Selective extraction of gold(III) from metal chloride mixtures using
ethylenediamine- N-(2-(1-imidazolyl)ethyl)chitosan ion-imprinted poly-
mer

Ahamed MEH, X.Y Mbianda, A.F Mulaba –Bafubiandi, L. Marjanovic

PII: S0304-386X(13)00165-5
DOI: doi: 10.1016/j.hydromet.2013.08.004
Reference: HYDROM 3753

To appear in: Hydrometallurgy

Received date: 26 February 2013

Revised date: 26 July 2013
Accepted date: 14 August 2013

Please cite this article as: MEH, Ahamed, Mbianda, X.Y., Mulaba –Bafubiandi, A.F.,
Marjanovic, L., Selective extraction of gold(III) from metal chloride mixtures using
ethylenediamine- N-(2-(1-imidazolyl)ethyl)chitosan ion-imprinted polymer, Hydrometal-
lurgy (2013), doi: 10.1016/j.hydromet.2013.08.004

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Selective extraction of gold(III) from metal chloride mixtures using

ethylenediamine- N-(2-(1-imidazolyl)ethyl)chitosan ion-imprinted polymer

MEH Ahamed a, X. Y Mbianda* a. A. F Mulaba – Bafubiandi b, L. Marjanovic c

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a b
Department of Applied Chemistry, Faculty of Science, Mineral Processing and Technology
Research Center, Department of Metallurgy – Faculty of Engineering and the Built Environment,

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c
Department of Chemistry, Faculty of Science, University of Johannesburg, South Africa

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In the present study, a novel chelating ion imprinted resin using chitosan as a scaffold material;
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N-ethylenediamine (1-imidazolyl ethyl) - type chitosan, has been prepared, and applied to the
selective extraction of gold(III) chlorides from complex aqueous solutions. Batch adsorption
experiments were carried out with various parameters, such as contact time, pH, initial Au(III)
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concentration and temperature. The kinetic studies revealed that the adsorption process could be
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described by pseudo-second-order kinetic model, while the adsorption data correlated well with
the Langmuir and Temkin model. The maximum adsorption capacities calculated from the
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Langmuir equation are 810.67 mg g-1and 649.35 mg g-1 at pH 3 and 6, respectively. Comparing
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these values with those cited in literature, showed that the adsorption capacity value obtained for
the IECS-GLA imprinted polymer is remarkably higher. Thermodynamic parameters (∆G < 0
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and ∆S > 0) showed the spontaneity and endothermic nature of adsorption process. Furthermore,
the selectivity study revealed that the ion imprinted polymer was highly selective to Au(III)
compared to Pb(II), Ni(II), Cu(II), Mn(II) and Fe(III), even at the optimum binding pH for the
other metal ions (pH 5-6). The adsorbent was successfully regenerated with a 0.7 M thiourea-2
M HCl solution.
Keywords: IIP IECS-GLA; gold(III) ions, Selective extraction, Equilibrium Isotherms, simulated
mining solution, acid mining drainage.

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1. Introduction
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In the recent years there has been a sustained tendency for the utilization of precious metals,
specifically gold, not only in traditional jewelry materials but also in new emerging applications.
The latter include electronic and electric devices, catalysts, and as sensor in the health and
environment sectors (Lama et al., 2008). However, gold resources in the world are scarce and

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crude gold is mainly associated with other metal deposits. In addition, conventional leaching
processes with aqua regia produce solutions consisting of chlorocomplexes of gold along with

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common base metals (Arrascue et al., 2003; Sanchez et al., 2001). Therefore, developing a more

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efficient method for the selective extraction and separation of gold from its primary and
secondary counterparts has become more important from a full utilization of resources

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prospective.
Various methods have been utilized for the extraction of gold(III) chlorocomplex ions
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from its chloride bearing solutions; these include solvent extraction, chemical precipitation,
adsorption, electro-deposition, membrane separation and ion exchange process (Arrascue et al.,
2003; Atia, 2005). Among these techniques, adsorption and ion exchange have proven to be
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more popular because they are economically favorable, easily implemented, simple to maintain
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and exhibit large extraction capacity (Fujiwara et al., 2007). However, the main obstacle
associated with adsorbents and ion exchange resins is their low selectivity for gold(III)
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chlorocomplex making the recovery of gold(III) difficult and expensive (Arrascue et al., 2003).
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This gives a compelling reason to develop more efficient, selective and low cost materials for the
separation and recovery of gold metal from lixiviation solutions.
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Chitosan is a natural aminopolysaccharide polymer obtained by deacetylation of chitin,

and it is the second most abundant polysaccharide after cellulose (Fujiwara et al., 2007). This
biopolymer is characterized by its hydrophilic nature, biodegradability; being harmless for living
organisms and also its high percentage of amino groups that serve as coordination sites. Hence,
chitosan is an interesting starting reactive material for the development of chelating resins. On
the other hand, chitosan has cationic behavior in acidic conditions (pKa near 6.2) making it a
suitable sorbent for the removal of anionic dyes and inorganic metal species (eg. chloro-
complexes of precious metals) through electrostatic attraction. However, the use of chitosan in
acidic conditions is hampered by its tendency to dissolve in dilute mineral and organic acids
(except H2SO4). To solve such a problem, some cross-linking agents such as epichlorohydrin
(Nishad et al., 2012), ethyleneglycol diglycidyl ether (Katarina et al., 2006) and glutaraldehyde
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(Atia, 2005), have been utilized to reinforce not only the chemical resistance in acidic solutions
but also the physical and mechanical properties of these materials. However, the cross-linking
approach results in significant loss in the chitosan adsorption capacity, due to the involvement of
chitosan amine groups in the cross-linking reaction; and also in difficulties in accessing some

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binding sites that might be blocked by cross linker moieties (Cao et al., 2001; Zhou et al., 2012).
Current trends in research are directed towards the modification of chitosan with sulfur

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and nitrogen containing groups for the selective recovery of precious metals. These chemical

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modifications of chitosan are intended (a) to increase its sorption properties by increasing the
number of available sorption sites; (b) to change the pH range for metal sorption and (c) to

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improve the adsorption selectivity toward precious metal ions (Guibal, 2004). Several ligands
such as sulfur containing groups (Arrascue et al., 2003; Atia, 2005; Bratskaya et al., 2011; Donia
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et al., 2007), amino acids (Fujiwara et al., 2007; Ramesh et al., 2008), poly(ethyleneimine)
(Katarina et al., 2006), heterocyclic nitrogen and/or sulfur compounds (Li et al., 2009; Pestov et
al., 2011; Sopena et al., 2011) have been used to functionalize the cross-linked chitosan and the
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resulting materials have shown moderate success in the adsorption of precious metals. Thus
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chitosan derivatives that are specific and selective towards precious metals, still need to be
developed. Hence, designing imprinted bio-polymers with higher selectivity and adsorption
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capacity for precious metals can make the process economically feasible and environmentally
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friendly.
To improve the adsorption selectivity, a great deal of attention has been directed towards
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the ion imprinting techniques, because they have the potential of designing ion-imprinted
chitosan polymers with ion recognition capability. In this technique a polymer derivative
containing a metal ion template, is cross-linked with a bifunctional reagent; then the metal ion is
removed from the polymer matrix thus generating a specific bonding site that is complementary
in size and shape to the target metal ion (Nishad et al., 2012).
The overall objectives of this study were (i) To synthesize and characterize new
ethylenediamine N-(2-(1-imidazolyl) ethyl) glutaraldehyde-crosslinked chitosan imprinted
polymer (IECS-GLA). It is anticipated that the combination of amine-, N-(2-(1-
imadazolyl)ethyl) moieties alongside ethylenediamine groups, will increase the number of
available binding groups and could also act synergistically for the gold(III) metal ions
adsorption; (ii) To evaluate the performance of this new material for the selective sorption of
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Au(III) ions in the presence of other base metals under different complexing conditions. Taking
into account previous promising reports for the modification of chitosan with pyridyl groups
(Bratskaya et al., 2012; Dhakal et al., 2008; Sopena et al., 2011), it is expected that the
incorporation of a new imidazoyl moiety, which is considered to be one of the best heterocyclic

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nitrogen ligands, into the chitosan biopolymer, will lead to the enhancement of gold(III) metal
ion coordination for planar geometry of the metal ion. Furthermore, it is anticipated that

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embedding molecular recognition phenomena of the chelating groups in ethylenediamine N-(2-

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(1-imidazolyl) ethyl) chitosan (IECS) to the planar metal ion will also enhance selectivity. This
assumption is supported by earlier works of imprinting U(VI) Co(II) (Nishad et al., 2012), and

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Ni(II) and Cu(II) (Dhakal et al., 2008) onto polymers where the selectivity of the metal ions was
improved. (iii) To optimize variables affecting the extraction efficiency of Au(III) ions from
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aqueous media. In order to get additional information about the adsorption characteristics, some
isotherms, kinetic and thermodynamic models were tested. Furthermore, the applicability of
these new materials under typical industrial conditions was tested by using solutions prepared in
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the laboratory to simulate mining solutions as well as real acid mining drainage (AMD)
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wastewater spiked with gold ions.

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2. Experimental
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2.1. Chemicals
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Chitosan (medium Mn ~ 9000, N- deacetylation degree > 75 %), epichlorohydrin (ECH),

glutaraldehyde solution (50%), ethylene diamine, 1- vinylimidazole, K2PtCl6 and k2PdCl4 were
obtained from Sigma–Aldrich (South Africa). Chloroauric acid (HAuCl4.3H2O), K2PtCl6 and
K2PdCl4 were obtained from South Africa Precious Metal (South Africa). Sodium hydroxide,
thiourea, EDTA, nitric acid, ethanol, and methanol, metal salts of CuCl2.2H2O, PbCl2, FeCl3
(anhydrous), NiCl2.6H2O and MnCl2.4H2O (Merck, South Africa) were used. All the chemicals
used were of analytical grade. Working standards were prepared by serial dilution of standard
Au(III), Pd(II), Cu(II), Fe(III), Pb(II) and Ni(II) solutions using ultrapure water (obtained from
an Elix/Milli- Q Element system (France))., and ultrapure water (18.3 μΩcm-1 at 25 ºC) was used.

2.2. Instrumentation
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Inductively coupled plasma optical emission spectroscopy (ICP –OES, Spectro Arcos, model
Arcos FH512 - Germany) was used to determine the concentration of Au. Temperature
controlled water bath-shaker (LABCON, Shaking water bath-25L, USA) was used for agitating
the sample solutions. pH measurements were done using a Hanna pH meter (Italy).

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2.3. Procedure

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2.3.1. Synthesis of N-(2-(1-imadazolyl)ethyl) chitosan (IECS)

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N-(2-(1-imadazolyl) ethyl)- chitosan was prepared following the method of Sopena et al., (2011)
with slight modification. A gel of chitosan was prepared by mixing 0.33 g of chitosan (2 mmol—

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NH2) with 0.36 mL of 1-vinylimidazole (0.38 g, 4 mmol) in 1.56 mL of a 4.6% w/w HCl
solution (2 mmol). The gel was heated for 24 h at 70 ºC. After cooling, a volume of 7.20 mL of
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HCl (0.85% w/w solution, 2 mmol) was added to the reactive suspension. The IECS
hydrochloride was precipitated using acetone. Then, the wet solid was purified with isopropanol
in a Soxhlet extractor for 24 h. Finally, the brownish polymer was dried at 50 ºC until a constant
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mass was reached. The preparation of IECS is illustrated on Scheme 1 (step 1).
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2.3.2. Synthesis of IECS ion imprinted polymer

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The IECS (2.50 g) was dissolved with constant sonication in 50 mL acetic acid solution (2 %,
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V/V) and then added into a 250 mL round bottom flask containing 50 mL gold(III) chloride
solution to give an Au(III) solution of 2000 mg.L-1. The mixture was stirred continuously at 60
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º
C for 12 h. Then, 2.85 mL glutaraldehyde solution (1.51 g, 15.09 mmol) was added to the
mixture to form a gel. The product formed was washed with acetone and distilled water.
Grafting of ethylenediamine groups was carried out according to a previous work (Katarina et
al., 2006). Cross linked chitosan (5.00 g) was suspended in 100 mL of 1: 1 ethanol-water
solution. Epichlorohydrin (5 ml, 5.9 g, 63.78 mmol) was then added to the suspension and the
mixture was stirred for 3 h under reflux, and then cooled to room temperature. The solid residue
was filtered and washed several times with water and ethanol. The residue was suspended in 100
mL of ethanol-water mixture (1:1), and to this, up to 5 g of ethylenediamine was then added.
Afterwards, 40 mL of 1M sodium hydroxide was added. The suspension was refluxed for 3 h.
The collected resin was washed with acetone and deionized water.
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Finally the template Au(III) ions were removed from the resins using 0.5M thiourea and few
drops of 1M H2SO4 until Au was not detected in the leaching solution, which was monitored by
ICP-OES. The resin was added into 0.1 M NaOH aqueous solution for 5 h to activate the amino
group and then dried overnight in a vacuum oven at 60 0C. The control (CP) IIECS-GLA was

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similarly synthesized in the absence of templates. The physical characteristic of the prepared
resin is presented in Table 1 and the preparation process is shown in Scheme 1 (step 2 to 5).

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2.4. Characterization and identification of the polymers

FT–IR Attenuated Total Reflection (ATR) (Perkin Elmer, USA) was used to analyze the

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functional groups in the adsorbents. The transmission spectra were acquired with 10 scans and 4
cm-1 resolution. 1H and 13
C NMR spectra were recorded at 400 and 75 MHz respectively, on a
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Bruker AV–400 spectrometer. Chemical shift for 1H spectra was recorded in ppm relative to
residual proton of D2O (1H: δ 4.65).
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The degree of substitution (DS) was calculated using 1H NMR spectra according to the
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following formulas (Bratskaya et al., 2012):

(m  2d)
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TotalDS  (1)
(m  d  a)
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m
monosubstitution DS (DSm)  (2)
(m  d  a)
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2d
disubstitution DS (DSd)  (3)
(m  d  a)

where m is the mole fraction of monoimidazolylethylated glucosamine units, d is the mole

fraction of diimidazolylethylated glucosamine units, and a is the mole fraction of glucosamine
units. The calculation of m, d, and a values were performed using integral intensities of
corresponding signals in 1H NMR spectrum.
Zeta potentials of the polymers were measured by a Malvern Nanosizer (ZENN 3600,
U.K). The pH values of polymer solutions were adjusted from 1.0 to 11.0 by adding 0.1 M
hydrochloric acid or sodium hydroxide solution to the glass beaker at 25 ºC. By measuring the
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zeta potential as a function of pH, the acidity of the polymers surface and the isoelectric point
(IEP) were determined.
Scanning Electron Microscope (SEM) (SEM Thermo Scientific, model 6658A-1NUS-
SN, USA) was used to study the surface morphologies of the polymers. Nitrogen

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adsorption/desorption experiments were carried out using Micrometric ASAI 2020 Surface area
and porosity analyzer (USA) and the surface areas of polymers were calculated according to the

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Brunauer–Emmett–Teller (BET) method.

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The number of active sites in the obtained polymers was evaluated using a method
reported by Latha et al (1991). A 15-mL HCl (0.05 N) solution was added to 10 mg resin and

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conditioned for 24 h on a shaker; then the solution was titrated by 0.05 N NaOH. The active
sites concentration was calculated by determining the number of moles of HCl that reacted with
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the nitrogen atoms.

2.5. Adsorption studies

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2.5.1. Effect of initial pH on the extraction of Au(III)

The effect of initial pH on the adsorption of Au(III) (160 mg L-1) was studied by mixing 10 mg
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of the sorbents with 10 mL Au(III) ion solutions in the pH range between 1.0 to 8.0. The pH
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values of the solutions were adjusted to the desired values with either 0.1 mol L-1 HCl or 0.1 mol
L-1 NaOH. The solutions were mechanically shaken for 90 min at 200 rpm. The mixtures were
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then filtered and the concentration of Au(III) in solution was measured by ICP-OES. The
experiment was performed in triplicates. From these values the percentage extraction efficiencies
(% EE) was evaluated using equation 4:

spiked concentration  unextracted concentration

% EE  x 100 (4)
spiked c oncentration

2.5.2. Sorption Kinetic

Sorption kinetic experiments of Au(III) were studied with the initial concentration 180 mg L-1
batch equilibration at 25 ± 1 ºC. 10 mg of polymers were added in 10 mL of Au(III) solutions in a
25 mL reagent bottles and consciously stirred (200 rpm) for different time intervals ranging from
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10 to 110 min. The amount adsorbed per unit mass of polymer at time t, (qt, mg g-1) was
calculated by mass balance equation.

Co  Ct
qt  xV (5)

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m

where m (g) is the mass of the polymer. Co and Ct (mg L-1) are the concentrations of the metal

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ion at the beginning and at time t, respectively.

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2.5.3. Sorption isotherms

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Batch adsorption experiments were conducted by placing a 10 mg of polymers in 25 mL reagent
bottles containing 10 mL of Au(III) solution of various concentrations. The bottles were agitated
(200 rpm) at 25 ºC for 90 min using a mechanical shaker to reach equilibrium. After filtration,
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the concentration of Au(III) in solution was analyzed by ICP-OES. To verify the effect of the
protonation and deprotonation of the N- atoms of the functional groups on the sorption
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performances of the polymer, isotherms were plotted at pH 3.0 and 6.0.

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2.5.4. Statistical Evaluation of the Kinetic and Isotherm Parameters

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In order to evaluate the goodness of the fit of experimental data and the prediction accuracy of
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the models utilized in this work, the linear correlation coefficients (R2) and relative function Ferror
are employed. The former statistical indices indicated the differences between the experimental
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and predicted values of the amount of metal ion adsorbed by the adsorbent; and it is given by Eq.
6 (Vaghetti et al., 2009):

². (6)

Where qi model is each value of q predicted by the fitted model and qi experimental is each value of q
measured experimentally, and p is the number of experiments performed.

2.6. Selectivity experiments

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Competitive adsorption of Au(III) ions was also investigated in a batch system. Both imprinted
and control polymers were used to obtain two sets of data. Polymer material (10 mg) was added
into mixed aqueous solutions (10 mL) containing Au(III), Cu(II), Ni(II), Pb(II), Fe(III) , Pd(II)
and Pt(IV) (125 mg L-1 for each ion). The pH was then adjusted accordingly to pH 3.0 and 6.0.

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These were placed in sealed containers and mechanically stirred (200 rpm) at 25 ºC for 90 min.
After the adsorption-equilibrium, the residual concentration of each ion was measured by ICP-

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OES. The experiments were performed in triplicates.

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The effect of imprinting on selectivity was defined by:

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Ci  Cf V
Kd  x (7)
Cf m MA
where Kd is the distribution coefficient, and Ci and Cf (mg L-1) are the initial and final metal
concentrations, respectively. The selectivity coefficient (β), for the binding of a particular metal
ion in the presence of a competing ion can be obtained by;
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K Au 3
 3
 (8)
Au / M n K competing ion
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The relative selectivity coefficient k`;

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k Au 3
k`  (9)
k nonimprinted

The results allow an estimation of the effect of imprinting on selectivity.

2.7. Effect of different eluents on desorption Au(III)-imprinting ions

Batch sorption/desorption experiments were conducted using various eluent solutions of
0.7 mol L-1 thiourea, 2.0 mol L-1 HCl and 0.7 mol L-1 thiourea-2.0 mol L-1 HCl. The Au(III) ions
(100 mg L-1) adsorbed onto prepared imprinted polymers (10 mg dry adsorbents) were washed
with deionized water several times, dried and transferred into stoppered reagent bottles. To these,
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10 mL of desorption agent was added, and then the bottles were agitated on a shaker (200 rpm)
at 25 ºC for 90 min. The concentration of Au(III) ions desorbed from the imprinted polymers into
the aqueous phase was quantified by ICP-OES. Desorption ratio (%) could be calculated from
the following equation:

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amount of ions desorbed to the elution medium
Desorptionratio  x 100
amount of ions adsorbed onto the sorbent (10)

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3. Results and discussion

3.1. Synthesis and Characterization of the polymers

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A new imidazolyl-functionalized chitosan derivative- N-(2-(1-imidazolyl)ethyl) chitosan
(Scheme 1, step 1) was prepared using an analogous synthetic approach developed previously for
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grafting vinyl pyridine on chitosan (Pestov et al., 2011; Sopena et al., 2011). The reaction is
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assumed to follow the Michael addition mechanism, where the primary and monosubstituted
aminogroups on chitosan backbone interact with vinyl imidazole. Since there is no assurance for
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completion of the reaction, the possible structure of the obtained polymer has glucosamine units
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where the NH2 group on C2 is mono and bis- substituted with N-(2-(1-imidazolyl)ethyl) moiety
and other in the free form.
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1
H NMR spectrum provides evidence for sucessuful synthesis of N-(2-(1-
imadazolyl)ethyl) chitosan. Compared with spectral data available in the literature for chitosan
(Desbrires et al., 1996), the new peaks at 8.8, 7.6, 7.3 and 7.0 ppm are characteristic to the
protons in imidazolyl ring (Fig. I in Supplementary data), indicating the success of grafting the
group onto chitosan. Other peak assignments were performed, based on the previous published
works (Pestov et al., 2011; Sopena et al., 2011) and they correlated well with those obtained in
this study. Additionally, 1H NMR spectra infer that the addition reaction between 1-vinyl
imidazole and chitosan occur only on its amino groups (Bratskaya et al., 2012). Indeed, as seen
from Fig. 2 and equations 1-3, the total degree of substitution (Total DS) value was 0.65; while
for the mono- and di-substituted amino groups it was found to be 0.20 and 0.45, respectively.
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FT-IR spectrum (Fig. II in Supplementary data) provides additional confirmation for

chemical functionalization of chitosan. In the IR spectrum of the grafted polymer, sharp bands
around 1610 and 1508 cm-1 due to stretching vibration of C=Cimidazole ring and a band at 1450 cm-1
(C=Nimidazole ring) are observed, which indicate the grafting of imidazole ring in the polymer. The

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other characteristic adsorption peaks at 3309, 2891, 1380 and 1063 cm-1 corresponding to
stretching vibration of the groups –O-H and N-H , C-H, C–N and C-O-C, respectively.

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According to these spectroscopic results (IR and 1H NMR) and the change in its physical

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apppearance, particulary colour and solubility behaviour, which resulted in colour of the grafted
chitosan to deep brown, the modification of chitosan into its imidazolyl derivative was assumed

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to be sucessful.
In order to synthesize IECS-GLA imprinted resin, the obtained product was initially
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complexed with the imprinted Au(III) ion via its coordination reaction with amino groups of
chitosan and imidazolyl moieties to form a planar complex. This was followed by a cross-linking
process using a conventional cross linker reagent, glutaraldehyde. Finally ethylenediamine group
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was grafted onto the formed resin (Step 2-4 in Scheme 1). By doing so, it was believed that more
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reactive functional groups on the material would be made available, and therefore the adsorption
capacity of the resin will increase. On the other hand, the obstacle of the solubility of the
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adsorbent in acidic solution was resolved.

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The numbers of active sites present on the resins were also determined by acid-base
titration method, and results summarized in Table 2, were found to be in line with what was
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anticipated. The number of active sites in the resins was in the following sequence: chitosan
cross-linked glutaraldehyde (CS-GLA) < imidazolyl chitosan cross-linked glutaraldehyde (ICS-
GLA) < IECS-GLA resins. The higher number of active sites on ICS-GLA and IECS-GLA
compared to CS-GLA indicates that the imidazole ring and ethylenediamine group moieties are
covalently bonded to the cross-linked resin.
FT-IR spectra of control (CP), IECS-GLA template (IIP) before and after leaching are
presented in Fig 1. Compared to the spectrum of imidazolyl chitosan polymer (Fig. II in
Supplementary data), CP and IIP IECS-GLA after leaching resins (Fig 1.(a) and (c)) present
distinctive and intense absorption bands at 1650 and 1568 cm-1, which could be attributed to the
NH2 bending over lapping C=N bands of imidazolyl ring and Schiff’s base (imine bond).
Additionally, the C–O stretching vibration at 1063 cm-1 shift to 1033 cm-1 as shown in spectrum
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(a). This was probably due to the fact that the intra- and inter- hydrogen bonding of the chain
polymer became weaker after the cross-linking process. Further evidence for the grafting of
ethylenediamine group onto the resin might be given by the relative increase in the peak intensity
at the frequency level around 3280 cm-1, indicating that more amino groups have been bonded on

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the resin. However, this band in unleached IIP (Fig 1. spectrum (b)) has low intensity and shifted
to 3209 cm-1. Additionally, reasonable shifting in the IR spectrum of the unleached IIP is

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observed at the frequency level of 1550–1650 cm-1 and 1453 cm-1 indicating the involvement of

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the imidazole ring and primary or secondary amino groups of the resin in the coordination
reaction with the Au(III) ions.

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3.2. Surface morphology and surface area measurement of the polymers
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The SEM images as presented in Fig 2. reveal the different surface morphologies of the
control and a leached imprinted polymers. Compared to the control polymer, the leached
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imprinted polymer has a more porous surface of a rougher texture which is the advantage for the
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adsorption of Au(III) ions onto the imprinted polymer. A similar observation was reported by
Dhakal et al., (2008) who attributed this difference in surface morphology to imprinting effect.
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The surface areas were determined using BET method and values of 2.689 and 1.555
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2 -1
m .g were obtained for IIP and CP, respectively. Furthermore, the pore size for IIP was also
found to be greater than that of CP and they were 58.071 and 49.978 Aº, respectively. These
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significant differences between IIP and CP in the surface area and pore size are attributed to the
specific recognition cavities for gold ions created on the surface of the imprinted polymer during
the ion imprinting process.

3.3. Adsorption studies

3.3.1. Effect of initial pH on extraction of Au(III) ions by IECS-GLA polymers

The effect of initial pH on the adsorption of Au(IIII) ions by the polymer powder was
studied by varying the pH of 160 mg L-1 metal solution for a constant adsorbent dose 1.0 g L-1 at
25 ºC and the results are shown in Fig. 3. The results reveal that the extraction was not affected
between pH 2.0 –6.0, thereafter (pH > 8) the percentage for the uptake of Au(III) ions by the
imprinted polymer declined significantly. The maximum adsorption capacity occurred at pH 2.0–
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3.0 which was found to be consistent with the literature (Arrascue et al., 2003; Bratskaya et al.,
2012).
In order to get a better understanding of the adsorption mechanism for binding Au(III) ions on
the sorbent, the zero point charge (pHZPC) for the sorbent was evaluated. The pHZPC of IIP IECS-

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GLA and its control polymer were found to be at 8.8 and 8.3, respectively (Fig. 4). At pH <
pHZPC the surfaces of the resins are protonated and tend to be positively charged, whereas at pH

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> pHZPC the sorbents surfaces are negatively charged. In the acidic chloride solution (pH between

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2-6), many negatively charged chloro-anioinc species of gold may be present in the solution,
resulting in the greater electrostatic attraction between these species and protonated amine

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groups of the resin (Arrascuea et al., 2003). Furthermore, the protonation of the amine groups on
the IECS-GLA induced an electrostatic attraction of chloro-anionic gold complexes by
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increasing the number of positively charged sites for gold metal ions adsorption. Based on this
finding, the dominant mechanism for adsorption Au(III) onto IECS-GLA in acidic conditions is
probably electrostatic interaction and ion exchange. Otherwise Au(III) ions may interact with
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lone pair of electron on nitrogen by chelation [equation 12] during adsorption and can be
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depicted as follows:
Ion exchange:
P
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2RNH3+ + Cl- + AuCl4- (RNH3+)2AuCl4- + 2Cl- (11)

Chelation:
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R1R2NH + AuCl4- (R1R2NH)AuCl3 + Cl- (12)

At higher pH values the reduction in adsorption capacity may be attributed to two reasons:
firstly; decreased availability of chloro gold complexes; secondly, the surface sites of the
adsorbent will be negatively charged causing electrostatic repulsion between the adsorbate
anionic species and adsorbent surface (Ramesh et al., 2008). It is also interesting to note that the
change in adsorption performance as a function of pH was considerably less sensitive to the pH
with IECS-GLA imprinted polymer than the available resins cited in literature (Atia, 2005;
Donia et al., 2007; Ramesh et al., 2008), where the adsorption capacity were found to slightly
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14

change between pH 2-4. These discrepancies can be explained based on the fact that pHZPC for
IECS-GLA imprinted polymer was higher than that reported for resins (Atia, 2005) due to the
presence of more basic nitrogen-based functional groups (imidazole and ethylenediamine) on the
polymeric material.

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3.3.2. Effect of contact time and initial concentration

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A time dependence study was conducted in order to evaluate the optimum time for
Au(III) ions binding to reach an equilibrium (Fig. 5). The results demonstrate that sorption of

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Au(III) ions onto IIP IECS-GLA is a rapid phenomenon in comparison to its sorption onto the
control polymer. Obviously, the sorption rate was fast during the first 30 min, and the uptake rate
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onto IIP and CP IECS-GLA attained to 75% and 40% respectively. Then it slowed considerably
and the equilibrium was established within 90 min. Previous studies on the adsorption rates of
gold(III) ions by various sorbents have shown a long adsorption time ranging from 4 to 90 h
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(Bratskaya et al., 2011; Kılıc et al., 2005; Sanchez et al., 2001). In this study, however, the
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adsorption time required for the sorption is short making the applicability of IIP in online real
time applications feasible.
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To examine the effect of initial Au(III) ions concentration on the adsorption process, the
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experiment was conducted with varying initial metal ion concentrations of Au(III) ions (viz 160
to 1200 mgL-1) at two different pH values (3.0 and 6.0). The evolution of the amount of Au(III)
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ions adsorbed by IIP and CP IECS-GLA polymer as a function of initial metal ion concentration
is presented in Fig. 6. Notably, an increase in the initial metal ion concentration lead to an
increase in the amount of Au(III) ions adsorbed until it reached the plateau. This is because with
the higher initial ion concentration, the strength of the driving force for the mass transfer is
increased as well and hence being favorable for the ion uptake (Huang et al., 2011). Thereafter
the adsorbed amount of ions became constant due to the fact that the total available sites on the
sorbent were fully occupied with the adsorbed ions.

3.3.3. Kinetic studies

In order to elucidate the kinetic mechanism that best describes the adsorption process, the
pseudo first order, pseudo second order, intra-particle diffusion and liquid film diffusion models
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15

were used to test the experimental data. The Lagergren pseudo-first-order rate equation has the
following form:
k1
log(q e  q t )  logq e  t (13)
2.303

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and the pseudo-second-order equation can be represented as:

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t 1 1
 2
 t (13)
q t k 2q e q e

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where qe and qt are the amounts of Au(III) ions adsorbed per unit mass of adsorbent (in mg g-1)

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at equilibrium and time t, respectively. k1 is the pseudo- first-order constant for adsorption
process (min-1), k2 is the pseudo- second-order constant (g mg-1 min-1).
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In order to test the applicability of these two models, the two linear forms of the
equations were plotted. The results of the kinetic parameters are listed in Table 3 and presented
in Figs. 7 and 8. Based on the correlation coefficients R2 and relative average error (Ferror) the
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adsorption of Au(III) ions is best described by the pseudo-second-order equation, indicating that
the rate-controlling step may be the chemisorption mechanism but not the mass transport.
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In order to identify if the transport of the adsorbate from the solution onto the bulk of the
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adsorbent is the rate limiting step, the adsorption data were then processed using the intra-
particle diffusion model which can be described as:
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q t  k id t 0.5 (15)

where kid is intra-particle diffusion rate constant (mg g-1 min-0.5), which can be obtained from the
slope of the plot of qt versus t0.5. As seen from Fig. 9, the plot of qt vs. t0.5 is linear over the
whole time range but did not pass through the origin point indicating that the intra-particle
diffusion may not be the rate controlling factor in determining the kinetics of the process. Clearly
the rate of uptake (Kid) Au(III) ions by IIP is relatively higher compared to CP. This indicate the
higher capability of Au(III) ions to diffuse through the porous network of the IIP. Consequently
the metal ions bind more efficiently with the reactive functional groups on the IIP. The lower
diffusivity of Au(III) ions through the CP resin could be ascribed to its less porous surface
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16

compare to IIP resin (Atia, 2005). This finding is consistent with SEM results (section 3.2) where
the IIP resin has more porous structure compared to the CP resin.

The role of liquid film diffusion in governing the adsorption process was also verified

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using the kinetic equation:

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ln(1  F)  k fd t (16)

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where F is the fractional attainment of equilibrium F = (qt/qe) and kfd is the liquid film diffusion
rate constant. The plot of –ln(1-F) versus time ( presented in Fig. III Supplementary data) and the
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fitting parameters (Table 3) gave a linear line with higher correlation coefficients (R2) varying
from 0.9705 to 0.9794. Therefore the adsorption mechanism also follows the liquid film
diffusion process. The calculated rate constant (Kfd) of uptake of Au(III) ions by the IIP resin
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was greater compared to the CP resin demonstrating the higher surface area of IIP compared to
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the CP resin. This result was found to be in agreement with experimental data for analyzing the
surface area of the resins (Section 3.2) where IIP has higher surface area compared to the CP
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resin.
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3.3.4. Adsorption isotherms

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The purpose of the adsorption isotherms studies is to correlate the amount adsorbed at the
adsorbent interface with the remaining concentration of the adsorbate in the solution at
equilibrium. In addition, it is important in estimating the efficiency of adsorption which can
provide clues for economic feasibility of the adsorption process. The adsorption data for the
adsorbing Au(III) ions onto imprinted polymer at two different pH values, 3.0 and 6.0, were
modeled using Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D-R) isotherms with
the quality of the fitting evaluated using the correlation coefficient and are presented in Table 4.
As state earlier, the reason for studying the adsorption isotherm at these two different pH values
was to investigate the effect of the protonation and deprotonation of the N- atoms of the
functional groups on the adsorption capacity of the polymer.

3.3.4.1. Langmuir isotherm

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The Langmuir adsorption isotherm model is restricted to the formation of the monolayer
adsorbed species onto uniform adsorption sites without any interaction between the adsorbed
molecules. The linear Langmuir equation is expressed as (Hu et al., 2011)

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Ce 1 C
  e (17)
qe K Lq m qe

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Where Ce is the concentration of Au(III) ions at equilibrium (mg L-1), qe the amount of Au(III)

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ions adsorbed (mg g-1), qm the theoretical saturation adsorption capacity (mg g-1) and KL
represents the Langmuir constant (L g-1).

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The isotherm data for Au(III) ions adsorption on imprinted and control polymers were
fitted with the Langmuir isotherm model and are depicted in Fig. 10. The values R2, qm and KL
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were calculated by the linear regression method and are listed in Table 4. The Langmuir model
for both imprinted and control polymers well fitted the experimental data with high correlation
coefficient (R2> 0.98). It is also interesting to note that the values of R2 and Ferror for IIP at pH
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6.0 were better than their corresponding values at pH 3.0, indicating that the adsorption at higher
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pH value favored the single layer model and the process is preferably chemisorption rather than
an electrostatic adsorption. On the other hand, the theoretical values of maximum adsorption
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capacity on IIP IECS-GLA and CP IECS- GLA polymers at room temperature and pH 3 were
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819.672 and 775.194 mg g−1, respectively. Comparison of these values with similar reported in
literature (Table 5), show that the qmax value obtained for the IECS-GLA imprinted polymer is
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remarkably higher, except for the sorbents reported by Sanchez et al., (2001) and Kılıc et al.,
(2005). However, the adsorption time and adsorbent dosage used in these two reported works
were higher than that used in this study, indicating the adsorption process for extraction of
Au(III) ions by the synthesized imprinted polymer has more economic value than the cited
polymers.

The sorption capacity for IIP IECS-GLA polymer at pH 6.0 was also found comparable
with that obtained at pH 3.0 (less than 21 %), demonstrating the strong bonding between Au(III)
metal ions and active sites of the adsorbent even at relatively high pH. In the case of the control
polymer, however, the maximum sorbent capacity was significantly decreased by more than 44
% confirming that the electrostatic effect was diminished.
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Additionally, the degree of suitability of the resin towards metal ions was estimated from
the values of the separation factor constant (RL) which identifies whether the adsorption system
is favorable or unfavorable. If RL > 1.0 then it is unfavorable; RL = 1 it is linear; 0 < RL < 1 it is
favorable; RL = 0 means it is irreversible (Solangi et al., 2009). The value of RL can be defined

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by the following equation:

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1

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RL  (18)
(1  K L C 0 )

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where KL (L mg-1) is the Langmuir equilibrium constant and C0 is the initial concentration of
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Au(III) ions (mg L-1). The values of RL calculated for both imprinted and control polymers at the
two different pH values were in the range between 0.03 and 0.2, thus indicating that the
adsorption of Au(III) metals by these polymeric materials was highly favorable.
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3.3.4.2. Freundlich isotherm

In contrast to the homogeneous Langmuir isotherm, the Freundlich equation basically

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assumes heterogeneous adsorption due to the diversity of adsorption sites and is valid for
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multilayer coverage on adsorbent surface. The linearised Freundlich equation is given as

(Boparai et al., 2011):
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1
log qe  log K F  log Ce (19)
n

KF and n are Freundlich constants (L g-1) are related to adsorption capacity and intensity,
respectively. The Freundlich isotherm constants KF and n are calculated from the intercept and
slope of a plot of logqe versus log Ce (Fig. 11). As seen from Table 4, the values of adsorption
intensity (n) for adsorption of Au(III) ions onto IIP and CP are larger than unity and the KF
values are high as well, indicating favorable adsorption condition and reflecting chemisorptions
process (Boparai et al., 2011; Solangi et al., 2009). On the other hand, the values of n and KF for
adsorption Au(III) ions onto IIP are greater than CP polymer, showing higher feasibility of
adsorbing Au(III) ions by IIP compared to CP.
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3.3.4.3. Temkin isotherm

This isotherm is based on the assumption that the adsorption energy of all molecules in
the layer would decrease linearly with the surface coverage due to some indirect sorbate/sorbent

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interactions. The Temkin isotherm has been generally applied in the following form (Hu et al.,
2011)

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RT RT
qe  ln K T 

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ln Ce (20)
b b

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where R is the gas constant (8.314x103- KJ mol-1 k-1), T is the absolute temperature (K), b is the
Temkin constant related to the heat of sorption (KJ mol-1) and KT is the Temkin isotherm
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constant (L g-1).
Thus, Linear plots between qe and lnCe were obtained (Fig. 12) and Temkin constants are
given in Table 4. The Temkin model fits quite well with the experimental data at pH 6.0 for both
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IIP and CP as indicated by high correlation coefficients (R2 > 0.98); however this model did not
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satisfactorily fit with the corresponding results at pH 3.0. Clearly, one can conclude that the
adsorption of gold(III) ions onto the sorbent at pH 6.0 is a chemisorption process (Boparai et al.,
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2011). This is in line with the prediction from Langmuir isotherm for the equilibrium data at pH
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6.0. On the other hand, values of b (0.031–0.016 KJmol-1) give further evidence that the
adsorption process of gold(III) ions onto the adsorbents involve chemisorptions and
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physisorption (Hu et al., 2011).

3.3.4.4. Dubinin–Radushkevich (D-R) isotherm

The Dubinin–Radushkevich (D–R) isotherm model is a general model for the physical
adsorption processes. It follows a pore filling mechanism and is related to the porous structure of
the sorbent. It assumes heterogeneity of adsorption heat over the adsorbent surface and the
adsorption has a multilayer character, involving van der Waals interactions. The linear form of
D–R isotherm model is expressed as:

ln qe  ln qmax  βε 2 (21)
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where β is the activity coefficient related to free energy and ɛ is the Polanyi potential which is
defined as:

1
ε  RTln(1 

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) (22)
Ce

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The experimental data obtained for the adsorption of Au(III) ions on present sorbents
plotted for the D-R isotherm model is not presented graphically, but the isotherm constants are

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shown in Table 4. The magnitudes of the correlation coefficients for the D–R isotherm are the
lowest compared to the other three isotherm models (Table 4), indicating that the application of

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D-R model does not give a good fit for the experimental equilibrium data. Additionally, the qmax
values are quite different from the qm values previously determined for the Langmuir isotherm.
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This indicates that the adsorption process of gold(III) ions onto the sorbents is not solely
governed by physisorption (Boparai et al., 2011).
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3.3.5. Adsorption thermodynamics

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The influence of solution temperature on the adsorption of Au(III) ions onto IIP and CP
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IECS-GLA resins was studied using 430 mg L-1 initial metal concentration at 25, 40 and 55 ºC.
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As can be observed from Fig III in Supplementary data, the adsorption capacity of both resins for
adsorption of Au(III) ions increased significantly when the temperature is elevated from 25 to 55
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ºC, indicating the endothermic nature of the adsorption process. This increase may be caused by
the promoted rate of intra-particle diffusion of Au(III) ions and the possible enlargement of the
size of the pores (Shawky, 2009) . It was also apparent that the adsorption process for uptake of
Au(III) ions was not dominated by physisorption, which was remarkably affected by the elevated
temperature (Zhou et al., 2004). This is consistent with previous results on platinum adsorption
using immobilized bayberry tannin (Wang et al., 2005).
The thermodynamic parameters including change in free energy (∆Gº), enthalpy (∆Hº)
and entropy (∆S) were calculated from the following equations:
ΔS ΔH o
logK C   (23)
2.303R 2.303RT
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G  H  TS (24)
qe
KC  (25)
Ce

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where Kc is the equilibrium constant, qe is the equilibrium concentrations of Au(III) ions on the

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adsorbent (mg g-1), Ce is the equilibrium concentration of Au(III) ions in the solution (mg L-1), R
is the universal gas constant (8.314 J K-1 mol-1) and T is the temperature in Kelvin. The values of

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∆Hº and ∆Sº were calculated from the slope and intercept of Van’t Hoff linear plot (Fig. IV in
Supplementary data) and the results listed in Table I (see Table I in Supplementary data). The

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positive value of ∆Hº indicates the endothermic nature of the adsorption process whereas the
positive values for (∆Sº) infer that the adsorption process is a spontaneous process. This suggest
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that a remarkable change have taken place in the internal structure of the sorbent during Au(III)
ions adsorption. The observed greater positive value of ∆Sº for adsorption of Au(III) ions onto
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IIP-IECS-GLA than for the CP resin could be related to the difference in their surface
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morphologies. In contrast to the imprinted polymer, the control polymer (CP) tends to have a
smoother surface and a less porous structure resulting in a decrease in the randomness at the
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solid/solute interface during the adsorption of Au(III) ions onto the CP resin. On the other hand,
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the negative values of Gibbs free energy of adsorption (∆Gº) also confirm that the adsorption of
Au(III) ions is spontaneous. The increase in absolute values of ∆Gº with increasing temperature
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suggests that adsorption of Au(III) ions becomes more favorable as the temperature increases.
3.3.6. Selectivity studies

Competitive adsorption characteristic of control and Au(III) ion imprinted polymers were
systematically conducted for gold(III) ions in the presence of other selected inorganic ions.
These competitor ions were chosen as they coexist with precious metals in the natural sources,
and exhibit some interference properties in an aqueous environment. Furthermore, they are close
in character to gold(III) ions in terms of ionic radii. They are also classified as soft or borderline
metal ions in the Pearson’s classification. The distribution coefficient (Kd), the selectivity
coefficient (β) and the relative selectivity coefficient (k`) values of the competing ions with
respect to the target ions, Au(III) ions at two different pH values are summarized in Table 6. It is
observed that at pH 3.0, the coexistence of base metals (Cu(II), Mn(II), Ni(II), Fe(III) and Pb(II)
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ions) in the solutions did not influence the distribution coefficient of Au(III) ions. Hence the
selectivity patterns of Au(III) ions in comparison to these metals are much higher. The excellent
selectivity of the imprinted polymer for gold(III) ions at this pH can be explained by electrostatic
repulsion from the positively charged sorbent surface thus preventing their adsorption (Fujiwara

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et al., 2007; Lama et al., 2008). The selectivity of imprinted polymer toward precious metals at
pH 3.0 was also studied. Using the data presented in Table 6, the following order of the given

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imprinted polymer toward precious metals is: Pd(II) > Au(III) > Pt(IV). This observation was not

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unexpected in view of the higher ionic charge and smaller hydrated radius of [PdCl4]2- ion
compared to [AuCl4] - , causing higher affinity of [PdCl4]2- at the exchange sites.

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Clearly, the selectivity at pH 3.0 is not governed solely by the imprinted factor, since the
pH on its own exerted much influence on the selectivity of Au(III) ions uptake. The finding at
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pH 3.0 invited a study on the selectivity at pH 6.0, since it was found to be the optimum pH for
the uptake of some competitive cationic transition metals (Ni(II) and Cu(II)) by hetero-cycle
nitrogen chitosan derivatives (Bratskaya et al., 2012). Under this condition, where the N-
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containing group on the sorbent surface is partially deprotonated and the competition between
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the proton and metal ions for N- functional groups is eliminated, one can estimate that the
selectivity will depend mainly on the stability constants of these ions with ligating nitrogen
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atoms as well as the imprinted effect. It can be seen from the results summarized in Table 6 that
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the relative selectivity coefficients of IIP IECS-GLA for Au(III)/Cu(II), Au(III)/Ni(II),

Au(III)/Pd(II) and Au(III)/Pt(IV) were all higher than 1. The influence of investigated coexisting
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metal ions on the adsorption of Au(III) ions can be summarized in the following sequence:
Pt(IV)> Pd(II)> Ni(II)> Cu(II). Comparing this selectivity order with those recorded in the
literature, revealed significant differences to the data reported by different authors. The
selectivity sequence in these former studies are: Cu(II) > Ni(II) > Co(II) while the order for
noble metals adsorbed by this type of polymer are: Pd(II) > Pt(IV) > Au(III) (Bratskaya et al.,
2012). This difference in the selectivity order could be attributed to the specific recognition
cavities for gold(III) ions created in IECS-GLA, which are developed by ion imprinting process.
Based on this data, it is evident that the IIP IECS-GLA selectively adsorbed gold(III) ions
amongst the other metal ions in aqueous solutions.

3.3.7. Desorption and reusability study

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The effect of desorption and reusability of the polymer was performed in a batch experimental
setup using HCl, thiourea (Tu) and HCl-Tu solutions. The results presented in Fig. 13, reveal that
only 54.5 % of the loaded Au(III) ions leached in 2 M HCl and 46.1% has stripped with 0.7 Tu,
while 0.7 M Tu–2 M HCl solution can effectively desorbs the Au(III) metal ions (≥ 100%) from

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IIP IECS-GLA material in the first elution cycle. The high desorption efficiency could be
explained by the formation of stable complexes along with electrostatic interaction between

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Au(III) ions and charged species from the desorbing solution. This can lead to less gold(III)

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metal ions binding to the adsorbent, thus enhancing desorption process (Fujiwara et al., 2007).
The potential regeneration of the adsorbent was also investigated using 0.7 M Tu-2 M HCl as

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desorbing agent. Thus, the IIP-IECS-GLA after leaching was reused for the next adsorption-
desorption cycle, and the process was repeated up to five consecutive cycles. As seen from Fig
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13, there were no remarkable changes on the adsorption efficiency of Au(III) ions on IIP IECS-
GLA up to 5 cycles and desorption efficiency was above 95%. This implies that the imprinted
polymer (IECS-GLA) had good reusability. Therefore, the gold(III) ion imprinted polymeric
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material could be successfully regenerated and repeatedly used in Au(III) ions recovery without
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significant losses in their adsorption capacity.

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3.3.8. Application to simulated mining solution and acid mining drainage (AMD)
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In order to explore the applicability of the prepared polymers to real-world samples, two
sets of experiments for the recovery of gold(III) ions from simulated mining solutions and acid
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mine drainage water were conducted. In the first set of experiments, the simulated mining
solution was prepared based on the conventional method for gold refinery using Miller
chlorination process followed by the Wohlwill electrolytic process. The composition of the
mining solution was adopted from the method described in the literature (Lama et al., 2008), and
it had: 84.0 ppm Au(III), 33.0 ppm Pd(II), Cu(II) and Fe(III), and 0.04 ppm Pt(IV) metal chloride
salts and the pH was adjusted to 2.5. Batch extraction was carried out by adding 0.01 g polymers
to each of three 10 mL of simulated mining solutions. The solutions were allowed to equilibrate
for 60 min at room temperature. The concentration and extraction percentages of gold(III) and
other metal ions in the solutions, after the extraction by IIP-IECS-GLA polymer were: 78.9
(93.9%), 33.0 (100.0%), 0.04 (100.0%) 0.0 (0.0 %) and 0.0 mg L-1 (0.0%) and for CP-IECS-
GLA were: 42.0 (50.0%), 33.0 (100.0%), 0.04 (100.0%), 4.5 (13.0%) and 2.0 mg L-1 (5.8%) for
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Au(III), Pd(II), Pt(IV), Fe(III) and Cu(II) ions, respectively. It can be concluded from these
results that IIP IECS-GLA adsorbed gold(III) ions (nearly 95%) and completely adsorbed
palladium(II) and platinum(IV), but not the copper(II) and iron(III) ions. This result is in
agreement with previous selectivity results. However, in the case of CP-IECS-GLA polymer the

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gold(III) ions were extracted up to 50% efficiency. Also palladium(II) and platinum(IV) ions
were completely adsorbed and small quantities of copper(II) and iron(III) ions were co-extracted.

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Thus, the IIP-IECS-GLA could be a promising alternative for the extraction and recovery of

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precious metals from chloride rich media.

In the second set of experiments, samples from acid mine drainage water (AMD) were

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used without pH adjustment to avoid solid precipitation. The extractions were determined as a
function of initial concentration of gold(III) ions. In this study, four samples of AMD samples
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were spiked with 20, 60, 90 and 180 mg L-1 Au(III) ions using HAuCl4 salt solution. The
experiments were performed in batch mode following the similar condition mentioned earlier.
Preliminary investigation indicates that the extraction efficiency for both IIP and CP IECS-GLA
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polymers was not affected by the presence of other metal ions at different initial gold(III) ions
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concentration (Fig 14). Nevertheless, Fe(III) ions were the only ions in AMD water significantly
co-extracted by the control polymer, but not by IIP. The extraction of Fe(III) ions by control
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polymer reached 73%, 62%, 64% and 63% at gold(III) ions initial concentration 20, 60, 90 and
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180 mg L-1, respectively. This discrepancy between IIP and CP is not surprising, since IIP
selectivity is based on metal geometry in addition to ionic interaction. The results indicate that
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IIP IECS-GLA polymer has higher affinity towards Au(III) ions than the other metal ions under
competitive and high ionic strength conditions.

4. Conclusions

The present study focuses on extraction or recovery of Au(III) ions from aqueous solution using
ion-imprinted IECS-GLA polymer as an effective adsorbent. The interest in using the IIP IECS-
GLA for the extraction or recovery of the Au(III) ions from aqueous solutions is driven by the
possibility of obtaining high adsorption capacity along with excellent selectivity. The results
demonstrated that the adsorption process was dependent on contact time, initial metal ion
concentration, solution acidity and solution temperature. A short contact time was observed at
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the beginning of the adsorption process making this resin suitable for online operation during the
extraction process. Kinetic studies suggested that the adsorption reaction is a pseudo-second
order and liquid film diffusion may be involved in the sorption process. Equilibrium experiments
fitted well with the Langmuir model and Temkin model. The imprinted resin showed higher

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adsorption capacity for the Au(III) ions compared with the control resin due to a large number of
cavities matching with gold ions by ion imprinting. In addition, the adsorption capacity for the

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imprinted polymer was found to be less influenced by the acidity change (up to pH 6.0) than the

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control polymer. Thermodynamic parameters obtained indicated that the adsorption process is an
endothermic spontaneous reaction. The sorbent is efficient for gold(III) ions extraction in

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aqueous media containing other closely related ions, such as base metals and other precious
metals. The selective adsorption of Au(III) ions by the IIP from strongly complex mixture such
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as acid mining drainage and stimulated mining solutions indicates its applicability in preferential
recovery of Au(III) ions from industrial solutions containing gold. Furthermore, 0.7M thiourea–
2.0M HCl solution can effectively desorbed Au(III) ions from the polymer. The regenerated
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adsorbents exhibited the same adsorption capacity as the fresh resin. The latter is very beneficial
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in practical applications for the specific recovery of Au(III) ions from aqueous solutions.
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Acknowledgements
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The authors are grateful to the University of Johannesburg (Republic of South Africa) for
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financial support, to Prof. Laetitia Den Drijver (Head of Chemistry Department), Eve Kroukamp
and Mr. Motlatsi Phali (University of Johannesburg) for the assistance in laboratory
measurement.

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application to retrieval of silver ions from processed photo films. Hydrometallurgy 80:
98– 106.
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Aydın, A., MustafaImamoglu and Gulfen, M., 2008. Separation and Recovery of Gold(III) From
Base Metal Ions Using Melamine–Formaldehyde– Thiourea Chelating Resin. J Appl
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Table 1 Physical properties of IECs-GLA used in the experiments

Physical characteristics Value

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Color Reddish-brown

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Particle size (mm) 0.420 - 0.354

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Bulk density (g cm−3) 0.664 ± 0.243

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Swellability (%) (in water) 51.297 ± 0.432

Water content (%) 14.298 ± 3.723

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Soluliblity (in acidic and orgnic solvent) insoluble
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Gel content 87.218 ± 1.759

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Crystalinity Amorphous
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CE
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Table 2 Concentration of active sites on the resins obtained.

Resin Concentration of active sites, mmol/g

Cs-GLA 0.5

I-Cs-GLA 2.1

IECs-GlA 5.3
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Table 3 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.

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Polymer Pseudo-first-order kinetics Pseudo-second-order kinetic Intra-particle diffusion

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qe(exp) K1 qe(cal) R2 k2(g.mg- qe (cal) R2 kid(mg.g- Intercepts

SC
(mg.g1) (mg.g-1) 1
min-1) 1
min0.5) (mg g-1) R2
(min-) (mg.g1)

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IIP 178.81 0.0530 223.111 0.9934 0.0002 234.74 0.9985 19.451 19.066 0.9684

Ferror - - - 0.0003
MA - - 0.00003 - - 0.0361

CP 123.11 0.0121 149.896 0.9821 0.0002 160.26 0.9449 13.079 6.597 0.9834

Ferror - - - 0.0020 - - 0.0006 - - 0.0226

D

Liquid film diffusion

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Intercept
Kfd (min-1) R2
P

-1
(mg.g )
CE

0.1779 0.2865 0.9705

- 0.0578
AC

Ferror

0.0162 0.129 0.9796

Ferror - 0.0554
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Table 4 Fitting parameters for the Freundlich, Langmuir, Temkin and D-R to experimental
adsorption isotherm of Au(III) ion imprinted and non imprinted polymers.

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Isotherm pH Parameters
R2 Ferror

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KF n

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IIP CP IIP CP IIP CP IIP CP

Freundlich 6 164.4598 17.2469 4.7596 1.8808 0.9713 0.9663 0.0115 0.0132

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3 268.1020 129.6582 6.0533 3.5211 0.9158 0.9694 0.0112 0.0067

Isotherm pH Parameters R2 Ferror

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KL(L mg-1) qm(mg g-1)

IIP CP IIP CP IIP CP IIP CP

D

Langmuir 6 649.3506 427.3504 0.9109 0.0197 0.0293

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0.0219 0.0218 0.9981

3 0.0321 0.0196 819.6720 775.1938 0.9844 0.9889 0.0510 0.0752

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pH Parameters
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Isotherm R2 Ferror
KT(L g-1) b(KJ mol-1)
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IIP CP IIP CP IIP CP IIP CP

Temkin 6 28.0677 0.0012 0.0308 0.0162 0.9846 0.9925 0.0390 0.0298

3 935.8170 0.2962 0.0301 0.0183 0.8712 0.9463 0.0931 0.2387

Isotherm pH Parameters
R2 Ferror
qd (mg g-1) βd

IIP CP IIP CP IIP CP IIP CP

D-R 6 286.1396 408.0337 1.15x10-5 6.97x10-4 0.9083 0.9416 0.1662 0.0191

3 578.4199 552.0949 5.61x10-7 3.51x10-5 0.7209 0.77144 0.0195 0.0172

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Table 5 Maximum adsorption capacities for the adsorption of Au(III) ions onto various
adsorbents.

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Adsorbents pH Adsorbent Contact qe (mg.g-1) Reference
-1
dose (g.L ) times (h)

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L-lysine modified cross-linked
2.0 3.3 4.0 70.34 (Fujiwara et al.,

SC
chitosan resin
2007)

Rubeanic acid grafted cross-

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2-3 0.05 120.0 70.34 (Arrascue et al.,
linked chitosan
2003)

Glycine modified cross-linked

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2.0 3.3 4.0 169.98 (Ramesh et al.,
chitosan resin
2008)

Bisthiourea- formaldehyde resin

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2.0 1.0 5.0 661.82 (Atia, 2005)

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Melamin–formaldehyde–
2.0 1.0 2.0 48.0 (Aydın et al.,
thiourea resin
2008)
P
CE

2.0 0.5 18.0 689.40 (Bratskaya et al.,

Thiocarbamoyl chitosan resin
2011)
AC

Magnetic chemically modified

0.5 2.0 3.0 709.09 (Donia et al.,
chitosan resin
2007)

poly(acrylamide-allylthiourea)
0.5 5.0 90.0 940.0 (Kılıc et al.,
hydrogels
2005)

Phosphine sulphide-chelating
0.0 0.8 22.0 551.52- (Sanchez et al.,
polymers
1280.31 2001).

IECS-GLA resin
3.0 1.0 1.5 810.67 This work
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Table 6 Competitive adsorption properties of Au(III)-IECS-GLA imprinted polymer: (mixtures:

Au(III)/Cu(II)/Ni(II)/Mn(II)/Pb(II)/Fe(III)/Pd(II)/Pt(IV)), T 25 ± 1 ºC, time 90 min; pH 6.0 and 3.0 ± 0.1)

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pH= 6 pH = 3

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Couple mixture KD Au3+ (ml/g) KD Mn+ (ml/g) βAu/M KD Au(III) (ml/g) KD Mn+ (ml/g) βAu/M
k` k`

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IIP CP IIP CP IIP CP IIP CP IIP CP IIP CP

ED
Au(III)/ Cu(II) 23.853 7.372 0.000 0.351 ∞ 21.027 ∞ 4.263
8.196 2.307 0.045 0.054 182.133 42.722

Au(III)/ Ni(II)
PT 6.290 3.405
CE
134.361 21.361 520.925 153.0
8.196 2.307 0.061 0.108 34.902 11.781 0.067 0.077
AC

Au(III)/ Mn(II) - - - - 2.287

26.402 14.067 0.032 0.039 825.063 360.692

Au(III)/ Pb(II) - - - - 538.816 152.902 3.524

26.402 14.067 0.049 0.092

Au(III) / Fe(III) - - - - 3.004

7.324 4.787 0.488 0.958 15.008 4.996
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pH= 6 pH = 3

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KD Au3+ (ml/g) KD Mn+ (ml/g) βAu/M KD Au3+ (ml/g) KD Mn+ (ml/g) βAu/M
Couple mixture k` k`

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IIP CP IIP CP IIP CP IIP CP IIP CP IIP CP

SC
Au3+/ Pd2+ 2.490 2.300 2.452 6.210 2.743 0.685 1.493 2.724 1.961 0.251 0.761 0.300

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1.015 0.370

MA
ED
PT
CE
AC
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Figure legends

Scheme 1. Preparation of Au(III) IECS -GLA ion imprinted polymer.

Fig.1. FT-IR spectra of (a) control; (b) Au(III) IIP- IECS-GLA before and (c) after leaching.

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Fig.2. Scanning electron micrographs of (a) ion imprinted IIP IECS-GLA, ×2, 000; and (b)

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control polymers CP IECS-GLA, ×2, 000.

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Fig.3. Effect of pH on adsorption capacity of Au(III) ions onto ion imprinted and control IECS-
GLA. Adsorbent dose, 1.0 g L-1; initial concentration, 160 mg.L-1; temperature, 25 ± 1 ºC;

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contact time, 60 min; agitation speed, 200 rpm.

Fig.4. Zeta potential curves vs. pH of IIP and CP polymers used to quantify the electrical
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potential of the polymers.

Fig.5. Influence of contact time on the adsorption of Au(III) ions onto IECS-GLA ion imprinted
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and control polymers (adsorbent dose, 1.0 g L-1; initial concentration, 180 mg L−1; pH value, 6.0;
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temperature, 298 K; agitation speed, 200 rpm.)

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Fig.6. Effect of initial concentration for the adsorption of Au(III) ions onto ion imprinted
polymers (metal ion concentration: 160 -1200 mg L-1; contact time: 1.5 h; pH 3.0 and 6.0;
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temperature: 25 ± 1oC, adsorbent dose: 1.0 g L-1.)

AC

Fig. 7. Pseudo-first-order kinetic model for the adsorption of Au(III) ions onto IECS-GLA
imprinted and control polymers (adsorbent dose, 1.0 g L-1; initial concentration, 180 mg L−1; pH
value, 6.0; temperature, 298 K; agitation speed, 200 rpm).

Fig.8. Pseudo-second-order kinetic model for the adsorption of Au(III) ions onto IECS-GLA
imprinted and control polymers (adsorbent dose, 1.0 g L-1; initial concentration, 180 mg L−1;
pH value, 6.0; temperature, 298 K; agitation speed, 200 rpm.)

Fig. 9. Intra-particle diffusion model plot for the adsorption of Au(III) ions onto IECS-GLA
imprinted and control polymers (adsorbent dose, 1.0 g L-1; initial concentration, 180 mg L−1; pH
value, 6.0; temperature, 298 K; agitation speed, 200 rpm
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Fig.10. Langmuir isotherms for the adsorption of Au(III) ions onto IECS-GLA ion imprinted
and control polymers; temperature: 25 ± 1 oC; pH 3.0 and 6.0.

Fig.11. Freundlich isotherms for the adsorption of Au(III) ions onto IECS-GLA ion imprinted

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and control polymers; temperature: 25 ± 1 oC; pH 3.0 and 6.0.

Fig.12. Temkin isotherm for the adsorption of Au(III) ions onto IECS-GLA ion imprinted and

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control polymers; temperature: 25 ± 1 oC; pH 3.0 and 6.

SC
Fig.13. Effect of desorbing solution and the performance of Au(III) ion imprinted polymer in
consecutive cycles.

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Fig. 14. Efficiency of IIP and CP IECS-GLA polymers in metal ion extraction from real acid
mine drainage water (AMD) using different Au(III) ions concentration. (Initial spiked
MA
concentration of Au(III) ions in AMD, 20, 60, 90 and 180 mg L-1; adsorbent dose; 1.0 g L-1, pH
3.01).
D
P TE
CE
AC
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OH OH
OH OH
O O
O O O O
Step 1
O O
O O
NH2 CH=CH2 NH2
NH2 N N N

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OH OH n OH OH n
N N N N

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i) Au3+
Step 2

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ii) O O
Cl

HO OH
OH
OH O

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O O
O
O O
O O O
O N
O OH N
OH n
N
N N N
OH OH
MA n N N
N N Step 3 Au
N N
Au Cl
CH2 N OH
CH2 CH
N OH O O
O
D

O O
O
O OH n
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OH n

Step 4 H2N
NH2
P

HN
NH2
HO
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OH
O NH2 H
N
O N
HN

O O
O Step 5 OH
AC

O N
N Leaching O
OH N NH
OH n
N N N N
Au
IIP IECS-GLA

N OH
O O
O

OH n

Scheme 1.
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Fig. 1
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(a) (b)

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Fig. 3
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Fig. 4
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Fig. 5
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MA
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Fig. 6
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P
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AC

Fig. 7
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D
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Fig. 8
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CE
AC

Fig. 9
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MA
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Fig. 10
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P
CE
AC

Fig. 11
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Fig. 12
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CE
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Fig. 13
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Fig. 14
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Highlights:

 Synthesis of New gold (III) ion imprinted polymers (IIPs) materials.

PT
 With outstanding selectivity and adsorption capacity.

RI
 Perform better than most of the existing gold (III) adsorption materials.

SC
 Suitable for adsorption online (short contact time).

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 Selectivity and adsorption capacity are not lost upon regeneration.
MA
D
P TE
CE
AC