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Graphene Oxide-Based Fe–Mg (Hydr)oxide Nanocomposite as Heavy Metals

Adsorbent

Article in Journal of Chemical & Engineering Data · May 2018

DOI: 10.1021/acs.jced.8b00100

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Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX pubs.acs.org/jced

Graphene Oxide-Based Fe−Mg (Hydr)oxide Nanocomposite as Heavy

Metals Adsorbent
Dayong Huang,†,‡ Boxuan Li,† Min Wu,*,† Shigenori Kuga,† and Yong Huang*,†
†
National Engineering Research Center of Engineering Plastics, Technical Institute of Physics and Chemistry, Chinese Academy of
Sciences, Beijing 100190, P.R. China
‡
University of Chinese Academy of Sciences, Beijing 100049, P.R. China
*
S Supporting Information

ABSTRACT: A novel adsorbent for divalent metal cations

was prepared as nanocomposite of Fe−Mg (hydr)oxide with
graphene oxide by one-step coprecipitation. This material
showed adsorption selectivity of Pb2+ > Cu2+ > Ag+ > Zn2+ ≫
Co2+, Ni2+, Cd2+ with high adsorption capacity of 100−600
mg/g for Pb2+, Cu2+, Ag+, and Zn2+. Distribution coefficient
(Kd) was as high as ∼107 mL/g for Pb2+ and Cu2+. The
adsorption isotherms for Pb2+, Cu2+, Ag+, and Zn2+ followed
the Langmuir model, indicating monolayer adsorption. The
adsorption kinetics for Pb2+, Cu2+, Ag+, and Zn2+ followed pseudo-second-order model, suggesting chemisorption. Removal of 50
ppm Pb2+ or Cu2+ from 100 mL solution by 0.1 g of the nanocomposite was over 99.7%. The thermodynamics studies implied
that the adsorption process toward heavy metals was spontaneous and endothermic. Together with recyclability through
magnetic separation, this adsorbent would be useful in polluted water processing.

1. INTRODUCTION for chemical modification.34,35 In addition, graphene oxide has

Water pollution by toxic heavy metals such as Pb2+, Cu2+, Ag+,
and Zn2+, either of natural or artificial origin, is a serious
problem in many areas in the world.1−4 Lead is one of the most
toxic heavy metals in the environment, which can destroy
human brain and nervous systems.5−7 Copper is a crucial
element for human health, but its excessive intake increases
hepatolenticular degeneration risk.8−10 A large amount of
wastewater containing silver and zinc ions occurs in industrial
electroplating.11,12 Thus, the efficient removal of harmful heavy
metals from water is intensely sought after.
Various methods have been applied for removal of heavy
metals from water, such as chemical precipitation,13 ion
exchange,14 coagulation,15 adsorption,16 ultrafiltration,17 and
photocatalysis.18 Of these techniques, adsorption is generally
identified as a promising method due to its efficiency,
reusability, and low cost.19 Various nanoparticles were
examined for removal of heavy metals, such as ferric oxides,
manganese oxides, aluminum oxides, titanium oxides, magne-
sium oxides, zinc oxides, and cerium oxides.8,15,20−24 However,
nanoparticle adsorbents suffer from aggregation, leading to the
decrease in the number of active sites; therefore, avoiding
aggregation is crucial for the adsorption method. For that
purpose, immobilization of nanoparticles onto certain sub-
strates would be effective. This has been reported in research
using graphene oxide (GO),25,26 cellulose,27,28 clay,29,30 carbon
nanotube,31,32 microspheres,33 etc. as substrates.
Graphene oxide has large theoretical surface area (∼2600
m2/g) and many oxygen-containing functional groups such as
hydroxyl, carboxyl, and epoxy groups, which can be readily used
been proven to be nontoxic and biodegradable.36 So far,
graphene oxide has been examined as nanoparticle support for
manganese dioxide,23 magnetite,37,38 and magnesium hydrox-
ide.39 Moreover, graphene oxide-based nanocomposites have
attracted more and more attention as adsorbents for heavy
metals such as ethylenediaminetetraacetic acid-graphene oxide
nanocomposite for Pb2+ removal;51 magnetite/graphene oxide
composite for Co2+ removal;37 graphene oxide-chitosan
composite for Pb2+ and Cu2+ removal;52 SnO2/reduced
graphene oxide nanocomposite for Cd2+, Pb2+, Cu2+, and
Hg2+ removal;53 graphene oxide nanosheets for U (VI)
removal;54 EDTA functionalized magnetic graphene oxide for
removal of Pb (II), Hg (II), and Cu (II); and so on.55 In this
study, we examined suitability of graphene oxide as supporting
medium of Fe−Mg (hydr)oxide nanoparticles. The double
oxide was uniformly loaded on graphene oxide by one-step
coprecipitation. We studied the adsorption behavior of the
product Fe−Mg (hydr)oxide@GO for divalent metal cations
and found this nanocomposite has very large adsorption
capacity and strong selectivity for Pb2+ and Cu2+. These features
would make this material highly useful in environmental
remediation efforts.
Received: February 1, 2018
Accepted: May 18, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.8b00100

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
2. EXPERIMENTAL SECTION
2.1. Materials. Graphene oxide powder was purchased from
XFNANO (Nanjing, China) as dry powder. Iron(III) chloride
hexahydrate (FeCl3·6H2O), iron(II) sulfate heptahydrate
(FeSO4·7H2O), magnesium nitrate hexahydrate (Mg(NO3)2·
6H2O), and ammonia−water (NH3·H2O, 25 wt %) were used
for preparing Fe−Mg(hydr)oxide nanoparticles. Lead(II)
acetate trihydrate (Pb(CH3COOH)2·3H2O), cupric sulfate
(CuSO4), silver nitrate (AgNO3), and zinc sulfate (ZnSO4)
were used for test solutions. All the reagents and solvents were
purchased from Beijing Chemical Works (Beijing, China) with
an analytical grade and used without further purification. All
solutions were prepared using distilled water.
2.2. Synthesis of Graphene Oxide-Based Fe−Mg
(Hydr)oxide Nanocomposite. About 50 mg of graphene
oxide was dispersed by sonication in 100 mL of aqueous
solution of FeCl3 (0.081 mol/L), FeSO4 (0.042 mol/L), and
Mg(NO3)2 (0.125 mol/L) (total ion concentration 0.25 mol/
L). Under nitrogen atmosphere, 10 mL ammonia−water (25 wt
%) was added dropwise into the solution with vigorous stirring
at 343 K for 2 h and then kept 363 K for 10 h. The precipitate
formed was collected by centrifugation, washed with water
several times, and dialyzed against water (dialysis bag with
8000−14 000 molecular weight cutoff). The resulting suspen-
sion was freeze-dried from water. For comparison, Fe−Mg
(hydr)oxide was synthesized in the same way without adding
graphene oxide.
2.3. Characterization. The specific surface area was
measured by nitrogen adsorption−Brunauer−Emmett−Teller
(BET) method using an automated gas sorption analyzer
(Quadrasorb SI-MP). The morphology of synthesized nano-
composite material was observed using a Hitachi S-4800
instrument equipped with energy-dispersive X-ray spectroscopy
(EDS). Transmission electron microscopy (TEM) was done
using a JEOL JEM-2100 instrument. Atomic force microscope
(AFM) images were acquired using a Bruker Multimode 8
instrument. Fourier transform infrared (FTIR) spectra were
recorded on an Excalibur 3100 instrument for 400−4000 cm−1.
The magnetic properties were characterized using a vibrating-
sample magnetometer (SQUID-VSM, Quantum Design).
2.4. Adsorption Experiments. Batch adsorption experi-
ments of heavy metals on the composite were carried out in
aqueous solution with different initial concentrations of ions
under stirring at room temperature for 24 h. The adsorbent
dose was 1 g/L for all the experiments. Metal ions were
quantified by an inductively coupled plasma emission
spectrometer (ICP) (710-OES, Varian). The adsorption
capacity qe (mg/g) was given by the following equation:
(C0 − Ce)V
qe =
m (1)
The % removal was calculated with the following eq 2:
C0 − Ce
% removal =
C0 (2)
where C0 (mg/L) and Ce (mg/L) are initial and equilibrium
concentrations of the heavy metals in the solution, respectively.
V (L) is the solution volume, and m (g) is the adsorbent
amount.
2.5. Adsorption Kinetics. Adsorption kinetic batch
experiments of Pb2+, Cu2+, Ag+, and Zn2+ on Fe−Mg(hydr)-
oxide@GO were carried out in various adsorption times (90−
B DOI: 10.1021/acs.jced.8b00100
Article
720 min) at room temperature. The adsorbent dose was 1 g/L
for all the experiments. For analyzing adsorption mechanism,
the pseudo-first-order and pseudo-second-order kinetic models
and intraparticle diffusion model were applied.56
Pseudo-first-order kinetic model:
ln(qe − qt) = ln qe − k1t (3)
Pseudo-second-order kinetic model:
t 1 t
= 2
+
qt k 2qe qe (4)
Intraparticle diffusion model:
qt = kit 1/2 + C (5)
where qe and qt (mg/g) are the adsorbed amount for heavy
metals at equilibrium and at any time t (min), and k1 (min−1)
and k2 (g/mg min−1) are the pseudo-first-order and pseudo-
second-order rate constants, respectively. Additionally, ki is the
rate constant of intraparticle diffusion.
2.6. Recycling. Continuous desorption−adsorption experi-
ments were carried out at room temperature. A certain amount
of the composite was first immersed in heavy metal ion
solutions, then magnetically separated from the solution, and
thoroughly washed with distilled water. Desorption of heavy
metal ions was carried out in 100 mL of saturated ethyl-
enediaminetetraacetic acid solution for 6 h. The adsorption−
desorption cycles were repeated four times.
3. RESULTS AND DISCUSSION
3.1. Characterization of Nanocomposite. Figure 1
shows scanning electron microscopy (SEM) images of the
Figure 1. SEM images of (a−c) Fe−Mg (hydr)oxide, (d−f) graphene
oxide, and (g−i) Fe−Mg (hydr)oxide@GO.
product. The Fe−Mg (hydr)oxide without GO is composed of
dense aggregates at any magnification (Figures 1a−c). The
graphene oxide as received consists of randomly curved thin
flakes (atomic force microscopy (AFM) image of GO is shown
in Figure S1), though not all of them are single-layer graphene
(Figures 1d−f). The hybrid nanocomposite of these two
maintained the sheet-like morphology of GO, which is
supporting Fe−Mg (hydr)oxide nanoparticles on the surface
(Figures 1g−i). The specific surface areas of Fe−Mg (hydr)-
oxide and Fe−Mg (hydr)oxide@GO are 27.1 and 113.5 m2/g
(the nitrogen adsorption−desorption curves are shown in
Figure S3), respectively, indicating that Fe−Mg (hydr)oxide
nanoparticles can be dispersed effectively on the GO surfaces to
provide adsorption sites. The morphology and element
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

distribution of Fe−Mg (hydr)oxide@GO (Figure 2) shows that
iron and magnesium are uniformly distributed on GO surface.
contrast, the neat Fe−Mg(hydr)oxide (Figure 3a) consisted of
heavily aggregated particles that were not discernible as
individual particles.
Figure 3f shows the magnetic behavior of Fe−Mg (hydr)-
oxide@GO showing typical superparamagnetism with saturated
magnetization of 25.42 emu/g. The Fe−Mg (hydr)oxide@GO
sample maintained magnetism with 15.73 emu/g. This level of
magnetism is enough to separate the hybrid nanocomposite by
a magnet, as shown in Figure 3f inset.
Figure 4 shows FTIR spectra of the samples. Graphene oxide
has peaks at 3413, 1720, 1400, 1219, 1053, and 1624 cm−1

Figure 2. (a) SEM image of Fe−Mg (hydr)oxide and EDS elemental

maps of the same area for (b) Fe and (c) Mg. (d) SEM image of Fe−
Mg (hydr)oxide@GO and EDS maps of (e) Fe, (f) Mg, and (g) C.

Figure 3 shows the TEM images of the products confirming

the features seen by SEM. Figure 3c shows good dispersion of
Fe−Mg (hydr)oxide particles on the surface of GO. Its electron
diffraction (Figure 3d) shows reflections from (220), (311),
(400), (422), (511), and (440) of Fe3O438 and (201), (202),
(113), and (104) of Mg(OH)2.6,39 Figure S4 shows the XRD
patterns of the products; the diffraction peaks of (220), (311),
and (440) can be assigned Fe3O4, and (101) and (110) can be
assigned Mg(OH)2. The particle size distribution determined Figure 4. FTIR spectra of (a) Fe−Mg (hydr)oxide, (b) graphene
oxide, and (c) Fe−Mg (hydr)oxide@GO.
by image analysis (Figure 3e, for 400 particles) ranged 2−22
nm, but mostly 4−12 nm. This sharpness of size distribution is
likely to result from the nucleation effect of GO when the ascribed to −OH, CO, carboxyl OC−O, epoxy C−O−C,
hydr(oxide) particles are formed by alkaline precipitation. In C−O groups, and CC stretching, respectively.23,40 The Fe−

Figure 3. TEM images of (a) Fe−Mg (hydr)oxide, (b) graphene oxide, and (c) Fe−Mg (hydr)oxide@GO. (d) Electric diffraction pattern of Fe−Mg
(hydr)oxide@GO. (e) Size distributions of Fe−Mg (hydr)oxide nanoparticles loaded on graphene oxide. (f) Magnetic hysteresis loops of Fe−
Mg(hydr)oxide and Fe−Mg (hydr)oxide@GO. The inset shows the dispersion and magnetic separation of the Fe−Mg (hydr)oxide@GO in water.

C DOI: 10.1021/acs.jced.8b00100
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Mg (hydr)oxides@GO has peaks at 1720 cm−1 (CO), 1400 Table 2. Adsorption of Fe−Mg (Hydr)oxide@GO toward
cm−1 (carboxyl OC−O) and 1053 cm−1 (C−O) diminshed, the Seven Mixed Ionsa
and the peak at 1624 cm−1 increased. The OH stretching
shifted from 3413 cm−1 of GO to 3433 cm−1 for Fe−Mg mixed ions C0 (mg/L) Ce (mg/L) removal (%) Kd (mL/g)
(hydr)oxides@GO, suggesting that the metal hydroxide Pb2+ 22.38 0.0013 99.99 1.7 × 107
particles were attached to the surface of graphene oxide Cu2+ 21.76 0.15 99.31 1.4 × 105
through oxygen-containing functional groups.23,41 The new Ag+ 20.45 2.78 86.41 6.4 × 104
peaks at 3699, 1110, 578, and 432 cm−1 were introduced by the Zn2+ 19.99 8.78 56.08 1.3 × 103
metal (hydr)oxides. The strong adsorption bands at 3699 and Cd2+ 23.01 22.89 0.52 5.24
432 cm−1 can be assigned to the Mg−O group.39,42 The 1110 Co2+ 21.95 21.28 3.05 31.48
cm−1 peak can be ascribed to Fe−OH group.43,44 The 578 cm−1 Ni2+ 20.33 19.99 1.67 17.01
a
band might be related to the lattice vibrations of Fe−O−Mg or Dose of Fe−Mg (hydr)oxide@GO = 1 g/L, contact time: 12 h. The
Mg−O−Mg.45,46 experiments of adsorption were carried out in room temperature.
3.2. Heavy Metals Selectivity of the Nanocomposite
Material. Selectivity of metal ion adsorption by Fe−Mg where Ce (mg/L) is the equilibrium concentration and qe (mg/
(hydr)oxide@GO was tested for a mixed solution of Pb2+, g) is the adsorption capacity. Q0 (mg/g) and b (L/mg) are the
Cu2+, Ag+, Zn2+, Cd2+, Co2+, and Ni2+. Selectivity is evaluated maximum adsorption capacity and adsorption energy related to
by distribution coefficient Kd, defined as Langmuir constants, respectively.
(V [(C0 − Ce)/Ce]) 1
Kd = lnqe = lnK f + lnCe
m (6) n (8)
where C0 (mg/L) and Ce (mg/L) are the initial and equilibrium where Kf (mg/g) and n are the adsorption capacity and
concentrations of the heavy metals in the solution, respectively. adsorption intensity of Freundlich constants, respectively. The
V (mL) is the solution volume, and m (g) is the adsorbent adsorption isotherms were fitted with eqs 7 and 8 as in Figure 5
amount.2 In general, materials with Kd values range between and Table 3. It can be noted that the behavior of the cations
104−105 are regarded as excellent adsorbents.47 The adsorption can be fitted with the Langmuir isotherm with high correlation
data for single ions by Fe−Mg (hydr)oxide@GO are listed in coefficient (R2 > 0.99), indicating that the adsorption is
Table 1. The Kd values for Pb2+ and Cu2+ are well above 106; monolayer-type.
On the basis of the Langmuir isotherm model, the theoretical
Table 1. Adsorption of Individual Seven Ions by Fe−Mg maximum adsorption capacities (Q0) for Pb2+, Cu2+, Ag+, and
(Hydr)oxide@GOa Zn2+ of Fe−Mg (hydr)oxide@GO were 617.3, 432.9, 142.2,
and 121.7 mg/g, which were close to the experimental values of
single ions C0 (mg/L) Ce (mg/L) removal (%) Kd (mL/g)
619.4, 441.5, 144.3, and 121.2 mg/g (Table 3 and Tables S1−
Pb2+ 20.52 0.00088 99.99 2.3 × 107 S4), respectively. More importantly, ions of Pb2+ and Cu2+
Cu2+ 21.32 0.0011 99.99 1.9 × 107 could be effectively down to 8 and 6 ppb even with high initial
Ag+ 19.89 0.010 99.95 2.0 × 106 concentrations of 99 and 61 ppm (Tables S1 and S2),
Zn2+ 20.13 0.023 99.89 8.7 × 105 respectively. This could satisfy the international standard for
Cd2+ 21.60 19.67 8.94 98.12 drinking water, so it has enormous potential for application of
Co2+ 18.97 17.54 7.54 81.53 water treatment.
Ni2+ 22.56 20.85 7.58 82.01 In addition, the removal rate for Pb2+ and Cu2+ could be up
a
Dose of Fe−Mg (hydr)oxide@GO = 1 g/L, contact time: 12 h. The to as high as 99.97 and 98.68%, even the initial concentrations
experiments of adsorption were carried out in room temperature. of 601.7 and 358.8 ppm (Tables S1 and S2). For comparison,
the theoretical maximum Pb2+, Cu2+, Ag+, and Zn2+ adsorption
after 12 h contact, these species were decreased to less than 1 capacity (Q0) of Fe−Mg(hydr)oxide also obtained from
ppb, achieving virtually complete removal. The adsorbent also Langmuir isotherm model were 210.1, 156.7, 85.5, and 40.7
showed high adsorption ability for Ag+ and Zn2+, both mg/g (Table S9); these values are much lower than the values
achieving about 99.9% removal rate and >105 mL/g Kd values of Fe−Mg (hydr)oxide@GO.
within 12 h. Thus, the Fe−Mg (hydr)oxide@GO is a high- For comparison, the maximum adsorption capacity (Q0)
performance adsorbent for Pb2+, Cu2+, Ag+, and Zn2+. On the values of heavy metals on other materials are listed in Table 4.
other hand, Table 1 shows the adsorbent is not effective for Clearly, the Fe−Mg (hydr)oxide@GO shows an excellent
Cd2+, Co2+, and Ni2+. adsorption capacity of 619.4, 441.5, 144.3, and 121.2 mg/g
Table 2 shows the adsorption behavior from a mixed solution compared to those of other adsorbents for Pb2+, Cu2+, Ag+, and
of seven metal ions. The adsorbent showed selectivity as Pb2+ > Zn2+, respectively. In addition, the Fe−Mg (hydr)oxide@GO
Cu2+ > Ag+ > Zn2+ ≫ Co2+ > Cd2+ > Ni2+. The Kd values of could be separated easily under the external magnetic field and
Pb2+, Cu2+, and Ag+ are close to those in single ion adsorption, obtained easily by one-step coprecipitation method with low
i.e. not affected by the presence of other ions. cost.
3.3. Heavy Metals Adsorption Behaviors of the 3.4. Heavy Metals Adsorption Kinetics of the Nano-
Nanocomposite. For understanding the adsorption mecha- composite Material. Figure 6 shows the time course of
nism of Fe−Mg (hydr)oxide@GO nanocomposite, Langmuir adsorption and pseudo-second-order kinetic plots for the four
and Freundlich isotherm models (eqs 7 and 8) were used. metal cations. Under mild stirring for 90 min, the adsorbent
Ce 1 C removed 99.75 and 99.73% of Pb2+ and Cu2+, respectively. For
= + e the Ag+ and Zn2+, the adsorption was slightly slower but still
qe bQ 0 Q0 (7) achieved 86.56 and 80.60% removal in 90 min, respectively.
D DOI: 10.1021/acs.jced.8b00100
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Journal of Chemical & Engineering Data Article

Figure 5. Adsorption isotherm for the adsorption of (a) Pb2+, (b) Cu2+, (c) Ag+, and (d) Zn2+ by Fe−Mg (hydr)oxide@GO. (e) Langmuir model
and (f) Freundlich model fittings of Pb2+, Cu2+, Ag+, and Zn2+ sorption by Fe−Mg (hydr)oxide@GO. All the experiments were carried out in room
temperature, pH 7, Fe−Mg (hydr)oxide@GO dosage = 1 g/L.

Table 3. Langmuir and Freundlich Parameters of Fe−Mg The pseudo-second-order kinetic model parameters for the
(Hydr)oxides@GO for Heavy Metals Adsorption adsorptions toward the four metals are summarized in Table 5.
From Figure 6d and Table 5, the excellent fit coefficient (R2)
Langmuir model parameters
very close to 1.000, suggesting that the adsorption for Pb2+,
Q0 (mg/g) b (L/mg) R2 Cu2+, Ag+, and Zn2+ by Fe−Mg (hydr)oxide@GO can be
2+
Pb 617.284 2.115 0.9998 expressed with pseudo-second-order kinetic model and proved
Cu2+ 432.900 0.951 0.9965 that the adsorption process is chemisorption. The intraparticle
Ag+ 142.247 0.571 0.9927 diffusion model gives nonlinear fittings of the experimental data
Zn2+ 121.654 0.119 0.9959 (Figure S5), indicating multistage adsorption process.56
Freundlich model parameters 3.5. Adsorption Thermodynamics. To study the effect of
Kf (mg/g) n R2 temperature on the adsorption process, the thermodynamic
Pb2+ 352.482 8.117 0.4325 parameters, Gibbs energy (ΔG), entropy (ΔS), and enthalpy
Cu2+ 201.341 5.349 0.9063 (ΔH) were calculated from eqs 9 and 10.49,50
Ag+ 79.519 7.694 0.9616 ΔG = −RT ln Kc (9)
Zn2+ 62.302 8.804 0.9890
ΔS ΔH
Table 4. Comparison of the Maximum Adsorption Capacity ln Kc = −
R RT (10)
of Different Adsorbents for Heavy Metals
where R is the gas constant (8.314 J/mol·k), T (K) is the
Q0 (mg/g) absolute temperature, and Kc is the equilibrium partition
adsorbent Pb2+ Cu2+ Ag+ Zn2+ ref coefficient and can be calculated from eq 11.49,50
layered double hydroxide 288.9 180.9 452.4 2 q
intercalated with the Kc = e
MoS42− ion Ce (11)
graphene/Co3O4 58 77 16
nanocpmposite where qe (mg/g) is the adsorption capacity of heavy metals at
functionalized graphene 310.1 282.3 9 equilibrium time and C e (mg/L) is the equilibrium
oxide concentration of heavy metals solution. ΔH and ΔS can be
magnetic porous Fe3O4− 208.2 111.9 100.2 48 calculated from the slope and intercept of the linear plot
MnO2
according to ln Kc vs 1/T. The calculated data are presented in
lignosulfonate-graphene 216.4 7
oxide-polyaniline ternary Table 6.
nanocomposite As shown in Table 6, the ΔG values are all negative, which
Fe−Mg (hydr)oxide 159.1 148.5 85.3 34.7 this showed that the adsorption process was spontaneous. The ΔS
study values are all positive, suggesting that there was an increased
Fe−Mg (hydr)oxide@GO 619.4 441.5 144.3 121.2 this
study
randomness during the adsorption of heavy metals on Fe−Mg
(hydr)oxide@GO. The positive values of ΔH implied that the
adsorption process was endothermic.49,50
3.6. Adsorption Mechanism. The adsorption of heavy
Near equilibrium was achieved in 90 min for Pb2+ and Cu2+ but metal ions usually includes ion exchange, precipitation, and
took 450 min for Ag+ and Zn2+. At 720 min, the removal levels complexation. In the present case, it could be concluded that
were 99.99, 99.99, 99.98, and 99.92% for Pb2+, Cu2+, Ag+, and chemisorption played a major role in the adsorption process.
Zn2+, respectively. Figure 7a shows the FTIR spectra of Fe−Mg (hydr)oxide@GO
E DOI: 10.1021/acs.jced.8b00100
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Figure 6. Adsorption kinetics curves for Pb2+, Cu2+, Ag+, and Zn2+ by Fe−Mg (hydr)oxide@GO: (a) ion concentration change following contact
time, (b) adsorption capacity (qt) with contact time, (c) removal % as a function of contact time, and (d) pseudo-second-order kinetic plots for ion
adsorption. All experiments were carried out in room temperature, pH 7, Fe−Mg (hydr)oxide@GO dosage = 1 g/L.

Table 5. Pseudo-First-Order and Pseudo-Second-Order before and after mixing four heavy metal ions adsorption. A
Kinetic Parameters for Adsorbing Heavy Metals onto Fe− notable change after metal adsorption is the shifts of 3699−
Mg (Hydr)oxide@GO 3680 cm−1 (Mg−O), 1110−1122 cm−1 (Fe−OH), and 578−
590 cm−1 (Fe−O−Mg or Mg−O−Mg). These changes indicate
pseudo-first-order model
that adsorption of heavy metal ions take place primarily by
qe,cal (mg/g) qe,exp (mg/g) k1 (min−1) R2 complexation.48 Figure 7b shows the changes in ion
2+
Pb 46.11 46.78 0.063 0.9731 concentration after addition of adsorbent. Simultaneously
Cu2+ 46.83 47.64 0.066 0.9676 with decrease in the adsorbates’ concentration, Mg2+ and
Ag+ 43.01 43.39 0.022 0.9254 Fe2+,3+ increased, representing ion exchange, but their total
Zn2+ 44.99 45.03 0.018 0.9878 amount was about 1/100 of the total adsorption. The
pseudo-second-order model morphologies and element distribution of Fe−Mg (hydr)-
qe,cal (mg/g) qe,exp (mg/g) k2 (g/mg min−1) R2 oxide@GO after adsorption of heavy metal ions are shown in
Pb2+
47.79 46.78 0.141 1.000 Figure S2. It could be suggested that a fringe of ion change
Cu2+ 47.66 47.64 0.132 1.000 occurred between heavy metal ions and Fe−Mg (hydr)oxide@
Ag+ 44.60 43.39 1.277 × 10−3 0.9998 GO. The major ion change reactions are listed as eqs 12−16.
Zn2+ 47.44 45.03 5.617 × 10−4 0.9991
Mg(OH)2 (s) ⇌ Mg 2 + + 2OH− (12)
Table 6. Thermodynamic Data for Heavy Metals Adsorption Pb2 + + 2OH− ⇌ Pb(OH)2 (s) (13)
on Fe−Mg (Hydr)oxide@GO
heavy temperature ΔG ΔH Cu 2 + + 2OH− ⇌ Cu(OH)2 (s) (14)
metals (K) (kJ/mol) ΔS (J/mol·K) (kJ/mol)
Pb2+ 288 −19.931 118.849 14.300 2Ag + + 2OH− → Ag 2O(s) + H 2O (15)
298
308 Zn 2 + + 2OH− ⇌ Zn(OH)2 (s) (16)
Cu2+ 288 −13.315 134.878 25.627
298
There are many oxygen-containing functional groups on the
308
surface of graphene oxide, and they may participate to the
Ag+ 288 −17.347 211.442 43.676
complexation of heavy metal ions working synergistically with
298
Fe−Mg (hydr)oxide.
308 3.7. Desorption and Regeneration. Recyclability is
Zn2+ 288 −16.481 173.023 33.471 important for environment-related adsorbents. The adsorp-
298 tion−desorption cycle was repeated four times under the same
308 conditions. Figure 8 shows the changes in adsorption capacity
of Fe−Mg (hydr)oxide@GO with recycling. The decrease is
moderate for all metal pieces after four cycles, which may have
resulted from aggregation of the adsorbent particles.
F DOI: 10.1021/acs.jced.8b00100
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Figure 7. (a) FTIR spectra of Fe−Mg (hydr)oxide@GO and Fe−Mg (hydr)oxide@GO adsorbed the four mixed heavy metal ions and (b) ion
concentration change following contact time.
Figure 8. Decrease in adsorption capacity of Fe−Mg (hydr)oxide@
GO for metal ions with cycle number. All experiments were carried out
in room temperature, pH 7, Fe−Mg (hydr)oxide@GO dosage = 1 g/
L.
4. CONCLUSIONS
A novel adsorbent Fe−Mg (hydr)oxide supported by graphene
oxide was prepared and applied to remove heavy metal ions
Pb2+, Cu2+, Ag+, and Zn2+ in aqueous phase. The adsorbent is
magnetic and easily separated from water by a magnet. The
adsorbent shows selectivity to heavy metals in the order of:
Pb2+ > Cu2+ > Ag+ > Zn2+ ≫ Co2+, Ni2+, Cd2+. The Langmuir
isotherm model describes well the adsorption behavior, and the
adsorption kinetics followed pseudo-second-order. The Fe−Mg
(hydr)oxide@GO shows exceptionally high adsorption capaci-
ties of 619.4, 441.5, 144.3, and 121.2 mg/g for Pb2+, Cu2+, Ag+,
and Zn2+, respectively. The adsorption is likely to be
chemisorption primarily by complexation with certain ion
change. The adsorbent could be recycled, maintaining high
level of adsorption capacity for heavy metal ions. Thus, the
material is potentially useful in treating contaminated water.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jced.8b00100.
AFM image of graphene oxide; adsorption data of Fe−
Mg (hydr)oxide and Fe−Mg (hydr)oxide@GO for Pb2+,
Cu 2+ , Ag + , and Zn 2+ ; Langmuir and Freundlich
parameters of Fe−Mg (hydr)oxide for Pb2+, Cu2+, Ag+,
and Zn2+ adsorption; and morphology and element
distribution of Fe−Mg (hydr)oxide@GO after adsorp-
tion of heavy metal ions (PDF)
G DOI: 10.1021/acs.jced.8b00100
Article
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: yhuang@mail.ipc.ac.cn.
*E-mail: wumin@mail.ipc.ac.cn.
ORCID
Min Wu: 0000-0003-0542-4235
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This study was supported by the National Natural Science
Foundation of China (Grant 51472253), National Key Project
of Research and Development Plan (Grant 2016YFC1402500),
and Chinese Academy of Sciences Visiting Professorships.
■ REFERENCES
(1) Shannon, M. A.; Bohn, P. W.; Elimelech, M.; Georgiadis, J. G.;
Marinas, B. J.; Mayes, A. M. Science and Technology for Water
Purification in the Coming Decades. Nature 2008, 452, 301−310.
(2) Ma, L.; Wang, Q.; Islam, S. M.; Liu, Y.; Ma, S.; Kanatzidis, M. G.
Highly Selective and Efficient Removal of Heavy Metals by Layered
Double Hydroxide Intercalated with the MoS42‑ Ion. J. Am. Chem. Soc.
2016, 138, 2858−2866.
(3) Hu, J.-S.; Zhong, L.-S.; Song, W.-G.; Wan, L.-J. Synthesis of
Hierarchically Structured Metal Oxides and their Application in Heavy
Metal Ion Removal. Adv. Mater. 2008, 20, 2977−2982.
(4) Li, Y.-H.; Ding, J.; Luan, Z.; Di, Z.; Zhu, Y.; Xu, C.; Wu, D.; Wei,
B. Competitive adsorption of Pb2+, Cu2+ and Cd2+ ions from aqueous
solutions by multiwalled carbon nanotubes. Carbon 2003, 41, 2787−
2792.
(5) Yan, C. H.; Xu, J.; Shen, X. M. Childhood Lead Poisoning in
China: Challenges and Opportunities. Environ. Health Perspect. 2013,
121, A294−A295.
(6) Liu, M.; Wang, Y.; Chen, L.; Zhang, Y.; Lin, Z. Mg(OH)2
Supported Nanoscale Zero Valent Iron Enhancing the Removal of
Pb(II) from Aqueous Solution. ACS Appl. Mater. Interfaces 2015, 7,
7961−7969.
(7) Yang, J.; Wu, J.-X.; Lü, Q.-F.; Lin, T.-T. Facile Preparation of
Lignosulfonate−Graphene Oxide−Polyaniline Ternary Nanocompo-
site as an Effective Adsorbent for Pb(II) Ions. ACS Sustainable Chem.
Eng. 2014, 2, 1203−1211.
(8) Nandi, D.; Basu, T.; Debnath, S.; Ghosh, A. K.; De, A.; Ghosh, U.
C. Mechanistic Insight for the Sorption of Cd(II) and Cu(II) from
Aqueous Solution on Magnetic Mn-Doped Fe(III) Oxide Nano-
particle Implanted Graphene. J. Chem. Eng. Data 2013, 58, 2809−
2818.
(9) Sahraei, R.; Hemmati, K.; Ghaemy, M. Adsorptive removal of
toxic metals and cationic dyes by magnetic adsorbent based on
functionalized graphene oxide from water. RSC Adv. 2016, 6, 72487−
72499.
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(10) Zhu, X.; Shan, Y.; Xiong, S.; Shen, J.; Wu, X. Brianyoungite/
Graphene Oxide Coordination Composites for High-Performance
Cu2+ Adsorption and Tunable Deep-Red Photoluminescence. ACS
Appl. Mater. Interfaces 2016, 8, 15848−15854.
(11) Vilela, D.; Parmar, J.; Zeng, Y.; Zhao, Y.; Sanchez, S. Graphene-
Based Microbots for Toxic Heavy Metal Removal and Recovery from
Water. Nano Lett. 2016, 16, 2860−2866.
(12) Ma, S.; Chen, Q.; Li, H.; Wang, P.; Islam, S. M.; Gu, Q.; Yang,
X.; Kanatzidis, M. G. Highly Selective and Efficient Heavy Metal
Capture with Polysulfide Intercalated Layered Double Hydroxides. J.
Mater. Chem. A 2014, 2, 10280−10289.
(13) Matlock, M. M.; Howerton, B. S.; Atwood, D. A. Chemical
Precipitation of Heavy Metals from Acid Mine Drainage. Water Res.
2002, 36, 4757−4764.
(14) Doula, M. K. Simultaneous removal of Cu, Mn and Zn from
drinking water with the use of clinoptilolite and its Fe-modified form.
Water Res. 2009, 43, 3659−3672.
(15) Santhosh, C.; Velmurugan, V.; Jacob, G.; Jeong, S. K.; Grace, A.
N.; Bhatnagar, A. Role of Nanomaterials in Water Treatment
Applications: A review. Chem. Eng. J. 2016, 306, 1116−1137.
(16) Yavuz, E.; Tokalıoğlu, Ş.; Şahan, H.; Patat, Ş. A Graphene/
Co3O4 Nanocomposite as A New Adsorbent for Solid Phase
Extraction of Pb(ii), Cu(ii) and Fe(iii) Ions in Various Samples.
RSC Adv. 2013, 3, 24650−24657.
(17) Yin, N.; Wang, K.; Wang, L.; Li, Z. Amino-Functionalized
MOFs Combining Ceramic Membrane Ultrafiltration for Pb (II)
Removal. Chem. Eng. J. 2016, 306, 619−628.
(18) Liu, W.; Sun, W.; Borthwick, A. G.; Wang, T.; Li, F.; Guan, Y.
Simultaneous Removal of Cr(VI) and 4-Chlorophenol Through
Photocatalysis by A Novel Anatase/Titanate Nanosheet Composite:
Synergetic Promotion Effect and Autosynchronous Doping. J. Hazard.
Mater. 2016, 317, 385−393.
(19) Wan Ngah, W. S.; Hanafiah, M. A. K. M. Removal of Heavy
Metal Ions from Wastewater by Chemically Modified Plant Wastes as
Adsorbents: A review. Bioresour. Technol. 2008, 99, 3935−3948.
(20) Hua, M.; Zhang, S.; Pan, B.; Zhang, W.; Lv, L.; Zhang, Q. Heavy
Metal Removal from Water/Wastewater by Nanosized Metal Oxides:
A review. J. Hazard. Mater. 2012, 211−212, 317−331.
(21) Li, Z. J.; Wang, L.; Yuan, L. Y.; Xiao, C. L.; Mei, L.; Zheng, L. R.;
Zhang, J.; Yang, J. H.; Zhao, Y. L.; Zhu, Z. T.; Chai, Z. F.; Shi, W. Q.
Efficient Removal of Uranium from Aqueous Solution by Zero-Valent
Iron Nanoparticle and Its Graphene Composite. J. Hazard. Mater.
2015, 290, 26−33.
(22) Hu, Z.-T.; Liu, J.; Yan, X.; Oh, W.-D.; Lim, T.-T. Low-
Temperature Synthesis of Graphene/Bi2Fe4O9 Composite for
Synergistic Adsorption-Photocatalytic Degradation of Hydrophobic
Pollutant under Solar Irradiation. Chem. Eng. J. 2015, 262, 1022−1032.
(23) Tang, J.; Huang, Y.; Gong, Y.; Lyu, H.; Wang, Q.; Ma, J.
Preparation of A Novel Graphene Oxide/Fe-Mn Composite and Its
Application for Aqueous Hg(II) Removal. J. Hazard. Mater. 2016, 316,
151−158.
(24) Peng, E.; Choo, E. S.; Chandrasekharan, P.; Yang, C. T.; Ding,
J.; Chuang, K. H.; Xue, J. M. Synthesis of Manganese Ferrite/
Graphene Oxide Nanocomposites for Biomedical Applications. Small
2012, 8, 3620−3630.
(25) Zhu, J.; Wei, S.; Gu, H.; Rapole, S. B.; Wang, Q.; Luo, Z.;
Haldolaarachchige, N.; Young, D. P.; Guo, Z. One-pot Synthesis of
Magnetic Graphene Nanocomposites Decorated with Core@Double-
shell Nanoparticles for Fast Chromium Removal. Environ. Sci. Technol.
2012, 46, 977−985.
(26) Sreeprasad, T. S.; Maliyekkal, S. M.; Lisha, K. P.; Pradeep, T.
Reduced Graphene Oxide-Metal/Metal Oxide Composites: Facile
Synthesis and Application in Water Purification. J. Hazard. Mater.
2011, 186, 921−931.
(27) Tian, Y.; Wu, M.; Lin, X.; Huang, P.; Huang, Y. Synthesis of
Magnetic Wheat Straw for Arsenic Adsorption. J. Hazard. Mater. 2011,
193, 10−16.
H DOI: 10.1021/acs.jced.8b00100
Article
(28) Yu, X.; Tong, S.; Ge, M.; Zuo, J.; Cao, C.; Song, W. One-step
Synthesis of Magnetic Composites of Cellulose@Iron Oxide Nano-
particles for Arsenic Removal. J. Mater. Chem. A 2013, 1, 959−965.
(29) Uddin, M. K. A. Review on the Adsorption of Heavy Metals by
Clay Minerals, with Special Focus on the Past Decade. Chem. Eng. J.
2017, 308, 438−462.
(30) Bulut, Y.; Akcay, G.; Elma, D.; Serhatli, I. E. Synthesis of Clay-
Based Superabsorbent Composite and its Sorption Capability. J.
Hazard. Mater. 2009, 171, 717−723.
(31) Fu, F.; Wang, Q. Removal of Heavy Metal Ions from
Wastewaters: A Review. J. Environ. Manage. 2011, 92, 407−418.
(32) Rao, G.; Lu, C.; Su, F. Sorption of Divalent Metal Ions from
Aqueous Solution by Carbon Nanotubes: A Review. Sep. Purif.
Technol. 2007, 58, 224−231.
(33) Zhou, L.; Wang, Y.; Liu, Z.; Huang, Q. Characteristics of
Equilibrium, Kinetics Studies for Adsorption of Hg(II), Cu(II), and
Ni(II) Ions by Thiourea-Modified Magnetic Chitosan Microspheres. J.
Hazard. Mater. 2009, 161, 995−1002.
(34) Zhu, Y.; Murali, S.; Cai, W.; Li, X.; Suk, J. W.; Potts, J. R.; Ruoff,
R. S. Graphene and Graphene Oxide: Synthesis, Properties, and
Applications. Adv. Mater. 2010, 22, 3906−3924.
(35) Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. The
Chemistry of Graphene Oxide. Chem. Soc. Rev. 2010, 39, 228−240.
(36) Akhavan, O.; Ghaderi, E. Toxicity of Graphene and Graphene
oxide Nanowalls against Bacteria. ACS Nano 2010, 4, 5731−5736.
(37) Liu, M.; Chen, C.; Hu, J.; Wu, X.; Wang, X. Synthesis of
Magnetite/Graphene Oxide Composite and Application for Cobalt(II)
Removal. J. Phys. Chem. C 2011, 115, 25234−25240.
(38) Chandra, V.; Park, J.; Chun, Y.; Lee, J. W.; Hwang, I.; Kim, K. S.
Water-Dispersible Maghetite-Reduced Graphene Oxide Composites
for Arsenic Removal. ACS Nano 2010, 4, 3979−3986.
(39) Li, B.; Cao, H.; Yin, G. Mg(OH)2@Reduced Graphene Oxide
Composite for Removal of Dyes from Water. J. Mater. Chem. 2011, 21,
13765−13768.
(40) Wang, J.; Chen, Z.; Chen, B. Adsorption of Polycyclic Aromatic
Hydrocarbons by Graphene and Graphene Oxide Nanosheets. Environ.
Sci. Technol. 2014, 48, 4817−4825.
(41) Liu, M.; Xu, J.; Cheng, B.; Ho, W.; Yu, J. Synthesis and
Adsorption Performance of Mg(OH)2 Hexagonal Nanosheet−
Graphene Oxide Composites. Appl. Surf. Sci. 2015, 332, 121−129.
(42) Benesi, H. A. Infrared Spectrum of Mg(OH)2. J. Chem. Phys.
1959, 30, 852−852.
(43) Tian, N.; Tian, X.; Liu, X.; Zhou, Z.; Yang, C.; Ma, L.; Tian, C.;
Li, Y.; Wang, Y. Facile Synthesis of Hierarchical Dendrite-Like
Structure Iron Layered Double Hydroxide Nanohybrids for Effective
Arsenic Removal. Chem. Commun. 2016, 52, 11955−11958.
(44) Alibeigi, S.; Vaezi, M. R. Phase Transformation of Iron Oxide
Nanoparticles by Varying the Molar Ratio of Fe2+:Fe3+. Chem. Eng.
Technol. 2008, 31, 1591−1596.
(45) Das, J.; Das, D.; Dash, G. P.; Parida, K. M. Studies on Mg/Fe
Hydrotalcite-like-compound (HTlc) I. Removal of Inorganic Selenite
(SeO3(2-)) from Aqueous Medium. J. Colloid Interface Sci. 2002, 251,
26−32.
(46) Zhao, D.; Sheng, G.; Hu, J.; Chen, C.; Wang, X. The Adsorption
of Pb(II) on Mg2Al Layered Double Hydroxide. Chem. Eng. J. 2011,
171, 167−174.
(47) Ma, S.; Huang, L.; Ma, L.; Shim, Y.; Islam, S. M.; Wang, P.;
Zhao, L. D.; Wang, S.; Sun, G.; Yang, X.; Kanatzidis, M. G. Efficient
Uranium Capture by Polysulfide/Layered Double Hydroxide
Composites. J. Am. Chem. Soc. 2015, 137, 3670−3677.
(48) Zhao, J.; Liu, J.; Li, N.; Wang, W.; Nan, J.; Zhao, Z.; Cui, F.
Highly Efficient Removal of Bivalent Heavy Metals from Aqueous
Systems by Magnetic Porous Fe3O4-MnO2: Adsorption Behavior and
Process Study. Chem. Eng. J. 2016, 304, 737−746.
(49) Liu, J. S.; Song, L.; Shao, G. Q. Novel zwitterionic inorganic-
organic hybrids: kinetic and equilibrium model studies on Pb2+
removal from aqueous solution. J. Chem. Eng. Data 2011, 56, 2119−
2127.
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
 Journal of Chemical & Engineering Data Article

(50) Lu, Z. Z.; Chu, W. W.; Tan, R. Q.; Tang, S. H.; Xu, F.; Song, W.
J.; Zhao, J. H. Facile synthesis of β-SrHPO4 with wide applications in
the effective removel of Pb2+ and mathyl blue. J. Chem. Eng. Data
2017, 62, 3501−3511.
(51) Madadrang, C. J.; Kim, H. Y.; Gao, G.; Wang, N.; Zhu, J.; Feng,
H.; Gorring, M.; Kasner, M. L.; Hou, S. Adsorption behavior of
EDTA-graphene oxide for Pb (II) removal. ACS Appl. Mater. Interfaces
2012, 4, 1186−1193.
(52) Chen, Y.; Chen, L.; Bai, H.; Li, L. Graphene oxide−chitosan
composite hydrogels as broad-spectrum adsorbents for water
purification. J. Mater. Chem. A 2013, 1, 1992−2001.
(53) Wei, Y.; Gao, C.; Meng, F.-L.; Li, H.-H.; Wang, L.; Liu, J.-H.;
Huang, X.-J. SnO2/Reduced Graphene Oxide Nanocomposite for the
Simultaneous Electrochemical Detection of Cadmium(II), Lead(II),
Copper(II), and Mercury(II): An Interesting Favorable Mutual
Interference. J. Phys. Chem. C 2012, 116, 1034−1041.
(54) Li, Z.; Chen, F.; Yuan, L.; Liu, Y.; Zhao, Y.; Chai, Z.; Shi, W.
Uranium(VI) adsorption on graphene oxide nanosheets from aqueous
solutions. Chem. Eng. J. 2012, 210, 539−546.
(55) Cui, L.; Wang, Y.; Gao, L.; Hu, L.; Yan, L.; Wei, Q.; Du, B.
EDTA functionalized magnetic graphene oxide for removal of Pb(II),
Hg(II) and Cu(II) in water treatment: Adsorption mechanism and
separation property. Chem. Eng. J. 2015, 281, 1−10.
(56) Duan, S.; Xu, X.; Liu, X.; Wang, Y.; Hayat, T.; Alsaedi, A.; Meng,
Y.; Li, J. Highly enhanced adsorption performance of U(VI) by non-
thermal plasma modified magnetic Fe3O4 nanoparticles. J. Colloid
Interface Sci. 2018, 513, 92−103.

I DOI: 10.1021/acs.jced.8b00100
J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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