Research Article

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Hierarchical Mesoporous MnO2 Superstructures Synthesized by Soft-

Interface Method and Their Catalytic Performances
Yanyu Liu,† Zhiwen Chen,*,†,‡ Chan-Hung Shek,*,‡ C. M. Lawrence Wu,‡ and Joseph K. L. Lai‡
†
School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, People’s Republic of China
‡
Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong

ABSTRACT: To obtain a highly efficient and stable

heterogeneous catalyst in catalytic wet hydrogen peroxide
oxidation, we have successfully synthesized hierarchical
mesoporous manganese dioxide (MnO2) superstructures by
a facile and environmental friendly method on a soft-interface
between CH2Cl2 and H2O without templates. The main crystal
phase of as-prepared MnO2 was proved to be ε-MnO2 by X-
ray diffraction techniques. The structure characterizations
indicated that the hierarchical MnO2 superstructures were
composed of urchin-like MnO2 hollow submicrospheres
assembled by one-dimension nanorods building blocks with
rich mesoporosity. The nitrogen sorption analysis confirmed that the as-synthesized MnO2 has an average pore diameter of 5.87
nm, mesoporous volume of 0.451 cm3 g−1, and specific surface area of 219.3 m2 g−1. Further investigations revealed that a
possible formation mechanism of this unique hierarchical superstructure depended upon the synthesis conditions. The catalytic
performances of the hierarchical mesoporous MnO2 superstructures were evaluated in catalytic degradation of methylene blue in
the presence of H2O2 at neutral pH, which demonstrated highly efficient catalytic degradation of the organic pollutant methylene
blue using hierarchical mesoporous MnO2 superstructures as catalyst at room temperature.
KEYWORDS: manganese dioxide, hierarchical mesoporous superstructure, formation mechanism, heterogeneous catalyst,
methylene blue

1. INTRODUCTION pollution1 and retarded biodegradation of the accompanying

The degradation of refractory organic pollutants has attracted pollutants.12 Advanced oxidation processes (AOPs), defined as
much attention in recent years because they can cause great those technologies that utilize the hydroxyl radical (·OH) for
harm to the natural environment and human health. In oxidation, have received increasing attention in the research of
particular, the industrial dyes are one of the largest groups of wastewater treatment technologies in the past decades. These
pollutants.1,2 These dyes usually have complex aromatic processes, such as photocatalytic oxidation, Fenton’s chemistry,
molecular structures which make them more stable and more and ozonation, have been applied successfully for the removal
difficult to degrade. If not treated, these hazardous substances or degradation of recalcitrant pollutants, or used as pretreat-
will induce certain health hazards and environmental pollution.3 ment to convert pollutants into shorter-chain compounds that
For example, methylene blue (MB), one of the colored organic can then be treated by conventional or biological methods.13 So
compounds, is widely used as a common dye for dying cotton, they have been developed as advanced strategies for the
wood, and silk, a common photosensitizer employed in solar degradation of dyes in aqueous media by the generation of very
cells, a photodynamic antimicrobial agent in biological materials active species in the presence of catalysts.14 One of them is the
and a test compound in semiconductor photocatalysis.4,5 It can classic Fenton process (dissolved Fe2+ and H2O2), which is
result in permanent burns to the eyes of human and animals, capable of degrading organic pollutants into harmless
nausea, vomiting, profuse sweating, mental confusion, and chemicals, such as CO2 and H2O.4 However, the application
methemoglobinemia.6 The widespread of dye industries, which of the classical Fenton reagent, i.e., Fe2+/Fe3+-H2O2, is limited
amounts to more than seven million tons annually produced by the narrow working pH range (2−4) associated with this
worldwide, combined with the potential carcinogenic risk, process15,16 and by separation and recovery of the iron species
causes severe environmental pollution.7 Therefore, the removal specially in industrial wastewater treatment.17,18 To overcome
of dyes from industrial effluents has been a major concern in these drawbacks, some efforts have been made to develop
wastewater treatments. heterogeneous Fenton systems which can be used over a wider
Although traditional treatment techniques, such as physical
adsorption,8,9 chemical oxidation,10 and biological method,11 Received: April 11, 2014
they have been investigated to removal dye from wastewater, Accepted: June 2, 2014
many problems are still unavoidable, such as secondary Published: June 2, 2014

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pH range for the degradation of organic pollutants.19 So far, been established as an alternative approach to conventional
many heterogeneous Fenton-like catalysts have been reported, homogeneous synthesis.52−54
such as iron oxides,20,21 iron oxide nanoparticles supported on Herein, we report a simple self-assembly synthesis of urchin-
mesoporous silica,19,22 supported on clays,23,24 combined with like ε-MnO2 hollow submicrospheres via a redox reaction
carbon materials,25,26 or iron-containing ZSM-5.27 In addition involving MnO4− and Mn2+ on the CH2Cl2/H2O interface,
to iron oxides, copper oxides,28 manganese oxides,1,15 rare which are composed of mesoporous MnO2 superstructures
earth,29 and noble metal elements30 can be also included in the with hierarchical porosity and large specific surface area.
heterogeneous catalysts for the AOPs. In the case of Further investigations revealed that a possible formation
heterogeneous catalysis, there are also some problems, like mechanism of this unique hierarchical superstructure depends
the lower use efficiency of H2O2, the high expense of noble upon the synthesis conditions. The catalytic performances of
metal, and the dissolution of copper oxides in solution. the hierarchical mesoporous MnO2 superstructures were
Therefore, further study is necessary to find out inexpensive, evaluated in the catalytic degradation of methylene blue in
highly efficient and stable heterogeneous catalyst to remove and the presence of H2O2 at room temperature.
degrade the organic dyes in catalytic wet hydrogen peroxide
oxidation. Obviously, the preparation of highly efficient and 2. EXPERIMENTAL SECTION
stable heterogeneous catalyst has been the key to industrial Sample Synthesis. The method of preparing mesoporous MnO2
applications of wet catalytic oxidation. in this study is from improvement of the previous works.44,52 MnSO4,
Since the Fenton reaction involves an electron transfer KMnO4, and CH2Cl2 were purchased from the Sino pharm Chemical
process, the catalysts with accessible multiple oxidation states Reagent Co. Ltd. (Shanghai, China). All chemicals used in this study
should have an excellent catalytic performance.4 Among were of analytical grade without further purification. All aqueous
transition metal oxides with various oxidation states, manganese solutions were freshly prepared using high-purity water. First, 30 mL of
oxides as technologically important materials have been widely 1 M MnSO4 solution was added into 80 mL of dichloromethane in a
used as effective catalysts, molecular adsorbent, magnetic beaker of 200 mL. After 5 min, the obvious H2O/CH2Cl2 interface was
obtained. Then 80 mL of 0.25 M KMnO4 solution, through the
materials, electrochemical supercapacitors, and electrode
CH2Cl2 layer by 30 drops/min controlled by a faucet of dropping
materials for batteries due to their outstanding structural funnel, reached the CH2Cl2/H2O interface along the tube of the
flexibility and physical and chemical properties.31−35 Among all funnel. During the reaction process, a brown material appeared at the
of manganese oxides, manganese dioxides (MnO2) have interface and the MnSO4 solution layer slowly turns to brown. After 48
different polymorphs, such as α-MnO2, β-MnO2, γ-MnO2, δ- h, the brown products were collected by the vacuum pumping
MnO2, and ε-MnO2, which can be applied in the area of filtration equipment, washed for 3 times with high-purity water and for
catalyst, ion exchange, electrochemical supercapacitor.4,35 In 1 time with absolute ethanol, and finally dried at 80 °C in the air for 12
particular, they can be used as heterogeneous catalyst for h. The collected sample was denoted as S-48. To investigate the
catalytic degradation of organic dyes.33−36 Developing new formation mechanism of MnO2 hollow microspheres, some com-
parative experiments in which the brown samples had collected at 12
materials with excellent performance depend not only on the and 24 h were carried out with keeping the other experimental
composition but also on their morphology and micro/ conditions unchanged. These collected samples were denoted as S-12
nanostructures.35 Various MnO2 micro/nanostructures, such and S-24, respectively. In order to improve the catalytic capacity of S-
as nanoparticles, nanorods/belts/wires/tubes/fibers, nano- 48, the S-48 sample was calcined in a muffle furnace in air from room
sheets, mesoporous/molecular sieves, branched structures, temperature to 300 °C with a ramp rate of 5 °C/min and kept at this
urchins/orchids, and other hierarchical structures, have been temperature for 2 h. This calcined sample was named S-48−300 °C.
synthesized by different methods.33 Mesoporous materials as Materials Characterization. All samples prepared in “Sample
catalysts, catalysts supports, adsorbents, and nanoreactor, have Synthesis” section have not undergone further thermal treatment
aroused enormous attention because of their high surface area, before various materials characterizations. The samples were examined
by powder X-ray diffraction (XRD) (18KW D/MAX2500 V+/PC,
tunable pore size, adjustable framework, and surface proper- Japan) using a CuKα source (λ = 0.1542 nm). Scanning electron
ties.37,38 From the mesoporous manganese oxide structures microscopy (SEM) images were taken with a field-emission scanning
reported by previous literatures,39−42 mesoporous manganese electron microscope (FESEM) at 15 kV (JSM-6700F, Japan). Micro/
oxides have attracted significant interest because of their unique nanostructures of the samples were observed with transmission
catalytic, electrochemical, magnetic, and adsorptive properties. electron microscope (TEM, JEM-2010F, Japan). Surface area and
In recent years, hierarchically structured mesoporous man- porosity of the samples were determined by Brunauer−Emmett−
ganese oxides self-assembled by nanostructures have attracted a Teller (BET) measurements on N2 adsorption/desorption at 77 K
concern of materials scientists because of their widespread with a Quantachrome Surface Area Analyzer (QUDRASORB SI,
USA).
potential applications in catalysis.43−45 Controlled self-assembly
Catalytic Performances. The measurement method of catalytic
of micro/nanostructures with hierarchy is a new challenge for activity in this study was based on the reports by Yang et al.2,55 The
new material synthesis and device fabrication.46,47 Currently, catalytic performances of the obtained mesoporous MnO2 super-
the synthesis of mesoporous MnO2 with larger specific surface structures were evaluated in the catalytic oxidation of methylene blue
area and proper pore size distribution usually needs extension (MB). In order to obtain the exact weight of catalyst, the 110 °C was
of the templating procedure,48−51 such as surfactant as soft selected as the thermal treatment temperature due to the moisture in
template or mesoporous silica as hard template. However, the the long-laid samples. The catalyst to be tested was dried at 110 °C for
use of templates is prone to import impurities in the post- 10 h. First, 50 mL of the MB dye solution (100 mg/L) and 10 mL of
treatment to remove the organic species so that it increases the the H2O2 solution (30 wt %) were combined in a 250 mL glass flask,
then 25 mg of the no-moisture MnO2 catalysts was added into the
production cost and complexity.52 Therefore, an easily flask. The catalytic reaction was carried out in a shaking incubator
controlled method without templates to prepare mesoporous (constant temperature at 30 °C, 100 r/min, and atmospheric
MnO2 structure is more promising than the template methods pressure). For a given time interval, 1 mL of the mixture solution
in industrial manufacturing because of its simplicity and low was pipetted into a centrifuge tube with 0.25 mL of tert-butanol and
cost. Recently, an organic-aqueous soft-interface method has quickly diluted with distilled water to 20 mL. The diluted solution was

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immediately centrifuged (rotating speed at 1000 r/min for 10 min) in MnO2 and ε-MnO2. Compared with the S-24 sample, the peaks
order to remove the catalyst particles, which tend to scatter the at 2θ = 22.0, and 55.7° have weakened or disappeared
incident beam. The filtered dye solution was then put into a quartz cell obviously in the XRD pattern of S-48. For the S-48 sample, the
(path length 1.0 cm) and the absorption spectrum was measured with peaks at 2θ = 37.0, 42.0, 55.6, and 66.9° are more aligned with
a double-beam ultraviolet−visible (UV−vis) spectrophotometer (TU-
1901, Beijing Puxi Universal Apparatus Co. Ltd., China). A linear
that of pure ε-MnO2. Above XRD results demonstrate that the
calibration curve for the dye concentrations was obtained by transformation of crystalline structure during the aging process:
monitoring the peak intensity at λmax = 664 nm for a series of γ-MnO2 turns to ε-MnO2. The crystal phase of the as-prepared
standard solutions according to the Beer’s law. Degradation rate of the MnO2 three samples in this study is different to the previous
MB in 60 min as a function of reused times of the catalyst and the reports by Yuan and co-workers,44,52 which is attributed to the
dissolubility of the catalyst in mixed solution were selected as indexes differences of reagent and soft interface. All diffraction peaks of
to assess the catalytic stability of the catalysts. The concentration of the MnO2 three samples are broad and weak because of the
Mn ion in the solution was determined by an inductive coupled plasma poor crystallinity or the small crystal domain in the products,
emission spectrometer (ICP, 2A051657, LEEMAN LABORATORIES which results from the low preparation temperature.32
INC, USA).
The morphologies of the obtained MnO2 three samples were
3. RESULTS AND DISCUSSION examined by SEM, TEM, and Brunauer−Emmett−Teller
(BET) measurements on N2 adsorption/desorption at 77 K.
The S-12, S-24, and S-48 samples were obtained at different Figure 2 shows the field-emission SEM (FESEM) images of the
reaction time of 12, 24, and 48 h, respectively. The crystal
phases of the as-prepared MnO 2 three samples were
characterized by powder XRD. Figure 1 shows the wide-angle

Figure 1. XRD patterns of the as-synthesized MnO2 three samples: S-

12, S-24, and S-48.

XRD patterns of the as-synthesized MnO2 three samples. As

seen from the wide-angle pattern of the S-12 sample, only three
weaker diffraction peaks at 2θ = 36.8, 37.0, and 66.3° are near Figure 2. FESEM images at different magnifications of the MnO2
to the characteristic peaks of MnO2 as shown in Table 1, three samples: (a, b) S-12, (c, d) S-24, and (e, f) S-48.

Table 1. Four Characteristic Peaks of XRD Patterns in γ-

MnO2 and ε-MnO2
as-synthesized MnO2 three samples. As seen from the lower-
crystal phases location of characteristic peaks (deg) magnification FESEM image of the S-12 sample as shown in
γ-MnO2 22.0 36.9 55.8 56.8 Figure 2a, the panoramic morphology is composed of
ε-MnO2 37.1 42.4 56.0 66.8 numerous submicrospheres with thorns on the surface. The
higher-magnification FESEM image of the S-12 sample as
shown in Figure 2b reveal that the surface of the urchin-like
indicating that the S-12 is in the early stage of forming MnO2. spheres seems to have numerous nanorods, which implies that
For the S-24 sample, there are obvious diffraction peaks at 2θ = the nanorods build automatically up the submicrospheres.
22.0, 36.8, 42.2, 55.7, and 66.1° in the XRD patterns. The peaks Compared to Figure 2a, b, the FESEM images of the S-24
at 2θ = 22.0, 36.8, and 55.7° can be easily identified for the (Figure 2c, d) and S-48 (Figure 2e, f) samples at different
(101), (210), and (212) planes of the γ-MnO2 crystalline magnifications indicate that the submicrospheres are larger,
structure (Ramsdellite, syn MnO2, JCPDS file No.: 44−0142). dense, and smooth than those of the S-12 sample, and the
While the peaks at 2θ = 42.2, and 66.1° can be indexed to ε- nanorods on the surface of urchin-like spheres become compact
MnO2 (Akhtenskite, syn MnO2, JCPDS file No.: 30−0820). and unobvious, which suggests that the morphologies of
The XRD results indicate that the S-24 sample is a mixture of γ- submicrospheres in the S-24 and S-48 samples have been
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improved in the growing stage because of increasing reaction can be also supported by the higher-magnification TEM images
time, such as 24 and 48 h. of the S-12, S-24, and S-48 three samples as shown in Figure
The morphologies and micro/nanostructures of the MnO2 3b, d, and f, respectively. The higher-magnification TEM
urchin-like spheres were further examined by TEM imaging. images offer an obvious view of the surface microstructure,
Figure 3 shows the TEM images of the S-12 (Figure 3a, b), S- which exhibits that the urchin-like hierarchical MnO2 submicro-
spheres are composed of numerous compactly nanorods
growing in all directions. This further reveals that the as-
prepared MnO2 submicrospheres are assembled from lots of
one-dimension MnO2 nanorods building blocks with rich
mesoporosity. The careful consideration on the higher-
magnification TEM image as shown in Figure 3f would tell
us the mesopores also exist in the gaps between submicro-
spheres.
To further analyze and quantify the specific porous
properties of the urchin-like hierarchical MnO2 superstructures,
we carried out the nitrogen adsorption−desorption measure-
ments at 77 K. Because of the little difference of the nitrogen
adsorption−desorption isotherms in the S-12, S-24, and S-48
three samples, the pore-size distributions would produce
serious mutual interference when their graphs stacked together,
which is not conducive to analyze the distinction in the porous
properties. So only the contrast of the S-12 and S-48 has been
investigated. Figure 4 shows the nitrogen adsorption−
desorption isotherms (Figure 4a) and corresponding pore-
size distributions (Figure 4b) of the S-12 and S-48 samples. As
the N2 adsorption−desorption isotherms as shown in Figure 4a,
they can be classified as type IV according to the international

Figure 3. TEM images at different magnifications of the MnO2 three

samples: (a, b) S-12, (c, d) S-24, and (e, f) S-48.

24 (Figure 3c, d) and S-48 (Figure 3e, f) at different

magnifications. It can be seen that the three samples
predominantly consist of the hollow urchin structure with
visible interior cavities as shown in Figure 3a, c, e. A few
spheres with surface damage as shown in Figure 3e are also
observed, further suggesting that the as-synthesized MnO2
submicrospheres have the hollow structures. Nanomeasurer
software was used to analyze SEM and TEM images, which
present that the S-12 sample has the submicrospheres with size
ranges from 150 to 300 nm, whereas the submicrospheres of
the S-24 and S-48 samples are confined to the size range of
200−400 nm and 200−500 nm, respectively. In a contrast to
the microspheres prepared by Yuan et al.44,52 and Chen et al.,34
the as-synthesized submicrospheres in this study have smaller
diameter, which may be ascribed to the different thickness of
soft-interface. The TEM images easily demonstrate the fact that
the average diameter (∼400 nm) of MnO2 submicrospheres in
the S-48 sample is larger than that (∼213 nm) of the S-12 and Figure 4. (a) N2 adsorption−desorption isotherms and (b)
that (∼362 nm) of the S-24, which indicates that the MnO2 corresponding pore-size distributions of the S-12 and S-48 samples,
submicrospheres are growing in the aging progress. This verdict respectively.

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union of pure and applied chemistry classification. A distinct 2H2O = 5MnO2 + 4H+. The theoretical yield of MnO2 is 4.35 g
type H3 hysteresis loop can be observed in the larger range of but the actual output is 4.18 g. So the productive rate is 96%,
0.4−1.0 P/P0, providing another evidence for the mesoporous which verifies the formation of MnO2 in the acidic reaction.
structure of the S-12 and S-48 samples. The measured The MnO2 particles produced in the reaction processes could
Brunauer−Emmett−Teller (BET) surface areas of the S-12 gradually change into the nanorods, which fell to the H2O/
and S-48 samples were 254.8 and 219.3 m2 g−1, respectively, CH2Cl2 interfaces. Because the solubility of MnO2 in H2O and
which suggests that specific surface area decreases along with CH2Cl2 is both very tiny, MnO2 nanorods distribute along the
the growth of MnO2 submicrospheres. The type H3 hysteresis unique convex interface. In order to minimize the surface
loop demonstrates that the samples consist of particles or split- energy, these nanorods accumulated at the convex interface
shape materials, which implies that the as-prepared MnO2 start to wrap the lower liquid to form hollow spheres with many
superstructures should possess hierarchical porosity. This mesopores. Thus, the hollow spheres with thorns occurred,
deduction can be further supported by the pore-size many nanorods further aggregated to the surface of the spheres
distributions of the S-12 and S-48 samples as shown in Figure and were dispersed by dynamical mixed liquid to form much
4b. The pore sizes of the S-48 sample are distributed in the bigger submicrospheres. However, the submicrospheres would
range 1.3−100 nm, with the majority clustering in the range stop increasing, even happen to burst when submicrosphere
1.3−15 nm. The smaller diameter ones are in the range 1.5−2.5 diameter increased to a certain degree, which may be related to
nm and larger diameter ones are in the range 5−10 nm. The the thickness of the interface. The thickness of interface mainly
hierarchical porosity should be ascribed to mesopores between results from the concentration difference of the two immiscible
submicrospherical superstructures and the mesopores existing fluids. The smaller the difference value is, the thinner the soft
in the one-dimension MnO2 nanorods building blocks. Using interface is larger. So H2O/CH2Cl2 interface is thicker than
Barrett−Joyner−Halenda (BJH) method to calculate the H2O/CCl4 interface. For MnO2 submicrospheres packing the
average pore diameter from the adsorption branch of the mixed liquid need to keep the balance of internal and external
isotherm, the measured average pore diameters of the S-12 and pressure, MnO2 submicrospheres would be restricted in the
S-48 samples were 3.88 and 1.82 nm, respectively. However, interface layer. As a result, the diameter of MnO2 submicro-
the average pore diameter (5.61 nm) of the S-12 sample was spheres is less than the thickness of the interface. For the
smaller than that (5.87 nm) of the S-48 sample. The seemingly average density of MnO2 submicrosphere packing, the mixed
contradictory results support the viewpoint that the nanorods liquid is between the densities of H2O and CH2Cl2, so the
arrange more closely and the gap mesopores become larger MnO2 submicrospheres always kept suspension in the H2O/
owing to the growth of submicrospheres in the aging stage. CH2Cl2 interface environment. The incompact urchin-like
Moreover, the mesoporous volumes of the S-12 and S-48 MnO2 submicrospheres have to form numerous mesoporous
samples are quantitatively determined to be 0.471 and 0.451 gaps among them so that the hierarchical MnO2 submicros-
cm3 g−1 as shown in Table 2, which further verify the above pherical superstructures possessed the gap mesopores between
submicrospheres and mesopores existing in the one-dimension
Table 2. Textural Properties of the MnO2 Three Samples: S- MnO2 nanorods building blocks. Therefore, the formation of
12, S-24, and S-48 this urchin-like hierarchical MnO2 submicrospherical super-
structure is mainly ascribed to the significant contribution of
BET area (m2· pore volume average pore diameter
g−1) (cm−3 g−1) (nm) the H2O/CH2Cl2 interfaces. This will provide a beneficial
S-12 254.8 0.471 5.61
reference for further study about the formation of hierarchical
S-24 228.4 0.459 5.75 superstructures.
S-48 219.3 0.451 5.87 The obtained urchin-like hierarchical MnO2 submicrospher-
ical superstructures (S-48) would be expected to show superior
surface-related properties because of tremendous specific
views. It is interesting that the pores in urchin-like hierarchical surface area, for example, catalytic properties. Herein, the S-
MnO2 submicrospherical superstructures were smaller and 48 will be used as a catalyst for wastewater treatment.
more uniform than those of the hierarchical mesoporous Methylene blue (MB), as a typical industrial pollutant, was
materials in previous reports.34,44,48 chosen as a model to examine the catalytic performance of this
As relevant reports have stated, the interfaces between mesoporous MnO2. The oxidative degradation of the MB dye
immiscible fluids have been shown to be ideal for the assembly was investigated under the neutral condition using H2O2 as
of nanometer-sized colloidal particles,53 the particles are highly oxidant and the S-48 as catalyst. The UV−vis absorption
mobile, and rapidly achieve an equilibrium assembly at a liquid/ spectra of the MB solution and mixed solutions added by
liquid soft-interface.54 Yuan and co-workers have given a hydrogen peroxide and S-48 (such as MB + H2O2, MB + H2O2
general explanation for the formation of mesoporous MnO2 on + S-48) as a function of the reaction time were shown in the
the H2O/CCl4 interface. Obviously, the dynamical soft- bottom of Figure 5 with chemical structure of MB molecular as
interface was formed in the immiscible H2O/CH2Cl2 system. shown in the top of Figure 5. The spectrum of the initial
Owing to the different surface tensions, a unique convex solution of MB (no H2O2) shows four absorption peaks located
occurred on the H2O/CH2Cl2 interface. We would like to at 246, 292, 614, and 664 nm, which originates from the
propose a possible self-assembly mechanism, such as molecular absorption of the MB.2,32,34 The MB bands at 292
equilibrium assembly mechanism, to explain the formation of and 246 nm were covered by the strong absorption of hydrogen
this urchin-like hierarchical MnO2 submicrospherical super- peroxide in the range of 185−300 nm2,43 after the MB solution
structure according to the above experimental results. This and H2O2 solution were mixed. As the S-48 was added, the
mechanism is described as follows: when the KMnO4 solution intensities of the peaks at 614 and 664 nm decreased rapidly
was dropped enter into the MnSO4 solution through the within 10 min. As the reaction proceeded, the characteristic
CH2Cl2 layer, the redox reaction occurred: 3Mn2+ + 2MnO4− + absorption of the MB at 664 nm gradually weakens, which is
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Figure 6. Degradation rate of the MB using H2O2 as oxidant and

Figure 5. Top: Chemical structure of the MB molecule. Bottom: UV− different catalysts: (a) no H2O2, (b) no catalyst, (c) commercial
vis absorption spectra of the MB solution and the mixtures such as MB MnO2, (d) the as-prepared mesoporous MnO2 (S-48), (e) the
+ H2O2, MB + H2O2 + mesoporous MnO2 (S-48) as a function of the calcined mesoporous MnO2 (S-48−300 °C).
reaction time.

as catalyst and ∼61.3% of the MB is decomposed after the

why it was chosen for monitoring the catalytic process of the decomposition reaction was conducted for 120 min (Figure 6,
mesoporous MnO2 superstructures. At the same time, the color line d), which manifests the catalytic reaction occurred rapidly.
of the mixture became shallow gradually. With the further Obviously, the catalytic activity of the S-48 is much higher and
elapse of reaction time after 60 min, the drop of the MB peaks faster than that of the commercial MnO2.
continued but much more slowly. The original absorption The catalytic performance was described only by the
maximum at 664 nm shifted to 657 nm after reaction for 10 conversion degree of MB is unconvincing and improper
min. The blue shift of the absorption band indicates that the because the catalytic capacity of the catalyst and the volume
catalytic degradation of the MB is similar to that reported by of 30 wt % H2O2 solution consumed were both responsible for
Zhang et al.4 Moreover, the band at 614 nm became very broad the conversion degree of MB. Since the H2O2 was always totally
and weak at 60 min. consumed in the catalytic reaction, the catalytic performance of
In general, the degradation efficiency of the MB molecules mesoporous MnO2 could be estimated by the equation as
denoted as r in this study was calculated as follows: follows
C0 − C I −I (C0 − C)V0 Mr
r= = 0 (when dilution multiple is the same) q= = 0
C0 I0 VW VW
where C0 (g L−1) is the initial concentration of the mixture of −1 −1
where q (g L g ) is the consumption of MB caused by 1 g of
the MB solution and H2O2 solution, C (g L−1) is the catalyst and 1 L of 30 wt % H2O2 solution, C0 (g L−1) has the
concentration of the mixture solution at different intervals same meaning as above but C (g L−1) is the concentration of
during the reaction, I0 is the absorbance at 664 nm at t = 0 min the mixture solution at 120 min. V0 (L) is the initial volume of
and I is the absorbance at the same wavelength at a given the mixture, i.e., 60 mL, V (L) is the volume of 30 wt % H2O2
reaction time. Some reports selected the corresponding solution added into MB solution, i.e., 10 mL, W (g) is the
absorbance of the MB solution as I0, neglecting the volume weight of the catalyst, i.e., 0.025 g, and M0 (g) means the initial
change of the solution when H2O2 solution was added. Thus, mass of MB. The q in this study is about 12.26 g L−1 g−1, which
the degradation ratio has got a bigger value. To get more exact is more effective than ∼2.46 and 8.13 g L−1 g−1 of β-MnO2
data, the mixture solution of 50 mL of MB and 10 mL of H2O nanorods (its surface area is 63.8 m2 g−1),2,55 ∼3.20 g L−1 g−1 of
is selected as the initial solution at t = 0 min in this study. The β-MnO2 hollow octahedral43 and ∼6.67 g L−1 g−1 of MnO2
results about degradation extent are shown in Figure 6. Line a nanofiber (its surface area is 104 m2 g−1).1 The excellent
in Figure 6 indicates that the mesoporous MnO2 (S-48) barely catalytic performance of the urchin-like hierarchical MnO2
adsorbs MB from the resolution, in agreement with previous submicrospherical superstructures (S-48) may be due to
results reported in the literatures.2,15,32 As line b in Figure 6 mesopores between hollow submicrospheres (high surface
demonstrates that only ∼7.2% of MB is decomposed without area) and mesopores existing in the one-dimension MnO2
catalyst even after reacting for 120 min. No obvious nanorods building blocks (high surface-to-volume ratio). The
decolorization is observed without H2O2 or S-48eVen after 2 catalytic performance of the as-prepared hierarchical MnO2
h (Figure 6, line a and b), which declares that the degradation superstructures may be related to their large surface areas.
of MB molecules is caused by H2O2-induced oxidation To further improve the catalytic efficiency of the as-prepared
catalyzed by MnO2. It can be seen that the ∼42.7% of MB mesoporous MnO2 superstructures, the S-48 sample has been
can be decomposed in 120 min using the commercial MnO2 treated by the calcination of 300 °C for 2 h. Further
(its specific surface area is 0.2 m2/g) as catalyst (Figure 6, line experiments reveal that the calcined S-48 sample (S-48−300
c). The similar catalytic performance of commercial MnO2 has °C) exhibits higher catalytic performance (in same weight, e.g.,
been reported by Zhang et al.2 The ∼57.8% of MB in the 25 mg) than that of S-48 with the increase of 10% in the
solution is decomposed within 20 min in the presence of S-48 degradation of MB (Figure 6, line e). Figure 7 shows the XRD
9781 dx.doi.org/10.1021/am502191k | ACS Appl. Mater. Interfaces 2014, 6, 9776−9784
ACS Applied Materials & Interfaces Research Article

superstructures show superior catalytic stability during the

Fenton-like reaction. The dissolubility of the catalyst in solution
is also selected as an index to assess the catalytic stability of the
catalyst. The concentration of Mn ion in mixed solution
detected by inductively coupled plasma-atomic emission
spectrometry is 11.3 mg/L, which is in coincidence with the
tiny degradation of the MB (∼1.2%) with the filtered solution
as catalyst. The two results also indicate that the catalytic wet
peroxide oxidation of MB using mesoporous MnO2 as catalyst
is in heterogeneous catalytic system. To conclude, the excellent
catalytic performance of the hierarchical MnO2 superstructures
favors their practical applications.

4. CONCLUSIONS
Figure 7. XRD pattern and SEM image (inset) of S-48−300 °C. In summary, a soft-interface between CH2Cl2 and H2O as a
facile approach has been used to successfully prepare the
pattern and SEM image (inset) of S-48−300 °C. The XRD hierarchical mesoporous MnO2 superstructures without
patterns of the calcined S-48 sample indicate that its crystal templates. The superstructures consist of the hierarchical
phase is also ε-MnO2 with the improvement of crystallinity. urchin-like MnO2 hollow submicrospheres with size ranges
The SEM image (inset) shows the lessened nanorods on the from 200 to 500 nm. The main crystal phase of as-prepared
surface of MnO2 hollow submicrospheres than that of the S-48 mesoporous MnO 2 was proved to be ε-MnO 2 . This
sample. Undoubtedly, the surface area of the calcined sample mesoporous MnO2 has an average pore diameter to be 5.87
has been decreased after calcination. The higher efficiency of nm, mesoporous volume to be 0.451 cm3·g−1, and specific
the calcined sample was achieved, which may be ascribed to surface area to be 219.3 m2 g−1. The formation mechanism of
better crystallinity21 and cleaner surface35 of the catalyst. this hierarchical urchin-like MnO2 superstructure was inves-
Different morphology of the crystals results in different exposed tigated reasonably, which is based on the self-assembly of one-
crystallographic facets that showed different adsorption ability dimension MnO2 nanorods, and replied on the synthesis
to the reacting agent and then different catalytic activity. The conditions such as the type of interface and aging time. This
reacting agent is absorbed easier on the clean surface of unique pathway may be applicable to the preparation of other
catalysts before the catalytic reaction. However, further transition metal oxide superstructures for its simplicity and
investigations on the promotion of the catalytic performance feasible control. Methylene blue, a common dye, was used as
by the calcination are necessary. model substrate to evaluate the catalytic activity of the as-
The stability of catalyst is crucial to its application during the prepared mesoporous MnO2. This catalyst exhibits excellent
catalytic process. Figure 8 shows the degradation of the MB in performance for the degradation of methylene blue in the
presence of H2O2 at neutral pH. This mesoporous MnO2
superstructure as heterogeneous catalyst can be recycled with
tiny decrease of catalytic activity and be stable with its tiny
dissolubility in solution. Further experiments reveal that the
calcined sample (e.g., 300 °C for 2 h) is able to improve the
catalytic performance of as-prepared mesoporous MnO2. This
study demonstrates that the hierarchical mesoporous MnO2
superstructures have highly efficient catalytic degradation for
the organic pollutant methylene blue at room temperature.

■ AUTHOR INFORMATION
Corresponding Authors
*Phone: +86 21 66137503. Fax: +86 21 66137787. E-mail:
zwchen@shu.edu.cn.
*E-mail: apchshek@cityu.edu.hk.
Notes
Figure 8. Degradation of the MB in 60 min as a function of reused The authors declare no competing financial interest.

■
time using the mesoporous MnO2 (S-48) as the catalyst.
ACKNOWLEDGMENTS
60 min as a function of reused times using the mesoporous The work described in this article was financially supported by
MnO2 (S-48) as the catalyst. The experiments indicate the the National Natural Science Foundation of China (Projects
slight decrease of catalytic capacity of the hierarchical 11375111 and 11074161), the Research Fund for the Doctoral
mesoporous MnO2 superstructures along with the increase of Program of Higher Education of China (Projects
the used times, which may result from the loss of catalyst and 20133108110021), the Key Innovation Fund of Shanghai
adsorption of organic reactants on the catalyst. The ∼55.6% of Municipal Education Commission (Projects 14ZZ098 and
the MB was decomposed with the catalyst used in fifth times 10ZZ64), the Science and Technology Commission of
only with the drop of 4% in comparison to the first time, Shanghai Municipality (Project Number: 10JC1405400), the
indicating that the as-prepared mesoporous hierarchical MnO2 Shanghai Pujiang Program (Project Number: 10PJ1404100),
9782 dx.doi.org/10.1021/am502191k | ACS Appl. Mater. Interfaces 2014, 6, 9776−9784
ACS Applied Materials & Interfaces Research Article

and the Program for Innovative Research Team in University particles Immobilized in Alumina Coated Mesoporous Silica. Chem.
(Project Number: IRT13078). This work was also supported Commun. 2006, 463−465.
by a General Research Fund from the Research Grants Council, (20) Hermanek, M.; Zboril, R.; Medrik, N.; Pechousek, J.; Gregor, C.
Hong Kong (Project Number: CityU 119212). Catalytic Efficiency of Iron(iii) Oxides in Decomposition of Hydrogen

■
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