Research Article

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Synthesis of Porous Hierarchical MgO and Its Superb Adsorption

Properties
Peng Tian, Xiu-ying Han, Gui-ling Ning,* Hai-xia Fang, Jun-wei Ye, Wei-tao Gong, and Yuan Lin
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
*
S Supporting Information

ABSTRACT: The porous hierarchical MgO with superb

adsorption properties has been synthesized by a facile and
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scaled-up method. The X-ray powder diffraction, electron

microscopy, Fourier transformed infrared, and N2 adsorption−
desorption were carried out to study the microstructure of the
as-synthesized precursor and product. It has been demon-
strated that the as-prepared MgO has a porous hierarchical
structure and a high specific surface area (148 m2 g−1). And the
MgO sample exhibited super adsorption properties, with
maximum adsorption capacity of 2409 mg g−1 for Congo red,
which is the highest reported value. Moreover, the adsorption
process of Congo red on porous hierarchical MgO was
systematically investigated, which was found to obey the pseudo-second-order rate equation and Langmuir adsorption model.
KEYWORDS: porous hierarchical structure, magnesium oxide, Congo red, adsorption

1. INTRODUCTION higher than those reported on other adsorbents. In addition,

Dye is recognized to be the first contaminant in wastewater.1,2 most of existed synthesis methods required surfactants or
How to rationally and efficiently deal with dye-contaminated hydrothermal/solvothermal process.
effluents before discharge is of great importance. Though a In this paper, we developed a facile and scaled-up route to
number of processes are available for dye removal from synthesize porous hierarchical MgO based on an ethanol-
aqueous systems, adsorption is the most convenient and assisted decomposition process, as a part of our continuous
popular method because of its simplicity, high efficiency, and study on magnesium chemistry.22−24 The as-synthesized
low energy requirements.3−7 Nevertheless, the common porous hierarchical MgO exhibited superb adsorption perform-
adsorbents often only have limited adsorption capacities and ance for removing the Congo red dye from water. Congo red
low adsorption rates.8 In recent years, porous hierarchically (1-naphthalene sulfonic acid, 3,30-(4,40-biphenylenebis(azo))
structured metal oxides and metal hydroxides were used for bis (4-amino-) disodium salt, C32H22N6O6S2Na2, CR), an azo
wastewater treatment and exhibited excellent adsorption anionic dye, is commonly used as a model pollutant to
performance.8−15 Their micrometer-sized overall structure investigate the dye removal ability of adsorbents.8−12,25−34 In
favors them to separate from water, and the porous hierarchical this paper, the maximum adsorption capacity of CR on the as-
structure can provide a high specific surface area and a large obtained MgO reached above 2400 mg g−1. To our knowledge,
surface-to-volume ratio for contact, plenty active sites for stay, this value is the highest in all the reported data. The facile, cost-
and hierarchical channels for mass transfer. effective and scaled-up preparation process, and superhigh
As a nontoxic, economical, and environmentally friendly adsorption capacity for CR make the porous hierarchical MgO
material, MgO has already been widely used to treat a promising candidate for practical applications.
wastewater.16−21 Recently, several highlighted works reported
the synthesis of porous hierarchical MgO and their application 2. EXPERIMENTAL SECTION
in water treatment. For example, Ai’s group developed a 2.1. Preparation of Porous Hierarchical MgO. All reagents
sacrificial template-directed way to prepare mesoporous used during the process were analytical grade, unless otherwise noted.
hierarchical MgO. The as-prepared MgO showed excellent First, the aqueous Mg(HCO3)2 solution was prepared by bubbling
removal capacities for Congo red.8 Ng et al. reported template- CO2 into 200 mL of an aqueous suspension of commercial light-burnt
free hydrothermal synthesis of mesoporous hierarchical MgO MgO (16 g L−1) at the rate of 200 mL min−1 for 45 min. Then, the as-
and their excellent ability of adsorbing the organic dye methyl obtained Mg(HCO3)2 solution was added into vigorously stirred
orange.20 Cao’s group presented controllable biomimetic
fabrication of MgO complex nanostructures with outstanding Received: August 13, 2013
ability for dye.18 In spite of these successes, the dye adsorption Accepted: November 13, 2013
capacities of the reported MgO materials were not significantly Published: November 13, 2013

© 2013 American Chemical Society 12411 dx.doi.org/10.1021/am403352y | ACS Appl. Mater. Interfaces 2013, 5, 12411−12418
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ethanol (100 mL, in a 500 mL three-necked flask) at 80 °C. After 5 magnesium carbonate. In the absence of ethanol, the
min, the stirring was stopped and the solution was maintained at 80 °C magnesium carbonate particles were agglomerate and irregular
for 2 h to form the Mg5(CO3)4(OH)2·4H2O precursor. After that, the (Figure S1, Supporting Information). This synthesis method is
precursor was collected, filtered off, washed with water and ethanol low-cost, environmentally benign, and quite easily scaled up to
three times, and dried in a blast drying oven at 60 °C for 4 h. Finally,
the precursor was annealed in air at 400 °C for 4 h to obtain the
produce more than 1 kg of the product in one batch (Figure S2,
porous hierarchical MgO. Supporting Information). In the second step, the morphology-
2.2. Characterizations. The crystalline phases of the as-prepared preserved MgO product was obtained by heat treating the
samples were investigated by X-ray powder diffraction (XRD, Rigaku- Mg5(CO3)4(OH)2·4H2O precursor (Mg5(CO3)4(OH)2·4H2O
DMax 2400) in reflection mode (Cu Kα radiation) at a scanning rate → 5MgO + 4CO2 + 5H2O ). Simultaneously, the thermal
of 0.02 S−1 in the 2θ from 5 to 80°. The scanning electron microscope decomposition process was accompanied by the generation of
and transmission electron microscopy (SEM, JEOL-6360LV, operated large amounts of gases (e.g., CO2 and H2O), thus pores easily
at 20 kV; TEM, Philips TecnaiG2 20, operated at 200 kV) were developed in the final annealed product.
performed to observe the shapes and structures of the as-obtained To examine as-prepared magnesium carbonate precursor, the
samples. The Fourier transform infrared (FTIR) spectra of the samples
were measured on JASCO FT/IR-4100 spectrometric analyzer. The
characterizations including X-ray powder diffraction (XRD),
thermogravimetry analysis (TGA) of the precursor was carried out by FTIR spectroscopy, Scanning electron microscopy (SEM),
a Mettler TG/SDTA851e thermogravimetric analyzer at a heating rate transmission electron microscopy (TEM), and thermogravi-
of 10 °C min−1 in air. The N2 adsorption−desorption isotherm was metric analysis (TGA) were carried out, as shown in Figures 1
determined on a ASAP 2020 physisorption apparatus at the
temperature of liquid nitrogen, in which the samples were degassed
at 120 °C for 24 h before measurement. The surface area was
calculated by the Brunauer−Emmett−Teller method.
2.3. Evaluation of Adsorption Performance. Congo red
solutions with different concentrations (200, 500, 800, 1000, 1200,
1300, 1400 mg L−1) were gained by dissolving CR with high purity
water. Adsorption experiments were performed by mixing as-obtained
porous hierarchical MgO with CR aqueous solution in a beaker (100
mL) under stirring at natural pH and room temperature. At different
adsorption times, 5.0 mL of the mixture was collected and separated.
The concentrations of CR in the filtrates were measured on Hitachi U-
4100 UV−visible spectrophotometer.
The adsorption capacity of CR on the MgO sample was calculated
by qt = (C0 − Ct)V/m, in which qt is the adsorption capacity, C0 and Ct
are the concentrations of CR (mg L−1) before and after adsorption, V
is the volume of solution (L), and m is the mass of the MgO sample
(g).
The effect of MgO dosage was performed by mixing a MgO sample
of different weight to 80 mL of CR solution of 200 mg L−1 for 60 min.
The weight of the MgO sample was adjusted to be in the range 0.008−
0.04 g. To study kinetic, 0.04 g of the MgO sample was mixed with 80
mL of CR solution (200, 500, 1000, 1200 mg L−1) for different times.
The adsorption isotherms were finished by mixing MgO (0.04 g) to
CR solutions (80 mL) of different initial concentrations for 60 min. Figure 1. XRD pattern (a), SEM image (b), and TEM image (c) of
The effect of pH was carried out by mixing MgO (0.04g) into a CR carbonate precursor.
solution (80 mL) of 1000 mg L−1 with different pH (9.0, 11.0, 12.0,
13.0) for 60 min.
and S3 (Supporting Information). Figure 1a shows the XRD
3. RESULT AND DISCUSSION pattern of the carbonate precursor that can match well with
3.1. Synthesis of Porous Hierarchical MgO. Scheme 1 Mg5(CO3)4(OH)2·4H2O (JCPDS No. 25-0513). The wide
illustrates the synthesis process of the porous hierarchical MgO. diffraction peaks in the XRD pattern indicate the poor
crystalline characteristic of the precursor. And no other
Scheme 1. Schematic Illustration of the Synthesis of Porous impurity peak is detected, which suggests the precursor is
Hierarchical MgO pure. Figure S3a (Supporting Information) shows the FTIR
spectrum of the carbonate precursor. The wide bands in 3600−
3000 cm−1 were attributed to hydroxyl stretching, which came
from H2O in Mg5(CO3)4(OH)2·4H2O. The sharp band at 3650
cm−1 corresponded to the free OH. The bands at 1480 and
1420 cm−1 were assigned to vibrations of the carbonyl group
(ν3 mode). The three absorption bands at 800, 850, and 880
cm−1 were due to carbonate bending vibrations. Thus, it can be
In the first step, the carbonate precursor could be directly seen that the features in IR are consistent with
obtained by decomposing Mg(HCO3)2 solutions at 80 °C in Mg5(CO3)4(OH)2·4H2O. Figure S3b (Supporting Informa-
the presence of ethanol: (5Mg(HCO3)2 → Mg5(CO3)4(OH)2· tion) displays the typical SEM image of the carbonate
4H2O + 6CO2 ). Xue’s study has demonstrated that the precursor. It can be observed that the precursor is a hierarchical
Mg5(CO3)4(OH)2·4H2O particles are easily self-assembled to flowerlike particle with a diameter of 4−6 μm. The SEM image
form hierarchical structures.35 The ethanol was used to in Figure 1b reveals that the flowerlike particles are made up of
accelerate reaction rate and control the morphology of a number of microsheets. Further structural information and
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characterization of the carbonate precursor were obtained by particles were found to be 4−6μm, which is similar to that of
TEM images in Figure 1c. The precursor particle is made up of the carbonate precursor. The SEM image in Figure 2c illustrates
a number of microsheets, which agrees well with the SEM that the microstructure of the as-prepared MgO was not
observations. Figure S3c (Supporting Information) shows the significantly different from those of the carbonate precursor
typical TGA curve of the precursor. The TGA curve presented (Figures 1b and S3b (Supporting Information)), except the
two significant weight loss steps: the first weight loss step existence of some cracks. As a result, it is reasonably expected
occurred at 100−300 °C (DTG peaks at 241 °C) and was that the pores would form in the MgO particles by generating
assigned to the loss of crystallized water and the decomposition gases (H2O and CO2) from the interior of the precursor during
of hydroxyl from Mg5(CO3)4(OH)2·4H2O; the second weight the thermal decomposition process.
loss step occurred in range 350−500 °C (DTG peaks at 398 To further examine the microstructure of the flowerlike
°C) and was attributed to the decomposition of the carbonate. MgO, TEM was performed (Figure 3). Figure 3a shows an
The weight losses of two steps were about 26.3% and 37.4%,
respectively. The theoretical values are 19.7% and 37.4%,
respectively. This difference should be attributed to the
existence of free water in the precursor. The TGA result
reveals that the calcination temperature should be no less than
350 °C to obtain MgO.
Figures 2 and S4 (Supporting Information) show the typical
XRD pattern, FTIR spectrum, and SEM images of the annealed

Figure 3. TEM (a, b, c) and SAED (d) images of the porous

hierarchical MgO.

individual flowerlike MgO with a size of 5 μm, which agrees

well with the SEM observations. The TEM image in Figure 3b
Figure 2. XRD pattern (a), SEM images (b, c) of MgO product.
reveals that the “petals” of flowerlike MgO are rather rough.
That is significantly different from the carbonate precursor
product. As shown in Figure 2a, the XRD diffraction peaks can (Figure 1c). The magnified TEM image in Figure 3c shows that
match well with the diffraction from the (200), (220), and the petals are fabricated by numerous MgO nanoparticles with
(222) planes of MgO (JCPDS No. 45-0946), indicating that sizes of 10−15 nm. The selected area electron diffraction
pure MgO can be obtained via the thermal decomposition of (SAED) of the product (Figure 3d) can match well with
the Mg5(CO3)4(OH)2·4H2O precursor at 400 °C. Moreover, periclase (JCPDS No. 45-0946), which is consistent with the
the relatively broad diffraction peaks reveal that the MgO XRD results.
product should be in a small crystallite size. The grain size was To analyze the porous structure of the as-obtained MgO, N2
determined to be 13.2 nm by Scherrer equation (D = Kλ/B cos adsorption−desorption measurement was carried out. The N2
θ). The FTIR spectrum of the annealed product further adsorption/desorption isotherm (Figure 4) of the as-prepared
confirms that the characteristic peaks assigned to the carbonate MgO can not simply be assigned to any representative
precursor completely disappeared after the thermal treatment. adsorption/desorption isotherms defined by IUPAC. At low
A new broad band around 400−800 cm−1 shown in Figure S4 relative pressure (P/P0) range (0−0.05), the adsorption rapidly
(Supporting Information) was the characteristic of well-defined reaches saturation, suggesting the presence of micropores in the
MgO. In addition, bands at about 3800−3100, 1610, and 1450 as-prepared MgO. At a higher relative pressure range (P/P0 >
cm−1 were attributed to hydroxyl stretching, hydroxyl bending, 0.4), well-defined H-3 type hystereses are observed, indicating
and symmetric stretching of carbonate, respectively. It indicates there exist disordered mesopores in the as-prepared MgO.
that the surfaces of the MgO product can easily adsorb H2O Moreover, in isotherm curves, N2 adsorption does not reach
and CO2 by chemistry when it is exposed to the atmosphere. saturation, and the adsorption capacity increases rapidly at
As shown in Figure 2b, the hierarchical flowerlike structures higher relative pressure (P/P0 > 0.9), indicating the existence of
of the precursor were successfully preserved in the MgO macropores. Therefore, the isotherm curves display that
product after calcination. The sizes of the flowerlike MgO micropores (<2 nm), mesopores (2−50 nm), and macropores
12413 dx.doi.org/10.1021/am403352y | ACS Appl. Mater. Interfaces 2013, 5, 12411−12418
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Figure 4. N2 adsorption/desorption isotherms and pore-size

distribution (inset) of the porous hierarchical MgO.

(>50 nm) coexist in the as-prepared MgO, suggesting the

successful preparation of hierarchically porous structured MgO
with micropores, mesopores, and macropores. The micropores
and mesopores were created via an aforementioned gas release Figure 5. (a) UV−vis spectra of CR after being treated by the as-
process during the thermal decomposition. And the macropores prepared MgO with different dosages: (A) 0 g L−1, (B) 0.05 g L−1, (C)
were made of flowerlike structures. The pore sizes exhibited 0.10 g L−1, (D) 0.25 g L−1, and (E) 0. 50 g L−1. (b) Photo of initial CR
bimodal distributions (inset in Figure 4), micropores with a (200 mg L−1) aqueous solution treated by the MgO architectures with
peak diameter 1.3−1.7 nm and mesopores with peak diameter different dosages.
2.7−4.5 nm, indicating hierarchical porous structure in the
MgO. Moreover, Brunauer−Emmett−Teller (BET) specific
surface area of as-prepared MgO was determined to be 148 m2
g−1. And the internal surface area and external surface areas
were found to be 107 m2 g−1 and 41 m2g−1, respectively. The
specific surface area of MgO is very high. To illustrate this
point, the reported specific surface area values of other reported
MgO samples are listed in Table 1. As can be seen the specific
surface area of the as-obtained MgO is similar with those of
other reported MgO samples.

Table 1. Specific Surface Areas of Various MgO Samples

adsorbent specific surface area (m2 g−1) references
porous hierarchical MgO 148 this paper Figure 6. Time profiles of CR adsorption on the porous hierarchical
cubelike porous MgO 80 8 MgO.
flowerlike MgO 72 19
mesoporous MgO 150 36
rodlike MgO 115 37
MgO nanoparticles 116 38
fast in the first 5 min under all concentrations. The adsorption
mesoporous MgO 151 39
nearly finished within 30 min, indicating the fast adsorption rate
of CR on the MgO in water. It is noteworthy that the MgO
exhibited an ultrahigh adsorption capacity of 2340 mg g−1
3.2. Congo Red Adsorption Property. Generally, if the toward CR after 60 min of adsorption at the initial
material has porous hierarchical structures and high surface concentration of 1200 mg L−1 (Figures 6 and S5 (Supporting
area, it will possess more available active adsorption sites, Information)). The porous hierarchical MgO is expected to
efficient transport pathways, and may exhibit excellent become a promising material for rapid and deep treatment of
adsorption performance. Herein, the as-synthesized porous high concentration dye-containing wastewater because of its
hierarchical MgO was used to adsorb Congo red. Figure 5a features of fast adsorption rate and ultrahigh capacity.
shows the UV−vis absorption spectra of CR solutions after The kinetics of CR removal on porous hierarchical MgO was
being treated by different dosages of the MgO with fixed initial further investigated. The pseudo-first-order kinetic models (eq
concentration of 200 mg L−1. With increase of MgO dosage, 1) and pseudo-second-order kinetic models (eq 2) were applied
the removal efficiency of the CR increased. In particular, at a to describe this adsorption process, respectively:
dosage of 0.50 g L−1, the CR can be almost completely k1t
adsorbed, which was also supported by the color of the CR log(qe − qt ) = log qe −
solution changing from deep red to colorless (in Figure 5b). 2.303 (1)
Figure 6 shows the time profile of Congo red adsorption at t 1 t
different initial concentrations with 0.50 g L−1 of the as- = +
qt k 2qe 2 qe (2)
synthesized MgO. The adsorption rates were extraordinarily
12414 dx.doi.org/10.1021/am403352y | ACS Appl. Mater. Interfaces 2013, 5, 12411−12418
ACS Applied Materials & Interfaces Research Article

where qe and qt (mg g−1) are the adsorption capacities at qmbCe

equilibrium and at any time t (min), respectively. k1 (min−1) qe =
1 + bCe (3)
and k2 (g mg−1 min−1) are the pseudo-first-order and pseudo-
second-order rate constants, respectively. The kinetic param-
qe = k f Ce1/ n (4)
eters and the correlation coefficients (R2) are given in Table S1
(Supporting Information). Figure 7 reveals that all the −1
in which qm (mg g ) is the maximum adsorption capacity
corresponding to complete monolayer coverage, b is the
equilibrium constant (L·mg−1), Kf is roughly an indicator of the
adsorption capacity, and n is the adsorption intensity. The
related parameters and the correlation coefficients (R2) are
listed in Table S2 (Supporting Information). The adsorption
data were found to fit better to the Langmuir model with R2 =
0.965, than to the Freundlich model with R2 = 0.622, suggesting
the monolayer adsorption.
The max adsorption capacity of Congo red on the as-
synthesized MgO was found to be above 2409 mg g−1. To our
knowledge, this value is the highest in all the reported data, and
is much higher than others. Up to now, many adsorbents have
been used for removing CR and their adsorption capacities are
normally below 500 mg g−1, rarely above 1000 mg g−1. Table 2
Figure 7. The pseudo-second-order kinetics plots of CR adsorption on
listed the removal capacities of porous hierarchical MgO and
the as-obtained MgO.
some typical adsorption materials reported previously.
experimental data can fit well to the pseudo-second-order Table 2. Adsorption Capacities of Congo Red on Various
model with high correlation coefficients (R2 > 0.999). The Adsorbents
values of qe,cal were also very close to the values of qe,exp, which
indicates that the adsorption process of CR on the porous adsorbent removal capacity (mg g−1) references
hierarchical MgO obeyed the pseudo-second-order model. The porous hierarchical MgO 2409 this paper
adsorption data also fit the pseudo-first-order model. However, Fe3O4@meso C 1657 26
the value of qe was smaller than the value of qt (Figure S6, α-Fe/Fe3O4 composite 1297 34
Table S1, Supporting Information). This case is not logical, porous MgO 689 8
suggesting the inapplicability of the pseudo-first-order model to hierarchical hollow NiO 440 32
describe the adsorption of CR on the as-prepared MgO. hierarchical hollow FeOOH 275 12
The effect of the initial concentration is shown in the activated carbon ∼200 25
adsorption isotherm (Figure S5, Supporting Information). It hierarchical hollow Fe2O3 160 33
can be observed that when the initial concentrations are below functionalized carbon nanotubes 148 28
1200 mg L−1, the adsorption capacity of CR on the as-obtained MgO nanoplates 131 29
MgO linearly ascends with the increase of initial concentration; Co3O4−Fe3O4 hollow spheres 125 30
when the initial concentrations are above 1200 mg L−1, with the commercial brucite 95 this paper
increase of initial concentration, the adsorption capacity of CR hierarchical Al2O3 90 11
on the as-obtained MgO slowly increase. jujuba seeds 56 31
The relation between the adsorption capacity of CR on the clay materials 20 27
as-obtained MgO and the equilibrium concentration of Congo
red is shown in Figure 8. The Langmuir (eq 3) and Freundlich 3.3. Analysis and Discussion. It is of deserved research to
(eq 4) isotherms were used to describe this adsorption process, make it clear why hierarchical structured MgO has such a
respectively. superb adsorption performance toward Congo red. According
to the reported references, the adsorption of ionic dyes or
organic pollutants may be associated with the electrostatic
attraction and surface complexation.4,40−43 First, the adsorption
of Congo red on MgO can be attributed to electrostatic
attraction. It is well known that if the pH of the solution is
below the isoelectric point of adsorbent, the adsorbent will have
positive surface charge and adsorb anionic dye molecules by
electrostatic attraction. Congo red is a kind of anionic dye. The
natural pH value (≈7.0) of the Congo red solution is much
lower than the isoelectric point of MgO (12.1−12.7).
Therefore, MgO can easily adsorb Congo red molecules at a
natural pH. Besides electrostatic attraction, the adsorption of
Congo red on MgO also may be associated with the other
action. To investigate this point, the Congo red adsorption
capacities of MgO were determined near the isoelectric point
Figure 8. Adsorption isotherm curves of CR adsorption on the porous (pH = 11−13). In this case, the adsorption capacities were still
hierarchical MgO. above 1500 mg g−1 (Figure S7, Supporting Information), which
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implies that Congo red can be adsorbed on the MgO even adsorbent is above the pH of CR solution, the adsorbent will
without electrostatic attraction. have more surface positive charge and adsorb more anionic dye
To further investigate the adsorption mechanism, SEM, molecules, and vice versa. Both our work (Figure S7,
XRD, and IR of the CR-loaded adsorbent were carried out. The Supporting Information) and the previous literature proved
morphology of the CR-adsorbed MgO showed appreciable this point.4,41 It is easy to understand that the MgO can more
change: the microsheets of flowerlike particles turned to rough easily adsorb more CR molecules at a natural pH than the other
(Figure S8a, Supporting Information) with the formation of adsorbents because of its high isoelectric point. The isoelectric
nanoflakes. The XRD patterns also exhibited significant points of common oxides are listed in the Table 3. It is clear
changes, as shown in Figure S8b (Supporting Information):
after adsorption, the MgO adsorbent changed into Mg(OH)2 Table 3. The Isoelectric Points of Common Oxides41,44
(JCPDS No. 07-0239). The FTIR spectrum in Figure 9a shows
oxide isoelectric point
the peak intensity of CR-adsorbed adsorbent at 3650 cm−1
(free OH) increase, which indicates that adsorption process Sb2O5 <0.4
WO3 <0.5
makes MgO change into Mg(OH)2.
SiO2 1−2
MnO2 3.9−4.5
SnO2 ∼5.5
TiO2 ∼6
γ-Fe2O3 6.5−6.9
γ-Al2O3 7.0−9.0
α-Fe2O3 8.4−9.0
ZnO 8.7−9.7
NiO ∼10.3
MgO 12.1−12.7

that the isoelectric point of MgO is the highest among the

common oxides. Moreover, the Congo red removal capacity of
porous hierarchical MgO near the isoelectric point is still much
Figure 9. FTIR spectra of Congo red (a), hydrated MgO (at room higher than that of the porous hierarchical NiO,41 which
temperature) (b), Mg(OH)2 (c), and CR adsorbed adsorbent (d). indicates that the surface complexation between Congo red and
MgO should be stronger than that between CR and other
adsorbents.
We know that the hydration degree of MgO is relatively low According to the reported studies,8,41 it can be speculated
at room temperature, which can be observed in Figure 9b. that such superior Congo red adsorption performance of the
Chen’s group reported that the oxygen atom of the SO hierarchical porous MgO should be attributed not only to its
group can be used as the hydrogen-bonding acceptor and form high isoelectric point and strong surface complexation but also
intramolecular hydrogen bonding with the oxygen-containing to its unique structure. To prove this point, MgO samples with
functional group of alkali-activated multiwalled carbon nano- different morphologies were synthesized and used to adsorb
tubes.4 Therefore, the formation of Mg(OH)2 may be closely Congo red (as shown in Experimental Section and Figures S9−
related to that SO group of Congo red and can form 11, Supporting Information). Table S3 (Supporting Informa-
intramolecular hydrogen bonding with the O group of MgO, as tion) lists the Congo red adsorption capacities on hierarchical
shown in Scheme 2. Moreover, FTIR spectra of CR adsorbed MgO, rodlike porous MgO, and cubelike porous MgO. It can
Mg(OH)2 show new peaks at 1166.8, 1045.8, and 551.9 cm−1, be obviously observed that the adsorption performance of
which suggests the surface complexation between CR and hierarchical MgO for CR is much better than those of rodlike
Mg(OH)2. porous MgO and cubelike porous MgO.
On the basis of the above analysis, the adsorption mechanism Hence, the superb adsorption performance of porous
of Congo red on MgO can be attributed to the electrostatic hierarchical MgO should be attributed to its high isoelectric
attraction and surface complexation. And the superb adsorption point, strong surface complexation, and unique structures: the
performance of MgO toward Congo red can be explained by high isoelectric point and strong surface complexation make it
this adsorption mechanism: when the isoelectric point of so the MgO can easily adsorb negative Congo red molecules;
the micropores and mesopores can provide a large number of
Scheme 2. Schematic Illustration of the Formation of active sites, whereas the coexisting macropores give short paths
Intramolecular Hydrogen Bonding to enhance mass transfer and prevent blocking of the channels.
3.4. Recycling the Porous Hierarchical MgO. The
regeneration performance of the adsorbent is an important
factor in the actual application. During adsorption of Congo
red, the molecular structure and microstructure of the porous
hierarchical MgO adsorbent have changed, which means the
recycling porous hierarchical MgO cannot be carried out by
common routes, such as desorption10 and catalytic oxidation.24
To recycle the porous hierarchical MgO, we present a novel
strategy, as shown in Scheme S1 (Supporting Information).
This strategy includes three steps. (I) The adsorption of dye:
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ACS Applied Materials & Interfaces Research Article

MgO + H2O + dye → dye loaded Mg(OH)2; (II) Degradation projects in the magnesium industry of the Liaoning Province,
and dissolution: dye loaded Mg(OH)2 + H2O2 + CO2 + H2O China.
→ Mg(HCO3)2 solution + mineralization product. (III)
Regeneration: Mg(HCO3)2 → Mg5(CO3)4(OH)2·4H2O →
MgO. This work is under way and will be detailedly reported in
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AUTHOR INFORMATION (27) Vimonses, V.; Lei, S. M.; Jin, B.; Chowd, C. W. K.; Saint, C.
Corresponding Author Chem. Eng. J. 2009, 148, 354−364.
*G.-l. Ning. E-mail: [email protected]. Fax/Tel: (+86)411- (28) Mishra, A. K.; Arockiadoss, T.; Ramaprabhu, S. Chem. Eng. J.
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The authors declare no competing financial interest. (30) Wang, X.; Zhong, Y. T.; Zhai, T. Y.; Guo, Y. F.; Chen, S. M.;

■ ACKNOWLEDGMENTS
This work was supported by National Natural Science
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