Journal of Colloid and Interface Science 395 (2013) 230240

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A comparative study on selective adsorption of metal ions using

aminated adsorbents
Len Foong Koong a, Koon Fung Lam a,b, John Barford a, Gordon McKay a,
a
Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
b
Department of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, United Kingdom

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

Article history: It is well-known that chitosan consists of amino groups for the chelation of metal ions while NH2-MCM-
Received 21 November 2012 41 has excellent adsorption selectivities for metals. This work compares both adsorption capacities and
Accepted 18 December 2012 selectivities of chitosan and NH2-MCM-41. It has been found that chitosan has adsorption capacities of
Available online 4 January 2013
1.76 mmol/g, 1.03 mmol/g and 1.30 mmol/g for Cu2+, Ni2+ and Zn2+ respectively whereas NH2-MCM-41
has adsorption capacity of 1.52 mmol/g, 0.8 mmol/g and 0.83 mmol/g for Cu2+, Ni2+ and Zn2+. The higher
Keywords: adsorption capacity in chitosan is attributed to its higher loading of amine groups. The single component
Mesoporous silica
adsorption isotherms were well-tted using Freundlich model. The binary adsorptions of Cu2+Zn2+ and
MCM-41
Chitosan
Ni2+Zn2+ systems showed similar adsorption selectivities for both adsorbents. However, chitosan has no
Selectivity preferential adsorption for Ni2+Zn2+ system while NH2-MCM-41 has a good selectivity towards Zn2+. It is
Adsorption believed that the difference can be attributed to the heterogeneous surface of chitosan due to its organic
nature. The multi-component adsorptions were best described by a multicomponent extended Freund-
lich model. Despite the surface functional group, this work indicates the importance of the adsorbent
support on selective adsorption.
2013 Elsevier Inc. All rights reserved.

1. Introduction
Adsorption is long perceived as a simple, effective environmen-
tal remediation process for the removal of heavy metals from
wastewater. In the past, activated carbon [1] and ion exchange res-
ins [2,3] are two major categories of adsorbents for metal adsorp-
tion with high capacities. Recently, adsorbents with both high
adsorption capacities and selectivities are being developed for
selective adsorption by which metal ions are separated and puri-
ed from multi-component systems simultaneously.
Chitosan, a low cost, natural material bearing nitrogen-contain-
ing functional groups derived from seafood wastes, has recently
been found to be effective for metal adsorption [4]. For instance,
Bailey et al. [5] reported that chitosan adsorbed 796 mg/g of
Pb2+, 1123 mg/g of Hg2+, 76 mg/g of Cr3+and 558 mg of Cd2+/g
respectively. Kim [6] used chitosan ake for the adsorption of chro-
mium, Pb2+ and Cd2+ with adsorption capacities around 0.5 mmol/
g. The adsorption capacity of chitosan was found to be between 1.8
and 2.8 mmol/g depending on the particle sizes [7]. Kwok and
McKay [8] studied the feasibility of arsenate ion removal from
drinking water using chitosan particles. In addition, the adsorption
selectivities of chitosan have been well reviewed by Varma et al.
Corresponding author. Fax: +852 2358 0054.
E-mail address: kemckayg@ust.hk (G. McKay).
[9]. Vold et al. [10] found that chitosan showed strong selectivity
towards Cu2+, Zn2+, Ni2+ and Cd2+ while Chen et al. [11] demon-
strated an excellent adsorption selectivity for gold ions using
chitosan.
Despite the natural-derived materials, adsorbents have also
been developed from synthetic materials. Amongst them, meso-
porous silica is widely applied for selective adsorption as it bears
large surface area, well-dened nano-structures and high exibil-
ity for surface modication. Researches have demonstrated high
capacities and excellent selectivities of metal ion adsorptions using
amino-grafted mesoporous silica [12,13]. Lam et al. [14] demon-
strated high adsorption selectivity using aminated mesoporous sil-
ica in the separation of Ag+/Cu2+ binary system. It was found that
NH2-MCM-41 preferentially adsorbed Cu2+. The adsorption selec-
tivity is modiable by changing the type of functional groups (i.e.
primary, secondary or tertiary amino-groups) on the mesoporous
silica [15]. Cu2+ was also reported to be adsorbed preferentially
from other metals such as Zn2+, Ni2+ and Co2+ by functionalized
mesoporous silica [16]. Aminated mesoporous silica could be
potentially applied for precious metal recovery [1719] and toxic
metal removal [2023].
This work aims at studying the adsorption behaviors of two
aminated adsorbents, chitosan and NH2-MCM-41 for the removal
of Ni2+, Cu2+ and Zn2+, which are commonly found from scraps of
printed circuit boards (PCBs) [24].

0021-9797/$ - see front matter 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.12.047
 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240
Nomenclature
aL Langmuir isotherm constant (L/mmol)
aF Freundlich isotherm constant (L/g)
aLF LangmuirFreundlich isotherm constant (L/mmol)
aR RedlichPeterson isotherm constant (L/mmol)
aij multicomponent Freundlich isotherm constant (dimen-
sionless)
bF Freundlich isotherm constant (dimensionless)
bR RedlichPeterson constant (dimensionless)
Co initial liquid-phase concentration (mmol/L)
Ce equilibrium liquid-phase concentration (mmol/L)
KF Freundlich isotherm constant (dimensionless)
K 0iF multicomponent Freundlich isotherm constant (dimen-
sionless)
KL Langmuir isotherm constant (L/g)
K 0L;i Langmuir isotherm constant in multicomponent (L/g)
KLF LangmuirFreundlich isotherm constant (L/g)
K0LF LangmuirFreundlich isotherm constant in multicom-
ponent (L/g)
Single component, binary and ternary adsorptions and the ef-
fects of metal concentration and solution pH on the adsorptions
are systematically studied. It would be interesting to compare
the adsorption selectivities of the adsorbents as they bear similar
functional group of primary amines, despite the fact that MCM-
41 is an inorganic matrix whereas chitosan is solely composed of
organic polymers. Another difference between the adsorbents is
that NH2-MCM-41 has homogenous surface functional groups
whereas chitosan is composed of heterogeneous functional groups
owing to the presence of acetylglucosamine and glucosamine.
2. Materials and methods
2.1. Adsorbents preparation and characterization
Chitosan for this study was sponsored by Dongguan Active
Tools Co. Ltd. The chitosan was ground and sieved to the range
of 90150 lm in particle size, followed by rinsing with boiling
water for three times to remove any impurities. The particles were
then dried at 45 C for 3 days before storing in a desiccator for fur-
ther usage. Scanning electron microscopy (JEOL, JSM-6300F) was
used to examine the physical structure of the particles while the
elemental composition (C, H, N, S) of the material was measured
using elemental analysis (EA, Elementar Vario EL III). The degree
of deacetylation, DDA, was deduced by the mass ratio of nitrogen
and carbon by the following equation:
N % 14
1 bioleaching solutions of printed circuit board using Acidithiobacillus
C % 96  24DDA %
MCM-41 adsorbent was prepared via the method described else-
where [14]. In brief, MCM-41 was synthesized by rstly mixing
3 L of Deionized (DI) water, 166 mL of ethanol, 337.5 mL of ammo-
nium hydroxide (NH4OH, Normapur, 2830 wt%) and 15 g of cetyl-
trimethylammonium bromide (CTABr, Acros, >99%). When the
CTABr was completely dissolved, 60 mL of tetraethyl orthosilicate
(TEOS, Aldrich, 98%) was added to the solution. The nal mixture
was vigorously stirred for 12 h at room conditions before ltration
using vacuum suction. The ltered cake was washed by DI water to
displace the residual synthesis solution. It was then dried in an oven
at 100 C overnight before calcination at 550 C for at least 12 h.
To graft aminopropyl groups on the mesoporous silica material,
5 g of calcined MCM-41 was added to into 250 mL of toluene
231
m weight of adsorbent (g)
n LangmuirFreundlich isotherm constant (dimension-
less)
aij competitive coefcient of modied Freundlich isotherm
(dimensionless)
qe equilibrium solid-phase concentration (mmol/g)
qmono monolayer capacity of Langmuir equation (mmol/g)
s mole fraction of sorbate in adsorbed phase
SSE sum of the squares of the error
t contact time (min)
V liquid-phase volume (L)
Subscripts
cal calculation
exp experiment
i ith component in a multisolute system
j jth component in a multisolute system
(ChromAR, >99.7%) with 2 M of 3-aminopropyltriethoxysilane (Sig-
ma Aldrich, >98%) in a round bottom ask. The reaction was taken
place under reux condition at 110 C (i.e. the boiling point of tol-
uene) for 18 h under continuous stirring. The surface-modied
MCM-41 was recovered and rinsed by toluene via vacuum ltra-
tion. Finally, the ltered cake was dried at 110 C in the oven over-
night, ground and kept in a dessicator for further use.
The qualities of the calcined MCM-41 and the NH2-MCM-41
powder were determined by X-ray diffraction (XRD, Philips 1830)
in order to conrm the characteristic MCM-41 structures. The
physical and chemical properties of the adsorbents were also
examined using scanning electron microscopy, nitrogen physisorp-
tion (Coulter SA 3100), Fourier transform infrared spectroscopy
(FTIR, PerkinElmer GX 2000) and elemental analysis. In addition,
X-ray photoelectron spectroscopy (XPS, Physical Electronics PHI
5000) was used to investigate the surface atomic concentration
of the adsorbents. The particle size distribution for NH2-MCM-41
was measured using Coulter Beckman Zeta-potential analyzer.
2.2. Adsorption studies
As the type of anion has a signicant effect on metal adsorption
[21], metal salts used in this study only consist of sulfate anions.
More specically, Copper(II) sulfate pentahydrate (CuSO45H2O,
SigmaAldrich, >98%), nickel(II) sulfate hexahydrate (NiSO46H2O,
SigmaAldrich, >99%) and zinc(II) sulfate heptahydrate
(ZnSO47H2O, SigmaAldrich, >99%) were used for this adsorption
study as sulfate salts of these metals were commonly found in
thiooxidans and Acidithiobacillus Ferrooxidans [24] and the selective
adsorption is expected to be a simple technology for the metal
recovery.
Single component adsorptions of Cu2+, Ni2+ and Zn2+, binary
component adsorptions of Cu2+Ni2+, Cu2+Zn2+ and Ni2+Zn2+ sys-
tems as well as ternary component adsorption of Cu2+Ni2+Zn2+
using both adsorbents were performed. In the experiments,
50 mL of solution with concentrations of each metal in the range
of 0.53.5 mM were prepared in 125 mL plastic bottles. The initial
pH of the solution was adjusted to pH 4.5 using 10100 lL of sul-
furic acid or sodium hydroxide, followed by adding 50 mg of adsor-
bent. The bottles were sealed and kept in a shaker at 120 rpm at
room temperature until equilibrium was reached. The equilibrium
pH of the solution was measured and the samples were then
232 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240

withdrawn and ltered using 0.22 lm syringe lters. Both initial
and nal metal concentrations of the solutions were determined
by ICP-AES (PERKIN ELMER Optima 3000XL Series). The metal
adsorption capacities of the adsorbents were calculated using the
following equation:
C 0  C e V
qe
m
where qe, equilibrium metal adsorption capacity (mmol/g); V, vol-
ume of metal solution for the adsorption (L); C0, initial concentra-
used for this study. The calculated modeling adsorption capacity,
qe,cal, was compared with the experimental adsorption capacity,
qe, for each isotherm model. The sum of the squares of the errors
(SSEs), Eq. (3), was then determined to evaluate the model tting.
The model parameters were used to minimize SSE using the solver
add-in function with Microsoft Excel. The best-tted model was
2 demonstrated with the least SSE value.
X
n
SSE qe  qe;cal 2i 3
i1

tion of metal ions in the solution (mM), Ce, equilibrium

concentration of metal ions in the solution (mM), and m, amount
of adsorbent used (g).
The effect of pH on the adsorption behaviors was also studied
by varying the initial pH of the metal solution in the range of pH
2 and 5 at constant initial metal concentrations. The effect of metal
ratio in the binary component systems was also carried out by
varying the metal composition at constant total metal concentra-
tion and pH.
2.3. Single and binary components equilibrium models
Various single component and binary adsorption models were
used to t adsorption isotherms. Table 1 summarizes the models
3. Results and discussion
3.1. Material characterization
The natural chitosan exists as bundles of bers with length
larger than a 100 lm, as shown in Fig. 1a. The chitosan is non-
porous with surface area below 10 m2/g (Table 2). Fig. 2a shows
the negligible physisorption of nitrogen. On the other hand,
NH2-MCM-41 adsorbent is successfully synthesized and its struc-
ture is conrmed using XRD (see Fig. S1 of Supplementary infor-
mation). Under scanning electron microscope, the NH2-MCM-41
particles are disc-shaped with an average diameter of 0.8 lm
(Fig. 1b).

Table 1
Summary of adsorption models applied in this study.

Model Description Assumptions Mathematical expression Model parameters Reference

Single component adsorption models
Langmuir The simplest and still the most Adsorption is at a xed number of KL, aL [26]
useful equilibrium equation denite, localized sites. Each site
can hold only one adsorbate K LCe
qe
molecule (monolayer) 1 aL C e
All sites are equivalent
No interaction between adsorbed
molecules, even on adjacent sites
Freundlich An empirical expression to Adsorption sites are not identical aF, bF [27]
correlate equilibrium isotherm The total adsorbed amount is
data summed over all types of sites qe aF C be F
Energy distribution decays
exponentially
Sips (Langmuir A three-parameter isotherm and it The adsorbate occupies two sites KLF, nLF, aLF [28]
Freundlich) is the hybrid LangmuirFreundlich n accounts for heterogeneity
isotherm isotherm system K LF C ne LF
qe
at low concentration the equation 1 aLF C ne LF
reduces to Freundlich equation
and does not obey Henrys Law
Equation approaches Langmuir
when n = 1
Binary adsorption models
Extended Predictive model provides Same as Langmuir model K 0L;i ; a0L;i (from [29,30]
Langmuir reasonable estimates for single isotherms)
multicomponent systems K 0L;i C e;i
if the qe values for each solute qe;i P
1 a0L;i C e;i
obtained from single isotherm
model are close to each other.
Extended Predictive model using single Same as LangmuirFreundlich 0
K 0LF;i ; bLFi ; a0LF;i [31,32]
Langmuir component model parameters model (from single
Freundlich K oLF;i C 1=b
e;i
LF ;i
isotherms)
equation qe;i P o 1=bLF ;j
1 aLF;j C e;j

Multicomponent Competition coefcients are Same as Freundlich model K 0F;i ; n0Fi , (from [33]
Freundlich introduced to describe the For each component in the binary !n F;i1 single isotherms),
equation different afnities of adsorbates system, the exponential energy X
N
aij (Competition
on the adsorbent surface decay is equivalent to that of qe;i K o F; iC e;i aij C e;j coefcients)
The coefcients can be deter- the single component system j1
minedfrom binary systems
 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240 233

(a) (b)

10 m 1 m

Fig. 1. SEM images of the aminated adsorbents: (a) chitosan, and (b) NH2-MCM-41.

Table 2
Physical and chemical properties of aminated adsorbents used in this study.

Adsorbent Specic surface area (m2/g) Bulk composition (wt%) Molar ratio of C:N NH2 loadinga (mmol/g)
C N
Chitosan 8.42 42.1 7.68 6.40 4.41
NH2-MCM-41 514 10.6 3.79 3.26 2.71
a
NH2 loading is determined from the nitrogen content of bulk composition of the adsorbents.

Fig. 2. Nitrogen physisorption isotherms of (a) chitosan, and (b) NH2-MCM-41.

The nitrogen physisorption isotherm of the NH2-MCM-41

(Fig. 2b) is Type IV which typically represents mesoporous struc-
ture and NH2-MCM-41 has a much higher surface area than chito-
san. Based on the bulk composition measured by elemental
analysis, the functional group loading of NH2-MCM-41 is
2.7 mmol/g which is around 40% lower than that of chitosan
(Table 2). The ratio of C:N of chitosan shows that each nitrogen
atom linked with 7.6 carbon atoms due to the organic backbone
of the structure while the ratio of NH2-MCM-41 is nearly equiva-
lent to the stoichiometric value of the grafted aminopropyl group
(i.e. CH2CH2CH2NH2).
The chemistry of the adsorbent surfaces was examined by FTIR.
Fig. 3 shows the FTIR spectra of both chitosan and NH2-MCM-41.
The spectrum of chitosan displays a strong, broad signal between
3250 and 3550 cm1, which indicates the presence of hydroxyl Fig. 3. FTIR spectra of (a) chitosan, and (b) NH2-MCM-41.
groups (OH). Since the characteristic peaks of amino groups
(NH2) are weaker and located at the same region, it does not
appear in the spectrum. However, we still observed the strong is indirect evidence for the presence of amino groups on the adsor-
characteristic peak for primary amine at 15601640 cm1 which bent. In the NH2-MCM-41 FTIR spectrum (Fig. 3b), in addition to
234 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240

the strong peak for primary amine, the weaker characteristic peaks Table 3
of amino groups at 3288 and 3360 cm1 are also clearly shown. Summary of adsorption of Ni2+, Cu2+ and Zn2+ by various adsorbents in literatures.

Adsorbent Maximum adsorption capacity (mmol/g) Reference

3.2. Single component adsorption Ni2+
Cu 2+
Zn 2+

Chitosan 1.03 1.76 1.30 This work

Single component adsorption isotherms of the selected metal NH2-MCM-41 0.80 1.52 0.83 This work
ions using chitosan and NH2-MCM-41 are shown in Fig. 4. Ceralite IR 120 1.86 1.61 2.58 [34]
Chitosan adsorbed all metals with an adsorption capacity above Imminodiacetic resin 2.18 [35]
2.27 [36]
1 mmol/g in general (Table 3) and it has higher afnity towards the
2.7 [37]
metal ions in the order of Cu2+ > Zn2+ > Ni2+. The uptake is mainly Activated carbon 0.500.68 0.791.02 0.620.87 [38]
coordinated via the chelation of metals with amino groups of the
chitosan [39], as follows:

Cu2 xRNH2 ! CuRNH2 2

x
Table 4
Stability constants of selected ions [49,50].
It is worth nothing that the hydroxyl groups (OH) of the adsor-
Metal ion Stability constant (log K)
bent may also play an additional role in the adsorption mechanism.
Studies have shown that two hydroxyl groups and one amino group NH3 OH SO2
4

grabbed a divalent metal ion whereas the fourth site of the metal Cu2+ 7.5 11.8 2.46
ion is likely occupied by a water molecule or another hydroxyl Ni2+ 4.9 9.0 2.59
group on the third carbon atom [4043]. As it is well-known that Zn2+ 4.5 11.1 2.59

nitrogen-containing groups form complex with metal ions by

chelation, the adsorption selectivity is governed by the strength
of stability constants between the metal ions and surface functional
group. For instance, Vilensky et al. [44] applied the stability con-
stant values to explain the preferential removal of Cu2+ from Cd2+.
The adsorption selectivity of Co2+, Ni2+, Cu2+ and Zn2+ using modi-
Fig. 4. Single component adsorptions of Ni2+, Cu2+ and Zn2+ by (a) chitosan, and (b)
NH2-MCM-41. The best tted models are plotted on the graphs. (Experimental
conditions: 50 mL metal solution at pH 4.5 0.2, initial metal concentration = 0.5
4 mM, 0.05 g adsorbent, equilibrium time = 15 days.)
ed polymer microbeads [45] and n-propylsalicylaldimino-func-
tionalized SBA-15 mesoporous silica [46] have also been studied
and the strength of the stability constant of metal ions and the sur-
face functional groups were successfully used to predict the adsorp-
tion selectivity. As there is a lack of the actual complexation data for
metal ions and surface functional groups, hereby, stability con-
stants of metals with selected free ligands are used as an analogy
(Table 4). From the literature values, Cu2+ has a higher stability con-
stant than Ni2+ and Zn2+ regardless of the type of ligand, therefore, it
is believed that Cu2+ interacts stronger with the surface amino
groups of chitosan than the other metals. On the other hand,
although the stability constant of Zn2+ and Ni2+ with ammonia
(NH3) is similar, the stability constant of [ZnOH]+ is higher than
[NiOH]+, thus Zn2+ is capable of forming a more stable complex with
chitosan, leading to a slightly higher adsorption capacity than Ni2+.
NH2-MCM-41 also adsorbed all metal ions by chelation and has
similar afnity towards the metal ions (Cu2+ > Zn2+ > Ni2+). It is
worth noting that the adsorption capacity of Cu2+ is almost twice
the capacities of Ni2+ and Zn2+ (Table 3). This could possibly be en-
hanced by the promotion effect of sulfate ions for Cu2+ adsorption
[25]. The metal adsorption capacities of chitosan and NH2-MCM-
41 are compared with other adsorbents reported in literature (Ta-
ble 3). Despite that, chitosan still has higher metal adsorption
capacities than NH2-MCM-41 for all metals, which is probably be-
cause it bears larger amount of surface functional groups.
The single component adsorption isotherms are modeled with
Langmuir, Freundlich and SIPS equations. Table 5 summarizes
the model parameters and the corresponding sum of squared er-
rors for comparison. By comparing the SSE values, the Langmuir
model provides better ts to the metal adsorptions using chito-
san. It is believed that the organic matrix of chitosan may reduce
the degree of interaction between adsorbed metal ions by either
steric hindrance or charge balance, so the adsorption isotherms
are well tted by the Langmuir model. In contrast, the metal
adsorptions by NH2-MCM-41 are tted by Freundlich model. De-
spite the expected homogeneity of the surface functional group
on the adsorbent, adsorbed metal species may interfere with
each other, causing a heterogeneous surface. In fact, although
SIPS equation also ts well the adsorptions using NH2-MCM-
41, it consists of one more model parameter which supposedly
should have a better result than Freundlich equation. Thus, the
simpler Freundlich equation is considered to be better for the
modeling.
 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240 235

Table 5
Model parameters of single component metal adsorptions using chitosan and NH2-MCM-41.

Adsorbent Metal Langmuir model Freundlich model SIPS (LangmuirFreundlich model)

KL aL qmax (mmol/g) SSE KF 1/n qmax (mmol/g) SSE KLF aLF bLF qmax (mmol/g) SSE
Chitosan Ni2+ 0.52 0.18 0.92 0.03 0.44 0.77 0.91 0.03 0.51 0.18 0.97 0.99 0.28
Cu2+ 17.77 9.21 1.76 0.04 1.7 0.25 1.79 0.1 10.9 5.26 0.82 1.77 0.05
Zn2+ 0.6 0.09 1.25 0.1 0.54 0.89 1.26 0.12 0.6 0.09 1 1.25 0.1
NH2-MCM-41 Ni2+ 164 204.9 0.8 0.06 0.82 0.12 0.87 0.01 101,000 122,500 0.88 0.87 0.01
Cu2+ 513 351.7 1.46 0.06 1.47 0.08 1.51 0.02 1.47 0.001 0.08 1.52 0.02
Zn2+ 45.1 54.9 0.84 0.06 0.79 0.07 0.84 0.05 98,760 124,400 0.93 0.84 0.05

Fig. 5. Binary adsorptions of Ni2+ and Cu2+ using (a) chitosan, and (b) NH2-MCM-41.
(Experimental conditions: 50 mL metal solution at pH 4.5 0.2, initial metal
concentration = 0.54 mM, Ni2+:Cu2+ = 1, 0.05 g adsorbent, equilibrium time = 1
5 days.) The best tted models are plotted on the graphs.
3.3. Binary adsorption
Binary adsorption isotherms of the metal ions using chitosan
and NH2-MCM-41 are shown in Figs. 57. The adsorption capaci-
ties and selectivities are listed Table 6. The total adsorption capac-
ities of all binary systems are higher than the single component
adsorption capacities. It is probably because of the doubled sulfate
concentrations from the metal salts in binary systems. The sulfate
ions induce a promotion effect on the adsorption as described in
[25]. This is supported by the presence of sulphur atoms on the
Fig. 6. Binary adsorptions of Cu2+ and Zn2+ using (a) chitosan, and (b) NH2-MCM-41.
(Experimental conditions: 50 mL metal solution at pH4.5 0.2, initial metal
concentration = 0.54 mM, Cu2+:Zn2+ = 1, 0.05 g adsorbent, equilibrium time = 1
5 days.) The best tted models are plotted on the graphs.
spent adsorbents measured by XPS. Becker et al. [47] also noted
the increased adsorption capacity for metal sulfate when com-
pared to chloride and nitrate species in his work of comparing hea-
vy metal adsorptions in chitosan derivatives.
In general, the adsorption selectivities of the binary adsorption
are high (Table 6). More specically, chitosan selectively adsorbs
Cu2+ from Ni2+ and Zn2+ ions, similar to the observation reported
by Juang and Shao [39]. Similar effect is also observed for
NH2-MCM-41, i.e. Cu2+ is preferentially adsorbed from Ni2+Cu2+
and Cu2+Zn2+ systems. As the adsorbents adsorb all these metals
in single component system, it is proven that the adsorption
selectivity of the binary systems cannot be estimated from the single
component adsorption capacity of the metal ions. Meanwhile, the
236 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240

Table 7
Surface compositions of the spent adsorbents measured by XPS.

Adsorbent Binary system Atomic concentrations (atm%)

S Ni2+ Cu2+ Zn2+
2+ 2+
Chitosan Ni Cu 2.75 0.15 3.64
Cu2+Zn2+ 2.64 2.62 0.04
Ni2+Zn2+ 2.09 1.46 1.43
NH2-MCM-41 Ni2+Cu2+ 1.60 0.58 3.03
Cu2+Zn2+ 1.99 2.82 0.09
Ni2+Zn2+ 0.43 0.24 1.8

Table 8
Sum of the squares of the errors (SSEs) of the binary adsorption models.

Adsorbent System SSE

Extended Extended Multicomponent
Langmuir Langmuir Freundlich
Freundlich
Chitosan Ni2+ 0.36 0.51 0.21
Cu2+
Cu2+ 0.56 4.20 0.34
Zn2+
Ni2+ 0.70 0.50 0.32
Zn2+
NH2- Ni2+ 9.59 21.5 1.11
MCM- Cu2+
41 Cu2+ 1.94 19.7 0.83
Zn2+
Ni2+ 4.00 3.58 0.05
Zn2+

The ndings from the binary adsorptions indicate two impor-

Fig. 7. Binary adsorptions of Ni2+ and Zn2+ using (a) chitosan, and (b) NH2-MCM-41.
(Experimental conditions: 50 mL metal solution at pH 4.5 0.2, initial metal
concentration = 0.54 mM, Ni2+:Zn2+ = 1, 0.05 g adsorbent, equilibrium time = 1
5 days.) The best tted models are plotted on the graphs.
stability constants of the metal ions as an indirect measurement of
the complexation ability between the metal ion and functional
group, can be used for such purpose. In this case, Cu2+ is the metal
that forms complex with the ligand most readily, resulting in an
exclusive selectivity in the binary adsorption. Similarly Inoue
et al. [48] reported selectivity in accordance to the stability con-
stants of the metal ligands of EDTA and DTPA on modied chitosan.
However, for the Ni2+Zn2+ system, the adsorption behaviors of
chitosan and NH2-MCM-41 are contradictory. Chitosan adsorbs
both metals without any selectivity whereas NH2-MCM-41 has
excellent selectivity towards Zn2+. Table 7 lists concentrations of
the adsorbed metals on the spent adsorbents and it double con-
rms the adsorption selectivities from the ICP measurements.
tant facts for designing selective adsorbents. First, in addition to
the nature of the surface functional groups, the organic matrix of
the adsorbent has a determining role on the adsorption selectivity.
Inoue et al. also reported that EDTA and DPTA immobilized on
polyallylamine resin did not exhibit similar selectivity as their
counterparts immobilized on chitosan [48]. This could be due to
the alteration of functional group orientation on the adsorbent in
which the formation of metal complex was affected. Second, the
adsorption selectivity cannot be predicted from the magnitudes
of the stability constants when these values are similar as observed
in the Ni2+Zn2+ system in chitosan.
The binary adsorption isotherms were tted by Extended Lang-
muir, Extended LangmuirFreundlich and modied Extended Fre-
undlich equations. Table 8 summarizes the SSE of the models. In
general, the multicomponent Freundlich model developed by
Sheindorf et al. [33] is found to be the best t to the experimental
data of all cases. Although it is mainly because of the additional
model parameter that provides an extra degree of freedom for the
modeling, it also indicates that it is inappropriate to ignore the

Table 6
Adsorption capacities and selectivities of metal ions using chitosan and NH2-MCM-41.

Adsorbent Binary system Adsorption capacity (mmol/g) Total adsorption capacity (mmol/g) Selectivitya
2+ 2+ 2+
Ni Cu Zn
Chitosan Ni2+Cu2+ <0.01 1.93 1.93 1
Cu2+Zn2+ 2.12 0.18 2.30 21
Ni2+Zn2+ 0.91 1.01 1.92 1.18
NH2-MCM-41 Ni2+Cu2+ 0.10 1.82 1.92 34.5
Cu2+Zn2+ 1.85 0.24 2.09 12.0
Ni2+Zn2+ 0.04 0.78 0.82 27.0
a
Adsorption selectivity is determined by dividing the ratio of adsorbed metals over the ratio of equilibrium metal concentrations in solution.
 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240 237

Table 9
Summary of competitive coefcients of multicomponent Freundlich and SSE of ternary system.

Adsorbent Metal 2 Metal 1 SSE of ternary system

Cu Ni Zn
Chitosan Cu 1 1.46  108 2.86  108 1.07
Ni 6.83  1009 1 769.92
Zn 3.50  1009 0.0013 1
NH2-MCM-41 Cu 1 1.21  105 39.15 0.34
Ni 8.30  1006 1 0.01
Zn 0.03 92.08 1

Fig. 8. pH effect on the binary adsorption using (ac) chitosan, and (df) NH2-MCM-41. (Experimental conditions: 50 mL metal solution at pH 2 to 5 0.2, initial metal
concentration = 4 mM, metal ratio = 1:1, 0.05 g adsorbent, equilibrium time = 15 days.)
238 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240

Fig. 9. Effect of metal ratio on the binary metal adsorptions using (ac) chitosan and (df) NH2-MCM-41. (Experimental conditions: 50 mL metal solution at pH 4.5 0.2,
initial metal concentration = 0.54 mM, metal ratio = 0.251, 0.05 g adsorbent, equilibrium time = 15 days.)

competition between the metal ions. The Extended Langmuir mod-
el and Extended LangmuirFreundlich model result in higher SSE
because it is assumed that there is no interaction between the
adsorbate molecules on the surfaces. The magnitudes of the deter-
mined competition coefcients from the model tting (Table 9) re-
ect the adsorption selectivity and these values are found to be
applicable for multi-component adsorption systems as well.
As a competition coefcient is essential for an accurate predic-
tion of the adsorption behavior, it would be interesting to conduct
the binary adsorption by varying the metal ratio while keeping the
total metal concentration constant. Adsorption capacities of the
metal ions are plotted against the percentage ratio of the more
dominant species, i.e. the dominant metal concentration over the
total metal concentration. It is observed that the adsorption capac-
ity of the less preferred species increased when the metal concen-
tration of the dominant metals decreased. It is because most of the
dominant metal ions are adsorbed when its concentration is low.
The unoccupied adsorption sites are then more favorable to adsorb
the remained metal ions from the solution. In contrast, the adsorp-
tion of the dominant metal increased by increasing the ratio of the
dominant metal. NH2-MCM-41 has the better adsorption perfor-
mance than chitosan because it exhibits selective adsorption at a
lower ratio of the dominant metal. In addition, the non-selective
adsorption of Ni2+Zn2+ system by chitosan (Fig. 8c) is strongly evi-
dent because the adsorption capacities of both metal ions are line-
arly proportional to the metal ratio.
The effect of solution pH on the adsorption capacity and selec-
tivity of the binary systems is performed and the results are shown
in Fig. 9. It is found that pH did not affect the adsorption selectivity
for both adsorbents, however, the adsorption capacity decreased
with the solution pH and there is negligible adsorption at pH 2
or below. The reduction of adsorption capacity is due to the pro-
tonation of the amino groups in which H+ competes for the adsorp-
tion sites with the metal ions.
 L.F. Koong et al. / Journal of Colloid and Interface Science 395 (2013) 230240
Fig. 10. Ternary adsorption of metal ions using (a) chitosan, and (b) NH2-MCM-4,
tted with Modied Extended Freundlich equation. (Experimental conditions:
50 mL metal solution at pH 4.5 0.2, initial metal concentration = 4 mM,
Cu2+:Ni2+:Zn2+ = 1, 0.05 g adsorbent, equilibrium time = 15 days.)
3.4. Ternary adsorption
Fig. 10 shows the ternary adsorption of Ni2+, Cu2+ and Zn2+ using
chitosan and NH2-MCM-41. Similar to the binary adsorption, Cu2+
is preferentially adsorbed by both chitosan and NH2-MCM-41. By
applying the Freundlich parameters from Single component
adsorption isotherms and the competition coefcients determined
from the binary adsorptions, the modied extended Freundlich
model ts well to the ternary adsorption data. Thus, it is possible
to accurately predict both adsorption capacities and selectivities
of higher-order multi-component adsorptions based on the single
component and binary adsorption.
4. Conclusions
In this work, multi-component adsorptions of Ni2+, Cu2+ and
2+
Zn using aminated adsorbents, chitosan and NH2-MCM-41, are
performed and adsorption capacity and selectivity of the adsor-
bents are compared. Chitosan has an adsorption capacity of
1.76 mmol/g, 1.03 mmol/g and 1.30 mmol/g for Cu2+, Ni2+ and
Zn2+ respectively whereas NH2-MCM-41 has an adsorption capac-
ity of 1.52 mmol/g, 0.8 mmol/g and 0.83 mmol/g for Cu2+, Ni2+ and
Zn2+. The binary adsorptions shows that chitosan preferentially ad-
sorbs Cu2+ from Cu2+Ni2+ and Cu2+Zn2+ systems. However, it does
not show any selectivity in Ni2+Zn2+ system. In contrast, NH2-
MCM-41 shows excellent adsorption selectivity towards Cu2+ in
both Cu2+Ni2+ and Cu2+Zn2+ systems while Zn2+ is selectively ad-
239
sorbed in Ni2+Zn2+ system. It is believed that the difference is due
to the heterogeneous surface of chitosan and its organic matrix.
This highlights the importance of the material nature on adsorp-
tion selectivity. Furthermore, the adsorption selectivity is found
to be predictable from stability constants of the metals with vari-
ous ligands. The modied extended Freundlich equation is found
to be applicable for predicting multi-component adsorption behav-
ior based on single component and binary adsorption model
parameters. These ndings offer an effective way for designing
selective adsorbents for metal recovery without conducting com-
prehensive experiments.
Acknowledgments
The authors gratefully acknowledge the funding from the Hong
Kong Research Grant Council. We would like to thank the Material
Characterization and Preparation Facility at HKUST for the use of
XRD, SEM, XPS and FTIR equipment as well as the Advanced Engi-
neering Material Facility for the use of Coulter SA3100 surface area
and pore size analyzer.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcis.2012.12.047.
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