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Journal of Hazardous Materials 297 (2015) 251–260

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Journal of Hazardous Materials


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

Adsorption of Cu2+ , Cd2+ and Ni2+ from aqueous single metal solutions
on graphene oxide membranes
Ping Tan a , Jian Sun c , Yongyou Hu a,b,∗ , Zheng Fang a , Qi Bi a , Yuancai Chen a,b ,
Jianhua Cheng a,b
a
School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, China
b
State Key Lab of Pulp and Paper Engineering, College of Light Industry and Food Science, South China University of Technology, Guangzhou 510640, China
c
Shcool of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China

h i g h l i g h t s

• Novel, well-ordered GO membranes were prepared and characterized.


• The GO membranes had high adsorption capacity and fast adsorption rate.
• The effects of pH and Na+ on Cd2+ , Cu2+ and Ni2+ sorption were studied.
• Adsorption mechanisms of Cd2+ , Cu2+ and Ni2+ on the GO membranes were elucidated.
• The GO membranes exhibited good reusability after repeated uses.

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

Article history: Novel, highly ordered layered graphene oxide (GO) membranes with larger interlayer spacing were pre-
Received 17 March 2015 pared by induced directional flow and were used as adsorbents for the removal of Cu2+ , Cd2+ and Ni2+
Received in revised form 22 April 2015 from aqueous solutions. The effects of pH, ionic strength, contact time, metal ion concentration and cycle
Accepted 24 April 2015
time on Cu2+ , Cd2+ and Ni2+ sorption were investigated. The results indicated that the adsorption of Cu2+ ,
Available online 25 April 2015
Cd2+ and Ni2+ onto GO membranes was greatly influenced by the pH and weakly affected by the ionic
strength. The adsorption isotherms for Cu2+ , Cd2+ and Ni2+ were well fitted by the Langmuir model. The
Keywords:
maximum adsorption capacities of the GO membranes for Cu2+ , Cd2+ and Ni2+ were approximately 72.6,
Graphene oxide membrane
Adsorption
83.8 and 62.3 mg/g, respectively. The adsorption kinetics of Cu2+ , Cd2+ and Ni2+ onto GO membranes fol-
Self-assembly lowed the pseudo-second-order model. The adsorption equilibrium was reached in a shorter time. The
Heavy metal ion GO membranes can be regenerated more than six times based on their adsorption/desorption cycles,
with a slight loss in the adsorption capacity. The results demonstrated that the GO membranes can be
used as effective adsorbents for heavy metal removal from water.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction metals from aqueous solutions due to its simplicity, flexibility and
high efficiency in industrial applications [1]. An ideal adsorbent
Heavy metal ions, such as Cu2+ , Cd2+ and Ni2+ , are the most should have a stable and insoluble matrix that offers abundant
common toxic pollutants found in industrial effluents and have binding sites for the adsorption of heavy metal ions [2]. Nano-
been a serious, rising problem worldwide. It is necessary to effec- materials have attracted a large amount of attention and research
tively remove toxic heavy metal ions from industrial effluents interest due to their larger specific surface areas and abundant
before releasing them into the environment. Adsorption is regarded active groups. So far, many carbon nanomaterials, such as carbon
as one of the most promising methods for the removal of toxic nanotubes [3] and graphene [4–7], have been used for fabricating
adsorbents to remove various organic pollutants and heavy metals
from wastewater.
Recently, graphene oxide (GO) has attracted a large amount
∗ Corresponding author at: School of Environment and Energy, South China
of attention due to its strong mechanical strength and high sur-
University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou
face area [8], which has led to many applications in reinforced
510006, China. Tel.: +86 20 39380506; fax: +86 20 39380508.
E-mail address: ppyyhu@scut.edu.cn (Y. Hu). materials [9,10]. Besides, oxygen-containing functional groups

http://dx.doi.org/10.1016/j.jhazmat.2015.04.068
0304-3894/© 2015 Elsevier B.V. All rights reserved.
252 P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260

on the GO surface and -electron system [11] offer abundant CuSO4 × 5H2 O, NiCl2 × 6H2 O and CdCl2 × 2.5H2 O were provided by
binding sites for the adsorption of heavy metals. The effective- Sinopharm Chemical Reagent Co., Ltd. All other chemicals were
ness of GO has been demonstrated for the removal of heavy obtained as analytical grade products and were used without fur-
metals from wastewater [12–15]. However, GO sheets tend to ther purification.
aggregate after adsorption due to the decreased electrostatic
repulsion between oxygen-containing groups [16]. In addition, 2.2. Preparation of GO and composite GO membranes
separating and recycling GO sheets after adsorption is very dif-
ficult due to its nanometer-sized volume. To promote phase GO was synthesized from purified natural graphite using mod-
separation and improve the adsorption efficiency, chemical meth- ified Hummer’s method [40]. Graphite (4 g) and NaNO3 (4 g) were
ods have been used to synthesize separable graphene-based mixed in 300 mL of H2 SO4 (95%) in a flask at ice temperature
composites, including magnetic graphene composites [17,18], GO- (0–5 ◦ C). KMnO4 (18 g) was slowly added to the suspension under
EDTA [19,20], GO-coated sand [21], polypyrrole-reduced graphene stirring. The rate of addition was carefully controlled to keep
oxide composites [22,23], porous chitosan-gelatin/graphene oxide the reaction temperature below 10 ◦ C. Then, the temperature was
monoliths [24], PD/GO composites [25], CS/GO-SH composites [26], increased to 25 ◦ C and maintained for 5 d under continuous stirring.
poly(N-vinylcarbazole)-graphene oxide composites [27] and other Next, 200 mL of distilled water was slowly added to the mixture,
composite materials [28–31]. However, these composites are unfit and the reaction temperature was controlled at 97–99 ◦ C. After 2 h,
to be industrialized because of their relatively poor stability or the temperature was reduced to 60 ◦ C. This mixture was diluted by
high cost. Furthermore, chemical methods generally involve com- adding 500 ml of distilled water and was finally treated with 12 ml
plex synthesis procedures and confront the potential risk that toxic of H2 O2 (30 wt%). Then, the mixture was repeatedly centrifuged
substances and organic solvents could leak. Therefore, it is neces- and washed several times with a 5% HCl aqueous solution to remove
sary to seek a simple and green method for preparing separable metal ions. Then, the mixture was washed with distilled water until
graphene-based composites. the solution was neutralized. The GO sample was obtained after
GO laminates have gained considerable attention due to their drying.
strong mechanical properties and easy industrial production [32]. The synthesis procedure of GO membranes was as follows: GO
GO sheets can be assembled to form GO membranes [33,34] was dispersed in distilled water in an ultrasonic bath for 30 min to
under vacuum filtration-induced directional flow. These mate- obtain a 5 mg/mL colloidal solution. PVA was dissolved in distilled
rials have shown many applications in separation [35,36] and water at 95 ◦ C to yield a 0.2 wt% solution. Then, the PVA solution was
super-capacitors [37]. Considering the oxygen-containing func- gradually added to the GO dispersion. The content of each mixture
tional groups on the GO membranes, the GO membranes should component was controlled by adjusting the volume ratio of GO to
have high adsorption capacity in the preconcentration of heavy PVA(VGO :VPVA = 1:0, 1:1, 1:2, 1:3, 1:4, 1:5). The mixture was soni-
metal ions from aqueous solutions. However, the application of cated for 60 min to obtain a uniform dispersion. This homogeneous
GO membranes as adsorbents in the removal of metal ions from GO/PVA solution was poured into a vacuum filter equipped with a
aqueous solution is still scarce. In addition, it was reported that the 0.22 ␮m porous polytetrafluoroethylene (PTFE) membrane and fil-
oxygen-containing functional groups on the GO surfaces can form tered to produce a composite membrane. A series of GO membranes
strong hydrogen bonding with hydroxy groups on the PVA chains with different PVA loading amounts were similarly prepared. The
[38,39]. Therefore, we assume that if the appropriate amount of GO membranes were dried under a vacuum for 12 h at 50 ◦ C and
PVA attaches to the interlamination of GO membranes, it can effec- were broken into several small pieces.
tively prevent their aggregation due to the effective support of PVA,
which should enhance the adsorption capacity of the GO mem- 2.3. Characterization
branes. In contrast, if the excessive amounts of PVA could cover
a large number of adsorption sites, the adsorption capacity of GO Scanning electron micrographs (SEM) were obtained using a
membranes should decrease. Moreover, GO membranes are use- FEI Sirion 200 scanning electron microscope. Transmission electron
ful for facilitating phase separation and improving the adsorption microscope (TEM) images were obtained using a JEM-2010 micro-
efficiency. Therefore, GO membranes could be an effective adsor- scope. Fourier transform infrared (FT-IR) spectra were measured
bent for the removal of heavy metals. Based on the considerations using a Nicolet 5700 spectrometer by incorporating the sample in
mentioned above, highly ordered GO membranes with PVA were a KBr disk. Raman spectra were recorded on a Renishaw Raman
prepared by vacuum filtration-induced directional flow for the pur- spectrometer with a 514 nm laser at a power of 4.7 mW. X-ray
pose of removing heavy metal ions from aqueous solutions. In the diffractions (XRD) were obtained using a D8 Advance (Bruker) X-ray
GO membranes, GO sheets form a lamellar layer, and PVA acts as a diffractometer with Cu K˛ radiation ( = 1.5418 Å).
physical cross-linking agent and support pillar.
Consequently, the objectives of this study were to: (1) prepare 2.4. Adsorption experiments
GO membranes and apply them as sorbents to remove Cu2+ , Cd2+
and Ni2+ from aqueous solutions; (2) explore the effects of pH, ionic All of the experiments were conducted in triplicate using a batch
strength, contact time and metal ion concentration on Cu2+ , Cd2+ equilibration approach at a constant temperature (30 ◦ C), and the
and Ni2+ sorption as well as the possibility of reuse; and (3) dis- glass tubes containing the GO membranes and metal solution were
cuss the mechanism of Cu2+ , Cd2+ and Ni2+ interaction with GO shaken in a thermostatic shaker bath, operating at 200 rpm. The
membranes. This study could provide a theoretical basis for the batch experiments of Cu2+ , Cd2+ and Ni2+ sorption on GO mem-
application of GO membranes for the removal of heavy metal ions. branes were conducted by adding 4 mg of GO membranes to 20 mL
of Cu2+ , Cd2+ and Ni2+ solution (0.2 g/L) with 0.01 M NaCl in 25 mL
glass tubes sealed with screw caps. The initial concentrations of
2. Materials and methods three adsorbates were maintained at 20 mg/L. The initial pH of the
solution was adjusted from 2 to 7 by adding different concentra-
2.1. Materials tions of HCl or NaOH solutions (0.01–1.0 mol/L) to study the effect
of pH on adsorption. The effect of ionic strength on adsorption
Graphite flakes were purchased from Sigma–Aldrich. Poly(vinyl was investigated by varying the NaCl concentration from 0.001 to
alcohol) (PVA 1799) was obtained from Aladdin Industrial Inc. 0.2 M. The adsorption kinetics study was performed by sampling a
P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260 253

Fig. 1. Effect of the PVA content on the adsorption capacity. (Ci = 50 mg/g, m/V = 0.2 g/L, T = 303 K, pH 5.7, I = 0.01 M NaCl).

certain volume of solution at various time intervals. The concentra- excessive or slight amount of PVA because some of the adsorp-
tion of the solution was analyzed for adsorption kinetics analysis. tive sites on the GO membranes would be occupied. Therefore, it
The effect of the metal ion concentration on the uptake capacities is necessary to optimize the loading of PVA on the GO membranes.
of the GO membranes was examined by varying the initial con- To eliminate the interference of other factors, at an early stage, PVA
centrations of the three metal ions from 5 to 100 mg/L to obtain was investigated as an adsorbent for the removal of Cu2+ , Cd2+ and
adsorption isotherms. The concentrations of Cu2+ , Cd2+ and Ni2+ Ni2+ , and the results showed that PVA has only a slight adsorp-
were determined using an atomic absorption spectrophotometer tion capacity for metal ions (1.2 mg/g for Cu2+ , 1.7 mg/g for Cd2+
(AAS). The amounts of Cu2+ , Cd2+ and Ni2+ ions adsorbed on the GO and 0.8 mg/g for Ni2+ ). Different GO membranes loaded with PVA
membranes were calculated as the difference between the initial were prepared by varying the volume of the PVA solution (0, 6,
and final concentration. The adsorption capacities were obtained 12, 18, 24, 30 ml) while keeping the volume of the GO dispersion
according to the following equation: (6 ml) constant. The resulting adsorbents were denoted as GOM1:0 ,
(Ci −Cj )Vm
GOM1:1 , GOM1:2 , GOM1:3 , GOM1:4 and GOM1:5 , respectively. Fig. 1
q= Mads shows the effect of the PVA content on the adsorption capacity
for Cu2+ , Cd2+ and Ni2+ . The results indicate that the adsorption
where q (mg/g) is the adsorption capacity, Ci (mg/L) is the initial capacity of the GO membranes for Cu2+ , Cd2+ and Ni2+ markedly
metal ion concentration, Cj (mg/L) is the final metal ion concentra- increased from GOM1:0 to GOM1:3 . The results can be attributed to
tion, Vm (L) is the volume of the metal ion solution, and Mads (g) is an increase in the effective adsorptive sites that might be caused by
the mass of adsorbent. a change in the interlayer spacing. However, the adsorption capac-
ity of GOM1:4 and GOM1:5 decreased with further addition of the
2.5. Desorption experiments PVA content, which is consistent with our previous assumptions.
This decrease might be attributed to the decrease in the effective
The GO membranes were added to 20 mL of 50 mg/L Cu2+ , adsorption sites that were covered by PVA. Therefore, GOM1:3 was
Cd2+ or Ni2+ solutions and stirred for 1 h. The Cu2+ , Cd2+ and Ni2+ selected as a model for further investigation. The GO membranes
adsorbed GO membranes were collected, thoroughly rinsed with mentioned below refer to GOM1:3 .
distilled water and dried under a vacuum. Then, they were placed
in 50 mL of a 1 mol/L hydrochloric acid solution under stirring
for desorption. When the metal ions were completely desorbed 3.2. Characterization
from the GO membranes, they were removed from the acid solu-
tion, thoroughly rinsed with water and dried in a freeze drier. A digital photograph of a GO membrane is shown in Fig. 2a.
The regenerated GO membranes were then used for repeated Clearly, a high-quality, flexible membrane was obtained. The TEM
adsorption/desorption cycles as described above to study their image of the obtained GO nanosheets is shown in Fig. 2b. Few-
recyclability. layered GO nanosheets with few wrinkles were also synthesized
successfully. The SEM images of the surface and fracture edges
3. Results and discussion of the GO membrane are shown in Fig. 2c and d. Fig. 2c clearly
reveals that the GO membrane has a relatively smooth surface and
3.1. Optimization of the GO/PVA ratio large lateral dimension. The fracture edges image, shown in Fig. 2d,
exhibits a well-ordered layered structure throughout the entire
The amount of PVA anchored on the interlamination of the cross-section of the GO membrane, which is probably caused by the
GO membranes is a crucial factor in determining the adsorption directional flow induced during vacuum filtration. The thickness of
capacity of the heavy metal ions by the GO membranes. The adsorp- the entire cross-section can be precisely controlled by adjusting the
tion capacity of the GO membranes for Cu2+ , Cd2+ and Ni2+ would volume of the mixed dispersions.
increase under the addition of a moderate amount of PVA, which Fig. 3 illustrates the X-ray diffraction (XRD) patterns of pure
can act as a cross-linking agent and support pillar. In contrast, a PVA, GO and the GO membrane. Pure PVA exhibits a character-
lower adsorption capacity would occur under the addition of an istic diffraction peak at 2 = 19.6◦ , which results from its (1 0 1)
254 P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260

Fig. 2. (a) Photograph of the GO membrane. (b) TEM image of GO. (3) SEM image of the surface of the GO membrane. (d) SEM image of the cross-section of the GO membrane.

GO membrane and the crystalline structure of the GO membrane


was slightly affected by the incorporation of the PVA component.
The Raman spectrum of PVA, GO and the GO membrane are
shown in Fig. 4. The spectrum of PVA shows a band at 2908 cm−1 .
The Raman spectrum of GO shows a G-band at ∼1590 cm−1 and a
D-band at ∼1340 cm−1 . The G-band is associated with the vibra-
tion of sp2 carbon atoms, and the D-band is related to the vibration
of sp3 defective or out-of-order graphitic carbon atoms. Compared
with GO, both G and D bands of the GO membrane are in accor-
dance with the spectral signature of GO, which indicates that the

Fig. 3. XRD patterns of pure PVA, GO and the GO membrane.

crystal planes. The diffraction peak of GO was found at approxi-


mately 2 = 10.41, which corresponds to the layer-to-layer distance
(d-spacing) of 0.84 nm. The diffraction peak of the GO membrane
appeared at 2 = 7.87, which corresponds to a d-spacing of 1.13 nm.
The d-spacing was significantly enlarged after PVA was anchored
on the GO membrane, which is favorable for exposing more adsorp-
tion sites and promoting the diffusion of metal ions. Moreover, the
tiny diffraction peak at 2 = 19.6◦ from PVA appears in the GO mem-
brane. The result indicates that PVA was uniformly dispersed in the Fig. 4. Raman spectrum of pure PVA, GO and the GO membrane.
P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260 255

Fig. 6. Adsorption of metal ions onto GO membranes as a function of pH.


Fig. 5. FTIR spectra of GO and the GO membrane.

Ni(OH)2 were 6.0 × 10−20 , 7.2 × 10−15 [43] and 2.0 × 10−15 , respec-
addition of PVA caused negligible impact on the structure of GO. In tively. The calculated maximum pH values for Cu2+ , Cd2+ or Ni2+
addition, the band at 2908 cm−1 from PVA is not observed in the GO were 6.0, 8.6 and 8.4, respectively. Therefore, Cu2+ started to pre-
membrane. The reason could be that PVA was uniformly dispersed cipitate above pH 6, and the GO membranes were responsible for
in the GO membrane. the adsorption of Cu2+ when the pH was less than 6. However, no
The FTIR spectra of GO and the GO membrane are shown in precipitation of Cd2+ and Ni2+ occurred, and all of the removed Cd2+
Fig. 5. The characteristic peaks of GO appear at 3407 cm−1 ( OH), and Ni2+ were adsorbed onto GO membranes under the given pH
1731 cm−1 (C O in the carboxyl group), 1401 cm−1 (C O in the car- values. To ensure that the three types of metal ions were completely
boxyl group), 1228 cm−1 (C O in the epoxide group) and 1080 cm−1 adsorbed, the pH 5.7 ± 0.1 was selected for Cd2+ , Cu2+ , and Ni2+ for
(C O in the alkoxy group), which indicate the existence of abundant further investigation of heavy metal removal to avoid heavy metal
oxygen-containing functional groups in GO. While in the spec- precipitation conditions.
trum of the GO membrane, the peak for hydroxyl and carboxyl
group stretching shifted from 3407 and 1731 cm−1 in GO to the 3.4. Effect of ionic strength on adsorption
lower wave numbers of 3394 and 1728 cm−1 in the GO membrane,
respectively. These results indicate that there are strong molecu- To assess the influence of ionic strength on the removal of
lar interactions between PVA and GO, which are mainly attributed Cu2+ ,Cd2+ and Ni2+ by GO membranes, adsorption experiments
to hydrogen bonding between the oxygen-containing groups on were designed to examine the adsorption efficiency in the pres-
GO and the hydroxyl groups on PVA chains [9,10,41]. The oxygen- ence of sodium ion. The adsorption capacity of three metal ions
containing groups of the GO membrane offer abundant binding on GO membranes in the presence of different ionic strengths
sites for the adsorption of metal ions. Furthermore, these groups were observed, as shown in Fig. 7. There was a weak reduc-
are favorable for facilitating interstitial diffusion of metal ions to tion in the amount of Cu2+ , Cd2+ and Ni2+ adsorbed onto the GO
GO membranes due to their hydrophilicity and water permeability
[42].

3.3. Effect of pH on adsorption

Fig. 6 shows Cu2+ , Cd2+ and Ni2+ sorption on the GO membranes


as a function of pH. The adsorption capacities of the GO membranes
for Cd2+ , Cu2+ and Ni2+ were low at a lower pH and high at a larger
pH. At a lower pH, there is a competition between hydrogen ions
and metal ions for a limited number of binding sites, which would
decrease the sorption of Cd2+ , Cu2+ and Ni2+ . With an increase of the
pH value, the number of hydrogen ions decreased and the GO mem-
branes allowed more ligands to form complexes with Cd2+ , Cu2+ and
Ni2+ , which leads to the sorption of Cd2+ , Cu2+ and Ni2+ onto the GO
membranes. At a larger pH, the adsorption capacity of Cd2+ , Cu2+
and Ni2+ were higher, this higher capacity might be not only due
to the adsorption of Cd2+ , Cu2+ and Ni2+ onto GO membranes but
also due to the precipitation of metal hydroxides formed at higher
pH values. Therefore, solubility product constants (Ksp) and known
concentrations (20 mg/L for Cd2+ , 20 mg/L for Cu2+ , and 20 mg/L for
Ni2+ ) of the metal ion solutions for Cd2+ , Cu2+ , and Ni2+ were used
to calculate the maximum pH at which these ions will not occur Fig. 7. Effect of ionic strength on the adsorption of Cd2+ , Cu2+ and Ni2+ on GO mem-
as hydrolyzed species. The Ksp used for Cu(OH)2 , Cd(OH)2 , and branes.
256 P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260

Fig. 8. Langmuir (a) and Freundlich (b) isotherms for the adsorption of Cd2+ , Cu2+ and Ni2+ onto GO membranes. (m/V = 0.2 g/L, T = 303 K, pH 5.7, I = 0.01 M NaCl).

membranes with increasing sodium concentrations. As a general A linearized plot was obtained from the Langmuir and Fre-
rule, the influence of the ionic strength on the adsorption are mainly undlich models, as shown in Fig. 8. All of the Langmuir and
the following aspects: (1) the ionic species would compete with Freundlich isotherm parameters calculated from the slopes and
metal ions for a limited number of active sites on the surface of the intercepts of different straight lines representing the GO mem-
adsorbent and, based on their affinities between the ionic species branes with different heavy metals are listed in Table 1. It is clear
and the adsorbents, would reduce the sorption of the adsorbates; that the data obtained for the adsorption of Cd2+ , Cu2+ , and Ni2+ onto
(2) the ionic strength can impact particle aggregation by influenc- GO membranes are well fitted to the Langmuir model, which indi-
ing electrostatic interactions [44]; and (3) the ionic strength would cates that Cd2+ , Cu2+ , and Ni2+ on GO membranes are monolayer
affect the activity coefficient of the metal ions and thus limit the coverage. The Freundlich constant (1/n) is smaller than 1, which
metal ion transfer from the solution to solid surfaces [12]. On the indicates a favorable process [18]. The qm calculated from the Lang-
basis of the above theory and research results, it can be deduced muir model were determined to be 83.8 mg/L for Cd2+ , 72.6 mg/L
that sodium ions have a weak effect on Cu2+ ,Cd2+ and Ni2+ sorption for Cu2+ and 62.3 mg/L for Ni2+ . Otherwise, the adsorption capaci-
on GO membranes. ties of Cd2+ , Cu2+ , and Ni2+ onto other sorbents collected from the
references are listed in Table 2, and the comparative results show
3.5. Effect of metal ion concentration and adsorption isotherms that the GO membranes possess the highest sorption capacity. The
excellent adsorption ability of the GO membranes can be mainly
Adsorption isotherm models are often used to describe the attributed to the following factors: (1) there are abundant oxygen-
mechanism of adsorption. Both Langmuir [45] and Freundlich [46] containing functional groups on the surface and interlayer of the
isotherms were applied to analyze the experimental data of the GO membranes (FT-IR analysis) that can easily bind heavy metal
sorption of Cd2+ , Cu2+ , and Ni2+ onto GO membranes. The Langmuir ions; (2) the delocalized  electron systems of the GO membranes
isotherm is expressed as follows: act as the Lewis base and the heavy metal ions can act as the Lewis
acid. The delocalized  electron systems can form electron donor
qmax kL ce acceptor complexes with heavy metal ions through the Lewis acid
qe =
1 + kL ce base interaction [61]; (3) based on the result of XRD analysis, the
It can be expressed in a linear form: GO membranes possess a d-spacing of 1.13 nm, which can expose
more adsorption sites for the adsorption of heavy metals and a suf-
ce 1 ce ficiently large space for heavy metals to enter into the interlayer
= +
qe kL qmax qmax space of the GO membranes; and (4) the support effect of PVA can
effectively prevent aggregation, which is extremely favorable for
where qe (mg/g) is the equilibrium adsorption capacity; qmax (mg/g)
the adsorption of heavy metals.
is the maximum adsorption capacity corresponding to the complete
monolayer coverage; ce (mg/L) is the equilibrium concentration;
and kL (L/mg) is the constant related to the free energy of adsorp- 3.6. Effect of contact time and adsorption kinetics
tion. The values of qmax and kL can be derived from the slope and
intercept of ce /qe versus ce . Fig. 9 shows the adsorption data of Cd2+ , Cu2+ , and Ni2+ by
The Freundlich isotherm is represented by the following equa- GO membranes at different time intervals. The pseudo-first-order
tion:
Table 1
qe = kF (ce )1/n Parameters for the Langmuir and Freundlich models of Cu2+ , Cd2+ and Ni2+
adsorption.
It can be linearly expressed as follows:
Metal ion Langmuir Freundlich
log qe = log kF + (1/n) log ce
qmax (mg/g) KL (L/mg) R2 KF (mg/g(L/mg)1/n ) 1/n R2

where qe (mg/g) is the equilibrium adsorption capacity and KF and Cu2+ 72.6 0.289 0.999 24.19 0.2791 0.964
n are Freundlich constants related to the adsorption capacity and Cd2+ 83.8 0.478 0.997 34.65 0.2351 0.943
Ni2+ 62.3 0.185 0.995 8.9 0.5162 0.948
adsorption intensity, respectively. The values of KF and n can be
obtained from the slope and intercept of logqe versus logce . *
m/V = 0.2 g/L; T = 303 K; pH 5.7 ± 0.1; I = 0.01 M NaCl.
P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260 257

Table 2
Comparison of the maximum adsorption capacity of Cu2+ , Cd2+ and Ni2+ on various adsorbents.

Adsorbent Metal ions Conditions qm (mg/g) References

Oxidized CNT Cd2+ pH 5.5 11 [47]


T = 298 K
Multiwalled CNT Cd2+ pH 5.0 10.9 [48]
T = 298 K
CEMNPs Cd2+ pH 9.0 1.8 [49]
T = 298 K
PD/GO composites Cd2+ pH 5.7 33.3 [25]
T = 298 K
GNSPF6 Cd2+ pH 6.2 73.4 [5]
T = 298 K
Carbon aerogel Cd2+ pH 6.0 15.5 [50]
T = 333 K
GO membranes Cd2+ pH 5.8 83.8 This study
T = 303 K
MWCNT Cu 2+ pH 5.0 24.5 [48]
T = 298 K
Graphene oxide Cu2+ pH 5.0 46.6 [16]
T = 298 K
GO-PAMAM Cu2+ pH 5.6 38.4 [51]
T = 298 K
GO aerogel Cu2+ pH 6.3 19.7 [42]
T = 298 K
GO–CS aerogel Cu2+ pH 6.0 25.4 [52]
T = 303 K
CEMNPs Cu2+ pH 9.0 3.2 [49]
T = 298 K
GO–CS hydrogels Cu2+ pH 5.1 70 [53]
T = 295 K
PD/GO composites Cu 2+ pH 6.0 24.4 [25]
T = 298 K
S-MWCNTs Cu2+ pH 5.0 43.2 [54]
T = 298 K
CSGO Cu2+ pH 6.3 53.7 [55]
T = 298 K
GO membranes Cu2+ pH 5.8 72.6 This study
T = 303 K
GNS/MnO2 Ni2+ pH 5.8 46.6 [56]
T = 298 K
Oxidized MWCNT Ni2+ pH 5.4 7.6 [57]
T = 293 K
Hydrous titanium(IV) Ni2+ pH 5.0 22.1 [58]
oxide T = 303 K
NaClO-modified Ni 2+ pH 5.0 47.8 [59]
SWCNTs T = 298 K
SDBS + MWCNTs Ni2+ pH 5.5 10.9 [60]
T = 293 K
GO membranes Ni2+ pH 5.8 62.3 This study
T = 303 K

Table 3
Parameters for the pseudo-first-order and pseudo second-order models of Cu2+ , Cd2+ and Ni2+ adsorptiongr.

Metal ion Pseudo-first-order Pseudo second-order

qe (cal) K1 R2 qe (cal) K2 R2 qe (exp)


(mg/g) (1/min) (mg/g) (g/mg min) (mg/g)

Cu2+ 30.38 0.20487 0.9489 56.7 0.01545 0.9997 55.9


Cd2+ 42.8 0.3114 0.9782 65.8 0.0179 0.9998 64.6
Ni2+ 25.89 0.1295 0.9451 49.2 0.0105 0.9994 48.0
*
Ci = 20 mg/L; m/V = 0.2 g/L; T = 303 K; pH 5.7 ± 0.1; I = 0.01 M NaCl.Ci

kinetic model [62], pseudo-second-order kinetic model [63] and where qe and qt (mg/g) are the adsorption capacities at equilibrium
intra-particle diffusion [64] were employed to fit the experimental time and time t, respectively. Here, k1 (1/min) is the pseudo-first-
data. The pseudo-first-order kinetic rate equation is expressed as order rate constant, and k1 and qe can be obtained from the slope
follows: and intercept of log(qe − qt ) versus t, respectively.
The pseudo-second-order kinetic rate equation is expressed as
dqt
= k1 (qe − qt ) follows:
dt

It can also be expressed as follows:


dqt
= k2 (qe − qt )2
log(qe − qt ) = logqe − k1 t dt
258 P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260

Table 4
Parameters of intra-particle diffusion model for Cu2+ , Cd2+ and Ni2+ adsorption.

Metal ion kp1 kp2 C1 C2 (R1 )2 (R2 )2


(mg/g min1/2 ) (mg/g min1/2 )

Cu2+ 13.411 0.265 13.413 54.059 0.922 0.945


Cd2+ 16.128 0.449 17.517 62.433 0.919 0.969
Ni2+ 9.244 0.402 12.469 46.08 0.918 0.947

the overall rates of the adsorption of Cd2+ , Cu2+ and Ni2+ onto GO
membranes are controlled by chemical adsorption.
In addition, the intra-particle diffusion model is expressed as
follows:

qt = kdi t 1/2 + Ci

where kdi (mg/g min 1/2) is the intra-particle diffusion rate constant
of stage i. Ci (mg/g) is the intercept of stage i. The values of kdi and
Ci can be obtained from the slope and intercept of qt versus t1/2 ,
Fig. 9. Effect of contact time on the adsorption of Cd2+ , Cu2+ and Ni2+ onto GO respectively.
membranes.
The plot of qt versus t1/2 for Cu2+ , Cd2+ and Ni2+ onto GO
membranes is shown in Fig. 11. To follow the intra-particle dif-
fusion model, the experimental data points are related by two
It can also be expressed as follows:
straight lines. The first sharper portion is attributed to the diffu-
t 1 t sion of adsorbate through the solution to the interface space of
= + the adsorbent (external diffusion). The second portion describes
qt k2 qe 2 qe
the gradual adsorption stage, corresponding to the diffusion of
where k2 (g/(mg min)) is the pseudo-second-order rate constant. adsorbate molecules inside the pore of the adsorbent (intra-particle
The values of qe and k2 can be obtained from the slope and intercept diffusion). The intra-particle diffusion model parameters of the two
of t/qt versus t, respectively. portions are summarized in Table 4. The intra-particle diffusion
Fig. 9 shows the adsorption rates of the three metal ions rate constant (kd1 ) for the first sharper portion is higher than that
occurred very fast initially, with most of the heavy metal ions being (kd2 ) for the second portion, and C1 is smaller than C2 , which indi-
removed within 10 min. This phenomenon could be due to the cates that the rate of Cu2+ , Cd2+ and Ni2+ removal were higher in
strong attractive forces between heavy metal ions and the sor- the beginning. As the adsorption of adsorbent gradually attained
bent [5,12,65], which lead to fast diffusion of heavy metal ions equilibrium, the rate of adsorption was controlled by intra-particle
into the interlayer space of the membrane to reach equilibrium. diffusion. Moreover, none of the plots passed through the origin,
The adsorption rate gradually decreased with contact time, and which indicate that the intra-particle diffusion was part of the
remained nearly constant after 15 min. The results indicate that the adsorption but was not the only rate-controlling step [42,66].
diffusion rate of the metal ions onto the GO membranes would not
be controlled due to the large interlayer spacing of the membrane. 3.7. Desorption and reuse studies
The linear fitting results of the two models are shown in Fig. 10,
and the kinetic model parameters calculated from the slope and An ideal adsorbent should show better desorption performance
intercept of each linear plot are summarized in Table 3. The correla- in addition to the higher adsorption capacity, which would sig-
tion coefficients (R2 ) for the pseudo-second-order kinetic model are nificantly enhance the efficiency of the adsorbent and reduce the
higher than those for the pseudo-first-order kinetic model, and the overall cost. Therefore, the adsorption capability of the eluting
qe values calculated from the pseudo-second-order kinetic model GO membranes was investigated by immersing the regenerated
are very close to the experimental ones. These results suggest that GO membranes in metal ion solution with known concentrations.

Fig. 10. Pseudo-first-order (a) and pseudo-second-order (b) models for Cu2+ , Cd2+ and Ni2+ adsorption onto GO membranes.
P. Tan et al. / Journal of Hazardous Materials 297 (2015) 251–260 259

and weakly affected by the ionic strength. The equilibrium adsorp-


tion data were well fitted with Langmuir isotherms. The maximum
adsorption capacities of the GO membranes for Cu2+ , Cd2+ and Ni2+
were approximately 72.6 mg/g, 83.8 mg/g and 62.3 mg/g, respec-
tively. The adsorption processes reached an equilibrium state in a
shorter amount of time due to a larger interlayer spacing of the
GO membranes, which is favorable for facilitating the interstitial
diffusion of heavy metal ions to active sites. The adsorption fol-
lowed the pseudo second-order kinetic model. The GO membranes
can be regenerated more than six times based on their adsorp-
tion/desorption cycles with a slight loss in the adsorption capacity.
This research demonstrates that GO membranes can be used as
rapid and efficient adsorbents for the removal of toxic heavy metal
ions from aqueous solution.

Acknowledgment

The authors gratefully acknowledge the financial support pro-


vided by the National Natural Science Fund of China (Foundation
of Guangdong Province of China; No. U1401235).
Fig. 11. Intra-particle diffusion model for the Cd2+ , Cu2+ and Ni2+ adsorption onto
GO membranes.
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