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Recovery of gold from mining solutions using Au(III)-imprinted polymeric

resins with pyridine, ethylenediamine and aminothiophosphate
functionalities

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DOI: 10.1080/25726641.2018.1430498

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 Mineral Processing and Extractive Metallurgy
Transactions of the Institute of Mining and Metallurgy

ISSN: 2572-6641 (Print) 2572-665X (Online) Journal homepage: http://www.tandfonline.com/loi/ympm21

Recovery of gold from mining solutions using

Au(III)-imprinted polymeric resins with pyridine,
ethylenediamine and aminothiophosphate
functionalities

Mohammed Elbushra Hassan Ahamed, Antoine Flauribert Mulaba

Bafubiandi, Ljiljana Marjanovic & Xavier Yangkou Mbianda

To cite this article: Mohammed Elbushra Hassan Ahamed, Antoine Flauribert Mulaba
Bafubiandi, Ljiljana Marjanovic & Xavier Yangkou Mbianda (2018): Recovery of gold from
mining solutions using Au(III)-imprinted polymeric resins with pyridine, ethylenediamine and
aminothiophosphate functionalities, Mineral Processing and Extractive Metallurgy, DOI:
10.1080/25726641.2018.1430498

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MINERAL PROCESSING AND EXTRACTIVE METALLURGY, 2018
https://doi.org/10.1080/25726641.2018.1430498

Recovery of gold from mining solutions using Au(III)-imprinted polymeric resins

with pyridine, ethylenediamine and aminothiophosphate functionalities
Mohammed Elbushra Hassan Ahameda, Antoine Flauribert Mulaba Bafubiandib, Ljiljana Marjanovicc and
Xavier Yangkou Mbiandaa,d
a
Department of Applied Chemistry, University of Johannesburg, Johannesburg, South Africa; bDepartment of Metallurgy – Faculty of
Engineering and the Built Environment, Mineral Processing and Technology Research Center, University of Johannesburg, Johannesburg,
South Africa; cDepartment of Chemistry, University of Johannesburg, Johannesburg, South Africa; dCentre for Nanomaterials Science
Research, Faculty of Science, University of Johannesburg, Johannesburg, South Africa

ABSTRACT ARTICLE HISTORY

New Au(III)-ion-imprinted polymers (Au(III)-IIPs) with pyridine (4-VP), ethylenediamine (EDA) or Received 24 March 2017
aminothiophosphate (ADT) functionalities were prepared and employed in recovering Au(III) Accepted 15 January 2018
ions from aqueous media. These polymers demonstrated good adsorption capability for Au
KEYWORDS
(III) ions owing to their faster kinetics adsorption, higher capacity and good recyclability. The Ion-imprinted polymers; Au
Au(III) ions kinetic data fitted well to pseudo-second-order rate equation. The equilibrium (III); adsorption; selectivity;
data were best described by the Langmuir isotherm, with the maximum adsorption capacity mining solution
of 418.41, 393.70 and 189.75 mg g–1 for IIPs with 4-VP, EDA and ADT, respectively. The IIPs
displayed excellent recognition towards Au(III) in its binary systems with Pb(II), Ni(II), Cu(II),
Mn(II) and Fe(III), Pt(IV) and Pd(II). The suitability of the developed IIPs for selective recovery
of Au(III) in real leach liquor samples and acid mine drainage spiked with standards was
successfully demonstrated.

Introduction
The unique characteristic of gold has made it com-
monly applicable in many fields including jewellery,
electronics, catalysis and environmental sectors
(Lama et al. 2008). The high demand for gold and its
natural scarcity require the best efforts to recycle it
from industrial effluents and electronic scrap (Pethkar
& Paknikar 1998; Ogata & Nakano 2005). In general,
these waste materials are treated using the aqua regia
approach and this produces solutions of gold chloro-
complexes and other base metals (Sanchez et al.
2001). These leachate solutions require further separ-
ation and recovery for the collection of the gold. As a
result, adsorbents that show efficient selectivity
capacities to recover gold from waste solution are
being sought by researchers.
Coordinating resins with various functionalities are
being extensively used for selective recovery of gold
ions from solutions of different chemical compositions
(Sanchez et al. 2004; Donia et al. 2005; Ertan & Gulfen
2009; Li et al. 2013; Monier et al. 2014; Xiong et al.
2014). It was established that gold, which is a soft
Lewis acid, forms stable complexes with soft Lewis
base (Iglesias et al. 1999). As a result, coordinating
resins bearing donor S, N or P atoms in their functional
groups have been developed to offer a selective means
of separating the precious metal of interest (Zuo &
Muhammed 1995; Arrascue et al. 2003). Ion imprint-
ing technique has been established as a method for
improving the adsorbent selectivity toward the metal
ion (Ahamed et al. 2013a). This paper focuses on the
preparation of new ion-imprinted Au(III) selective
polymers using three different coordinating mono-
mers: 4-vinyl pyridine (4-VP), N-(4-vinyl benzyl)
ethylene diamine (EDA) and N-(allyl)-N-diethyl thio-
phosphate (ADT).
A detailed examination of the role of the coordi-
nating monomer on the adsorption behaviour of
the IIP (ion-imprinted polymer) resins toward Au
(III) was conducted. In addition to optimising var-
ious parameters, the adsorption parameters for the
recovery of gold ion using these new IIPs and selec-
tivity studies with respect to selected inorganic ions
were also investigated. By virtue of nitrogen donor
atoms of the coordinating moieties, the three kinds
of IIPs were expected to exhibit dual interaction
mechanisms, namely ion exchange and coordination
mechanisms. This would occur within a single poly-
mer which could yield selective complexation at rapid
uptake rates. Furthermore, the possible applications
of the IIPs to the recovery of gold from solutions
simulating mining solution, acid mining drainage
(AMD) and acidic leach liquor of electronic scrap
were investigated.

CONTACT Xavier Yangkou Mbianda mbianday@uj.ac.za Department of Applied Chemistry; Centre for Nanomaterials Science Research, Faculty of
Science, University of Johannesburg, Johannesburg, South Africa
Supplemental data for this article can be accessed at http://doi.org/10.1080/25726641.2018.1430498
© 2018 Institute of Materials, Minerals and Mining and The AusIMM Published by Taylor & Francis on behalf of the Institute and The AusIMM
2 M. E. AHAMED ET AL.
Experimental
Chemicals and reagents
4-Vinyl pyridine, 4-vinyl benzyl chloride, diethyl
chlorothiophosphate, allyl amine and 2,2′ -Azobis(2-
methylpropionamidine) dihydrochloride (AMP) were
supplied by Sigma-Aldrich (Saint Louis, MO, U.S.A.).
Chloroauric acid (HAuCl4·3H2O), K2PtCl6 and
K2PdCl4 were obtained from South Africa Precious
Metal (South Africa). Ethylene diamine, sulphuric
acid, dimethyl sulphoxide (DMSO) (99%), triethyl-
amine, hexane, toluene, methanol, thiourea and all
metal salts were purchased from Merck (South Africa).
Ultrapure water used in all experiments was obtained
from an Elix/Milli-Q Element system (France)
(18.3 μΩ cm–1 at 25°C).
Preparation of IIPs
The synthesis of the IIPs was carried out in three steps:
(i) synthesis of the coordinating monomers, (ii) prep-
aration of metal–monomer complex and (iii) copoly-
merisation of the complex monomer with EGDMA
(cross-linker).
Preparation of the coordinating monomers
EDA coordinating monomer was prepared following
the literature procedure of Tokuyama et al. (2005).
To a dichloromethane solution (50 mL) of ethylenedia-
mine (0.67 mL, 10 mmol) was added dropwise 4-vinyl
benzyl chloride (1.41 mL, 10 mmol) over a 10-h period
under stirring. The reaction was allowed to proceed for
72 h at 25°C. The solvent was then evaporated. The
crude product was purified by flash chromatography
on silica gel with dichloromethane/methanol (9:1 v/v)
as eluent. This procedure yielded 1.50 g of the product
(85.75% yield). The product was characterised using
NMR spectroscopy with the following data obtained:
1
H NMR (DMSO-d6): δ 2.82 (t, 2H), 2.89 (t, 2H),
3.83 (s, 2H), 5.28 (d, 1H), 5.83 (d, 1H), 6.77 (dd,
1H), 7.39 (dd, 2H), 7.46 (dd, 2H). 13C NMR (DMSO-
d6, 400 MHz): δ 136.48 (=CH), 129.00, 128.49
and 126.68 (C=C, benzene ring), 112.36 (=CH2),
52.46 (benzene–CH2), 50.83 (CH2–NH), 45.65 (CH2–
NH2).
ADT coordinating monomer was prepared as fol-
lows: to a hexane/triethylamine solution (50 mL,
9:1 v/v) of diethyl chlorothiophosphate (2.25 mL,
0.03 mol) was added allylamine (4.72 mL, 0.03 mol).
The stirring was continued for 24 h at 25°C. Sub-
sequently, the solvent was removed under reduced
pressure producing pale yellow oil with a white precipi-
tate. The oil (yield = 4.39 g, 70.47%) was separated
from the solid and analysed by 1H, 13C and 31P NMR
spectroscopies. 1H NMR (CD3OD): δ 1.25 (t, 6 H),
3.52 (t, 2 H), 4.00 (q, 4 H), 5.06 (d, 2 H), 5.22 (d, 1
H), 5.84. 13C NMR (CD3OD, 400 MHz):16.11(CH3–
CH2), 44.53(CH2–CH3), 65.17(CH2–NH), 115.37
(CH=CH2) and 137.79(CH2=CH). 31P NMR:
73.15 ppm (P=S).
Formation of the pre-polymerisation complex
monomer
The complex of gold(III) ion with 4-vinyl pyridine [Au
(III)4–VPCl3] was prepared using the procedure
reported by Cinellu et al. (2009). To aqueous solution
of HAuCl4.3H2O (0.42 g, 1.07 mmol) was added 4-
vinylpyridine (0.12 mL, 1.07 mmol). The solution was
stirred for 5 min at 25°C. The resulting complex was fil-
tered and thoroughly washed with water, ethanol and
diethyl ether before being allowed to dry in vacuo.
Yield: 67%; 1H NMR (DMSO-d6): δ 8.86 (d, 2H, pyridine
ring); 8.15 (d, 2H, pyridine ring); 7.02 (q, 1H, pyridine
ring-CH=CH2); 6.60 (d, 1H, pyridine ring – CH=CH2);
5.97 (d, 1H, pyridine ring – CH=CH2. Later 0.5 mmol
of this complex was dissolved in a solution of DMSO
(1.66 mL)–toluene (1.25 mL) (Scheme 1(a)).
For the preparation of Au(III)–EDA and Au(III)–
ADT complex monomers, a solution containing either
EDA or ADT (0.5 mmol) in DMSO (0.66 mL)/toluene
(1.25 mL) was mixed with a solution of AuCl4.3H2O
(0.5 mmol in 1 mL DMSO) with continuous stirring
to form the template Au(III)/monomer complex
(Scheme 1(b,c)).
Copolymerisation of the complex monomer with
EGDMA
To the solution of pre-polymerisation complexes (pre-
pared above) were added EGDMA (12.282 mmol) and
AMP (62.5 mg). The reaction mixture was sonicated
for 5 min, purged with nitrogen, and heated to 60°C
for 24 h. The resulting polymer was milled and sieved.
25–90 μm size particles of the polymers were collected.
The imprinted Au(III) ion was then removed from the
IIPs by adding an aliquot of acidified thiourea (40 mL)
to the polymeric material (2 g), followed by stirring for
6 h. The polymer particles were then filtered and
washed thoroughly with deionised water before being
allowed to dry in an oven at 80°C for 24 h. Control
polymers were prepared in a similar way to IIPs but
without the addition of the template Au(III) ion. Typi-
cal polymerisation procedures of IIPs: 4-VP-EGDMA,
EDA-EGDMA and ADT-EGDMA are presented in
Scheme 1.
Characterisation studies
The prepared IIPs and CPs were characterised using
FTIR Attenuated Total Reflection (Perkin Elmer,
U.S.A.). Scanning Electron Microscope fitted with
energy-dispersive X-ray analysis (SEM-EDX; Thermo

Scheme 1. Schematic representation of the imprinting processes for IIP-4VP-EGDMA (a), EDA-EGDMA (b) and ADT-EGDMA (c). L
refers to 4VP, EDA or ADT.
Scientific, model 6658A-1NUS-SN, U.S.A.) was
employed to observe the morphology and surface
structure. Zeta potentials of the polymers were
measured by a Malvern Nanosizer (ZENN 3600,
U.K.). Surface area and porosity measurements were
determined by Micrometric ASAI 2020 Surface
Area and Porosity Analyser (U.S.A.). X-ray diffraction
(XRD) analyses were done using a Philips PAnalytical
Xpert PRO powder diffractometer. Inductively
coupled plasma optical emission spectroscopy (ICP-
OES; Spectro Arcos FH512, Germany) was utilised
to determine the concentration of the metal.
Adsorption studies
Aliquots of aqueous solutions of Au(III) (30 mL,
100 mg L–1 at pH 4) were contacted with different
amounts of the polymer (5, 10, 15, 20, 30, 35, 25, 40
and 45 mg).The mixture was mechanically shaken at
200 rev min−1 for 60 min, filtered and the concen-
tration of the residual Au analysed by ICP-OES. Each
experiment was carried out in triplicate. Statistical
methods were used to determine the mean values and
standard deviations.
The effect of pH on the adsorption of Au(III)
(90 mg L–1) was studied by contacting the sorbents
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 3
(10 mg) with Au(III) ion solutions (10 mL) in the pH
range 1.0–8.0. The pH of the solution was maintained
at the desired value using 0.10 M HCl or NaOH sol-
utions. The mixture was then mechanically agitated
for 60 min at 200 rev min−1, filtered and the concen-
tration of the Au metal in the filtrate was measured
using ICP-OES.
Sorption kinetics experiments were conducted by
adding Au(III) solution (10 mL, 190 mg L–1, pH 4.0)
to 10 mg polymers. The reaction mixtures were shaken
for predetermined time intervals ranging from 30 s to
90 min, filtered and the concentration of Au metal
remained in the solution was determined by ICP-OES.
Batch adsorption experiments were conducted by
adding Au(III) solution (10 mL) with different metal
concentrations (from 96.5 to 1150.0 mg L–1) to 10 mg
of polymers. The solutions were mechanically shaken
at 200 rev min−1 for 60 min at 25°C, filtered and the
concentration of Au in the filtrated was analysed by
ICP-OES.
Selectivity experiments
Competitive adsorption of Au(III) was also carried out
in a batch system. Both imprinted and control poly-
mers were employed to obtain two sets of data. An
4 M. E. AHAMED ET AL.
aqueous solution (10 mL) of Au(III) with Cu(II), Ni
(II), Pb(II), Fe(III), Pd(II) and Pt(IV) (125 mg L–1 for
each ion) was added to the polymer material (10 mg).
The pH was then adjusted accordingly to pH 4.0 and
pH 6.0. These mixtures were placed in sealed contain-
ers and mechanically shaken at 200 rev min−1 for 60
min. The residual concentration of each individual
metal was analysed by filtering the mixture before
being measured using ICP-OES. The experiments
were performed in triplicate. The distribution coeffi-
cient (Kd), selectivity coefficient (β) and relative selec-
tivity coefficient (K’) were calculated using the
following equations:
Ci − Cf V
Kd = × (1)
Cf m
KdAu(III)
bAu(III)/competitorion = (2)
Kdcompetitorion
bIIP
K′ = (3)
bCP
Reusability study
Batch sorption/desorption experiments were conducted
using an aliquot of 0.7 M thiourea + 2.0 M HCl as eluting
agent. The Au(III) ions (132 mg L–1) adsorbed onto the
prepared imprinted polymer (20 mg) was thoroughly
washed with deionised water before being allowed to
dry. Then, eluting agent (10 mL) was added to the dry
polymer. The mixture was shaken for 60 min at 200 rev
min−1 at room temperature, filtered and the concen-
tration of Au(III) ion desorbed from the polymer in the
filtrate was quantified by ICP-OES.
Results and discussion
Characterisation of Au(III)-IIPs
FTIR
FTIR spectra of the control polymers (CPs), Au(III) 4-
VP-EGDMA-IIP, Au(III) EDA-EGDMA and Au(III)-
ADT-EGDMA IIP, both loaded and leached are pre-
sented in Figure 1(a–c). It is observed that all the IR
spectra were nearly similar, suggesting that all the poly-
meric materials have almost identical structure. This
similarity originated from the high amount of
EGDMA which was used as a cross-linking monomer
during synthesis (Pakade et al. 2011). The IR spectrum
of Au(III)-IIPs is the same as that of the CPs. A distinc-
tive absorption band at ∼2985 cm–1 in all polymers is
related to (–CH3) stretching vibration. The other
characteristic strong absorption bands around 1721
and 1141 cm–1 were assigned to C=O and C–O stretch-
ing vibrations of EGDMA, respectively. Meanwhile, the
spectra of the leached IIPs differ slightly from those
unleached. For 4-VP-EGDMA IIPs (Figure 1(a)), the
absorption band at 1621 cm–1 (C=N pyridine ring)
(Cinellu et al. 2009; Yilmaz et al. 2014) for unleached
polymer moved to 1637 cm–1 in the leached polymer.
This may indicate the participation of the pyridine
ring in the metal coordination bond. It can also be
indicative of the complete removal of Au(III) from
IIP during the leaching process.
In the case of the IIPs EDA-EGDMA polymers
(Figure 1(b)), the unleached IIP FTIR spectrum
showed an N–H band of ethylene diamine group at
3410 cm−1 (stretching vibration), 1629 cm−1 (bending
vibration) and symmetric C–N–C stretching vibration
band (Lin-Vien et al. 1991) at 952 and 812 cm−1. After
leaching process, these adsorption peaks were notice-
ably shifted by about 10 cm−1, demonstrating that
there is an interaction between Au(III) ions and the
ethylenediamine groups of the polymer. Comparing
the IR spectrum of the leached and unleached ADT-
EGDMA-IIPs (Figure 1(c)), the band associated with
N–H and P=S groups appeared at 1593 and
581 cm−1, respectively (Sanchez et al. 2001). It is also
observed that the peaks of the unleached IIP shifted
to 1559 and 593 cm−1, in the leached polymer. More-
over, the clear intensity and the number of bands
between 1049 and 653 cm−1 related to C–C–O, P–N
and P–O–C (Lin-Vien et al. 1991) in the unleached
IIP changed significantly after leaching. These obser-
vations confirm the coordination of the Au(III) ion
with the P=S group in the ADT-EGDMA polymer.
Scanning electron microscopy
SEM examination of the 4-VP-EGDMA, EDA-
EGDMA and the ADT-EGDMA coordinated polymers
for both leached IIP and CP particles were undertaken
to attain a better understanding of the effect of imprint-
ing Au(III) ions in the IIPs. As observed, the three
kinds of IIPs displayed a porous structure (see Fig. S1
(a,c,e)). This could be a result of the removal of Au
(III) on the surface of the coordinated imprinted poly-
mer leaving behind numerous voids. This observation
suggests a successful imprinting of the polymers. Note-
worthy, there are noticeable morphological differences
between the three types of IIPs. IIP 4-VP-EGDMA (see
Fig. S1(a)) exhibited a clearly porous structure and to a
lesser extent than IIP EDA-EGDMA (see Fig. S1(c))
and ADT-EGDMA (see Fig. S1(e)), as evident by the
large pore size. The porous material offers a higher
reactional surface and good diffusivity (Santos et al.
2012). In the absence of imprinting process (CPs)
(see Fig. S1(b,d,f)), smooth surface materials were
observed on non-imprinted polymers.
Energy-dispersive X-ray spectroscopy (EDX)
analysis
EDX was employed for the identification of elements in
the Au(III)-IIPs. Fig. S2(a,c,e) confirms the incorpor-
ation of the coordinated monomer within the

Figure 1. FTIR spectra of 4-VP-EGDMA (a); EDA-EGDMA (b) and ADT-EGDMA (c) polymers.
unleached imprinted matrices of 4-VP-EGDMA and
EDA-EGDMA-based polymers. This was by virtue of
the presence of N element peak, and with the existence
of N, S and P for IIP ADT-EDGMA observed. Further-
more, an Au(III) signal was clearly noted for the three
kinds of unleached IIP particles. However, subsequent
to the leaching process, the peak due to Au disappeared
(Figure 1(b,d,f)) suggesting complete removal of the
template ion Au(III). This result is in good agreement
with the FTIR results (Figure 1(a–c)) that indicated the
successful removal of Au(III) ions from the polymer
after the leaching process.
Surface area and pore size
The surface area and pore diameter measurements for
the IIPs and their corresponding CPs particles are sum-
marised in Table S1. The results demonstrate that the
surface area and the pore diameter for both IIPs were
higher compared to CPs. This could be attributed to
the fact that leaching of Au(III) ions from IIPs particles
left considerable amounts of imprinting cavity sites,
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 5
which became accessible for nitrogen adsorption in
the BET measurement thereby increasing the surface
area. The surface area and the pore diameters for IIP
particles prepared by three different coordinated
monomers were 270.705 m2 g–1 and 225.615 Å for 4-
VP-EGDMA, 263.830 m2 g–1 and 219.931 Å for EDA-
EGDMA, and 258.259 m2 g–1 and 184.886 Å for
ADT-EGDMA, respectively. The surface area and the
porosity differences could have varying implications
on the adsorption performance and selectivity par-
ameters of Au(III) obtained by the three EGDMA-
based polymers.
Adsorption studies
Effect of adsorbent quantity on the extraction of
Au(III) by the polymers
The influence of the adsorbents quantity on the extrac-
tion efficiency of Au(III) is presented in Figure 2.
Clearly, the extraction efficiency increased with an
increase in the adsorbent amount between 5 mg and
20 mg (corresponding to an adsorbent dose of 0.2
6 M. E. AHAMED ET AL.
Figure 2. Effect of adsorbent quantity on the extraction of Au(III) by ion-imprinted and control 4-VP-EGDMA, EDA-EGDMA and ADT-
EGDMA polymers.
and 0.7 g L–1, respectively). This is due to the existence
of a high number of the unoccupied adsorption sites on
the polymer. Thereafter, no significant increases in the
extraction efficiency were observed with an increase in
the adsorbent quantity. This might be due to the ten-
dency of the polymer to aggregate at a higher adsorbent
quantity which effectively decreased the surface area
resulting in less accessible adsorption sites for Au(III)
ions (Wang et al. 2011). The IIPs exhibited more
than 80% Au(III) uptake compared to the CPs with
an extraction efficiency of less than 60%. The better
performance of IIPs compared to CPs could be
ascribed to the fact that cavities created on the surface
of the imprinted polymer during the imprinting pro-
cess facilitate the fast binding of template ions to the
recognition sites of IIPs. The maximum gold uptake
was found when the quantity of the polymers was
30 mg (equivalent to 1.0 g L–1). This amount of poly-
mer was used for the subsequent adsorption
experiments.
Effect of pH
The binding affinity of the studied polymers is highly
dependent on the pH of the solution. This is because
of the charge density on the adsorbent, as well as the
speciation chemistry of the adsorbing ions, changes
with the solution pH. Therefore, the Zeta potentials
of the three imprinted and control polymers (4-VP-
EGDMA, EDA-EGDMA and ADT-EGDMA) under
different solution pH values were studied and are pre-
sented in Figure 3(a). It can be observed that the IIP
and CP of EDA-EGDMA had of zero charge (ZPC,
the charge density on the surface at this pH is zero)
at about pH 7.3. In contrast, the IIPs and CPs of 4-
VP-EGDMA and ADT-EGDMA beads had a zero
point charge at about pH 6.0 and pH 5.5, respectively.
Consequently, these polymers had positive zeta poten-
tials when the pH < ZPC and had negative zeta poten-
tial at pH > ZPC. The positive zeta potentials of the
adsorbents would favour the adsorption of metal ion
complexes which carry negative zeta potentials in
solutions.
It is also evident from the speciation chemistry of
gold chloro complexes that many negative gold
chloro-species may be present in the solution. The
dominant species of these anions depend on the sol-
ution acidity as well as chloride concentration (Arras-
cue et al. 2003). Under the selected experimental
conditions of 2×10−2 M chloride concentration,
AuCl–4 was the predominant complex when the pH
was below 3.2. Other chloro-species such as AuOHCl–3
and Au(OH)2Cl–2 are found at pH 3.2–5.0 and 5.0–6.0,
respectively. In the alkaline solutions (pH > 8.0), Au
(OH)–4, Au(OH)3 and Au(OH)3Cl– coexist and/or are
predominant (Arrascue et al. 2003).
Figure 3(b) shows the influence of pH on Au(III)
adsorption by the Au(III)-imprinted and control poly-
mers at pH values between 1.0 and 8.0. At all pH levels,
the IIPs showed higher extraction efficiency of Au(III)
values compared to the CPs, indicating the occurrence
of specific interactions between the recognition active
sites and Au(III) ions. In addition, for all polymers,
the maximum extraction was obtained at pH 4.0. A
decrease in Au(III) uptake was observed at pH < 4 for

Figure 3. Zeta potential curves versus pH (a) and effect of pH on the adsorption capacity of Au(III) onto ion-imprinted and control 4-
VP-EGDMA, EDA-EGDMA and ADT-EGDMA polymers (b).
all polymers which may be due to the existence of gold
(III) as chloroauric acid (HAuCl4) which could not be
readily adsorbed by the positive adsorption sites (Ebra-
himzadeh et al. 2011). Another possible contributing
factor to the observed decline in adsorption efficiency
could be the competition between Cl– and the
chloro-anionic species of gold for adsorption on the
protonated nitrogen active sites of the polymers (Li
et al. 2013). Above pH 4.0, the adsorption capacities
of all the polymers declined. This may be due to the
decreasing of the chloro gold complexes concen-
tration as well as deprotonation of the surface active
sites, which resulted in a lowering of the electrostatic
attraction between the AuCl–4 and the adsorbent sites
(Ramesh et al. 2008). Based on these considerations,
the dominant adsorption mechanism under acidic
conditions (below ZPC) was the electrostatic inter-
action coupled with ion exchange. At pH > ZPC,
where the negatively charged surface hindered the
electrostatic adsorption, gold may coordinate with
donating nitrogen (4-VP, EDA) or sulphur and
nitrogen (ADT) atoms of ligands during adsorption.
As a consequence, the most probable mechanism for
the adsorption of Au(III) onto the prepared poly-
mers is a coupling of electrostatic and coordination
mechanisms.
Effect of contact time and kinetic studies
Uptake–time dependence graphs are presented in
Figure 4, where the percentage extraction is plotted
versus time of equilibration. The adsorption of gold
onto the polymers took place in two distinct stages.
In the initial step, there was a rapid increase in the
uptake of the Au(III) ions on the vacant external sur-
faces of the imprinted polymers. This stage was com-
pleted within about 5 min for IIP 4-VP-EGDMA and
40 min for the other two imprinted polymers. The
observed faster uptake of Au(III) onto the IIP 4-VP-
EGDMA compared to the other two IIPs could be
due to its larger surface area and porous structure
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 7
making the functional groups easily accessible to Au
(III) (Trochimczuk 2001), which is in agreement with
findings regarding the surface area and pore size dis-
cussed earlier (see Table S1). After attaining equili-
brium (after 5 and 40 min) in the second step, there
was no further increase in the Au(III) uptake owing
to the occupation of all adsorption sites by the adsor-
bate ion.
Similar studies on Au(III) uptake by several sorbents
revealed that the optimum equilibrium adsorption time
ranged between 1.5 and 90 h (Sanchez et al. 2001; Kılıc
et al. 2005; Bratskaya et al. 2012; Ahamed et al. 2013b).
In this study, the adsorption rate appeared to be fast
(5–60 min), which can minimise the energy consump-
tion, thus the Au(III)-imprinted polymers could be
economical for practical extraction of Au(III) ions in
effluent treatment. It is also noted from Figure 4 that
the IIPs have faster Au(III) uptake than CPs, thus
demonstrating the accessibility of the recognition
sites on the IIP surface for interaction with adsorbate
ion. For subsequent adsorption studies, a contact
time of 60 min was employed.
The investigation of the adsorption kinetics is valu-
able for determining the adsorption mechanism and
for evaluating the feasibility of the adsorption. In this
regard, the metal sorption data was subjected to the
pseudo-first-order kinetic analysis as well as pseudo-
second-order kinetic analysis. Table 1 summarises the
fitting parameters obtained. The validity of each
model is judged on the basis of the correlation coeffi-
cient (R 2) as well as the theoretical qe (cal) value. The
results in Table 1 show that the adsorption of Au(III)
ions onto the three IIPs and their corresponding CPs
correlate better with the pseudo-second-order kinetic
model (R 2 = 0.9995–0.9999) than with the pseudo-
first-order kinetic model (R 2 = 0.8562–0.9809). This
indicates that the rate-limiting process for the adsorp-
tion of Au(III) onto IIPs and CPs could be chemisorp-
tion that involved electron sharing between the
adsorbate and adsorbent (Liu et al. 2011). In addition,
8 M. E. AHAMED ET AL.

Figure 4. Effect of contact time on the adsorption of Au(III) by 4-VP, EDA and ADT-EGDMA ion-imprinted and control-based
polymers.

Table 1. Parameters of the pseudo-first-order, pseudo-second-order, intra-particle diffusion and liquid film diffusion for the
adsorption of Au(III) ions on the studied resin.
Polymer Pseudo-first-order kinetics Pseudo-second-order kinetics
qe (exp) (mg g−1) k1 (min-1) qe (cal) (mg g−1) R2 k2 (g mg−1 min−1) qe (cal) (mg g−1) R2
IIP 4-VP 110.110 0.324 25.262 0.9754 0.102 105.931 0.9999
CP 4-VP 67.350 0.003 55.017 0.8794 0.007 68.871 0.9997
IIP EDA 100.500 0.012 30.718 0.9809 0.004 102.249 0.9995
CP EDA 52.322 0.002 68.568 0.9501 0.007 53.362 0.9993
IIP ADT 66.450 0.004 63.394 0.9635 0.003 68.681 0.9987
CP ADT 44.691 0.002 79.128 0.8562 0.005 46.361 0.9995
Intra-particle diffusion Liquid film diffusion
Polymer kid (mg g–1 min0.5) Intercept (mg g–1) R2 kfd (min–1) Intercept (mg g–1) R2
IIP 4-VP 12.455 80.821 0.9709 0.324 1.487 0.9754
CP 4-VP 1.864 51.716 0.9353 0.054 1.349 0.9474
IIP EDA 2.815 75.007 0.9830 0.031 1.473 0.9936
CP EDA 1.382 39.688 0.9710 0.033 1.471 0.9467
IIP ADT 2.744 41.583 0.9856 0.033 1.0403 0.9896
CP ADT 2.127 26.723 0.9173 0.045 0.9107 0.9723

this could also imply that the equilibrium data con-
forms to the Langmuir isotherm. This is later con-
firmed by the adsorption isotherm analysis.
It is also evident that the rate constant for pseudo-
second order (k2) of the Au(III)-IIP sorbents strongly
depends on the polymer porosity and type. The k2
value for IIP 4-VP-EGDMA is greater than IIP-
EGDMA EDA by a factor of 26 and IIP ADT-
EGDMA by a factor of 34, thus indicating the high affi-
nity of Au(III) to bind with 4-VP based IIP compared
to the other two IIPs. Again, the porous matrix struc-
ture of IIP 4-VP-EGDMA structure may result in
favourable penetration by the Au(III) ions, thereby
boosting the interaction of the pyridine active site
with the adsorbate ions. On the other hand, the depen-
dence of k2 on the polymer type can be explained on
the basis of the electrostatic affinity between their pro-
tonated active sites and the negatively charged gold
complexes (kinetic study conducted at pH 4). Accord-
ing to zero point charges of the studied polymers
(Figure 3(a)), it is anticipated that the value of k2 for
IIPs should follow the order EDA > 4-VP > ADT.
However, it was found that the order of the k2 values
is 4-VP > EDA > ADT. This is because the stability
of the protonated pyridine is higher than aliphatic
amine since the cationic pyridinium is stabilised by
the aromatic system. As a result, the ion-pair adduct
of gold chloro complexes with the polymer containing

Figure 5. Intra-particle diffusion plot (a) and liquid film diffusion plot (b) for the adsorption of Au(III) onto 4-VP-EGDMA, EDA-
EGDMA and ADT-EGDMA imprinted and control polymers.
pyridine (IIP 4-VP-EGDMA) is more stable than that
with an aliphatic amine (IIP EDA-EGDMA and IIP
ADT-EGDMA).
To investigate if the diffusion of the adsorbate from
the bulk liquid to the adsorbent surface is the rate
controlling step, the uptake time data was treated
according to Fick’s diffusion law. The plot of qt versus
t 0.5 gave two separate lines, neither of which passed
through the zero point (Figure 5(a)), thus suggesting
that intra-particle diffusion is not the only rate-deter-
mining step. Moreover, the intra-particle diffusion
constants (Table 1) show that the rate of uptake
(Kid) of Au(III) ions by IIPs was higher than that of
CPs. This finding indicates that the diffusion of Au
(III) ions within the pores on the surface of the IIPs
was much higher than that of CPs, resulting in the
strong interaction of Au(III) ion with the reactive
functional groups (Atia 2005; Ahamed et al. 2013b).
It was also noted that the values of the intercept
were larger for IIPs than for CPs which further
suggests better intra-particle diffusion of gold ions
in the IIPs during the adsorption process. Addition-
ally, the magnitude of these two parameters for IIP
4-VP-EGDMA is much greater than those of the
other two IIPs. One possible reason for the variation
in the intra-particle diffusion behaviour through the
different polymers may be linked to their differences
in morphology.
To verify the role of liquid film diffusion in gov-
erning the gold uptake, the fractional attainment of
equilibrium (F) was plotted against time and dis-
played in Figure 5(b). The fitting parameters listed
in Table 1 show high correlation coefficients, ranging
from 0.9467 to 0.9936, suggesting that the adsorption
process also followed the liquid film diffusion
process.
Effect of initial concentration and adsorption
isotherms
Figure 6 displays the relation between the uptake of Au
(III) ions by the three types of IIPs and their
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 9
corresponding CPs, and the initial metal concentration.
It can be seen that there was a significant increase in the
amount of gold adsorbed with increasing Au(III) ions
concentration (from 96.5 to 440.0 mg L–1). The obser-
vable increase in the Au(III) uptake with increase of
metal ion concentration in the initial region of adsorp-
tion profile could be due to higher driving force for the
mass transfer, which resulted in a greater metal ion
uptake (Huang et al. 2011). Beyond 440.0 mg L–1, the
adsorbed amount of ions becomes independent of the
metal concentration, owing to insufficient adsorption
sites. It is also evident that the maximum uptake of
Au(III) by IIP ADT-EGDMA is the lowest
(187.92 mg g–1) compared to the other two IIPs
(419.39 and 392.00 mg g–1 for IIP 4-VP-EGDMA and
IIP EDA-EGDMA, respectively), because its active
group offered higher steric hindrance and the lowest
alkalinity of N atom (low ZPC value) (Donia et al.
2005).
The adsorption isotherms are useful in determin-
ing the feasibility of the adsorption systems. In this
work, the sorption results for Au(III) onto IIPs and
CPs were analysed using the Langmuir (Aksu
2002), Freundlich (Li et al. 2005), Temkin (Kiran &
Kaushik 2008) and Dubinin–Redushkevich (D–R)
(Jain et al. 2010) isotherm models. The quality of
the fitting was evaluated based on the correlation
coefficient (R 2) which represents the agreement
between the experimental and theoretical values.
Table 2 summarises the parameters from the four
isotherm models tested and the R 2 values. The values
of R 2 acquired from applying the Langmuir isotherm
to the sorption data were much higher (R 2 > 0.98 for
IIPs and R 2 > 0.97 for CPs) than those of the other
three models. Additionally, the maximum monolayer
adsorption capacity (qm) was in agreement with their
corresponding experimental values. This suggests that
the sorption of Au(III) onto IIPs and CPs conforms
to Langmuir model.
The maximum monolayer adsorption capacity of
Au(III) on IIP 4-VP-EGDMA, IIP EDA-EGDMA
10 M. E. AHAMED ET AL.

Figure 6. Effect of initial concentration of the adsorption of Au(III) onto ion-imprinted and control polymers.

and IIP ADT-EGDMA was found to be 418.41, 393.70
and 189.75 mg g–1, respectively, and were 125.00,
137.17 and 103.31 mg g−1 for their corresponding
CPs, respectively. Furthermore, the degree of suitability
of the investigated polymers for the adsorption of gold
ions was determined from the separation factor con-
stant (RL= 1/(1 + KL C0)). Its value indicates whether
the adsorption process is favourable (0 < RL < 1) or
not (RL > 1). The calculated RL for both IIPs and CPs
varied between 0.001 and 0.635, indicating that the
adsorption of Au(III) onto these polymers is a favour-
able process.
The values of the Freundlich constant for the
adsorption of Au(III) by the IIPs and CPs, 1/n, are in
the range between 0 and 1 reflecting favourable sorp-
tion conditions. Furthermore, the numerical values of

Table 2. Fitting parameters for the Freundlich, Langmuir, Temkin and D–R to experimental adsorption isotherm of Au(III) ion-
imprinted and control polymers.
Parameters
Isotherm Polymer KF 1/n R2
IIP CP IIP CP IIP CP
Freundlich 4-VP 162.33 20.41 0.149 0.252 0.9389 0.9843
EDA 164.46 17.25 0.210 0.531 0.9713 0.9663
ADT 46.39 24.29 0.209 0.199 0.9752 0.9258
Isotherm Polymer Parameters
KL (L mg–1) qm (mg g–1) R2
IIP CP IIP CP IIP CP
Langmuir 4-VP 0.060 0.009 418.410 125.000 0.9875 0.9913
EDA 0.060 0.006 393.701 137.174 0.9887 0.9822
ADT 1.000 0.011 189.753 103.306 0.9971 0.9724
Isotherm Polymer Parameters
KT (L g–1) b (KJ mol–1) R2
IIP CP IIP CP IIP CP
Temkin 4-VP 236.09 0.277 0.0729 0.1228 0.9623 0.9726
EDA 28.067 0.0012 0.0308 0.0162 0.9846 0.9925
ADT 1.37 0.76 0.095 0.174 0.9895 0.8945
Isotherm Polymer Parameters
qd (mg g–1) .βd R2
IIP CP IIP CP IIP CP
13
D–R 4-VP 2 × 10 1.017 3.9975 0.00374 0.8988 0.8626
EDA 286.14 408.0337 1.15 × 10−5 6.97 × 10−4 0.9083 0.9416
ADT 1.12 1.02 5.61 × 10−7 3.51 × 10−5 0.9488 0.8669

KF for IIPs are higher than those for CPs, indicating
that the adsorption of Au(III) ions is more feasible
on IIPs than that of CPs. It is also observed from
Table 2 that the adsorption of Au(III) onto the IIPs
and CPs can be described by the Temkin model
(R 2 > 0.96 for IIPs and R 2 > 0.89 for CPs). It has been
reported that when the interaction energy is greater
than −40 kJ mol−1, the adsorption is physical, whereas
when adsorption energy is 8–16 kJ mol−1 the adsorp-
tion is an ion exchange process (Hu et al. 2011). The
obtained values of b (0.03–0.1 kJ mol−1 for IIPs,
0.016–0.174 kJ mol−1 for CPs) show that the adsorp-
tion could be a physicochemical process. Compared
to the Langmuir, Freundlich and Temkin models, the
D–R model yielded the lowest correlation coefficient
(R 2 < 0.94 for IIPs and CPs). Furthermore, the qd
values differed significantly from the qm values calcu-
lated from the Langmuir model. This means that the
adsorption process is not mainly controlled by
physisorption.
Adsorption thermodynamic
Fig. S3 illustrates the amount of gold(III) ion adsorbed
on the three types of imprinted polymers in solutions
of metal concentration 153.0 mg L–1, pH value 4, at
25, 35 and 50°C. It was observed that as the solution
temperature increased, the adsorption efficiency
increased for all three IIPs and CPs, showing that the
adsorption process is endothermic. This increase in
adsorption efficiency with temperature may be related
to the enhanced rate of intra-particle diffusion of Au
(III) ions as the temperature increases resulting in fas-
ter kinetics of the adsorption process (Shawky 2009). It
may also be due to the increase of dehydration rate at a
higher temperature, which resulted in better inter-
actions between the Au(III) and adsorbent active sites
(Elwakeel et al. 2009). Similar trends were reported
for the uptake of gold ions with thioamide-group nano-
fibre membranes, IIP IECS-GLA and sorption of plati-
num with immobilised bayberry tannin (Wang et al.
2005).
The above adsorption data were treated using the
Vant’t Hoff equation, and the calculated values of
ΔH° and ΔS° and ΔG° are presented in Table S2. The
values of enthalpy change were positive indicating the
adsorption process is endothermic. On the other
hand, the values of ΔS° were greater than 0 implying
the adsorption is a spontaneous process, being
accompanied by an increase in the randomness at the
internal structure of the sorbent during Au(III) adsorp-
tion. The values of ΔS° for adsorption of Au(III) onto
IIPs are larger than ΔS° values obtained from CPs
owing to their rougher and porous structure compared
to CPs.
Table S2 shows the Gibbs energy (ΔG°) calculated
employing the relation DGo = DH o − TDS. With the
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 11
exception of the adsorption of Au(III) by IIP ADT-
EGDMA at 25°C, the ΔG° is negative which indicates
the favourability of the adsorption process. According
to the ΔG° value, the adsorption on the IIP 4-VP-
EGDMA is the most negative followed by IIP EDA-
EGDMA and the least is IIP ADT-EGDMA. This is
in accordance with the equilibrium isotherm data
where the adsorption capacities of the IIPs follow the
same order. In comparison with ΔG° for the adsorption
of Au(III) on CPs, the adsorption of Au(III) on IIPs is
more negative, and the driving force for this
spontaneity is the ease of access to the binding sites
on Au(III)-IIP.
By definition, an adsorption with ΔG°≥–15 kJ mol–1
is indicative of a physical adsorption, while ΔG° ≤ –
30 kJ mol–1 is an indication of a chemical adsorption
(Ghasemi et al. 2012). On the other hand, adsorption
with ΔH° ranging between 20.9 kJ mol–1 to 418.4 kJ
mol–1 is indicative of chemisorptions (Li et al. 2013).
The obtained ΔG° values were between −16.63 to
+0.99 kJ mol–1, suggesting that the adsorption of gold
ions on all IIPs is a physisorption process driven by
the electrostatic interaction. In contrast, the values of
ΔH° (18.24–167.30 kJ mol–1) indicated that the
adsorption process is a chemical adsorption. Therefore,
the adsorption of Au(III) onto the studied IIPs could be
a physicochemical process.
Selectivity studies of the imprinted polymers for
Au(III) versus closely related ions
To compare the extractive capability of the three kinds
of imprinted polymers and their corresponding control
polymers towards gold (III), complex synthetic mix-
tures of Au(III) in hydrochloric acid (at pH 4 and 6)
containing metal ions Cu(II), Ni(II), Mn(II), Pb(II),
Fe(III), Pd(II) and Pt(IV) were studied. These compe-
titor ions were selected as they are likely to coexist with
gold in gold ores. The values of distribution ratios (Kd,
mL g–1) and selectivity coefficients (β) of Au(III) with
respect to the above metal ions determined for 4-VP,
EDA and ADT IIP and CP materials are presented in
Table 3. The values of β for the adsorption of Au(III)
ions onto the IIPs were found to be higher than one,
thus demonstrating the minimal influence of these
ions on the binding affinity of IIPs for Au(III) ions.
The values of relative selectivity coefficients (k’) at
pH 4 for the three types of polymers were also found
to be greater than one. This is attributed to the imprint-
ing effect. According to the magnitude of K’, the selec-
tivity order followed the sequence Au(III) > Cu(II) = Ni
(II) = Mn(II) (K’ = ∞) > Fe(III) (282.8) > Pb(II) (70.7)
> Pt(IV) (20.8) > Pd(II) (2.2) for 4-VP-EGDMA, Au
(III) > Mn(II) (K’ = ∞) > Cu(II) (82.6) > Ni(II) (72.5)
> Pb(II) (53.7) > Fe(III) (49.4) > Pt(IV) (13.0) > Pd
(II) (1.6) for EDA-EGDMA, and for ADT-EGDMA:
Au(III) > Cu(II) (K’ = 69.9) > Ni(II) (53.0) > Fe(III)
 12
M. E. AHAMED ET AL.
Table 3. Selectivity coefficients of CP and gold (III) imprinted polymers (mixtures: Au3+/Cu2+/Ni2+/Mn2+/Pb2+/Fe3+/Pd2+/Pt4+) (T 25 ± 1°C, time 30 min; pH 4.0 and pH 6.0*±0.1).
4-VP-EGDMA EDA-EGDMA ADT-EGDMA
Distribution ratio Selectivity coefficient Distribution ratio Selectivity coefficient Distribution ratio Selectivity coefficient
Metal ion (Kd, mL g−1) βAu3+/Mn+ K’ (Kd, mL g−1) βAu3+/Mn+ K’ (Kd, mL g−1) βAu3+/Mn+ K’
IIP CP IIP CP IIP CP IIP CP IIP CP IIP CP
Au3+ 51.43 2.78 – – 12.24 1.35 – – 2.49 0.87 – –
10.24* 0.72* 3.89* 0.39* 2.13* 1.75*
Cu2+ 0.00 0.11 ∞ 25.27 ∞ 0.03 4.94 408.00 4.94 82.6 0.02 0.49 124.50 1.78 69.9
0.02* 0.48* 512.0* 1.50* 341.3* 0.20* 0.80* 19.45* 0.49* 39.7* 0.05* 1.05* 42.60* 1.67* 25.5*
Ni2+ 0.00 0.04 ∞ 69.50 ∞ 0.005 0.04 2448.00 33.75 72.5 0.02 0.37 124.50 2.35 53.0
0.012* 0.19* 853.33 3.79* 225.2* 0.06* 0.09* 64.83* 4.33* 15.0* 0.019* 0.21* 112.11* 8.33* 13.5*
Mn2+ 0.00 0.13 ∞ 21.38 ∞ 0.00 0.00 ∞ ∞ ∞ 0.03 0.06 83.00 14.50 5.7
Pb2 0.17 0.65 302.53 4.28 70.7 0.017 1.00 71.93 1.34 53.7 0.38 0.4 6.55 2.18 3.0
Fe3+ 3.03 46.33 16.97 0.06 282.8 2.25 12.27 5.43 0.11 49.4 0.54 1.43 4.61 0.61 7.6
Pd2 27.95 3.35 1.84 0.83 2.2 3.39 0.61 3.61 2.20 1.6 1.84 0.64 1.35 1.04 1.3
16.79* 5.53* 0.61* 0.13* 4.7* 1.32* 0.45* 2.95* 0.87* 3.4* 4.26* 7.29* 0.50* 0.24* 2.1*
Pt4+ 0.08 0.09 642.88 30.89 20.8 0.21 0.30 58.29 4.50 13.0 0.11 0.09 22.64 9.97 2.3
0.04* 0.12* 256.0* 6.0* 42.7* 0.02* 0.06* 243.13* 6.50* 37.4* 0.05 0.55 42.60* 3.18* 13.4*
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 13

Table 4. The adsorption selectivity for Au(III) from multi-component systems.

Adsorbent Composition Selectivity coefficient Reference
Phenyl thiosemicarbazide modified Au(III) Au(III), Cu(II) 114.2 Monier et al. (2014)
ion-imprinted cellulosic cotton fibres Au(III), Fe(III) 111.3
Au(III), Cd(II) 150.2
Polystyrene-supported 3-amino-1,2- Au(III), Hg(II) 2.5 Changmei et al. (2011)
propanediol Au(III), Pb(II) 3.6
Au(III), Cu(II) 3.7
Au(III), Ni(III) 3.5
Au(III), Cu(II), Pb(II) 3.3
Duolite GT-73 Au(III), Cu(II), Ni(II), Pd(II) 1.9 Iglesias et al. (1999)
Notren resin Au(III), Cu(II) 1.3 Dicinoksi (2000)
Thiourea-formaldehyde resin Au(III), Cu(II), Zn(II) 1.4 Ertan and Gulfen
(2009)
Silk sericin Au(III), Cu(II) 2.6 Chen et al. (2011)
Au(III), Cu(II), Ni(II), Co(II), Zn(II) 1.2
Au(III), Cu(II), Ni(II), Pd(II), Co(II), Zn(II) 2.8
IIP 4-VP-EGDMA Au(III), Cu(II), Ni(II), Mn(II), Pb(II), Fe(III), Pt(IV), ∞, ∞, ∞, 302.5, 17.0, 1.8 This work
Pd(II) and 642.9, respectively (pH 4)
IIP EDA-EGDMA Au(III), Cu(II), Ni(II), Mn(II), Pb(II), Fe(III), Pt(IV), 408.0, 2448.0, ∞, 71.9, 5.4, This work
Pd(II) 3.6,
and 58.3, respectively (pH 4)
IIP ADT-EGDMA Au(III), Cu(II), Ni(II), Mn(II), Pb(II), Fe(III), Pt(IV), 124.5, 124.5, 83.0, 6.6, 4.6, 1.4 This work
Pd(II) and 22.6, respectively (pH 4)

(7.6) > Mn(II) (5.7) > Pb(II) (3.0) > Pt(IV) (2.3) > Pd
(II) (1.3).
The high adsorption selectivity of the IIPs to gold
ion compared to base metal ions at this pH can be
attributed to several factors. The first factor could be
the geometry of the complex anions in which gold
(III) forms a square planar complex with the chloride
anions (Trochimczuk 2001). The other base metal
ions form tetrahedral or octahedral complexes result-
ing in different interactions with the IIPs. A second
factor could be the soft acid–soft base interactions
where Au(III) ion, a soft acid, has a strong affinity
for the group containing nitrogen and or sulphur
(soft base) in the polymers. A third factor is the pH
of the solution. As we found earlier, the adsorbent
sites are positively charged at pH 4. For this reason,
the binding sites at this pH became more repulsive
to Cu and Ni ions and more attractive to anionic
gold cholorocomplexes, which resulted in greater
binding affinity for gold toward IIPs compared to
the other two ions. In contrast, there is a notable com-
petition between Au(III) and Pd(II) ions which could
be due to the higher ionic charge and smaller
hydrated radius of [PdCl4]2− ion compared to [AuCl4-
]− together with the similarity in their complexes geo-
metry, leading to higher affinity of [PdCl4]2− to the
adsorption sites.
At pH = 6, the electron pair of nitrogen and/or sul-
phur donor atom is partially available and the compe-
tition between the proton and the metal ions to the
active sites on the polymers became less significant.
Under this condition, the selectivity is governed by
the stability constants of the metal ions with the func-
tional group and the recognition effect. Despite the fact
that pH = 6 is the suitable pH for reacting Cu(II) and
Ni(II) with N and S containing group, the IIPs prefer-
entially adsorbed the Au(III) rather than other
competitor ions. This demonstrates the suitability of
the imprinted polymers to separate Au(III) from the
interfering ions even at their optimum pH. It is also
observed that the three kinds of polymers have a simi-
lar selectivity pattern at pH = 6, and the order of selec-
tivity was Au(III) > Pd(II) > Pt(IV) > Ni(II)> Cu(II).
On the other hand, the selectivity coefficients for the
IIP 4-VP-EGDMA were more pronounced than for
EDA-EGDMA and much higher than for ADT-
EGDMA. This demonstrates the role of the functional
groups on the adsorption behaviour and selectivity of
the adsorbent. In agreement with our present study,
Daniel et al (2005) found that the nitrogen-based qui-
noline derivative was more selective for Pd(II) than the
sulphur analogue. The authors ascribed this to the stab-
ility constants of metal–ligand complexes, where metal
capable of π donation (e.g. Au, Pd, Pt and Ag) forms a
stable complex with donor atom in the following order
N > O > S.
A comparison of the Au(III) adsorption selectivity
values calculated in this work with values reported by
some researchers (Table 4) indicated that the three
IIPs prepared in this study exhibit higher affinity for
Au(III). This demonstrates, therefore, the capabilities
of imprinted polymers to selectively adsorb Au(III)
from coexisting binary metal ions system.
Adsorption mechanism
As discussed previously in the IR analysis, certain
peaks on the IR spectra of IIPs containing Au(III)
(unleached polymers) were shifted and other peaks
disappeared, suggesting the coordination of Au(III)
ions with the functional groups of IIPs. Adsorption
kinetic analysis implied that the adsorption of gold (III)
onto the three IIPs is primarily a chemisorption process.
On the other hand, earlier studies (Liu et al. 2002;
14 M. E. AHAMED ET AL.
Figure 7. XRD patterns of ion-imprinted polymers before load-
ing and loaded: 4-VP-EGDMA (a), EDA-EGDMA (b) and ADT-
EGDMA (c).
Li et al. 2013) indicated that the adsorption process of
Au(III) by polymers with nitrogen or sulphur donor
atoms might take place via chelation–reduction reac-
tions. Therefore, to examine the reducing properties
of the three IIPs, (XRD) spectra of the Au(III)-IIPs
before and after loaded with gold (III) were recorded
and the results presented in Figure 7.
The results from XRD illustrate that the crystallinity
at 2θ = 15.0° for IIPs 4-VP- and EDA-based materials
decreased after the adsorption process (Figure 7(a,b)).
A new peak at ∼30° was also observed but without
gold metallic crystalline phase peaks. This is indicative
of an interaction between the adsorbate (Au(III) ion)
and the IIP materials without any indication of a
chemical redox reaction. However, in the diffractogram
of IIP ADT-EGDMA loaded polymer (Figure 7(c)),
new peaks appeared after adsorption at 2θ values of
38.3°, 44.2°, 64.9° and 77.5° assigning to the (111),
(200), (220) and (311) crystal planes of metallic Au
(0), respectively (Liu et al. 2002). Thus far, it can be
deduced that the adsorption mechanism of Au(III)
onto ADT-EGDMA occurred via reduction–chelation
interaction.
On the basis of the XRD results, the possible mech-
anism for adsorption of the Au(III) ions onto the IIP
ADT-EGDMA is a reduction–coordination mechan-
ism that involved reduction of some gold(III) to gold
(I) and to metallic gold, being accompanied by the che-
lation of trivalent and monovalent gold ions with ADT
group of the polymer. In the case of adsorption gold
(III) ions onto of 4-VP- and EDA-based IIPs, the
coordination and ion exchange are the two possible
adsorption mechanisms.
Computational simulation and possible
interaction between Au(III) and the studied
polymers
The adsorption experimental results show that the 4-
VP-based polymer had superior adsorption capacity
than the other two polymers. Here, we present compu-
tational investigations to better understand the adsorp-
tion behaviour of the three prepared polymers. The
binding interactions between Au(III) ion and func-
tional groups were evaluated using the density func-
tional theory (DFT) method based on the Becke’s
three parameter-Lee–Yang–Parr hybrid functional
(B3LYP). The 6–31G with polarisation (d) and
LANDL2DZ basis sets were used for all of the atoms
of the functional groups and gold atom (Yilmaz et al.
2014), respectively. The optimisations were carried
out using the Gaussian 09 software. This is a simulation
software that uses quantum mechanic laws to predict
the energies, molecular structures, vibrational frequen-
cies and molecular properties of reactions in various
chemical environments. In this study, it is used to
simulate the adsorption performance of adsorbents
for gold(III) ions.
The Gibbs energies (ΔGformation), the heat of for-
mation (ΔHformation) and the entropies of formation
(ΔSformation) for possible products were calculated at
298.15 K and 1 atm by the following equations (Ogun-
laja et al. 2014):
DHformation = Hproduct − (Hligand + Hgoldion ) (4)
DGformation = DHformation − TDSformation (5)
Two (for 4-VP and EDA groups) and five (for ADT
group) possible products that may be formed by the
interaction of these groups with Au(III) or Au(I) ions
were modelled. Inspection of the thermodynamic par-
ameters (enthalpy and Gibbs free energy) compiled in

Table S3 shows that the interaction between AuCl–4 and
4-VP, as well as EDA groups (products I and III,
respectively) and the coordination of Au(III) with
ADT functional group (product IX) are the most
favourable interaction.
As a consequence, the most likely binding mechan-
ism for the formation of the first two products (product
I and product III) is the ion-pair formation where the
positively charged 4-VP and EDA groups interact
with AuCl–4 (see Fig. S4(II,III)). On the contrary, the
probable interaction mechanism between ADT group
and Au(III) is the complexation of Au(III) with the
nitrogen atom of ADT group (see Fig. S5(IX)). Other
modelled structures are displayed in Figs. S4 and S5.
From Gibb’s free energies acquired (see Table S3),
the trend of the interaction energies for the gold is 4-
VP > EDA >>>> ADT. The poor binding between
Au(III) and the ADT group may be due to steric effect
(Ogunlaja et al. 2014). The order of Gibbs energies of
formation of products is in accordance with the exper-
imental findings.
Reusability study
The reusability of the prepared Au(III)-imprinted
polymers is an important aspect in determining the
ability of the resultant leached IIPs to recover the Au
(III) from the tested solution. To examine the reusabil-
ity of the Au(III)-IIP, the polymer was subjected to five
adsorption–desorption cycles (see Fig. S6). A 0.7 M
thiourea + 2 M HCl solution was used as the eluting
agent. The results demonstrate that the imprinted poly-
mers preserved their adsorption performance for Au
(III) uptake after repeating usage four times. After
four cycles, the amount of Au(III) adsorbed onto IIP
4-VP-EGDMA, IIP EDA-EGDMA and IIP ADT-
EGDMA dropped respectively by 9.37 mg g–1 (from
65.47 mg g–1 for the fresh polymer to 56.10 mg g–1,
14.31%), 15.18 mg g–1 (from 64.81 mg g–1 for the
fresh polymer to 49.63 mg g–1, 23.42%) and
6.60 mg g–1 (from 52.14 mg g–1 for the fresh polymer
to 45.54 mg g–1, 12.66%).
Application to simulant mining solution and real
sample
To evaluate the practical applicability of the prepared
IIPs for gold(III) extraction, the IIPs were applied in
laboratory prepared solutions that corresponded to
typical mining solution, acid mining drainage water
samples and acidic leach liquor of electronic scrap.
The batch experiments were performed by equilibrat-
ing 10 mg of the polymer with 10 mL sample solution.
The results are collected in Table 5. In the first set of
experiments, the IIPs recovered Au(III) ions from arti-
ficial mining solution prepared according to our pre-
vious report (Ahamed et al. 2013b), with extraction
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 15
efficiencies between 75.6% and 93.9%. Pd(II) and Pt
(IV) ions were nearly completely extracted (>95%),
while Cu(II) and Fe(III) ions were not. Accordingly,
the obtained IIPs were ideal candidate materials for
the effective extraction and separation of a group of
precious metals in chloride-rich solution. Nevertheless,
the extraction efficiencies of the Au(III) ions on the
corresponding CPs were much lower, with recoveries
in the range 52.9%–58.2%. Furthermore, large quan-
tities of Pd(II), Pt(IV), Fe(III) and Cu(II) ions were
co-extracted.
For the extraction of gold from AMD, the extraction
efficiency on all IIPs and CPs was boosted with increas-
ing initial Au metal concentration (Table 5). With the
exception of iron, the presence of other metal ions in
the AMD wastewater had no influence on the extrac-
tion efficiencies of gold(III). Iron showed a significantly
higher affinity toward the control polymers and to a
lesser extent to the IIPs, which in both cases decreased
with increasing initial Au(III) concentration. This
difference in the adsorption behaviour between IIPs
and CPs could be related to the selectivity of IIPs
which is based on the metal geometry as well as the
ionic interactions. The findings demonstrated that
under competitive and high ionic strength the IIPs
favour Au(IIII) ion than the other ions.
In addition, adsorption experiments were per-
formed from acidic leach liquor of electronic scrap
and the results are listed in Table 5. It can be concluded
that the IIPs adsorbents can extract more than 96% of
Au(III) from the leaching solution and the efficiency
correlated well with the selectivity values obtained.
Hence, the IIPs could be implemented in gold recovery
from electronic waste liquors.
Conclusion
In this study, three Au(III)-imprinted polymers were
successfully prepared using 4-VP, EDA and ADT as
coordinating monomers. The IIP materials displayed
high extraction efficiency for Au(III) ions. The study
showed that the adsorption process depended on the
quantity of polymer, the solution pH, contact time,
the initial gold concentration and solution tempera-
ture. A very low amount of IIP materials, e.g. 30 mg,
was found to be enough for the quantitative extraction
of 100 mg L–1 gold from 30 mL of sample solution. The
adsorption rates of Au(III) by the three polymers were
kinetically fast and reached the saturation values within
5–60 min depending on the monomer type used. The
results showed that the Au(III) ions adsorption con-
forms to pseudo-second-order rate equation and
obeys the Langmuir equation. The competitive study
showed that the imprinted polymers have a preference
to gold than other ions. Moreover, the comparative
results revealed that the efficiency of three Au(III)
IIPs in terms of the uptake time, sorption capacity
 16
M. E. AHAMED ET AL.
Table 5. Application of Au(III) IIPs and the corresponding CPs on the mining simulant solution, acid mining drainage (AMD) water and acidic leach liquor of electronic scrap.
4-VP-EGDMA EDA-EGDMA ADT-EGDMA
Metal Amount found (mg L–1) Recovery (%) Amount found (mg L–1) Recovery (%) Amount found (mg L–1) Recovery (%)
IIP CP IIP CP IIP CP IIP CP IIP CP IIP CP
Mining simulant solution
Au 5.1 (1.6) 35.1 (1.6) 93.9 58.2 15.3 (0.8) 39.5 (1.4) 81.9 53.0 20.5 (3.3) 39.6 (1.6) 75.6 52.9
Fe 31.7 (1.5) 6.3 (2.2) 3.9 80.9 31.0 (1.3) 10.1 (3.3) 6.1 69.4 30.5 (1.4) 7.9 (1.2) 7.8 76.1
Cu 32.7 (2.3) 22.6 (4.1) 0.9 31.5 31.7 (2.6) 22.3 (0.9) 3.9 32.4 32.2 (0.9) 23.8 (2.8) 2.4 27.9
Pd 0.6 (2.4) 1.6 (1.7) 98.2 95.2 0.4 (1.2) 1.3 (4.1) 98.8 96.1 0.6 (2.9) 1.0 (3.1) 98.2 97.0
Pt <DL <DL 100 100 <DL <DL 100 100 <DL <DL 100 100
Spiked 4-VP-EGDMA* EDA-EGDMA* ADT-EGDMA*
Au (mg L–1) Amount found (mg L–1) Recovery (%) Amount found (mg L–1) Recovery (%) Amount found (mg L–1) Recovery (%)
IIP CP IIP CP IIP CP IIP CP IIP CP IIP CP
Acid mine drainage water
20.0 2.2 (1.2) 8.5 (1.8) 90.0 57.5 1.1 (2.8) 8.7 (3.5) 94.4 56.3 5.0 (0.5) 10.8 (1.3) 75.0 10.8
615.6 (2.4) 184.1 (1.3) 12.1 73.7 567.0 (0.7) 267.4 (0.9) 5.6 61.8 567.0 (0.9) 343.7 (1.9) 19.0 50.9
60.0 3.2 (0.8) 16.0 (2.0) 92.7 73.3 3.7 (2.9) 20.6 (2.1) 93.8 65.7 12.1 (0.8) 29.0 (1.2) 79.8 51.6
638 (2.9) 207.9 (2.9) 8.9 70.3 567.0 (2.2) 274.4 (0.9) 5.8 60.8 568.0 (2.9) 391.3 (2.8) 18.8 44.1
90.0 4.4 (0.7) 16.5 (0.6) 96.4 81.7 4.7 (1.5) 28.0 (1.2) 94.8 68.8 8.6 (1.8) 38.5 (2.7) 90.4 57.2
675.2 (1.7) 219.8 (3.1) 3.5 68.6 567.0 (1.4) 267.4 (0.9) 5.9 61.8 570.5 (1.3) 429.8 (3.1) 18.5 38.6
180.0 2.0 (2.5) 10.4 (0.2) 98.8 94.2 10.0 (2.6) 29.7 (1.1) 94.4 83.5 8.8 (3.1) 30.8 (1.1) 95.1 82.9
692.6 (2.1) 235.2(1.1) 1.1 66.4 567.0 (1.2) 403.9 (0.9) 8.4 42.3 574.0 (2.2) 574.7 (2.9) 18.0 17.9
Metal 4-VP-EGDMA EDA-EGDMA ADT-EGDMA
Amount found (mg L–1) Recovery (%) Amount found (mg L–1) Recovery (%) Amount found (mg L–1) Recovery (%)
IIP CP IIP CP IIP CP IIP CP IIP CP IIP CP
Acidic leach liquor of electronic scrap
Au 0.0 (1.0) 6.4 (1.0) 100.0 31.9 9.4±3.1 7.5 (4.5) 100.0 20.2 0.3 (1.2) 8.1 (3.7) 96.8 13.8
Cu 8332.9 (3.5) 8157.4 (2.1) 0.3 2.4 8307.9±1.2 6251.8 (3.0) 0.6 25.2 8224.3 (1.4) 8082.2 (2.5) 1.6 3.3
Zn 4358.6 (1.7) 4306.3 (2.3) 0.0 1.2 4358.6 (4.8) 4319.4 (3.8) 0.0 0.9 4284.5 (2.7) 4345.5 (2.8) 0.3 1.7
Ni 152.1 (2.1) 152.1 (1.7) 0.0 0.0 151.9 (1.0) 150.1 (1.2) 0.1 1.3 151.4 (2.1) 149.2 (1.7) 0.4 1.9
Bi 2021.3 (0.8) 2007.2 (1.8) 0.0 0.7 1986.9 (1.2) 1950.6 (2.4) 1.7 3.5 2005.1 (2.9) 1980.9 (2.0) 0.8 2.0
The first lines of data in the AMD water table are for the gold concentration while the second lines for iron concentration.
<DL: Below detection limit.
RSD (%) values in parenthesis.

and selectivity is in the order 4-VP > EDA > ADT. It
was also observed that the three Au(III)-IIPs can be
reused up to four times. The study also demonstrated
that the three types of IIPs can be employed for the
recovery of Au(III) ions from mining waste, leach
liquor of electronic scrap and gold mining industry
feed simulant solutions.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by National Research Foundation
[Grant Number 0000525]; University of Johannesburg
[Grant Number FRC/URC].
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