Chemical Engineering Journal 306 (2016) 7785

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Chemical Engineering Journal

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

In situ NH2-functionalized graphene oxide/SiO2 composites to improve

Cu(II) removal from ammoniacal solutions
Lingni Yang, Jiugang Hu , Weiwei Wu, Jia Tang, Kuixing Ding, Jie Li
College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China

h i g h l i g h t s

Amino groups were in situ grafted on the GO/SiO2 composites in ammoniacal media.

A special adsorption behavior for Cu(II) removal was elucidated.

The special affinity of amino groups with Cu(II) is beneficial for the adsorption.
1

The maximum adsorption capacity of Cu(II) is 158.9 mg g at equilibrium conditions.

a r t i c l e i n f o a b s t r a c t

Article history: A special adsorption manifestation for Cu(II) removal from ammoniacal solutions was elucidated. In this
Received 11 May 2016 process, the graphene oxide/SiO2 composites (GO/SiO2) were prepared by a facile method, and the amino
Received in revised form 6 July 2016 groups were successfully grafted on the surface of GO/SiO2 through an in situ functionalized reaction in
Accepted 9 July 2016
the ammoniacal media. The composites were thoroughly characterized by scanning electron microscopy
Available online 11 July 2016
(SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Raman and X-ray photoelectron (XPS)
spectroscopies. The spectral analyses proved that the amino groups can be in situ generated through the
Keywords:
reaction between ammonia molecules and functional groups on the surface of composites. The results
Cu(II) adsorption
Ammoniacal media
indicate that the NH2-functionalized GO/SiO2 composites are beneficial for the adsorption of Cu(II) due
GO/SiO2 composites to the special affinity of amino groups with Cu(II). The effects of solution pH, mass percentage of GO
In situ amination in composites and temperature have been discussed by batch adsorption experiments. The experimental
data can be well fitted with the pseudo-second order kinetics and Freundlich isotherm models. The max-
imum adsorption capacity of Cu(II) is 158.9 mg g1 at equilibrium conditions. In addition, thermodynam-
ics study confirmed the endothermic nature of Cu(II) adsorption, and the adsorption mechanism was
discussed. Hence, the GO/SiO2 composites have great potential for the efficient removal of Cu(II) from
ammoniacal solutions.
2016 Elsevier B.V. All rights reserved.

1. Introduction media, ammonia molecules replace the inner-sphere coordinated

Heavy metals wastewaters pose a serious threat to human
beings and environments because of their toxicity and accumula-
tion characteristics in nature. It has become very urgent to find
the appropriate solutions to remove heavy metals from wastewa-
ters [13]. Copper is one of the toxic heavy metals discharged by
various industries, such as printed circuit boards (PCB), electroplat-
ing, dye painting, textile and paper industries. Among them, the
treatments of PCB and dye painting wastewaters are the most
tough problem due to the fact that copper exists in the
ammonia-bearing industrial effluents [4,5]. In the ammoniacal
Corresponding author.
E-mail address: hjg.csu@gmail.com (J. Hu).
water molecules of hydrated copper ions, thus the coexisted cop-
per ammonia species and their strong stability can evidently
depress the Cu(II) removal. Thus, after treating with the general
precipitation method, several hundred ppm of copper can still pre-
sent in the ammoniacal wastewaters and is deleterious for the
environments.
In recent years, various contaminant remediation technologies
have been developed for the elimination of copper and other toxic
metals from wastewaters, such as ion exchange, chemical precipita-
tion, reverse osmosis, membrane separation and adsorption.
Adsorption is one of the promising and extensive methods, because
of its high efficiency, stability characteristics, easy handling as well
as availability of diverse adsorbents [610]. Some traditional adsor-
bents have been used for toxic metals removal, including activated

http://dx.doi.org/10.1016/j.cej.2016.07.035
1385-8947/ 2016 Elsevier B.V. All rights reserved.
78 L. Yang et al. / Chemical Engineering Journal 306 (2016) 7785
carbon [11,12], minerals [13] and so on. However, these adsorbents
have the weak affinity with heavy metal ions and the evident disad-
vantage of low adsorption capacity for heavy metal removal. The
rapid development of nanomaterials provides a good alternative
to solve these problems, which benefiting from their higher specific
surface area and sequestration characteristics [9,14]. Carbon mate-
rials are a kind of traditionally and widely used engineering adsor-
bents for the wastewater treatment [2,15]. Especially, graphene
oxide (GO), an oxidized derivative of graphite, presents a good
adsorbent performance for heavy metals, radioactive elements
and rare earths in various wastewaters [1620], because of the
abundant functional groups on its surface, such as hydroxyl,
epoxide, carbonyl and carboxyl groups. However, due to the pp
interaction, the aggregation features of two-dimensional GO
nanosheets can restrict the active sites to be exposed. Although
sonochemical approach is generally used to prevent the GO aggre-
gation and tune the surface chemistry of graphene oxides [21], the
GO-based composites with metal/nonmetal oxides can be generally
considered as the promising candidates for toxic ions adsorption
[3,6]. Considering the low cost, non-toxicity and chemical stability
of SiO2, the GO/SiO2 composites exhibit a great potential as adsorp-
tion and catalysis materials. In addition, the support SiO2 has a good
compatibility in the ammoniacal media due to its low solubility,
thus favoring for the absorbent stability.
Although there are abundant surface chemistry on GOs [22], it
is well known that the GOs decorated with nitrogenous ligands
can exhibit a stronger adsorption ability due to their special coor-
dination and affinity with metal ions [7,23,24]. There is generally
involved a beforehand functionalized processes to modify the sur-
face properties of GOs through various methods, including chemi-
cal crosslinking, chelation and graft. Xing et al. [25] found that the
GOs crosslinked with NH2-rich polymers can be used for Cu(II)
removal with the high adsorption capacity. Luo et al. [26] found
that GOs can selectively remove Pb(II) with the high capacity
through linking with amino siloxane oligomer. For the graphene
oxide-supported polyaniline composites, Sun et al. concluded that
the chemical affinity of nitrogen-containing functional groups for
radionuclides is stronger than that of oxygen-containing functional
groups [24]. Moreover, some typical amino ligands including
ethylenediaminetetraacetic acid [7], ethylenediamine triacetic
acid [23] and amino acids [27] can be chemically grafted to the
host adsorbents to markedly improve the toxic metal removal.
Therefore, optimizing the surface properties of GOs by amination
is preferred for metal adsorption.
Unlike the general amination process of GOs, herein in view of
the specific ammoniacal media, an in situ NH2-functionalized
process was proposed to introduce amino groups on the surface
of graphene oxide/SiO2 composites. The composition of GO/SiO2
composites was optimized by consideration of the mass percent-
age of GO in composites. And the IR, Raman and XPS spectroscopies
have been used to clarify the in situ generated amino groups on the
GO/SiO2 composites. The Cu(II) adsorption abilities of GO/SiO2
composites from the ammoniacal media were evaluated at
different feed pH conditions and temperatures. Meanwhile, the
Cu(II) adsorption mechanism was studied through the adsorption
kinetics and isotherm analyses.
2. Experimental
2.1. Reagents and chemicals
Natural graphite powder (average particle size is 40 lm), copper
sulfate pentahydrate (CuSO45H2O), tetraethyl orthosilicate (TEOS)
and all other chemicals were used without further purification.
Deionized water (Millipore MilliQ System, 18.2 MX cm1) was used
in all experiments.
2.2. Preparation of GO/SiO2 composites
Graphene oxide was synthesized via the modified Hummers
method. Firstly, under the ice bath condition, 10 g graphite pow-
ders and 5 g NaNO3 were mixed with 230 mL concentrated
H2SO4 and stirred for 30 min. Subsequently, 30 g KMnO4 was
added slowly with continuous stirring. After the mixture was stir-
red for 30 min at 35 C, 460 mL deionized water was added drop-
wise under vigorous stirring. The reaction temperature was
rapidly increased to 98 C and kept for 40 min until the color of
mixture was changed from sepia into luminous yellow. Subse-
quently, 30% H2O2 was added into the mixture to reduce the resid-
ual MnO 4 anions. Finally, the product was purified and washed
with 5% HCl and deionized water for several times until the solu-
tion was neutral. The as-prepared GO was dried at 60 C in vacuum
after centrifuging.
Silica particles were synthesized as follows: TEOS (50 mL) and
ethanol (100 mL) were completely mixed in 100 mL DI water. After
100 mL ammonium hydroxide was added, the mixed solution was
stirred for 2 h at 30 C. Finally, the white suspension was acquired
through centrifuging. The gel was dried at 60 C in vacuum and
calcined at 500 C for 3 h to obtain the SiO2 particles.
GO/SiO2 composites were prepared in a water/alcohol
mixed solution. Briefly, as-obtianed GOs and SiO2 particles were
re-dispersed in 1:1 ethanol aqueous solution, which was stirred
and refluxed for 4 h at 95 C. Then, the centrifuged products were
dried at 60 C in vacuum for 24 h. Finally, a series of GO/SiO2
composites were obtained with different weight percentages of
GO in the GO/SiO2 composites (20 wt%, 50 wt% and 80 wt%) by
the same method, named as GOS1, GOS2 and GOS3, respectively.
2.3. Characterization methods
The morphologies of GO/SiO2 composites were characterized by
scanning electron microscopy (SEM, JSM-6360LV). The X-ray
diffraction (XRD, D/Max2250, Rigaku Corporation, Japan) analyses
were performed with a nickel-filtered Cu Ka radiation
(k = 1.5406 ). The diffraction angles were ranged from 10 to
80 with a rate of 1.0 min1. The Fourier transform infrared
(FT-IR) spectra of samples were recorded in KBr pellet at room
temperature using a Thermo Fisher Nicolet 6700 FT-IR spectropho-
tometer, with a resolution of 4 cm1 in the range from 400 to
4000 cm1. The Raman spectra were obtained from a Renishaw
inva confocal Raman system with a 532 nm excitation laser. The
surface chemical information of simples was measured by a XPS
(X-ray photoelectron spectroscopy) spectrometer (K-Alpha 1063,
Thermo Fisher Scientific) using monochromatized Al Ka
(1486 eV) radiation. Specific surface areas of the adsorbents were
determined by nitrogen adsorption and desorption at 77 K using
an ASAP 2020 (Micromeritics) volumetric adsorption analyzer.
2.4. Batch adsorption experiments
The stock solution of 100 mmol L1 Cu(II) was prepared by dis-
solving a certain amount of CuSO45H2O in deionized water. The
different concentration of Cu(II) solutions were prepared by dilut-
ing of the stock solution in 100 mL of 0.1 mol L1 (NH4)2SO4. The
pH of Cu(II) solutions was adjusted to the desired value from 4.5
to 10.5 using sodium hydroxide and sulfuric acid. All batch adsorp-
tion experiments of Cu(II) on GO/SiO2 composites were carried out
by shaking the Cu(II) solutions containing 0.5 g L1 adsorbent in a
20 mL glass bottle at 298 K (400 rpm for 4 h). Other parameters
including initial Cu(II) concentration (0.22.5 mmol L1), contact
time (05 h) and temperatures (293313 K) were studied at the
pH 8 to evaluate the isotherm, kinetics and thermodynamics of
Cu(II) adsorption. The suspensions were separated by centrifuging.
 L. Yang et al. / Chemical Engineering Journal 306 (2016) 7785
After phase separation, the concentrations of Cu(II) in solutions
before and after adsorption were determined by using inductively
coupled plasma-atomic emission spectrometry (ICP-AES, Perkin
Elmer 5300DV). Then, the adsorption percentage (E%) and capacity
(Qe, mg g1) of Cu(II) were calculated with the follow equations:
C0  Ce
E%  100
C0
C o  C e V
Qe
m the hydroxyl replaces the inner-shell coordinated ammonia ligands
where C 0 and C e are the initial and equilibrium concentration of Cu
(II), respectively (mg/L); V (L) is the volume of suspensions, and m
(g) is the weight of GO/SiO2 composites.
3. Results and discussion
3.1. Cu(II) adsorption behaviors
In ammoniacal media, as shown in Fig. 1a, the copper species
are diverse and dependent on the solution pH. Fig. 1b presents a
special swing phenomenon on Cu(II) adsorption. It is observed
that Cu(II) adsorption efficiency shows a gradual increase with
Fig. 1. (a) pH dependence of Cu(II) species and (b) effect of pH on the adsorption
behaviors of Cu(II). Initial concentration of Cu(II) 1 mmol L1, 0.1 mol L1
(NH4)2SO4, adsorbent dosage 0.5 g L1, contact time 4 h, temperature 298 K.
79
changing the solution pH from 4.5 to 7.0, and reaches the maxi-
mum at pH 7, 7.5 and 8 for GOS1, GOS2 and GOS3 respectively.
Afterwards, it is noteworthy that all of the adsorption efficiency
decline to the minimum at the pH of 9, and then continuously
increases with increasing pH beyond 9. The special Cu(II) adsorp-
tion behaviors can be attributed to the complicated copper species.
1 Compared Fig. 1a with Fig. 1b, the decreasing trend of Cu(II)
absorption is consistent with the increasing trend of Cu(NH3)2+ 4 .
Previous work also indicated that the most stable tetra-ammonia
copper species can inhabit Cu(II) extraction [28]. When pH > 9,
2
to form the mixed hydroxyammine and hydroxo complexes. There-
fore, the geometric symmetry of Cu(II) species decreases and the
negative charge on the surface of adsorbents increases, thus fur-
ther improving the Cu(II) adsorption [29].
The sequence of the removal efficiency of three composites is
GOS3 > GOS2 > GOS1, indicating that the higher GO content pre-
sents a better absorption ability for Cu(II). Its well known that
the surface functional groups of GO/SiO2 composites consist of
hydroxyl, carboxyl and other groups, which are responsible for
Cu(II) removal. With the increase of GO content, more functional
groups can coordinate with Cu(II), thus increasing the removal effi-
ciency. Meanwhile, it should be noted that Cu(II) adsorption effi-
ciency reaches the maximum at different pH for GOS1, GOS2 and
GOS3 respectively. It can be inferred that some new functional
groups could be formed when GO/SiO2 composites contact with
the ammoniacal solutions. When the solution pH is larger than 7,
the ammonia molecules could predominately react with the hydro-
xyl and carboxyl groups of GOs to generate amino groups on the
surface of GO/SiO2 composites (denoted as GO/SiO2-NH2). Lai
et al. [30] also found that the NH2-GO can be obtained within
ammonia solutions by a one-pot solvothermal process. The amount
of amino groups on the composites can be accrued with the
increase of GO and solution pH, thereby improving the Cu(II)
adsorption capacity. Thus, the in situ generated amino groups
can benefit for the Cu(II) removal from ammoniacal solutions with
GO/SiO2 composites.
In order to further clarify the role of the formed amino groups,
the parallel adsorption experiments for GO/SiO2 composites and
GO/SiO2-NH2 composites were performed in the ammonia-free
Cu(II) solutions. The GO/SiO2-NH2 composites were previously pre-
pared by stirring GO/SiO2 composites in the 0.1 mol L1 (NH4)2SO4
solutions of pH 8 without copper ions about 4 h. The products have
been dried at 60 C in vacuum after washed with deionized water
for several times until the pH is neutral. Taking into consideration
of the formation of copper precipitate in the absence of ammonia,
the 0.15 mmol L1 Cu(II) solution of pH 7 was used to evaluate the
adsorption ability of two kinds of composites. As shown in Fig. 2,
the adsorption ability of GO/SiO2 composites can be enhanced
above 10% as the result of amination reaction. The high absorption
percentages of both GO/SiO2 and GO/SiO2-NH2 composites should
result from the absence of ammonia and the low Cu(II) concentra-
tion in the feed solutions at the same absorbent dose of 0.5 g L1.
Meanwhile, these results clearly indicate that the GO/SiO2-NH2
composites could be directly generated in the ammoniacal media.
The in situ generated amino groups have the stronger affinity
with Cu(II), thereby leading to excellent adsorption performance
of GO/SiO2 composites in ammoniacal solutions.
3.2. Characterizations of GO/SiO2 composites
The SEM images of GO/SiO2 composites were shown in Fig. 3.
Comparing the morphology of SiO2 particles before and after com-
bined with the GOs, the GO/SiO2 composites present a greater
aggregation with the wrinkle-like surface as increasing the mass
percentage of GOs. Although the more rough surface of composites
80 L. Yang et al. / Chemical Engineering Journal 306 (2016) 7785
Fig. 2. The comparison on Cu(II) removal efficiency between GO/SiO2 and GO/SiO2-
NH2 composites. 0.15 mmol L1 Cu(II) solutions without ammonia, pH = 7, adsor-
bent dosage 0.5 g L1, contact time 4 h, temperature 298 K.
could induce a larger surface area for the higher loading capacity
[31], the determined surface areas of SiO2, GO and their composites
presented in Fig. 4a indicate that the specific surface area of com-
posites decreases when increasing the GO content. Compared the
calculated surface areas by summing with respect to the mass
percentage, the experimentally determined value of composites
is relative lower at the higher GO content, which could result from
the formation of the greater aggregation. However, the previous
results show that the absorption ability of GO/SiO2 composites
can be enhanced by increasing GO ratio, thereby indicating
that the more excellent absorption ability of GOS3 should result
from the abundant NH2-functionalized surface of composites.
Fig. 3. SEM images of SiO2 particles and GO/SiO2 composites.
The X-ray diffraction (XRD) patterns of GO/SiO2 composites and
primordial SiO2 particles and GO were shown in Fig. 4b. Through
the characteristic analysis of XRD spectra, it can be found a unique
intense diffraction peak of GO at 2h = 10.968, indicating an inter-
layer spacing of 8.06 for pure GO due to the introduction of the
oxygen functional groups [32]. For pure silica particles, there is
only a wide diffuse scattering and the maximum occupied at
2h = 22.4 due to their amorphous structures. For the GO/SiO2 com-
posites of three compositions, a similar patterning of silica pow-
ders can be observed at 2h = 22.4. Meanwhile, although the
diffraction peak for GO (1 0 0) plane was masked by the diffuse
scattering of silica, it can be found that the diffraction peak for
GO (0 0 2) plane shifts toward right direction with the increasing
mass percentage of GO, which can be attributed to the structural
shrink and/or residual stress of GO after combined with SiO2
particles.
Raman spectroscopy can effectively provide the structural
information of carbonaceous materials. The GOS3 and its NH2-
functionalized composite (GOS3-NH2) were compared before and
after Cu(II) adsorption. Fig. 5 shows the Raman spectra of GOS3,
GOS3-NH2, GOS3-Cu and GOS3-NH2-Cu. Obviously, all of the sam-
ples provide the prominent characteristic peaks of GOs around
1353 cm1 (D band) and 1595 cm1 (G band) due to the resonant
Raman processes [21,33]. The D band is related to the stretching
vibration of sp3 carbon atoms and the G band is attributed to the
stretching vibration of sp2 carbon atoms, which corresponding to
the first-order scattering of the E2g mode and A1g mode, respec-
tively [34]. The intensity ratio (ID/IG) of the D and G peaks can be
used to estimate the defect degree of the GO samples. The ID/IG
value of GOS3 changes from 0.92 to 0.99 after modified with amino
groups, indicating the more structural defects and an increase of
amorphous carbon in the GOS3-NH2 due to the introduction of
N-atoms in their aromatic graphene network [24,35]. On the other
hand, the Raman spectra of both GOS3-Cu and GOS3-NH2-Cu
present three new feature peaks at 239, 612 and 800 cm1, which
 L. Yang et al. / Chemical Engineering Journal 306 (2016) 7785 81

Cu(II), thus leading to the stretching vibration of Cu-NH2 [36]. The

Raman studies are indicative that amino groups of the GO/SiO2
composites can be in situ formed in the ammoniacal media.
The FT-IR spectra of GOS3, GOS3-NH2 and GOS3-NH2-Cu were
shown in Fig. 6. Two characteristic peaks located at 3436 cm1
and 1718 cm1 are observed for GOS3, corresponding to the
stretching vibration of OAH and C@O stretching frequencies of
the ACOOH groups on the GO surface, respectively. The peak
appearing at 1629 cm1 is attributed to the skeletal vibration of
AOH in epoxide groups. The peak at 1398 cm1 is ascribed to the
CAO bond, whereas the strong vibration band at 1089 cm1 is
caused by the SiAO asymmetrical stretching vibration of SiO2.
These structural features indicate that the diverse oxygen-
containing functional moieties exist on the frameworks of GOS3
composites. It is noteworthy that some differences can be observed
from the FT-IR spectrum of GOS3-NH2 sample. The broad peaks at
3188 cm1 and 1584 cm1 can be assigned to the symmetrical
stretching vibration and the plane bending vibration of ANH2
groups. The new peak observed at 1153 cm1 can be corresponded
to the CAN stretching vibration of amino groups [37]. In addition,
the new peak at 1208 cm1 is attributed to CAN vibration of
ACANHAC groups [38]. These results clearly provide the evidence
for the presence of amino groups on the GOS3 composite after trea-
ted with ammoniacal solutions. After adsorbed with copper ions,
the vibration peaks of amino groups present the red shift phe-
nomenon. It could result from the decrease of electron density of
functional groups after coordination between Cu(II) and the nitro-
gen atoms, thereby the vibration frequencies move to the low-
frequency direction.
The surface chemical compositions of GOS3, GOS3-NH2 and
GOS3-NH2-Cu were further confirmed by XPS spectra (Fig. 7). The
prominent peaks in the survey scan spectrum of GOS3 can be
observed at 104.0, 154.3, 285.3 and 532.6 eV, corresponding to
the Si 2p, Si 2s, C 1s and O 1s (Fig. 7a), respectively. Compared with
Fig. 4. The experimental and calculated specific surface areas (a) and XRD spectra
GOS3, the XPS full-scan spectrum of the GOS3-NH2 presents a rel-
(b) of GO/SiO2 composites and the individual SiO2 and GO.
atively low N 1s peak, which suggests the presence of N-atom in
this sample. Based on the XPS survey result, the atom ratios of four
elements in the GOS3-NH2 composite are as follows: carbon
(62.14%), oxygen (30.36%), silicon (4.68%) and nitrogen (2.81%).
As shown in Fig. 7b, the C 1s XPS spectrum of GOS3 clearly indi-
cates the presence of four different oxygen functional groups,
including the non-oxygenated ring carbon at 284.6 eV, the carbon
in CAO at 285.5 eV, the carbonyl carbon (C@O) at 286.9 eV and the
carboxylate carbon (OAC@O) at 288.2 eV [21,39]. For the GOS3-

Fig. 5. Raman spectra of GOS3, GOS3-Cu, GOS3-NH2 and GOS3-NH2-Cu.

corresponding to the CuAO stretching modes. Moreover, a new dis-

tinct peak is found at 504 cm1 for GOS3-NH2-Cu. It can be inferred
that the in-situ generated amino groups have a coordination with Fig. 6. FT-IR spectra of GOS3 (a), GOS3-NH2 (b) and GOS3-NH2-Cu (c).
82 L. Yang et al. / Chemical Engineering Journal 306 (2016) 7785

Fig. 7. XPS spectra of GOS3 and GOS3-NH2. (a) XPS full scan spectrum, (b) C 1s XPS spectra of GOS3, (c) C 1s XPS spectra of GOS3-NH2, (d) N 1s XPS spectra of GOS3-NH2.

NH2, an additional component peak can be observed at 285.9 eV

from the C 1s XPS spectrum (Fig. 7c), which can be ascribed to
the formed CAN groups [30]. Whats more, it is non-ignorable that
the peak intensities for most of the oxygen-containing groups of
GOS3 decrease dramatically after treated with the ammoniacal
media, especially for the C@O and OAC@O peaks. These observa-
tions indicate that amino groups can be successfully grafted on
the surface of GO/SiO2 composite through the reaction between
ammonia and the part of the oxygen-containing functional groups
[40]. Deconvolution of the N 1s spectrum (Fig. 7d) of GOS3-NH2
shows three component peaks with the binding energies of
398.8, 399.8 and 401.9 eV, which verify the formation of amide
(398.8 eV), amine (399.8 eV), and N+ species (401.9 eV) on the
GO/SiO2 composites [41], respectively.

3.3. Adsorption kinetics and thermodynamics

The adsorption kinetics is a significant index to estimate the

efficiency and economy of adsorbents. Batch experiments on the
Cu(II) adsorption kinetics for three GO/SiO2 composites were per-
formed by varying the contact time from 0 to 5 h in the same other
conditions. The adsorption kinetic results are presented in Fig. 8. It
can be seen that the adsorbing capacity can rise rapidly and reach
to equilibrium in 50 min. Two conventional kinetic models were
employed to investigate and compare the dynamic adsorption data
for three composites [6,8]. The pseudo first-order kinetic model is
expressed as following equation:
K1
lnQ e  Q t lnQ e  t 3
2:303
where Qe and Qt (mg g1) is the adsorption amount of Cu(II) on
adsorbents at equilibrium and time t (min), K1 (min1) is the rate
constant of pseudo first-order adsorption. The pseudo second-
order kinetic model equation can be presented as:
t 1 t between Cu(II) and amino groups.
K2 Q 2e
Qt 2 Qe
Fig. 8. Adsorption kinetics of Cu(II) on GO/SiO2 composites. Initial concentration of
Cu(II) 1 mmol L1, pH = 8, 0.1 mol L1 (NH4)2SO4, adsorbent dosage 0.5 g L1,
temperature 298 K, contact time 05 h; dash line, pseudo first-order fitting; solid
line, pseudo second-order fitting.
where K2 (g mg1 min1) is the rate constant of pseudo second-
order adsorption.
The corresponding parameters of two kinetic models were
obtained via fitting the experimental data, and the results are illus-
trated in Table 1. The correlation coefficient (R2) shows that the
pseudo second-order kinetic model provides a more excellent
description for the Cu(II) absorption process, indicating that the
chemical absorption of Cu(II) on GO/SiO2 composites is the
rate-controlling step. And it might be supposed that the reaction
mechanism involves the ion exchange between Cu(II) and
oxygen-containing functional groups, as well as the coordination
4 The adsorption thermodynamics, including Gibbs free energy
DG0 , the enthalpy change DH0 and entropy change DS0 , can
 L. Yang et al. / Chemical Engineering Journal 306 (2016) 7785 83

Table 1 Table 2
Parameters of two kinetic models for the adsorption of Cu(II). Thermodynamic parameters of Cu(II) adsorbed by GO/SiO2 composites.

Pseudo first-order model Pseudo second-order model Adsorbents T DG0 DH0 DS0 R2
Qe K1 R 2
Qe K2 R 2 (K) (kJ mol1) (kJ mol1) (J (mol K)1)
(mg g1) (min1) (mg g1) (g (mg min)1) GOS1 293 0.47 4.31 16.29 0.9847
GOS1 47.1484 0.5286 0.9880 48.2273 0.00132 0.9932 303 0.61
GOS2 69.8862 0.4208 0.9806 71.8747 0.00088 0.9937 313 0.79
GOS3 86.1239 0.4584 0.9867 88.7699 0.00054 0.9954 GOS2 293 2.63 6.82 32.19 0.9389
303 2.89
313 3.28
be further evaluated with the following thermodynamic formulas GOS3 293 4.04 17.43 73.56 0.8831
[10,25]: 303 5.02
313 5.51
C 0  C e V
K0 5
mC e
on the general Langmuir and Freundlich isotherm models
0 0 [17,18,20]. The Langmuir isotherm model is an adsorption equa-
DG RTlnK 6
tion based on the monomolecular layer adsorption mode, which
assumes that metal ions are adsorbed on the homogeneous adsorp-
0 DG0 DH 0 DS0 tion sites on the surface of adsorbent. The equation is given as:
lnK   7
RT RT R
Ce Ce KL
where R is the universal gas constant (8.314 J mol1 K1), T (K) is 8
0
Q e Q max Q max
the adsorption experiment temperature. K is the adsorption equi-
librium constant. As shown in Fig. 9, the plots of lnK0 against 1/T The Freundlich adsorption isotherm is an empirical model,
present a linear relationship for Cu(II) adsorption. Thus, based on which is established on heterogeneity of adsorption surface. It
the equations above, DH0 and DS0 could be calculated from the can be described as follows:
slope and intercept, respectively. All the calculated value are listed 1
in Table 2. Combining with the thermodynamics point of view, the lnQ e lnKF lnC e 9
n
0
negative values of DG confirm the thermodynamic spontaneity of
where Qe (mg g1) is the adsorption amount of Cu(II) on GO/SiO2
the adsorption process [3]. Meanwhile, the positive values of DH0
composites at equilibrium; Qmax (mg g1) is the saturated adsorp-
indicate endothermic nature of the Cu(II) adsorption. Thus, the
tion capacity of Cu(II) for monolayer absorption; Ce (mg g1) is
adsorption capacity can be increased with increasing temperature.
the concentration of metal ions in solutions at equilibrium; KL is
On the other hand, the positive values of DS0 suggest that the the Langmuir adsorption equilibrium constant related to the
solid/solution interface has an increasing disorder during Cu(II) adsorption energy; KF and n are the characteristic parameters of
adsorption on the GO/SiO2 composites. Moreover, the Cu(II) adsorp- the Freundlich isothermal model.
tion on GOS3 has a more obvious dependence on temperature, thus As shown in Fig. 10, Cu(II) ions can be favorably adsorbed on the
indicating that the composites with higher content of GO favor for GO/SiO2 composites. The maximum adsorption capacity increases
the Cu(II) adsorption at the higher temperature. with increasing GO content, and reaches to 158.9 mg g1 for
GOS3 at the equilibrium concentration of 59 mg L1. Compared
3.4. Adsorption isotherms the Qmax with other carbon-based adsorbents reported in litera-
tures (listed in Table 3), its could be observed that GO/SiO2 com-
In order to obtain the adsorption capacity of adsorbents and posites present a relatively higher Cu(II) adsorption capacity than
explore the microscopic mechanism between Cu(II) and GO/SiO2 other materials, thus the in situ amination reaction of GO/SiO2
composites, adsorption isotherms have been investigated based

Fig. 10. Adsorption isotherms of Cu(II) on GO/SiO2. Initial concentration of Cu(II)

Fig. 9. The relationship of lnK0 against 1/T for Cu(II) adsorption of three GO/SiO2 0.22.5 mmol L1, pH = 8, 0.1 mol L1 (NH4)2SO4, adsorbent dosage 0.5 g L1, tem-
composites. Initial concentration of Cu(II) 1 mmol L1, pH = 8, 0.1 mol L1 (NH4)2- perature 298 K, contact time 4 h. dash line, Freundlich model; solid line, Langmuir
SO4, adsorbent dosage 0.5 g L1, contact time 4 h. model.
84 L. Yang et al. / Chemical Engineering Journal 306 (2016) 7785

Table 3 Definitely, the increase of pH is favorable for the in situ graft of

Comparison on maximum adsorption capacity of various adsorbents for Cu2+. ANH2 groups. The second step is the specific metal coordination
Adsorbents Solution condition Qmax (mg g1) Refs. process between ANH2 groups and Cu(II):
GO-PAMAMs H2O 68.68 [32]
GO aerogel H2O 29.59 [43]
nGO-NH2 Cu2 ! GO-NH2 n -Cu2 n 6 4
Activated carbon H2O 86.01 [44]
CNTs H2O 64.9 [45] GO-CONH2 n Cu2 ! GO-CONH2 n -Cu2 n 6 4
GO H2O 117.5 [46]
Silica/GO H2O 27.4 [47] Because the lone pair electrons of nitrogen atoms in amino
GO-CS NaCl 25.4 [48]
groups was shared with metal ions [26], the stability constant of
GO/Fe3O4 NaNO3 18.26 [49]
GO/SiO2 (NH4)2SO4 158.9 This work copper complexes with amino groups is generally larger than that
of Cu(NH3)2+
n . Thus, the in situ functionalized GO/SiO2 composites
has the greater competitive adsorption ability of Cu(II) in ammoni-
acal media.
Table 4
Fitting parameters of Langmuir and Freundlich isotherm models for Cu(II) adsorption.
4. Conclusions
Langmuir model Freundlich model
KL Q cal R2 KF n R2 In this work, the amino groups were successfully grafted on the
(L mg1) (mg g1) (mg1n Ln g1) surface of GO/SiO2 through an in situ functionalized reaction in the
GOS1 49.21 49.21 0.9133 5.59 1.73 0.9321 ammoniacal media. And the efficient removal of Cu(II) from
GOS2 23.12 153.94 0.8645 18.56 2.24 0.9699 ammoniacal solutions was achieved with the in situ NH2-
GOS3 11.75 175.41 0.9099 31.87 2.59 0.9692 functionalized GO/SiO2 composites. The absorption behaviors of
Cu(II) present a special swing phenomenon, and the removal effi-
ciency is dependent on the solution pH, temperature and the mass
composites in the ammoniacal media is beneficial for Cu(II) percentage of GO in composites. The Cu(II) adsorption is a
removal. A nonlinear fitting was applied to match the experimental endothermic process, thus increasing temperature can improve
data and adsorption isotherm equations. The obtained parameters Cu(II) removal. The higher GO contents can be beneficial for the
of Langmuir and Freundlich isotherms are listed in Table 4. The Cu(II) absorption, indicating that the more amino groups can be
results show that the Freundlich model has a better correlation generated on the surface of composites. The IR, Raman and XPS
coefficient than Langmuir model, indicating that the surface multi- spectra proved that the amino groups were in situ grafted through
layer adsorption is predominant, and the adsorption sites are the reaction between ammonia molecules and functional groups
heterogeneous and nonspecific for Cu(II) on the adsorbents. Taking on the surface of composites. The experimental data can be well
into consideration the diverse surface functional groups of GO/ fitted with the pseudo-second order kinetics and Freundlich iso-
SiO2-NH2 composites, it can be inferred that the interaction mech- therm models. Due to the affinity of amino groups with Cu(II),
anism of Cu(II) with adsorbents is multiple and complicate because the maximum adsorption capacity of GO/SiO2 composites can
of the existence of different types of adsorption sites on the surface reach 158.9 mg g1 in the ammoniacal media, which is superior
of adsorbents [42]. to other similar composite materials. These results indicate that
the efficient removal of Cu(II) from ammoniacal solutions can be
3.5. Adsorption mechanism achieved with the in situ NH2-functionalized GO/SiO2 composites,
thereby presenting a great potential for the efficient removal of Cu
The adsorption mechanism of Cu(II) on GO/SiO2 composites is a (II) and other heavy metals from ammoniacal wastewaters.
complicated process, especially in the ammoniacal media due to
the diverse Cu(II) species. Generally, the microscopic adsorption Acknowledgements
process of metal ions can be achieved by electrostatic interaction,
complex formation and ion-exchange. It has been certified that This work was financially supported by the National Basic
metal ions can be strongly bound with hydroxyl and carboxyl Research Program of China (No. 2014CB643401), National Natural
groups of GOs by formation of inner-sphere surface complexes Science Foundation of China (Nos. 51134007 and 51304244), China
[18,20]. For the GO/SiO2 composites, the reactions between Cu(II) Postdoctoral Science Foundation (2014M552152) and Hunan
and ACOOH and AOH groups can be shown as follows: Provincial Natural Science Foundation of China (2015JJ3154).

2GO-COOH Cu2 ! GO-COO 2 -Cu2 2H

2GO=SiO2 -OH Cu2 ! GO=SiO2 -O 2 -Cu2 2H
In the ammoniacal media, the copper ions can coordinate with
ammonia molecules, thus the stable copper ammonia species can
depress the Cu(II) adsorption on the GO/SiO2 composites, espe-
cially the Cu(NH3)2+
4 species. In addition, it is worth noting that
amino groups can be in situ formed on the composite surface
through the interaction between GO with free ammonia molecules.
Thus, two processes are responsible for the adsorption of Cu(II)
with ANH2 groups. The first step is the in situ formation of
ANH2 groups [50,51]:
GO-COOH NH3 ! GO-CONH2 H2 O
GO-OH NH3 ! GO-NH2 H2 O
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