (mg g21)
1 Activated carbon fabric cloth78 116.9
2 Activated carbon79 144.4
3 Brown coal70 50.95
4 Sugarcane bagasse71 13.40
5 Fly ash82 1.4
6 Magnetic cyclodextrin-graphene 120.19
oxide83
7 Exfoliated graphene 67.52
oxide (present study)
8 Ionic liquid impregnated 285.71
EGO (present study)
of the interference due to excess chloride and sulphate present
in the effluent. The analysis of chromium in the solution
phase revealed the quantitative retention of chromium (97.2
¡ 0.6%) with three replicate determinations. The adsorbed
chromium(VI) on the IL-EGO adsorbent could also be desorbed
with ammonium hydroxide as the eluent. In order to adsorb
Cr(III), the sample (after removal of organic matter by acid
treatment) was passed through the column at an alkaline pH
(8.0). The cationic Cr(III) is associated with the deprotonated
hydroxy and carboxylic groups through electrostatic interac-
tion (Fig. 12) as Cr(OH)2+ and Cr(OH)2+ species7 respectively.
The retention of Cr(III) was also very good with an adsorption
efficiency of 97.4 ¡ 1.1%. The adsorbed Cr(III) could be eluted
from the column using dilute sulphuric acid as chromium(III)
sulfate. Keeping in mind the environmental impact of
chromium, the eluates were not directly discarded in the sink.
These solutions were preserved and utilized in the supple-
mentary methods which we are developing currently in our lab
for chromium detoxification.
The adsorption capacity of the IL-EGO adsorbent was
compared with other carbon based adsorbents.78–83 The high
adsorption capacity (Table 5) offered by this novel adsorbent
material highlights its efficacy in extending the applications to
diverse chromium based industrial effluents.
Conclusions
In conclusion, the IL-EGO adsorbent has shown admirable
ability towards the adsorption of Cr(VI). There are no bottle-
necks that impede the adsorption process and the facile
adsorption is favored by a high adsorption capacity of 285.71
mg g21 and fast sorption kinetics. The thermodynamically
favorable adsorption process has paved the way for detoxifying
chromium from a tannery industry effluent. A notable feature
is that Cr(VI) as well as Cr(III) interact with graphene oxide
depending on the pH of the medium. This is of considerable
significance in the remediation of chromium. Regeneration
and stability of the adsorbent for 12 repetitive cycles is yet
another fitting tribute to this interesting adsorbent material.
The ionic liquid-EGO combination has carved a niche among
2708 | RSC Adv., 2013, 3, 2697–2709
RSC Advances
the various other carbon based adsorbents. Certainly, the
interaction between Aliquat 336 and exfoliated graphene oxide
has laid the basis for the removal of diverse metal ions as well
as other pollutants.
Acknowledgements
We thank Alagappa University, Karaikudi, India, Karunya
University Coimbatore, India for their assistance in character-
ization of the adsorbent material.
References
1 O. J. de Blas, M. C. Alonso, A. G. Sanchez and E. Alvarez
Ayuso, Commun. Soil Sci. Plant Anal., 2007, 38, 2091–2101.
2 R. Aravindhan, B. Madhan, J. Raghava Rao, B. U. Nair and
T. Ramasami, Environ. Sci. Technol., 2004, 38, 300–306.
3 D. Park, Y. S. Yun and J. M. Park, Environ. Sci. Technol.,
2004, 38, 4860–4864.
4 H. J. Park and L. L. Tavlarides, Ind. Eng. Chem. Res., 2008,
47, 3401–3409.
5 R. Saha, R. Nandi and B. Saha, J. Coord. Chem., 2011, 64,
1782–1806.
6 S. Kalidhasan, A. Santhana Krishna Kumar, V. Rajesh and
N. Rajesh, J. Hazard. Mater., 2012, 213–214, 249–257.
7 N. Rajesh, A. S. Krishna Kumar, S. Kalidhasan and
V. Rajesh, J. Chem. Eng. Data, 2011, 56, 2295–2304.
8 D. D. Maksin, A. B. Nastasovic, A. D. M. Nikolic, L.
T. Surucic, Z. P. Sandic, R. V. Hercigonja and A. E. Onjia, J.
Hazard. Mater., 2012, 209–210, 99–110.
9 S. Edebali and E. Pehlivan, Chem. Eng. J., 2010, 161,
161–166.
10 A. Santhana Krishna Kumar, S. Kalidhasan, V. Rajesh and
N. Rajesh, Ind. Eng. Chem. Res., 2012, 51, 58–69.
11 S. Kalidhasan, A. Santhana Krishna Kumar, V. Rajesh and
N. Rajesh, J. Colloid Interface Sci., 2012, 367, 398–408.
12 B. Saha and C. Orvig, Coord. Chem. Rev., 2010, 254,
2959–2972.
13 S. L. Wang and J. F. Lee, Chem. Eng. J., 2011, 174, 289–295.
14 L. Dupont and E. Guillon, Environ. Sci. Technol., 2003, 37,
4235–4241.
15 D. Park, Y. S. Yun, H. Y. Cho and J. M. Park, Ind. Eng. Chem.
Res., 2004, 43, 8226–8232.
16 H. Seki, A. Suzuki and H. Maruyama, J. Colloid Interface
Sci., 2005, 281, 261–266.
17 V. K. Gupta, D. Mohan, S. Sharma and K. T. Park, The
Environmentalist, 1999, 19, 129–136.
18 D. Mohan and C. U. Pittman Jr, J. Hazard. Mater., 2006,
137, 762–811.
19 D. Mohan, K. P. Singh and V. K. Singh, J. Hazard. Mater.,
2006, 135, 280–295.
20 G. Cimino, A. Passerini and G. Toscano, Water Res., 2000,
34, 2955–2962.
21 C. Selomulya, V. Meeyoo and R. Amal, J. Chem. Technol.
Biotechnol., 1999, 74, 111–122.
22 N. K. Hamadi, X. D. Chen, M. M. Farid and G. Q. Lu Max,
Chem. Eng. J., 2001, 84, 95–105.
23 M. Kobya, Adsorpt. Sci. Technol., 2004, 22, 51–64.
This journal is ß The Royal Society of Chemistry 2013
RSC Advances
24 V. K. Gupta, P. J. M. Carrott, M. M. L. Ribeiro Carrott and T.
L. Suhas, Crit. Rev. Environ. Sci. Technol., 2009, 39, 783–842.
25 M. Baikousi, A. B. Bourlinos, A. Douvalis, T. Bakas, D.
F. Anagnostopoulos, J. Tucek, K. Safarova, R. Zboril and M.
A. Karakassides, Langmuir, 2012, 28, 3918–3930.
26 C. N. Rao, A. K. Sood, K. S. Subrahmanyam and
A. Govindaraj, Angew. Chem., Int. Ed., 2009, 48, 7752–7777.
27 D. Li, M. B. Muller, S. Gilje, R. B. Kaner and G. G. Wallace,
Nat. Nanotechnol., 2008, 3, 101–105.
28 D. R. Dreyer, S. Park, C. W. Bielawski and R. S. Ruoff, Chem.
Soc. Rev., 2010, 39, 228–240.
29 S. T. Yang, Y. Chang, H. Wang, G. Liu, S. Chen, Y. Wang,
Y. Liu and A. Cao, J. Colloid Interface Sci., 2010, 351,
122–127.
30 G. Zhao, J. Li, X. Ren, C. Chen and X. Wang, Environ. Sci.
Technol., 2011, 45, 10454–10462.
31 W. Gao, M. Majumder, L. B. Alemany, T. N. Narayanan, M.
A. Ibarra, B. K. Pradhan and P. M. Ajayan, ACS Appl. Mater.
Interfaces, 2011, 3, 1821–1826.
32 A. K. Mishra and S. Ramaprabhu, J. Hazard. Mater., 2011,
185, 322–328.
33 X. Liu, L. Pan, T. Lv, G. Zhu, T. Lu, Z. Sun and C. Sun, RSC
Adv., 2011, 1, 1245–1249.
34 T. Hartono, S. Wang, Q. Ma and Z. Zhu, J. Colloid Interface
Sci., 2009, 333, 114–119.
35 G. K. Ramesha, A. V. Kumara, H. B. Muralidhara and
S. Sampath, J. Colloid Interface Sci., 2011, 361, 270–277.
36 P. Bradder, S. K. Ling, S. B. Wang and S. M. Liu, J. Chem.
Eng. Data, 2011, 56, 138–141.
37 S. T. Yang, S. Chen, Y. Chang, A. Cao, Y. Liu and H. Wang,
J. Colloid Interface Sci., 2011, 359, 24–29.
38 H. L. Ma, Y. Zhang, Q. H. Hu, D. Yan, Z. Z. Yu and M. Zhai,
J. Mater. Chem., 2012, 22, 5914–5916.
39 M. Acik, D. R. Dreyer, C. W. Bielawski and Y. J. Chabal, J.
Phys. Chem. C, 2012, 116, 7867–7873.
40 J. P. Mikkola, P. Virtanen and R. Sjoholm, Green Chem.,
2006, 8, 250–255.
41 P. Ramesh, S. Bhagyalakshmi and S. Sampath, J. Colloid
Interface Sci., 2004, 274, 95–102.
42 W. S. Hummers and R. E. Offeman, J. Am. Chem. Soc., 1958,
80, 1339–1339.
43 L. S. Clesceri, A. E. Greenberg and A. D. Eaton, Standard
Methods for the Examination of Water and Wastewater,
American Public Health Association, ISBN: 0875530478,
Washington, 1998.
44 A. M. Donia, A. A. Atia, H. A. El-Boraey and D. H. Mabrouk,
Sep. Purif. Technol., 2006, 49, 64–70.
45 W. Li, X. Z. Tang, H. B. Zhang, Z. G. Jiang, Z. Z. Yu, X. S. Du
and Y. W. Mai, Carbon, 2011, 49, 4724–4730.
46 V. Singh, A. K. Sharma, P. Kumari and S. Tiwari, Ind. Eng.
Chem. Res., 2008, 47, 5267–5276.
47 A. Santhana Krishna Kumar, T. Gupta, S. S. Kakan,
S. Kalidhasan, Manasi, V. Rajesh and N. Rajesh, J.
Hazard. Mater., 2012, 239–240, 213–224.
48 J. C. Ma and D. A. Dougherty, Chem. Rev., 1997, 97,
1303–1324.
49 T. J. Mooibroek, P. Gamez and J. Reedijk, CrystEngComm,
2008, 10, 1501–1515.
50 E. Malkoc and Y. Nuhoglu, Chem. Eng. Process., 2007, 46,
1020–1029.
This journal is ß The Royal Society of Chemistry 2013
View publication stats
Paper
51 M. V. Lopez-Ramon, F. Stoeckli, C. Moreno-Castilla and
F. Carrasco-Marin, Carbon, 1999, 37, 1215–1221.
52 I. Langmuir, J. Am. Chem. Soc., 1918, 40, 1361–1403.
53 H. M. F. Freundlich, Z. Phys. Chem., 1906, 57, 385–470.
54 S. Chatterjee, D. S. Lee, M. W. Lee and S. H. Woo, J. Hazard.
Mater., 2009, 166, 508–513.
55 V. Srivastava, C. H. Weng, V. K. Singh and Y. C. Sharma, J.
Chem. Eng. Data, 2011, 56, 1414–1422.
56 O. Redlich and D. L. Peterson, J. Phys. Chem., 1959, 63,
1024–1026.
57 C. S. Sundaram, N. Viswanathan and S. Meenakshi, J.
Hazard. Mater., 2008, 155, 206–215.
58 S. Y. Elovich and O. G. Larinov, Izv. Akad. Nauk. SSSR, Otd.
Khim. Nauk., 1962, 2, 209–216.
59 O. Hamdaoui and E. Naffrechoux, J. Hazard. Mater., 2007,
147, 381–394.
60 M. I. Temkin, Zh. Fiz. Chim., 1941, 15, 296–332.
61 S. Liang, X. Guo, N. Feng and Q. Tian, J. Hazard. Mater.,
2010, 174, 756–762.
62 K. R. Hall, L. C. Eagleton, A. Acrivos and T. Ver Meulen, Ind.
Eng. Chem. Fundam., 1966, 5, 212–218.
63 K. Selvi, S. Pattabhi and K. Kadirvelu, Bioresour. Technol.,
2001, 80, 87–89.
64 V. K. Garg, R. Gupta, R. Kumar and R. K. Gupta, Bioresour.
Technol., 2004, 92, 79–81.
65 I. Qureshi, S. Memon and M. Yilmaz, J. Hazard. Mater.,
2009, 164, 675–682.
66 C. H. Giles and R. B. Mckay, J. Bacteriol., 1965, 89, 390–397.
67 S. Lagergren and K. Sven, Vetenskapsakad. Handl, 1898, 24,
1–39.
68 Y. S. Ho, J. Hazard. Mater., 2006, 136, 681–689.
69 H. K. Boparai, M. Joseph and D. M. O’Carroll, J. Hazard.
Mater., 2011, 186, 458–465.
70 W. J. Weber and J. C. Morris, J. Sanit. Eng. Div. Am. Soc. Civ.
Eng., 1963, 89, 31–60.
71 M. M. A. El-Latif, A. M. Ibrahim and M. F. El-Kady, J. Am.
Sci., 2010, 6, 267–283.
72 R. Gounder and E. Iglesia, Acc. Chem. Res., 2012, 45,
229–238.
73 A. Santhana Krishna Kumar, S. Kalidhasan, V. Rajesh and
N. Rajesh, Ind. Eng. Chem. Res., 2012, 51, 11312–11327.
74 H. Zhao, J. Chem. Technol. Biotechnol., 2006, 81, 877–891.
75 K. N. Houk, A. G. Leach, S. P. Kim and X. Zhang, Angew.
Chem., Int. Ed., 2003, 42, 4872–4897.
76 A. Santhana Krishna Kumar, R. Ramachandran,
S. Kalidhasan, V. Rajesh and N. Rajesh, Chem. Eng. J.,
2012, 211–212, 396–405.
77 Y. Bulut, G. Akcay, D. Elma and I. E. Serhatli, J. Hazard.
Mater., 2009, 171, 717–723.
78 D. Mohan, K. P. Singh and V. K. Singh, Ind. Eng. Chem. Res.,
2005, 44, 1027–1042.
79 L. Khezami and R. Capart, J. Hazard. Mater., 2005, 123,
223–231.
80 F. Gode and E. Pehlivan, Energy Sources, Part A, 2006, 28,
447–457.
81 D. C. Sharma and C. F. Forster, Bioresour. Technol., 1994,
47, 57–264.
82 S. S. Banerjee, M. V. Joshi and R. V. Jayaraman, Sep. Sci.
Technol., 2004, 39, 1611–1629.
83 L. Fan, C. Luo, M. Sun and H. Qiu, J. Mater. Chem., 2012,
22, 24577–24583.
RSC Adv., 2013, 3, 2697–2709 | 2709