Journal of Hazardous Materials 299 (2015) 664–674

Contents lists available at ScienceDirect

Journal of Hazardous Materials

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

Investigation on the efficiency and mechanism of Cd(II) and Pb(II)

removal from aqueous solutions using MgO nanoparticles
Chunmei Xiong, Wei Wang ∗ , Fatang Tan, Fan Luo, Jianguo Chen, Xueliao Qiao
State Key Laboratory of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074, Hubei, PR China

h i g h l i g h t s

• MgO nanoparticles exhibited high removal abilities toward Cd(II) and Pb(II).
• The mechanism for Cd(II) and Pb(II) removal was precipitation and adsorption.
• The adsorbed heavy metals on MgO were difficult to be desorbed by water washing.

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

Article history: In this study, the removal of Cd(II) and Pb(II) from aqueous solutions using MgO nanoparticles prepared
Received 1 May 2015 by a simple sol-gel method was investigated. The efficiency of Cd(II) and Pb(II) removal was examined
Received in revised form 1 August 2015 through batch adsorption experiments. For the single adsorption of Cd(II) and Pb(II), The adsorption kinet-
Accepted 4 August 2015
ics and isotherm data obeyed well Pseudo-second-order and Langmuir models, indicating the monolayer
Available online 6 August 2015
chemisorption of heavy metal ions. The maximum adsorption capacities calculated by Langmuir equation
were 2294 mg/g for Cd(II) and 2614 mg/g for Pb(II), respectively. The adsorption process was controlled
Keywords:
simultaneously by external mass transfer and intraparticle diffusion. In the binary system, a competitive
MgO nanoparticle
Cadmium ion
adsorption was observed, showing preference of adsorption followed Pb(II) >Cd(II). Significantly, the elu-
Lead ion tion experiments confirmed that neither Cd(II) nor Pb(II) could be greatly desorbed after water washing
Adsorption even for five times. XRD and XPS measurements revealed the mechanism of Cd(II) and Pb(II) removal by
Precipitation MgO nanoparticles was mainly involved in precipitation and adsorption on the surface of MgO, resulting
from the interaction between active sites of MgO and heavy metal ions. Easy preparation, remarkable
removal efficiency and firmly adsorptive ability make the MgO nanoparticles to be an efficient material
in the treatment of heavy metal-contaminated water.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, heavy metal ions, such as Pb(II), Cd(II), and Hg(II),
especially in water, have posed a serious threat to public health and
ecological system due to their high toxicity, non-biodegradation
and long-term damage by accumulation [1]. Therefore, the effi-
cient removal of heavy metal ions from aqueous systems is of
great significance in protecting the earth’s ecosystems. Up to now,
various methods such as chemical precipitation, adsorption, evap-
oration, ion exchange, membrane filtration, electrodialysis and
reverse osmosis, have been developed to treat water containing
heavy metals [2–5]. Among them, adsorption has been universally
accepted as one of the most commonly practiced techniques for
∗ Corresponding author. Fax: +86 27 87541540.
E-mail address: weiwang@hust.edu.cn (W. Wang).
the removal of heavy metal ions because of its simple and stable
handling process, high efficient wastewater treatment, absence of
secondary pollution and low operating cost [6]. A number of mate-
rials including activated carbon [7], bentonite [8], magnetite [9],
chitosan [10], etc., have been reported to be capable of adsorbing
heavy metal ions from aqueous solutions. However, these adsor-
bents usually suffer from low adsorption capacities or removal
efficiencies of heavy metal ions. Therefore, a lot of efforts are still
continued to explore highly efficient adsorbents for the removal of
heavy metal ions.
Recently, some metal oxides or metal hydroxides as adsorbents
have attracted much attention due to their low cost, environ-
mentally benign nature and excellent adsorption properties for
environmental applications [11–13]. Magnesium oxide (MgO),
a typical metal oxide adsorbent, is a promising candidate for
the treatment of water pollutants [14,15]. Particularly, nanosized
MgO has exhibited higher efficiency and faster adsorption rate

http://dx.doi.org/10.1016/j.jhazmat.2015.08.008
0304-3894/© 2015 Elsevier B.V. All rights reserved.
 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674
in wastewater treatment, owing to its higher surface areas and
much more surface active sites than bulk materials. Feng et al.
[16] reported mesoporous MgO nanosheets had the maximum
adsorption capacity of 1684.25 mg/g for Ni(II) removal from aque-
ous solutions. Tian et al. [17] found porous hierarchical MgO
exhibited superb adsorption performance toward Congo red dye,
with the maximum adsorption capacity of 2409 mg/g. In short,
micro/nanosized MgO can efficiently remove heavy metal ions
[18–20], fluoride [21], toxic dyes [22,23], etc. The pioneering work
inspires us to further explore the adsorption capacities of MgO
nanoparticles for heavy metal ions in solutions. On the other hand,
the mechanism of heavy metal ions removal using MgO as an
adsorbent is still controversial. Campbell and Starr [24] proved
that metal (Cu, Ag and Pb) could combine with the oxygen or
magnesium of MgO in the form of covalent bond. Zhu and Li
[14] found that the dominant mechanism of Cd(II) removal was
precipitation of Cd(OH)2 on the surface of MgO. Cao et al. [25]
proposed a removal mechanism involving solid−liquid interfacial
cation exchange between MgO and Pb(II) or Cd(II) to form PbO or
CdO. Mahdavi et al. [26] proposed MgO nanoparticles had a much
greater metal adsorption capacity than TiO2 and Al2 O3 nanopar-
ticles due to the occurrence of adsorption and precipitation of
heavy metal ions with MgO. Thus, an in-depth investigation into the
mechanism of heavy metal ions removal using MgO nanoparticles
is needed urgently.
In this work, the removal capacity and mechanism of Cd(II) and
Pb(II) from aqueous solutions using MgO nanoparticles prepared
by a simple sol-gel method were systematically investigated. The
influences of contact time, initial metal ion concentration and solu-
tion pH on removal of Cd(II) and Pb(II) from single and binary metal
solutions were examined in details. Besides, the adsorbed products
were further analyzed by XRD, XPS and SEM equipped with an EDX
analyzer to study the mechanism of heavy metal removal and the
adsorption action between heavy metal ions and MgO nanoparti-
cles.
2. Materials and methods
2.1. Materials
Magnesium nitrate hexahydrate (Mg(NO3 )2 ·6H2 O) was
obtained from Shanghai Experimental Reagent Co., Ltd. Citric acid
(C6 H8 O7 ) was purchased from Sinopharm Chemical Reagent Co.,
Ltd. Cadmium chloride(CdCl2 ·2.5H2 O) and lead nitrate (Pb(NO3 )2 )
were purchased from Tianjin Kemiou Chemical Reagent Co., Ltd. All
the chemical reagents were of analytical grade and used without
further purification in this study. Doubly distilled (DI) water was
used throughout the experiments.
2.2. Preparation of MgO nanoparticles
The preparation procedure for MgO nanoparticles was similar to
our previous work [27]. Typically, 0.02 mol of Mg(NO3 )2 ·6H2 O was
dissolved in 20 mL of DI water. Subsequently, an aqueous solution
containing equimolar amount of C6 H8 O7 was added into the above
solution under stirring. Then the mixture was placed in a water bath
at 80 ◦ C with continuous stirring until it completely turned into a
gel. Finally, the wet gel was dried at 150 ◦ C to obtain a white fluffy
precursor and followed by calcination at 600 ◦ C for 1 h to yield MgO
nanoparticles.
2.3. Characterization of MgO nanoparticles
Crystal structure of samples was characterized by XRD
(Philips/X’ Pert PRO). Morphology of samples was observed
using transmission electron microscope (TEM, FEI Tecnai G2
665
20) and scanning electron microscope (SEM, FEI/Nova NanoSEM
450) equipped with an energy-dispersive X-ray (EDX) ana-
lyzer (Oxford/X-Max 50). Molecular structure was analyzed by
Fourier tranaform infrared (FTIR) spectrometer (Bruker VERTEX70).
Brunauer–Emmett–Teller (BET) surface area measurements were
carried out on a Micromeritics ASAP 2020 M surface area analyzer.
X-ray photoelectron spectroscopy (XPS) analysis was acquired on
a Kratos/Axis Ultra DLD-600W spectrometer.
2.4. Batch adsorption experiments
Stock solutions with different concentration of Cd(II) and Pb(II)
were prepared using Pb(NO3 )2 and CdCl2 ·2.5H2 O as the sources of
heavy metal ions, respectively. The pH of the stock solutions was
adjusted using NaOH (0.1 M) and HNO3 (0.1 M).
Adsorption kinetics experiments were conducted in a series of
250 mL beakers containing 0.01 g (100 mg/L) of MgO nanoparticles
and 100 mL (100 mg/L) metal ion solutions with continuous stir-
ring at pH 5 and 25 ◦ C. After different time intervals, aliquots of
the samples were collected and filtered through a 0.25 ␮m mem-
brane. A PDV6000 plus (Cogent Environmental Ltd.) analyzer was
used to measure the concentrations of metal ions in the remaining
solutions.
Adsorption isotherms experiments were conducted following
similar procedure except using metal ion solutions with different
concentrations. In binary metal system, the solutions containing
the same initial concentrations of Cd(II) and Pb(II) were used to
investigate the competitive adsorption of Cd(II) and Pb(II) on MgO
nanoparticles. The amounts of Cd(II) and Pb(II) adsorbed on MgO
nanoparticles, qt (mg/g) are calculated by using Eq. (1):
[W (CO − C)]
qt = (1)
V
where C0 (mg/L) is the initial metal ion concentration and C
(mg/L) is residual metal ion concentration in solution at time t, V
(L) and W (g) are the volume of the solution and the weight of MgO
nanoparticles, respectively. In the Eq. (1), Ce and qe are the equi-
librium concentration and the adsorption amount at equilibrium
time, respectively.
Effects of initial pH values (pH 2.0, 3.0, 4.0 and 5.0) were also
studied in the single and binary systems in the similar procedure
except using 250 mg/L of metal ion solutions. All the above exper-
iments were performed in duplicate.
2.5. Elution experiments of the adsorption products
Firstly, 0.03 g (1000 mg/L) of MgO nanoparticles was preloaded
by 30 mL (1000 mg/L) of metal ion solutions according to the above
adsorption procedure. Then, the resulting powders were dispersed
in 30 mL of DI water under stirring for 4 h at 25 ◦ C. Finally, the mix-
ture was centrifuged and the concentrations of heavy metal ions in
the supernatant were measured to calculate the eluted amounts of
Cd(II) and Pb(II) from the products after adsorption.
3. Results and discussion
3.1. Structures and morphologies of MgO nanoparticles
The XRD pattern and SEM image of the as-prepared MgO
nanoparticles were shown in Fig. 1(a). Five diffraction peaks at
2␪ = 36.8◦ , 42.8◦ , 62.1◦ , 74.5◦ and 78.4◦ could be indexed to the
(1 1 1), (2 0 0), (2 2 0), (3 1 1), and (2 2 2) planes of MgO with a peri-
clase structure (JCPDS 87-0653). No impurity peaks were observed,
indicating that the products were pure MgO nanoparticles. More-
over, the average grain size of MgO was calculated to be 20.9 nm by
using the Scherrer equation (Table 1S), according to the full width
666 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674

Fig. 1. XRD pattern, SEM image (a), and N2 adsorption–desorption isotherms (b) of MgO nanoparticles.

at half-maximum (FWHM) of all the peaks. From the SEM image
and TEM image (Fig. 1S(a)), the prepared MgO nanoparticles were
found to exhibit plate-like nanoparticles with relatively uniform
size distribution. The average particle size of MgO nanoparticles
was measured to be 20.23 nm by using Nano Measurer 1.2 software,
which corresponded to the result of XRD analysis.
FTIR spectra of the as-prepared MgO nanoparticles was shown
in Fig. 1S(b). A absorption band at 3438 −1 was assigned to the
adsorbed water during sample preparation. Bands in the range of
1458–1640 cm−1 were attributed to the OH stretching mode of
water molecule [28]. Two characteristic bonds at 415 and 695 cm−1
occurred which confirmed the presence of Mg O groups. The N2
adsorption–desorption isotherms and pore size distribution of the

Fig. 2. Effect of contact time on single Cd(II) (a), Pb(II) (b), and competitive (c) adsorption on MgO nanoparticles; (d) Pseudo-second-order model for single adsorption of
Cd(II) and Pb(II) on MgO nanoparticles.
 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674
Fig. 3. Adsorption isotherms (a) and Langmuir isotherm plots (b) for single adsorption of Cd(II) and Pb(II) on MgO nanoparticles.
as-prepared MgO nanoparticles were shown in Fig. 1(b). The results
revealed that the MgO nanoparticles possessed high BET surface
area of 101.95 m2 /g and an average pore diameter of 4.9 nm. The
single point surface area at P/P0 = 0.299 was 112.19 m2 /g and the
pore volume at P/P0 = 0.995 was 0.12 cm3 /g.
3.2. Effect of contact time
The effect of contact time on the single and binary adsorption
of Cd(II) and Pb(II) on MgO nanoparticles was examined. As shown
in Fig. 2(a) and (b), initially the adsorption amount qt increased
quickly, then reached equilibria in about 30 min and 15 min for
the single adsorption of Cd(II) and Pb(II), respectively. Clearly, the
time to reach equi librium adsorption is much shorter than those
of zeolite [29,30], activated carbon [31], and coal fly ash [32]. Such
fast adsorption rate could be attributed to the abundance of active
sites on the surface of MgO nanoparticles. Also, the binary adsorp-
tion of Cd(II) and Pb(II) exhibited a similar trend (Fig. 2(c)). Hence,
a contact time of 60 min was sufficient to reach equilibrium for
MgO nanoparticles in the adsorption of heavy metal ions, which
was selected in the further experiments. In addition, the change of
solution pH was also measured during the adsorption process and
667
shown in Fig. 2. The solution pH values gradually increased with
time and reached equilibria in about 180 min, which was assigned
to the hydration of MgO nanoparticles in aqueous solutions.
In order to understand the characteristics of the adsorption
process, three kinetic models detailed in the supplementary data,
including pseudo-first-order [33], pseudo-second-order [34], and
Weber-Morris kinetic models [35] were applied to fit the experi-
mental data obtained from the single adsorption system (Fig. 2(d)
and Fig. 2S), and the kinetic parameters were listed in Table S2.
In the both case of Cd(II) and Pb(II), the linear regression correla-
tions (R2 ) from pseudo-second-order model were higher than those
from pseudo-first-order model. In addition, the calculated qe values
(qe,cal ) from the pseudo-second-order model were much closer to
the experimental ones (qe,exp ). Therefore, the pseudo-second-order
model was more appropriate for describing the single adsorption
behavior of Cd(II) and Pb(II), indicating that the adsorption behav-
ior of heavy metal ions on MgO nanoparticels mainly involved the
chemical adsorption [34].
The analysis of Weber–Morris model (Fig. 2S(b)), was applied to
discuss the actual rate-controlling step in the single adsorption of
Cd(II) and Pb(II), and three linear portions was observed. The first
line portion represented external mass transfer. The second linear
668 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674
Fig. 4. Adsorption isotherms (a) and Langmuir isotherm plots (b) for competitive adsorption of Cd(II) and Pb(II) on MgO nanoparticles.
portion, intra-particle diffusion, showed sorption. And the third lin-
ear portion showed adsorption/desorption equilibrium. The plots
did not through the origin, suggesting that intra-particle diffusion
was not the only rate-controlling step, and the external mass trans-
fer also contributed significantly in the rate-controlling step due
to the large intercepts of the second linear portion of the plots. So
the adsorption process was collectively controlled by external mass
transfer and intra-particle diffusion.
3.3. Effect of initial metal ion concentrations
To explore the adsorption capacities of MgO nanoparticles
toward Cd(II) and Pb(II), the adsorption of metal ions with different
initial concentrations was investigated. Fig. 3(a) showed that single
adsorption isotherms with the initial concentrations ranging from
50 to 400 mg/L. It was observed that the adsorption amount of MgO
nanoparticles toward Cd(II) and Pb(II) increased gradually at low
concentrations (0–250 mg/L), then reached a plateau and stayed
steady despite a continuing increase in the initial concentrations of
metal ions.
The adsorption data of MgO nanoparticles toward single
Cd(II) and Pb(II) were analyzed using three different isother-
mal adsorption models, namely Langmuir model [36], Freundlich
model [37] and Dubinbin-Radushkevich model [38], respectively
(Fig. 3(b) and Fig. 3S), and the calculated isothermal parame-
ters were presented in Table 3S. Compared with the Freundlich
and Dubinbin–Radushkevich models, the Langmuir model fitted
better with the experimental data due to the higher correlation
coefficients (R2 > 0.999). In particular, the maximum adsorption
capacities (qmL ) calculated by Langmuir model were 2294 and
2614 mg/g for Cd(II) and Pb(II), respectively, which are higher
than the reported results of micro/nano structured MgO [14,18],
activated carbon [31] and coal fly ash [32]. As documented, the
Langmuir model assumes monolayer coverage of the adsorbent
surface, on which the binding sites have the same affinity for
the adsorption [36]. Therefore, the formed monolayer was possi-
bly due to the chemical interaction between MgO nanoparticles
and heavy metal ions. In order to further verify chemisorption
was dominant in the adsorption process of Cd(II) and Pb(II), the
Dubinbin–Radushkevich model was applied to distinguish between
 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674
Fig. 5. Effect of initial solution pH on single Cd(II) (a), Pb(II) (b), and competitive (c) adsorption on MgO nanoparticles.
physisorption and chemisorption. The mean free energies (E) of
adsorption for Cd(II) and Pb(II) were 392.9 and 292.5 kJ/mol, respec-
tively, suggesting that chemisorption was dominating in the single
adsorption process of Cd(II) and Pb(II) (Table 3S).
The competitive adsorption isotherms of Cd(II) and Pb(II) were
also shown in Fig. 4(a). As expected, MgO nanoparticles simul-
taneously adsorbed Cd(II) and Pb(II) ions at low concentrations
(0–100 mg/L), whereas a clear affinity order of Pb(II) >Cd(II) was
observed at high concentrations. The adsorption capacity of MgO
nanoparticles for Pb(II) increased rapidly and attained saturation at
the initial concentration of 300 mg/L, while for Cd(II) it decreased
gradually after a period of elevation. This could be attributed to the
fact that the active adsorption sites of MgO particles were occu-
pied mainly by Pb(II) rather than Cd(II) at high initial concentration
[39,40].For the binary metal system, the three models also were
used to analyze the adsorption data of MgO nanoparticles toward
Cd(II) and Pb(II), respectively (Fig. 4(b) and Fig. 4S), and the model
parameters were summarized in Table 4S. Obviously, the experi-
mental data for Pb(II) adsorption fitted well with Langmuir model
(R2 ≈1), while the data for Cd(II) adsorption did not fit any of the
three models. That is to say, the three models could not be used to
describe the Cd(II) adsorption in binary metal system. Moreover,
the E for Pb(II) adsorption calculated by Dubinbin–Radushkevich
model was 656.6 kJ/mol, implying the involvement of a chemisorp-
tion process. Combined with the results of single metal system,
the monolayer chemisorption represented well the adsorption pro-
cess of Pb(II) on MgO nanoparticles whether in the single or binary
metal systems, while it wasn’t suitable for the adsorption of Cd(II)
in the binary metal system. Additionally, in binary metal system
669
the adsorption capacities of MgO nanoparticles toward Cd(II) and
Pb(II) followed the order of Pb(II) >Cd(II), which is in agreement
with the results reported in literatures [39,41].
3.4. Effect of initial solution pH
In practice, wastewater may be acidic or alkaline, so the solution
pH is one of the most important factors in the adsorption process.
According to the solubility product of Cd(OH)2 and Pb(OH)2 , when
the concentrations of Cd(II) and Pb(II) in solutions are less than
400 mg/L, they will not generate insoluble species at pH < 8 and
pH < 6, respectively. Hence, the pH values in the range of 2–5 were
chosen in the following experiments.
Fig. 5(a) and (b) showed the effect of initial solution pH on the
single adsorption of Cd(II) and Pb(II), respectively. Apparently, the
pH value had a considerable influence on the adsorption capacity of
MgO nanoparticles. It was found that the higher adsorption capacity
for heavy metal ions was achieved at higher pH values. Note that
the adsorption capacity for Cd(II) and Pb(II) increased rapidly in the
pH range of 2–3. This result was attributed to that at very low initial
pH (pH 2) the high concentration of H+ in solution could react with
MgO nanoparticles, which would consume most of the adsorbents
and cause a decrease of the adsorption capacity. In addition, at low
pH value Cd(II) and Pb(II) had low affinity to Mg(OH)2 generated
from hydration of MgO nanoparticls, resulting in a decrease in the
adsorption capacities for Cd(II) and Pb(II) [42,43].
The effect of initial solution pH on the competitive adsorption of
Cd(II) and Pb(II) on MgO nanoparticles was shown in Fig. 5(c). The
adsorption capacities for Cd(II) and Pb(II) were both very low at the
670 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674

Table 1
Experimental parameters for the mechanism investigation of metal ion removal using MgO nanoparticles.

Sample MgO dose(mg/L) Cd(II) concentration (mg/L) Pb(II) concentration (mg/L)

1 100 250 0
2 100 0 250
3 100 250 250
4 100 0 0

Fig. 6. Quantitative analysis and EDX spectra of MgO nanoparticles after adsorbing heavy metal ions.

Fig. 7. SEM image (a) and SEM-EDX elemental mapping (b–e) of MgO nanoparticles after adsorbing Cd(II) and Pb(II).
 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674
Fig. 8. XRD patterns of MgO nanoparticles after absorbing Cd(II) (a) and Pb(II) (b).
pH value of 2. As the initial solution pH increased, the adsorption
capacity for Pb(II) increased sharply, and achieved almost complete
adsorption when the initial solution pH value was more than 3,
while only a small increase was observed for Cd(II) adsorption. The
higher adsorption capacity for Pb(II) than that for Cd(II) could be
attributed to their different affinities to MgO nanoparticles.
3.5. Mechanisms of Cd(II) and Pb(II) removal
To study the removal mechanism of MgO nanoparticles toward
Pb(II) and Cd(II), the changes of MgO nanoparticles after adsorp-
tion (Table 1) were also analyzed by SEM-EDX, XRD and XPS. First,
elemental compositions of the adsorbed products were analyzed
by EDX spectra, and the results were shown in Fig. 6. From the
EDX spectra, the signals from C, O, Mg, Pt, Pb and Cd elements were
detected. Here the C element could be from the adsorption of CO2 or
organics, while the Pt element resulted from the sprayed platinum
for SEM observation. Hence, it can confirm that the adsorbed prod-
671
ucts are mainly composed of O, Mg, Pb and Cd elements. Notably,
the signal from Cd atom in binary metal system was very weak,
which indicated the adsorbed products (Sample 3) contained a
small amount of Cd. Furthermore, the weight ratios of heavy metal
ions to MgO were calculated according to the molar ratios of Cd/Mg
and Pb/Mg from quantitative analysis of EDX spectra. Interest-
ingly, the calculated adsorption capacities (heavy metal ions/MgO)
were 2286.2 mg/g for single Cd(II) (Sample 1), 2547.4 mg/g for sin-
gle Pb(II) (Sample 2), and 18.2 mg/g for Cd(II) and 2626.4 mg/g for
Pb(II) in the binary metal system (Sample 3), respectively. These
values were nearly consistent with the results of the above adsorp-
tion experiments, which indicated MgO nanoparticles could almost
completely removed Cd(II) and Pb(II) in single system, and Pb(II) in
the binary system from aqueous solutions.
The SEM image and EDX mapping of MgO nanoparticles after
adsorbing Cd(II) and Pb(II) (Sample 3) were shown in Fig. 7. The
obtained product after adsorption displayed plate-like morphology
with an average diameter of 1.5 ␮m (Fig. 7a). Clearly, the parti-
672 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674

Fig. 9. High-resolution XPS spectra of Cd 3d (a) and Pb 4f (b).

cle size of the obtained product after adsorbing heavy metals was
larger than that of the sample without heavy metal ions in solution
(Sample 4, Fig. 5S(a)), which can be attributed to the adsorption of
heavy metals ions besides the hydration of MgO. Moreover, EDX
mapping showed that Cd and Pb elements were uniformly dis-
persed in the adsorbed product, implying MgO nanoparticles had
a large number of active sites to be combined with heavy metals.
Note that the density of Cd was far lower than that of Pb, indicat-
ing a small amount of Cd contained in the adsorbed product and
adsorption preference of MgO nanoparticles toward Pb(II), which
were consistent with the above analysis.
The adsorbed products (Sample 1 and Sample 2) for single Cd(II)
and Pb(II) removal were further analyzed by XRD, shown in Fig. 8.
All the diffraction peaks of the adsorbed product for Cd(II) could
be assigned to Cd(OH)2 (JCPDS 84-1767), CdO (JCPDS 05-0640),
Mg(OH)2 (JCPDS 84-2163) and MgO (JCPDS 87-0653), while the
diffraction peaks for Pb(II) could be indexed to Pb3 (CO3 )2 (OH)2
(JCPDS 01-0687), PbO (JCPDS 72-0094), Mg(OH)2 (JCPDS 84-2163)
and MgO (JCPDS 87-0653), which were quite different from the
results reported in the literature [25]. As we all know, MgO
nanoparticles are easily hydrated by water to generate Mg(OH)2
[19], which is further proved by the experimental result (Sample
4, Fig. 5S(b)). Hence, the Mg(OH)2 phase in the adsorbed prod-
ucts resulted from the hydration of MgO nanoparticles in aqueous
solution. The generated Mg(OH)2 would partially dissociate to
produce OH− ions, which were near the surface of MgO nanopar-
ticles. As a result, heavy metal ions in aqueous solutions could
combine with the produced OH− to form insoluble hydroxides
(Cd(OH)2 , Pb(OH)2 ), which nucleated and grew on the surfaces
of Mg(OH)2 /MgO. Because the resulting Pb(OH)2 was unstable, it
could react with dissolved CO2 to form Pb3 (CO3 )2 (OH)2 [18]. As for
the presence of CdO and PbO phases, it could be attributed to the
adsorption of Cd and Pb ions on the surface defect sites of MgO
nanoparticles. It is well known that MgO nanoparticles have plenty
 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674
Table 2
Elution rates of the adsorbed Cd(II) and Pb(II) on MgO nanoparticles.
Metal Adsorption capacity(mg/g)
Cd 999.9
Pb 995.2
of vacancy defects on the surface of MgO, especially magnesium
vacancies, which can combine heavy metal ions (Cd2+ and Pb2+ )
to form metal oxides (CdO and PbO). Significantly, when Mg(OH)2
was used instead of MgO to remove Pb(II), the obtained product
was composed of only Pb3 (CO3 )2 (OH)2 and Mg(OH)2 , and no PbO
phase was found (Fig. 6S). Consequently, the mechanism of Cd(II)
and Pb(II) removal from aqueous solutions by MgO nanoparticles
was proposed to be cooperative effects of the precipitation and
adsorption of heavy metal ions on the surface of MgO.
To further confirm the composition of the absorbed products,
the MgO nanoparticles after absorbing Cd(II) and Pb(II) were also
analyzed by XPS technique. Pronounced signals from C, O, Mg, Pb
and Cd could be observed from the survey spectra (Fig. 7S), fur-
ther validating the existence of these elements in the adsorbed
products, which was in good accordance with the results of EDX
analysis. Moreover, the relatively high intensities of Cd and Pb sug-
gested a lot of heavy metal ions on the surface of MgO/Mg(OH)2 .
The high resolution scan of Cd 3d and Pb 4f regions were shown
in Fig. 9(a) and (b), respectively. Fig. 9(a) displayed two peaks
centered at 405.57 and 412.31 eV corresponding to Cd 3d5/2 and
Cd 3d3/2 , respectively. The two peaks were asymmetric, and each
could be deconvoluted into two subpeaks: 405.43 and 406.21 eV
for Cd 3d5/2 , 412.10 and 412.94 eV for Cd 3d3/2 . These deconvo-
luted subpeaks with a peak separation of ∼6.7 eV between Cd 3d5/2
and 3d3/2 states could be assigned to Cd(OH)2 and CdO, respec-
tively [44], which were in agreement with the above XRD analysis
(Fig. 8(a)). The high-resolution XPS spectrum of Pb 4f also exhibited
two distinguishable peaks located at 138.33 and 143.22 eV, origi-
nating from Pb 4f7/2 and Pb 4f5/2 . Similarly, the peaks of Pb 4f7/2 and
Pb 4f5/2 could be fitted individually into two subpeaks: 138.26 and
138.90 eV for Pb 4f7/2 , 143.10 and 143.79 eV for Pb 4f5/2 . The fitted
subpeaks with a peak separation of ∼4.8 eV between Pb 4f7/2 and
Pb 4f5/2 could be attributed to Pb3 (OH)2 (CO3 )2 and PbO, respec-
tively [45,46], which was consistent with the above XRD analysis
(Fig. 8(b)). Additionally, the Mg 1s spectra of the absorbed prod-
ucts with (Sample 2) and without (Sample 4) heavy metal ions in
solutions were examined, and shown in Fig. 8S. Comparatively, the
binding energy of Mg1s was observed to shift to high energy side
after adsorption. It could be due to the formation of Mg O Pb bond
in the adsorbed product, resulting in the decrease of electron cloud
density of Mg O bond. This result also indicated indirectly some
heavy metal ions could be adsorbed on the surface of MgO/Mg(OH)2
in the form of oxides.
3.6. Cd(II) and Pb(II) elution experiments
To further explore the adsorption action between heavy metal
ions and MgO nanoparticles, elution experiments were performed
by washing with water. The tested data showed that neither Cd(II)
nor Pb(II) could be washed largely out from the adsorbed prod-
ucts by water washing, and the maximum elution rates of Cd(II)
and Pb(II) were only about 0.07% and 0.05%, respectively (Table 2),
indicating that both Cd(II) and Pb(II) could be adsorbed tightly on
the surface of the adsorbent and suggesting a strong interaction
between heavy metal ions and MgO nanoparticles. In other words,
MgO nanoparticles have a fixing action on heavy metal ions to
keep heavy metal ions from moving with water, which exhibited
673
Elution rate of heavy metal ions (%)
1 2 3 4 5
0.060 0.065 0.068 0.072 0.066
0.053 0.048 0.052 0.050 0.042
promising potentials for the practical application in wastewater
treatment.
4. Conclusion
In summary, this study investigated the Cd(II) and Pb(II) removal
from aqueous solutions using MgO nanoparticles prepared by a
simple sol-gel method. Batch adsorption experiments were car-
ried out at different contact time, initial concentrations of heavy
metal ions and pH values, respectively. It was found that the
adsorption rates were very fast and adsorption equilibriums were
obtained in about 30 min and 15 min for the adsorption of Cd(II)
and Pb(II), respectively. The best models to describe the kinetics
and isotherms of single adsorption were the pseudo-second-order
kinetic and Langmuir models, respectively, indicating the mono-
layer chemisorption of Cd(II) and Pb(II) on MgO nanoparticles. The
maximum adsorption capacities calculated by applying the Lang-
muir equation were 2294 mg/g for Cd(II) and 2614 mg/g for Pb(II),
respectively. The competitive system showed that the affinity order
of these two metal ions was Pb(II) > Cd(II). Moreover, the solu-
tion pH was found to be a key factor in the adsorption of heavy
metal ions on MgO, because the solution pH will influence pre-
cipitation of heavy metal ions and dissolution of the adsorbent in
solutions. The analysis of the adsorbed products indicated the main
mechanism for Cd(II) and Pb(II) removal was the precipitation and
adsorption of heavy metal ions on the surface of MgO. Significantly,
the elution experiments confirmed that neither Cd(II) nor Pb(II)
could be greatly desorbed largely after water washing even for
five times. Considering the advantages of low cost, mild condition,
high adsorption capacity as well as eco-friendly to environment,
MgO nanoparticles have very promising applications for removal
of heavy metals from aquatic ecosystems.
Acknowledgements
The authors gratefully acknowledge the support from the
National Natural Science Foundation of China (No.50902054). The
authors also acknowledge the experimental help from Huazhong
University of Science & Technology Analytical and Testing Center.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jhazmat.2015.08.
008
References
[1] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review, J.
Environ. Manage. 92 (2011) 407–418.
[2] J.O. Esalah, M.E. Weber, J.H. Vera, Removal of lead, cadmium and zinc from
aqueous solutions by precipitation with sodium di-(n-octyl) phosphinate,
Can. J. Chem. Eng. 78 (2000) 948–954.
[3] H.K. An, B.Y. Park, D.S. Kim, Crab shell for the removal of heavy metals from
aqueous solution, Water Res. 35 (2001) 3551–3556.
[4] K.Y. Kumar, H.B. Muralidhara, Y.A. Nayaka, J. Balasubramanyam, H.
Hanumanthappa, Hierarchically assembled mesoporous ZnOnanorods for the
removal of lead and cadmium by using differential pulse anodic stripping
voltammetric method, Powder Technol. 239 (2013) 208–216.
674 C. Xiong et al. / Journal of Hazardous Materials 299 (2015) 664–674
[5] T. Mahmood, M.T. Saddique, A. Naeem, S. Mustafa, B. Dilara, Z.A. Raza, Cation
exchange removal of Cd from aqueous solution by NiO, J. Hazard. Mater. 185
(2011) 824–828.
[6] T. Sheela, Y.A. Nayaka, R. Viswanatha, S. Basavanna, T.G. Venkatesha, Kinetics
and thermodynamics studies on the adsorption of Zn(II), Cd(II) and Hg(II)
from aqueous solution using zinc oxide nanoparticles, Powder Technol. 217
(2011) 163–170.
[7] C. Faur Brasquet, K. Kadirvelu, P. Le Cloirec, Removal of metal ions from
aqueous solution by adsorption onto activated carbon cloths: adsorption
competition with organic matter, Carbon 40 (2002) 2387–2392.
[8] C.M. Futalan, C.C. Kan, M.L. Dalida, K.J. Hsien, C. Pascua, M.W. Wan,
Comparative and competitive adsorption of copper, lead, and nickel using
chitosan immobilized on bentonite, Carbohyd. Polym. 83 (2011) 528–536.
[9] H. Karami, Heavy metal removal from water by magnetite nanorods, Chem.
Eng. J. 219 (2013) 209–216.
[10] Y. Zhu, J. Hu, J. Wang, Competitive adsorption of Pb(II), Cu(II) and Zn(II) onto
xanthate- modified magnetic chitosan, J. Hazard. Mater. 221 (2012) 155–161.
[11] M. Hua, S. Zhang, B. Pan, W. Zhang, L. Lv, Q. Zhang, Heavy metal removal from
water/wastewater by nanosized metal oxides: a review, J. Hazard. Mater. 211
(2012) 317–331.
[12] R. Liu, H. Fu, H. Yin, P. Wang, L. Lua, Y. Tao, A facile sol combustion and
calcination process for the preparation of magnetic
Ni0.5 Zn0.5 Fe2 O4 nanopowders and their adsorption behaviors of Congo red,
Powder Technol. 274 (2015) 418–425.
[13] H.R. Mahmoud, S.A. El-Molla, M. Saif, Improvement of physicochemical
properties of Fe2 O3 /MgO nanomaterials by hydrothermal treatment for dye
removal from industrial wastewater, Powder Technol. 249 (2013) 225–233.
[14] Z. Zhu, W. Li, Effect of magnesium oxide on adsorption of Cd2+ from aqueous
solution, RSC Adv. 2 (2012) 5178–5184.
[15] C. Gao, W. Zhang, H. Li, L. Lang, Z. Xu, Controllable fabrication of mesoporous
MgO with various morphologies and their absorption performance for toxic
pollutants in water, Cryst. Growth Des. 8 (2008) 3785–3790.
[16] J. Feng, L. Zou, Y. Wang, B. Li, X. He, Z. Fan, Y. Ren, Y. Lv, M. Zhang, D. Chen,
Synthesis of high surface area, mesoporous MgO nanosheets with excellent
adsorption capability for Ni(II) via a distillation treating, J. Colloid Interf. Sci.
438 (2015) 259–267.
[17] P. Tian, X. Han, G. Ning, H. Fang, J. Ye, W. Gong, Y. Lin, Synthesis of porous
hierarchical MgO and its superb adsorption properties, ACS Appl. Mater.
Interfaces 5 (2013) 12411–12418.
[18] L. Zhang, W. Zhu, H. Zhang, S. Bi, Q. Zhang, Hydrothermal–thermal conversion
synthesis of hierarchical porous MgO microrods as efficient adsorbents for
lead(II) and chromium(VI) removal, RSC Adv. 58 (2014) 30542–30550.
[19] V. Srivastava, Y.C. Sharma, M. Sillanpää, Green synthesis of magnesium oxide
nanoflower and its application for the removal of divalent metallic species
from synthetic wastewater, Ceram. Int. 41 (2015) 6702–6709.
[20] S. Tresintsi, K. Simeonidis, M. Katsikini, E.C. Paloura, G. Bantsis, M. Mitrakas, A
novel approach for arsenic adsorbents regeneration using MgO, J. Hazard.
Mater. 265 (2014) 217–225.
[21] L. Li, D. Xu, X. Li, W. Liu, Y. Jia, Excellent fluoride removal properties of porous
hollow MgO microspheres, New J. Chem. 11 (2014) 5445–5452.
[22] G. Moussavi, M. Mahmoudi, Removal of azo and anthraquinone reactive dyes
from industrial wastewaters using MgO nanoparticles, J. Hazard. Mater. 168
(2009) 806–812.
[23] J.P. Dhal, M. Sethi, B.G. Mishra, G. Hota, MgO nanomaterials with different
morphologies and their sorption capacity for removal of toxic dyes, Mater.
Lett. 141 (2015) 267–271.
[24] C.T. Campbell, D.E. Starr, Metal adsorption and adhesion energies on MgO
(100), J. Am. Chem. Soc. 124 (2002) 9212–9218.
[25] C. Cao, J. Qu, F. Wei, H. Liu, W. Song, Superb adsorption capacity and
mechanism of flowerlike magnesium oxide nanostructures for lead and
cadmium ions, ACS Appl. Mater. Interfaces 4 (2012) 4283–4287.
[26] S. Mahdavi, M. Jalali, A. Afkhami, Heavy metals removal from aqueous
solutions using TiO2 , MgO, and Al2 O3 nanoparticles, Chem. Eng. Commun. 200
(2013) 448–470.
[27] Y. Rao, W. Wang, F. Tan, Y. Cai, J. Lu, X. Qiao, Influence of different ions doping
on the antibacterial properties of MgO nanopowders, Appl. Surf. Sci. 284
(2013) 726–731.
[28] M. Rezaei, M. Khajenoori, B. Nematollahi, Synthesis of high surface area
nanocrystalline MgO by pluronic P123 triblock copolymer surfactant, Powder
Technol. 205 (2011) 112–116.
[29] Q. Cai, B.D. Turner, D. Sheng, S. Sloan, The kinetics of fluoride Sorption by
zeolite: effects of cadmium, barium and manganese, J. Contam. Hydrol.
177–178 (2015) 136–147.
[30] P. Castaldi, L. Santona, S. Enzo, P. Melis, Sorption processes and XRD analysis
of a natural zeolite exchanged with Pb2+ , Cd2+ and Zn2+ cations, J. Hazard.
Mater. 156 (2008) 428–434.
[31] C. Gabaldon, P. Marzal, J. Ferrer, A. Seco, Single and competitive adsorption of
Cd and Zn onto a granular activated carbon, Water Res. 30 (1996) 3050–3060.
[32] A.D. Papandreou, C.J. Stournaras, D. Panias, I. Paspaliaris, Adsorption of Pb(II),
Zn(II) and Cr(III) on coal fly ash porous pellets, Miner. Eng. 24 (2011)
1495–1501.
[33] W.S. Ngah, S. Fatinathan, Adsorption characterization of Pb(II) and Cu(II) ions
onto chitosan-tripolyphosphate beads: kinetic, equilibrium and
thermodynamic studies, J. Environ. Manage. 91 (2010) 958–969.
[34] B. Cheknane, F. Zermane, M. Baudu, O. Bouras, J.P. Basly, Sorption of basic dyes
onto granulated pillared clays: thermodynamic and kinetic studies, J. Colloid
Interface Sci. 381 (2012) 158–163.
[35] X. Liu, L. Zhang, Removal of phosphate anions using the modified chitosan
beads: adsorption kinetic, isotherm and mechanism studies, Powder Technol.
277 (2015) 112–119.
[36] Y. Vijaya, S.R. Popuri, V.M. Boddu, A. Krishnaiah, Modified chitosan and
calcium alginate biopolymer sorbents for removal of nickel (II) through
adsorption, Carbohyd. Polym. 72 (2008) 261–271.
[37] A. Kamari, W.S. Ngah, Isotherm, kinetic and thermodynamic studies of lead
and copper uptake by H2 SO4 modified chitosan, Colloids Surf. B. Biointerfaces
73 (2009) 257–266.
[38] A.M.A. Al-Haidary, F.H.H. Zanganah, S.R.F. Al-Azawi, F.I. Khalili, A.H. Al-Dujaili,
A study on using date palm fibers and leaf base of palm as adsorbents for
Pb(II) ions from its aqueous solution, Water Air Soil Pollut. 214 (2011) 73–82.
[39] Y. Li, J. Ding, Z. Luan, Z. Di, Y. Zhu, C. Xu, D. Wu, B. Wei, Competitive
adsorption of Pb2+ , Cu2+ and Cd2+ ions from aqueous solutions by multiwalled
carbon nanotubes, Carbon 41 (2003) 2787–2792.
[40] Y. Xue, H. Hou, S. Zhu, Competitive adsorption of copper(II), cadmium(II),
lead(II) and zinc(II) onto basic oxygen furnace slag, J. Hazard. Mater. 162
(2009) 391–401.
[41] C. Mahamadi, T. Nharingo, Competitive adsorption of Pb2+ , Cd2+ and Zn2+ ions
onto Eichhornia crassipes in binary and ternary systems, Bioresour. Technol.
101 (2010) 859–864.
[42] M. Minceva, R. Fajgar, L. Markovska, V. Meshko, Comparative study of Zn2+
Cd2+ , and Pb2+ removal from water solution using natural clinoptilolitic
zeolite and commercial granulated activated carbon. equilibrium of
adsorption, Sep. Sci. Technol. 43 (2008) 2117–2143.
[43] M. Zhang, Adsorption study of Pb(II), Cu(II) and Zn(II) from simulated acid
mine drainage using dairy manure compost, Chem. Eng. J. 172 (2011)
361–368.
[44] H. Khallaf, C. Chen, L. Chang, O. Lupan, A. Dutta, H. Heinrich, A. Shenouda, L.
Chow, Investigation of chemical bath deposition of CdO thin films using three
different complexing agents, Appl. Surf. Sci. 257 (2011) 9237–9242.
[45] A. Swiatkowski, M. Pakula, S. Biniak, M. Walczyk, Influence of the surface
chemistry of modified activated carbon on its electrochemical behaviour in
the presence of lead (II) ions, Carbon 42 (2004) 3057–3069.
[46] H. Wang, A. Zhou, F. Peng, H. Yu, J. Yang, Mechanism study on adsorption of
acidified multiwalled carbon nanotubes to Pb(II), J. Colloid Interface Sci. 316
(2007) 277–283.