Article BULLETIN OF THE

DOI: 10.1002/bkcs.11239 H. Su et al. KOREAN CHEMICAL SOCIETY

Enhancing the Adsorption Capacity of Hematite by Manganese

Doping: Facile Synthesis and its Application in the Removal of
Congo Red
Huaifen Su, Xiaoxue Wang, Yuanwei Sun, Dan Xu, Lei Li, Caihua Liu, Suyuan Zeng,* and
Dezhi Sun*

Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology,
Department of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, China.
*E-mail: drzengsy@163.com; sundezhi@lcu.edu.cn
Received March 27, 2017, Accepted July 31, 2017

This work aims to provide a facile method for the preparation of Mn-doped hematite microrods and
reveals the relationship between Mn doping and the enhanced adsorption properties. The adsorption per-
formance of hematite could be greatly enhanced by Mn doping. The maximal adsorption capacity of the
Mn-doped α-Fe2O3 is calculated to be 84.54 mg/g, which exhibits obviously enhanced adsorption capac-
ity as compared to the un-doped α-Fe2O3 (33.02 mg/g). To further understand the adsorption process, the
adsorption kinetic as well as thermodynamic behaviors are carefully investigated. The results suggest that
the adsorption process of CR onto the adsorbents follows the pseudo-second-order kinetic model. Mean-
while, the adsorption process can be designated to be a Langmuir process. The adsorption capacities of
CR vary as a function of Mn contents, which are regarded as the synergistic effect between surface areas
and pore sizes.
Keywords: Hematite, Mn doping, Congo red, Enhanced adsorption performance, Dye removal

Introduction hierarchical structure, the as-obtained bundle-like α-Fe2O3

Congo red (CR) is an important anionic dye that has been
widely used in industries. However, direct disposal of CR
into the natural water system will usually cause serious
environmental and health problems. To date, a large num-
ber of methods such as coagulation–flocculation, biodegra-
dation, ion-exchange, chemical oxidation, nano-filtration,
physical/chemical adsorption, and so forth have been
employed for the removal of CR from wastewater.1–5
Among these methods, adsorption is attracting more and
more attentions because of its high efficiency, low cost, and
simple operation process.6 As a result, a large number of
adsorbents have been employed for the removal of dyes
from wastewater, such as activated carbon,7 orange peel,8
sawdust,9 montmorillonite,10 wheat bran and rice bran,11
porous metal oxides,12 magnetic adsorbents,13 and so forth.
Hematite (α-Fe2O3) is considered to be a promising can-
didate for dye removal because of its low cost and environ-
mental friendliness. For this reason, a large number of
researches have been conducted to fabricate absorbents
based on hematite nanostructures. For instance, Li et al.
have synthesized hollow α-Fe2O3 nanostructures via a
microwave-assisted hydrothermal method, which exhibit an
adsorption capacity of 160 mg/g for the removal of CR.14
By decomposing oxalate precursor with hierarchical struc-
tures, Li and co-workers have also successfully prepared
bundle-like hematite nanostructures. Because of the unique
nanostructures exhibit adsorption capacity of about
139.86 mg/g for CR.15 Cauliflower-like α-Fe2O3 micro-
structures were also successfully prepared via a bi-phasic
interfacial reaction process, which possesses maximal
adsorption capacity of 71.63 mg/g for CR.16 Liu’s group
has also reported the selective synthesis of α-Fe2O3 nano-
polyhedra, nanorods, and rice-shaped nanoparticles,
employing 2,4,6-tris(pyrazol-1-yl)-1,3,5-triazine (Tptz) as
the template. And all these α-Fe2O3 nanostructures exhibit
exciting adsorption performances for the removal of CR.17
Using a two-step method, Shi et al. have also succeeded in
the preparation of α-Fe2O3 nanostructures, all of which
exhibit satisfying adsorption capacities for the removal of
CR.18 Despite the progress that has been made in this field,
the adsorption performances of hematite nanostructures are
still far away from practical applications. It still remains a
great challenge for the chemists to further improve the
adsorption performances of hematite-based adsorbents,
especially by a facile and economical method.
Recently, it has been reported that the adsorption capaci-
ties of metal oxides could be greatly enhanced by the tran-
sitional metal doping method. For example, Zhao et al.
have synthesized a series of transitional metal-doped fer-
rites CoFe2−xMxO4 (M = Al3+, In3+, and Cu2+) nanoparti-
cles, all of which show greatly enhanced adsorption
capacities as compared to CoFe2O4 nanoparticles.19 Wang
et al. have also observed similar phenomena for the doped

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Article
ISSN (Print) 0253-2964 | (Online) 1229-5949
cobalt ferrite nanoparticles, which also exhibit enhanced
adsorption performances towards the removal of CR.20
Inspired by these exciting experimental results, a series of
Mn-doped hematite nanorods have been designed and synthe-
sized in this report. Although the Mn-doped hematite has been
widely reported by various groups,21 the researches mainly
focus on the photo-electrochemical or electrochemical proper-
ties of the Mn-doped hematite nanostructures. Few reports are
concerned on the enhanced adsorption capacities of the Mn-
doped hematite. Meanwhile, the relationship between Mn
doping and adsorption performance still remains unclear. In
our experiments, the as-obtained Mn-doped hematite exhibits
greatly enhanced adsorption capacity for CR, which may
result from the increasing surface areas of the adsorbents. This
method not only provide a method for the preparation of
hematite-based absorbent, but also shed a new light for the
design of high-efficient adsorbent.
Experimental
Materials and Reagents. All the reagents are of analytical
grade and used without further purification. De-ionized
water is employed during the whole experiment.
Synthesis of the Mn-doped α-Fe2O3 Structures.
Typically, 1.5 g of PVP was first dissolved in the mixed
solution containing 10 mL ethylene glycol (EG) and 4 mL
water. The resulting solution was subsequently stirred for
30 min. In the next step, 1 mmol H2C2O4
2H2O and
1 mmol metal salts (Mn(CH3COO)2
4H2O and FeS-
O4
7H2O with different molar ratios) were dissolved into
the two solutions mentioned above, respectively. The
resulting two solutions were later mixed slowly and stirred
at room temperature for 20 min. The as-obtained homoge-
neous yellow slurry was then transferred to a 50 mL
Teflon-lined autoclaves and kept at 120 C for 12 h. After
reacting for 12 h, the autoclaves were cooled down to room
temperature naturally. The as-obtained precursor was sepa-
rated by centrifugation and vacuum dried (60 C, 12 h). To
obtain the Mn-doped α-Fe2O3 nanostructures, the as-prepared
precursor was decomposed in the muffle furnace (400 C, 2 h,
heating rate: 1 C/min). Brown powders were obtained after
the heating process, which were collected for further investi-
gations. For comparison purpose, products with different
Mn/Fe ratios were also synthesized using the similar method.
To facilitate the following discussion, the samples obtained
with the initial Mn/Fe ratios of 0/10, 0.5/9.5, 1.0/9.0, 1.5/8.5,
2.0/8.0, 2.5/7.5, and 3.0/7.0 are denoted as MF0, MF1, MF2,
MF3, MF4, MF5, and MF6, respectively.
Characterization. The XRD analysis of the samples was
conducted on a Philips X’Pert Pro Super diffractometer
(Amsterdam, Netherlands) with Cu Kα radiation
(λ = 1.54178 Å). The sizes and morphologies of the pro-
ducts were investigated using field emission scanning elec-
tron microscope (FESEM, Hitachi S-4800, Hitachi, Tokyo,
Japan). The transmission electron microscopy (TEM) as
well as the high-resolution transmission electron
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microscopy (HRTEM) images were taken on a JEOL-
2010 (Tokyo, Japan) at an accelerating voltage of
200 kV. The BET surface areas of the samples were
measured using a nitrogen adsorption apparatus and
adopting the well-known BET procedure (Quantachrome
Autosorb IQ-C Boynton Beach, Florida, USA). X-ray
photoelectron spectroscopy (XPS Thero Fisher, 81
Wyman Street, Waltham, MA, USA) was conducted on
ESCALAB 250 system with a monochromatic Al Kα
source (1486.6 eV, 15 kV, 150 W).
Adsorption Experiments. In a typical process, solutions
with desired concentrations were obtained by diluting
0.01 mol/L stock solution of CR. During the adsorption
process, the absorption changes of solution were deter-
mined at certain time intervals. The adsorption amount of
CR can be calculated by the following equation:
qe = ðC0 − Ct ÞV=m ð1Þ
where C0 is the initial concentration of CR ( mmol/L), Ct is
the concentration of CR at desired time t (mmol/L), V is
the volume of suspension (L), and m is the mass of adsorb-
ent (g). The kinetic experiments were carried out using a
series of flasks that contain 0.8 g/L of absorbents. At cer-
tain time interval, the absorbents were separated by centrif-
ugation. The concentration of the CR after adsorption was
calculated according to the intensity of the maximal absorb-
ance (λmax = 497 nm). All of the experiments were con-
ducted three times to guarantee the consistency of data.
Results and Discussion
The hydrothermal process will result in the formation of
metal oxalates according to the XRD patterns of precursors.
According to the XRD patterns (Figure 1(a)), the Mn-doped
oxalate precursor is supposed to possess the similar structure
Figure 1. (a) XRD patterns of the un-doped (black line) and Mn-
doped precursor (red line, Mn:Fe = 1:4); (b and c) SEM images
of the un-doped and Mn-doped precursors.
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Article Enhancing the Adsorption Performance by Mn Doping KOREAN CHEMICAL SOCIETY

as FeC2O4
2H2O (JCPDS No. 72–1305), indicating the par-

tial substitution of Fe atoms by Mn atoms. Thus, the chemi-
cal formula of the as-obtained Mn-doped precursor could be
designated to be MnxFe1−xC2O4
2H2O tentatively. And this
result is in agreement with the previous works that we have
reported for the Ni- and Co-doped FeC2O4
2H2O precur-
sors.22 The existence of element Mn in the precursor could
also be confirmed by the EDS (Energy Dispersive Spectros-
copy) investigation (Figure S1 in Appendix S1, Supporting
Information). The atomic ratio between Fe and Mn is meas-
ured to be 82:18 according to the EDS result, which is con-
sistent with the initial ratio between Fe and Mn (4:1). The
morphology and size of the as-synthesized precursors were
investigated using FESEM, and the corresponding SEM
images of the precursors are shown as Figure 1(b) and (c).
The SEM observations clearly reveal that the as-synthesized
precursors are mainly composed of uniform rod-like struc-
tures. It should be noted that sizes of the precursors slightly Figure 3. (a and b) High and low magnification SEM, (c and d)
decrease after the doping of Mn. For the as-obtained TEM and HRTEM images of sample MF4.
FeC2O4
2H2O microrods, the average lengths and diameters
of the microrods are determined to be 80 and 1.5 μm. While the Mn-doped precursor, the size of sample MF4 is a little
for the Mn-doped FeC2O4
2H2O, the corresponding values smaller. And this phenomenon could be attributed to the
are determined to be 50 and 1.0 μm. removal of H2O and CO2 molecules during the thermal
According to the XRD patterns, calcination of the Mn- decomposition process. The atomic ratios between Mn and
doped precursor will result in the formation of the Mn- Fe is determined to be 19:81, which is close to the theoreti-
doped α-Fe2O3 microstructures (denoted as sample MF4). cal value (Figure S2(e) in Appendix S1). Figure 3(c) is the
The red line in Figure 2 is the XRD pattern of the Mn-doped TEM image taken on a rod-like structure, which ambigu-
α-Fe2O3, and all the peaks can be indexed to be a rhombohe- ously reveals the porous nature of the sample. Figure 3
dral cell with cell constants of a = 5.040 Å and (d) is the HRTEM image of the as-obtained microrod, on
c = 13.75 Å. The XRD pattern clearly indicates the structur- which the parallel lattice fringes can be clearly observed.
ally similarities between sample MF4 and pristine α-Fe2O3 The typical lattice spacing is measured to be approximately
(JCPDS Card, No. 89–2810), showing the homogeneous 0.391 nm, which can be ascribed to the lattice distance of
distribution of Mn atoms within α-Fe2O3 crystal lattice. the (110) planes of the Mn-doped hematite.
Figure 3(a) and (b) are the high and low magnification The chemical states as well as surface compositions of sam-
SEM images of sample MF4, which clearly reveal the rod- ple MF4 were further analyzed using the XPS technique. The
like morphology of the as-obtained sample. Compared with overall XPS spectrum of sample MF4 is shown as Figure 4(a),

Figure 2. XRD patterns of the as-synthesized samples MF0

Figure 4. XPS spectra of (a) survey spectrum, (b) O 1s, (c) Mn
and MF4.
2p, and (d) Fe 2p for sample MF4.

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Article Enhancing the Adsorption Performance by Mn Doping
Figure 5. Adsorption–desorption isotherms of N2 on sample MF4
determined at 77.35 K. (inset: pore size distribution calculated
from the desorption data by the BJH method).
which clearly indicates the presence of elements Mn, Fe, and
O. The binding energy of O 1s is measured to be 529.4 eV
(Figure 4(b)), which is consistent with the previous reports for
hematite nanostructures.23–25 The XPS spectrum of Mn 2p
can be fitted when considering the two spin-orbit doublet char-
acteristics of Mn3+ and Mn2+ (Figure 4(c)), suggesting the
existence of Mn with different valence states. The two peaks
locating at 643.2 and 641.1 eV can also be ascribed to Mn3+
and Mn2+, respectively. Similarly, the XPS spectrum of Fe 2p
also suggests the existence of Fe3+ and Fe2+. The peaks locat-
ing at 712.5 and 710.2 eV can be designated to be Fe3+ and
Fe2+, respectively. The atomic ratios to be 4.3:1, which is also
consistent with the theoretical value.
N2 adsorption–desorption experiments were performed to
get further insight into the porous structure of sample MF4,
and the corresponding result is shown as Figure 5. The iso-
therm can be classified as type V with a H3-type hysteretic
loop, which clearly reveals the mesoporous nature of sam-
ple MF4. The surface area of sample MF4 is determined to
be 165.34 m2/g and the pore size of the sample centers at
approximately 3.51 nm (inset of Figure 5), indicating the
mesoporous nature (2–50 nm in size) of sample MF4.
These pores may result from the void spaces between the
interconnected nanoparticles that constitute the nanorods.
Generally speaking, large surface areas will facilitate the
dye removal process by providing more adsorption sites,
which would be helpful to the elevation of adsorption
capacity.26,27 According to our previous research, the
molecular size of CR is determined to be 31.00 × 12.48 Å,
which is much smaller than the pore size of the sample.22
Thus, CR molecules can diffuse easily from the external to
the internal part during the adsorption process. And this
kind of configuration between surface areas and pore size
distributions will facilitate the adsorption of CR molecules,
which will be advantageous for the removal of pollutants
from water.28–30
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Figure 6. Effect of contact time on the adsorption amount of CR
at 298.15K.
Adsorption kinetic is one of the most important para-
meters when evaluating the adsorbents’ performances. In
this study, the adsorption kinetics of CR (Congo red) on
the Mn-doped hematite microrods (denoted as sample
MF4) were systematically investigated. To find out the rela-
tionship between Mn doping and adsorption kinetics, the
adsorption kinetic behavior of the un-doped hematite
microrods (denoted as sample MF0) was also investigated.
The adsorption kinetics of CR onto the adsorbents were
indicated by Figure 6, which clearly indicates that CR
molecules in the solution can be effectively removed within
2 h. Compared to sample MF0, sample MF4 exhibits a
much higher adsorption rate and nearly 90% of its maximal
adsorption capacity can be achieved within the initial
20 min. After adsorption for 20 min, the adsorption rate
becomes low. The fast uptake of CR in the initial 20 min
can be attributed to the large surface area as well as the
abundant adsorption sites on the adsorbents’ surfaces.
When these adsorption sites are gradually occupied by CR
molecules, the adsorption rate of CR becomes low.
To further understand the kinetic behavior of the adsorp-
tion process, both the pseudo-first-order and pseudo-sec-
ond-order kinetic models were employed to analyze the
kinetic data of the adsorption process.31,32 The detailed
description of the equation is given in the supporting infor-
mation. According to the pseudo-first-order kinetic model,
the calculated correlation coefficients (R2) are determined
to be 0.9897 and 0.9605 for sample MF0 and MF4, respec-
tively (Figure 7(a)). However, the calculated value of qe is
much smaller than the experimental value, which suggests
that the adsorption processes do not follow the pseudo-first-
order kinetic model. Besides the pseudo-first-order kinetic
model, the pseudo-second-order kinetic model was also
employed to analyze the adsorption data. The values of k2
and qe can be calculated from the slope and intercept of the
plots between t/qt and t (Figure 7(b)). And the calculated
results are summarized in Table 1. The values of the
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Article Enhancing the Adsorption Performance by Mn Doping
Figure 7. Plot of (a) log (qe–qt) vs. t for the adsorption of CR
onto sample MF4 using the pseudo-first-order kinetic model; (b) t/
qt vs. t for the adsorption of CR onto sample MF4 using the
pseudo-second-order kinetic model; (c) qt vs. t1/2 for the adsorp-
tion of CR onto sample MF4; (d) Bt vs. t for the adsorption of CR
onto sample MF4.
correlation coefficient (R2) are 0.9998 and 0.9998 for sam-
ple MF0 and MF4, respectively, indicating that the adsorp-
tion of CR can be better fitted using the pseudo-second-
order model. Indeed, the adsorption of CR follows the
pseudo-second-order kinetic model for most of the adsor-
bents, for instance, magnetic nanoparticles CoxNi1−xFe2O4
(x = 0, 0.3, 0.7, 0.9, 1.0),33 hierarchical porous NiO,34 clay
materials,35 gadolinium-doped cobalt ferrite
nanoparticles,20 non-magnetic metal-ions-doped cobalt
ferrites,36 and so on. What is more, for the as-synthesized
samples with different Mn contents, the adsorption pro-
cesses of CR also follow the pseudo-second-order kinetic
model (Figure S2 in Appendix S1).
To find out the steps involved during the adsorption
process, the intra-particle diffusion model was also
employed.37 Obviously, multi-linearity can be clearly
observed on the plot, which simply suggests that the
adsorption process is comprised of several steps. The entire
plot can be divided into three regions (Figure 7(c)). The
first region on the plot is related to the diffusion adsorption
stage during which dye molecules diffuse to the external
surfaces of adsorbents from aqueous solution. The second
section is a gradual adsorption stage, during which the dye
molecules diffuse to the internal surfaces of the adsorbents
through the in-built pores. The third section is related to the
final adsorption equilibrium, accompanied by the slowdown
Table 1. Parameters for pseudo-first-order and pseudo-second-order models.
Pseudo-first-order
−1
Sample k1 (min ) qe (mg/g)
MF0 1.868 36.92
MF4 0.0973 48.38
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of adsorption rate. The slowdown of adsorption rate can be
attributed to the decrease of active sites on the surfaces as
well as the low concentration of adsorbate in solution.38
To find out the actual rate-determining step during the
adsorption process, the Boyd model was also employed.39
The plot obtained from Boyd model (Bt vs. time) is called
Boyd plot (Figure 7(d)), which can be utilized to judge
whether the rate-determining step is an intra-particle diffu-
sion or film diffusion (external transport) process. If the
plot passes through the zero point, the rate-determining step
can be judged as an intra-particle diffusion process. Other-
wise, the adsorption process is dominated by a film diffu-
sion process. In our experiment, the Boyd plot do not pass
through the zero point, indicating that the external mass
transport is the rate-determining step during the adsorption
process.
Besides the enhancement of adsorption rate, the doping of
Mn also exerts positive influence on the adsorption amount of
the rod-like α-Fe2O3 nanostructures. To clarify this view,
both Langmuir40 and Freundlich41 models were employed.
And the linear fitting results of the adsorption data are shown
as Figure 8. Both of the two samples can be described using
the Langmuir model and the linear fitting results are summar-
ized in Table 2. Obviously, sample MF4 displays much
higher adsorption capacity as compared to sample MF0, indi-
cating that the doping of Mn does have a positive effect on
enhancing the adsorption performance of hematite microrods.
Compared to pristine hematite microrods, the adsorption
capacity increases from 33.02 to 84.54 mg/g, indicating that
the doping of Mn is helpful to increase the adsorption capaci-
ties of the hematite-based adsorbents.
The adsorption isothermal parameters are calculated
according to the Langmuir and Freundlich models, and the
corresponding results are summarized in Table 2. By com-
paring the linear correlation coefficients (R2) in Table 2, the
adsorption isotherm can be better fitted using the Langmuir
model, indicating a monolayer coverage on the surfaces of
the adsorbents.
The adsorption process of CR onto sample MF4 is fur-
ther characterized using the Langmuir dimensionless sepa-
ration factor (RL) that can be expressed as:
RL = 1=ð1 + KL C0 Þ ð2Þ
Benhammou43 had shown that the values of RL informed
us about the favorability of the adsorption process. When
0 < RL < 1, the adsorption process is thermodynamically
favorable. Whereas RL > 1, the adsorption process is
Pseudo-second-order
2
R k2 (min.mg/g) qe (mg/g) R2
0.9897 1.493 36.93 0.9998
0.9605 0.0077 49.24 0.9998
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Figure 9. (a) Langmuir isotherm for the adsorption of CR onto

Mn-doped α-Fe2O3 nanostructures at different concentrations
(298.15 K); (b) Adsorption amount vs. molar %(Mn) curve for
adsorption of CR onto Mn-doped α-Fe2O3 nanostructures
(298.15 K).

Figure 8. Linear fitting of the adsorption isotherms for the adsorp-

tion of CR onto samples MF0 and MF4 respectively: (a and b)
Langmuir model and (c and d) Freundlich model (adsorption con-
ditions of CR: 8 mL of CR dye; adsorbent dosage 6.4 mg; tem-
perature: 25 C).

thermodynamically unfavorable. The values of RL in this

study were all in the range from 0 to 1 (listed in Table 2),
suggesting that the adsorption of CR is a thermodynami-
cally favorable process.
According to the above experimental results, the doping of
Mn is helpful to increase the adsorption capacity of hematite-
based adsorbents. To further illustrate the effect of Mn doping,
samples containing different amount of Mn were prepared.
The exact Mn contents of the adsorbents were investigated
using the EDS method (Figure S3 in Appendix S1) and the
corresponding results are summarized in Table 3. The
adsorption experiments clearly show that the adsorption
amount of CR is strongly influenced by the contents of Mn
in the final products. For all the samples, the adsorption pro-
cesses of CR follow the Langmuir adsorption model, which
is similar to the two samples above (Figure 9(a)). The calcu-
lated adsorption capacities for samples MF1 (4%), MF2
(8%), MF3 (14%), MF5 (23%), and MF6 (29%) were calcu-
lated to be 52.25, 53.87, 60.23, 62.59, 66.41 mg/g, respec- Figure 10. Adsorption–desorption isotherms of N2 on a series of
tively. Evidently, the adsorption amount of CR keeps Mn-doped α-Fe2O3 nanostructures with different Mn contents,
increasing when the contents of Mn change from 0 to 19%. (a) MF0; (b) MF1; (c) MF2; (d) MF3; (e) MF5; (f ) MF6. (inset:
The adsorption amount of CR will decrease when the con- pore size distributions calculated from the desorption data using
tent of Mn is higher than 19%. The maximal adsorption the BJH method).
amount of CR can be observed when the doping amount is
19% (Figure 9(b)). These experimental facts clearly indicate To figure out the relationship between the adsorption
that the doping of Mn has great influence on the adsorption capacity and Mn contents, the BET surface areas as well as
performance of hematite. pore size distributions of samples MF0, MF1, MF2, MF3,

Table 2. Parameters for Langmuir and Freundlich isotherm models.

Freundlich Langmuir
Sample KF (mol1−nLn/g) R2 n KL (L/mol) R2 Q0 (mg/g) RL
−4
MF0 1.50 × 10 0.6831 0.108 4.22 × 10 5
0.9834 33.02 0–1
MF4 1.69 × 10−3 0.9916 0.214 2.76 × 106 0.9965 84.54 0–1

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Article Enhancing the Adsorption Performance by Mn Doping
Table 3. Mn contents, BET surfaces areas and pore sizes of a series of Mn-doped α-Fe2O3 nanostructures.
Samples MF0 MF1
Mn contents (measured) 0 4%
Pore area (m2/g) 72.50 86.30
Pore diameter (nm) 15.44 8.09
MF5, and MF6 are investigated and the corresponding
results are summarized in Figure 10. Calculated from the
N2 adsorption–desorption curves, the BET surface areas of
the samples mentioned above are calculated and listed in
Table 3. The surface areas of the samples keep increasing
along with the increase of Mn doping amount. Without
doping, the BET surface area of hematite nanorods is 72.5
m2/g. And the corresponding value will shift to 295.99
m2/g as the Mn content reaches 30% (atomic ratio). The
increase in surface area will inevitably lead to the increase
of adsorption capacity during the experiments.
However, it should be noted that the pore sizes of sam-
ples greatly decrease as the Mn contents increase. When
the Mn content reaches 29%, the pore size of the sample
will reduce to 1.31 nm. Although the surface area reaches a
maximum under this situation, the small pore size will pre-
vent the migration of CR from the external surface to the
interior part, which will result in the decrease of adsorption
capacity. Therefore, the adsorption capacities of CR can be
regarded as the cooperating effects of both surface areas
and pore sizes. These experimental data clearly suggest that
the Mn doping is an effective route to increase the adsorp-
tion capacities of hematite-based adsorbents, which open a
new door for the design and synthesis of adsorbents with
superior performances.
Conclusion
In summary, we have reported a simple Mn doping method
to enhance the adsorption performance of α-Fe2O3 nanor-
ods. The as-synthesized Mn-doped α-Fe2O3 nanorods show
enhanced adsorption performance of CR as compared to
pristine hematite nanorods. The adsorption of CR onto the
Mn-doped α-Fe2O3 nanorods follows the pseudo-second-
order kinetic model. And the entire adsorption process can
be described using the Langmuir adsorption model. Mean-
while, the adsorption capacities of CR vary as a function of
Mn contents in the samples. When the Mn content is less
than 19%, the adsorption capacities keep increasing with
the Mn contents. As the Mn content is greater than 19%,
the adsorption capacities begin to decrease. The variation
of adsorption capacities versus Mn contents is considered
to be the synergistic effects of the surface areas and pore
sizes.
Acknowledgments. The authors thank the National Basic
Research Program of China (Grant No. 2011CBA00701),
National Natural Science Foundation of China (Grant Nos.
21171084, 21373106), the Natural Science Foundation of
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MF2 MF3 MF4 MF5 MF6
8% 14% 19% 23% 29%
177.32 195.82 248.07 265.69 295.99
6.80 6.276 3.51 3.23 1.31
Shandong Province (Grant No. ZR2016BQ41), and the
Program for Scientific Research Innovation Team in Col-
leges and Universities of Shandong Province for financial
support.
Supporting Information. Additional supporting informa-
tion is available in the online version of this article.
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