Research Article

Adsorption Science & Technology

0(0) 1–16
Adsorptive removal of ! The Author(s) 2019
DOI: 10.1177/0263617419827438
methylene blue from journals.sagepub.com/home/adt

aqueous solution using coal

fly ash-derived mesoporous
silica material

Ning Yuan , Hui Cai, Tian Liu, Qi Huang and

Xinling Zhang
School of Chemical & Environmental Engineering, China University of
Mining & Technology, Beijing, China

Abstract
In the present work, coal fly ash-derived mesoporous silica material (CFA-MS) has been success-
fully fabricated without employing any extra silica source. The obtained CFA-MS was characterized
by Fourier transform infrared spectroscopy, nitrogen adsorption–desorption measurement,
powder X-ray diffraction and transmission electron microscopy. Nitrogen adsorption–desorption
measurement disclosed that CFA-MS possesses Brunauer–Emmett–Teller-specific surface area of
497 m2
g1 and pore volume of 0.49 cm3
g1, respectively. Furthermore, CFA-MS was evaluated
for the adsorptive removal of methylene blue from aqueous solution. Several influence parameters
on the removal of methylene blue including contact time, pH, initial concentration and temperature
were studied in detail. Moreover, Langmuir, Freundlich, Temkin and Dubinin-Radushkevich
isotherm models were employed for interpretation of the adsorption process, while the
pseudo-first-order and pseudo-second-order kinetics equations were applied to investigate the
adsorption kinetics. Results in the current work demonstrate that CFA-MS can be used as an
efficient adsorbent for methylene blue removal.

Keywords
Coal fly ash, mesoporous silica, dye adsorption, isotherm, kinetics
Submission date: 1 October 2018; Acceptance date: 9 January 2019

Corresponding author:
Ning Yuan, School of Chemical & Environmental Engineering, China University of Mining & Technology, Beijing 100083,
China.
Email: ning.yuan@hotmail.com

Creative Commons CC BY: This article is distributed under the terms of the Creative Commons Attribution
4.0 License (http://www.creativecommons.org/licenses/by/4.0/) which permits any use, reproduction and
distribution of the work without further permission provided the original work is attributed as specified on the SAGE and
Open Access pages (https://us.sagepub.com/en-us/nam/open-access-at-sage).
2 Adsorption Science & Technology 0(0)

Introduction
Nowadays, water pollution caused by dye contaminants has become a severe global issue
and aroused tremendous attention, since it is estimated that more than 100 thousand types
of commercial organic dyes and pigments have been produced. Meanwhile, huge amounts of
dyes have been discharged into natural environment during the production process, which
thus causes serious environmental problems (Yagub et al., 2014). Furthermore, the color of
dye-containing water is highly visible even at an extremely low concentration and is thought
to be aesthetically unpleasant. Therefore, it is quite urgent to remove the dyestuffs from
water, and several methods have been devoted to resolving this issue, including photode-
gradation, adsorption, biodegradation, coagulation–flocculation and so forth (Cai et al.,
2017). Among the various strategies for water purification, physical adsorption has attracted
great attention due to its simple treatment procedure and sound effectiveness as well as low
cost. Conventionally, activated carbons and zeolites are among the major adsorbents
applied for the removal of dyes from aqueous solution. However, their adsorption capacities
for dyes are limited due to the microporous nature of activated carbons and zeolites (Joo
et al., 2009). Recently, mesoporous silica materials have been widely used for the treatment
of contamination in water, such as heavy metal ions, dyes, phenolic compounds, pesticides,
etc., which is due to their large specific surface area, high pore volume, excellent stability,
low toxicity and transparency (Gibson, 2014; Walcarius and Mercier, 2010). For the prep-
aration of mesoporous silica materials, some commercial silica precursors including sodium
metasilicate and tetraethyl orthosilicate have been commonly used as silica sources (Gibson,
2014). However, with the increase in consumption of mesoporous silica materials for large-
scale industrial applications, the cost of mesoporous silica materials utilizing commercial
silica precursors is relatively high (Chandrasekar and Ahn, 2008; Sari Yilmaz and
Karamahmut Mermer, 2016). Therefore, it is highly desirable to realize the production of
this type of materials through employing cheaper silica sources.
In view of the silicon content in abundance in many industrial solid wastes, such as fly ash
and bottom ash, these raw materials have been utilized for the production of mesoporous
silicas (Lee et al., 2017). The strategy possesses the advantage of low cost and environmental
friendliness (Misran et al., 2007). During the past decades, these industrial solid waste-
derived porous silicate materials have been investigated for the applications in the fields
of carbon dioxide capture (Panek et al., 2017; Park et al., 2012), catalysis (Dhokte et al.,
2011; Zhang et al., 2013), removal of phosphate (Li et al., 2013) and heavy metal ions (Sun
et al., 2014). For example, Prof. Ahn and coworkers (Park et al., 2012) reported the syn-
thesis of mesoporous silicas from bottom ash, and the obtained mesoporous materials were
further modified with polyethyleneimine for carbon dioxide capture with high efficiency.
Arbad and colleagues (Dhokte et al., 2011) synthesized MCM-41 from fly ash and the
obtained material was used as catalyst for the synthesis of b-amino carbonyl compounds
through Mannich reaction.
However, only very limited works reported the fly ash-derived mesoporous silica materi-
als for the removal of dye from aqueous solution up to date (Zhou et al., 2015). Very
recently, Zhou and coworkers synthesized spherical Al-containing MCM-41 materials
from coal fly ash (CFA), and further evaluated their adsorption performance for methylene
blue (MB) (Zhou et al., 2015). In spite of the pioneering work, for the practical application
in industry, the adsorption capacity of fly ash-derived mesoporous silica materials needs to
be further enhanced and the adsorption process should be completed in a shorter time. In
Yuan et al. 3

the present work, a coal fly ash-derived mesoporous silica material (CFA-MS) has been
successfully fabricated by employing a triblock copolymer P123 as structure directing agent
under acidic condition, and no commercially available silica source was used during the
preparation procedure. CFA-MS was fully characterized by infrared spectroscopy, nitrogen
physisorption, powder X-ray diffraction (PXRD) and transmission electron microscopy
(TEM). Several influence parameters such as contact time, pH, initial concentration and
temperature were studied on the adsorption of MB in detail. Besides, the adsorption process
was evaluated using pseudo-first- and pseudo-second-order kinetic models as well as adsorp-
tion isotherms including Langmuir, Freundlich, Temkin and Dubinin-Radushkevich
models. Results reported in this article demonstrate that CFA-MS can serve as an efficient
adsorbent for MB removal with excellent adsorption capacity (323.62 mg
g1) and relatively
rapid adsorption process (90 min).

Experimental section
Materials
The CFA used in this study was obtained from an electric power plant in Shandong, China.
Concentrated hydrochloric acid (HCl, 36–38%) was purchased from the Sinopharm
Chemical Reagent Co., Ltd. Sodium hydroxide (NaOH) was bought from Beijing Tong
Guang Fine Chemicals Company. Pluronic P123 (EO20PO70EO20; Mav ¼ 5800) and MB
were from Aldrich and Macklin, respectively. All chemicals were directly used and without
further purification.

Extraction of silicon from CFA

The pre-treatment process for CFA was performed for the removal of impurities such as
iron and calcium ions. Specifically, the as-received CFA was dried in an oven at 100 C until
no weight loss. Then, the dried CFA was mixed with 20% HCl and the mixture was stirred
at 80 C for 4 h. The mixture was filtrated and the solid was washed sufficiently with
deionized water several times until the filtrate became neutral. Afterwards, the obtained
powder was dried in an oven at 100 C.
The alkali fusion method was adopted for the extraction of silica from CFA, which was
based on the procedure reported by Kumar et al. (2001) with some slight modification. The
CFA powder after pre-treatment was mixed with NaOH at a mass ratio of 1:1.2 and then
the mixture was heated in an oven at 550 C for 1 h. The fine milled alkali-fused CFA was
added to deionized water with a ratio of 1:4 and then stirred at room temperature for 24 h.
Then the sodium silicate-containing supernatant was obtained by centrifugation and filtra-
tion of the mixture. The silicon, aluminium and sodium ion concentrations of the superna-
tant were measured by inductively coupled plasma optical emission spectrometry (ICP-OES)
method to be approximately 5097.5, 816 and 45,275 ppm, respectively.

Synthesis of mesoporous adsorbent CFA-MS

In a typical procedure for the synthesis of mesoporous adsorbent, 0.720 g Pluronic P123 was
dissolved in 30 g HCl (2 M) at 40 C, and then 30 mL supernatant extracted from CFA was
dropped into the solution under stirring at room temperature. Thereafter, 5 g of concen-
trated HCl and 10 mL of deionized water were added rapidly, and the obtained mixture was
4 Adsorption Science & Technology 0(0)

continued to be stirred at room temperature for 24 h. Afterwards, the mixture was aged at
an oven at 100 C for 72 h. The as-synthesized product was obtained by centrifugation and
then washed by deionized water. After being dried at 100 C overnight, the as-synthesized
product was calcinated at 550 C for 24 h. After cooling to room temperature, a white
powder was obtained and denoted as CFA-MS.

Adsorption of MB
The adsorption behavior of MB onto CFA-MS was investigated by varying several param-
eters including contact time, pH, initial concentration and temperature. Typically, 10 mL of
200 mg
L1 MB solution was added into a vial containing CFA-MS fine powder (5 mg), and
then the vial with mixture solution was shaken in a shaker at 298 K for 90 min (150 r/min).
Afterwards, CFA-MS was separated from MB solution by centrifugation. Then, concentra-
tion of the supernatant containing remained MB was analyzed by UV-vis spectrophotom-
eter at 664 nm. To obtain the standard curve between absorbance and MB concentration,
MB solution with different concentrations (2, 4, 6, 8 and 10 mg
L1) was prepared, and then
its absorbance was, respectively, measured by UV-vis spectrophotometer at 664 nm (kmax of
MB). The standard curve was drawn according to the Lambert-Beer Law, and the linear
regression equation obtained by linear fitting is y ¼ 0.06687x–0.00386, where the correlation
coefficient R2 ¼ 0.9993.
The adsorption capacity (qe) and removal efficiency (E) of MB onto CFA-MS were
calculated by the following equations

ðc0  ce ÞV
qe ¼ (1)
m

c0  ce
E ¼  100% (2)
c0

where c0, ce and qe are initial concentration (mg
L1), concentration at equilibrium (mg
L1)
and adsorption capacity at equilibrium (mg
g1) for MB, respectively, m represents the mass
of CFA-MS (g) and V stands for the volume of MB solution (L).

Measurements
The chemical composition of CFA was determined by X-ray fluorescence (XRF) method
(PANalytical B.V.), while the Si, Al and Na concentrations of CFA supernatant were
detected by ICP-OES method on a PerkinElmer Optima 8300 Spectrometer. The PXRD
patterns for CFA and mesoporous adsorbent were recorded on an X’ Pert Pro X-ray dif-
fractometer using Cu-Ka radiation with a wavelength of 1.54184 Å. Nitrogen adsorption–
desorption measurement was carried out on a Micromeritics TriStar II 3020 surface area
and porosity analyzer (Micromeritics Instrument Corporation, USA) at 77 K. Before the
measurement, the synthesized adsorbent was degassed under vacuum at 120 C for 12 h. The
specific surface area was calculated through Brunauer–Emmett–Teller (BET) method,
whereas the pore size distribution was determined using the Barrett–Joyner–Halenda
(BJH) method. Fourier transform infrared (FT-IR) spectrum was collected on a
PerkinElmer Spectrum Spectroscopy using KBr as standard reference in the range of
Yuan et al. 5

400–4000 cm1. TEM measurement was performed using a JEM 1200EX microscope
(JEOL, Japan) operated at an accelerating voltage of 120 kV. The concentrations of the
MB solution were analyzed using a UV-5100 spectrophotometer (Shanghai Metash
Instrument Co., Ltd, China).

Results and discussion

Characterization of CFA and CFA-MS
The chemical composition of as-received CFA was disclosed by XRF, which establishes that
the major components in oxide form are SiO2 (50.76%), Al2O3 (36.04%), CaO (3.64%) and
Fe2O3 (3.31%). Table 1 summarizes the chemical composition in oxide form. As shown in
Figure 1(a), the room temperature PXRD pattern of as-received CFA reveals that the major

Table 1. Chemical composition of as-received CFA used in the present

contribution.

No. Compound Content (wt%) CFA (mol/100 g)

1 SiO2 50.76 0.845

2 Al2O3 36.04 0.353
3 CaO 3.64 0.065
4 Fe2O3 3.31 0.021
5 TiO2 1.79 0.022
6 K2O 1.14 0.012
7 SO3 1.39 0.017
8 CdO 0.54 0.004
9 Na2O 0.53 0.009
10 MgO 0.43 0.011

Figure 1. Powder X-ray diffraction (PXRD) patterns of as-received CFA (a) and alkali-fused CFA (b). M, Q,
S and F represent mullite, quartz, sodium silicate and faujasite, respectively.
CFA: coal fly ash.
6 Adsorption Science & Technology 0(0)

crystalline phases are mullite, quartz and aluminosilicate glass, which is in accordance with
the results from XRF measurement (Kumar et al., 2001; Misran et al., 2007; Panek et al.,
2017). After the alkali fusion treatment, the CFA predominantly consists of sodium silicate
phase, suggesting that the crystalline silica had been successfully transformed into soluble
sodium silicate phase (Figure 1(b)) (Kumar et al., 2001; Misran et al., 2007). Therefore, the
alkali fusion method can effectively extract available silica species in CFA and convert
them into soluble sodium silicate, thereby facilitating the fabrication of mesoporous
silica material.
FT-IR spectroscopy was used to investigate the chemical components of the synthesized
CFA-MS. As shown in Figure 2(a), the absorption peaks emerged at 1069, 801 and
456 cm1 corresponds to the asymmetric stretching, symmetric stretching and in-plane
bending vibrations of Si–O–Si bond, respectively (Yuan et al., 2018). In addition, a weak
peak located at 1630 cm1 is due to the physically adsorbed water molecules. Therefore,
these absorption bands demonstrate the successful formation of silica framework.
Nitrogen physisorption measurement was also performed to investigate the porosity of
the obtained adsorbent CFA-MS. As displayed in Figure 2(b), CFA-MS possesses a type IV
isotherm on the basis of IUPAC classification, indicative of the presence of characteristic
mesoporous structure (Thommes et al., 2015). Meanwhile, the isotherm exhibits a large
H2-type hysteresis loop in the p/p0 range of ca. 0.45–1.0, which is typical for materials
with ink-bottle pores interconnected with narrow necks by either pore blocking or cavitation
(Thommes et al., 2015). Furthermore, the BET-specific surface area and pore volume were
calculated to be ca. 497 m2
g1 and 0.49 cm3
g1, respectively. These values are quite close to
that of the SBA-15 material prepared from CFA (Kumar et al., 2001). In addition, its pore
size distribution is relatively broad with pore diameter centered at 3.9 nm, whereas its
average pore diameter was measured to be 4.9 nm as evaluated from the nitrogen desorption
branch of the isotherm by the BJH method. Moreover, the BET-specific surface area and
pore volume of CFA were measured to be ca. 9.82  103 m2
g1 and 4.84  104 cm3
g1,
respectively. In comparison to its derived mesoporous material CFA-MS, these values are
quite small. Therefore, the results indicate the nonporous nature of CFA and the successful
fabrication of mesoporous material CFA-MS in this work.

Figure 2. Fourier transform infrared (FT-IR) spectrum (a) and nitrogen adsorption–desorption isotherms
(b) of the obtained CFA-MS.
Yuan et al. 7

However, the low-angle PXRD pattern of the obtained material CFA-MS (not shown
here) does not show any obvious diffraction peak at the two-theta angle from 0.5 to 10 ,
indicative of the absence of uniform mesoporous structure. This is in accordance with the
previous reports by Chandrasekar and Ahn (2008) and Kumar et al. (2001), because addi-
tional sodium metasilicate is usually introduced to improve the order of the mesostructure,
while no additional silica form except the supernatant extracted from CFA was used in the
present work (Chandrasekar et al., 2008; Sun et al., 2014). In spite of the absence of ordered
mesoporous structure, CFA-MS displays enhanced adsorption properties on cationic dye
such as MB, which will be discussed in the following section of this article.
The morphology of CFA-MS was observed by TEM. As depicted in Figure 3, the
obtained material CFA-MS exhibits irregular shape and worm-like mesostructure, which
is consistent with results from aforementioned nitrogen adsorption–desorption measure-
ment and low-angle PXRD.

Effects of factors on adsorption

The rapid removal of organic dye from aqueous solution is crucially important to an
adsorbent. To investigate the effect of contact time on the adsorption of MB, 5 mg of
synthesized adsorbent CFA-MS was added into 10 mL of 200 mg
L1 MB solution at
room temperature. As displayed in Figure 4(a), it was observed that the initial adsorption
rate increases quickly with increasing contact time, which can be attributed to the large
amount of available adsorption sites. When contact time reaches 90 min, the uptake amount
is up to the maximum of 316.8 mg
g1. After the further increase in contact time, the
adsorption capacity remains almost constant.
Furthermore, the effect of pH on the adsorption of MB from aqueous solution over
obtained adsorbent CFA-MS was also investigated at 298 K. As shown in Figure 4(b),
the adsorption amount increases gradually with varying the pH value from 3 to 10, which
can be interpreted by the electrostatic interaction between negatively charged silica and
positively charged MB molecule. Therefore, the adsorption of MB onto CFA-MS prefers
an alkaline condition and the optimal initial pH value is 10. Results shown here are in
accordance with the previous reports (Anbia and Hariri, 2010; Han et al., 2009; Zhou
et al., 2015).

Figure 3. TEM images of the obtained CFA-MS showing its irregular shape (a) and worm-like meso-
pores (b).
8 Adsorption Science & Technology 0(0)

Figure 4. Effects of contact time (a), pH (b), initial concentration and temperature (c and d) on the
adsorption of methylene blue (MB) from aqueous solution onto CFA-MS.

The effects of initial concentration and temperature for the removal of MB by CFA-MS
were also investigated via varying the initial concentration in the range of 25–200 mg
L1
and temperature at 298, 308 and 318 K, respectively. As depicted in Figure 4(c) and (d), for
all the three different temperatures, the adsorption capacity is enhanced with the increase in
initial concentration, while the removal efficiency generally decreases when increasing the
initial concentration. With regard to the effect of temperature, it is well known that eval-
uating the temperature is beneficial to the diffusion of the adsorbate molecules from liquid
to solid phases because of the decrease in viscosity of dye solution (Dogan et al., 2004).
However, both the adsorption capacity and removal efficiency of MB decrease in general
with evaluating the temperature in the present work. This can be interpreted by the fact that
the increase in temperature can enhance the mobility of adsorbed MB molecules, and thus
gives rise to the serious desorption of MB molecules (Alkan et al., 2000; Gao et al., 2014).
This trend indicates that the adsorption of MB onto CFA-MS underwent a physisorption
process, where the interactions can be attributed to weaker van der Waals and dipole forces,
which are usually associated with low heat of adsorption (Alkan et al., 2000).

Adsorption isotherms
For interpretation of the adsorption of MB onto the adsorbent surface of CFA-MS,
four different isotherm models including Langmuir, Freundlich, Temkin and
Yuan et al. 9

Dubinin-Radushkevich models were investigated at 298 K in detail. The Langmuir isotherm

(Langmuir, 1916, 1917, 1918) is the most common and still useful model to describe the
adsorption of dye onto the surface of adsorbent, which is on the basis of assumptions that
the adsorbed molecules are arranged in a monolayer and the adsorbent surface can be viewed
as homogeneous. The linear form of Langmuir isotherm can be written as equation (3)

ce 1 ce
¼ þ (3)
qe kL qm qm

where kL is the Langmuir constant (L
mg1) related to energy of adsorption, ce is the

equilibrium concentration of MB solution (mg
L1), and qe and qm represent the adsorption
capacities (mg
g1) at equilibrium and the maximum adsorption capacities (mg
g1) of MB
onto adsorbent, respectively.
Conversely, the Freundlich isotherm model (Freundlich, 1906, 1931) assumes that the
adsorbent surface is heterogeneous and the adsorbate prefers to occupy the stronger binding
sites. Its linear form can be expressed as equation (4)

1
log qe ¼ log ce þ logkF (4)
n

where kF is the Freundlich adsorption constant ((mg
g1)/(mg
L1)1/n) related to adsorption

capacity and 1/n represents the adsorption intensity and surface heterogeneity.
Temkin isotherm model (Kim et al., 2004; Temkin and Pyzhev, 1940) takes into account
the interactions between adsorbent and adsorbate and can be linearized as equation (5)

RT RT
qe ¼ ln ce þ ln kT (5)
bT bT

where kT means the Temkin isotherm constant (L
g1), bT is a constant related to the heat of
adsorption, R is universal gas constant (8.314 J
mol1
K1) and T is absolute temperature
in Kelvin.
The linear isotherms of MB adsorption onto obtained CFA-MS are plotted in Figure 5,
and the relevant parameters are listed in Table 2. Based on the linear regression coefficient
R2 values, the adsorption equilibrium data can be best presented by Langmuir isotherm
model rather than Freundlich or Temkin isotherm models. This suggests that the adsorption
of MB occurs at specific homogeneous sites and follows a monolayer adsorption process. In
addition, the separation factor RL defined from the Langmuir model in equation (6) can be
employed to evaluate the feasibility of adsorption (Weber and Chakraborti, 1974).

1
RL ¼ (6)
1 þ kL c 0

The calculated RL value in this study is 0.017, indicative of a favorable adsorption pro-
cess (Heidari et al., 2009). From the Langmuir model, the theoretical maximum adsorption
capacity is calculated to be 323.62 mg
g1, which is in accordance with the experimentally
obtained data. It is worth mentioning that this value is much higher than most of the
10 Adsorption Science & Technology 0(0)

Figure 5. The Langmuir (a), Freundlich (b), Temkin (c) and Dubinin-Radushkevich (d) adsorption isotherms
fitted to the adsorption equilibrium data in linear forms.

Table 2. Linear isotherm parameters for MB adsorption on the obtained CFA-

MS at 298 K.

Isotherms Parameters

Langmuir qm (mg
g–1) 323.62

kL (L
mg–1) 0.29
R2 0.980
Freundlich kF ((mg
g–1)/(mg
L–1)1/n) 91.22
1/n 0.35
R2 0.798
Temkin bT 45.10
kT (L
g–1) 6.08
R2 0.908
Dubinin-Radushkevich qmD-R (mg
g–1) 240.07
b 2.73  10–7
R2 0.848

previously reported adsorption capacity by applying mesoporous silica materials (Yagub

et al., 2014) and other types of adsorbents as summarized in Table 3. Furthermore, in light
of the previously published literature, this result represents the highest adsorption capacity
for MB with comparison to the fly ash-derived porous materials (Zhou et al., 2015).
Yuan et al. 11

Table 3. Adsorption capacities qm (mg
g1) for methylene blue (MB) by various adsorbents.

Adsorption
No. Adsorbents capacity (mg
g–1) References

1 Activated carbon of coir 15.59 Sharma and Upadhyay (2009)

2 CaHAp-Alg 77.3 Guesmi et al. (2018)
3 Raw KT38 kaolin 52.76 Mouni et al. (2018)
4 MGC-4 65.8 Wang et al. (2014)
5 ZFA/HZ 45.09 Lin et al. (2016)
6 Ti-SBA-15 208.3 Qiang et al. (2019)
7 Al-MCM-41 277.78 Zhou et al. (2015)
8 CFA-MS 323.62 This work

For example, Zhou et al. (2015) reported a fly ash-derived Al-MCM-41 material with max-
imum adsorption capacity of MB of 277.78 mg
g1 very recently.
Moreover, the Dubinin-Radushkevich (D-R) model (Dubinin and Radushkevich, 1947)
was also applied to calculate the apparent free energy of adsorption, and this model is
usually used to distinguish the adsorption types, i.e. physical or chemical adsorption. The
D-R isotherm can be computed by equation (7) as follows

D -R
ln qe ¼ ln qm  be2 (7)


1
e ¼ RT ln 1 þ (8)
ce

1
E ¼ pffiffiffiffiffiffi (9)
2b

D-R
where qm represents the D-R adsorption capacity (mg
g1), e is Polanyi potential, b is D-R
constant and E is the mean free energy of adsorption (Hobson, 1969). As for adsorption of
MB onto synthesized adsorbent CFA-MS, the calculated E value is 1.35 kJ
mol1 (below
8 kJ
mol1), thereby indicating that the adsorption underwent a physical process
(Hobson, 1969).

Adsorption kinetics
Several kinetics models can be employed to evaluate the rate and mechanism of mass transfer
of MB from liquid phase to the surface of CFA-MS. In the present study, the pseudo-first-
order and pseudo-second-order kinetics models were adopted to understand the adsorption
mechanism of MB to the obtained mesoporous adsorbent. The pseudo-first-order model was
described by Lagergren (1898) in a linear form as displayed in equation (10), and the linear
form of pseudo-second-order model was summarized by Ho and McKay (1999) as written in
equation (11)

lnðqe  qt Þ ¼ ln qe  k1 t (10)
12 Adsorption Science & Technology 0(0)

Figure 6. Pseudo-first-order and pseudo-second-order kinetics linear plots for adsorption of MB onto
CFA-MS at 298 K.

Table 4. Coefficients of pseudo-first-order and pseudo-second-order adsorp-

tion kinetics models.

Parameters

Pseudo-first order qe,cal (mg
g–1) 0.789

k1 (min–1) 0.015
R2 0.615
Pseudo-second order qe,cal (mg
g–1) 316.5
k2 (g
mg–1
min–1) 0.114
R2 1.000

t 1 t
¼ þ (11)
qt k2 q2e qe

where qe and qt represent the adsorption capacities (mg
g1) of MB at equilibrium and at

time t, respectively, and k1 (min1) and k2 (g
mg1
min1) are the corresponding rate con-
stants. The linear curves plotted based on pseudo-first-order and pseudo-second order-
kinetics models are given in Figure 6, and the values of qe, k1, k2 and R2 are summarized
in Table 4. According to Table 4, it can be seen that the calculated adsorption capacity from
pseudo-second-order model (316.5 mg
g1) is very closer to experimental data
(316.8 mg
g1) than that of the pseudo-first-order model (0.789 mg
g1). Furthermore, the
comparison of two correlation coefficients (R2) also demonstrates that the adsorption pro-
cess of MB from aqueous solution fits to the pseudo-second-order model better.

Adsorption mechanism
Several probable adsorption mechanisms, including electrostatic interaction, hydrogen
bonding, ion exchange, coordination, acid-base interaction, have been proposed to under-
stand the interactions between solid adsorbent and dye molecules in aqueous solution. In the
Yuan et al. 13

Figure 7. The possible adsorption mechanisms of MB onto CFA-MS.

present research, as a cationic organic molecule, MB was adsorbed onto the surface of
synthesized mesoporous silica mainly through electrostatic interaction. This can be
explained by the presence of a large amount of silanol groups Si–OH on the silica surface.
The adsorption capacity increases with increasing the pH of the MB solution, suggesting
that more deprotonated silanol groups exist in the form of Si–O–, which possess stronger
electrostatic interaction with cationic dye MB (Zhou et al., 2015). In addition, the silanol
group on the surface of CFB-MS can also interact with the amine group of MB molecule via
hydrogen bonding (Wang et al., 2016). Therefore, the adsorption mechanisms can be inter-
preted by electrostatic interaction and hydrogen bonding (Figure 7).

Conclusions
A CFA-MS has been successfully synthesized without employing any commercially available
silica source and then characterized through TEM, FT-IR spectroscopy, PXRD and nitrogen
physisorption. CFA-MS was utilized for the removal of MB from aqueous solution. The
adsorption capacity increased with contact time and the optimum pH was found to be 10.
Furthermore, the adsorption amount decreased with increasing the temperature, indicative of
exothermic adsorption behavior. In addition, the adsorption equilibrium process can be best
described as Langmuir isotherm model, while adsorption kinetics was found to follow the
pseudo-second-order equation rather than pseudo-first-order equation. The experimental max-
imum uptake amount was 316.8 mg
g1, which is close to the theoretical maximum dye
adsorption capacity of 323.62 mg
g1. This value is much higher than the previously reported
counterparts. The present research provides a promising approach for adsorptive removal of
MB by mesoporous silica materials prepared from inexpensive industrial solid waste CFA.

Acknowledgement
The authors are thankful to China University of Mining & Technology at Beijing for supporting
our work.

Declaration of Conflicting Interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.
14 Adsorption Science & Technology 0(0)

Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or
publication of this article: The work was supported by the Fundamental Research Funds for the
Central Universities (2017QH01) and the National Training Program of Innovation and
Entrepreneurship for Undergraduates (C201803841).

ORCID iD
Ning Yuan http://orcid.org/0000-0002-5470-3209

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