Journal of Solid State Chemistry 302 (2021) 122406

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Journal of Solid State Chemistry

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Removal of Cu (II) from aqueous solutions using ZIF-8@GO composites

Dan Li a, Feigao Xu b, *
a
Key Laboratory of Poyang Lake Environment and Resource Utilization, Ministry of Education, School of Resources Environmental & Chemical Engineering, Nanchang
University, Nanchang, 330031, PR China
b
College of Chemistry, Nanchang University, Nanchang, 330031, PR China

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

Keywords: ZIF-8@GO-X (X ¼ 0, 2.48%, 4.07%, 7.83%, and 20.03%) composites were prepared using GO and ZIF-8. The
Adsorption composites were used to absorb Cu(II) from aqueous solutions. With increasing GO content, the adsorption of the
GO ZIF-8@GO-X composites first increased and then decreased. The Cu(II) adsorption of ZIF-8@GO-7.83% reaches a
ZIF-8@GO
maximum among ZIF-8@GO-X composites (X ¼ 0, 2.48%, 4.07%, 7.83%, and 20.03%). The adsorption kinetics,
adsorption isotherm, adsorption thermodynamics, and adsorption mechanism of Cu (II) by ZIF-8@GO-7.83%
were studied in this paper. The results showed that the adsorption reached equilibrium at 120 min, and ZIF-
8@GO-7.83% approached equilibrium relatively quickly. When the temperature was 45  C and the Cu(II) con-
centration was 40 mg/L, the maximum adsorption capacity of ZIF-8@GO-7.83% for Cu(II) reached 482.29 mg/g.
The equilibrium data and kinetics were well described by Langmuir and pseudo-first-order models, respectively.
Final experiments with real factory wastewater (initial Cu(II) concentration of 670 mg/L) revealed that 0.37 g/L
ZIF-8@GO-7.83% can efficiently reduce the Cu(II) concentration to below 2 mg/L.

1. Introduction
Currently, the problem of water pollution is becoming increasingly
severe, and water pollution has become one of the main concerns in
environmental pollution. The existence of heavy metals in water bodies is
currently one of the issues that need to be solved. Toxic heavy metals in
water bodies are present and not biodegradable and will continue to
accumulate and stay in the body tissues, ultimately endangering human
health [1]. Copper-containing wastewater must be treated to reduce its
concentration before being discharged. The World Health Organization
stipulates that the copper ion content in drinking water should not
exceed 2 mg/L [2–4]. In recent years, there have been various treatment
methods for copper-containing wastewater including adsorption [5–8],
membrane filtration [9–11], and photocatalysis [12–14]. Among these
treatment methods, the most widely used method is adsorption, which
has the advantages of low cost, good removal effect, and environmental
friendliness.
Commonly used adsorbents include activated carbon [15,16], chito-
san [17–19], silica [20], hydroxyapatite [21,22], and graphene oxide
(GO) [23–25]. These materials still have shortcomings to a certain extent,
which limits the use of the adsorbents. GO has a unique two-dimensional
nanosheet structure and a large specific surface area (theoretical value of
2620 m2/g) [26]. GO is water soluble with low conductivity, and its
surface is rich in oxygen-containing functional groups (hydroxyl,
carboxyl, epoxy, and other hydrophilic functional groups). GO has a
special electronic structure and a special surface structural features and
other advantages, which give GO have obvious advantages in adsorbing
heavy metal ions. However, GO as a separate adsorbent still has some
shortcomings, such as slightly higher preparation cost and longer cycle,
with insufficient separation and recovery capacity. To overcome these
shortcomings, an increasing number of scholars have begun to study the
modification of GO. For example, GO can be compounded with other
substances to reduce costs while improving removability.
Metal-organic frameworks (MOFs) are formed by connecting metal-
containing units with organic linkers and using strong bonds (network
synthesis). MOF materials not only have the rigidity of organic materials,
but also have the flexibility of organic materials. They have superior
comprehensive performance and can be widely used in various fields
[27–29]. MOFs have an open frame structure with permanent porosity,
so we think MOFs are suitable for fixing materials to synthesize more
efficient adsorption materials. The advantages of MOFs are not limited to
their pore structure and functional characteristics. Studies have shown
that the morphology of nanocrystals can be controlled by adjusting the
synthesis conditions.

* Corresponding author.
E-mail address: Xufeigao@ncu.edu.cn (F. Xu).

https://doi.org/10.1016/j.jssc.2021.122406
Received 14 May 2021; Received in revised form 27 June 2021; Accepted 1 July 2021
Available online 2 July 2021
0022-4596/© 2021 Elsevier Inc. All rights reserved.
D. Li, F. Xu
Recently, zeolitic imidazolate frameworks (ZIFs), a subfamily of
MOFs, have attracted increasing attention. ZIFs are prepared by imid-
azole or imidazole derivatives as organic ligands and Zn or Co used as
metal sources to react in a solvent to generate MOF materials with a
zeolite framework structure. The framework of ZIFs contains regular
pores and channels, and guest molecules are allowed to enter, and pro-
vide good conditions for preparing composite materials [30,31]. Among
these composite materials, ZIF-8 is a typical representative of ZIFs ma-
terial, which is a kind of albite zeolite with a nanoporous structure. ZIF-8
nanoparticles and GO can be linked by the hydrogen bonding, ionic
bonding, and coordination bonding interactions. Recently, ZIF-8@GO
composites were prepared for gas separation, pervaporation application
and wastewater treatment [32,33]. The adsorption of Pb2þ and dye on
ZIF-8@GO had been demonstrated to be attributed mainly to surface
complexation, electrostatic attraction, and the π-π interactions. There-
fore, we speculated that the ZIF-8@GO could also be used as an efficient
adsorbent for the removal of Cu(II) from aqueous solutions.
In this experiment, ZIF-8@GO-X composites were synthesized and
characterized. The adsorption properties of ZIF-8@GO-X composites for
Cu(II) were estimated, and the difference in the adsorption effect of
products with different ratios of GO was compared. The effects of
aqueous solution pH, adsorption time, and temperature on the adsorption
of Cu(II) by ZIF-8@GO composites were discussed. Furthermore, the
mechanism of Cu(II) removal from aqueous solution by ZIF-8@GO
composites was proposed. Finally, real factory wastewater treatment
experiments were performed.
2. Experimental section
2.1. Materials
All chemicals, including graphite powder, H2SO4 (98% w/w), po-
tassium sulfate, P2O5, NaNO3, KMnO4, H2O2, 2-methylimidazole
(C4H6N2), zinc nitrate hexahydrate (Zn(NO3)2⋅6H2O), and methanol
employed in the experiments were obtained from Shanghai Aladdin
Chemical Reagent Corporation (Shanghai, China). All chemicals were of
analytical grade and used without further purification. All water used
was ultrapure water (resistivity18 MΩcm).
2.2. Synthesis of GO
GO was synthesized by the modified Hummers' method. First, 3 g
graphite powder, 2.5 g K2S2O8 and 2.5 g P2O5 were added to 12 mL
H2SO4 (98% w/w) under vigorous stirring for 5 h at 80  C. Then, 500 mL
of deionized water was added to the mixture. After filtering, the mixture
was dried under natural conditions to complete the preoxidation step.
In the second oxidation step, 3.0 g preoxidized graphite and 1.5 g
NaNO3 were added to 70 mL H2SO4 (98% w/w), and the mixture was
vigorously stirred under ice bath conditions. Then, 9.0 g KMnO4 was
slowly added to the mixture. The temperature of the system was quickly
increased to 35~40  C and maintained for 30 min. Then 50 mL of water
was added to the mixture, and the temperature of the mixture was raised
to 98  C, and the mixture was stirred for 15 min. Finally, 170 mL H2O and
40 mL H2O2 (30% w/w) were added to the system to terminate the re-
action. After cooling under natural conditions, the mixture was centri-
fuged for 10 min, and washed with 10% HCl to remove metal ions, and
then repeatedly washed the residual acid with water to pH ¼ 5 to obtain a
GO suspension. GO suspension was dried in an oven at 60  C to obtain GO
powder.
2.3. Synthesis of ZIF-8@GO composites
The ZIF-8@GO composites were prepared according to Ref. [33]. The
procedure was mainly divided into four main parts. First, GO was added
2
Journal of Solid State Chemistry 302 (2021) 122406
to a methanol solution with a volume ratio of 9:1, then, 0.811 g of
2-methylimidazole (C4H6N2) was dissolved in 25 mL of methanol, and
the GO suspension was added to the 2-methylimidazole solution. Then,
0.366 g Zn(NO3)2⋅6H2O was dissolved in 25 mL methanol, and stirred at
room temperature for 3 h. Then the mixture was centrifuged for 15 min,
and washed with methanol for 3 times, and finally dried in a vacuum
drying oven for 12 h. The final product ZIF-8@GO was prepared. The
composites obtained were designated ZIF-8@GO-X, where X was the GO
content (wt%) in the synthesis process of ZIF-8@GO composite. The X
value was calculated as follows:
mGO
X¼ (1)
mGO þ mZnðNO3 Þ2 þ mC4 H6 N2
where mGO (g), mZnðNO3 Þ2 (g), and mC4 H6 N2 (g) are the weight of reactant,
respectively.
We prepared ZIF-8@GO, ZIF-8@GO-2.48%, ZIF-8@GO-4.07%, ZIF-
8@GO-7.83%, and ZIF-8@GO-20.03% (X ¼ 0, 2.28%, 4.07%, 7.83%, and
20.03%) to compare the difference in the adsorption effect of products
with different ratios of GO.
2.4. Removal of Cu (II) ions from aqueous solutions
This experiment used the controlled variable method to analyse the
influence of different factors on the adsorption experiment. We designed
different variables including initial Cu(II) concentration (20~50 mg/L),
reaction time (5~120 min), temperature (25~45  C), pH (3~8) and ZIF-
8@GO-X (Table .1). For Cu(II) adsorption measurements, 10 mg of ZIF-
8@GO-X was added to 100 mL of Cu(II) solution. The mixture was
shaken for 120 min, and then the supernatant was separated by filtration
through a 0.22 μm polyethersulfone membrane. The Cu (II) concentra-
tion in solution was measured according to a previously described
method [8].
2.5. Apparatus and instrumentation
The chemical bonds of the GO, ZIF-8 and ZIF-8@GO-X (X ¼ 0, 2.28%,
4.07%, 7.83%, and 20.03%) were analysed by Fourier transform infrared
spectrophotometry (FTIR). The spectra of the materials were recorded
using an FTIR spectrometer (Nicolet 5700, USA) over a spectral range of
4000 to 400 cm1.
X-ray diffraction (XRD) patterns of the GO and ZIF-8@GO-X (X ¼ 0,
2.28%, 4.07%, 7.83%, and 20.03%) were obtained using a diffractometer
(D8 ADVANCE, Germany) at a scan rate of 3 min1 over a scan range of
2 –80 .
The structural properties of the GO and ZIF-8@GO-X (X ¼ 0, 2.28%,
4.07%, 7.83%, and 20.03%) were analysed by a physical adsorption
analyser (ASAP-2020, USA). The samples were degassed at 200  C for 5 h
under high vacuum. The specific surface area was calculated by the BET
method. The total pore volume was obtained from the amount of vapor
adsorbed when the relative pressure (P/P0) was close to 1, where P and
P0 are the measured and equilibrium pressures, respectively. The pore
size distribution was evaluated from the desorption curve of the isotherm
using the Barrett-Joyner-Halenda method (BJH).
A differential thermal analysis system (TGA 4000) was used to
determine the stability performance of GO and ZIF-8@GO-X (X ¼ 0,
2.28%, 4.07%, 7.83%, and 20.03%) with a heating rate of 10  C/min in a
nitrogen environment.
XPS (ESCALAB25OXi) was used to determine the peak positions of
different elements in the material and the relative intensity of each peak.
The palladium-gold alloy was separately vacuum evaporated onto the
GO and ZIF-8@GO-X (X ¼ 0, 2.28%, 4.07%, 7.83%, and 20.03%) sam-
ples. The outer surface of the samples and the elements in the samples
were then separately investigated at various magnifications using a JSM
6701F (Japan) scanning electron microscope (SEM).
D. Li, F. Xu Journal of Solid State Chemistry 302 (2021) 122406

Table 1
Adsorption experiments conditions.
Experiments Initial Cu (II) concentration Temperature Adsorbent dose Contact time pH
(mg/L) ( C) (g/L) (min)

Effect of contact time 40 35 0.1 5, 10, 30, 50, 80, 120 6

Effect of initial Cu (II) concentration 20, 30, 40, 50 35 0.1 120 6
Effect of temperature 40 25, 35, 45 0.1 120 6
Effect of pH 40 35 0.1 120 3, 4, 5, 6, 7, 8

3. Results and discussion
3.1. Characterization of samples
The FTIR spectra of GO and ZIF-8@GO-X (X ¼ 0, 2.48%, 4.07%,
7.83%, and 20.03%) are shown in Fig. 1 (a). The absorption peaks at
2928 and 3135 cm-1 were attributed to the stretching vibration peaks of
C-H bonds in the methyl and imidazole rings, respectively. As shown in
Fig. 1(a), the bands at 1730, 1620, and 1050 cm-1 represented C¼O,
COOH, and C-O-C peaks of GO, respectively [34]. The bands at 692, 754,
1580, and 2930 cm1 were attributed to Zn-N, Zn-O, C¼N, and C-H from
ZIF-8, respectively [35]. The surface chemistry of ZIF-8@GO-X com-
posites, including characteristic peaks from both GO and ZIF-8 can be
found, confirming the successful preparation of composites. In addition,
the infrared spectra of ZIF-8 were almost identical to the infrared spectra
of ZIF-8@GO-X, possibly because ZIF-8 particles are dispersed on the
surface of GO, and diffraction peaks of ZIF-8 disturbed the weak char-
acteristic peaks of GO, which further proved that ZIF-8@GO was effec-
tively synthesized.
The XRD patterns of the GO and ZIF-8@GO-X (X ¼ 0, 2.48%, 4.07%,
7.83%, and 20.03%) are shown in Fig. 1(b). The broad peak with 2θ
values of 10.37 (001) was the characteristic diffraction peak of GO.
Compared with the PDF standard card JCPDS 60-2542, the ZIF-8 peaks
with high crystallinity are located at 7.3 , 10.3 , 12.7 , 14.7 , 16.4 ,
18.0 , 22.16 , 24.6 and 26.7 , which represent the (011), (002), (112),
(022), (013), (222), (114), (233), and (134) planes, respectively. The
XRD pattern of the ZIF-8@GO after Cu (II) adsorption shows poor crys-
tallinity and less intense peaks compared to the ZIF-8@GO. The ZIF-8
peaks at 10.3 were also shifted which might be due to coordination
bonding between Cu (II) and COOH or OH groups.
The spectra of the synthesized ZIF-8 and GO were similar to spectra
from the relevant literature [33,36]. ZIF-8@GO-X has characteristic
peaks at 2θ ¼ 7.3 , 10.3 , 12.7 , 14.7 , 16.4 , 18.0 , 22.16 and 24.6 ,
which are consistent with the peaks of the ZIF-8 [37], showing that the
structure of ZIF-8@GO-X prepared by using GO as a template did not
change, which proved that ZIF-8@GO-X was successfully prepared.
TGA curves of GO and ZIF-8@GO-X (X ¼ 0, 2.48%, 4.07%, 7.83%,
and 20.03%) are shown in Fig. 1(c). GO was thermally unstable, and the
major mass loss occurred between 200 and 700  C. This weight loss was
presumably due to the pyrolysis of the labile oxygen-containing func-
tional groups, yielding water vapor, CO2, and CO [38]. ZIF-8@GO-X
showed a weight loss of approximately 54.2%~65.3% due to the

Fig. 1. FTIR (a), XRD (b), TGA (c) and nitrogen adsorption isotherms (d) of the ZIF-8@GO-X composite (X ¼ 0, 2.48%, 4.07%, 7.83%, and 20.03%).

3
D. Li, F. Xu
volatilization of water, the release of methanol molecules, and the
decomposition of GO after 800  C.
Fig. 1(d) shows the N2 adsorption-desorption isotherms of the ZIF-
8@GO-X composite. Fig. 1(d) shows that they were all type IV iso-
therms, indicating that the composite materials were mesoporous, and
the relative pressure started to increase from 0.4, and there was a larger
adsorption capacity. According to BET analysis, the pore size of ZIF-
8@GO was in the range of 2~50 nm, which confirmed the existence of
mesoporous structure on the surface of ZIF-8@GO. The BET surface area
of ZIF-8@GO-X first increased and then decreased with increasing GO
content (Table. s1).
As shown in Fig. 2, GO and ZIF-8@GO-X in different proportions were
observed by scanning electron microscopy. Fig. 2(a) shows that GO has a
layered structure with a relatively smooth surface, wavy edges and slight
Fig. 2. SEM of GO and ZIF-8@GO-X composite (X ¼ 0, 2.48%, 4.07%, 7.83%, and 20.03%) (40000  ) (a):GO, (b):ZIF-8, (c):ZIF-8@GO-2.48%, (d):ZIF-8@GO-4.07%,
(e):ZIF-8@GO-7.83%, (f): ZIF-8@GO-20.03%
4
Journal of Solid State Chemistry 302 (2021) 122406
wrinkles. Regular ZIF-8 particles (Fig. 2(b)) gathered together. Fig. 2(c)–
2(e) show that excess ZIF-8 nanoparticles in ZIF-8@GO-X composites
decrease gradually with decreasing of ZIF-8 content, and the size of ZIF-8
on the surface of ZIF-8@GO-X increases. The SEM image of the ZIF-
8@GO-X composite (Fig. 2 (e)) shows that ZIF-8 nanoparticles are
distributed on the surface of GO nanosheets, indicating that ZIF-8 is
successfully grown on the surface of GO.
3.2. Adsorption kinetics
3.2.1. The effect of adsorption time
The change in adsorption capacity with time is shown in Fig. 3. As
time increased, the adsorption capacity gradually increased, and the
adsorption capacity in a short period of time showed obvious differences,
D. Li, F. Xu

Fig. 3. Change in adsorption capacity with time (40 mg/L Cu(II), 35 C, pH
¼ 6).
respectively. The adsorption reached equilibrium at 120 min. With
increasing GO content, the adsorption of the ZIF-8@GO composites first
increased and then decreased. Therefore, we chose ZIF-8@GO-7.83% as
an adsorbent for later adsorption experiments.
3.2.2. The effect of initial concentration
As shown in Fig. s1, we found that as the Cu (II) concentration
increased from 20 mg/L to 50 mg/L, the adsorption capacity increased
and the removal rate reached between 88% and 98%. Therefore, we
thought that ZIF-8@GO-7.83% in this study can effectively treat copper-
containing wastewater.
Fig. 4. The Langmuir (a), Freundlich (b) and Temkin (c) isotherms for the adsorption of 40 mg/L of Cu (II) on the ZIF-8@GO-7.83% composite.
5
Journal of Solid State Chemistry 302 (2021) 122406
3.2.3. The effect of pH
The experiment was carried out in a pH range of 3~7 since Cu(II) will
dissolve under strong acid conditions, and Cu(OH)2 precipitation will be
formed under strong alkaline conditions. The results are shown in
Fig. s2a. In the pH range of 3–7, the adsorption capacity of copper ions
increased rapidly with the increasing pH. The adsorption of Cu (II) was
approximately 371.5 mg/g at a pH of a 7.0 and only 59.8 mg/g at a pH of
3.0 for ZIF-8@GO-7.83%. When the adsorption experiments were carried
out at a pH value above 6.2, Cu(OH)2(s) chemical precipitation was
observed. Fig. s2b shows the zeta potential of the ZIF-8@GO-7.83%
composites in the pH range of 2–10. The zeta potentials of ZIF-8@GO-
7.83% in acidic and alkali media were -1.3 and -27.2 mV, respectively.
The surface of the ZIF-8@GO-7.83% composites was negative after pH
2.0, which means that electropositive Cu(II) ions were easily adsorbed
onto the surface of the ZIF-8@GO-7.83% composites.
3.3. Adsorption isotherms
Three nonlinear forms of the Langmuir, Freundlich, and Temkin
models were applied to analyse the isotherm experimental data. The
equations and all parameters of the above models are shown in text S1.
Fig. 4(a, b and c) represents the experimental data at different temper-
atures for the three model isotherms. Table .2 summarizes the isotherm
factors for Cu(II) on ZIF-8@GO-7.83% at various temperatures. Accord-
ing to the analysis of the calculation results in Table .2, the Langmuir
model was more suitable for describing the balance data of Cu(II) than
the Freundlich and Temkin models (R2L> R2F or R2T, higher R2 value). The
maximum value of qm of ZIF-8@GO-7.87% for Cu(II) ions was 482.29
mg/g at 45  C, which was better in comparison to other different ad-
sorbents described in the literature for the removal of the same metal ion
[8,39–46] (Table 3).
D. Li, F. Xu Journal of Solid State Chemistry 302 (2021) 122406

Table 2
The quasi-first model, quasi-second model and Temkin model of Cu (II) adsorption on ZIF-8@GO-7.83% (adsorbent ¼ 0.01 g, V ¼ 100 mL, pH ¼ 6, Cu (II) ¼ 40 mg/L).
Temperature Adsorbent Langmuir constants Freundlich constants Temkin constants qe exp
( C) (mg/g)
qm KL R2L n KF R2F RT RT R2T
ln A
(mg/g) (L/mg) (mg/g) B B

25 ZIF-8@GO-7.83% 464.06 0.94 0.9941 11.83 235.15 0.8935 228.59 90.54 0.9542 361.74
35 ZIF-8@GO-7.83% 469.75 2.86 0.7796 18.55 317.63 0.5795 324.99 71.67 0.6176 386.97
45 ZIF-8@GO-7.83% 482.29 2.84 0.8303 16.06 394.67 0.8226 331.45 75.59 0.6916 388.92

3.4. Kinetic model
An ideal adsorbent needs both a high adsorption capacity and a high
removal rate. To further evaluate the relevant properties of the adsorp-
tion process of ZIF-8@GO-7.83% for Cu(II), three nonlinear form of
pseudo-first-order, pseudo-first-order and Elovich models were used to
investigate the reaction mechanism and rate of the adsorption process of
Cu(II) onto ZIF-8@GO-7.83%. The equations and all factors of the above
models are shown in text S2. Fig. 5 shows a graph of the quasi-first-level,
the quasi-second-level and Elovich models of the adsorption process of
ZIF-8@GO-7.87%. The adsorption kinetic parameters and correlation
coefficients calculated by fitting the kinetic equation are shown in
Table .4. The comparison shows that the simulation effect of the quasi-
first-order kinetic model is better than the simulation effect of the
quasi-second-order and Elovich models, and the correlation coefficient
(R2) is closer to 0.999. The experimental capacity qe exp (361.74 mg/g)
was closer to the maximum capacities qe cal (361.90 mg/g) of pseudo-
second-order. Based on these data, we can conclude that the adsorp-
tion of Cu(II) by ZIF-8@GO-7.87% is more suitable for the first-order
kinetic equation, and a factor dominates the reaction rate during the
adsorption process.
study, the ΔGθ values of several different materials are negative values.
Moreover, it can be shown that the adsorption process of Cu(II) for ZIF-
8@GO-7.87% can be shown to be feasible and spontaneous. In addition,
both ΔHθ and ΔSθ are positive values. A positive value of ΔHθ indicates
that the adsorption process of Cu(II) on the material is endothermic, and
a positive value of ΔSθ reflects that the adsorbent has a good affinity for
Cu(II).
3.6. Reusability of ZIF-GO-X
After the completion of adsorption, the solution was poured out to
separate adsorption materials. The 0.1 mol/L EDTA solution was used to
carry out desorption experiments. The results of five consecutive ad-
sorptions and desorptions are shown in Fig. s4. Fig. s4 shows that the
adsorbent can still have a high adsorption effect, and the adsorption
capacity can still reach more than 290 mg/g, indicating that the material
in this experiment has good regeneration ability. Therefore, the reuse of
the adsorbent showed that ZIF-GO composites were an effective and
stable adsorbent for Cu(II) removal.
3.7. Adsorption mechanism

The adsorption mechanism of Cu(II) on the surface of ZIF-8@GO-

3.5. Adsorption thermodynamics 7.83% was studied by XPS. Fig. 6 shows the XPS survey spectra before
and after the adsorption, respectively. Fig. 6(a) shows that different el-
To further explore the nature of the adsorption process, we calculated ements (C 1s, N 1s, O 1s, Zn 2p) were present. The peak of Cu 2p3 after
thermodynamic parameters. The Gibbs free energy change during the
adsorption can be seen to appear at 935 eV, which confirmed that Cu(II)
adsorption process (ΔGθ ) is calculated from equations (2) and (3): was adsorbed on the surface of ZIF-8@GO. Fig. 6(b) showed the peak of C
ls. Peaks at 284.7 eV corresponded to the -C-C bond, and peaks at 286 eV
ΔH θ ΔSθ
ln KL ¼  þ (2) corresponded to the -C-O-C bond. It can be seen from the Figure that the
RT R
shift has occurred after adsorption, indicating that the functional group
played a role in the adsorption process. Fig. 6(c) showed the peak of O ls.
ΔGθ ¼ ΔH θ  TΔSθ (3)
The peaks at 530.9, 531.1 and 532.1 eV corresponded to COOH, -C¼O,
and -C-OH, respectively. The three oxygen-containing functional groups
ΔH θ represents the standard enthalpy change (KJ/mol), and ΔSθ repre-
declined after the adsorption, and the greatest decrease was attributed to
sents the standard entropy change (J/(mol⋅k)).
-C¼O groups. The peaks at 399.1, 399.5 and 400.8 eV in Fig. 6(d) cor-
The study of adsorption thermodynamics was carried out at a tem-
responded to -N ¼ , -NH-, and N-Zn, respectively. The peaks at -N ¼ had a
perature of 25~45  C. The adsorption of ZIF-8@GO-7.87% to the same
significant attenuation after the adsorption of Cu(II). In Fig. 6(e), peaks at
concentration of Cu(II) solution at different temperatures was studied.
1022 and 1044.9 eV represented the -Zn-O bond. The functional groups
The data obtained by the reaction are collated (Fig. s3), and the rela-
declined after adsorption.
tionship between lnKc and T1is obtained based on the Van't Hoff equation.
In previous studies, many factors were found to affect the adsorption
The thermodynamic parameters are shown in Table. s4 according to the
process, including ion exchange, electrostatic attraction, and complexa-
experimental data. Table. s4 shows that under the conditions of this
tion. The adsorption effect of the adsorbent depends on the nature and
content of the surface functional groups. GO is rich in -COOH and -OH,
Table 3 both of which are hydrophilic groups, while the surface groups of ZIF-8
Comparison of the adsorption capacity of several adsorbents for Cu (II). are hydrophobic and have high stability in aqueous media. There is a
Absorbent Capacity (mg/g) Refs. hydrogen bond between the -NH group and -COOH. At the same time, the
ZIF-8@GO-7.83% 482.29 This study adsorbent has a unique pore structure and has a certain adsorption effect
Hydroxyapatite-coated-limestone 90.95 [8] on small molecules. The adsorption of Cu(II) in ZIF-8 and -COOH are
Graphene oxide 45.20 [39] different. There is coordination between GO and ZIF-8, and the pore size
Graphene oxide/Fe3O4 18.26 [40]
becomes larger after GO and ZIF-8 are compounded, which provides
Activated carbon 19.50 [41]
Fe3O4/hydroxyapatite/graphene 41.90 [42] more favourable conditions for adsorption. There is -COOH in the
FO-BC-450 219.8 [43] structure of the ZIF-8@GO-7.83%, and -COOH is more polar and easily
Modified SBA-15 55.75 [44] complexes with Cu(II). Two adsorption processes are responsible for the
Biochar from mushroom substrates 52.6~65.6 [45] removal of Cu(II) with ZIF-8@GO-7.87%: ion-exchange reaction between
Hydroxyapatite-coated-limestone/chitosan 130.75 [46]
Cu(II) and COOH or OH groups and surface complexation. The

6
D. Li, F. Xu Journal of Solid State Chemistry 302 (2021) 122406

Fig. 5. The adsorption kinetic model for the adsorption of 40 mg/L of Cu (II) on the ZIF-8@GO-7.83% composite: (a):quasi-first-order, (b):quasi-second-order,
and (c):Elovich.

Table 4
The Langmuir, Freundlich and Elovich isothermal constants of Cu (II) adsorption on ZIF-8@GO-7.83% (adsorbent ¼ 0.01 g, V ¼ 100 mL, pH ¼ 6).
Temperature Adsorbent Quasi-first order coefficient Quasi-second order coefficient Elovich coefficient qe exp
( C) (mg/g)
qe Cal K1 R2 qe Cal K2 R2 α β R2

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

25 ZIF-8@GO-7.83% 361.90 0.05 0.9947 400.60 0.0019 0.9961 73.14 60.62 0.9634 361.74
35 ZIF-8@GO-7.83% 389.33 0.05 0.9989 477.99 0.0001 0.9871 -102.18 107.28 0.9739 386.97
45 ZIF-8@GO-7.83% 383.50 0.06 0.9661 411.37 0.0004 0.9145 221.49 35.70 0.47515 388.92

surface reactions are as follows:
ZIF  8@GO  COOH þ Cu2þ → ZIF  8@GO  COO  Cu2þ þ H þ
ðZIF  8@GO  COOHÞ2 þ Cu2þ → ðZIF  8@GO  COO Þ2  Cu2þ
þ 2H þ
solution is stable at the same time. Similar result was reported by
Madadrang et al. [26]. Based on the above results and analysis, the
possible mechanisms for Cu(II) adsorption onto ZIF-8@GO-7.87% are
presented in Fig. 8.
3.8. Practical implications

ZIF-8@GO-7.83% was used for the treatment of the wastewater with

ZIF  8@GO  OH þ Cu2þ → ZIF  8@GO  O  Cu2þ þ 2H þ
ðZIF  8@GO  OHÞ2 þ Cu2þ → ðZIF  8@GO  O  Þ2  Cu2þ þ 2H þ
The above reaction mechanism is supported by the pH change when
the ZIF-8@GO-7.87% is mixed with a Cu(II) solution. The reaction be-
tween COOH and OH with Cu(II) releases protons into the solution
and then decreases the pH value of the solution. We measured the pH
change of the solution to explore the abovementioned mechanism before
and after adsorption (Fig. 7). As the concentration of the initial copper
ion solution increases, the pH gradually decreases, and more copper ions
react with the -COOH and -OH groups on the surface to release Hþ. As the
adsorbent reaches the saturation state of adsorption, the pH of the
a high Cu(II) content from a factory in Ji'an city, China, to investigate the
practical implications of our research. The characteristics of the waste-
water samples are displayed in Table .5, demonstrating the complexity of
the substances and the high concentration of Cu(II) (670 mg/L). The
effect of adsorbent dose on Cu(II) removal of the water sample after 120
min treatment was shown in Fig. 9. At an adsorbent dose of 0.37 g/L, the
Cu(II) concentration in the water sample was reduced from 670 mg/L to
approximately 2.0 mg/L after the treatment, which completely meets the
guideline limit of Cu(II) in wastewater regulated by the WHO (2.0 mg/L).
This application implied that the adsorbents could be used in the prac-
tical treatment of wastewater.

7
D. Li, F. Xu
Fig. 6. XPS of the ZIF-8@GO-7.83% composite before and after the adsorption of 40 mg/L of Cu (II).
4. Conclusion
In this work, ZIF-8@GO-X (X ¼ 0, 2.48%, 4.07%, 7.83%, and 20.03%)
composites were synthesized and served as an adsorbent for Cu(II)
removal. The composites were characterized by FTIR, XRD, BET, TGA,
SEM, and XPS. The results showed that ZIF-8@GO-X has a good effect on
the adsorption of Cu(II). With increasing GO content, the adsorption of
the ZIF-8@GO-X composites first increased and then decreased. The
Cu(II) adsorption of ZIF-8@GO-7.83% reaches a maximum among ZIF-
8@GO-X. When the temperature was 45  C and the Cu(II) concentra-
tion was 40 mg/L, the maximum adsorption capacity of ZIF-8@GO-
7.83% for Cu(II) reached 482.29 mg/g. By fitting the adsorption model,
we found that the ZIF-8@GO-7.83% composite was fitted by the
8
Journal of Solid State Chemistry 302 (2021) 122406
Langmuir model, indicating that the adsorption process was monolayer
adsorption, and fitted by the pseudo-first-order kinetic equation, indi-
cating that the reaction process was controlled by the physical adsorption
mechanism. By calculating the thermodynamic coefficients, we found
that the adsorption process was endothermic and spontaneous. After five
cycles of experiments, the adsorption effect of the material can still reach
more than 290 mg/g, indicating that the material has good reusability
and good application prospects. Final experiments with real factory
wastewater (initial Cu(II) concentration of 670 mg/L) revealed that 0.37
g/L ZIF-8@GO-7.83% can efficiently reduce the Cu(II) concentration to
below 2 mg/L. In general, this work provides an attractive adsorbent
with good separability and reusability, and high adsorption capacity,
which could be promising adsorbent in treating Cu(II)-rich wastewater.
D. Li, F. Xu Journal of Solid State Chemistry 302 (2021) 122406

Fig. 7. (a) pH change at different initial Cu (II) concentrations with 10 mg of

Fig. 9. Effect of adsorbent dose on Cu(II) removal of the wastewater after
adsorbent at 35  C; (b) pH change with added ZIF-8@GO-7.83% composite in
120 min.
100 mL of 40 mg/L of Cu (II) at 35  C.

Fig. 8. Possible mechanism for Cu (II) adsorption onto the ZIF-8@GO-7.83% composite surface.

Table 5
Characteristics of the wastewater sample from a factory in Ji'an city, China (pH ¼ 3.0).
Species Naþ Kþ Ca2þ Cu2þ Mg2þ Cl- NO-3 SO2-
4

Concentrations 760 30 9.75 670 3.5 228.6 33.3 769.3

(mg/L)

9
D. Li, F. Xu
CRediT authorship contribution statement
Dan Li: Methodology, Writing – original draft. Feigao Xu: Concep-
tualization, Writing – review & editing, Supervision, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The work was supported by State Key Laboratory of Pollution Control
and Resource Reuse open foundation for financial support under research
projects PCRRF20008.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://do
i.org/10.1016/j.jssc.2021.122406.
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