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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

1 High surface area and mesoporous graphene/activated carbon

2 composite for adsorption of Pb(II) from wastewater
3 Q1 Navid Saeidi* , Mehdi Parvini, Zahra Niavarani
4 Faculty of Chemical, Gas and Petroleum Engineering, Semnan University, Semnan 35195-363, Iran

A R T I C L E I N F O A B S T R A C T

Article history: Since lead is a carcinogenic and non-biodegradable substance, its removal from water is of vital
Received 20 August 2015 importance. Of all different removal pollutants techniques the adsorption is a promising method to
Received in revised form 27 September 2015 remove Pb(II). The choice of adsorbent is a key factor to carry out this process efficiently. As already the
Accepted 28 September 2015
adsorption of Pb(II) onto different porous materials have been studied, however the adsorption
Available online xxx
properties of graphene/activated carbon composite (GAC) to metal ions have not been reported yet. In
this work, GAC was synthesized from graphene oxide and glucose. The samples were characterized by X-
Keywords:
ray diffraction, Raman spectroscopy, SEM image and N2 adsorption–desorption isotherms. The GAC
Graphene
Activated carbon composite
possessed high surface area (2012 m2/g), large pore volume (1.61 cm3/g) and mesopore structure. To
Mesoporous study the adsorption behavior of Pb(II) on GAC, effects of solution pH, GAC dosage and stirring speed were
Pb(II) examined. Afterwards the adsorption isotherms and kinetics of the GAC for removal of Pb(II) were
Adsorption kinetics and isotherms studied by different models. The GAC was found to follow the pseudo-second order kinetic model better
than the pseudo-first order. In addition it was understood that the intraparticle diffusion which studied
by the Weber–Morris equation addressed the mechanism of the adsorption properly. Since the
adsorption isotherm experimental data was fitted better by Langmuir model than Freundlich, the Pb(II)
adsorption on the GAC is mainly homogeneous and monolayer. Finally, the maximum adsorption
capacity of Pb(II) was measured up to 217 mg/g, which is higher than many other adsorbents.
ã 2015 Published by Elsevier Ltd.

5 1. Introduction treatment methods. Many researches for adsorption removal of 23

heavy metals including Pb(II) ions have been reported in the 24

6 Lead(II) is a serious environmental health threat because of its literature [1–3,6–8] however, search for adsorbents with high 25
7 non-biodegradability, toxicity, wide-spread presence and tenden- adsorption capacities is still in great need. It means that the choice 26
8 cy to accumulate in living organisms. It can damage nervous of adsorbent when attempting to isolate Pb(II) is of special 27
9 system and cause renal kidney disease, mental retardation, cancer importance. 28
10 and anemia in humans. Water systems are polluted by lead ions in In the past, apart from activated carbon (AC) which has been a 29
11 various ways, including mining, painting and printing processes, traditional adsorbent for different pollutants, the adsorption of Pb 30
12 plumbing, automobile batteries and petroleum industries [1]. As a (II) onto zeolites [6], CNT [7], graphene [8], graphene oxide (GO) [9] 31
13 priority contaminant, the EPA has set a permissible limit of and different graphene based materials such as functionalized 32
14 0.015 mg/L in drinking water [2]. magnetic graphene oxide [10], amino siloxane oligomer-linked 33
15 Various methods have been proposed for the treatment of lead- graphene oxide [11] and SiO2/graphene composite [12] has been 34
16 contaminated water such as chemical precipitation [3], electro- researched extensively; however, the adsorption properties of 35
17 chemical reduction [4] and ion exchange [1]. However, confine- graphene/activated carbon composite (GAC) for metal ions have 36
18 ments of these treatment processes appear by virtue of high not been reported yet. 37
19 operational cost, low treatment efficiency and secondary problems GO has been demonstrated to have a very high adsorption 38
20 from generation of metal-bearing toxic sludge [5]. capacity in the removal of Pb(II), Cd(II), and Co(II) from aqueous 39
21 Among these methods, adsorption is a promising one as it is solutions [9,13,14]. The oxygen containing functional groups on the 40
22 more efficient, economical and easier to handle than other surfaces of GO played important roles in the metal ions sorption. In 41

* Corresponding author. Fax: +98 231 3354120.

E-mail address: N_saeidi@semnan.ac.ir (N. Saeidi).

http://dx.doi.org/10.1016/j.jece.2015.09.023
2213-3437/ ã 2015 Published by Elsevier Ltd.

Please cite this article in press as: N. Saeidi, et al., High surface area and mesoporous graphene/activated carbon composite for adsorption of Pb
(II) from wastewater, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.09.023
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45
44
43
42 graphene/activated carbon composite, AC is annealed with GO. In was heated up to activation temperature (400
C) under N2 flow at 104
46 the composite, a layer of porous AC is coated on graphene sheets, the rate of 10
C/min and held at the activation temperature for 1 h. 105
47 which not only inhibits agglomeration and increases surface area, The resulting solids were boiled at about 90
C with 100 mL of 1 M 106
48 but also enhances mesoporosity. In other words, chemically HCl solution for 30 min to leach out the remaining ZnCl2, then 107
49 modified graphene is ideal filler for the microporous carbon due filtered and rinsed by warm distilled water several times to remove 108
50 to its high mesoporous structure. Comparing to large AC particles, the excess agent. They were then dried at 100
C for 12 h. The 109
51 it is worth pointing out that the nanosheet composite will reduce second step was carried out the same as the first one with some 110
52 the adsorption pathway significantly [15,16]. alterations as follows: arranging weight ratio of the resultant 111
53 In this work, high surface area and mesoporous GAC was powder to KOH up to 1–3, soaking for 1 h at 50
C, activating at 112
54 synthesized by means of GO and glucose as precursor and through 750
C under N2 flow at the rate of 10
C/min and holding at the 113
55 a two-step activation method. Then, the resultant GAC was activation temperature for 1 h. KOH played the role of activating 114
56 characterized by X-ray diffraction, Raman spectroscopy, scanning agent in the second step. Actually it was used to boost the surface 115
57 electron microscopy (SEM) and nitrogen adsorption–desorption area of the resultant composite. The obtained composite was 116
58 isotherms. Afterwards, the adsorption isotherms and kinetics of Pb denoted as GAC. 117
59 (II) onto the GAC were studied.
2.4. Synthesis of AC from glucose 118
60 2. Materials and methods
Glucose was dried and then carbonized under N2 flow in a 119
61 2.1. Chemicals
tubular furnace at 350
C for 5 h. For further activation, the 120

resultant black powder was impregnated with KOH (KOH/carbon 121

62 All chemicals were analytical reagents with mass fraction purity
mass ratio 4:1) for 8 h under continuous agitation. Afterwards, it 122
63 greater than 0.99 and were used without any further purification.
64 was heated up to 800
C under N2 flow at the rate of 5
C/min and 123
All solutions were prepared using deionized water. The pH of 124
65 kept at the temperature for 1 h. Then, the sample was washed by
working solutions were adjusted with 10% (wt/wt) NaOH and 10%
66 boiled deionized water several times and dried at 100
C overnight. 125
(vol.:vol.) HNO3. 126
The AC prepared from glucose was named as ACG.
67 2.2. Synthesis and purification of GO
2.5. Structural characteristics 127
68 GO powder used in this work was obtained from chemical
69 The XRD patterns were obtained by using a 128
exfoliation of natural graphite using NaNO3, H2SO4, and KMnO4
70 following a modified Hummers method [17,18]. The procedure was PW1840 diffractometer employing Cu Ka radiation 129
71 as follows: 2 g of graphite and 2 g of NaNO3 were placed in a flask (l = 1.54056 Å), u –2u geometry and a scintillation detector. Each Q2 130
72 and 92 mL of concentrated H2SO4 was added with constant stirring, diffraction pattern was recorded at a step of 0.04
and 0.5 s per step. 131
73 The measurements were made at ambient condition. 132
followed by the slow addition of 12 g of KMnO4 in an ice-water
74 133
bath. The solution was stirred for 3 h, and the reaction flask was Raman spectroscopy plots were obtained by a Handheld Raman
Analyzer (FirstguardTM, Rigaku). 134
75 then transferred to a water bath at 30
C and stirred for another 4 h.
76 A morphological characterization of GAC was carried out with a 135
Next, 200 mL of water was added and the temperature of the
136
77 suspension was maintained at 95
C for 30 min. Then, 20 mL of scanning electron microscope (MIRA//TESCAN). The sample was
78 placed on a sample holder with an adhesive carbon foil and then 137
H2O2 (30%) was added, whereupon the solution changed color
79 the sample was then laid under a vacuum at room temperature. It 138
from brown to yellow. After centrifugation at 7000 rpm for 15 min,
80 was coated with gold before the examination. 139
the solid phase was washed three times with 0.1 M HCl. The sample
81 The nitrogen adsorption and desorption isotherms for the 140
was then rinsed with deionized water until the pH of the solution
82 was neutral. The desired products were exfoliated using powerful sample was measured at 196
C on a Belsorp 18 (BEL Japan, Ltd.). 141
83 ultrasonication and then were dried under vacuum for 24 h to The sample was heated at 200
C for 3 h and degassed overnight. 142
84 The specific surface area was determined by the Brunauer– 143
obtain dark brown GO powder.
Emmet–Teller (BET) method using am (N2 = 16.2 Å2), where am is 144
85 2.3. Synthesis of GAC the molecular area of nitrogen at 196
C. The BET formula is valid 145

over a range of N2 relative partial pressure p/p0 varying from 146

86 0.01 to 0.30 [19]. Accordingly, the BET surface area of the sample 147
Firstly, 0.15 g of obtained GO powder was added into 100 mL of
87 was calculated on the mentioned range of relative partial pressure. 148
deionized water and then dispersed by ultrasonication with power
88 The mesopore volume and the pore size distribution of GAC were 149
of 300 W for 60 min, resulting in an inhomogeneous yellow–brown
89 determined based on BJH method. The total pore volume, Vtotal, 150
dispersion. Afterwards, 10 g glucose was added to the dispersion
90 was obtained using the adsorbed nitrogen at a relative pressure 151
gradually during 5 h ultrasonic bath (80 W). Then, the solvent was
152
91 vaporized at 60
C in the oven overnight. The dried powder was p/p0 of approximately 0.99.
92 heated up to 350
C under N2 flow at the rate of 2
C/min in a
93 2.6. Adsorption experiments 153
tubular furnace and held at the temperature for 2 h. For further
94 activation, the obtained carbonized powder underwent a two-step
95 The adsorption isotherms were carried out in fixed volumes of 154
chemical activation. In first step, the powder and ZnCl2 as
96 activating agent with impregnation ration of 1–2, respectively, pollutant solution (10 mL) at 30
C and pH 5, for 4 h to reach the 155
97 adsorption equilibrium, using a temperature-controlled shaker 156
were added into 100 mL deionized water and agitated for 7 h at
157
98 60
C. In fact, ZnCl2 was used to create porosity in the carbonized operated at 200 rpm. The solutions were prepared by diluting lead
99 nitrate with deionized water (100 mg/L, 10 mL, pH 5). Then, the 158
powder. Evaporation during this time was avoided using a close-up
100 adsorption capacities were determined by atomic absorption 159
glass container. Then the supernatant solution was separated by
160
101 vacuum filtration and the remaining solid was oven-dried at 90
C spectrophotometry using a PerkinElmer 2380 instrument. All
102 experiments were performed in duplicate at least and mean values 161
for 2 h. The impregnated sample was placed on a quartz dish,
103 were presented. 162
which was then inserted in a quartz tube. The impregnated sample

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(II) from wastewater, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.09.023
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Fig. 1. XRD diffraction patterns of GO and GAC.

163 The Pb(II) uptake at the equilibrium qe (mg/g) and removal

164 efficiency (E%) were calculated as follows:
ðC 0  C e ÞV
qe ¼ ð1Þ
m

C0  Ce
E% ¼  100 ð2Þ
C0
where C0 and Ce (mg/L) are the initial and equilibrium concen-
165 trations of Pb(II), respectively; V (L) is the volume of the solution;
166 and m (g) is the dosage of the adsorbent.

Fig. 3. N2 adsorption isotherm data of GAC (a) and GO (b) as well as pore size
distribution of GAC (c).
Fig. 2. Raman spectra of GO and GAC.

Please cite this article in press as: N. Saeidi, et al., High surface area and mesoporous graphene/activated carbon composite for adsorption of Pb
(II) from wastewater, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.09.023
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Table 1
Structural characteristics of GO, GAC and ACG.

Sample Surface area (m2/g) Mean pore diameter (nm) Vmeso Vtotal Vmeso/Vtotal
GO 85 17.5 0.3 0.34 0.88
GAC 2012 3.3 1.01 1.61 0.63
ACG 660 4.3 0.40 0.72 0.55

2.7. Adsorption isotherms 167

2.7.1. The Freundlich and Langmuir isotherms are represented by the 168

following equations: 169

Langmuir isotherm [20] Q3 170

Q m bC e
qe ¼ ð3Þ
ð1 þ bC e Þ
where Ce (mg/L) and qe (mg/g) are the equilibrium concentrations
of Pb(II) in the liquid and solid phases, respectively; Qm and b are 171

Langmuir constants. Qm is the maximum metal uptake (mg/g), 172

whereas b is adsorption equilibrium constant (L/g) and related to 173

the energy of adsorption. 174

Freundlich isotherm [21] 175

qe ¼ kf C 1=n
e ð4Þ

in which qe (mg/g) and Ce (mg/L) are the equilibrium concen- 177

176
trations of Pb(II) in the adsorbed and liquid phases, kf and n are the 178

Freundlich constants, indicating the adsorption capacity and 179

adsorption intensity. 180

To determine whether the adsorption is favorable, a dimen- 181

sionless constant separation factor or equilibrium parameter RL is 182

defined based on the following equation [22]: 183

1
RL ¼ ð5Þ
1 þ bC 0
where b (L/mg) is the Langmuir isotherm constant, and C0 (mg/L) is 185
184
the initial Pb(II) concentration. The RL value indicates whether the 186

type of the isotherm is favorable (0 < RL < 1), unfavorable (RL > 1), 187
Fig. 4. SEM image of GAC. 188
linear (RL = 1), or irreversible (RL = 0).

Fig. 6. Effect of pH on the adsorption of Pb(II) by GAC.

Fig. 5. Effect of GAC dosage on adsorption of Pb(II).

Please cite this article in press as: N. Saeidi, et al., High surface area and mesoporous graphene/activated carbon composite for adsorption of Pb
(II) from wastewater, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.09.023
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189 2.8. Adsorption kinetics

190 The pseudo-first order model was used to analyze the

191 adsorption kinetics. The non-linear pseudo-first order model is
192 expressed as [23]:

qt ¼ qe ð1  ek1 t Þ ð6Þ
193 This equation can be linearized in logarithmic form as:
½ðq  qt Þ
ln e ¼ k1 t ð7Þ
qe
194 The pseudo-second order model was also used to the same
195 purpose. The non-linear form of this model is as follows:

q2e k2 t
qt ¼ ð8Þ
ð1 þ qe k2 tÞ
196 This equation can be linearized in logarithmic form as:
t 1
¼ ð9Þ
qt ðk2 q2e Þ
198
197 where qt (mg/g) and qe (mg/g) are the adsorption capacity at time t
199 (min) and at equilibrium, respectively, while k1 (min1) and k2
200 (min1) are the pseudo-first-order and pseudo-second-order rate
201 constant, respectively.
202 The intra-particle diffusion model (Weber–Morris equation) is
203 expressed as [24]:

qt ¼ kid t1=2 þ C ð10Þ

205
204 where kid (mg/g min) is the intra-particle diffusion rate constant,
206 and C (mg/g) is the constant proportional to the extent of boundary
207 layer thickness.

208 3. Results and discussion

209 3.1. Characterization of GAC

210 As shown in Fig. 1, The XRD pattern of GO showed a sharp peak

211 at about 12
, corresponding to interlayer spacing of 0.85 nm, and
212 no obvious peak at the position of the (0 0 2) peak of graphite
213 (about 26
) is observed, indicating that the graphite has been fully
214 expanded and successfully oxidized into graphite oxide. After
215 activation and thermal treatment, the sharp diffraction peak of GO
216 vanished, instead a weak and broad peak at 2u = 26
appeared. It
217 can be contributed to the decreasing of the D-spacing value caused
218 by removing most oxygen-functional groups intercalated into
219 spacing of graphite the interlayer during thermal carbonization
220 and reducing the particle size of composite during chemical
221 activation steps [25].
222 The Raman spectra of GO and GAC are shown in Fig. 2,
223 displaying both two characteristic D and G bands of chemically
224 modified graphene. The Raman spectrum of GO displays a D-band
225 at approximately 1354 cm1 and G-band at about 1615 cm1. The
226 G-band originates from the in-phase vibration of the graphite
227 lattice, while the D-band mainly comes from the structure defects
228 created by the attachment of oxygen functional groups on the
229 carbon basal plane. The D:G intensity ratio of GO is 0.81, indicating
230 the high oxidation degree and/or relatively small domain size.
231 After activation steps and thermal treatment, this ratio was
232 remarkably increased to 1.25. This could be caused by the creation
233 of defects of the sample [25,26].
234 The N2 adsorption isotherm data of GAC are shown in Fig. 3a.
235 Adsorption measurements were followed by desorption measure-
236 ments under the same conditions. This isotherm is a combination Fig. 7. Kinetics data of Pb(II) onto GAC (a), kinetic modeling of pseudo-first-order
237 of type I and IV based on the IUPAC classification and is typical of model (b) and pseudo-second-order model (c) of Pb(II) adsorption.

Please cite this article in press as: N. Saeidi, et al., High surface area and mesoporous graphene/activated carbon composite for adsorption of Pb
(II) from wastewater, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.09.023
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Table 2
Parameters of the kinetic models for Pb(II) adsorption by GAC.

Pseudo-first order model Parameters

Pseudo-first order model k1 (min1) qe (mg/g) R2

0.005 0.546 0.74
Pseudo-second order model k1 (min1) qe (mg/g) R2
0.007 0.148 0.99
Intra-particle diffusion model (Weber–Morris) kid,1 (mg/g min) kid,2 (mg/g min) R12
14.6 1.66 0.99
C1 C2 R22
3.71 99.74 81

238 mesoporous materials with contributions of microporosity. On the works the specific surface area of the adsorbents is much less 274
283
282
281
280
279
278
277
276
275
239 contrary, the isotherm of GO (Fig. 3b) is a type IV which shows very than 2000 m2/g and in some limited works it reaches to the 284
240 low volume of nitrogen uptake compared with GAC. In these mentioned amount, although in such kind of works the mesopore 285
241 materials, capillary condensation normally takes place, leading to volume is very low and microporosity is the dominant structure. 286
242 hysteresis loops. Micropore filling occurs at very low relative Table S1 (see Supplementary material) lists some porous 287
243 pleasures. From the N2 adsorption–desorption isotherms it was materials textural properties with high surface area reported 288
244 clear that the adsorbed volume increases with increasing p/p0, by other researchers. Since all samples shown in Table S1 have 289
245 indicating the wider pore size distribution. The pore size microporous structure, it can be concluded that increasing 290
246 distribution of GAC illustrates in Fig. 3c . The graph reveals that surface area in many cases led to decreasing mesopore volume. 291
247 the sample has a well-defined pore structure presenting high In addition, total pore volume in all the samples is lower than that 292
248 mesoporosity (1–25 nm) with ignorable contributions of macro- of GAC reported here. 293
249 porosity (>25 nm). Table 1 summarizes the textural properties of Mesoporous structure of GAC can be contributed to coating high 294
250 GAC, GO and ACG. It can be seen that the surface area of GAC is porous structure of activated carbon by mesoporous graphene 295
251 2012 m2/g, which is close to the theoretical value of graphene nanosheets [15]. The morphology of GAC shown by SEM image in 296
252 (2630 m2/g) and far more than that of thermally reduced graphene Fig. 4 confirms that. In this structure, graphene nanosheets with 297
253 reported in other works. thickness less than 5 nm lied on activated carbon and this 298
254 As mentioned above, GAC possesses not only very high surface phenomenon could lead to covering micropores. 299
255 area but also it has mesopore structure and high pore volume.
256 This feature is very useful in different applications including 3.2. Effect of stirring rate 300
257 waste water treatment. Many researchers have tried to improve
258 both surface area and mesoporosity of porous materials, in Stirring rate can affect the distribution of the solute in the bulk 301
259 particular activated carbon, simultaneously; however, a few solution as well as the formation of the external boundary film 302
260 limited works have been successful in this regard. In most of the [27]. Thus, various stirring rates (100, 200, 500 and 1000 rpm) were 303

studied. The results showed that the effect of stirring rate on the 304

adsorption of Pb(II) by GAC was insignificant. Higher stirring speed 305

could slightly increase the initial adsorption rate but it became 306

nullified with passage of time, and the equilibrium adsorption 307

capacity of Pb(II) for all stirring speeds was almost the same. 308

3.3. Effect of GAC dosage 309

Different GAC doses (10–50 mg/10 mL) on adsorption of Pb(II) 310

261 were analyzed at a constant concentration of lead ion solution 311
262 (100 mg/L) under fixed parameters: pH 5 and contact time 4 h. The 312
263 percentage of removal of Pb(II) increased from 70.35 to 94.84% (see 313
264 Fig. 5). This can be explained as adsorbent dose increased, more 314
265 and more surface area will be available which exposed more active 315
266 sites for binding metal ions [28]. 316
267
268 3.4. Effect of pH on the adsorption 317
269
270 The effects of pH on metal ions adsorption have been studied by 318
271 many researchers previously, and the results indicated that pH of 319
272 solution exerts a great effect on uptake of metal ions [29,30]. In 320
273 Fig. 8. Kinetics of intra-particle diffusion model. order to investigate the effect of pH on the adsorption of Pb(II) onto 321

Table 3
Results of adsorption data modeling using Langmuir and Freundlich models.

Adsorption isotherms Parameters

Langmuir isotherms Qm (mg/g) b (L/mg) RL R2

217.6 0. 08 0.11 0.99
Freundlich isotherm kf (L/mg) 1/n – R2
109.466 0.312 0.92

Please cite this article in press as: N. Saeidi, et al., High surface area and mesoporous graphene/activated carbon composite for adsorption of Pb
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Fig. 9. Langmuir (a) and Freundlich (b) models fitting.

322 GAC, a series of lead solutions containing single component at the Pb(II) by GAC is poor at pH < 3. The results can be explained based 327
323 same initial conditions (100 mg Pb(II)/L with 20 mg of GAC in 10 mL on the competition between Pb(II) and H3O+ for adsorption sites on 328
324 solutions at 298 K) were adjusted to a pH range of 2.0–6.0, then the GAC. At low pH levels, an excess H3O+ could compete with Pb(II), 329
325 batch experiments were conducted. Effect of pH on the adsorption resulting in a low level of adsorbed Pb(II). With the pH increased, 330
326 of Pb(II) by GAC is shown in Fig. 6. It can be seen that the uptake of there are fewer hydrogen protons in solution, this means that there 331

Table 4
Comparison of maximum adsorption capacities (Qm) of Pb(II) on different adsorbents.

Adsorbent Qm (mg/g) References

Sludge biomass-based activated carbon 58 [49]
Sugarcane bagasse-based activated carbon 135 [50]
Hazelnut husk-based activated carbon 13.05 [51]
Coconut shell-based activated carbon 76.66 [52]
Peanut hull-based activated carbon 30.43 [53]
Palm shell-based activated carbon 82.0 [54]
332
Pecan shell-based activated carbon 64.20 [55]
Algal waste-based activated carbon 44.00 [56] 333
Date pit-based activated carbon 30.70 [57] 334
Rice straw-based activated carbon 36.05 [58] 335
Polygonum orientale Linn-based activated carbon 98.39 [59]
336
CNT 102 [60]
CNT 97 [61]
337
Acidified CNT 85 [62] 338
Zeolite 78.6 [6] 339
Bare GO 131.37 Present work 340
Bare ACG 39.07 Present work
341
GAC 217.6 Present work
342

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343
352
351
350
349
348
347
346
345
344 are less competition of binding sites and more binding sites are solution (100 mg/L, 10 mL, pH 5) and contacting time 240 min. Two 410
353 released, the surface charges GAC become more negative, which mentioned models were fitted in Fig. 9a and b for Pb(II) adsorption 411
354 causes electrostatic interactions and results in that the adsorption on the GAC. The correlation coefficients (R2) for the above models 412
355 of Pb(II) increases dramatically in the range of pH value from 3.0 to (Table 3) show that the Langmuir model fitted better than 413
356 6.0. These results indicate that the adsorption of metal ions onto Freundlich model. Therefore, Langmuir model can be used to best 414
357 GAC depends highly on the pH of solution. describe the Pb(II) adsorption behavior on the GAC. It can be 415

deduced that Pb(II) adsorption process is mainly homogeneous and 416

monolayer adsorption. In addition, RL < 1.0 (Table 3) is a further 417

358 3.5. Adsorption kinetics
indication that Langmuir adsorption is dominant. 418

In order to compare the adsorption capacity of Pb(II) on GAC, 419

359 To study adsorption kinetics of GAC, the data related to
bare GO and ACG, the maximum adsorption capacities (Qm) of 420
360 adsorption capacity at time t (Fig. 7a) was used. The adsorption
various adsorbents including activated carbon, CNT and zeolite are 421
361 kinetics was modeled by means of the pseudo-first order and
given in Table 4. Compared to other adsorbents including bare GO 422
362 pseudo-second order models. GAC was found to follow the pseudo-
and ACG synthesized here, it is obvious that GAC’s adsorption 423
363 second order model better than the pseudo-first order model
capacity is higher than those of other adsorbents. 424
364 (Fig. 7b and c and Table 2). It is elucidated that the adsorption
365 kinetics depends greatly on the physical and/or chemical
366 4. Conclusion 425
characteristics of the adsorbents [31]. In addition the pseudo-
367 second order equation did describe the adsorption results of Pb(II)
368 High surface area and mesoporous graphene/activated carbon 426
onto GAC adequately, with correlation coefficients of 0.99, which
369 composite was synthesized from graphene oxide and glucose. The 427
implies that the basic adsorption is chemisorptions, involving a
370 samples were characterized by X-ray diffraction pattern, Raman 428
sharing of electrons between the adsorbate and surface of the
371 spectroscopy, SEM image and nitrogen adsorption–desorption 429
adsorbent [32] such as the Lewis acid sites and COxHy surface
372 isotherms. The GAC’s surface area (2012 m2/g), total pore volume 430
functional groups with acid properties [33]. Chemisorption is
373 (1.61 cm3/g) and ratio of mesopore to total pore volume (0.61) 431
usually restricted to just one layer of molecules on the surface,
374 revealed that the GAC can be considered as a promising adsorbent 432
although it may be followed by additional layers of physically
375 for removal of different pollutants from water. To study the 433
adsorbed molecules [34].
adsorption behavior of Pb(II) on GAC, effects of pH, GAC dosage and 434

stirring speed were studied. The results showed that the effect of 435
376 3.6. Intra-particle diffusion study stirring speed on adsorption of Pb(II) on GAC is insignificant; 436

however solution pH played an important role in this regard. 437

377 The Weber–Morris equation was applied to investigate the Adsorbent dosage also influenced the adsorption of Pb(II) 438
378 intra-particle diffusion. The intra-particle diffusion is the sole rate- significantly. In addition, the adsorption performance and capacity 439
379 limiting step if the regression of qt against t1/2 is linear and passes of the GAC for removal of Pb(II) from aqueous solution were 440
380 through the origin [35]. However, multi-linearities can be observed studied by measuring adsorption kinetics and isotherms. The 441
381 in Fig. 8. adsorption kinetics was modeled by means of the pseudo-first 442
382 The first, sharper portion was the external surface adsorption order and pseudo-second order models. The GAC was found to 443
383 or the instantaneous adsorption. The second portion was the follow the pseudo-second order model better than the pseudo-first 444
384 gradual adsorption stage where intraparticle diffusion was rate- order model. In addition, the Weber–Morris equation was applied 445
385 limiting. to investigate the intra-particle diffusion. It was concluded that the 446
386 Table 3 lists the corresponding model parameters based on the intraparticle diffusion was part of the adsorption but was not the 447
387 respective equation. For all initial concentrations, k1 was higher only rate-controlling step. Langmuir and Freundlich equilibrium 448
388 than k2 and C2 was larger than C1. This showed that the rate of Pb(II) isotherms models were used to study the adsorption of Pb(II) 449
389 removal was higher in the beginning because of large surface area under the certain conditions. The correlation coefficients for the 450
390 of the adsorbent available for the adsorption of metal ions. After above models showed that the Langmuir model fitted better than 451
391 the adsorbed material formed a thick layer (caused by the inter- Freundlich model. Therefore, the Pb(II) adsorption on the GAC is 452
392 ionic attraction and molecular association), the capacity of mainly homogeneous and monolayer adsorption. A comparison 453
393 adsorbent got exhausted and the uptake rate was controlled by between the maximum adsorption capacity of the GAC and several 454
394 the rate at which the adsorbate was transported from the exterior other porous materials including bare ACG and GO synthesized 455
395 to the interior sites of the adsorbent particles. None of the plots here disclosed that the GAC has higher maximum adsorption 456
396 passed through the origin (Fig. 8), which revealed that the capacity (217 mg/g) to Pb(II) than other adsorbents. 457
397 intraparticle diffusion was part of the adsorption but was not the
398 only rate-controlling step. Some other mechanisms such as
399 Uncited references Q4 458
complexes or ion-exchange may also control the rate of adsorption
400 [36,37].
[38–48]. 459

401 3.7. Adsorption isotherms 460

Appendix A. Supplementary data
402 To optimize the use of adsorbents, adsorption isotherms are 461
Supplementary data associated with this article can be found, in
403 important criteria since they describe the nature of interaction 462
the online version, at http://dx.doi.org/10.1016/j.jece.2015.09.023.
404 between adsorbate and adsorbent. In addition, it is important to
405 establish the most appropriate correlation for the equilibrium 463
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