Journal of Alloys and Compounds 701 (2017) 740e749

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Rapid adsorptive removal of naphthalene from water using graphene

nanoplatelet/MIL-101 (Cr) nanocomposite
Sahika Sena Bayazit a, *, Mahmut Yildiz b, Yavuz Selim Asi c, Musa Sahin d,
Mustafa Bener d, Songl Eglence d, Mohamed Abdel Salam e
a
Chemical Engineering Department, Faculty of Engineering & Architecture, Beykent University, P.O. Box 34396, Istanbul, Turkey
b
Department of Chemistry, Faculty of Science, Gebze Technical University, 41400, Gebze, Kocaeli, Turkey
c
Chemical Engineering Department, Faculty of Engineering, Istanbul University, 34320, Avclar, Istanbul, Turkey
d
Department of Chemistry, Faculty of Engineering, Istanbul University, 34320, Avclar, Istanbul, Turkey
e
Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80200, Jeddah, 21589, Saudi Arabia

articleinfo abstract

Article history: The study of the adsorption equilibria of naphthalene onto graphene nanoplatelet supported MIL -101
Received 21 November 2016 composite material (GNP/MIL-101) has been conducted. In the experimental context of this study,
Received in revised form rstly GNP/MIL-101 was synthesized by applying hydrothermal method and characterized via FTIR, XRD,
9 January 2017 SEM, TEM and surface area analyses. The effects of GNP/MIL-101 amount, temperature and initial
Accepted 14 January 2017
naphthalene concentration on the adsorption process have been investigated. Results show that the
Available online 18 January 2017
maximum removal of naphthalene was obtained as about 93% by 0.075 g GNP/MIL-101 at 298 K. The
isothermal data were tted to linear and non-linear Langmuir, Freundlich, and Temkin adsorption
Keywords:
isotherm models and the kinetic data were tted to Elovich and other kinetic models. Adsorption
Adsorption
depended on initial naphthalene concentration at investigated various temperatures (298, 308, 318 K)
GNP/MIL-101
signicantly. The temperature dependence of adsorption process is associated with the changes in
Naphthalene
Kinetics several thermodynamic parameters such as standard free energy (DG), enthalpy (DH) and entropy
Thermodymics (DS).
2017 Elsevier B.V. All rights reserved.

1. Introduction the polycyclic aromatic hydrocarbons (PAH) that are comprised of

Water pollution, otherwise known as wastewater, was not a
massive dilemma to society until the industrial revolution age.
However, the development of this wastewater in reneries, surface
petroleum operations and industries of coke-making, textile, dye,
petrochemical, pharmaceutical, pulp, chemical and paper has
brought with it numerous problems due to large discharges of
these industrial wastewaters to the environment. These industry
areas are the main sources of the industrial wastewaters that
contain inorganic and/or organic compounds as pollutant [1e3],
which is aside from the fact that they also cause ground water and
surface water contamination [2] which is directly related to the
public health and environment.
One of the most important contaminant groups in wastewater is
* Corresponding author. Postal address: Beykent Universitesi, Ayazaga Kampusu,
34396, Saryer, Istanbul, Turkey.
E-mail address: sahikasena@gmail.com (S .S. Bayazit).
two or more aromatic rings [4,5]. The two- or three-ring PAH are
rather toxic for the environment while the PAH which have high
molecular weight are genotoxic compounds [6]. Thus, such haz-
ardous compounds in wastewaters have to be removed completely
or converted into nonhazardous compounds or the amount of such
compounds have to be reduced up to the acceptable limits of the
lawmakers before it is released to the environment.
For these purposes, there are a lot of applied methods on these
drawbacks in literature:
a. Adsorption on different type of adsorbents (e.g. activated car-
bon, carbon molecular sieves, activated carbon bers, carbon-
based nanomaterials [7], inorganic or polymeric resins [8e10],
zeolites and aluminophosphates [7,11e13], clays as natural ad-
sorbents [5], biosorbents (biomass or natural substances)
[2,14,15], silica gel [16], metal-organic frameworks [17], com-
posites [18,19].
b. Advanced oxidation technologies [20,21] (UV light in combina-
tion with ozone and/or H2O2, heterogeneous catalysis using

http://dx.doi.org/10.1016/j.jallcom.2017.01.111
0925-8388/ 2017 Elsevier B.V. All rights reserved.
 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749
TiO2/UV light [22], sonolysis and the electron beam process [4],
aeration and ozonation [23], etc.
Among other processes used for water remediation, the
adsorption process by using solid adsorbents is one of the most
effective and appropriate method to reduce, convert or remove the
organic and/or inorganic pollutants in wastewaters or from
wastewaters. Simple design, low investment costs, low-cost ad-
sorbents and reusability of adsorbents depending on the material
type make the adsorption process superior to the other methods
[10].
Metal organic frameworks (MOFs), a novel group of porous and
crystalline compounds, consist of metallic centers and bridging
organic linkers [24,25]. Through their large surface area, adjustable
porosity and different topologies, MOFs are rather promising ma-
terials to be implemented in ion exchange, catalysis, adsorption and
separation processes like CO 2 capture, storage of gas molecules,
disposal of hazardous components [25e33]. In particular, MOFs are
a good candidate for adsorptive separations in liquid phase for a
sustainable chemical industry [17].
Amongst the most MOF compounds MIL-101 material, which
was prepared from benzene-1,4-dicarboxylate (terephtalic acid)
and trimetric clusters of chromium (III), possesses a high porosity
and zeotype crystalline structure with a very large surface area
(~5900 m2/g) [34,35]. Furthermore, MIL-101 exhibits a high ther-
mal stability, resistance to water steam and humidity that are
crucial properties for materials constructed to heterogeneous
catalysis, heat transformation, adsorptive applications and drug
delivery [36e39].
Some attempts are present in literature about the combination
of graphene materials with MIL-101 metal organic framework.
Petit and Bandosz showed a formation of new pores at the
interface of MOF and graphene layers that improves the adsorption
performance [40e42].
Liu et al. prepared a composite of MIL-101 and graphene oxide
(GO) applying different compositions. The incorporation of GO
layers exhibited a strong effect on the formation of MIL-101 units,
composite porosity and crystal size [43].
Sun et al. synthesized MIL-101 (Cr)/Graphite oxide composites
for adsorption of n-hexane and showed that the composite per-
formed better than only MIL-101 material alone. Furthermore,
excellent reversibility feature makes the composite a good candi-
date for practical application [44].
Graphene nanoplatelets were used recently as a sorbent in solid
phase extraction for the extraction of phthalate esters (PAE) in
aqueous solutions. It was shown that higher efcient extraction of
targeted compounds by using graphene nanoplatelet sorbent
compared to the other applied sorbents is promising and owing to
the good recovery opportunity, it became a potential candidate to
detect PAEs in environmental samples [45].
Since naphthalene is one of the most discharging and toxic
pollutant for the environment and society [46,47], herein we pre-
pared a graphene nanoplatelet supported MIL-101 composite ma-
terial (GNP/MIL-101) as solid adsorbent to adsorb hazardous
naphthalene compound from aqueous solutions, particularly from
industrial wastewaters. A main expectation of the authors was
obtained preparing an adsorbent for highly efcient naphthalene
removal.
2. Materials and methods
2.1. Materials
Chromium (III) nitrate nonahydrate (Cr(NO3)3$9H20), ethanol
(C2H5OH) and naphthalene (C10H8) and N,N dimethyl formamide
741
were obtained from Merck (Germany). Terephthalic acid (Benzene-
1,4-dicarboxylic acid) (H 2BDC) was obtained from Sigma Aldrich
(Germany). Graphene nanoplatelets (GNP) were obtained from XG
Science (USA) and were used as received. Hydrouoric acid (47%)
was obtained from Sigma Aldrich (Germany). To prepare all solu-
tions, deionized water was used.
2.2. Methods
2.2.1. Preparation of GNP/MIL-101
GNP was purchased from XG Science and was used as received.
The bare MIL-101 was prepared using the mass ratio of 1
Cr(NO3)3$9H2O: 1 H2BDC: 1 HF: 278 H2O. The mixture was put in a
hydrothermal autoclave at 210 C for 8 h. The preparation ratio of
GNP/MIL-101 was 1 GNP: 10 Cr(NO3)3$9H2O [48,49]. The same
procedure was repeated. After 8 h, the autoclave was left for cooling
to room temperature. The obtained crystals were washed with N,N-
dimethyl formamide a few times for removing the unattached MIL-
101 particles and unreacted H 2BDC. Then the washing procedure
was maintained with hot ethanol. The GNP/MIL-101 was dried at
100 C overnight.
2.2.2. Characterization of GNP/MIL-101
The morphological structure of the modied GNP-MIL101 was
determined using a JEM-1011 JEOL transmission electron micro-
scope (TEM) operated at 100 kV and scanning electron microscope
(SEM), operated on FE-SEM, FEI Quanta FEG 450 at 30 kV and 10 kV.
Specimens for TEM analyses were prepared by dispersing the GNP-
MIL101 in ethanol and placing one drop onto a holey-carbon-
coated copper supported grid. Textural properties were evaluated
by means of N 2 adsorptionedesorption isotherms recorded at
liquid N2 temperature with a Micromeritics ASAP 2000 apparatus.
Samples were degassed at 150 C under vacuum for 24 h. Specic
areas were calculated by applying the BET equation within the
relative pressure range P/P 0 0.05e0.30. The crystals were char-
acterized by Fourier Transform Infrared Spectroscopy (FTIR) oper-
ated on Bruker Alpha. KBr method was applied for FTIR analysis. X-
Ray Diffraction (XRD) patterns were taken at room temperature
using RigakuD/Max-2200 diffractometer (CuKa radiation with
l 0.15418 nm). The diffraction intensity of the samples was
measured in the 2q range between 1 and 80 with 2/min scan
speed.
2.2.3. Adsorption studies
To determine the effects of time, amount of adsorbent, initial
naphthalene concentration and temperature on the adsorption
processes, several experiments were carried out. Stock solution was
prepared freshly by dissolving 0.01 g of naphthalene in 15 ml EtOH
and then it was diluted to 100 ml by distilled water addition. Until
the analysis is performed, it was maintained at4 C in a fridge. For
the whole experimentations, GNP/MIL-101 composite was used
and put in to 50 ml of naphthalene solution. The solutions were
mixed at proper temperature and speed by using a thermostatic
shaker at 298 K. Each sample was taken regularly in every 1 min in
the equilibrium time (10 min). The graphs for the calibration
(concentration vs. absorbance) of naphthalene were drawn for
calculating naphthalene in the present work.
A219 0.5678c 0.0055
(r 0.9999) is the equation for the cali-
bration graph of naphthalene which was constructed at 219 nm. At
the same wavelength the solution absorbance was recorded against
water. For investigation of kinetic parameters, 10 Erlenmeyer asks
were used. Under same conditions, stock solution of naphthalene
(50 ml) and 0.01 g GNP/MIL-101 were included in every Erlenmeyer
ask. The concentration of naphthalene was determined by taking
sample in every 1 min from each ask. Thus some potential errors
742 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749
can be avoided during sample obtaining procedure. Taken samples
were mixed by a shaker at different temperatures (298, 308 and
318 K) to determine the inuence of temperature on adsorption.
Initial naphthalene concentrations of the experiments were 10, 20,
30, 40, 50 mg/L as adsorbate and 0.01 g GNP/MIL-101 was used as
adsorbent for each solution. To observe the effect of amount of
adsorbent dose on the adsorption, 50 mL solution was added to
0.005e0.075 g GNP/MIL-101 and the experiment was concluded
with this procedure.
The results were given as adsorption loading Qe (mg/g) (Eq. (1))
and percentage of naphthalene removal (Eq. (2)).
C0
Qe
CeV
m
In Eq. (1), C0 (mg/L) is the initial naphthalene concentration, C e
(mg/L) is the equilibrium naphthalene concentration, V (L) is the
volume of solution and m (g) is the adsorbent dose.
C Ce
%Removal 0 100
C0
3. Results and discussions
3.1. Characterization of GNP/MIL-101
The FTIR plots of GNP, MIL-101 and GNP/MIL-101 nanoparticles
were given in Fig. 1. The strong characteristic peaks of MIL-101;
1384, 1515 and 1619 cm1 are related to benzene dicarboxylate C]C
and OeC]O vibrations can be seen in Fig. 1. The CeH defor-
mation peaks can be observed at 1018 and 747 cm1 [50]. The
characteristic CreO vibration peaks at 598 cm 1 can be seen at FTIR
plots of MIL-101 [51]. And the same peak is at 581 cm 1 of GNP/
MIL-101.
The XRD patterns of MIL-101 and GNP/MIL-101 can be seen in
Fig. 2. The XRD pattern of MIL-101 has typical MIL-101 diffraction
peaks, especially at 5 and 9 [34]. The same peaks can be observed
at GNP/MIL-101 patterns. At the 2q degree is 26, very small peak of
pristine graphene in the form of nanoplatelets is seen. The
diffraction peaks of MIL-101 crystals are more intense than GNP
Fig. 1. FTIR plots of GNP, MIL-101 and GNP/MIL-101 composite.
particles.
The SEM images of MIL-101, GNP/MIL-101 and the TEM image of
GNP/MIL-101 are given in Fig. 3. The MIL-101 nanoparticles can be
observed clearly. The sizes of MIL-101 crystals are nearly
45e50 nm. The surrounded MIL-101 nanoparticles by GNP layers
are seen at SEM image of GNP/MIL-101. The transmission electron
microscope image of the GNP/MIL101 show that GNP exists as
layered structures with a smooth surface, and many wrinkles, and
the MIL-101 distributed at the surface.
It was shown in Fig. 4 the N2 adsorption/desorption isotherms of
the G-MIL101 that were determined at 77 K. The calculated BET
specic surface area for the GNP/MIL101 was found to be
(1) 134.7 m2 g1. According to the original IUPAC classication, the
adsorption/desorption isotherm could be classied as a type IV
isotherm with an H3 type hysteresis loop classication corre-
sponding to solids with plate-like particles [52].
3.2. Adsorption experiments
(2)
The effect of contact time for naphthalene adsorption on 0.01 g
GNP/MIL-101 for an initial naphthalene concentration of
30 mg L1 has been determined at 298 K. The adsorption loading
and the percentage of naphthalene removal results according to
time are given in Fig. 5. The results indicate that maximum
adsorption of naphthalene was reached to the equilibrium in
10 min, which is also used for all other experiments. The kinetic
parameters were obtained in light of the adsorption contact time
experiments.
To investigate the effect of adsorbent dose, we changed the
amount of GNP, MIL-101 and GNP/MIL-101 from 0.005 to 0.075 g for
the case of 30 mg L1 of initial concentration of naphthalene at
298 K. The results have shown that the quantity of adsorbed
naphthalene increases with the increasing of the adsorbent dose.
For a GNP/MIL-101 dose of 0.075 g, the adsorption capacity was
about 93%. The adsorption loading was obtained as 162.8 mg g 1 at
0.005 g of adsorbent dose. As shown in Fig. 6, the adsorption ef-
ciency of GNP/MIL-101 and GNP is very close. The adsorption up-
take of GNP is 184.60 mg/g and GNP/MIL-101 is 162.80 mg/g at
0.005 g of adsorbent. But MIL-101 has very low adsorption uptake.
At same conditions MIL-101 can adsorb only 11.40 mg/g. The pre-
pared composite has increased 14 times of the adsorption capacity
 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749 743

Fig. 2. XRD patterns of MIL-101 and GNP/MIL-101 composite.

Fig. 3. SEM images of MIL-101(left), GNP/MIL-101 (right) and TEM image of GNP/MIL-101.

of MIL-101. The preparing of MIL-101 is easier and cheaper than
GNP, so the performance of this composite is successful for both
feasible and economic perspectives.
The effect of initial naphthalene concentration at three different
temperatures on the adsorption by GNP/MIL-101 is shown in Fig. 7.
The initial naphthalene concentrations are differed between
10 mg L1 - 50 mg L1. Three different temperature values are 298,
308 and 318 K; the adsorbent dose is 0.01 g. The separation capa-
bility of the GNP/MIL-101 was decreased with increasing temper-
ature (Fig. 7). The adsorption loadings, while the initial
naphthalene concentration is 50 mg/L, are 170.10 mg/g, 158.15 mg/g
and 153.15 mg/g at 298, 308 and 318 K respectively.
744 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749

Fig. 4. Adsorption/desorption isotherms for HSANGs using nitrogen at 77 K.

Fig. 5. The effect of contact time on naphthalene adsorption on GNP/MIL-101.

Isotherms of adsorption can lead to nd out the adsorption

mechanism and to implement novel practical applications. There- 1 Ce
Ce
fore, isotherms of Temkin, Langmuir and Freundlich have been
investigated to work on the adsorption characteristics. The linear (4)
Qe KL Q 0 Q0
and non-linear forms of isotherms were applied to experimental In these equations (3) and (4), the concentration of naphthalene
data. The Origin Pro 8 was used for these calculations. in equilibrium and the capacity of saturation are shown by C e and
Langmuir isotherms [53] can be established either from the rst Qe, respectively. KL means the ability of adsorption. K L (intercep-
concentration of GNP/MIL-101 or dose data of adsorptive material. tion) and Q o (line slope) can be found by means of the equations.
For this study we preferred the initial GNP/MIL-101 concentration 298, 308 and 318 K temperatures were applied for the calculation of
which is more reliable than adsorbent dose according to the Langmuir isotherm parameters.
experimental data. Freundlich equation can be dened as in Eq (5) [54].

Q0KLCe (3)
1
Q
e
Qe Kf $Ce=n (5)
1 KL Ce
Eq (5) can be linearized to determine the n and K f values:
 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749
Fig. 6. The effect of amount of adsorbent on naphthalene adsorption on GNP, MIL-101 and GNP/MIL-101.
. isotherm parameters differ between 103 and 104. So both forms
logQe logKf 1 of the isotherms were given in this study.
=n logCe
The log Qe - log Ce diagram can be used to calculate the Kf and 1/
n constants.
One of the other methods for elucidation the adsorption
mechanism of an adsorptive system is the Temkin isotherm. Tem-
kin isotherm reveals the differences about the decreasing energy of
adsorption in the molecular sheet with GNP/MIL-101-acid in-
teractions. Also, Temkin isotherm assumes that binding energies
which have the same values up to the maximum energy point are
the characteristic properties of adsorption [55].
The equation of Temkin Isotherm can be dened as in Eq (7)
[56];
RT
Qe lnKTCe
b dQ
The linearized equation is;
Qe B1 lnKT B1 lnCe
where
RT
B1
b Eq (11) by means of the mentioned interpretation;
The diagram of the Q e vs. ln (Ce) can be used for the calculation
of B1 and K T. In the diagram, B 1 and KT represent the slope and the
interception point, respectively. KT (L mol1) is the binding con-
stant in the equilibrium which indicates the maximum binding
energy. B 1 is the heat constant of the adsorption.
The non-linear and linearized versions of the Temkin, Langmuir
and Freundlich isotherms were applied for the determination of the
isotherms. Both of the isotherm graphs for 298, 308, and 318 K were
given in Fig. 7. Similarly, parameters of these isotherms can be seen
in Table 1. The non-linear isotherm parameters and the linear
isotherm parameters were approximate to each other. In this study,
all of the isotherms give high compatibility with experimental data
for naphthalene according to their R2 values. The standard errors of
non-linear Langmuir isotherm parameters increased while tem-
perature increasing, but the standard errors of linear Langmuir
745
(6)
The mechanism of the adsorption between naphthalene and
GNP/MIL-101 based on p-p interactions. Between the aromatic
rings and sp2 carbon materials, p-p interactions were occurred
[57,58]. The PAHs have delocalized p electrons. These p electrons
cause p ep interaction with the terephthalic acid molecules in MIL-
101. There are Lewis acid sites inside the pores of MIL-101 and p-
complexation is occurred between the p-electrons of aromatic
rings and these acidic sites [59].
The kinetics of naphthalene adsorption onto GNP/MIL-101 were
foreseen by applying the adsorption data to the Lagergren rate
equation, Elovich equation and Pseudo-second-order model.
The adsorption and desorption kinetics of different compounds
on an adsorptive material was calculated by applying the Elovich
equation. It is dened as in the following equation [60].
(7)
aexp bQ (10)
dt
(8) 1 1 1
a (mg g min ) and b (g mg ) indicate the initial adsorption
rate and the desorption constant in equation (10), respectively. The
equation can be simplied by reformulation, abt is much higher
than t and two boundary conditions are assumed; Q t 0 0 and
(9) Qt t
0; are also applied. The equation of the model changes into
1 1
Qt lna$ b lnt (11)
b b
The Qt vs ln(t) graph can be utilized to calculate Elovich con-
stants. On the graph, (1/ b) is the slope and (1/ b) ln(ab) is the
intercept.
Lagergren [61] empirical model is another accepted kinetics
model for the adsorption. It can be dened as in the following
equation:
dQt
k1Qe Qt (12)
dt
The equation is referred to the pseudo rst order rate equation
[61]. Below the linearized equation can be seen:
746 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749

Fig. 7. The linear and non-linear equilibrium isotherm plots of naphthalene adsorption on GNP/MIL-101 at different temperatures. a) Langmuir isotherm, b) Freundlich isotherm
and c) Temkin isotherm.

Table 1
Isotherm parameters for adsorption of naphthalene onto GNP/MIL-101.

T (K) Linear isotherm parameters Non-linear isotherm parameters

Q0 (mg g1 ) KL(L g1 ) R2 Q0 (mg g1) Std. Error KL (L g1) Std. Error R2

Langmuir Isotherm 298 740.74 0.018 0.998 764.17 25.08 0.018 7.2 10 4 0.999
308 769.23 0.014 0.988 784.66 43.31 0.014 9.1 10 4 0.999
318 900.90 0.010 0.975 1088.58 214.09 0.008 0.002 0.991

T (K) n Kf R2 n Std. Error Kf Std. Error R2

Freundlich Isotherm 298 1.134 15.02 0.999 1.16 0.019 15.87 0.56 0.999
308 1.118 11.92 0.999 1.15 0.023 12.59 0.58 0.999
318 0.098 10.27 0.999 1.10 0.015 10.35 0.34 0.999

T (K) B1 KT R2 B1 Std. Error KT Std. Error R2

Temkin Isotherm 298 33.11 0.52 0.962 33.11 3.83 0.52 0.09 0.949
308 37.26 0.40 0.955 36.28 4.3 0.44 0.078 0.946
318 38.46 0.40 0.955 38.29 4.96 0.39 0.076 0.936
 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749 747

Fig. 8. Kinetic model plots of naphthalene adsorption on GNP/MIL-101. A) Elovich model, b) Lagergren Pseudo-rst order kinetic model, c) Pseudo-second order kinetic model.

Table 2 The following equation is dened as Pseudo-second-order

Kinetic parameters for the removal of naphthalene by GNP/MIL-101. model [62]:
Elovich equation a b R2
7.3 107 0.176 0.97
Pseudo rst order Qe k1 R2 dQt
29.78 0.53 0.93 k2 Qe Qt 2 (14)
Pseudo second order Qe k2 R2
dt
107.53 0.039 0.99 In Eq (14), k2 (g.mg1.min1) means the model rate coefcient of
adsorption. The modied equation can be written as;

Table 3
Thermodynamic parameters for the adsorption of naphthalene by GNP/MIL-101. t 1 1
T (K) DG (kJ mol1) DH (kJ mol1) DS (Jmol1K1) e2 t (15)
Qt k2Q Qe
298 2.38 6.19 12.85
In Eq (15), the slope of the t/Qt vs t graph gives the value of k 2.
308 2.22
318 2.12
Another variable, Qe, is estimated by means of the intercept point.
Linear regression correlation coefcient was calculated for the
kinetic models. For Elovich, Lagergren and pseudo-second-order
models, this value is 0.97, 0.93, and 0.999, respectively. Elovich,
Lagergen and Pseudo-second order models plots and results are
k1
logQe Qt log Qt t (13) presented in Fig. 8 and Table 2.
2:303 In the adsorption processes, the temperature depends on
In the equation, k1 (min1), Qe and Qt (mg/g) and t (min) (model various parameters such as standard free energy ( DG), enthalpy
parameters) represent the pseudo rst order rate constant, the (DH) and entropy (DS) of adsorption. In these processes (DG) is
adsorption capacities in the equilibrium and time, respectively. determined by using the following equation.
748 S.S. Bayazit et al. / Journal of Alloys and Compounds 701 (2017) 740e749
DG RT lnK (16)
Where R is the universal gas constant, T is temperature and K is
calculated by extrapolating ln(Q e/Ce) Ce plot [56]. Van't Hoff equa-
tion is utilized to determine the values of ( DH) and (DS):
DH DS
lnK (17)
RT R Separation and Catalysis, Wiley-VCH, 2010.
DH and DS were calculated from the slope and the intercept of
the line in graph of ln (K) versus 1/T, respectively.
The thermodynamic parameters can be seen in Table 3. We can
understand from negative DG values that the adsorption of
naphthalene onto GNP/MIL-101 mechanism is the spontaneous
nature. The negative value of DH (6.19 kJ mol1) at various
temperatures indicates physical adsorption and this reaction is
exothermic. the randomness on the surface is decreased because of
DS value is negative [63].
4. Conclusions
The main aim of the present work was to study the removal of
naphthalene compound from aqueous solutions by means of its
adsorption on the GNP/MIL-101. The experimental results showed
that the maximum adsorption of naphthalene was achieved with
93% efciency for 0.075 mg GNP/MIL-101 at 298 K and also the
equilibrium was obtained rapidly during the adsorption process.
The adsorption of naphthalene process is well tted by all iso-
therms. The calculated thermodynamic parameters reveal that the
process is physical adsorption having a spontaneous nature.
Different kinetic approaches were tried out to investigate the re-
action rate and kinetic of the adsorption of naphthalene on the
GNP/MIL-101 composite material as adsorbent. The second order
model was suggested for the kinetic process of the naphthalene
adsorption. As a consequence, it is clear that GNP/MIL-101 is an
efcient and rapid adsorptive composite material for the elimina-
tion treatment of naphthalene from an aqueous media. For the
future researches, GNP/MIL-101 can be offered as a promising
adsorbent and applied for the disposal of various components via
adsorption method.
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