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A novel mesoporous silicate material (MS) preparation from dolomite

and enhancing methylene blue removal by electronic induction
Pei Chen a,b, Zhan-fang Cao a,b,, Xin Wen a,b, Jing Wang a,b, Fan Yang a,b, Pei Qiu a,b,
Ya-jun Yue a,b, Guang-yi Liu a,b, Shuai Wang a,b, Hong Zhong a,b,
a
Hunan Provincial Key Laboratory of Ecient and Clean Utilization of Manganese Resources, Central South University, Changsha 410083, Hunan, China
b
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, China

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

Article history: In this investigation, a novel mesoporous silicate material (MS) was successfully synthesized from
Received 20 April 2017 dolomite and applied for removal of hazardous dye Methylene Blue (MB). Properties of the material were
Revised 12 July 2017
characterized by XRD, FT-IR, BET, SEM-EDS, TEM, and TG-DSC. During the adsorption process, conditions
Accepted 26 August 2017
like contact time, dye concentration, temperature and pH were studied to investigate the adsorption char-
Available online xxx
acteristics of the material. The adsorption capacity for MB could reach 111.65 mg/g. Thermodynamic and
Keywords: kinetic studies were also carried out in this paper. Moreover, a relative reasonable adsorption mecha-
Mesoporous silicate material nism was revealed by XPS analysis. The results showed that the electronic induction between calcium
Dolomite and magnesium ions is advantageous to enhance the MB adsorption.
Methylene blue 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Adsorption
Electronic induction

1. Introduction
Dye pollution has been a prominent problem to the earth
ecosystem in recent years. It is estimated that 1015% of total
production of dyes are discharged into waste water during dying
process [1]. These dyes are easily soluble in water and are highly
visible and generally toxic to aquatic life, so it is of great necessity
to get rid of them from waste water [2,3]. Up to now, various
textile dyes like methylene blue [4], azorubine [57], methyl
orange [8] and astrazon blue [9] have been used to investigate
decolorization abilities of different methods. Correlative solutions
for dye removal typically include chemical and physical methods
like coagulation, occulation, biosorption and photodecomposition
[10]. Adsorption is generally considered to be an economic and
ecient way among other choices [11,12]. There are many different
adsorbents including aminofunctionalized acrylamidemaleic acid
hydrogels [13], bottom ash, deoiled-soya [14], Brazil nut shells [15],
cross-linked chitosan [16], banana pith [17], coir pith [18], bagasse
pith [19], corn cob [20], sawdust [21], apple pomace [22] and
activated carbon [2326], which have been developed to wipe off
hazardous dyes by scholars and researchers.
Dolomite is widespread in nature in the form of carbonatite
and mostly employed in preparation of MgO [27], cement concrete
Corresponding authors at: College of Chemistry and Chemical Engineering, Cen-
tral South University, Changsha 410083, Hunan, China.
E-mail address: huagongyejin@163.com (Z.-f. Cao).
[28], soil improvement [29] and adsorbent for heavy metal ions
like Cu2+ , Pb2+ and Cd2+ [30].
It is known that dolomite contains plenty of calcium and mag-
nesium ions. Meanwhile, calcium silicate hydrate and magnesium
silicate both show some ability to adsorb MB [31,32]. Hence, there
is a great possibility to synthesize an effective silicate adsorbent
from dolomite by adding extra resource of silica. Besides, it is
of great signicance to investigate the mode of action between
adsorbent and adsorbate.
The purpose of this work is to prepare a novel and ecient
adsorbent for MB by utilizing the low-cost dolomite via a sim-
ple chemical precipitation process and to reveal the adsorption
mechanism through spectroscopy study.
2. Materials and methods
2.1. Materials
The dolomite is purchased from Xingtang County, Hebei
Province of China, and its size is less than 48 m. The chem-
ical compositions were listed in Table 1. Moreover, the XRD
pattern of dolomite was shown in Fig. 1. It is apparent that
CaMg(CO3 )2 is the major component in dolomite in accor-
dance with composition analysis. The other reagents are intro-
duced below: Na2 SiO3 9H2 O(AR), HCl(AR), NaOH(AR), CaCO3 (AR),
4MgCO3 Mg(OH)2 5H2 O(AR), deionized water, methylene blue
(85%, Kermel).

http://dx.doi.org/10.1016/j.jtice.2017.08.044
1876-1070/ 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: P. Chen et al., A novel mesoporous silicate material (MS) preparation from dolomite and en-
hancing methylene blue removal by electronic induction, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.044
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2 P. Chen et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 19
Table 1
The major compositions of dolomite.
Composition CaO MgO SiO2 Al2 O3 Fe2 O3
Mass(w%) 30.5 0.5 22.5 0.5 1.2 0.5 0.1
Fig. 1. XRD pattern of dolomite.
2.2. Synthesis of materials
2.0 g of dolomite powder was dissolved in 20 mL of 10%(v/v)
HCl aqueous solution. After leaching under certain conditions
(leaching time = 2 h, stirring rate = 300 rpm, 298.15 K), solution A
was obtained by ltering the precipitation. 12.7 g of Na2 SiO3 9H2 O
was completely dissolved into 40 mL deionized water and this was
solution B. Next, solution A was dropwise added into solution B.
Finally, the mixture was continuously stirred at room temperature
for 2 h. Stewing and aging for 12 h, solid phase labeled sample
A could be eventually collected through ltration, washing and
drying under 373.15 K for 10 h. Sample B and Sample C were
prepared with the same method by using 2.2 g of CaCO3 as cal-
cium source and 2.134 g of 4MgCO3 Mg(OH)2 5H2 O as magnesium
source, respectively. Molar ratios between Si and metal element
(Si:Me) in all samples were kept around 2:1.
2.3. Characterization
The phases of MS were determined by X-ray diffraction (D8
Discover, Bruker, Germany). Field emission scanning electron mi-
croscopy (Mira3, Tescan, Czech Republic) and transmission electron
microscopy (1004961S, JEM-2100F) were employed to observe the
surface topography and inner structure of MS. The Fourier trans-
form infrared spectra (Nicolet 6700, Thermo Electron Scientic
Instruments) was performed over the range of 40 0 040 0/cm to
investigate chemical bonds in MS. Pore size distribution was calcu-
lated using BarrettJoynerHalenda (BJH) method based on the N2
adsorptiondesorption analysis (Kubo, X10 0 0). Moreover, thermal
analysis (STA449C, NETZSCH) was carried out to explore the law of
mass loss at a heating rate of 10 K/min. X-ray photoelectron spec-
troscopy (ESCALAB, 250Xi) was performed to determine elements
contained in prepared powders and their chemical states.
2.4. Adsorption experiment
Stock solution of MB was prepared by dissolving MB powder
into deionized water. The concentration of experiment solution
ranged from 100 mg/L to 500 mg/L.
Adsorption experiment was performed by agitating experiment
solution under 200 rpm in a stable temperature horizontal shaking
Please cite this article as: P. Chen et al., A novel mesoporous silicate material (MS) preparation from dolomite and en-
hancing methylene blue removal by electronic induction, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.044
[m5G;September 14, 2017;12:41]
Fig. 2. Adsorption experiments for different samples (adsorbent dose = 0.08 g/20
mL; pH value = 10; dye concentration = 300 mg/L).
bath (SHA-C). Portions of solution were collected at predetermined
time intervals. Concentration of solution was measured by spec-
troscopy (UV-2100 SPECTROPHOTO-METER). To investigate effects
of process factors on adsorption, adsorption conditions were set
as below: temperature ranging from 298.15 k to 318.15 k, pH
ranging from 4 to 12, dye concentration ranging from 100 mg/L to
500 mg/L. Adsorption capacity Qt (mg/g) at a specic interval was
calculated using the following equation:
( Co Ct ) V
Qt = (1)
m
Where, C0 and Ct (mg/L) are concentrations of dyes at initial time
and at a predetermined time interval, respectively. V(L) is the
volume of experiment solution and m(g) is the mass of adsorbent.
2.5. Adsorption characteristics of different materials
For an intuitive understanding of differences among sample A,
B and C, adsorption experiments were operated under the same
condition. Fig. 2 shows that the order of adsorption capacity for
MB follows sample A > sample B > sample C. The order suggests
that a mutual promoting relationship might exist in sample A
during its adsorption process. Further studies are conducted to
explain its adsorption mechanism.
3. Results and discussion
3.1. XRD analysis
Fig. 3 shows that there are no obvious diffraction peaks in the
pattern, which may be due to the amorphous structure in all sam-
ples. However, these dispersion peaks have great chances to grow
up to mature peaks with proper crystallization methods. 29, 34
and 60 in sample C generally agree with the positions of typical
peaks of magnesium silicate hydrates [33] while 29.2 in sample B
belongs to calcium silicate hydrates. The peak at 29.5 is the only
dispersion peak in sample A and that position agrees with the
typical peak of calcium magnesium silicate hydrates [34]. There-
fore, the material synthesized from dolomite is likely classied as
a sort of uncrystallized calcium magnesium silicate hydrates.
3.2. FT-IR study
The FT-IR spectra results were shown in Fig. 4a. The most inten-
sive band at 1008/cm corresponds to the asymmetric and symmet-
ric stretching vibrations of SiO bonds in silicate tetrahedral units.
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350 0.04 Adsorption

Volume dV/dD(cm /g/nm)

Pore Volume
Desorption

3
0.03
300

Volume(cm /g)
0.02
250

3
0.01
200
0.00
0 10 20 30 40 50
150 Pore Diameter (nm)

100
Structural properties of MS
50 2
Surface Area(m /g)
3
Pore Volume(cm /g) Average pore radius(nm)
368.3 0.53 2.87

0
0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure(P/Po)

Fig. 3. XRD pattern of samples. Fig. 5. Nitrogen adsorption/desorption isotherms and pore size distribution of MS.

Table 2
Elements in the spectrum.

Element O Si Mg Ca Na Cl

Weight(%) 54.32 24.87 7.69 9.92 3.14 0.06

Atomic(%) 68.14 17.77 6.34 4.97 2.74 0.03

which also can be certied by TEM images (Fig. 6d and e) and

many prominent particles formed by some lamellae stacking
together. Electron microscope results show that the material
presents a coarse, irregular and porous structure.
The result of EDS spectrum (Table 2) indicates that Si, Ca, O and
Mg are the major elements making up 97%(w%) of present area.
Peaks of Na and Cl can be also observed due to washing residual.

3.5. Thermal analysis

Fig. 4. FT-IR spectrum of MS (a) as-synthesized sample; (b) calcined sample at
673.15 K for 3 h.
The obvious broad at 3448/cm is regarded as OH groups stretch-
ing vibrations of water molecules in the material [35]. The band at
1645/cm is due to HOH bending vibration of molecular H2 O [36].
The band at 1483/cm accounts for the asymmetric stretching of
CO3 2 [37]. The band at 653/cm and 773/cm are attributed to Si
OSi vibrations [38]. Meanwhile, the band at 455/cm is thought to
be the deformation of TO4 tetrahedra (T = Si, Mg, Ca, etc.) [39]. The
characteristic bands near 3440, 1633, 1024, 782 and 466/cm also
appear in Fig. 4b, while the band at 653/cm standing for stretching
vibration of SiOSi cannot be found in Fig. 4b. The weaker band
peak at 1517/cm implies that the carbonate has been decomposed
at 673.15 K, and the disappearance of band at 653/cm means the
inner structure of adsorbent has been damaged under 673.15 K.
In order to test the thermostability of MS, TG-DSC technique
was applied from room temperature to 980 K under the heating
rate of 10K/min. The thermogravimetric plot (Fig. 7) reveals a
continuous mass loss of 11.94% between room temperature and
980 K. Mass loss under 450 K is due to loss of water (8%) which
may be physical water and crystal water in the material [40].
Weight loss (4%) between 450 K and 940 K is due to the slow de-
composition of carbonate and dehydroxylation of metal hydroxide,
which has been conrmed by FT-IR study. It can be concluded that
the structure of absorbent has been slowly destroyed after 450 K.
3.6. Adsorption studies
The basic data were collected from three replicate experiments
and the average values were obtained for the adsorption studies.

3.3. BET analysis 3.6.1. Effect of contact time

Fig. 5 shows the N2 adsorption/desorption proles and pore
size distribution of MS. Nitrogen adsorption/desorption isotherm
can be classied as type IV isotherm with hysteresis loop for
mesoporous materials [33]. The BET surface area and the pore
volume are 368.3 m2 /g and 0.53 cm3 /g, respectively. The average
pore radius is 2.87 nm by analysis. The material can be identied
as a mesoporous material with high surface area.
3.4. SEM-EDS and TEM analysis
Electron microscope images of MS were shown in Fig. 6. Fig. 6a
shows that the absorbent possesses abundant disordered apertures
The effect of contact time under different initial MB concentra-
tions was illustrated in Fig. 8. It shows that MB adsorption curves
of 10 0 mg/L, 20 0 mg/L and 30 0 mg/L do not change any more
after 30, 50 and 110 min, respectively. That means MB has been
completely absorbed. As to 450 mg/L and 500 mg/L, the adsorption
has already reached equilibrium after 170 min as those curves
increase little later. For all adsorption curves, the removal rate is
obviously faster at initial stage. It is due to that all adsorbent sites
are vacant and the solute concentration gradient is high [41].
3.6.2. Effect of temperature
The effect of temperature on the removal of MB was studied in
the range of 298.15 K318.15 K and the result was shown in Fig. 9.

Please cite this article as: P. Chen et al., A novel mesoporous silicate material (MS) preparation from dolomite and en-
hancing methylene blue removal by electronic induction, Journal of the Taiwan Institute of Chemical Engineers (2017),
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Fig. 6. Electron microscope images of MS: (a) SEM image; (b), (c) EDS images; (d), (e) TEM images.

It indicates that the time for reaching equilibrium decreases with
the increasing of temperature. The favorable aspect is that the
adsorption capacity reached 111.65 mg/g at 318.15 K. In addition,
adsorption capacity increasing with the temperature indicates
that the adsorption process is endothermic. This may due to the
increase of interaction between adsorbate and adsorbent.
3.6.3. Effect of concentration of dye
The initial concentration of adsorbate in solution provides
an important driving force to overcome mass transfer resistance
between the aqueous and solid phases. MB adsorption on MS
was studied with initial concentrations ranging from 100 mg/L
to 500 mg/L. The result was shown in Fig. 10. It indicates that
the adsorption capacity increases with the increase of the initial
concentration at the same level of temperature before equilibrium.
This fact can be explained as increasing in the driving force of
concentration gradient [42].
vestigated ranging from 4.0 to 12.0 (adsorbent dose = 0.08 g/20 mL;
dye concentration = 450 mg/L; temperature = 298.15 K; contact
time = 170 min). The result was displayed in Fig. 11.
For a better understanding of inuence rule of pH, the degra-
dation curve of MB under the same condition is also necessary.
Fig. 11 shows that the removal amount is larger in base region
than in acid region and the capacity increases with pH values
increasing in base region. That may be due to the electrostatic
force between hydroxyl ions absorbed on MS and cationic dye
MB enlarges the removal amount. It is worth noting that net
adsorption amount is crucial to the study of adsorption property.
Net adsorption curve obtained from the difference between re-
moval amount and degradation amount shows that net adsorption
amount is largest when pH value is 10. Therefore, pH value is
xed to be 10 during adsorption experiment.
3.7. Adsorption kinetics

3.6.4. Effect of pH Kinetics study is necessary as it provides valuable insights into

The pH values of waste water exhausted from dyestuff industry the reaction pathway and the rate-controlling mechanism. In this
is mainly kept mild, so the impact of pH on MB adsorption was in- paper, pseudo-rst-order and pseudo-second-order kinetic models

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Fig. 7. TG-DSC thermogram of MS.

Fig. 10. Effect of initial concentration on MB adsorption (adsorbent
dose = 0.08 g/20 mL; pH value = 10; contact time = 170 min).

Fig. 8. Effect of contact time on MB adsorption (adsorbent dose = 0.08 g/20 mL; pH
value = 10; temperature = 298.15 K).
Fig. 11. Effect of pH on MB adsorption.

Where, Qe and Qt are adsorption capacities (mg/g) at equilibrium

and at time t (min), respectively. K1 (/min) and K2 (g/mg/min)
are rate constants of pseudo-rst-order and pseudo-second-order
models. Linear plots of ln(Qe - Qt ) vs. t and t/Qt vs. t were given in
Fig. 12a and b. The constants calculated from slope and intercept
of those plots were given in Table 3.
The results show that pseudo-second-order model matches bet-
ter with experimental date than pseudo-rst-order model from R2
values. Moreover, Qe values calculated from the pseudo-rst-order
model are far away from experimental date.

3.8. Adsorption isotherm

In this paper, Langmuir and Freundlich isotherms were tted

Fig. 9. Effect of temperature on MB adsorption (adsorbent dose = 0.08 g/20 mL; pH
value = 10; dye concentration = 450 mg/L).
were employed to test the experimental data. The pseudo-rst-
order and pseudo-second-order models are respectively described
below:
with experimental data to investigate the distribution of MB
between adsorbent and solution.
3.8.1. Langmuir adsorption isotherm
Langmuir adsorption isotherm describes that adsorption behav-
ior belongs to a homogeneous monolayer adsorption reaction. The
Langmuir equation is represented as:

ln(Qe Qt ) = ln Qe K1 t (2) Ce 1 Ce
= + (4)
Qe Qmax KL Qmax
t 1 t Where, KL is the adsorption equilibrium constant (L/mg). Qe
= + (3) and Ce are equilibrium concentrations of dyes on adsor-
Qt K2 Q2e Qe

Please cite this article as: P. Chen et al., A novel mesoporous silicate material (MS) preparation from dolomite and en-
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Fig. 12. Linear forms of kinetic plot of MB on MS: (a) pseudo rst order model; (b) pseudo second order model.

Table 3
The kinetic parameters of different kinetic models.

Parameters Qe(exp) (mg/g) Pseudo rst order model Pseudo second order model

T(K) Co (mg/L) Qe (mg/g) K1 R2 Qe (mg/g) K2 R2

298.15 450 92.11 64.80 0.020 0.977 97.56 6.78 104 0.996
308.15 450 100.54 62.20 0.019 0.965 104.82 7.84 104 0.997
318.15 450 111.65 58.94 0.027 0.944 115.34 1.30 104 0.999

Fig. 13. Linear forms of adsorption isotherm plot of MB on MS: (a) Langmuir isotherm model; (b) Freundlich isotherm model.

Table 4
Langmuir and Freundlich adsorption isotherm parameters.

Parameters Langmuir isotherm Freundlich isotherm

T(K) Time(min) pH Qmax(mg/g) KL R2 1/n KF R2

298.15 200 10 107.42 0.121 0.992 0.362 21.33 0.937

308.15 200 10 117.37 0.177 0.991 0.356 27.73 0.622
318.15 200 10 145.13 0.134 0.972 0.530 22.04 0.806

bent (mg/g) and in solution (mg/L), respectively. Qmax is the 3.8.2. Freundlich adsorption isotherm
maximum monolayer capacity (mg/g). Plots of Ce /Qe vs. Ce The Freundlich equation employed to describe the heteroge-
at different temperature are several straight lines shown in neous system is expressed as:
Fig. 13a. Qmax and KL can be calculated from slope 1/Qmax and 1
intercept 1/(Qmax KL ). The results were listed in Table 4. Qmax and ln Qe = ln KF + lnCe (5)
n
correlation coecient values suggest that MB adsorption on the
Where, KF and 1/n are the Freundlich constants representing for
adsorbent belongs to a homogeneous monolayer adsorption.
adsorption capacity and adsorption intensity. Plots of lnQe vs.

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Table 5
Adsorption capacity of different adsorbents for MB.

Adsorbent EMRZ AlPO4 SBA-15 AlMCM-41 MS

Adsorption capacity(mg/g) 25.93 35.2 49.26 66.53 111.65

Reference [43] [10] [44] [45] This work

Table 6
Thermodynamic parameters for adsorption of MB.

Experimental parameters Thermodynamic parameters

pH T(K) R2 H(KJ/mol) S(KJ/mol/K) G(KJ/mol)

10 298.15 0.978 62.59 0.2108 0.260

10 303.15 62.59 0.2108 1.314
10 308.15 62.59 0.2108 2.368
10 313.15 62.59 0.2108 3.422
10 318.15 62.59 0.2108 4.476

Fig. 14. Linear form of adsorption thermodynamic plot of MB on MS.

Fig. 15. XPS result of Ca 2p.

lnCe at different temperature are several straight lines shown in

Fig. 13b. (1/n) and KF listed in Table 4 are calculated from slope
and intercept. 1/n values indicate that MB adsorption is not tted
with Freundlich adsorption isotherm because a smaller value of
(1/n) suggests a stronger bond between adsorbate and adsorbent.
This can be conrmed by the smaller R2 values as well.
In order to highlight adsorption advantages of the material,
various adsorbents were listed in Table 5. The result suggests that
the material is exactly an effective adsorbent for MB.

3.9. Adsorption thermodynamics

Thermodynamic parameters like free energy (G), enthalpy

(H) and entropy (S) have a critical role in determining
spontaneity and heat exchange of adsorption. Thermodynamic
equations are introduced below:
Qe
KD = (6)
Ce
Fig. 16. XPS result of Mg 1s.

G = RT ln KD
G = H T S
where, KD is the distribution coecient of MB. R is the universal
gas constant (8.314 J/mol/K) and T stands for temperature (K). The
plot of ln(Qe /Ce ) vs. 1/T is a straight line shown in Fig. 14. Similarly,
H and S can be calculated from slope and intercept. G values
can be calculated from Eq. (8). The results were listed in Table 6.
62.59 KJ/mol for H and positive S mean that the adsorption
(7)
belongs to an endothermic chemical adsorption. Moreover, the
minus G values indicate that the adsorption is spontaneous.
(8)
4. Mechanism study
X-ray photoelectron spectroscopy (XPS) was used to monitor
changes of chemical states of elements. As shown in Figs. 15a and
16a, the peaks at 1304.54 eV and 347.19 eV belong to Mg(1s1/2 )
in SiOMg and Ca(2p3/2 ) in SiOCa, respectively [46]. As to

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Fig. 17. XPS result of N 1s.
Fig. 18. XPS result of S 2p.
MB, the major peak at 399.91 eV in Fig. 17a is assigned to N in
the conjugate state formed by C = N(400.2 eV), benzene and
N(CH3 )2 (399.2 eV) [47,48]. The weaker peak at 402.49 eV reveals
the existence of the protonated amino groups (402.0 eV) [42]. In
Fig. 18a, the two peaks at 164.59 eV and 165.77 eV represent for
binding energies of S(2p3/2 and 2p1/2 ) in the structure of CSC
[49].
After adsorption, the peak of Mg(1S1/2 ) has moved from
1304.54 eV to 1304.24 eV. Meanwhile, binding energies of N(1 s)
and S(2p3/2 ) have decreased by 0.37 eV and 0.7 eV, respectively.
That means chemical states of Mg, N and S have changed after
adsorption. However, these shifts are much smaller than changes
for forming Mg3 N2 (3.5 eV for N) and MgS(3.7 eV for S) [50,51].
A reasonable explanation for this situation is the existence of
coordination bond. It is a weak type of chemical bond and formed
through a lone pair electrons of N or S and the outer vacant orbital
of Mg. These coordination bonds certainly weaken the stability
of MgO as the tetrahedral structure of MgO is damaged and
accordingly weaken the polarity of CN and CS. That accounts for
those decreases in binding energy of Mg, N and S.
As for Ca, the banding energy has increased by 0.15 eV after
adsorption. It can be considered that some coordination bonds
exist between Ca, N and S as well. The reason for banding energy
of Ca increasing may be Ca mostly locating outside of the skeleton
and playing the role of balance charge. Thus, the structure of CaO
will be more stable with the help of these coordination bonds.
Please cite this article as: P. Chen et al., A novel mesoporous silicate material (MS) preparation from dolomite and en-
hancing methylene blue removal by electronic induction, Journal of the Taiwan Institute of Chemical Engineers (2017),
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[m5G;September 14, 2017;12:41]
Fig. 19. Explanation for adsorption mechanism.
Based on above analysis, the adsorption mechanism is likely de-
scribed in Fig. 19. When only one type of metal ion (Ca or Mg) ex-
ists in the material, nucleophilic atoms (N and S) will form coordi-
nation bonds with metal atoms outside of the skeleton rather than
in the stable tetrahedral skeleton. When it comes to two types
of metal ions, coordination bonds will also exist in the skeleton
because the stronger eletrophilicity of Ca outside of the skeleton
endows extra eletrophilicity of Mg in the skeleton by transferring
electrons. Eventually, adsorption capacity for MB will be enlarged.
5. Conclusions
In this work, mesoporous calcium magnesium silicate hydrates
material was synthesized successfully from dolomite. Moreover,
the adsorption capacity for MB could reach 111.65 mg/g. Pseudo-
second-order model matched better with experimental date
than pseudo-rst-order model by adsorption kinetics study. The
adsorption of MB belonged to homogeneous monolayer adsorp-
tion instead of heterogeneous adsorption according to adsorption
isotherm analysis. In addition, thermodynamic studies showed that
adsorption process was a spontaneous, endothermic and chemical
process. The adsorption was likely achieved by forming coordina-
tion bonds between metal atoms (Ca, Mg) in the material and nu-
cleophilic atoms (N, S) in MB by XPS analysis. Electronic induction
in simple A might account for a larger adsorption capacity for MB.
Acknowledgments
This research was supported by National Key Technology
Support Program (no.2015BAB17B01) and the Hunan Provincial
Science and Technology Plan Project (no.2016TP1007) and National
Natural Science Foundation of China (no.21776320).
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