Journal of Colloid and Interface Science 510 (2018) 207–220

Contents lists available at ScienceDirect

Journal of Colloid and Interface Science

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

Regular Article

Synthesis of MnO2 nanosheets on montmorillonite for oxidative

degradation and adsorption of methylene blue
Yi He a,1, De Bin Jiang b,1, Jie Chen a,⇑, De Yi Jiang a, Yu Xin Zhang a,b,⇑
a
College of Resources and Environmental Science, State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing 400044, PR China
b
State Key Laboratory of Mechanical Transmissions, College of Materials Science and Engineering, Key Laboratory of Fundamental Science of Micro/Nano-Devices and
System Technology, Chongqing University, Chongqing 400044, PR China

g r a p h i c a l a b s t r a c t

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

Article history: In this research, MnO2 nanosheets on montmorillonite (MnO2 nanosheets@MMt) was synthesized by one-
Received 1 June 2017 pot hydrothermal method and characterized by X-ray diffraction, Fourier transform infrared spectra, nitro-
Revised 23 August 2017 gen adsorption and scanning electron microscopy. It was found that honeycomb-like MnO2 nanosheets
Accepted 15 September 2017
vertically grew on the surface of montmorillonite. MnO2 nanosheets@MMt exhibited high methylene blue
Available online 18 September 2017
(MB) removal rate, which reached 97.7% within 5 min under the condition of pH 2, MnO2 nanosheets
dosage of 0.1 g L
1 and initial dye concentration of 10 mg L
1. Additionally, the influencing factors such
Keywords:
as pH value, amount of MnO2 nanosheets@MMt, and MB concentration were also investigated in this
MnO2
MMt
paper. Results showed the MB degradation process was correlated with pH value, and the MnO2
Degradation nanosheets@MMt achieved MB removal rate of 92.8% within 5 min under pH 11 because of its absorption
Nanocomposites capacity of MB. The kinetics of the adsorption process complied with the Pseudo-second-order model. The
Langmuir model was found to be the most suitable for describing the experimental equilibrium data of
MnO2 nanosheets@MMt. The MnO2 nanosheets@MMt showed high adsorption capacity of 363.63 mg g
1
for MB dye. The oxidative decomposition of MB was conducted in the presence of MnO2 nanosheets@MMt
in the low pH, finding that the lower the pH was, the faster the degradation rate was. This research demon-
strates that MnO2 nanosheets@MMt has potential applications in wastewater treatment.
Ó 2017 Elsevier Inc. All rights reserved.

⇑ Corresponding authors at: College of Resources and Environmental Science, State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University,
Chongqing 400044, PR China (Y.X. Zhang).
E-mail addresses: chenjie_cqu@163.com (J. Chen), zhangyuxin@cqu.edu.cn (Y.X. Zhang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.jcis.2017.09.066
0021-9797/Ó 2017 Elsevier Inc. All rights reserved.
208 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220
1. Introduction
Wastewater pollution has become one of major threatens to
people’s life. Electroplating wastewater contains large amounts of
heavy metals, and printing wastewater contains a large number
of chromophoric groups. If wastewater were not effectively trea-
ted, serious damage will be caused to human health and ecological
environment. Wastewater treatment has attracted increasing
attention in recent years. It’s very gratifying to see that the China
government has issued the ‘‘Water pollution control action plan”
to take full control of pollutant discharge and initiate wastewater
treatment, so as to ensure the security of water ecological
environment.
Methylene blue (MB) is a common cationic phenothiazine dye
[1], which has been widely used in printing, textile, leather indus-
tries, also been used as biochemical colorants [2]. However, MB has
various negative effects on human and animals, such as causing
increased heart rate, nausea and vomiting [3,4], and is resistant
to biodegradation because of its complex aromatic structure [5].
Various techniques, such as adsorption [6] and biological treat-
ment [7], membrane processes [8], coagulation [9], photo decom-
position [10–12], ozonation [13] and electrochemical oxidation
[14], have been used to remove dyes from wastewater. Among
these techniques, adsorption is a preferred choice because of easy
operation and low cost [15]. However, the adsorption method may
not degrade pollutants thoroughly, moreover, some adsorbents
will display disadvantages such as low adsorption efficiency, long
adsorption time, and poor mechanical strength [16].
Fortunately, the development of nanostructured materials
make up this shortcoming. Manganese dioxide (MnO2) is identified
as a promising material for its low cost, high stability,
environmental-compatibility and abundant availability [17]. Nano
manganese dioxide composites may act as adsorbent [18,19] and
degradant [20] for different kinds of organic pollutants and dyes
because of its [MnO6] octahedral crystal structure with large sur-
face area and high redox potential [21]. In addition, montmoril-
lonite (MMt) is a typical layered clay mineral consisting of one
Al3+ octahedral sheet placed between two Si4+ tetrahedral sheets
[22], which possesses large surface areas, high cation exchange
capacities and swelling ability [23]. More importantly, montmoril-
lonite, as a raw materials, enjoys abundant sources and lowered
cost, which has been widely used as adsorbent [24,25], catalyst
[26], coating agent [27] in various industrial branches.
It has been reported that manganese dioxide coated montmoril-
lonite compounds can improve adsorption performance and redox
reactivity for organic pollutants [28]. In this work, MnO2
nanosheets@MMt was synthesized via a simple hydrothermal
method (one-pot synthesis). The removal effect of the prepared
product for cationic dye MB was investigated at different concen-
trations of MB, different dosages of MnO2 nanosheets@MMt, and
different pH values. Moreover, the degradation ability of MnO2
nanosheets@MMt was compared with that of unmodified MMt in
this work. Thus, it can be concluded that MnO2 nanosheets@MMt
holds a great promise for the degradation of complex and various
dye wastewaters in practical applications.
2. Experimental methods
2.1. Materials
Montmorillonite K 10 clay was obtained from Aladdin Chem-
istry Co., Ltd. (Shanghai, China). The chemical compositions (wt.
%) of montmorillonite include: SiO2 73.0%, Al2O3 14.0%, Fe2O3
2.7%, MgO 1.1%, CaO 0.2%, Na2O 0.6%, K2O 1.9%. The chemicals were
of analytical grade and used without any further purification.
2.2. Experimental methods
2.2.1. Preparation of MnO2 nanosheets@MMt
The MnO2 nanosheets@MMt was prepared using a simple
hydrothermal method without any surfactant. In the experimental
procedure, 100 mg of montmorillonite K 10 was added into 30 mL
KMnO4 solution (0.05 mol), and then subjected to stirring at room
temperature for 10 min and then ultrasonic treatment for 15 min.
After that, the mixture was added into a Teflon-lined stainless steel
autoclave, and maintained at 160 °C for 24 h. Subsequently, collect
the precipitate, wash it with distilled water and ethyl alcohol.
Finally, dry the precipitate in a vacuum at 60 °C before obtaining
the final product MnO2 nanosheets@MMt.
2.2.2. Preparation of MnO2 nanowires@MMt
The MnO2 nanowires on montmorillonite (MnO2 nanowir-
es@MMt) was prepared by low-temperature hydrothermal
method. Firstly, dissolve 0.21 g of MMt in 30 mL of deionized water
in a 100 mL beaker, and then add 2.212 g of (NH4)2S2O8 and 1.85 g
of KMnO4 while keeping magnetic stirring. After that, pour the
mixture solution into an autoclave, and then put the autoclave into
an oven for hydrothermal treatment at 90 °C for 12 h. Similarly, the
MnO2 nanowires@MMt was obtained.
2.2.3. Degradation of dye aqueous solution
Three contrast experiments were carried out.
(i) The effect of pH on the removal rate of MB dye aqueous solu-
tion was investigated within the pH range from 2 to 11 in
100 mL of MB solution (10 mg L
1). First, adjust the initial
pH using HCl or NaOH solutions, and then add 10 mg of
MnO2 nanosheets@MMt into the above solutions while stir-
ring at 30 °C.
(ii) The effect of MnO2 nanosheets@MMt dosage on the degra-
dation of MB was studied by adding different dosages (10–
30 mg) of MnO2 nanosheets@MMt into MB solution
(50 mg L
1) in pH = 2 while stirring constantly.
(iii) The effect of MB concentration on the degradation of MB
was investigated by adding 10 mg of MnO2
nanosheets@MMt into MB solution with the concentration
ranging from 10 mg L
1 to 50 mg L
1 at pH = 2 while stirring
for a certain time.
Aqueous sample (4 mL) was collected from the solution at cer-
tain time interval and then centrifuged for removing the MnO2
nanosheets@MMt particles within. The concentrations of MB solu-
tion were determined by using a UV–vis spectroscopy (SHIMADZU,
Model UV-2450) at wavelengths of 663 nm. The degradation effi-
ciency of MB was estimated by Eq. (1):
 
C0
Ct
MB removal rateð%Þ ¼  100% ð1Þ
C0
where C0 and Ct (mg L
1) represent the initial concentration of
aqueous dye and its concentration at time t, respectively.
2.3. Characterization
The crystallographic information and chemical composition of
as-prepared products were characterized by powder X-ray diffrac-
tion (XRD, D/max 1200, Cu Ka) and Fourier transform infrared
(FTIR) spectroscopy (Nicolet, iS50). Nitrogen adsorption-
desorption isotherms were measured at 77 K with a Quantachrome
Surface Area Analyzer (QUDRASORB SI, USA). The specific surface
area was calculated with the Brunauer–Emmett–Teller (BET) equa-
tion using the adsorption data within the (P/P0) ranging from 0.05
 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220
to 0.35. The pore size distributions were calculated from desorp-
tion branch of the isotherm by the Barrett–Joyner–Halenda (BJH)
method. The structure and morphology of the samples were inves-
tigated by focused-ion-beam scanning electron microscopy (FIB/
SEM, Zeiss Model Auriga). To further identify the degradation pro-
cess of MB, the aqueous sample which obtained at different time
intervals during the reaction was filtered, then performed with
the positive ion mode ESI-MS of an ultra-performance liquid
chromatograph-mass spectrometer (UPLC-MS, Agilent, 1290-
6530). Typical ESI conditions involved a heated capillary tempera-
ture of 110 °C, cone voltage of 20 V, cone gas at a flow rate of
80 L h
1 and capillary voltage of 3.1 eV. Analyses of the dissolved
Mn2+ concentrations in the MB solution after different reaction
times were conducted using Atomic Absorption Spectroscopy
(AAS, SHIMADZU, AA-6300C).
3. Results and discussion
3.1. Characterization
3.1.1. XRD patterns and FTIR spectra analysis
Fig. 1 shows the broad-angle X-ray diffractograms of MMt,
MnO2 nanosheets@MMt and MnO2 nanowires@MMt within the
2h range of 5–80°. As shown in Fig. 1a, MMt exhibits strong peaks
at 2h = 5.89°, 19.89°, 35.30°, 54.23°, 61.80° and 73.33°, which is
ascribed to the typical crystal structure of bentonite (JCPDS file
No. 03-0015) [29]. Additionally, a number of additional peaks are
observed Fig. 1a, which are originated from cristobalite SiO2 (JCPDS
file No. 39-1425) presented in this commercial MMt.
According to XRD patterns of MnO2 nanosheets@MMt in Fig. 1b,
the diffraction peaks at 2h = 12.55°, 25.24°, and 37.31° are respec-
tively corresponded to the (0 0 1) (0 0 2) and (
1 1 1) planes of
crystal structure of birnessite (JCPDS No. 80-1098) [30]. According
to XRD patterns of MnO2 nanowires@MM in Fig. 1c, the diffraction
peaks at 12.74°, 18.06°, 25.65°, 28.74°, 37.63°, 42.04°, 49.90°,
56.18°, 60.24°, 65.52°, 69.60° and 73.07° are respectively corre-
sponded to the (1 1 0), (2 0 0), (2 2 0), (3 1 0), (1 2 1), (3 0 1),
(4 1 1), (6 0 0), (5 2 1), (0 0 2) and (4 5 1) crystal planes of man-
ganese oxide a-MnO2 (JCPDS card No. 72-1982) [31]. Notably,
the diffraction intensities of MMt are very weak, which is due to
that they are overlapped or covered by the strong diffraction of
the MnO2 nanowires (SiO2), indicating that a lower content in
weight, and MMt is warned up by denser MnO2 nanowires.
Fig. 1. XRD patterns of (a) MMt, (b) MnO2 nanosheets@MMt and (c) MnO2
nanowires@MMt.
209
The FTIR spectra of MMt, MnO2 nanosheets@MMt and MnO2
nanowires@MMt are shown in Fig. S1. There is a group of absorp-
tion peaks between 3445 and 3629 cm
1, which is assigned to the
OAH groups stretching bands of the interlayer water molecules
and framework hydroxyl groups. The band at 1635 cm
1 may be
ascribed to the bending vibrations of OAH groups of the adsorbed
water molecules [32]. The intense absorption peaks at 1085 cm
1
and 1041 cm
1 are both attributed to SiAO stretching vibration
within the layer, which decrease with loading of MnO2 [33]. The
peaks at 916 cm
1 and 840 cm
1 are ascribed to the SiAOASi bend-
ing vibration [22]. In the region of the spectrum below 1000 cm
1,
the peaks are attributed to some small lattice absorption bands,
which can be assigned to the SiAOAAl bending vibrations and
MgAO stretching modes at 519 cm
1 and 466 cm
1, respectively
[34]. Compared with the absorption band of MMt, the absorption
bands at 3629 cm
1 of MnO2 nanosheets@MMt and MnO2 nano-
wires@MMt are mostly disappeared. It indicates that the H2O con-
tent was reduced as the hydrated cation was replaced by MnO2
[35]. Besides, the apparent intensity declines in the range from
1100 cm
1 to 400 cm
1, and the MMt structure is intact, suggest-
ing that three materials shared similar functional groups.
3.1.2. N2 sorption isotherm and pore size distribution
The N2 sorption isotherms and pore size distributions of MMt,
MnO2 nanosheets@MMt, and MnO2 nanowires@MMt are shown
in Fig. 2. According to IUPAC classification, the N2 sorption iso-
therm of the three materials was very similar to type IIb isotherm
[2]. Under low relative pressure (P/P0 < 0.3), the amount of the
adsorbed nitrogen volume increases slowly with the relative pres-
sure, and the adsorption and desorption lines almost coincide with
each other due to effect of the monolayer adsorption [20]. In addi-
tion, there is a rapid augmentation of the adsorbed volume near
the high relative pressure range (P/P0 > 0.3). The apparent H2 type
hysteresis loop within relative pressure (P/P0) range from 0.45 to
0.9 has been regarded as a characteristic of capillary condensation.
It also can be deduced from the type of isotherm and the shape of
hysteresis loop that mesoporous structure of as-prepared sample
consists of slit-shaped pores. The inference can be further con-
firmed by pore size distribution of the as-prepared samples. As
shown Fig. 2d–f, the samples possesses a hierarchically porous
structure of which the pore size is ranging from 3 nm to 50 nm,
with the majority of clustering in the range of 3–10 nm. The textu-
ral properties such as BET surface area, pore diameter, and pore
volume derived from N2 sorption measurements are shown in
Table 1. The BET surface areas of MMt, MnO2 nanosheets@MMt
and MnO2 nanowires@MMt were measured to be 132.86, 100.42,
and 63.64 m2 g
1, respectively. Although the surface areas of
MnO2 nanosheets@MMt and MnO2 nanowires@MMt were reduced
after modification, the synergistic effect increase because of the
existence of MnO2.
3.1.3. Morphological and structural analysis
SEM micrographs of MMt, MnO2 nanosheets@MMt and MnO2
nanowires@MMt are shown in Fig. 3. In Fig. 3(a), the microscale
flakes and layer structure of clay with massive and nonporous sur-
face in aggregated morphology can be observed. Fig. 3(b) reveals
that MnO2 nanosheets are uniformly coated on the surface of
montmorillonite, forming seamless network like honeycomb. The
surfaces of MnO2 nanosheets@MMt composites are highly porous.
It is estimated that the lateral size of lamellar structure is 100–
200 nm. Fig. 3(c) and (d) show that the dense nanowires are cover-
ing on the surface of montmorillonite and in the clearance, respec-
tively. The length of MnO2 nanowires is larger than 200 nm, and
the surface of the nanowires is smooth and clean.
210 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220
Fig. 2. N2 adsorption/desorption isotherms of (a) MMt, (b) MnO2 nanosheets@MMt and (c) MnO2 nanowires@MMt and the BJH pore size distribution plot of (d) MMt, (e)
MnO2 nanosheets@MMt and (f) MnO2 nanowires@MMt.
Table 1
Textural properties of MMt, MnO2 nanosheets@MMt and MnO2 nanowires@MMt.
materials BET area Pore volume Average pore
(m2 g
1) (cm3 g
1) diameter (nm)
MMt 132.86 0.11 16.51
MnO2 nanosheets@MMt 63.64 0.17 17.30
MnO2 nanowires@MMt 100.42 0.28 17.29
3.2. Oxidative degradation of dye aqueous solution
3.2.1. Effect of pH on the degradation of MB
Fig. 4 shows that the decolorization efficiency of MB at different
pH values. When pH < 5 (Fig. 4a–d), it is clearly found that the
characteristic peak (kmax = 663 nm) intensity decreases sharply
with an evident blue shift after 5 min. New characteristic peaks
at 654 nm, 628 nm, 613 nm, 601 nm are corresponded to interme-
diates Azure B, Azure A, Azure C and Thionin, respectively [36,37] .
This blue shift may be attributed to the N-demethylation of alkyl
amine groups and oxidative decolorization in which the chro-
mophore of MB was damaged by MnO2 nanosheets@MMt [38].
As the reaction time progresses, the characteristic peak
(kmax = 663 nm) continues to shift (Fig. 4b and c) with rapidly
declined intensity. The color of solution becomes lighter containing
a little light purple, and finally becomes colorless which is associ-
ated with occurrence of the blue shift. In detail, the absorbance of
kmax = 663 nm almost reaches zero in a short time (5 min) at pH 2.
Yet, to achieve the similar MB removal effect at pH 3, the degrada-
tion process should be set longer (20 min). Compared to the previ-
ous reports [35,39,40], the decolorization result is distinctively
excellent. The pH of the dye solution has been identified as an
important influencing factor to the removal rate of dye. The lower
the pH value is, the more severe the characteristic peak shift is, and
the faster the intensity decays.
According to the UV–vis absorbance spectra in Fig. 4e–g, when
the pH value varies from 5 to 11, no shifted characteristic peaks
can be found, which suggests there was no generation of interme-
diates during the interaction between MB dye molecules and MnO2
nanosheets@MMt composites. The decrease in peak intensity may
be attributed to the adsorption removal of MB molecules. With the
extending of reaction time, the characteristic peaks gradually dis-
appear from the spectrum, which is extraordinarily close to peaks
of pure water in corresponding locations (Please see the Supple-
mentary information, Fig. S2), demonstrating the complete discol-
oration of the MB molecules.
Fig. 4h displays the removal percentage of MB by MnO2
nanosheets@MMt as the pH value increasing from 2 to 11 at
5 min. It is observed that 97.7% of MB is degraded due to the oxida-
tive decomposition at pH 2, while 92.8% of MB is removed by
adsorption at pH 11. MnO2 nanosheets@MMt is proved to be effi-
cient for removal of MB both in acid and alkaline conditions.
3.2.2. Effect of MnO2 nanosheets@MMt dosage on the oxidative
degradation of MB
The oxidative degradation of MB solution (50 mg L
1) with dif-
ferent dosages of MnO2 nanosheets@MMt (0.15, 0.20, 0.25, and
0.30 g L
1) was studied. Fig. 5 shows that with the increase of
MnO2 nanosheets@MMt dosage, the intensity of the newly formed
characteristic peak at kmax = 601 nm is gradually decreased. The
color change is significant enough to be observed by naked eyes
with the increase of MnO2 nanosheets@MM dosage. At the begin-
ning of the reaction, the color is mazarine, which is the character-
istic color of MB solution (the first bottle). After the addition of
MnO2 nanosheets@MMt, the color becomes dark violet (Fig. 5a),
suggesting that the oxidative process generated a new purple aux-
ochrome. The apparent color of MB changes from dark violet to
light purple as the dosage increases from 15 mg to 25 mg
(Fig. 5b). As the reaction proceeds, the color gradually turns into
light purple, and eventually becomes colorless. It’s worth noting
that the absorbance closing to zero (Fig. 5d) is mainly due to that
MnO2 nanosheets@MMt offered a wide range of reaction site for
the oxidative degradation. According to the results (Fig. 6), the
effect of the amount of MnO2 nanosheets@MMt on the oxidative
degradation of MB is relatively small. The removal rate of MB is
keeping above 99% after 5 min, indicating that the MnO2
nanosheets@MMt is an excellent candidate for degradation of MB
 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220
Fig. 3. SEM images of the (a) MMt, (b) MnO2 nanosheets@MMt and (c) (d) MnO2 nanowires@MMt.
dye. From above analyses, it can be concluded that pH may be the
most significant influencing factor to the oxidation removal of MB.
3.2.3. Effect of MB concentration
Fig. 7 shows the effect of MB concentration on the degradation
of MB by MnO2 nanosheets@MMt. It is found that the removal rate
of MB is decreased with the increase of MB concentration. When
the MnO2 nanosheets@MMt is added into the MB solution, the
color of MB solution is change acutely (Fig. 7a–d inset) from deep
blue to violet within 5 min, moreover, the greater the initial MB
concentration is, the deeper the purple is. Specifically, the color
change is inconspicuous when the initial concentration of MB is
50 mg L
1. Similarly, the characteristic peak shifts from 663 nm
to 601 nm, which is attributed to the thionin which is the product
from oxidation decomposition of MB. With the extending of reac-
tion time, the intensity of new peak is reduced, which is much
lower than that during the initial 5 min. It demonstrates that the
reaction between MnO2 nanosheets@MMt and MB dye molecules
was rapid redox reaction, followed by adsorption reaction.
3.2.4. Effect of different materials
Three control experiments were conducted to prove the superi-
ority of MnO2 nanosheets@MMt. Fig. 8a indicates that degradation
is not significant when only MMt is added in the MB solution. This
result testifies that the adsorption capacity of MMt is weaker, and
the MB removal rate of MMt is only 26.8% after 120 min. However,
the MB concentration is significantly decreased when MnO2 is
poured into the MB solution. Compared with MnO2 nanowir-
es@MMt and birnessite MnO2 nanosheets, MnO2 nanosheets@MMt
shows higher decolorization activity, making the Ct/C0 almost zero
after 5 min. Fig. 8b indicates the degrees of MB decolorization with
211
addition of different materials, from which we can see the decol-
orization capacities of the added materials can be ranked in follow-
ing order: MnO2 nanosheets@MMt > MnO2 nanosheets > MnO2
nanowires@MMt > MMt. This is due to the special lamellar struc-
ture of birnessite MnO2 and the larger surface area of the MMt.
The results are in agreement with the results of previous research
[28].
3.3. Adsorption kinetics
The adsorption kinetics is an important issue in adsorption
studies. A good understanding on adsorption kinetics helps us to
predict the removal rate and provides valuable data for under-
standing the mechanism of sorption reactions. To evaluate the
adsorption behavior of the as-prepared MnO2 nanosheets@MMt,
10 mg of adsorbent was added into 100 mL of 10 mg L
1 MB solu-
tion at room temperature under pH = 5.14. Aqueous sample (4 mL)
was taken from the solution at certain time interval (2, 4, 6, 8, 10,
15, 20, 30, 40, 60 min).
The adsorption capacity (qe) can be calculated according to
Eq. (2):
ðC 0
C e Þ  V
qe ¼ ð2Þ
m
where Ce (mg L
1) is the equilibrium dye concentration in the liquid
phase, V (L) is the volume of solution, and m (g) is the amount of
adsorbent.
The adsorbed mass per unit mass qt (mg g
1) at adsorption time
t (min) is calculated by following Eq. (3).
ðC 0
C t Þ  V
qt ¼ ð3Þ
m
212 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220

Fig. 4. UV–vis absorbance spectra of MB dye solution at different time intervals with the same MnO2 nanosheets@MMt dosage (10 mg) and the same MB concentration
(10 mg L
1) at different pH values: (a) pH 2.04, (b) pH 2.54, (c) pH 3.08, (d) pH 4m.10, (e) pH 5.14, (f) pH 9.30, and (g) pH 11.07. (h) Comparison of the removal rate of MB at
different pH values (t = 5 min). Inset (a–g) show the digital photographs of the initial MB solution (10 mg L
1) color and the color of MB solution (10 mg L
1) after
decolorization by MnO2 nanosheets@MMt at different time.
 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220 213

Fig. 5. UV–vis absorbance spectra of MB dye solution at different time intervals with the same pre-determined MB concentration (50 mg L
1) and the same pH value (pH = 2)
at different MnO2 nanosheets@MMt dosages: (a) 0.15 g L
1, (b) 0.20 g L
1, (c) 0.25 g L
1, (d) 0.30 g L
1. Inset of (a–d) show the digital photographs of the initial MB solution
(50 mg L
1) color and the color of MB solution (50 mg L
1) after decolorization by MnO2 nanosheets@MMt at different time.

k1
logðqe
qt Þ ¼ log qe
t ð4Þ
2:303

where k1 is rate constant of first-order adsorption (min
1). Value of

k1 is calculated from the plots of log (qe–qt) versus t (Fig. 9a).
Although the correlation coefficient R2 is 0.96, the experimental
qe values does not match with the calculated values obtained from
the linear plots (Table 2).
Pseudo-second-order model is based on adsorbents equilibrium
capacity, which can be expressed as:

t 1 t
¼ þ ð5Þ
qt k2 q2e qe

where k2 is rate constant of second-order adsorption

Fig. 6. Comparison of the removal rates of MB at different dosages of MnO2
nanosheets@MMt.
In order to analyze the adsorption kinetics for the adsorption of
MB onto MnO2 nanosheets@MMt, four kinetic models including
pseudo-first-order kinetic model, pseudo-second-order kinetic
model, intra-particle diffusion model and liquid film diffusion
model are used to fit the experimental data.
A simple kinetic model which can describe the process of
adsorption is the pseudo-first-order equation, which is given as:
(g mg
1 min
1). The slope and intercept of the plot of t/qt versus t
(Fig. 9b) are used to calculate the k2. As shown in Table 2, the value
of pseudo-second order rate constant k2 is calculated to be
3.55  10
3 g mg
1 min
1, while the equilibrium adsorption capac-
ity is calculated to be 102.77 mg g
1. The correlation coefficient R2
obtained is as high as 0.99 and the value of experimental qe is very
close to the value of calculated qe obtained from the linear plots,
indicating that the pseudo-second order kinetic model is the most
effective theoretical model to describe the adsorption process of
dye onto the MnO2 nanosheets@MMt nanocomposites. The results
suggest that the adsorption process in this research was chemical
adsorption caused by electrostatic attraction [41].
The adsorbate can be transferred from the solution to the sur-
face of adsorbent in several steps, including external diffusion, pore
diffusion, surface diffusion and adsorption on the pore surface [42].
214 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220

Fig. 7. UV–vis absorbance spectra of MB dye solution at different time intervals with the same MnO2 nanosheets@MMt dosage (0.10 g L
1) and the same pH value (pH = 2) at
different MB concentrations: (a) 50 mg L
1, (b) 40 mg L
1, (c) 30 mg L
1, (d) 20 mg L
1. Inset of (a–d) show the digital photographs of the color change of MB solution at
different time.

Fig. 8. (a) Time profiles of MB degradation. (b) Comparison of the MB removal rates at t = 5 min using different materials.

However, in order to gain further insight into the rate determining
step involved in the adsorption of MB dye on MnO2
nanosheets@MMt adsorbent, intra-particle diffusion model was
examined according to the Weber and Morris Eq. (6):
qt ¼ kid t 1=2 þ C
where kid is the intra-particle diffusion rate constant
(mg g
1 min1/2), C is the intercept representing the boundary layer
thickness(mg g
1). Plot of qt values against t1/2 values is shown in
Fig. 10c. If the model passes through the origin, then the rate deter-
mining step will be the intra-particle diffusion. Otherwise, boundary
layer diffusion or chemical reaction is the rate determining step. In
this case, the fitting line is a multi-linear pattern and does not pass
ð6Þ the origin, indicating that the overall adsorption process may pro-
ceed by multiple mechanisms such as chemical reaction, film diffu-
sion, and intra-particle diffusion [43]. The first fitting line in this
diffusion model may be attributed to the mass transfer of adsorbate
 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220 215

Fig. 9. (a) Pseudo-first-order model (b) pseudo-second-order model (c) intra-particle diffusion model and (d) liquid film diffusion model for adsorption of MB on MnO2
nanosheets@MMt.

Table 2 3.4. Adsorption isotherms

Parameters of four kinetic models for the adsorption of MB on MnO2
nanosheets@MMt with initial MB concentration of 10 mg L
1.
Langmuir and Freundlich models were applied to analyze the
qe,exp Models Model coefficients R2 adsorption experiments data. The Langmuir model is based on
(mg g
1) the assumption that monolayer adsorption occurs on the surface
98.36 Pseudo-first-order qe = 56.91 mg g
1 0.96 of adsorbents and all adsorption sites are identical, which can be
k1 = 9.13  10
2 min
1 expressed as follow:
Pseudo-second-order qe = 102.77 mg g
1 0.99
k2 = 3.55  10
3 g mg
1 min
1
qmax K L C e
Intra-particle diffusion kid = 1.63 mg g
1 min1/2 0.92 qe ¼ ð8Þ
C = 85.72 mg g
1 1 þ K LCe
Liquid film diffusion kfd = 1.13  10
3 min
1 0.82
Eq. (8) can be linearized to the following equation:

molecule from the bulk solution to the adsorbent surface or instan-
taneous stage, while the second fitting line should be the intra-
particle diffusion on MnO2 nanosheets@MMt nanocomposites [44].
The last kinetic model is liquid film diffusion model, of which
the equation is given as below (7):
 
q
ln 1
t ¼
kfd t
qe
where kfd is the liquid film diffusion rate constant (min
1). The
value of correlation coefficient R2 is calculated to be 0.96, which
is less than the correlation coefficient R2 of Pseudo-second-order
model.
Ce 1 Ce
¼ þ ð9Þ
qe qmax K L qmax
where qmax is the maximum adsorption capacity of the adsorbent
(mg g
1), and KL is the Langmuir constant related to the energy of
the adsorption process (L mg
1). As shown in Table 3, the qmax
and KL are calculated from the intercept and slope of lines obtained
ð7Þ from plots between Ce/qe versus Ce, respectively (Fig. 10b). As
shown in Fig. 10b, the adsorption behavior displays a good linear
Langmuir relationship with the theoretical maximum adsorption
value (qmax = 363.63 mg g
1) which is close to the experimental
capacity (358.14 mg g
1), wherein the correlation coefficient R2
value is higher than 0.99.
216 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220

Fig. 10. (a) Non-linear Langmuir and Freundlich adsorption isotherms for MB adsorbed onto MnO2 nanosheets@MMt, (b) Linear Langmuir isotherms, and (c) Linear
Freundlich isotherms.

Table 3 Table 4
Adsorption isotherm parameters of MB adsorbed on MnO2 nanosheets@MMt. Comparison of adsorption capacities of between MnO2 nanosheets@MMt and other
adsorbents.
Isothermal models Parameters
Adsorbent Objects Qm (mg g
1) Ref.
Langmuir KL (L mg
1) 3.87
qmax (mg g
1) 363.63 MnO2-modified diatomite MB 714.3 [40]
RL 5.14  10
2–2.52  10
2 CTA/MnO2 MB 489 [15]
R2 0.99 MnO2-NPs-AC MB 263.16 [1]
PProDOT/MnO2 MB 13.94 [16]
Freundlich KF ((mg g
1) (L mg
1)1/n) 243.56
H-d-MnO2 nanosheets MO 357 [45]
n 5.91
MnO2 nanosheets@MMt MB 363.63 This work
R2 0.66
5SSTA-MMT MB 204.08 [35]
jC–PVA/NaMMT Crystal violet 151 [46]
montmorillonite–alginate Basic red 46 35 [47]

For the Langmuir-type adsorption process, the influence of the

isotherm shape on adsorption is determined by a dimensionless
separation factor RL which is considered as a more reliable indica-
tor of the adsorption capacity. The Langmuir isotherm is character-
ized by a dimensionless constant, and the separation is defined by
the following equation:
1 bents is presented in Table 4. In the case of Langmuir model, the
RL ¼
1 þ K LC0
where C0 is the initial concentration. RL indicates the nature of
adsorption, which is unfavorable when RL > 1, linear when RL = 1,
favorable when 0 < RL < 1, irreversible when RL = 0. As shown in
Table 3, the RL value is identified within the range of 5.14  10
2–
2.52  10
2, indicating that the adsorption of MB onto MnO2
nanosheets@MMt was favorable.
The Freundlich model is based on the assumption that multi-
layer adsorption occurs on the surface of adsorbents with
unequally available sites of different adsorption energies. Fre-
undlich equation is expressed as following equation:
1
qe ¼ K F C en
Eq. (11) can be linearized by taking logarithms:
1 Likewise, MnO2 also shows pH sensibility. Firstly, the MB
ln qe ¼ ln K F þ ln C e
n
where KF is the Freundlich constant ((mg g
1) (L mg
1)1/n), n is the
heterogeneity factor. As shown in Table 3, the KF and n are calcu-
lated from the intercept and slope of the Freundlich plots, respec-
tively (Fig. 10c). It is generally considered that if the values of n
are within the range of 1–10, the adsorption is favorable. In this
case, the adsorption is favorable because the n = 5.91.
As shown in Table 3, the Langmuir isotherm has a better appli-
cability than the Freundlich isotherm does, and the correlation
coefficient R2 of the Langmuir isotherm is much higher than of Fre-
undlich isotherm, indicating that the homogeneous nature of sam-
ple surface and the formation of monolayer coverage of dye
molecule on the outer surface of adsorbent.
As mentioned before, numerous adsorbents have been tested in
terms of adsorption capacity of organic dye. Comparison of adsorp-
tion capacity between MnO2 nanosheets@MMt and other adsor-
ð10Þ
maximum adsorption capacity of MB on MnO2 nanosheets@MMt
is approximately 363.63 mg g
1, which is larger than MB adsorp-
tion capacities of modified MMt and manganese dioxide composite
reported before, but smaller than the MB adsorption capacity of
MnO2-modified diatomite. This comparison clearly indicates that
MnO2 nanosheets@MMt is a more effective adsorbent for MB.
3.5. Possible degradation mechanism
According to the results mentioned above and in previous
reports, we proposed a possible degradation mechanism of MB
by MnO2 nanosheets@MMt as illustrated in Fig. 11:
ð11Þ (i) Oxidative degradation in low pHs. On one hand, MB is a
heterocyclic aromatic compound, of which chromophores
are alkyl amine groups depending on the pH of the solution.
ð12Þ dyes may be subjected to different degrees of demethylation
(mono-N-demethylation, di-N-demethylation, tri-N-
demethylation and complete N-demethylation) under the
interaction between birnessite MnO2 nanosheets and MMt
in acidic aqueous solution, and then be subjected to deami-
nation until the aromatic ring is decomposed, resulting in
small molecules with one benzene ring and some inorganic
ions such as NO
2
+
3 , SO4 and NH4. This degradation process
is accompanied by a rapidly-diminished absorbance at the
wavelength of 663 nm and a blue shift in the UV–Vis spectra
as shown in Fig. 4d–a. What is more, the crystal stability of
the layered structure of birnessite is weak at a lower pH,
 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220 217

Fig. 11. Schematic illustration of proposed mechanism of the MnO2 nanosheets@MMt in degradation of the MB dyes.

which is beneficial to the redox reaction between MnO2/
Mn2+ and MB [48]; In addition, according to the Nernst
equation [49,50] (MnO2(s) + 4H+ + 2e
? Mn2+(aq) + 2H2O),
high H+ concentration can improve the reduction potential
of the system. In other words, the lower the pH is, the higher
the reduction potential of MnO2/Mn2+ and oxidizing power
of the system are. According to the results of AAS analysis
(Fig. 12a), the Mn2+ concentration in the MB suspension
increases rapidly from 0 to 16.5 ppm at the initial one min-
ute, then slowly increases and finally reaches equilibrium
(24.0 ppm, 120 min). Interesting, with the rapidly increasing
of Mn2+ concentration, the characteristic peak intensity of
MB decreases sharply with an evident blue shift at also the
initial one minute, then the intensity continuously reducing,
and the color of solution gradually faded into nothingness
(Fig. 12b). The intermediates of the degradation as shown
in Fig. 13. The signal of MB cations are detected with a strong
peak located at m/z = 284 amu before oxidative degradation.
After 5 min, the peak at m/z = 284 amu disappears, while
more new peaks appear at m/z = 278, 256, 122 amu. The
peak at 256 amu is likely to the intermediates azure A,
which is in consistent with the characteristic peak
kmax = 628 nm in the UV–Vis spectra (Fig. 4c). Other new
peaks at m/z = 226, 167, 125 amu are corresponded to the
further oxidation of aromatic rings after 60 min.
On the other hand, according to other reports, the pHzpc of bir-
nessite is about 1.5–2.2 [51]. when pH < pHzpc, the surfaces of
MnO2 nanosheets@MMt were positively charged through the pro-
tonation reaction, which repelled the cationic dye MB, and made
the adsorption between MB dye molecules and MnO2
nanosheets@MMt negligible. The removal of MB indicates that
the oxidative degradation is pH-dependent and efficient.
(ii) Multi-processes were associated with oxidative degradation
and adsorption decolorization in medium-low pHs, N-
demethylation effect was gradually weakened with the
increase of pH. The oxidative degradation did not play a
leading role in the degradation mechanism any more.
Through partial N-demethylation, the intermediates were
adsorbed on the surface of MnO2 nanosheets@MMt because
of increasing electrostatic adsorption, which is consistent
with the experimental results in Fig. 4d. With the extending
of time, the new characteristic absorption peak at 654 nm

Fig. 12. (a) The corresponding changes of the Mn2+ concentration in the MB suspension. (b) UV–vis absorbance spectra of MB dye solution at different time intervals. The MB
dye concentration is 100 mg L
1, the content of MnO2 nanosheets@MMt is 0.5 g L
1 and pH 2.56.
218 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220
Fig. 13. ESI-MS analysis on the solution during the reaction process. Reaction
conditions: MB = 100 mg L
1, MnO2 nanosheets@MMt = 0.5 g L
1 and pH = 2.56.
has no new migration. FTIR results of MnO2
nanosheets@MMt with the high oxidative degradation and
adsorption capacity were evaluated before and after the
reaction with MB, as shown in Fig. 14. As can be seen from
Fig. 14, the band at 2924 cm
1 is related to the stretching
vibration of ACH2 groups of MB, which almost disappears
after the reaction with MnO2 nanosheets@MMt in pH 2.56
and pH 4.0 indicating the N-demethylation in low pHs.
Fig. 14. FTIR spectra of (a) MB, (b) MnO2 nanosheets@MMt, (c) MnO2
nanosheets@MMt after the reaction with MB in pH 2.56, (d) MnO2
nanosheets@MMt after the reaction with MB in pH 4.0, (e) MnO2 nanosheets@MMt
after the reaction with MB in pH 11.0.
(iii) Adsorption decolorization in high pHs. The removal of MB is
owed to pure adsorption of MB on the MnO2
nanosheets@MMt surface on account of weak redox reac-
tion, which is consistent with the experimental results when
pH exceeds 5.14. As shown in Fig. 4h, the UV–vis absorbance
spectra have no blue shift, and the MB removal rate
increases from 63.9% to 92.8% as pH increases from 5.14 to
11.07. Similarly, the FTIR results also show that the band
at 2924 cm
1 of MB shifts to 2917 cm
1 after reaction with
MnO2 nanosheets@MMt in pH 11.0 indicating the adsorp-
tion in high pHs. Additionally, the band located at
1591 cm
1 is assigned to stretch vibration of C@N band con-
tained in the benzene ring of MB, the bands at 1134 cm
1 is
assigned to be stretch vibration of CAS band, and the charac-
teristic bands of MB are at 1385, 1323 1165, and 666 cm
1 .
All the characteristic bands above which are recorded
accompanied with them in the FTIR spectrum of MnO2
nanosheets@MMt after adsorption of MB. The peak at
m/z = 284 amu in the results of ESI-MS analysis also indicat-
ing the presence of MB cations (see the Supplementary
information, Fig. S3).
4. Conclusion
In summary, the honeycomb-like MnO2 nanosheets are uni-
formly decorated on the surface of montmorillonite to form a nov-
elty hybrid structure (MnO2 nanosheets@MMt) was synthesized by
a simple one-pot hydrothermal method. The as-prepared MnO2
nanosheets@MMt exhibited remarkable efficiency compared with
either pristine MMt, MnO2 nanosheets, or MnO2 nanowires@MMt.
The MB removal rate of MnO2 nanosheets@MMt reached as high as
97.7% in 5 min (pH = 2) and 92.8% in 5 min (pH = 11), indicated that
MnO2 nanosheets@MMt has more extensive application for MB
removal both in acid and alkaline conditions. The Pseudo-second-
order model and Langmuir model were found to be the more appli-
cable for describing the experimental data. The theoretical maxi-
mum adsorption value was qmax = 363.63 mg g
1. Subsequently,
the possible degradation mechanism was proposed. The highly
porous surface morphology supply more active sites for MB mole-
cule and weaker crystal stability of MnO2 nanosheets@MMt at low
pHs is beneficial to the redox reaction between Mn(IV/II) and MB.
Consequently, it can be concluded that the MnO2
nanosheets@MMt is a promising, environmentally friendly, and
easily synthesized material to be used in wastewater treatment.
Acknowledgements
This research was supported by National Natural Science Foun-
dation of China (Nos. 21576034, 41672292 and 51604044),
Chongqing University Postgraduates’ Innovation Project (Nos.
CYB16014, CYB16029 and CYB17046), the Innovative Research
Team of Chongqing (CXTDG201602014), Chongqing Science and
Technology Commission (No. cstc2015jcyjA90011), the State Key
Laboratory of Coal Mine Disaster Dynamics and Control
(2011DA105287-FW201504), the Fundamental Research Funds
for the Central Universities (Nos. 106112017CDJQJ138802,
106112016CDJZR245518 and 106112016CDJZR135506). The
authors also thank Electron Microscopy Center of Chongqing
University for materials characterizations.
Notes
The authors declare no competing financial interest.
 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220 219

Appendix A. Supplementary material [22] D. Chen, J. Chen, X. Luan, H. Ji, Z. Xia, Characterization of anion–cationic
surfactants modified montmorillonite and its application for the removal of
methyl orange, Chem. Eng. J. 171 (3) (2011) 1150–1158.
The FTIR spectrum of MMt, MnO2 nanosheets@MMt and MnO2 [23] P. Yuan, M. Fan, D. Yang, H. He, D. Liu, A. Yuan, J. Zhu, T. Chen,
nanowires@MMt; UV–vis absorbance spectra of pure water; ESI- Montmorillonite-supported magnetite nanoparticles for the removal of
hexavalent chromium [Cr(VI)] from aqueous solutions, J Hazard Mater. 166
MS analysis on the solution during the reaction process. Reaction
(2–3) (2009) 821–829.
conditions: MB = 100 mg L-1, MnO2 nanosheets@MMt = 0.5 g L-1 [24] K.G. Bhattacharyya, S.S. Gupta, Adsorption of a few heavy metals on natural
and pH = 11.0. Supplementary data associated with this article and modified kaolinite and montmorillonite: a review, Adv. Colloid Interface
Sci. 140 (2) (2008) 114–131.
can be found, in the online version, at http://dx.doi.org/10.1016/j.
[25] C.C. Wang, L.C. Juang, T.C. Hsu, C.K. Lee, J.F. Lee, F.C. Huang, Adsorption of basic
jcis.2017.09.066. dyes onto montmorillonite, J. Colloid Interface Sci. 273 (1) (2004) 80–86.
[26] H.-M. Berends, T. Homburg, I. Kunz, P. Kurz, K10 montmorillonite supported
manganese catalysts for the oxidation of water to dioxygen, Appl. Clay Sci. 53
References (2) (2011) 174–180.
[27] S. Li, J. Ding, N. Shawgi, S. Qi, Effect of organic montmorillonite on the
performance of modified waterborne potassium silicate zinc-rich anti-
[1] A. Asfaram, M. Ghaedi, S. Hajati, A. Goudarzi, Ternary dye adsorption onto
corrosion coating, Res. Chem. Intermed. 42 (4) (2015) 3507–3521.
MnO2 nanoparticle-loaded activated carbon: derivative spectrophotometry
[28] M.X. Zhu, Z. Wang, S.H. Xu, T. Li, Decolorization of methylene blue by delta-
and modeling, RSC Adv. 5 (88) (2015) 72300–72320.
MnO2-coated montmorillonite complexes: emphasizing redox reactivity of
[2] Y. Liu, Z. Chen, C.H. Shek, C.M. Wu, J.K. Lai, Hierarchical mesoporous MnO2
Mn-oxide coatings, J Hazard Mater. 181 (1–3) (2010) 57–64.
superstructures synthesized by soft-interface method and their catalytic
[29] K.A. Hernández-Hernández, M. Solache-Ríos, M.C. Díaz-Nava, Removal of
performances, ACS Appl. Mater. Interfaces 6 (12) (2014) 9776–9784.
brilliant blue FCF from aqueous solutions using an unmodified and iron-
[3] Y. Wang, X. Zhang, X. He, W. Zhang, X. Zhang, C. Lu, In situ synthesis of MnO2
modified bentonite and the thermodynamic parameters of the process, Water
coated cellulose nanofibers hybrid for effective removal of methylene blue,
Air Soil Pollut. 224 (5) (2013).
Carbohydr. Polym. 110 (2014) 302–308.
[30] F. Li, Y. Xing, M. Huang, K.L. Li, T.T. Yu, Y.X. Zhang, D. Losic,
[4] A. Palinska, A. Grodzka, H. Elzanowska, B. Kepska, E. Zwierkowska, S.
MnO2nanostructures with three-dimensional (3D) morphology replicated
Achmatowicz, M. Maj-Zurawska, Methylene blue interactions with
from diatoms for high-performance supercapacitors, J. Mater. Chem. A 3 (15)
chromosomal and plasmid DNA on screen-printed carbon electrodes,
(2015) 7855–7861.
Electroanalysis 22 (12) (2010) 1306–1313.
[31] Z.Q. Wen, M. Li, F. Li, S.J. Zhu, X.Y. Liu, Y.X. Zhang, T. Kumeria, D. Losic, Y. Gao,
[5] J. Mei, L. Zhang, Ultrasonic-assisted self-assembly synthesis of highly dispersed
W. Zhang, S.X. He, Morphology-controlled MnO2-graphene oxide-
b-MnO2 nano-branches interwoven with graphene flakes for catalytic
diatomaceous earth 3-dimensional (3D) composites for high-performance
oxidation of aromatic compounds, RSC Adv. 5 (19) (2015) 14843–14850.
supercapacitors, Dalton Trans. 45 (3) (2016) 936–942.
[6] M. Arshadi, M. Mehravar, M.J. Amiri, A.R. Faraji, Synthesis and adsorption
[32] Y.X. Zhang, M. Huang, F. Li, X.L. Wang, Z.Q. Wen, One-pot synthesis of
characteristics of an heterogenized manganese nanoadsorbent towards methyl
hierarchical MnO2-modified diatomites for electrochemical capacitor
orange, J. Colloid Interface Sci. 440 (2015) 189–197.
electrodes, J. Power Sources. 246 (2014) 449–456.
[7] C.V. Gomez-Pacheco, J. Rivera-Utrilla, M. Sanchez-Polo, J.J. Lopez-Penalver,
[33] A.S. Ozcan, A. Ozcan, Adsorption of acid dyes from aqueous solutions onto
Optimization of the preparation process of biological sludge adsorbents for
acid-activated bentonite, J. Colloid Interface Sci. 276 (1) (2004) 39–46.
application in water treatment, J Hazard Mater. 217–218 (2012) 76–84.
[34] C. Li, J. Zhang, Y. Lin, Y. Chen, X. Xie, H. Wang, L. Wang, In situ growth of
[8] S.M. Doke, G.D. Yadav, Novelties of combustion synthesized titania
layered double hydroxide on disordered platelets of montmorillonite, Appl.
ultrafiltration membrane in efficient removal of methylene blue dye from
Clay Sci. 119 (2016) 103–108.
aqueous effluent, Chemosphere 117 (2014) 760–765.
[35] D.M. Chen, J. Chen, X.M. Wang, X.L. Luan, H.P. Ji, F. Xu, Adsorption of methylene
[9] S. Jorfi, G. Barzegar, M. Ahmadi, R. Darvishi, Cheshmeh Soltani, N. Alah
blue from aqueous solution by anionic surfactant modified montmorillonite,
Jafarzadeh Haghighifard, A. Takdastan, R. Saeedi, M. Abtahi, Enhanced
Adv. Mater. Res. 178 (2010) 29–34.
coagulation-photocatalytic treatment of Acid red 73 dye and real textile
[36] T.Y. Zhang, T. Oyama, A. Aoshima, H. Hidaka, J.C. Zhao, N. Serpone,
wastewater using UVA/synthesized MgO nanoparticles, J. Environ. Manage.
Photooxidative N-demethylation of methylene blue in aqueous TiO2
177 (2016) 111–118.
dispersions under UV irradiation, J. Photochem. Photobiol. A 140 (2) (2001)
[10] B. Nanda, A.C. Pradhan, K.M. Parida, A comparative study on adsorption and
163–172.
photocatalytic dye degradation under visible light irradiation by mesoporous
[37] T.Y. Zhang, T. Oyama, S. Horikoshi, H. Hidaka, J.C. Zhao, N. Serpone,
MnO2 modified MCM-41 nanocomposite, Microporous Mesoporous Mater.
Photocatalyzed N-demethylation and degradation of methylene blue in
226 (2016) 229–242.
titania dispersions exposed to concentrated sunlight, Sol. Energy Mater. Sol.
[11] Y. Tang, R. Wang, Y. Yang, D. Yan, X. Xiang, Highly enhanced
Cells 73 (3) (2002) 287–303.
photoelectrochemical water oxidation efficiency based on triadic quantum
[38] B. Lan, M. Sun, T. Lin, G. Cheng, L. Yu, S. Peng, J. Xu, Ultra-long a-MnO2
dot/layered double hydroxide/BiVO4 photoanodes, ACS Appl. Mater. Interfaces
nanowires: control synthesis and its absorption activity, Mater. Lett. 121
8 (30) (2016) 19446–19455.
(2014) 234–237.
[12] X. Xiang, L. Xie, Z. Li, F. Li, Ternary MgO/ZnO/In2O3 heterostructured
[39] W. Zhang, Z. Yang, X. Wang, Y. Zhang, X. Wen, S. Yang, Large-scale synthesis of
photocatalysts derived from a layered precursor and visible-light-induced
b-MnO2 nanorods and their rapid and efficient catalytic oxidation of
photocatalytic activity, Chem. Eng. J. 221 (2013) 222–229.
methylene blue dye, Catal. Commun. 7 (6) (2006) 408–412.
[13] S. Zhang, D. Wang, X. Zhang, P. Fan, Zero-valent iron immobilized on multi-
[40] Y.X. Zhang, X.D. Hao, F. Li, Z.P. Diao, Z.Y. Guo, J. Li, pH-Dependent Degradation
walled carbon nanotubes for heterogeneous catalytic ozonation of methylene
of Methylene Blue via Rational-Designed MnO2 Nanosheet-Decorated
blue as model compound, CLEAN Soil Air Water 42 (5) (2014) 609–616.
Diatomites, Ind. Eng. Chem. Res. 53 (17) (2014) 6966–6977.
[14] A. Alaoui, K. El Kacemi, K. El Ass, S. Kitane, S. El Bouzidi, Activity of Pt/MnO2
[41] M. Fayazi, M. Ghanei-Motlagh, M.A. Taher, The adsorption of basic dye
electrode in the electrochemical degradation of methylene blue in aqueous
(Alizarin red S) from aqueous solution onto activated carbon/c-Fe2O3 nano-
solution, Sep. Purif. Technol. 154 (2015) 281–289.
composite: kinetic and equilibrium studies, Mater. Sci. Semicond. Process. 40
[15] K. Mori, S. Iguchi, S. Takebe, M. Nakayama, A thin film sorbent of layered
(2015) 35–43.
organo-MnO2 for the extraction of p-aminoazobenzene from aqueous solution,
[42] H.Y. Zhu, R. Jiang, L. Xiao, W. Li, A novel magnetically separable gamma-Fe2O3/
J. Mater. Chem. A 3 (12) (2015) 6470–6476.
crosslinked chitosan adsorbent: preparation, characterization and adsorption
[16] R. Jamal, L. Zhang, M. Wang, Q. Zhao, T. Abdiryim, Synthesis of poly(3,4-
application for removal of hazardous azo dye, J. Hazard Mater. 179 (1–3)
propylenedioxythiophene)/MnO2 composites and their applications in the
(2010) 251–257.
adsorptive removal of methylene blue, Prog. Nat. Sci. Mater. Int. 26 (1) (2016)
[43] M.Y. Nassar, I.S. Ahmed, T.Y. Mohamed, M. Khatab, A controlled, template-free,
32–40.
and hydrothermal synthesis route to sphere-like a-Fe2O3 nanostructures for
[17] B. Yin, S. Zhang, Y. Jiao, Y. Liu, F. Qu, X. Wu, Facile synthesis of ultralong MnO2
textile dye removal, RSC Adv. 6 (24) (2016) 20001–20013.
nanowires as high performance supercapacitor electrodes and photocatalysts
[44] H.R. Mahmoud, S.A. El-Molla, M. Saif, Improvement of physicochemical
with enhanced photocatalytic activities, CrystEngComm. 16 (43) (2014) 9999–
properties of Fe2O3/MgO nanomaterials by hydrothermal treatment
10005.
for dye removal from industrial wastewater, Powder Technol. 249 (2013)
[18] N. Caliskan, A.R. Kul, S. Alkan, E.G. Sogut, I. Alacabey, Adsorption of Zinc(II) on
225–233.
diatomite and manganese-oxide-modified diatomite: a kinetic and
[45] Y. Liu, C. Luo, J. Sun, H. Li, Z. Sun, S. Yan, Enhanced adsorption removal of
equilibrium study, J. Hazard Mater. 193 (2011) 27–36.
methyl orange from aqueous solution by nanostructured proton-containing d-
[19] J. Mei, L. Zhang, Y. Niu, Fabrication of the magnetic manganese
MnO2, J. Mater. Chem. A 3 (10) (2015) 5674–5682.
dioxide/graphene nanocomposite and its application in dye removal from
[46] H. Hosseinzadeh, S. Zoroufi, G.R. Mahdavinia, Study on adsorption of cationic
the aqueous solution at room temperature, Mater. Res. Bull. 70 (2015) 82–86.
dye on novel kappa-carrageenan/poly(vinyl alcohol)/montmorillonite
[20] J. Tang, B. Mu, W. Wang, M. Zheng, A. Wang, Fabrication of manganese
nanocomposite hydrogels, Polym. Bull. 72 (6) (2015) 1339–1363.
dioxide/carbon/attapulgite composites derived from spent bleaching earth for
[47] A. Hassani, R.D.C. Soltani, S. Karaca, A. Khataee, Preparation of montmorillonite
adsorption of Pb(II) and Brilliant green, RSC Adv. 6 (43) (2016) 36534–36543.
– alginate nanobiocomposite for adsorption of a textile dye in aqueous phase:
[21] Y. Xin, Zhang, X. Long Guo, M. Huang, X. Dong, Hao, Y. Yuan, C. Hua,
isotherm, kinetic and experimental design approaches, J. Ind. Eng. Chem.
Engineering birnessite-type MnO2 nanosheets on fiberglass for pH-dependent
1197–1207 (2015).
degradation of methylene blue, J. Phys. Chem. Solids 83 (2015) 40–46.
220 Y. He et al. / Journal of Colloid and Interface Science 510 (2018) 207–220

[48] H.J. Cui, H.Z. Huang, B. Yuan, M.L. Fu, Decolorization of RhB dye by
manganese oxides: effect of crystal type and solution pH, Geochem. Trans.
16 (2015) 10.
[49] M. Qin, H. Zhao, W. Yang, Y. Zhou, F. Li, A facile one-pot synthesis of three-
dimensional microflower birnessite (d-MnO2) and its efficient oxidative
degradation of rhodamine B, RSC Adv. 6 (28) (2016) 23905–23912.
[50] G. Zhao, J. Li, X. Ren, J. Hu, W. Hu, X. Wang, Highly active MnO2 nanosheet
synthesis from graphene oxide templates and their application in efficient
oxidative degradation of methylene blue, RSC Adv. 3 (31) (2013) 12909.
[51] H. Sun, K. Xu, M. Huang, Y. Shang, P. She, S. Yin, Z. Liu, One-pot synthesis of
ultrathin manganese dioxide nanosheets and their efficient oxidative
degradation of Rhodamine B, Appl. Surf. Sci. 357 (2015) 69–73.