You are on page 1of 5

Chemosphere 214 (2019) 738e742

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

A biomimetic SiO2@chitosan composite as highly-efficient adsorbent


for removing heavy metal ions in drinking water
Jinyun Liu a, *, Yu Chen a, Tianli Han b, Mengying Cheng a, Wen Zhang a, Jiawei Long a,
Xiangqian Fu c
a
Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002,
PR China
b
College of Chemistry and Material Engineering, Chaohu University, Chaohu, Anhui 238000, PR China
c
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A unique biomimetic SiO2@chitosan


composite adsorbent is prepared.
 Leaf-like SiO2@chitosan shows high
adsorption performance toward
As(V) and Hg(II).
 Agglomeration and loss of adsorbents
are reduced by biomimetic structure.

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

Article history: Highly efficient adsorbents for drinking water purification are demanded since the contaminants are
Received 7 July 2018 generally in a low concentration which makes it difficult for conventional adsorbents. Herein, we present
Received in revised form a novel biomimetic SiO2@chitosan composite as adsorbent with a high adsorption capability towards
19 September 2018
heavy metal ions including As(V) and Hg(II). The hollow leaf-like SiO2 scaffold within the adsorbent has a
Accepted 29 September 2018
Available online 2 October 2018
stable chemical property; while on the surface SiO2, the chitosan nanoparticle provide a large amount of
active sites such as amino and hydroxyl groups for adsorbing heavy metal ions. The special SiO2 structure
Handling Editor: T.S. Galloway also prevents the agglomeration and loss of chitosan, which enables the efficient contact between the
functional groups of chitosan and heavy metal ions. The SiO2@chitosan composite exhibits maximum
Keywords: adsorption capacities of 204.1 and 198.6 mg g1 towards Hg(II) and As(V), respectively. In addition, the
Adsorbents removal efficiency reaches over 60% within 2 min. The adsorption performance enables the presented
Composite biomimetic adsorbent suitable for adsorbing low-concentration heavy metal ions, especially possessing a
Adsorption promising potential for drinking water purification.
Heavy metal ion
© 2018 Elsevier Ltd. All rights reserved.
Drinking water

1. Introduction

Contaminants in drinking water are mainly in the form of micro-


* Corresponding author. pollution with a low concentration, which is different from the
E-mail address: jyliu@ahnu.edu.cn (J. Liu).

https://doi.org/10.1016/j.chemosphere.2018.09.172
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
J. Liu et al. / Chemosphere 214 (2019) 738e742 739

industrial pollution containing a high concentration of toxic sub- 2. Experimental


stances (Kokkinos et al., 2018; El-Moselhy et al., 2017; Al-Qodah
and Al-Shannag, 2017). Among many contaminants, inorganic 2.1. Synthesis of CdS micro-/nanostructure
micro-pollutants mainly include heavy metal ions such as Pb(II),
As(III), Hg(II), Cu(II), and Cr(V) which are highly harmful to human The biomimetic CdS micro-/nanostructure was prepared by
body. The sources of heavy metal ions in drinking water are using dimethyl sulfoxide (DMSO) as the growth template via a
extensive including industrial production and dissolution of heavy hydrothermal method. All the chemicals were purchased from
metals in natural materials (Sener et al., 2017). The purification purchased from Baierdi Chemical Technology Co., Ltd., and used
process is commonly complicated, high-cost, and time-consuming. without further purification. First, 1 mmol of CdCl2$5H2O and
Therefore, how to efficiently remove the low-concentration heavy 1 mmol of thiourea (CH4N2O4S) were dissolved in 35 mL of deion-
metal ions from drinking water resource remains a great challenge. ized water and stirred at room temperature to form a homogeneous
Among many purification approaches, adsorption strategy using solution. Then, 0.15 mL of DMSO was added to the solution, stirring
adsorbents is currently one of the most attractive one (Onur et al., was continued for 10 min until the solution was homogeneous.
2018; Ko et al., 2018). However, because of the low concentration of Finally, the solution was transferred into a 50 mL Teflon-lined
heavy metal ions in the drinking water, it is difficult to achieve deep stainless steel autoclave and sealed, then maintained at 170  C for
adsorption. Since that, emerging adsorbents with a highly-efficient 8 h. After that, the autoclave was naturally cooled to room tem-
adsorption performance are desired. perature. The orange precipitate at the bottom was collected,
Chitosan (CS), which is obtained from deacetylation of chitin, is washed for several times with ethanol and Millipore water, and
widely existed in shells of crustacean shrimps and crabs, carapace dried at 60  C for 6 h.
of insects, cell walls of fungals and plants. CS has a good biocom-
patibility and biodegradability, and is broadly used in pharmaceu- 2.2. Preparation of hollow leaf-like SiO2
tical, chemical, papermaking and environmental protection
industries (Wu et al., 2018; Mittal et al., 2016). The solubility of CS is To achieve a hollow SiO2 structure as the carrier of CS, 0.04 g of
related to the degree of deacetylation, relative molecular mass, and CdS, 40 mL of ethanol, and 8 mL of deionized water were mixed,
viscosity. It contains a large number of functional groups including then 2 mL of aqueous ammonia solution was added and stirred for
eNH2 and eOH, which enables a good adsorption capacity towards 30 min. Subsequently, 1.6 mL of ethyl silicate solution was slowly
heavy metal ions. Researchers have reported many methods to added, and kept stirring for 2 h. The sample was collected and
modify CS such as introducing a cross-linking reaction to stabilize centrifuged. The reddish-brown precipitate was washed alternately
chitosan (Zhang et al., 2018; Taghizadeh and Hassanpour, 2017; with water and ethanol for several times, and placed in a vacuum
Ngwabebhoh et al., 2016; El-Salam et al., 2017). In addition to the oven at 60  C for 6 h. Finally, the dried sample was dispersed in a
complex operation, the quantity of functional groups decreases, diluted hydrochloric acid solution (0.2 mol L1) in a fume hood, and
which reduces the adsorption capacity of CS. stirred for 15 min. The sample was centrifuged and washed with
Here, we present a novel CS-based nanocomposite adsorbent water and ethanol for several times. The product was dried in an
consisting of a biomimetic SiO2 micro-/nanostructure and CS oven at 60  C for 6 h.
nanoparticles coating on the surface. As illustrated in Fig. 1, at first, a
CdS micro/nanostructure with a biomimetic leaf-like morphology 2.3. Preparation of SiO2@CS nanocomposite
was synthesized. Then, a layer of SiO2 was coated on the surface.
After the CdS core was removed by acid, a hollow SiO2 shell with a The CS particles were loaded on the obtained SiO2 on the basis of
leaf-shaped structure was constructed. At last, on the surface of a dissolution-deposition mechanism since the CS dissolves in acid
SiO2, a CS layer was coated through a dissolution-deposition solution and deposits in natural and alkaline surroundings. At first,
mechanism, forming a biomimetic SiO2@CS nanocomposite. In 0.05 g of CS was added into 40 mL of acetic acid solution at a pH
this composite, the leaf-like structure enables the tip of each leaf value of 3. After the CS was fully dissolved by sonication for 15 min,
contacts with each other in solution. Since that, a frame structure 0.01 g of the hollow SiO2 was added and continuously stirred for
would be formed, resulting in a remained apace between each 2 h. A certain amount of Na2CO3 was added to adjust the pH value of
SiO2@CS structure, instead of severely overlapping by tight the solution to ~8. At last, the sample was centrifuged and washed
agglomeration. It enables the sufficient exposing of adsorption sites for several times with water, and dried in a vacuum oven at 60  C
on the composite for capturing heavy metal ions in solution. The for 4 h.
prepared SiO2@CS composite exhibits a high adsorption perfor-
mance towards As(V) and Hg(II). The maximum adsorption ca- 2.4. Characterizations
pacities towards As(V) and Hg(II) are 198.6 and 204.1 mg g1,
respectively, which are much exceeding many adsorbents such as The morphology, structure and composition of the samples
iron-chitosan composite (Gupta et al., 2009), chitosan flakes (Gupta were characterized by using scanning electron microscopy (FEI
et al., 2012), cross-linked magnetic chitosan (Abou El-Reash et al., Sirione200 fieldeemission scanning microscope microscope,
2011), ethylenediamine-modified activated carbon (Li et al., 2009), FESEM), transmission electron microscopy (TEM) and high resolu-
etc. tion TEM (HRTEM, JEM-2010 Microscope equipped with Oxford
INCA EDX system, accelerating voltage 200 kV), photoelectron
spectroscopy (XPS, ESCALab MK II, Mg Ka X-rays as excitation light
source) and Philips X-ray scattering meter with Cu Ka1.5418 Å as X-
ray source). The XRD peaks of this material were compared to
standard JCPDS (Joint Committee on Powder Diffraction Standards)
cards. Fourier transform infrared spectroscopy (FTIR) was deter-
mined by a JASCO 410 spectrometer and by KBr pelleting. The
concentration of the heavy metal ion was measured on an induc-
Fig. 1. Illustration for the preparation of the SiO2@CS composite with a biomimetic tively coupled plasma (ICP) atomic emission spectrometer (Jarrell-
leaf-like structure. Ash model ICAP 9000).
740 J. Liu et al. / Chemosphere 214 (2019) 738e742

2.5. Adsorption measurements

Prior to adsorption, As(V) and Hg(II) aqueous solutions with a


series of concentrations using sodium arsenate and mercury nitrate
as ion sources were prepared, respectively. It should be noted that
the pH value of the Hg(II) solution was adjusted to 6e7 in order to
avoid the precipitation of Hg(II). At this pH value, the CS is stable
with tiny dissolution. All adsorption experiments were performed
at room temperature (298 ± 1 K). The amount of ion adsorbed (qe,
unit: mg g1) can be calculated by the following formula:

ðC0  Ce Þ  V
qe ¼ (5-1)
m

where, qe represents the amount (mg g1) of As(V) and Hg(II)


adsorbed on the nanocomposite at equilibrium, while Co and Ce
represent the concentration of the target ions (mg L1) at the Fig. 3. (aec) FESEM and (d), (e) TEM images of the CdS@SiO2.

beginning and equilibrium, respectively. V represents the total


volume (L) of the solution during the adsorption; while m repre-
sents the mass (mg) of the adsorbent.
For the investigation of the kinetic adsorption property, 20 mg of
the prepared SiO2@CS composite was dispersed into 60 mL of target
ion solution at an initial concentration of 2 ppm. Then the solution
was placed on a shaker and oscillated. Sample solutions were
collected at regular intervals, rapidly centrifuged at a high speed,
labeled for ICP measurements. For the adsorption isotherm mea-
Fig. 4. Hollow SiO2 after removing CdS: (a), (b) FESEM, and (c) TEM images.
surement, 20 mg of SiO2@CS was dispersed into 30 mL of As(V) and
Hg(II) solutions with different concentrations, respectively. The
solution was shacked in a shaker for 6 h. The residual concentration seen that there are a large number of particles on the surface of leaf
of As(V) and Hg(II) was detected by ICP to calculate the maximum SiO2 which is initially transparent and smooth (Fig. 4), indicating
adsorption capacity. the loading of CS. The diameter of the particles is between 20 and
60 nm. In the TEM image (Fig. 6c and d), the transparency of the leaf
is significantly reduced, and the edge is obviously rough, demon-
3. Results and discussion strating the coating of CS on the surface of. Furthermore, the
infrared (IR) spectroscopy was used to analyze the composition of
3.1. Structure and composition of the composites the composite. Fig. 7 shows that the IR spectrum of the SiO2@CS
exhibits a broad absorption peak at 1379, 1416, 1580 cm1, and an
As seen in Fig. 2, leaf-like CdS structure was synthesized through absorption peak at around 2868e2911 cm1, which are the char-
the hydrothermal route. Each leaf has a length of about 3 mm and a acteristic peaks of CS (Elwakeel et al., 2017; Jiang et al., 2018),
thickness between 50 and 80 nm. A uniform layer of SiO2 was further confirming the loading of CS on SiO2@CS composite.
coated on the surface of the leaf-like CdS, as displayed in Fig. 3. The
thickness of the SiO2 layer is about 50 nm. Then, the CdS@SiO2 was
dispersed in an acid solution. Due to the reaction of between acid 3.2. Adsorption properties
and CdS, a turbid yellow liquid was obtained after the reaction,
indicating the dissolution of CdS, which is confirmed in Fig. 4, As the adsorption kinetics is one of the most important factors of
showing a hollow SiO2 with a leaf shape. As seen, the hollow SiO2 the adsorbent, the time-dependent adsorption performance was
maintains a biomimetic leaf-like morphology. The shell thickness is
about 50 nm. Furthermore, in order to verify the complete removal
of CdS after dissolution with hydrochloric acid, XPS analysis was
performed. As displayed in Fig. 5, there is no Cd signal, indicating
the complete removal of CdS.
Fig. 6 displays the SEM and TEM images of the samples after
loading CS on SiO2. In the FESEM image (Fig. 6a and b), it can be

Fig. 2. (a) Low- and (b) high-magnification FESEM images of the leaf-like CdS. Fig. 5. XPS spectrum of the leaf-like CdS and the hollow SiO2.
J. Liu et al. / Chemosphere 214 (2019) 738e742 741

time was 30 min, the removal efficiency becomes stable. The rapid
increase of the adsorption efficiency at the initial stage is ascribed
to the fact that the surface of SiO2@CS composite contains a large
amount of functional groups (i.e., amine groups and hydroxyl
groups) which interact with heavy metal ions. When the adsorp-
tion time is extended, the heavy metal ions adsorbed on the
adsorbent surface would hinder the contact between the heavy
metal ions and SiO2@CS composite. In this condition, the adsorp-
tion amount of As(V) and Hg(II) gradually reaches an equilibrium.
In order to further explore the adsorption kinetics, a pseudo-
second-order model was used to fit the kinetics. The second-
order kinetics equation is expressed as follows:

t 1 t
¼ þ
qt k2 q2e qe

where qe and qt represent the adsorption capacity of the adsorbent


at the equilibrium time and at the time t, respectively; k2 represents
the rate constant for the second order reaction, and the unit is g
mg1 min1. The value of k2 can be calculated by the slope and
intercept of the line obtained by t/qt. As shown in Fig. 8b, the
Fig. 6. (a), (b) FESEM and (c), (d) TEM images of the leaf-like SiO2@CS composite.
pseudo-second-order kinetic models are well fitted with the
adsorption results in terms of the equations below:

As(V): y ¼ 0.2453x þ 0.5829 r2 ¼ 0.9964;

Hg(II): y ¼ 0.1981x þ 0.5851 r2 ¼ 0.9977

The adsorption isotherms of the SiO2@CS composites towards


As(V) and Hg(II) are displayed in Fig. 9a. The adsorption capacity of
SiO2@CS composites for Hg(II) is higher than that of As(V).
Adsorption results were fitted using Langmuir and Freundlich
adsorption models, respectively. The Langmuir model is used to
describe the homogeneous adsorption of monolayers. The
adsorption sites are uniformly distributed, and can be expressed by
the following equation:

Ce 1 Ce
¼ þ
qe qm KL qm

where Ce represents the equilibrium concentration of heavy metal

Fig. 7. IR spectra of the hollow SiO2 and the SiO2@CS composite.

investigated. In Fig. 8a, the adsorption capacity rapidly increases at


the initial stage of adsorption (~2 min). When the adsorption time
is continuously extended to 20 min, the adsorption capacity in-
creases slowly and tends to be equilibrium. When the adsorption

Fig. 9. (a) Adsorption isotherms of SiO2@CS composites towards As(V) and Hg(II); (b)
Fig. 8. (a) Adsorption kinetic curves of SiO2@CS towards As(V) and Hg(II), and (b) the Fitted Freundlich adsorption model towards As(V); (c) Fitted Langmuir adsorption
corresponding pseudo-second-order kinetics models. model towards Hg(II).
742 J. Liu et al. / Chemosphere 214 (2019) 738e742

Table 1
Comparison of maximum adsorption capacity of some adsorbents.

Heavy metal ions Adsorbents Maximum adsorption capacity (mg g1) Ref.

As(V) Magnetic chitosan/biochar composite 11.96 Liu et al., 2017


Iron-chitosan composite 22.47 Gupta et al., 2009
Biogenic Fe(III) (oxy) hydroxides 134.3 Kleinert et al., 2011
Chitosan flakes 20 Gupta et al., 2012
Chitosan thiomer 19 Singh et al., 2016
Cross-linked magnetic chitosan 62.42 Abou El-Reash et al., 2011
CeeTi oxide 40.2 Deng et al., 2010
Biomimetic SiO2@CS composite 198.6 Our study
Hg(II) Mesoporous chitosan 164 Fu et al., 2018
Poly-chitosan composite membranes 50 Genc et al., 2003
Ethylenediamine-modified activated carbon 60.9 Li et al., 2009
Dithiocarbanate-magnetite particles 140 Figueira et al., 2011
Cross-linked chitosan-phenylthiourea resin 135 Monier and Abdel-Latif, 2012
Ethylhexadecyldimethyl ammonium bromide impregnated chitosan 43.43 Shekhawat et al., 2017
Biomimetic SiO2@CS composite 204.1 Our study

ions in the remained solution with the units of mg L1, qe repre- modifications, some high-performance adsorbents will be devel-
sents the equilibrium adsorption capacity with the unit of mg g1, oped for removing both inorganic and organic pollutants in water.
qm represents the maximum adsorption capacity with the unit of
mg g1, and KL represents the Langmuir adsorption constant related Acknowledgements
to the adsorption energy and the unit is L mg1. A straight line can
be plotted from Ce by Ce/qe. The values of qm and KL can be calcu- This work was supported by the National Natural Science
lated by the slope and intercept of the straight line. Foundation of China (51672176, 21471005, 61203212, and
The Freundlich adsorption model is used to describe the het- 661573334), the Major Project of the Department of Education of
erogeneous adsorption process. The equation is expressed as Anhui Province (KJ2018ZD034), and the Intergovernmental Inter-
follows: national Scientific and Technological Cooperation of Shanghai
(17520710200).
1
In qe ¼ In Ce þ In KF
n
References
where n and KF are Freundlich constants, respectively, which
Abou El-Reash, Y.G., Otto, M., Kenawy, I.M., Ouf, A.M., 2011. Int. J. Biol. Macromol. 49,
represent the adsorption strength and the adsorption capacity. 513e522.
From lnqe to lnCe, a straight line is obtained. From the slope and Al-Qodah, Z., Al-Shannag, M., 2017. Separ. Sci. Technol. 52, 2649e2676.
intercept of the line, the values of n and KF are calculated. As seen in Deng, S., Li, Z., Huang, J., Yu, G., 2010. J. Hazard Mater. 179, 1014e1021.
El-Moselhy, M.M., Ates, A., Celebi, A., 2017. J. Colloid Interface Sci. 488, 335e347.
Fig. 9, the adsorption model of SiO2@CS for As(V) is a Freundlich El-Salam, H.M., Emad, H.M., Ibrahim, M.S., 2017. J. Polym. Environ. 25, 973e982.
adsorption model; while the adsorption for Hg(II) is a Langmuir Elwakeel, K.Z., El-Bindary, A.A., Kouta, E.Y., 2017. J. Environ. Chem. Eng 5,
adsorption model. The maximum adsorption capacity of the 3698e3710.
Figueira, P., Lopes, C.B., Daniel-da-Silva, A.L., Pereira, E., Duarte, A.C., Trindade, T.,
SiO2@CS composite towards Hg(II) and As(V) are 204.1 and 2011. Water Res. 45, 5773e5784.
198.6 mg g1, respectively. The comparison of adsorption perfor- Fu, Y., Huang, Y., Hu, J.S., 2018. Royal Soc. Open Sci. 5, 171921.
mance with some other adsorbents is shown in Table 1, which Genc, O., Soysal, L., Bayramoglu, G., Arica, M.Y., Bektas, S., 2003. J. Hazard Mater. 97,
111e125.
shows that the presented leaf-like SiO2@CS has a competitive
Gupta, A., Chauhan, V.S., Sankararamakrishnan, N., 2009. Water Res. 43,
adsorption performance for removing Hg(II) and As(V). 3862e3870.
Gupta, A., Yunus, M., Sankararamakrishnan, N., 2012. J. Chem. Technol. Biotechnol.
4. Conclusions 87, 546e552.
Jiang, T.S., Dong, M.F., Yan, L., Fang, M.L., Liu, R.F., 2018. J. Nanosci. Nanotechnol. 18,
4692e4699.
A novel biomimetic SiO2@CS composite is presented, which Kleinert, S., Muehe, E.M., Posth, N.R., Dippon, U., Daus, B., Kappler, A., 2011. Environ.
exhibits a high adsorption performance towards heavy metal ions Sci. Technol. 45, 7533e7541.
Ko, D., Mines, P.D., Jakobsen, M.H., Yavuz, C.T., Hansen, H.C.B., Andersen, H.R., 2018.
As(V) and Hg(II) in solution. The SiO2 has good mechanical strength, Chem. Eng. J. 348, 685e692.
stable chemical properties, and can effectively prevent the Kokkinos, E., Soukakos, K., Kostoglou, M., Mitrakas, M., 2018. Environ. Sci. Pollut.
agglomeration of adsorbent; while the CS nanoparticles coated on Res. 25, 12263e12273.
Li, Z., Chang, X.J., Zou, X.J., Zhu, X.B., Nie, R., Hu, Z., Li, R.J., 2009. Anal. Chim. Acta
SiO2 provide many functional groups including amino and hydroxyl 632, 272e277.
groups for adsorbing heavy metal ions. The leaf-like SiO2@CS Liu, S.B., Huang, B.Y., Chai, L.Y., Liu, Y.G., Zeng, G.M., Wang, X., Zeng, W., Shang, M.R.,
composite nanomaterials adsorbed quickly and efficiently in the Deng, J.Q., Zhou, Z., 2017. RSC Adv. 7, 10891e10900.
Mittal, A., Ahmad, R., Hasan, I., 2016. Desalination Water Treat 57, 19820e19833.
water with low-concentration heavy metal ions. The SiO2@chitosan Monier, M., Abdel-Latif, D.A., 2012. J. Hazard Mater. 209, 240e249.
composite exhibits maximum adsorption capacities of 204.1 and Ngwabebhoh, F., Erdem, A., Yildiz, U., 2016. J. Appl. Polym. Sci. 133, 43664.
198.6 mg g1 towards Hg(II) and As(V), respectively. The removal Onur, A., Ng, A., Garnier, G., Batchelor, W., 2018. Separ. Purif. Technol. 203, 209e216.
Sener, S., Sener, E., Davraz, A., 2017. J. Water Health 15, 112e132.
efficiency reaches higher than 60% within 2 min of adsorption. The
Shekhawat, A., Kahu, S., Saravanan, D., Jugade, R., 2017. Int. J. Biol. Macromol. 104,
good adsorption properties show that the presented composite has 1556e1568.
a potential for removing heavy metal ions in drinking water, Singh, P., Chauhan, K., Priya, V., Singhal, R.K., 2016. RSC Adv. 6, 64946e64961.
especially applied for rapidly adsorbing heavy metal ions with a Taghizadeh, M., Hassanpour, S., 2017. Polymer 132, 1e11.
Wu, D., Hu, L.H., Wang, Y.G., Wei, Q., Yan, L.G., Yan, T., Li, Y., Du, B., 2018. J. Colloid
low concentration. In addition, it is expected that through prepar- Interface Sci. 523, 56e64.
ing biomimetic structure, along with some target-directed surface Zhang, C.Z., Yuan, Y., Guo, Z.Y., 2018. Separ. Sci. Technol. 53, 1666e1677.