Journal of Molecular Liquids 286 (2019) 110746

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Journal of Molecular Liquids

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

Rapid and selective removal of Hg(II) ions and high catalytic performance
of the spent adsorbent based on functionalized mesoporous silica/poly
(m-aminothiophenol) nanocomposite
Yong Fu a, Jinwen Jiang a, Zhangpei Chen a, Shaoming Ying b,c, Jiwei Wang b,c,⁎, Jianshe Hu a,⁎⁎
a
Center for Molecular Science and Engineering, College of Sciences, Northeastern University, Shenyang 110819, PR China
b
Fujian Provincial Key Laboratory of Featured Materials in Biochemical Industry, College of Chemistry and Materials, Ningde Normal University, PR China
c
Fujian Province University Engineering Research Center of Mindong She Medicine, College of Chemistry and Materials, Ningde Normal University, PR China

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

Article history: The toxic Hg(II) being released excessively into the water body from various sources has threatened the environ-
Received 21 January 2019 ment and human health. The aim of this study is to design a rapid and selective adsorbent, and propose an alterna-
Received in revised form 1 April 2019 tive way to dispose the spent adsorbent. To this end, a new material (MAP) was designed by inducing the
Accepted 4 April 2019
polymerization of m-aminothiophenol onto MCM-41 (Mobil Composition of Matter) surface obtained using
Available online 3 May 2019
cheap diatomite as a silica source and modified by APTES ((3-aminopropyl) triethoxysilane), and the spent adsor-
Keywords:
bent was further converted into an active catalyst for acetophenone synthesis. The adsorption properties of the
MCM-41 MAP were systematically explored under different parameters, and the corresponding results were analyzed
Poly(m-aminothiophenol) based on different adsorption kinetic and isotherm models. The study found the removal rate and adsorption capac-
Hg(II) ions ity of the MAP could reach 96.56% and 242.42 mg/g within 15 min. The coexisting cations showed little competition
Adsorption effect on the removal of Hg(II), and the adsorption capacities after five cycles did not obviously decrease. Kinetic
Catalyst study indicated that the adsorption data were well fitted to the pseudo-second-order model, and the adsorption
Acetophenone equilibrium data followed the Langmuir model. After adsorption studies, the Hg(II)-MAP was used as a catalyst in
the reaction of phenylacetylene to acetophenone with high yield of 97.01%. This work not only provides a rapid
and selective adsorbent for removal of Hg(II) ions, but also opens a novel avenue for reusing the toxic spent adsor-
bent for catalytic application.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction is regarded as a global pollutant by the United Nations Environment

Due to the increasing emission of heavy metal-containing wastewa-
ter into the environment, the pollution of heavy metal ions has become
one of the hot topics in environmental researches and attracted global
attentions [1–3]. Particularly, mercury is regard as one of the most
toxic elements since it is not biodegradable and tends to accumulate
in living organisms [4]. Mercury in aqueous solutions, even at trace
levels, can cause the behavioral, reproductive and genotoxic of aquatic
organism, and enters the food chain, finally accumulates in the human
body via consumption of fish and other marine species [5]. Mercury
ingested in the human body can damage the liver, kidney, bones,
brain functions and reproductive system etc., causing symptoms of mer-
cury poisoning such as hair loss, vision and hearing loss, central nervous
system disorders [6]. Additionally, it easily passes through the blood-
brain barrier and affects the fetal brain [7]. As a consequence, mercury
⁎ Correspondence to: J. Wang, Fujian Provincial Key Laboratory of Featured Materials in
Biochemical Industry, College of Chemistry and Materials, Ningde Normal University, PR China.
⁎⁎ Corresponding author.
E-mail addresses: jlwjw@sina.com (J. Wang), hujs@mail.neu.edu.cn (J. Hu).
Program, and it is the only chemical pollutant that has an impact on
the whole world except greenhouse gases, so the effective removal of
Hg(II) ions from wastewater has been a crucial issue related to the qual-
ity of human life. In addition, the maximum permissible limitation of 6
μg/L for mercury in drinking waters has been required, while the corre-
sponding limit regulated by the US Environmental Protection Agency is
reduced to 2 μg/L [8,9]. Considering the hazards of Hg(II) ion and strict
environmental regulations, looking for efficient methods and materials
to remove of Hg(II) ions has become a challenging task.
Currently, there are many separation methods applied to eliminate
heavy metals in contaminated water, such as chemical precipitation,
ion exchange, membrane separation, reverse osmosis, coagulation/floc-
culation and adsorption [10,11]. Compared to other technologies re-
ported, adsorption is one of the most efficient and widely used
methods for heavy metal removal from wastewater duo to its unique
features including wide range of available materials, low-cost and easy
operation process and the suitability for the treatment of low concentra-
tions [12,13]. Consequently, many materials such as activated carbon
[14], different types of biosorbents [15–17], natural inorganic ion-
exchange materials [18,19], zeolites [20,21] and mesoporous silica

https://doi.org/10.1016/j.molliq.2019.04.023
0167-7322/© 2019 Elsevier B.V. All rights reserved.
2 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746
[22], are used to capture Hg(II) ions from aqueous solutions. Particu-
larly, mesoporous silicas has received considerable attention due to
their large surface area, high porosity, and controllable pore diameters
[23].
MCM-41, as a solid support, has gained great attention for prepara-
tion of effective adsorbents because of its high surface areas, regular
pore structure and fast adsorption kinetics [24–27]. However, consider-
ing the factor that pristine mesoporous silica surface lacks active groups
that can chelate Hg(II) ions, it is necessary to modify mesoporous silica
by anchoring ligands such as -SH and -NH2 for removal of Hg(II) ions
[28–30]. In addition, organic polymers can also be successfully grafted
to mesoporous silica surface for selective uptake Hg(II) ions [31]. To-
ward this end, functionalized mesoporous silica/organic polymers
nanocomposite with many active groups can be obtained by the grafted
functional polymers.
In order to keep in view the interesting properties of the MCM-41
and obtain the best performance for a Hg(II) ions adsorbent, in this
study, the poly(m-aminothiophenol) amino functionalized MCM-41
nanocomposite (MAP) was prepared and characterized by FT-IR, TG,
XRD, and N2 adsorption-desorption. As a good grafted polymer, the
poly(m-aminothiophenol) not only advantageously bears thiol, amino
and imino groups, but also was grafted onto functionalized mesoporous
silica via in-situ polymerization. The nanocomposite as a new adsorbent
for Hg(II) ions was investigated versus pH, initial concentration and
time to define the optimal sorption conditions, adsorption kinetics and
adsorption isotherm. In addition, in order to make full use of spent ad-
sorbents and minimize the environmental impact from conventional
methods, the Hg(II)-MAP was reused as a catalyst in the conversion of
phenylacetylene to acetophenone, which provided new an insight that
spent mercury loaded adsorbent could be re-used for the catalytic or-
ganic transformation of phenylacetylene to acetophenone.
2. Materials and methods
2.1. Materials
The diatomite (92.8% SiO2) was supplied from Jilin Kaida Diatomite
Co. Ltd. (Jilin, China). Cetyltrimethylammonium bromide (CTAB), (3-
aminopropyl) triethoxysilane (APTES), ammonium persulfate ((NH4)
2S2O8) (98%), hydrochloric acid (HCl) (37%) and sodium hydroxide
(AR) were purchased from Damao Chemical Agent Company (Tianjin,
China). m-Aminothiophenol (97%) and phenylacetylene was purchased
from Aladdin Industrial Corporation. Mercurium nitrate was purchased
from Guizhou Tongren Tailuier Chemical Plant (Guizhou, China).
2.2. Preparation of MAP
2.2.1. Preparation of MCM-41
For the preparation of MCM-41 as reported elsewhere [32]. Firstly,
5 g of diatomite powder (200 mesh) was dispersed in 20 mL of 40%
H2SO4 solution. After ultrasonic treatment for 30 min, the mixture was
mechanically stirred at 80 °C for 8 h, then filtered, washed several
times with distilled water and dried in the vacuum oven at 60 °C for
24 h, finally calcined at 450 °C for 6 h in a muffle furnace. Secondly,
2.70 g of pre-treated diatomite was introduced in a 100 mL flask with
1.02 g of sodium hydroxide and 25 mL of distilled water. The mixture
was refluxed for 4 h. After that, a solution containing CTAB (3.06 g)
and water (51 mL) was prepared, and the above mixture was trans-
ferred to the solution of CTAB, followed by stirring for 1 h. Then, the pre-
cursor was diverted into a stainless steel autoclave at 100 °C for 24 h
after the pH adjusted to 10 with 2 mol/L H2SO4. The white precipitate
formed in the autoclave was obtained by filtration, washing with deion-
ized water and ethanol and drying at 60 °C for 12 h. Finally, MCM-41
was successfully prepared when the white solid was calcined to remove
the template of CTAB at 550 °C for 5 h.
2.2.2. Preparation of MCM-41-NH2
The MCM-41-NH2 were prepared by surface modify with a silylation
agent (3-aminopro-pyl) trimethoxysilane (APTES) [33]. Typically, a sus-
pension of MCM-41 (1.00 g) in 100 mL of pyridine and 2.5 mL of
NH3·H2O was sonicated for 30 min. After ultrasonic treatment, 1 mL
of APTES was introduced to the obtained mixture under stirring,
followed by purging with nitrogen for 10 min. After vigorous stirring
at room temperature for 24 h under nitrogen atmosphere, the MCM-
41-NH2 was collected and washed repeatedly with deionized water
and ethanol, and then placed in vacuum oven dried over night at 45 °C.
2.2.3. Preparation of functionalized mesoporous silica/poly(m-
aminothiophenol) nanocomposite (MAP)
The solution containing 0.4 mL of HCl, 0.36 mmol of m-
aminothiophenol and 0.5 g of MCM-41-NH2 was sonicated at room
temperature for 30 min. After ultrasonic treatment, the temperature of
the solution was cooled at 0 °C with an ice bath under magnetic stirring
in a round-bottomed flask, followed by purging with nitrogen for
10 min. Then, the solution of (NH4)2S2O8 (0.8208 g, 20 mL distilled
water) was dropped into the above solution with continuous stirring
for 30 min under nitrogen atmosphere. The reaction mixture was per-
formed in the ice bath for 5 h under nitrogen atmosphere. The product
was filtered and washed several times with deionized water, and dried
in vacuum oven at 30 °C for 24 h. Fig. 1 provides schematic depiction of
the formation of the MAP.
2.3. Characterization
Fourier transform infrared (FT-IR) spectra of KBr pellets were per-
formed using a PerkinElmer spectrum One (B) spectrometer in the
500 cm−1-4000 cm−1. Electron scanning microscopy (SEM) of samples
were obtained using a JEOL 6500F. X-ray diffraction (XRD) patterns of
the samples were recorded by a Bruker D8 Advance equipped with
Cu-Kα radiation (λ = 1.54 A) between 1° and 10° (2θ) at 40 kV and
40 mA. Thermogravimetric (TG) analyses of samples were performed
with a Netzsch 209C under N2 flow with a heating rate of 20
°C min−1. N2 adsorption-desorption isotherms and pore size distribu-
tion of samples Barret-Joyner Halenda (BJH) methods were used to de-
termine surface area and pore size distribution of nanocomposite in the
N2 adsorption-desorption. The zeta potentials of the samples with vari-
ation of pH were measured by Zetasizer Nano ZS/ZEN3690.
2.4. Adsorption and desorption study
The adsorption study of Hg(II) ion including the effect of some phys-
icochemical parameters (pH, adsorption time, initial Hg(II) ion concen-
tration, temperature and interfering ions) were performed using MAP
as follows. Firstly, 1000 mg/L of Hg(II) ion stock solution was prepared
by dissolving a known quantity of Hg(NO3)2, and the working solutions
(50–300 mg/L) was obtained by further dilution. The initial pH solution
was adjusted from 1 to 6 with 0.8 mol/L HNO3 and NaOH. To explore the
effect of pH, 50 mL of Hg(II) ion solution (100 mg/L) with pH ranging
from 1.0 to 6.0 was mixed with 0.02 g of MAP for 60 min at 298 K;
The effect of adsorption time was investigated at pH 4,with 50 mL of
Hg(II) ion solution (100 mg/L) and 0.02 g of MAP by varying the adsorp-
tion time from 1 to 60 min. For effect of initial Hg(II) ion concentration,
0.02 g of MAP was added into 50 mL of different Hg(II) solution with
concentration ranging from 50 to 300 mg/L at pH of 4. In addition, the
concentration of Hg(II) ions after adsorption was determined by the col-
orimetric method of National Standard of China (GB/T 5750.6–2006),
meanwhile, the adsorbed amount and removal efficiency of MAP was
determined based on Eqs. (1), (2).
ðC0 −Ce Þ  V
Qe ¼ ð1Þ
m
 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746
Fig. 1. The schematic depiction of the preparation of MAP.
ðC0 −Ce Þ
R¼  100%
C0
Here Qe (mg/g) denotes adsorbed amount at equilibrium; C0 and Ce
are the initial and equilibrium concentration of Hg(II) ion (mg/L); m and
V are the mass of substrates (g) and volume of solution (L); R represents
removal efficiency (%).
In addition, for desorption study, 0.02 g of MAP was dispersed into
50 mL of Hg(II) ion solution (100 mg/L) at 298 K, pH 4 and adsorption
time of 60 min. After adsorption equilibrium, the saturated Hg(II)-
MAP was separated from the solution, freeze-dried and added to
50 ml of the mixture with HNO3 (0.2 mol/L) and thiourea (0.1 mol/L)
for 4 h to desorb the Hg(II) ions from the adsorbent. The MAP was
then separated from the eluent, washed with distilled water and
freeze-dried, finally, the regenerative adsorbent was reused in the
next adsorption step.
2.5. Catalytic performances of spent Hg(II)-MAP
After adsorption equilibrium, the saturated Hg(II)-MAP was col-
lected and freeze-dried, then, 0.0425 g of spent Hg(II)-MAP was loaded
into a round-bottomed flask with 1 mmol of phenylacetylene and 5 mL
of water. The mixture was refluxed at 90 °C for 5 h, and the yield was
monitored by HPLC. After the reaction, the device was cooled to room
temperature, and the organic layer was obtained by extraction with
ethyl acetate and dried by anhydrous magnesium sulfate. The products
were analyzed by HPLC and 1H NMR.
3. Results and discussion
3.1. Characterization of MAP
3.1.1. FT-IR analysis
FT-IR spectra of MCM-41, MCM-41-NH2 and MAP are illustrated in
Fig. 2(a). As seen in FT-IR spectra of MCM-41, the peak at 3659 cm−1
was ascribed to the stretching vibration of surface silanols (Si-OH),
while the bands at 1090 cm−1 and 800 cm−1 resulted from the asym-
metric stretching and symmetric stretching of Si-O-Si [34]. After
3
amine functionalization, the peak of surface silanols disappeared dis-
ð2Þ tinctly in FT-IR spectra of MCM-41-NH2, meanwhile, the peaks at 2976
and 2932 cm−1 were attributed to the asymmetrical stretching vibra-
tion of –CH2 groups. In addition, the peaks at 1568 and 1465 cm−1
were attributed to δNH of the -NH2 groups. These observations con-
firmed that APTES had been successfully grafted onto the MCM-41
[35]. For the MAP, the peaks at 3421 and 3110 cm-1 were assigned to
the N\\H stretching vibrations of -NH- and -NH2 groups, while the
peaks at 1620 and 1492 cm−1 were corresponded to the C_C stretching
vibrations of quinoid and benzoid rings [36]. In addition, the peak at
1373 cm−1 was assigned to the C\\N stretching of quinoid rings [37].
These indicated successful preparation of poly(m-aminothiophenol)
on MCM-41-NH2.
3.1.2. TG analysis
Fig. 2(b) shows TG curves of MCM-41, MCM-41-NH2 and MAP. Ob-
viously, the first stage of mass loss for three TG curves (below 150 °C)
could be associated with the desorption of water, meanwhile, the
weight loss between 150 and 600 °C could be ascribed to the organic
moieties of each sample. According to the curve of MCM-41, the weight
loss of 3.78% at the range of 40–150 °C was attributed to physisorbed
water, and the weight loss of MCM-41 between 150 and 600 °C
remained essentially unchanged. By comparing the TG curves of
MCM-41, a second weight loss9.21%for MCM-41-NH2 between 150
and 600 °C was attributed to the aminopropyl loaded on the surface of
MCM-41 surface, which suggested the MCM-41 were successfully func-
tionalized by the APTES. The weight loss difference between MCM-41-
NH2 and MAP was 27.89%, which was an indication of substantial an-
choring of poly(m-aminothiophenol) to the mesoporous silica surface
via in-situ polymerization.
3.1.3. XRD analysis
Fig. 2(c) displays the small-angle XRD patterns of MCM-41, MCM-
41-NH2 and MAP. The diffraction patterns of MCM-41 displayed three
reflections corresponding to d spacings of 2.5, 4.5, and 5.0 nm, which
were assigned as (100), (110), and (200) reflections, respectively.
They were consistent with the characteristic diffraction peaks of
MCM-41 reported in the literature [38,39]. In addition, although the
4 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746
Fig. 2. (a) FT-IR spectrum of MCM-41, MCM-41-NH2 and MAP; (b) TG curves of MCM-41, MCM-41-NH2 and MAP; (c) XRD patterns of MCM-41, MCM-41-NH2 and MAP; (d) Nitrogen
adsorption-desorption loops for MCM-41, MCM-41-NH2 and MAP.
intensity of the peaks of MCM-41-NH2 and MAP gradually decreased
due to the silanization and grafted polymer, the main characteristic
peak still existed, suggesting that the MAP still had a well-ordered
structure.
3.1.4. N2 adsorption-desorption isotherms and BET study
N2 adsorption-desorption isotherms and pore size distribution of
MCM-41, MCM-41-NH2 and MAP measured by N2 physisorption tech-
niques at 77 K are shown in Fig. 2(d) and Fig. S1, and the corresponding
physical properties are shown Table S1. As seen in Fig. 2(d), it was evi-
dent that the isotherms of all samples exhibited characteristic type IV
isotherms of MCM-41 according to the IUPAC classification [40]. With
increasing relative pressure, a sharp jump was observed at a relative
pressure P/P0 of ~0.48 due to capillary condensation of N2 in the litera-
ture [41]. Compared with the MCM-41, obviously, the much lower
sharp jump of MCM-41-NH2 and MAP could be explained by the re-
duced order degree of mesoporous structure due to the modification
and grafted polymer. Furthermore, the total pore volumes (Vtotal,
cm3/g), the pore diameters (DBJH, nm), and the BET surface area
(SBET, m2/g) are summarized in Table S1. Compared with the surface
areas of MCM-41 (793.51 m2/g), those of MCM-41-NH2 and MAP re-
duced to 257.12 and 239.16 m2/g, respectively. Meanwhile, compared
with the pore volume of MCM-41 (0.59 cm3/g), that of MCM-41-NH2
and MAP reduced to 0.59 and 0.25 cm3/g. In contrast, compared with
the pore size of MCM-41 (3.26 nm), that of MCM-41-NH2 increased to
4.59 nm since interconnection of the particles, and the silanization cre-
ated new big holes, but the pore size of MAP reduced to 4.35, which in-
dicated that poly(m-aminothiophenol) on MCM-41-NH2 was
successfully prepared and never blocked the tunnel structures.
3.1.5. SEM analysis
SEM images of MCM-41 (a), MCM-41-NH2 (b) and MAP (c) are
shown in Fig. 3. The MCM-41 mesoporous silica particles exhibited a
well-defined morphology with a diameter in the 300–700 nm range,
and MCM-41-NH2 showed an interconnection of the particles due to
the silanization. Compared with MCM-41 (a) and MCM-41-NH2 (b),
the MAP (c) had much rougher and denser surface, revealing that
many smaller particles had been assembled on the surface of MCM-
41-NH2, which showed the presence of polymer on the surfaces of the
MCM-41-NH2 synthesized via in situ polymerization of m-
aminothiophenol.
3.2. Effect of pH value on adsorption
In the aqueous phase, pH is one of the dominant parameters to opti-
mize, since pH variations can significantly affect the degree of metal ion-
ization and metal binding sites on the surface of the adsorbents [42].
Fig. 4(a) shows the effect of pH on the adsorption of Hg(II) ions and
Zeta potentials of MAP at the range of 1–6. It was clear to see that the
adsorbed amount of Hg(II) ions increased from 14.04 to 242.43 mg/g
 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746
Fig. 3. SEM images of MCM-41 (a), MCM-41-NH2 (b) and MAP (c,d).
with the increase of solution pH value from 1 to 4, and then decreased to
161.79 mg/g with the further increasing pH value from 4 to 6, which
could be explained as follows:
In strongly acidic medium (pH = 1), the functional groups such as
thiol groups (-SH) on the surface of MAP were protonated and lost
the chance of binding to Hg(II) ions. When the pH was increased (1
b pH b 4), the ionization degree of the functional groups decreased,
and it was consistent with the sharp reduction of Zeta potentials,
which suggested the number of available binding sites gradually in-
creased, resulting in a rapid increase in the adsorption capacity. While
the other mercury forms including Hg(OH)+ and Hg(OH)2 gradually
appeared with the pH increasing, especially, Hg2+ and HgOH+ and spe-
cies were the main form of existence at the pH range of 1–4, and the cor-
responding complexation reactions were described by the following
equations [43,44]:
ðMAPÞ−SH þ Hg 2 þ ↔ðMAPÞ−S−Hgþ þ Hþ
ðMAPÞ−SH þ H g OHþ ↔ðMAPÞ−S−Hg−OH þ H þ

maining active groups became difficult to be occupied owing to strong
ðMAPÞ−SH þ Hg OH 2 ↔ðMAPÞ−S−Hg−OH þ H2 O
These results indicated the surface complexation of the thiol groups
played an effective role in the remove of Hg(II) ions. In addition, with
the Zeta potentials decreasing, the attractive force between MAP and
Hg(II) ions due to the nitrogen lone pair electrons (-NH-) and the posi-
tive charge of Hg(II) gradually increased, and also improved the adsorp-
tion capacity of Hg(II) ions.
However, continued increase of pH value (4 b pH b 6) could lead to
the hydrolysis of Hg(II) ions and gradual formation of Hg-hydroxo spe-
cies, which generally possess lower positive charge and lower affinity to
the functional groups, meanwhile, hydroxide form of Hg(II) ions gener-
ated on the surface of MAP would block the pores and the binding sites,
5
which would prevent further adsorption [45]. Therefore, the optimum
pH for adsorption of Hg(II) ions was 4, and the corresponding surface
charge after adsorption of Hg(II) was 35.7 mV.
3.3. Effect of contact time on adsorption and adsorption kinetics
3.3.1. Effect of contact time
In order to investigate the effect of contact time on the adsorption
capacities of MAP, the time of adsorption was varied from 0 to 60 min.
The effect of contact time on the adsorption behavior of Hg(II) onto
the MAP is represented in Fig. 4(b). As seen, the adsorbed amount in-
creased rapidly at the initial stage (b10 min), however, beyond a certain
contact time (10 min), the rate of adsorption decreased and finally
reached a dynamic equilibrium. This adsorption phenomenon could
be explained as follows, firstly, the abundant and availability of active
binding sites, such as -NH2 and -SH on surface of MAP, were initially
ð3Þ available for interaction with the Hg(II) ion resulting in rapid increase
in the adsorbed amount with the increase of the contact time from 0
ð4Þ to 10 min, Secondly, as the contact time increased (N10 min), the re-
ð5Þ charge repulsion between Hg(II) ions and those already adsorbed on
the adsorbent surface, meanwhile, Hg(II) ions concentration also grad-
ually declined, which leaded to the decrease of driving force of mass be-
tween the bulk liquid phase and the solid phase, causing a decrease for
rate of adsorption. It was clear to see that the adsorbent reached equilib-
rium sorption within a very short period of time (~15 min), meanwhile,
the removal percentage and the adsorbed amount were found to be
96.56% and 242.42 mg/g, respectively.
3.3.2. Kinetic studies
To determine the suitable model for the reaction rates and mecha-
nism, it is necessary to study the kinetics of adsorption. In this study,
the experimental data obtained from the adsorption capacity (Qt) at
6 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746

Fig. 4. (a) Effect of pH on the sorption of Hg(II) ions and Zeta potentials of MAP; (b) Effect of contact time of on adsorption Hg(II) ions onto MAP; (c) Fit of kinetic data to pseudo-first-order
model; (d) Fit of kinetic data to pseudo-second-order model; (e) Fit of kinetic data to intraparticle diffusion model; (f) Effect of initial concentration on the adsorption of Hg(II) ion by MAP;
(g) Freundlich isotherm plots for the adsorption of Hg(II) ion onto MAP; (f) Langmuir isotherm plots for the adsorption of Hg(II) ion onto MAP.
 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746 7

different time intervals (t) was fitted by several kinetic models includ-
ing pseudo first order, pseudo second order and intraparticle diffusion
model to examine the controlling mechanisms of biosorption process,
chemical reaction, diffusion control, and the mass transfer process. Sub-
sequently, the adsorption capacity (Qt) at different time intervals
(t) obtained was fitted by pseudo-first and pseudo-second models to
elucidate the adsorption kinetic process, and the pseudo-first-order
and pseudo-second-order models were expressed in Eqs. (6), (7).
ln ðQ e −Q t Þ ¼ ln Q e −k1 t
t 1 1 The effect of initial Hg(II) ion concentration (C0) from 50 to 300 mg/L
¼ þ t
Q t k2 Q 2e Q t
where Qt and Qe (mg·g−1) are the adsorbed amount at time t and equi-
librium time, respectively. k1 and k2 are the pseudo-first order model
rate constant and the pseudo-second order model rate constant,
respectively.
The Hg(II) ions adsorption kinetic plots are shown in Fig. 4(c,d), and
the corresponding kinetic parameters, including correlation coefficients
(R2), k1, k2 and calculated adsorption capacity Qe(cal), are listed in
Table 1. According to Table 1, the R2(0.9999) value of the pseudo-first-
order model was higher than that of pseudo-first-order R2(0.9464),
which proved the pseudo -first-order model was more suitable to de-
scribe the adsorption kinetic. Meanwhile, the calculated Qe(cal) value
of the pseudo-second-order model was more adjacent with the experi-
mental value, which also suggested the suitability of the pseudo-
second-order kinetic model. These results illustrated the adsorption
mechanism of MAP for Hg(II) ions was the electrostatic adhesion and
chemical chelation [46].
Intra-particle diffusion model can be described by the following ki-
netic equation:
rate control step, and the total adsorption rate was controlled by both
external diffusion and internal diffusion.
Based on results of kinetic analysis, the adsorption process of Hg(II)
ions onto MAP followed the pseudo-second-order kinetic model, which
indicated that the remove of Hg(II) ions belonged to chemical adsorp-
tion by electrostatic adhesion and chelation, and the external diffusion
was determinant of the adsorption process.
3.4. Effect of initial Hg(II) ion concentration and adsorption isotherm
ð6Þ
3.4.1. Effect of initial Hg(II) ion concentration on Hg(II) ion uptake
ð7Þ
on the adsorbed amount of MAP was investigated, and the results are
shown in Fig. 4(f). As C0 varied from 50 to 100 mg/L, the adsorbed
amount increased from 123.27 to 242.42 mg/g. However, the amount
of Hg(II) ion uptake increased slowly after that. The results could be ex-
plained as follows: at less concentrations, the ratio of accessible active
sites to initial Hg(II) ion concentration is greater, which increased the
chance collision of the active sites and Hg(II) ion, while driving force be-
tween liquid phase and adsorbent gradually increase, therefore, the
adsorbed amount increased rapidly with the increase of Hg (II) concen-
tration. Whereas, at higher concentrations, although the larger initial
metal ion concentrations provide an intense driving force between liq-
uid phase and adsorbent, the number of active sites is limited. As Hg
(II) concentration was N200 mg/L, the active sites of MAP tended to be
saturated, finally the amount of Hg(II) ion uptake tended to be stable.
3.4.2. Adsorption isotherm
To further study the adsorption properties and interactions, the
equilibrium data are fit by Langmuir and Freundlich adsorption iso-
therm models. The linear form equations of Langmuir and Freundlich
isotherm models can be expressed as follows:

Q t ¼ kp t 0:5 þ C
where kp is the intra-particle diffusion rate constant, C represents a con-
stant related to the boundary layer thickness. The intra-particle diffu-
sion kinetic plot can be obtained from plot of Qt versus t0.5, shown in
Fig. 4(e), and the values of relevant parameters are shown in Table 1.
The intra-particle diffusion kinetic plot was composed of two kinetic
stages, which indicated that the adsorption process was composed of
two kinetic stages. In the first stage, the solute diffused from the solution
to the surface of the adsorbent and passed through the boundary layer,
which is described as external diffusion, and the second step described
the intra-particle diffusion, which is characterized by a gradual adsorp-
tion. Based on the value of relevant parameters including kp1 (56.48),
kp2 (2.07), C1 (90.80), and C2(227.68) in Table 1, the first stage was de-
terminant of the adsorption process. In addition, the value of C2 was
larger than C1, which indicated that internal diffusion was not the only
Table 1
Parameters of adsorption kinetic and intraparticle diffusion model.
ð8Þ Ce 1 Ce
¼ þ ð9Þ
Q e Q mK L Q m
1
ln Q e ¼ ln k F þ ln C e ð10Þ
n
where Qe and Ce (mg/g) are the adsorbed amount and ions concentra-
tion in equilibrium respectively. Qm represents the maximum adsorp-
tion capacity of the absorbent. KL is Langmuir constant. KF and n are
Freundlich constants. The separation factor (RL = 1/(1 + KLC0)) is cal-
culated to determine whether the adsorption is favorable.
According to analysis of data, the fitted plots of the Langmuir and
Freundlich isotherm model are illustrated in Fig. 4(g,h), the correspond-
ing parameters of sorption isotherm models calculated are listed in
Table 2. A remarkable correlation could be observed in the case of the
Langmuir model because the corresponding R2 (0.9991) was the higher
than R2 (0.6872) of Freundlich isotherm model, as well, the Qm
(286.53 mg/g) estimated by Langmuir isotherm was more adjacent
with the experimental value (Qe = 286.01 mg/g). In addition, the values
of the RL ([0.0415–0.0072] ≪ 1) were in the favorable boundary, which

Models Parameters Value

Pseudo-first-order equation Qe(cal) (mg/g) 70.10

k1 (min−1) 0.1491 Table 2
R2 0.9464 Langmuir and Freundlich isotherm parameters.
Pseudo-second-order equation Qe(cal) (mg/g) 245.70
Models Parameters Value
k2 (g·mg−1·min−1) 0.0061
R2 0.9999 Langmuir Qm(cal) (mg/g) 286.53
Intra-particle diffusion kp1 (mg (g min0.5)−1) 56.48 KL (min−1) 0.4616
C1 90.80 R2 0.9992
R21 0.9517 RL [0.0415–0.0072]
kp2 (mg (g min0.5)−1) 2.07 Freundlich KF 159.53
C2 227.68 n 8.1826
R22 0.7674 R2 0.6872
8 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746
showed that the adsorption of Hg(II) ions onto MAP was favorable, in-
dicating MAP was an efficient adsorbent. These results proved that the
adsorption process for Hg(II) ions followed the Langmuir isotherm.
Based on the Langmuir adsorption isotherm model, the adsorption of
Hg(II) onto MAP belonged to the monolayer adsorption process and oc-
curred on the homogeneous surface of all identical sites, which were en-
ergetically and sterically independent of the adsorbed quantity.
3.5. Effect of interfering ions
In natural water, coexisting ions may compete with Hg(II) ions on
the active sites of the adsorbents, which can affect the removal process.
To investigate the competitive adsorption, the uptake of Hg(II) on the
MAP was measured in the presence of different cations with the initial
concentration of 0.01 M, seen in Fig. 5(a). It could be seen that the
coexisting cations including Na(I), K(I), Ca(II), Mg(II) and Al(III) had
no obvious competition effect on the adsorption capacity of MAP,
which indicates that MAP has good selectivity for mercury ions.
3.6. Regeneration of MAP
Considering the practical application, the reusability is an important
technical index to evaluate an excellent adsorbent. According to the pre-
vious investigations that have considered Hg(II) desorption from thiol-
functionalized materials, the mixtures of acid and thiourea was used as
an effective eluent to recover Hg(II) from the adsorbents [13,47,48]. In
this work, several eluents including EDTA-2Na, HNO3, the mixtures of
HNO3 and thiourea were examined as the desorption solvent, the corre-
sponding results are shown Table S2. From the Table S2, the mixture of
HNO3 (0.2 mol/L) and thiourea (0.1 mol/L) was be chosen as an optimal
eluent to regeneration of the MAP, which was consistent with litera-
tures reported. The adsorption-desorption process was conducted for
5 cycles and the results were shown in Fig. 5(b). The results showed
that the adsorption capacity for Hg(II) of the recycled MAP reached
190 mg/g after 5 cycles. The reduction of the adsorption capacity
might be attributed to associated adsorbent material loss during the re-
peating experiences. Thus, the obtained results indicated that MAP ex-
hibited good reusability and good potential in the environmental
treatment.
3.7. Possible mechanism of Hg(II) adsorption onto MAP
The adsorption mechanism of Hg(II) removed by MAP usually in-
volved several kinds of interactions including surface complexation or
chelation, electrostatic attraction, ion-exchange and physical adsorp-
tion, which could be described as follows. Firstly, Hg(II) from bulk
Fig. 5. (a) The effect of coexisting cations on the Hg(II) adsorption, (b) regeneration test of MAP.
solution were adsorbed onto the surface of MAP by thiol groups via sur-
face complexation, leading to a rapid increase in the uptake of Hg(II),
and the surface complexation of the thiol groups played an important
role in the remove process of Hg(II) and was shown Fig. 6(a). Secondly,
surface chelation also increased the adsorption capacity of Hg(II) by
forming coordination bonds between Hg(II) and thiol (-SH) and imino
(-NH) according to the Fig. 6(b). In addition, the electrostatic attraction
between Hg(II) and the imino(-NH) or the ion exchange reaction be-
tween Hg(II) and the remnants of NH2 groups could also improve the
adsorption capacity of Hg(II) ions based on the Fig. 6(c). Finally, when
the surface active sites of MAP gradually reach the saturation state, ex-
cept for physical adsorption, Hg(II) may be migrated from the MAP sur-
face to the nano-pores by intra-particle diffusion and adsorbed by the
complexation reaction of Hg(II) and (MCM-41)-O− from ionization of
silanol according to the Fig. 6(d).
3.8. Comparison of MAP with other adsorbents for Hg (II) adsorption
Table 3 showed the comparison of MAP obtained in this study and
other adsorbents prepared based on mesoporous and polymer compos-
ites in terms of adsorption capacity for Hg(II) under similar operating
condition. According to Table 3, the MAP has superior adsorption capac-
ity for Hg(II) ions, therefore, the MAP will be a good candidate for Hg (II)
adsorption with simple technology and cheap cost.
3.9. Catalytic application of spent Hg(II)-MAP material
After adsorption studies, the Hg(II) adsorbed MAP was further used
for catalytic application in acetophenone synthesis, and the catalytic
transformation mechanism was proposed, as shown in Scheme 1.
Based on the Hg(II)-MAP as a catalyst, the suspension of
phenylacetylene in water was heated at 90 °C for 5 h under an open at-
mosphere. The product of acetophenone was confirmed by 1H NMR
(600 MHz, CDCl3): δ = 7.67–7.54 (m, 2H), 7.24–7.13 (m, 1H),
7.12–6.82 (m, 2H), 2.18 (s, 3H) ppm (Fig. S2), the corresponding yield
of 97.01% was determined by HPLC. In addition, no desired product
was monitored without Hg(II)-MAP under the same reaction condi-
tions, obviously, which indicated Hg(II)-MAP was a critical role in the
reaction. However, to expand the scope of this process, further compre-
hensive research is still needed to be explored.
4. Conclusions
In this work, an efficient and selective adsorbent (MAP) with high
specific surface area and rich groups was designed to adsorb the Hg
(II) ion, and subsequently the spent Hg(II)-MAP was applied for
 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746 9

Fig. 6. The adsorption mechanism of Hg(II) removed by MAP.

catalytic reactions of acetophenone synthesis. The results showed
the as-prepared MAP exhibited the excellent removal efficiency
and adsorption capacity, up to 96.56% and 242.42 mg/g within
about 15 min under pH value of 4, meanwhile, it could still remove
efficiently Hg(II) ions in the presence of the different cations or
after five cycles. The adsorption process of Hg(II) ions followed the
Table 3
Comparison of the adsorption capacity (Qe) of Hg(II) ions on MAP with other adsorbents
reported in the literature.
Adsorbent
Polypyrrole/thiol-functionalized zeolit Beta/MCM-41
Polyaniline/hexagonal mesoporous silica
nanocomposite
PAAM-NH2-MCM-41
Chitosan/MCM-41-PAA
Poly(aniline-co-o-aminophenol)/mesoporous
Silica SBA-15 composite
This study (MAP)
pseudo-second-order kinetic model, and the equilibrium data was
well fitted by the Langmuir isotherm. The efficient adsorption of Hg
(II) ions was attributed to electron-rich functional groups (-SH,
-NH- and -NH2 ) on the surface of the MAP which could strongly
bind positive Hg(II) ions via surface complexation or chelation, elec-
trostatic attraction and ion-exchange. In addition, the spent Hg(II)-
MAP material was utilized as a catalyst in the organic transformation
reaction of phenylacetylene to acetophenone with 97.01% yield. To
determine the general reaction, further ongoing researches are still
in progress. Overall, these results confirmed that MAP was not only
a rapid and selective adsorbent, but also an effective catalyst of or-
ganic transformation, which made it a good candidate for wastewa-
ter treatment to purify the Hg(II) contaminated wastewater and
Qe (mg/g)
reuse the toxic spent adsorbent for catalytic application.
47.2 [49]
51.8 [50]
Acknowledgements
177.0 [31]
164 [32] This work was supported by the Fundamental Research Funds for
218 [51] the Central Universities (N180506002), National Natural Science Foun-
dation of China (31560268), and Scientific research fund project of
242.42
Ningde Normal University (2018Y06, 2018T02, 2018Z02).
10 Y. Fu et al. / Journal of Molecular Liquids 286 (2019) 110746
Scheme 1. Catalytic transformation mechanism of phenylacetylene to acetophenone.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2019.04.023.
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