The contamination of water caused by metals is a serious environmental problem due to their

toxicity, persistency and bioaccumulation tendency in nature [1]. Therefore, it is important to

remove heavy metals from water and wastewater in terms of protecting public health and
environment. Removal of heavy metals from water and wastewater can be achieved by
chemical precipitation, coagulation, solvent extraction, membrane separation, reverse
osmosis, ultrafiltration, electrochemical deposition, ion exchange and adsorption [2]. Among
these methods, adsorption is generally considered to be a simple, relatively low-cost and
effective method in removing heavy metal from water and wastewater [3–6].

The heavy metals such as Cr, Hg, Cd, and Pb evacuated into the environment have became a
serious issue relating to health and environmental owing to their high toxicity and
bioaccumulation in the human body [1].

M. Jain, V.K. Garg, K. Kadirvelu, Adsorption of hexavalent chromium from aqueous

medium onto carbonaceous adsorbents prepared from waste biomass, J.
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and thermodynamic parameters of adsorption of copper(II) ions onto
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174–185.
[3] S.S. Banerjee, D.H. Chen, Fast removal of copper ions by gum arabic modified
magnetic nano-adsorbent, J. Hazard. Mater. 147 (2007) 792–799.
[4] W.S. Wan Ngah, M.A.K.M. Hanafiah, Adsorption of copper on rubber (Hevea
brasiliensis) leaf powder: kinetic, equilibrium and thermodynamic studies,
Biochem. Eng. J. 39 (2008) 521–530.
[5] S.B Wang, T. Terdkiatburana, M.O. Tade, Single and co-adsorption of
heavy metals and humic acid on fly ash, Sep. Purif. Technol. 58 (2008)
353–358.
[6] H. Chen, G.L. Dai, J. Zhao, A.G. Zhong, J.Y. Wu, H. Yan, Removal of copper(II) ions
by a biosorbent—Cinnamomum camphora leaves powder, J. Hazard. Mater. 177
(2010) 228–236.
Many conventional methods have been used for the rapid removal of toxic metal ions from
aqueous solutions including sedimentation, chemical treatment, oxidation, electrochemical
methodology [5–13], biological treatment, reduction, precipitation, membrane filtration, ion
exchange and adsorption [14]. Among all the techniques, adsorption is a well-known
equilibrium separation process and an effective method for water decontamination
applications [15]. Adsorption was found to be superior over other traditional techniques for
water purification and decontamination in terms of initial cost, flexibility and simplicity of
design, ease of operation and insensitivity to toxic pollutants. It also does not result in the
formation of any other harmful secondary pollutant [15].

An ideal adsorbent should have a stable and insoluble matrix that offers abundant binding
sites for the adsorption of heavy metal ions [2]. Nano-materials have attracted a large amount
of attention and researchinterest due to their larger specific surface areas and abundantactive
groups. So far, many carbon nanomaterials, such as carbonnanotubes [3] and graphene [4–7],
have been used for fabricatingadsorbents to remove various organic pollutants and heavy
metalsfrom wastewater.
Recently, graphene oxide (GO) has attracted a large amount of attention due to its strong
mechanical strength and high surface area [8], which has led to many applications in
reinforced materials [9,10]. Besides, oxygen-containing functional groups on the GO surface
and _-electron system [11] offer abundant binding sites for the adsorption of heavy metals.
The effectiveness of GO has been demonstrated for the removal of heavy metals from
wastewater [12–15]. However, GO sheets tend toaggregate after adsorption due to the
decreased electrostatic repulsion between oxygen-containing groups [16].

In the past three years, we have seen intense interest grow in graphene (G). Since the first
experimental evidence of the electronic properties of G in 2004 [7], G has become the most
intensively studied material. This results from its unique electrical, electrochemical, optical
and mechanical properties. G is a new form of carbonaceous material, which possesses a
single-layer or few-layer thickness of sp2-hybridized carbon atoms arranged in a honeycomb
pattern. Many methods of synthesizing G have been proposed [8], but the most popular is the
chemical method based on the oxidation of graphite to graphene oxide (GO) and subsequent
chemical reduction of GO to G using a suitable reducing agent (e.g. hydrazine) (Fig. 1). The
oxidation approach {e.g., Hummers method [9,10]} is considered one of the most efficient
methods of low-cost, large scale production of G. Due to their huge surface area and
spectacular physical and chemical properties, G and GO have attracted the greatest interest in
many fields, including analytical chemistry. G and GO seem to be ideal sorbents in SPE or
SPME because of their huge surface area {e.g., theoretical value for G is 2630 m2 g_1 [11]}
and the hexagonal arrays of carbon atoms in G sheets that are ideal for strong interactions
with other molecules. insoluble and hard to disperse in all solvents due to strong van der
Waals interactions that can hamper sorption of organic compounds or metal ions. GO, in
contrast, possesses large quantities of oxygen atoms on the surface of GO as epoxy, hydroxyl,
and carboxyl groups [12], so GO is much more hydrophilic than G and can form stable
colloidal suspensions. GO provides rich functional groups for the formation of hydrogen
bonding or electrostatic interaction with organic compounds or metal ions. In general, G is
considered a non-polar, hydrophobic sorbent with strong affinity for carbon based ring
structures, which can be applied in reversed-phase SPE. GO contains many more polar
moieties, so it has a much more polar character than G and can therefore be applied as a
sorbent in normalphase SPE for preconcentration of organic compounds containing oxygen-
and nitrogen-functional groups and metal species (Fig. 1).
Due to the very large delocalized p-electron system, G seems to be an ideal sorbent for
organic compounds. Unfortunately, metal ions present in hydrated forms or as complexes
associated with simple anions are not asorbed on G sheets. The adsorption of metal ions
therefore requires the formation of hydrophobic complexes. A completely different situation
can be observed in the case of GO. Functional groups containing oxygen atoms have a lone
electron pair and, through sharing an electron pair, can efficiently bind a metal ion to form a
metal complex. Table 1 shows that GO has impressive adsorption capacities toward Co(II),
Cd(II), Cu(II), Cr(VI), Zn(II), Au(III), Pd(II), Pb(II), U(VI) and Eu(III) ions [26–36]. In
many cases, the adsorption capacity of GO is much higher than that of any of the currently
reported sorbents, including nanomaterials, such as modified CNTs [37]. This results from
not only the huge surface area of GO but also, first of all, the high oxygen content of GO (i.e.
30 wt.%).
Graphene, a molecular sheet of graphite, has potential applications in different fields of
material science for developing nanocomposites, sensors, supercapacitors, hydrogen storage
and optoelectronic devices [1e5]. The function of graphene in it’s burgeoning applications is
based on it’s one or more fundamental properties such as it’s excellent thermal [6],
mechanical [7], electrical [8], transport [9], gas barrier [10] and thermoelectric properties[11].
Because of these intriguing properties a great deal of interest is generated on the graphene
research and to exploit these important properties inclusion of graphene sheets within a
polymer matrix with homogeneous dispersion and a fine interface control is utmost
necessary. In graphite, the graphene layers have strong cohesive force hence it is difficult to
get exfoliated graphene sheets. To reduce the cohesive force between the graphene sheets and
also to impart specific interaction with the host polymer matrix functionalization of graphene
is very much essential. Graphite on oxidation produces graphite oxide (GO) having
hydrophilic functional groups (-OH, epoxide, -COOH) which promotes the intercalation of
water molecules into the gallery and the graphene sheets can be easily detached from each
other by sonication, thus producing highly dispersible GO sheets in aqueous medium [12e15].
These exfoliated GO sheets are usually used for different applications and/or are further
functionalized to use for targeted applications.

Graphene is a fascinating new member of carbon materials with honeycomb and one-atom-
thick structure. This excitement is greatly attributed to its excellent mechanical and
physicochemical properties (Rao et al., 2009). Recent researches have indicated that graphene
oxide proved to be a promising material to adsorb dyes and support for catalyst due to their
extraordinary mechanical strength and relatively large specific area (Ramesha et al., 2011).
Graphene oxide (GO) is an oxidized form of graphene (Dreyer et al., 2010) consisting of
various functional groups such as hydroxyl, carboxyl, and epoxy groups. One of the major
advantages with GO is that it is hydrophilic with very high negative charge density arising
due to the oxygen containing functional groups. In solution phase, GO exists as single layer.
GO can act as weak acid cation exchange resin because of the ionizable carboxyl groups,
which allow ion exchange with metal cations or positively charged organic molecules
(Ramesha et al., 2011).

Graphene oxide (GO) nanosheets are novel engineered nanomaterials with exceptional
properties, including a doubled external surface area, straight forward modification,
acceptable dispersivity, the ability to serve as a planar support for biomaterials, and high
mechanical strength. Thus, GO nanosheets have been applied in various fields for
electrochemical devices, energy storage, catalysis, cell imaging, photochemotherapy, drug
delivery, biosensors, and contamination purification [1e3].

In particular, the unique surface properties (oxygenated functional groups on the basal planes
and edges), large surface area, layered structure, and easy exfoliation into monolayers under
water mean that graphene oxide (GO) is a suitable building block for fabricating versatile
functional materials via covalent or non-covalent approaches [6,7]. In recent years, there has
been a rush of interest in functionalizing graphene oxide materials for medical and
biomedical applications.

Such advanced functional materials based on GO are applied in several interesting

applications such as the removal of pollutants [14], desalination [15], nanofluids [16], and
solid state chemistry [17], among which biosensors whose functions are based on their
electrochemical properties are predominant.
Cyclodextrins (CDs) and their derivatives have received considerable attention in the
biological field for the past few years and an increased number of reviews have been
dedicated to their biological applications [6–16]. CDs and their derivatives have wellknown
effects on drug solubility and dissolution, bioavailability, safety and stability, and their
applications in different areas of drug delivery have been also reported. However, the cavity
size of a-CD is insufficient for many biogenic amines and x-CD is expensive. Among CDs,
ß-CD is receiving increasing attention due to its low cost and cavity size suitable for the
widest range of biogenic amines in aqueous media. CDs are a well-known class of natural
host molecules obtained from the enzymatic degradation of starch [17–21]. CDs with their
largely hydrophobic cavities of variable size and numerous ways of chemical modification
are the subject of intensive electrochemical research including both their behavior in
homogeneous solutions and in thin films attached to the electrode surfaces [22–24].

Many organic and inorganic materials, such as activated carbon (Daifullah, Yakout, &
Elreefy, 2007), graphene (Wu et al.,2011; Xu, Wang, & Zhu, 2012), purolite (Balan, Volf, &
Bilba,2013), b-cyclodextrin (Ozmen, Sezgin, Yilmaz, & Yilmaz, 2008), and chitosan (Hu et
al., 2011), have been applied to removeheavy metal ions and organic substances. B-CD
produced from the enzymatic degradation of starch by bacteria is a doughnut-shape cyclic
oligosaccharide with a hydrophilic exterior and hydropho-bic internal cavity (Ozmen et al.,
2008; Pan et al., 2011). It is widely known that b-CD can form inclusion complexes with
various organic compounds and metal ions in its hydrophobic cavity through host–guest
interactions (Chen, Chen, & Chung, 2007;Szejtli, 1998). Besides, the hydroxyl groups on b-
CD are known to form stable complexes with various metal ions. Therefore the b-CD may be
favorable for contaminants removal from wastewaters. However, b-CD can be dispersed in
aqueous media due to its hydrophilic exterior, so it is difficult to be separated from the
solution using traditional separation methods after the sorption process, which may increase
the cost of industrial application and/or cause the treated water to be repolluted (Hu et al.,
2013). Therefore, many researchers undertook a lot of attempts to graft b-CD on some
supports for removal of organic compounds and heavy metal ions, such as grafting b-CD
onto attapulgite (Pan et al.,2011), chitosan (Fan et al., 2012) and Fe3O4 (Badruddoza,
Shawon,Daniel, Hidajat, & Uddin, 2013). These materials can be easily separated from the
reaction medium and reused in next sorption cycle.

Graphene oxide (GO), also called graphite oxide sheet, is a two dimensional nanomaterial
prepared from chemical oxidation of natural graphite (Allen, Tung, & Kaner, 2009; Chen et
al., 2011;Hu et al., 2013). The oxidation process of graphite to GO can introduce abundant
oxygen-containing functional groups such as epoxy,carbonyl, hydroxyl and carboxyl on the
GO surfaces (Madadranget al., 2012). These groups and large specific surface area make GO
a superb platform for loading magnetic nanoparticles and grafting b-CD (Li et al., 2012).

In order to increase the sorption ability, a great number of GO derivates have been obtained
by grafting new chemical substances such as sulfanilic acid (Huet al., 2013), EDTA
(Madadrang et al., 2012) and ethylenediamine(Ma et al., 2012) on GO backbone. Guo et al.
(2010) and Guo, Guo, Li,Wang, and Dong (2011) have prepared the cyclodextrin-
graphenehybrid nanosheets by reacting GO with cyclodextrin in the pres-ence of hydrazine.
On the basis of the above considerations, wesuspect that grafting _-CD onto magnetic
graphene oxide (MGO)will offer the possibility to combine the high sorption capacity of _-
CD and the separation convenience of MGO. Ethylenediamine,the simplest 1,2-diamine, has
similar physical–chemical proper-ties to hydrazine. Besides, the amino groups of
ethylenediamineare known to form stable complexes with various heavy metals.Therefore, in
this work, we fabricated a novel _-CD polymer namedCD-E-MGO by grafting _-CD onto
MGO through the ethylenediamine, and applied it as a sorbent to remove Cr(VI) from
aqueous solution.

The large-scale production of functionalized graphene at low cost should result in good adsorbents for water
purification.3 This is due to the two-dimensional layer structure, large surface area, pore volume and presence of
surface functional groups in these materials; the inorganic nanoparticles also prevent aggregation of the
adsorbent. Water, as is known (from several good handbooks), can be treated and purified by ultipletechniques,
such as desalination, filtration, membranes, flotation, adsorption, disinfection, sedimentation. Certainly,
adsorption has advantages over other methods (some of these will be shown in the following), such as for
example ease of operation and comparatively low cost. Adsorption is the surface phenomenon whereby
pollutants are adsorbed onto the surface of a material (adsorbent) via physical and/or chemical forces. It depends
on many factors such as temperature, solution pH, concentration of pollutants, contact time, particle size,
temperature, nature of the adsorbate and adsorbent, etc.

In a mono-component system, the maximum adsorption capacity in ultrapure water for Cd2+ was 91.29 mg g− 1.
Comparable results for the maximum adsorption capacity were obtained earlier for cadmium biosorption. 42

Cadmium (Cd), widely distributed in soils and water bodies, is harmful to both public health and natural ecosystems [1]. To eliminate these
deleterious effect, various methods have been used in removal of Cd(II) from aqueous solution such as ion exchange [2], precipitation [3]
and adsorption [4], but high cost or limited capacity restricts their application on a large scale. Recently, the rapid development of
nanoscale science and engineering is creating new opportunities to prepare cost-effective and high-capacity adsorbents [5]. Li et al. [6]
reported that surface oxidized carbon nanotubes showed high adsorption efficiency for Cd(II) removal from water. Liu et al. [7]
synthesized L-cysteine functionalized multi-walled carbon nanotubes and proposed their use as selective solid-phase extraction of Cd2+.
Very recently, graphene, a two-dimensional nanomaterial, has attracted strong interest because of its unique physicochemical properties
(e.g., theoretically surface area up to 2630 m2 g_1, which benefits for adsorption) [8]. Based on graphene or graphene composites, effective
adsorbents are made and applied in removing heavy metal ions from aqueous solution [9,10],