Journal of Cleaner Production 264 (2020) 121644

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Journal of Cleaner Production

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Adsorption and desorption behaviors of antibiotic ciprofloxacin on

functionalized spherical MCM-41 for water treatment
Dongwei Lu a, Shu Xu a, Wei Qiu a, Yan Sun b, *, Xianbin Liu c, **, Jingjing Yang d, Jun Ma a
a
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, 150090, PR China
b
College of Life Science and Biotechnology, Heilongjiang Bayi Agricultural University, Daqing, 163319, China
c
The School of Chemistry and Environmental Engineering, Harbin University of Science and Technology, Harbin, 150040, PR China
d
Center for Separation and Purification Materials & Technologies, Suzhou University of Science and Technology, 215009, PR China

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

Article history: Extensively used antibiotic ciprofloxacin increases in water environment, which is not efficiently
Received 10 August 2019 removed by means of conventional adsorbents. MCM-41 has great potential for ciprofloxacin removal.
Received in revised form There has been little research on ciprofloxacin removal by MCM-41 and their corresponding adsorption/
12 March 2020
desorption behaviors. In this study, amorphous SiO2, MCM-41 and diamine-functionalized MCM-41 were
Accepted 10 April 2020
Available online 16 April 2020
used as adsorbents to remove ciprofloxacin. In the adsorption process, their adsorption capacity followed
the order of SiO2≪MCM-41< diamine-functionalized MCM-41. Ciprofloxacin adsorption behaviors were
Handling Editor: Prof. S Alwi revealed through the analysis of adsorption isotherms and kinetics model: i. Adsorption process for
MCM-41/diamine-functionalized MCM-41 mainly included three steps; and ii. Diamine-functionalized
Keywords: MCM-41 had higher adsorption capacity because of its more and stronger chemical-monolayer
MCM-41 adsorption. In the desorption process, strong acid facilitated desorption by inhibiting the interaction
Diamine-functionalized MCM-41 between ciprofloxacin and diamine-functionalized MCM-41, and the mechanism was proposed and then
Adsorption supported by salt elution experiment. Last, the breakthrough bed volume and capacity of these absor-
Desorption
bents were tested in column operation. Diamine-functionalized MCM-41 had better performance with
Ciprofloxacin
550 bed volume and 18.3 mg/g adsorption capacity in the treatment of 5.0 mg/L ciprofloxacin. Both batch
Water treatment
and column results demonstrated that diamine-functionalized MCM-41 was highly efficient for cipro-
floxacin removal. This study indicates great application prospect of mesoporous silica materials for
ciprofloxacin removal and reveals their adsorption/desorption behaviors, which could provide guidance
on adsorbent modification/regeneration for antibiotics removal.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction has become a great environmental concern, which potentially cau-

In modern society, an ever-increasing amount of antibiotics such
as ciprofloxacin is extensively used to prevent and treat bacterial
diseases in humans and animals. Large and continual input of an-
tibiotics can pose significant environmental risks due to the failure
of properly disposing expired/unused drugs (Benotti et al., 2009).
Most of the antibiotics are poorly absorbed by humans and animals,
which are then discharged via faeces or urine, unaltered. Especially
in aquaculture, antibiotics are cast into the lakes and ponds directly
(Kolpin et al., 2002). Recent studies have shown that varieties of
antibiotics are present in wastewater, surface and groundwater. It
* Corresponding author.
** Corresponding author.
E-mail addresses: yansun@hit.edu.cn (Y. Sun), 50541xb@sohu.com (X. Liu).
ses a variety of physiologic responses on organisms in the aquatic
environment, even on animals and human being (Kim et al., 2007).
Many methods, i.e. adsorption (Kamagate et al., 2018; Rivera-
Utrilla et al., 2010), oxidation by ozone (Sui et al., 2010), biolog-
ical treatment and membrane separation (Zhao et al., 2018) have
been investigated to treat the antibiotics and pharmaceuticals in
drinking water and wastewater. Among the techniques, adsorption
is still the most cost-efficient and promising method for the
advanced purification to eliminate the antibiotics considering their
relatively low concentration and low biodegradability etc. in the
water system. Activated carbon is a generally used adsorbent for
antibiotics/pharmaceuticals adsorptions, where its pore structure
and surface properties play important roles (Caliskan and Gokturk,
2010; Mohanta and Ahmaruzzaman, 2018). The fate of antibiotics
and pharmaceuticals in the pilot-scale water treatment process of

https://doi.org/10.1016/j.jclepro.2020.121644
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644
present water plants showed that most drugs could be fully elim-
inated through the ozonation and two-step granular activated
carbon filtration. However, the high-use fluoroquinolone antibiotic
ciprofloxacin (CIP) was found to directly pass through the whole
treatment process with extremely low adsorption (Vieno et al.,
2007; Morasch et al., 2010). It is imperative to explore an efficient
absorbent for the removal of CIP fluoroquinolone antibiotic from
drinking water and wastewater.
As an absorbent, the ordered mesoporous silica material, so-
called mobile composition of matter (MCM-41), with 2D hexago-
nal p6m structure, has multiple advantages including a large sur-
face area, uniform pore distribution (about 2.5 nm) and ordered
mesoporous channel structure. Its mesoporous surface has
amounts of hydroxyl functional groups (SieOeH) which could be
modified with different functional groups through OeH grafting
and substantially expands its application. For instance, the reported
mesoporous silica-based materials modified with amine and thiol
functional groups were proved particularly efficient for seques-
tering heavy metals from water (Mercier and Pinnavaia, 1997).
Moreover, unmodified and modified mesoporous materials using
alkyl groups had achieved a good performance on adsorption of
organic pollutants (Baccile and Babonneau, 2008; Wang and Tan,
2007). The mesoporous MCM-41 can be used as matrix to design
an implantable delivery system for drug delivery (Vallet-Regi et al.,
2001; Munoz et al., 2003). It has also been applied for catalytic
cracking because of its sufficient acid sites and high cracking ac-
tivity. Up to now, the MCM-41 has been mainly applied to the
adsorptive elimination of heavy metals and common organic pol-
lutants (Walcarius and Mercier, 2010; Arica et al., 2017), medical
delivery and catalytic cracking (Manzano and Vallet-Regi, 2010;
Roik et al., 2017). Considering the special physical and chemical
properties of MCM-41, it would be a promising adsorbent for CIP
removal. However, the adsorptive removal of CIP antibiotic using
MCM-41 and the corresponding adsorption-desorption behaviors
between antibiotics and mesoporous silica materials were barely
investigated in depth, which is significantly critical to select,
modifying and regenerating absorbent to efficiently remove CIP
fluoroquinolone antibiotic from water.
In this study, the MCM-41 with perfect sphericity and mono-
dispersity was prepared, which is beneficial to on-going research
on adsorption/desorption study, especially on column operation.
Amorphous SiO2, unfunctionalized MCM-41 (both as references),
and diamine-functionalized spherical MCM-41 (N-MCM-41) were
used as adsorbent to remove CIP from water. Their performances
were investigated in batch and column operations. In batch ex-
periments, CIP adsorption behaviors on these adsorbents were
proposed through the fitting analysis of the adsorption isotherms
and adsorption kinetics models (Ho et al., 2000; Song et al., 2018).
The adsorption of CIP on N-MCM-41 at different pH was investi-
gated to determine the optimized desorption condition, and
possible desorption behaviors were proposed and then verified by
salt elution experiment. A continuous fixed-bed column packed
with these absorbents was then applied for CIP removal, and their
breakthrough bed volume and breakthrough capacity were inves-
tigated in detail. This study highlights the potential of mesoporous
MCM-41 for antibiotic CIP removal and proposes the adsorption-
desorption behaviors between CIP and mesoporous silica mate-
rials. The results should provide basic knowledge on how to select/
modify/regenerate adsorbent for antibiotic removal from water.
2. Materials and methods
2.1. Materials
All the chemicals used in experimental section were of reagent
grade. Cetyltrimethyl ammonium bromide (CTAB, 99%), 3- (2-
aminoethyl aminopropyl) trimethoxysiliane (ATMS, 97%) from
Sigma-Aldrich, and tetraethoxysilane (TEOS, 99%) from Shanghai
Chemical were used for experimental studies without further pu-
rification. CIP (99% purity) was purchased from Wuhan Yuancheng
technology development company limited (China). An amorphous
SiO2 was supplied by Sinopharm Chemical (Shanghai, China). Other
reagents were commercially available and used as received.
2.2. Synthesis and characterization methods
The preparation process of the material consists of two parts:
preparation of the parent MCM-41 with spherical morphology and
diamine-functionalized MCM-41 via the post-synthesis method
(Liu et al., 2008; Pauwels et al., 2001). Briefly, 2.5 g of CTAB was fully
dissolved in deionized (DI) water, followed by adding 13.2 g of an
ammonia solution (32 wt %) and then mixing with 60 g of ethanol.
TEOS (4.7 g) was added after the mixture solution was stirred
vigorously for 15 min. The obtained synthetic gel was further stir-
red at room temperature for an additional 2 h. The solid product
was obtained by filtration and repeated washing (DI water, 3 times),
and drying at 80
C for 12 h. The surfactants in the as-synthesized
sample (1.0 g) were removed by extraction in a mixture of
concentrated hydrochloric acid (1.0 mL) and anhydrous ethanol
(100 mL) for 12 h the process is repeated again for the completely
removal of CTAB. The product was filtered, washed several times
with anhydrous ethanol, and dried at 60
C. The N-MCM-41 was
prepared as followed: MCM-41 (1.0 g) with the free surfactant was
dispersed in prepared anhydrous toluene solution containing 0.3 g
ATMS, followed by a reflux for 6 h. The resultant materials were
then obtained by filtration, solvent-washing anhydrous toluene,
and drying process for solvent removal.
The samples were characterized by a complementary combi-
nation of X-ray diffraction (XRD), N2 adsorption-desorption, scan-
ning electron microscopy (SEM), FT-IR spectroscopy and surface
zeta potential measurement. Powder X-ray diffraction patterns
were recorded using a Bruker diffractometer with data collected at
2q from 1.5
to 8
. Nitrogen adsorption/desorption experiments
were performed at 77 K to examine the specific surface area and the
pore size distributions. The surface zeta potential was measured
using a Particle Size & Zeta Potential Analyzer. The IR analysis of the
samples prepared with KBr pellets were performed on a Bruker FT-
IR spectrometer in the range of 400e4000 cm1. The morphology
and structure of the materials were investigated by SEM observa-
tion (FFESEM, JSM-6700). For further analysis, the samples were
also examined by transmission electron microscopy (TEM, JEM-
2010).
2.3. Adsorption experiments
A stock solution of CIP (1000 mg/L) was prepared using deion-
ized water. CIP concentrations from 10 to 300 mg/L in our study
were prepared by diluting the stock solution. In the batch pro-
cedure, 20 mg adsorbent material was added to a 20 mL CIP solu-
tion with the different concentrations. The suspension was stirred
for 2 h using a water shaker bath at 25
C. Then the adsorbents were
filtrated through a syringe filter (0.22 mm) and the CIP concentra-
tion was measured by UVeVis spectrometer at 277 nm. The CIP
amount adsorbed at equilibrium was calculated using Eq. (1):
ðC0  Ce ÞV
qe ¼ (1)
M
where qe (mg/g) is the amount of CIP adsorbed at equilibrium, C0
(mg/L) and Ce (mg/L) are the concentration of CIP at the initial and
 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644
equilibrium time, M (g) is the mass of the added adsorbent.
The initial CIP concentration were prepared in the range of
10e300 mg/L. In addition, for the experiments of adsorption ki-
netics, initial CIP concentration was fixed to be 200 mg/L and the
volume of solution was enlarged to 150 mL. At time intervals of 0.5,
1.0, 2.0, 5.0, 8.0, 10.0, 15.0, 20.0, 25.0, 30.0, 40.0, 50.0, 60.0, 90.0 and
120.0 min, 0.5 mL of sample was taken each time for analysis of
residual CIP concentration.
2.4. Desorption experiment
The influence of pH on the interaction between CIP and N-MCM-
41 was firstly investigated to establish the optimal desorption
condition as the following procedure: 20 mg samples and 20 mL
solution with different initial CIP concentration and pH pre-
adjusted using HCl or NaOH were prepared at 25
C for 2 h. The
residual CIP concentration was measured by UVeVis spectrometer
at 277 nm.
Desorption experiments were conducted immediately after
absorption experiments. Deionized water, pH 3.0 acidic solutions
pre-adjusted using HCl and 3.0 mol/L NaCl solution were employed
as eluents. The desorption procedure was as followed: 15 mL of
supernatant was removed after centrifuge, and the same volume of
eluent solution was added and then shaken for an additional 24 h.
The above procedure was repeated, and the CIP concentrations of
the first and second elution solutions were determined. The release
ratio was calculated according to Eq. (2):
15C1 þ 15C2
Release ratio ð%Þ ¼  100%
20qe
where C1 (mg/g) and C2 (mg/g) are the CIP concentration in first and
second elution solution; qe (mg/g) is the equilibrium adsorption
amount.
2.5. Column experiments
A cylindrically shaped microcolumn (12 mm length and 8.8 mm
i.d.) was used. SiO2 and the unmodified and functionalized MCM-41
adsorbents of 300 mg were prepared in suspension, and then
packed into the microcolumn. The CIP solution at a concentration of
5.0 mg/L was fed on the gravitation. The breakthrough point was
defined as the bed volume at which the normalized CIP concen-
tration exceeded a predefined value (i.e. 10 %.). The normalized CIP
concentration was calculated according to Eq. (3). The break-
through capacity was the corresponding adsorption capacity at the
breakthrough point.
Normalized CIP concentration (%) ¼ Cout/Ci ✕100%
where Cout and Ci are the CIP concentration at the outlet of the
column and the initial feed CIP concentration.
3. Results and discussion
3.1. Materials characterization
Fig. S1 gave the XRD analysis of the diffraction peaks for MCM-
41 and N-MCM-41. Three diffraction peaks at 2.2
, 3.8
and 4.4
,
corresponded to (100), (110) and (200) diffractions could be
observed, which indicated that hexagonal mesostructure phase
existed in MCM-41. For N-MCM-41, the intensive (100) accompa-
nied by weak peaks at (110) and (200) was still obvious and
demonstrated an ordered hexagonal structure as shown in the
spectra of MCM-41. compared to MCM-41, introducing ATMS into
3
the mesoporous channel surface of MCM-41 led to the decrease of
the peak intensity at 2.2
and the less resolved peaks of the higher
odder (110) and (200) diffractions, which is most likely due to the
overlap of diffraction peaks with higher refractive indices caused by
the decreased structural ordering. The phenomenon could be
explained by that ATMS would be successfully grafted on the
mesoporous channel surface and reduced electron contrast in the
electron density. The nitrogen adsorption/desorption isotherms
were type IV and exhibited a sharp step increase at P/P0 ¼ 0.3e0.4
(Fig. S2 Left), indicating their uniform-size mesoporous structure.
The sample exhibited a less sharp step when ATMS was introduced,
and the pore size of N-MCM-41 was slightly smaller than that of
MCM-41 shown in Fig. S2 right. Table S1 listed the calculated spe-
cific surface area, pore size and pore volume. As expected for N-
MCM-41, its surface area and pore sizes decreased with the addition
of ATMS, which was ascribed to the occupancy of structural chan-
nels by amino functional groups (Liu et al., 2009).
The SEM image of MCM-41 and N-MCM-41 showed perfect
sphericity and monodispersity in Fig. S3A and Fig. S3B. TEM image
confirmed that the N-MCM-41 material still maintained well or-
dered, one-dimensional pore structure (Fig. S3C), which suggested
that the introducing ATMS into the mesoporous channel surface of
MCM-41 do not lead to the decrease of mesoporous ordering and
destruction of spherical morphology of product. The spherical
morphology of MCM-41 with well monodispersity was beneficial
for adsorbent, especially as adsorbent on adsorption/desorption
study in column adsorption/desorption research. The spherical
geometric shape facilitated a homogeneous column packing and
effectively reduced the operating pressure and pressure drop. The
(2)
particle sizes of MCM-41 and N-MCM-41 were about 2.0 mm from
the SEM images, which had better performance and lower oper-
ating pressure than the common mesoporous nanoparticles for
removal of pharmaceuticals (Walcarius and Mercier, 2010).
In order to explore the surface character of mesoporous parti-
cles, the relationship between adsorbent and ciprofloxacin, the FT-
IR spectra of materials were detected and shown in Fig. 1. FT-IR
spectra of the as-MCM-41, MCM-41 and N-MCM-41 showed the
typical characteristic peaks of silica at ~808 cm1, 978 cm1 and
1088 cm1, corresponding to the vibrations of the SieOeSi sym-
metric bond, SieOH stretching bond and SieOeSi asymmetric
bond. In the MCM-41 spectrum, the absorption peaks of 2900 cm1,
2858 cm1, and 1480 cm1 in the as-MCM-41 material disappeared,
indicating that the surfactant CTAB was removed clearly (Liu et al.,
2005). Comparing the to that of MCM-41, absorption peaks of N-
MCM-41 were observed at 2980 cm1, 1480 cm1 and 965 cm1,
corresponding to the grafted amino groups in the material.
Compared FT-IR spectrum of CIP with MCM-41-CIP, the
stretching vibration of OeH band at 3446 cm1 and the stretching
(3) vibration peak of C]O at 1627 cm1 originated from CIP still pre-
sented, indicating that CIP was adsorbed to the mesoporous
channel of MCM-41. In the N-MCM-41-CIP spectrum, the vibration
peaks at 3445 cm1, 1680 cm1 and 1629 cm1 were normally be
observed, probably due to the OeH vibration and C]O stretching
vibration of amide bond formed by N-MCM-41 and CIP.
According to the zeta potential data (Fig. S4), MCM-41 showed
negatively charged from pH 3.0 to pH 11.0, which was consistent
with the results of earlier researcher (Kecht et al., 2008), because of
the SieOH groups presentation on MCM-41 surface. When the
ATMS was grafted on mesoporous channel surface of MCM-41, the
incorporated aminoethyl and aminopropyl moieties were proton-
ated at acidic pH values and carried a positive charge. A higher
density of such groups on the mesoporous channel surface leads to
increased zeta potential curves as they affect the overall surface
charge. As result, the zeta potential for N-MCM-41 shifted toward
positively charged below pH 9.0 (Kecht et al., 2008; Rosenholm
4 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644
Fig. 1. FTIR spectra for the nanoparticles and ciprofloxacina
) as-MCM-41, b) MCM-41, c) N-MCM-41, d) MCM-41-CIP, e) N-MCM-41-CIP, f)
ciprofloxacin.
et al., 2008), and negatively charged above pH 10.0 because amines
were not protonated under the pH condition. The structure and
charge of the dominant species in solution as a function of pH with
pKa values of CIP were shown in Fig. S5A. According to the disso-
ciation constants of 5.46 (pKa1) and 7.67 (pKa2) of the amphoteric
compound CIP, the proportion of three ionic situations (i.e., cation,
zwitterion and anion) could be calculated and shown in Fig. S5B.
3.2. Adsorption analysis
3.2.1. Adsorption isotherm
In batch adsorption experiment, the adsorption isotherms of CIP
on amorphous SiO2, MCM-41 and N-MCM-41 with 2 h equilibrium
time were presented in Fig. 2. MCM-41 and N-MCM-41 exhibited an
enhanced CIP adsorption performance in comparison with amor-
phous SiO2. The adsorption capacity of N-MCM-41 is 110 mg/g,
more than twice that of the parent MCM-41 (45 mg/g) despite of its
relatively low specific surface area. The reasons for the phenome-
non were explained in following adsorption behavior analysis.
In Fig. 2, three common isotherms equation (i.e., Langmuir
equation, Freundlich equation and Redlich-Peterson equations
shown in Text S1, Supporting Information) were applied to analyze
adsorption behavior of amorphous SiO2, MCM-41 and N-MCM-41.
The parameters of three isotherms were listed in Table 1. The co-
efficient of determination (R2) was used as a measure of the fitness,
and higher R2 close to 1 indicates better fitness for the corre-
sponding isotherms equation. Freundlich equation and Langmuir
equation were firstly used to analyze the adsorption process. As for
amorphous SiO2, R2 of Freundlich equation (0.92) was significantly
higher than that of Langmuir equation (0.11). This result indicated
that the adsorption process of amorphous SiO2 was mainly multi-
layer adsorption, allowing for the possibility that the monolayer
adsorption was also involved to a minor extent. For MCM-41, R2
values of Freundlich equation (0.98) was still the highest, yet only
slightly higher than R2 values of Langmuir equation (0.91). The
adsorption process of MCM-41 may be explained by that the
SiO2(Experiment) MCM-41(Experiment) N-MCM-41(Experiment)
SiO2(Langmuir) MCM-41(Langmuir) N-MCM-41(Langmuir)
SiO2(Freundlich) MCM-41(Freundlich) N-MCM-41(Freundlich)
SiO2(R-P) MCM-41(R-P) N-MCM-41(R-P)
120
Ciprofloxacin Adsorbed, q e(mg/g)
80
40
0
0 50 100 150 200 250
Equilibrium Ciprofloxacin Concentration, Ce (mg/L)
Fig. 2. Adsorption isotherms of ciprofloxacin on SiO2, MCM-41 and N-MCM-41 in
deionized water solution.
multilayer adsorption mainly occurred and the monolayer
adsorption also partially existed. For N-MCM-41, R2 of Langmuir
equation (0.99) was higher than that of Freundlich equation (0.94)
both close to 1. This phenomenon suggested that the monolayer
and multi-layer concurrently took place, where the monolayer
adsorption dominated the adsorption process. The adsorption co-
efficient qm of Langmuir equation and qF of Freundlich equation
were both related to the adsorption capacity for the certain
adsorbate in Table 1 qm and qF of mesoporous materials (MCM-41
and N-MCM-41) were much higher than that of amorphous SiO2
(SiO2 ≪ MCM-41< N-MCM-41), indicating that the adsorption ca-
pacity was in order of SiO2 ≪ MCM-41< N-MCM-41. This result was
well consistent with the adsorption results in Fig. 1. In addition, a
further empirical isotherm (i.e., Redlich-Peterson equation) was
also applied to analyze the adsorption process. N-MCM-41 and
MCM-41 were both well fitted by Redlich-Peterson equation, where
R2 was 0.98 and 0.97. The values of b were 1 for N-MCM-41 in
Redlich-Peterson equation. In this case, Redlich-Peterson equation
can be well reduced to the Langmuir model, which showed good
consistence with above fitting results. KR is positively related to the
energy of adsorption in Redlich-Peterson equation. The adsorption
energy of these absorbents was in the same order as KR value
(SiO2 < MCM-41< N-MCM-41), which further confirmed the
stronger absorption capacity of N-MCM-41 than amorphous SiO2
and MCM-41.
3.2.2. Adsorption kinetics
The time dependence curves of CIP adsorption by MCM-41 and
N-MCM-41 at room temperature were presented in Fig. 3A. A rapid
initial uptake took place within the first 2 min for both MCM-41 and
N-MCM-41 implying their high affinity for CIP. Subsequently, the
adsorption process slowed. Finally, equilibrium was reached after
30 min. This rapid adsorption process would be of benefit for CIP
removal from water in practical application. Four adsorption ki-
netics models (equations shown in Text S2, Supporting Informa-
tion) were used to investigate the adsorption kinetic behavior in
Fig. 2 (Ho et al., 2000). The correspondingly fitting parameters were
listed in Table 2. Nonlinear regression results showed that the
pseudo-first-order equation could only fit the initial stage in Fig. 2A,
which was usually the diffusion process of the solute to the outer
surface of the absorbent (Girish and Murty, 2016). In contrast,
Pseudo-second-order model well fitted the experimental data in
 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644 5

Table 1
Parameters of the isotherms models for CIP adsorptionby the adsorbentsa.

Adsorbents Langmuir isotherm Freundlich isotherm Redlich-Peterson isotherm

qm(mg/g) KL(L/mg) R2 qF ((mg/g) (L/mg)1/n) 1/n R2 KR (mg/g) aR(L/mg) b R2

Amorphous SiO2 19.71 0.01 0.11 0.16 0.97 0.92 0.22 0.03 1.00 0.84
MCM-41 69.70 0.02 0.91 2.54 0.65 0.99 1.60 0.10 0.69 0.97
N-MCM-41 139.25 0.02 0.99 6.15 0.59 0.94 2.73 0.02 1.00 0.98
a
Data were obtained from Fig. 2.

120
MCM-41(Experiment) N-MCM-41(Experiment) MCM-41 N-MCM-41
140
MCM-41(First) N-MCM-41(First)
Ciprofloxacin Adsorbed, qe (mg/g)

MCM-41(Second) N-MCM-41(Second) 100

Ciprofloxacin Adsorbed, qt (mg/g)

120 MCM-41(Elovich) N-MCM-41(Elovich)

100 80

80
60

60
40
40

20 First stage
20

A B Second stage
Third stage
0 0
0 20 40 60 80 100 120 0 2 4 1/2
6 0.5
8 10 12
Time (min) t (min )

Fig. 3. Adsorption kinetics of ciprofloxacin on MCM-41 and N-MCM-41in deionized water solution. Adsorption kinetics was fitted by four models, including the pseudo-first-order
(first), the pseudo-second-order (second), the Elovich equation (A) and intraparticle diffusion model (B).

the whole adsorption process based on the values of R2 in Table 2. equilibrium where the adsorption rate was equal to the desorption
The qe value (i.e., adsorption capacities at equilibrium) from the rate.
pseudo-second-order kinetic equation for N-MCM-41 was signifi-
cantly higher than that for MCM-41, demonstrating its higher
3.2.3. Adsorption behavior analysis
adsorption capacity. This result was in good consistence with the
Based on the analysis of the adsorption isotherm and kinetics,
results in Table 1. Both the parameter h in pseudo-second-order
the possible adsorption behaviors of CIP on amorphous SiO2, MCM-
model and the parameter a representing the initial sorption rate
41 and N-MCM-41 were proposed in Scheme 1. The CIP absorbed on
showed that the CIP adsorption rate of N-MCM-41 was higher than
the surface of SiO2, MCM-41and N-MCM-41, while it also absorbed
MCM-41 in the initial stage (Table 2).
the inner pores of mesoporous MCM-41and N-MCM-41 in mono-
Fig. 3B showed the plots for the adsorption using intraparticle
layer and multilayer. The absorption in the pores of MCM-41and N-
diffusion model. The curves showed the three-phase plot suggested
MCM-41 in Scheme 1 largely accounted for their higher adsorption
that the adsorption process included three stages. Based on the
capacity than that of SiO2. The adsorption capacity of N-MCM-41
intraparticle diffusion model and the adsorption theoretics of so-
with low surface area was significantly higher than that of high
lute on porous adsorbent (Badruzzaman et al., 2004), a possible
surface area MCM-41 (496 m2/g vs. 828 m2/g in Table S1), which
adsorption process of CIP on mesoporous MCM-41 materials was
can be explained as followed: According to Fig. S5, the protonation
proposed: i. In the first stage, CIP quickly diffused into the outer
of both carboxylic acid group and amino group of CIP took place
surface of mesoporous MCM-41 materials and absorbed onto their
simultaneously in deionized water, and the zwitterion was main
outer surface. The slop of the first-stage adsorption curve was the
dissociation form of CIP. CIP can interact with SiO2 and MCM-41
largest indicating that this stage was minor rate-controlled step; ii.
through hydrogen bonding between ¼ NHþ 2 of CIP and SiO of

In the second stage, CIP gradually migrated into the pores and
MCM-41, while CIP can interact with N-MCM-41 through conden-
subsequently reached into the pore surface, and consequently
sation interaction between R-COO- of CIP and ReNHþ 3 of N-MCM-41
absorbed on the pore internal surface. The CIP adsorption amount
in Scheme 2. ReNH2 group of N-MCM-41 is protonated more easily
slowly increased suggesting that the second pore diffusion process
into ReNHþ 
3 than SiOeH group of MCM-41 into SiO under neutral
was the main rate-controlled step but not exclusive rate-controlled
condition (Leung et al., 2009), indicating more ReNHþ 3 available
step; iii. In the last stage, the absorption reached a dynamic
than SiO to interact with CIP. N-MCM-41 would adsorb more CIP

Table 2
Parameters of the kinetics models for CIP adsorption by the adsorbentsa.

Adsorbents Pseudo-first-order Pseudo-second-order Elovich equation

k1(1/min) qe(mg/g) R2 qe(mg/g) k2(g/mg$min) h(mg/g$min) R2 a(mg/g$min) b(g/mg) R2

MCM-41 0.38 39.92 0.93 44.04 0.01 18.90 1.00 2.66 6.32 0.92
N-MCM-41 0.88 90.41 0.83 108.40 0.003 32.77 1.00 7.18 11.79 0.99
a
Data were obtained from Fig. 3.
6 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644
Scheme 1. Adsorption behaviors of CIP on the three absorbents in monolayer and multilayer.
than MCM-41 through its more dissociated functional groups
(Scheme 2). The interaction between the adsorbents and the ad-
sorbates by the dissociated functional group mainly contributed to
chemical monolayer absorption. This explained why the N-MCM-
41 would have more monolayer adsorption (i.e., more ReNHþ 3 ) and
SiO2 have less monolayer adsorption (i.e., less SiO) in the results of
Fig. 1 and Table 1, which in turn further supported our proposed
mechanism in Scheme 2. In addition, the condensation interaction
between CIP and N-MCM-41 was stronger and more likely occurred
compared to the hydrogen bonding between CIP and MCM-41,
which accounted for the higher adsorption energy (KR in Table 1)
and high initial sorption rate (h and a in Table 2) for N-MCM-41.
3.3. Desorption analysis
Desorption process is of significance for the adsorbent regen-
eration in practical application, which is the reverse process of
adsorption. Weaker adsorption interaction between adsorbent and
adsorbate means easier desorption process. Based on the adsorp-
tion behavior analysis, the dissociation of surface functional groups
of SiO2, MCM-41 and N-MCM-41 largely determined their adsorp-
tion interaction with CIP. The pH was an essential factor in deter-
mining the extent of dissociation, influencing the adsorption
interaction and consequently the desorption process. The adsorp-
tion interaction between CIP and N-MCM-41 at different pH was
investigated to determine the optimized desorption condition,
where the less CIP absorption indicated weaker adsorption inter-
action (i.e., easier desorption process).
Fig. 4 showed the CIP adsorption capacity of N-MCM-41 at
different pH values from 1.0 to 11.0. In general, CIP adsorption
amount increased with its initial concentration increasing from
50 mg/L to 200 mg/L at all pH values. At pH 1.0 and pH 3.0, the CIP
adsorption amount (qe) at equilibrium kept low. This phenomenon
may be explained by that more than 96% CIP changed into the
protonated form (i.e., R2-N-Hþ 2 ) at strong acid conditions, which
was resistant to interact with ReNHþ 3 of N-MCM-41 contributing to
CIP desorption as shown in Scheme S1. With the increase of pH
value, the qe increased quickly because of more deprotonated CIP
(i.e., R-COO-) available to interact with ReNHþ 3 of N-MCM-41
(Scheme 2), and reached the maximum at pH 7.0. After that, the CIP
adsorption decreased despite the increase of deprotonated CIP. Two
reasons may account for this phenomenon: i). the dissociation of
amino functional groups of N-MCM-41 was inhibited under alka-
line condition (i.e., more ReNH2 of N-MCM-41 resistant to interact
with R-COO- of CIP) in Scheme S1, which can be supported by the
surface zeta potential of N-MCM from positive at pH 9.0 to negative
at pH 10.0 in Fig. S4; ii). MCM-41 material (including N-MCM-41)
cannot be resistant to strong alkaline solutions, due to increasing
deprotonation of silanol groups and hydrolysis of SieOeSi bonds
which is catalyzed by mucleophilic attack by OH ions (Xiao and
Lasaga, 1994; Braun et al., 2016). The structure of MCM-41 may
be destroyed in the basic solution (pH value is greater than 11.0) to
some extent, leading to the decrease of its adsorption capacity. That
is one of disadvantage of MCM-41 and N-MCM-41 as adsorbents for
the removal of the antibiotics. It should be mentioned that N-MCM-
41 had the CIP removal rate great than or close to 80% in different
CIP initial concentration solutions at optimum pH 7.0 in Fig. S6,
again indicating that N-MCM-41 is an efficient adsorbent for the
elimination of fluoroquinolones antibiotic.
Based on the above results, pH 3.0 acidic solutions could be used
 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644 7

Scheme 2. Interaction between CIP and three adsorbents via monolayer chemical adsorption.

180 the two adsorbents were illustrated in Fig. 5. The release ratio of CIP
pH 1.0 pH 3.0 pH 5.0 pH 6.0 for N-MCM-41/CIP in pH 3.0 solution was significantly higher than
pH 7.0 pH 9.0 pH 11.0
that in deionized water (release ratio 65.8% vs. 5.1% in Fig. 5). The
150 release ratio of CIP for MCM-41 in pH 3.0 solution was also higher
than that in deionized water (release ratio 70.6% vs. 38.6%). This
Ciprofloxacin asorbed (mg/g)

was probably ascribed to the dissociation inhibition of hydroxyl

120 functional groups of MCM-41 (i.e., less SiO available interacted
with ¼ NHþ 2 of CIP) under acid condition, which can be supported
by its less negative zeta potential in Fig. S4. Since high ionic
90
strength would inhibit the dissociation of amino functional groups
of N-MCM-41, it may promote desorption process based on our
60 proposed behavior in Scheme S1. 3.0 mol/L NaCl solution was
employed as eluents to verify the proposed mechanism. The CIP
release ratios for MCM-41 and N-MCM-41 in 3.0 mol/L NaCl solu-
30 tion were obviously higher than that in deionized water in Fig. 5,
which further confirmed our proposed mechanism. It should be
noticed that N-MCM-41 still had more CIP remained than MCM-41
0
50 100 150 200 after elution by different solutions in Fig. 5, demonstrating the
Initial concentration (mg/L) stronger interaction between N-MCM-41 and CIP than that be-
tween MCM-41 and CIP. The results of desorption process consisted
Fig. 4. Adsorption amounts of ciprofloxacin on N-MCM-41 with different initial con- well with our proposed mechanism in Scheme 2.
centrations and different pH.

as an efficient eluent for desorption process to regenerate the N- 3.4. Column breakthrough behavior
MCM-41. Deionized water (as blank) and pH 3.0 solution were used
as eluents for MCM-41 and N-MCM-41. Desorption performances of The MCM-41 used conventional synthesis method had very fine
particle size and exhibited a low mechanical strength. Though the
8 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644
100
N-MCM-41
90
MCM-41
80
Release ratio (%)
70
60
50
40
30
20
10
0 0
Salt solution
Acid solution Deionized water
Fig. 5. Desorption of ciprofloxacin from N-MCM-41 using different eluents.
materials could perform the adsorption/desorption operation in
batch measurement, it could not be packed into the column to
perform the adsorption test. This is another disadvantage of MCM-
41 as adsorbents for the removal of the antibiotics. MCM-41 and N-
MCM-41 were prepared in our synthesis method and showed
almost perfect spherical morphology and monodispersity with
particle size of ca. 2.0 mm shown in the SEM and TEM images. The
spherical geometric shape facilitated a homogeneous column
packing. Based on the results from the batch experiment, a
continuous fix-bed column was packed with SiO2, MCM-41 and N-
MCM-41 to remove CIP from water in the aspect of the practical
application.
The bed volume of columns and the liquid flow velocity through
column under gravitation were shown in Table S2. The column of
amorphous SiO2 particles had the minimum bed volume and high
compact, causing the low flow velocity. In contrast, the column of
MCM-41 and N-MCM-41 had relatively larger bed volume and
significantly higher flow velocity possibly ascribed to their porous
structures and uniform sphericity. Fig. 6 showed the breakthrough
curves of the materials. The adsorption capacity of amorphous SiO2
column was too low to keep the normalized CIP concentration (i.e.,
Cout/Ci) less than 10%, and the bed volume on breakthrough was
only about 30. The breakthrough point for N-MCM-41 was 550 bed
volumes, two times than that for MCM-41 (i.e., 290 bed volumes).
The breakthrough capacities of SiO2, MCM-41 and N-MCM-41
calculated from the breakthrough points were 0.13, 10.35, 18.32 mg/
g in continuous fix-bed column (SiO2 ≪ MCM-41< N-MCM-41),
which were well consistent with the results in batch experiments.
Taking the surface water from Songhua River in Harbin, China as
example (CIP concentration 230 ng/L), 300 mg N-MCM-41 could
roughly process about 20 m3 water, and the breakthrough bed
volume could get 1.0  107, which demonstrates its great applica-
tion prospect for CIP removal from real water.
4. Conclusions
Unmodified and diamine functionalized spherical MCM-41 with
well-ordered mesoporous structure were prepared and used as
absorbents for CIP removal from water. Based on the fitting analysis
of adsorption isotherms and kinetics models, the adsorption pro-
cess of MCM-41/N-MCM-41 mainly included three phases of sur-
face adsorption, intraparticle diffusion and equilibrium. N-MCM-41
100
Amorphous SiO2
MCM-41
Normalized CIP Concentration (Cout/Ci)
80 N-MCM-41
60
40
20
0
200 400 600 800
Bed Volume
Fig. 6. Column adsorption breakthrough behaviors of ciprofloxacin on three
adsorbents.
had higher adsorption capacity and adsorption energy than SiO2/
MCM-41, probably because of its more and stronger chemical-
monolayer adsorption through the condensation interaction be-
tween R-COO- of CIP and ReNHþ 3 of N-MCM-41 than that through
hydrogen bonding between ¼ NHþ 
2 of CIP and SiO of SiO2/MCM-41.
The strong acid conditions contributed to the desorption process
through the inhibition of the interaction between CIP and MCM-41/
N-MCM-41. Both batch and column adsorption results demon-
strated that MCM-41 and N-MCM-41 were efficient for CIP elimi-
nation, and N-MCM-41 had best performance for CIP removal from
water. Overall, this research indicates the potential of mesoporous
MCM-41 materials for antibiotic CIP removal from water and re-
veals the adsorption-desorption behaviors between CIP and mes-
oporous materials. The result will be indicative for selecting,
modifying and regenerating adsorbents to efficiently remove an-
tibiotics/pharmaceuticals for water treatment.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Dongwei Lu: Conceptualization, Writing - original draft, Inves-
tigation, Methodology. Shu Xu: Data curation, Formal analysis,
Investigation. Wei Qiu: Visualization, Validation. Yan Sun:
Conceptualization, Validation, Writing - review & editing. Xianbin
Liu: Project administration, Supervision. Jingjing Yang: Writing -
review & editing. Jun Ma: Funding acquisition, Supervision.
Acknowledgments
This work was financed by National Natural Science Foundation
of China (No.51908162), Science and Technology Commission
Foundation of Jiangsu Province of China (No. BE2016695), the sci-
entific research team support plan (TDJH201904) and the scientific
Research Foundation for Scholars (XYB201920) of Heilongjiang Bayi
Agricultural University, China, the China Postdoctoral Science
Special Foundation (No. 2018T110304), China Postdoctoral Science
Foundation (No. 2017M621288) and Heilongjiang Postdoctoral
 D. Lu et al. / Journal of Cleaner Production 264 (2020) 121644 9

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