Chemical Engineering Journal 483 (2024) 149325

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Chemical Engineering Journal

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Constructing a cationic pyridine for the highly selective and efficient

recovery of gold from waste printed circuit boards
Shuliang Chen a, b, Li Zhao b, c, Xinrong Li b, c, Zhen Chen a, b, Xianzhi Hu a, b, *, Futing Zi a, b, *
a
Faculty of Science, Kunming University of Science and Technology, Kunming 650000, China
b
Yunnan Province University Key Laboratory for Chemical Separation Enrichment & Application, Kunming 650000, China
c
Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650000, China

A R T I C L E I N F O A B S T R A C T

Keywords: Recovering gold from rich waste printed circuit boards (WPCBs) resource are of great significance to gold
Waste printed circuit boards development and utilization. In this paper, cationic pyridine polymers with different configurations were
Au(III) designed and synthesised for highly selective and efficient recovery of gold from a WPCB leaching solution. The
Selectivity
structures and performances of the cationic pyridine polymers were analysed using a 4–aminopyridine poly­
Recovery
Cationic pyridine skeleton
chloromethylstyrene (4–AP/PCMS). The results indicate that the 4–AP/PCMS performed well in an acidic
environment, including in the 5 % aqua regia solution. Gold adsorption on the 4–AP/PCMS followed pseu­
do–second–order kinetics and Langmuir isotherm models, suggesting that chemisorption occurred via a single­
–layer mechanism with a maximum loading capacity of 437.68 mg/g. Further, Au(III) adsorption on the 4–AP/
PCMS involved electrostatic interactions and reduction between pyridine and AuCl−4 . After five adsorp­
tion–desorption cycles, the adsorption rate remained above 99 %, whereas in actual leaching solutions it reached
92.24 %. All five pyridine polymers demonstrated outstanding Au(III) selectivity over binary and multicompo­
nent solutions containing Cu(II), Ni(II), Co(II), Zn(II), Fe(III), Cd(II), and Mg(II), benefitting from the cationic
pyridine skeleton. Contact patterns between the cationic pyridine polymers and AuCl−4 considerably affected the
gold loading capacity, and a single–point contact was found to be favourable for gold adsorption. These results
indicated that cationic pyridine polymers are promising for recovering gold from WPCB leaching solutions.

1. Introduction species in a WPCB leaching solution is considerably higher than that of

Natural gold resources are limited and low in abundance, and they
can only be mined in a few geographically valuable areas. The recent
increase in the consumption of high–grade gold has led to a significant
increase in gold mining and extraction costs [1]. Discarded electronic
goods, such as WPCBs, often contain a higher gold content than that in
the natural resources. Therefore, resource recycling, wherein gold is
recovered and recycled from such discarded electrical goods, is urgently
required [2]. WPCBs are characterised by large quantities, high pollu­
tion levels, and high resource value [3,4].
Hydrometallurgy is one of most promising methods for gold recovery
from WPCBs due to its efficiency, low gas emissions and cost­
–effectiveness [5,6]. Hydrometallurgical processes typically involve
acid or alkaline solutions, followed by separation and enrichment pro­
cedures such as electrowinning, replacement, extraction, and adsorption
[5,7,8]. What is remarkable that the concentration of metal ion and
natural minerals, caused the conventional recycling method cannot
meet industrial production demand. In particularly, the concentration
difference of gold and other co–leached metals (e.g., copper, nickel) is
significantly greater than that observed in ore leaching solution, which
reduces both the gold recovery efficiency and product purity. Therefore,
gold separation and enrichment procedure from WPCB leaching solu­
tions help ensure that the leaching solutions contain high concentrations
of co–leached metals. Nitrogenous adsorbents exhibit excellent capa­
bilities in terms of recovering gold from acid leaching solutions because
of their high efficiency and selectivity for separating gold ions from
multiple ions. For example, Choudhary [9] employed a poly­
ethylenimine–modified leaf powder as an adsorbent for gold enrich­
ment, Kong [10] synthesised triazine framework adsorbents (NH2–CTFs)
for recovering gold(III), and Zhao Li [11] developed aminated micro­
spheres (PS–TETA) for recovering gold(I) from a thiosulfate alkaline
solution. Although there have been previous studies on gold resource

* Corresponding authors at: No 727 Jingming South Road, Kunming, China.

E-mail addresses: xianzhihu2@sina.com (X. Hu), 404800439@qq.com (F. Zi).

https://doi.org/10.1016/j.cej.2024.149325
Received 14 September 2023; Received in revised form 22 January 2024; Accepted 1 February 2024
Available online 6 February 2024
1385-8947/© 2024 Elsevier B.V. All rights reserved.
S. Chen et al.
separation and concentration, the efficient and selective recovery of
gold from multiple metal ions solutions is crucial for gold resource cyclic
utilization.
Compared to conventional neutral adsorbents, constructing mate­
rials with an antielectric skeleton for electrostatic attraction with target
ions is a promising method to improve the efficiency and selectivity of
adsorption by enhancing the host–guest repulsion/attraction [12]. The
cationic skeleton material of SCU–CPN–1 (Soochow University–Cationic
Polymeric Network–1) exhibits efficient separation of TcO−4 from spent,
highly acidic nuclear fuel [13]. An ionic–functionalized ordered mac­
ro–microporous viologen–unit grafted organic–framework (iVOFm)
demonstrates the effective removal of toxic pollutants from water [14].
Cationic adsorbents with robust electrostatic interaction exhibit pro­
nounced affinity and repulsion for oppositely and positively charged
ions, respectively. The construction of an adsorbent with a cationic
framework is an effective approach for the efficient and selective re­
covery gold from acid–leaching solution.
Pyridine is a six–membered heterocyclic compound with N atoms
that form a cyclic conjugated structure; the N atoms have a pair of lone
electrons that form complexes with metal ions [15,16]. The charge
density of pyridine can be modulated by the N atom through cyclic
conjugated structure to form a charged six–membered ring. Moreover,
pyridine substances can form cantilevered structures suspended by
amino groups derived from the adsorbent. These properties confirm that
pyridine can be used as a functional monomer on solid–phase supports
and to separate metal ions. The n-aminomethylpyridine demonstrated a
strong affinity towards gold [17]. But, further investigation is required
to explore the correlation between the selectivity mechanism or
adsorption properties and the structural characteristics of pyridine.
In this study, a series of cationic aminopyridine–based poly­
chloromethylstyrene polymers (short name pyridine polymers) were
designed and synthesized via a nucleophilic substitution reaction to
realise the efficient and highly selective recovery of gold(III) form a
WPCB leaching solution. The chemical structure, morphology and
porosity of 4–aminopyridine polychloromethylstyrene (4–AP/PCMS)
polymer, which is a representative pyridine polymer, were characterised
by Fourier transform infrared (FT–IR) spectroscopy, scanning electron
microscopy energy–dispersive X–ray spectrometry (SEM–EDS), N2
adsorption–desorption isotherms, zeta potential, and X–ray photoelec­
tron spectra (XPS). Further, the effects of solution acidity and gold
adsorption process were tested, and the gold selectivity of pyridine
polymers in binary and multiple component metal solutions was ana­
lysed. The relative location of pyridine and amino groups on the gold
loading capacity and selectivity was investigated through an electro­
static potential (ESP) analysis, and weak interactions were concluded
with quantum chemical calculations. The obtained results are expected
to guide future design strategies in enhancing the binding ability and
selectivity of adsorbents for gold separation and purification from WPCB
leaching solutions.
2. Method
2.1. Reagent
Polychloromethylstyrene (PCMS) with a chlorinity of 17 % and
divinylbenzene content of 7–8 % was obtained from the Tianjin Reagent
Company. 2–aminopyridine (2–AP, 99 %), 3–aminopyridine (3–AP, 99
%), 4–aminopyridine (4–AP, 98 %), 2–picolylamine (2–PA, 99 %),
3–picolylamine (3–PA, 99 %) and 4–picolylamine (4–PA, 98 %) were
purchased from Aladdin Reagent Co., LTD (Shanghai, China). N,
N–dimethylformamide (DMF) was obtained from Tianjin Fengchuan
Chemical Reagent Technology Co., LTD. All other reagents used in the
experiments were of analytical grade.
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Chemical Engineering Journal 483 (2024) 149325
2.2. Preparation of pyridine polymers
Cationic pyridine polymers were produced via the nucleophilic re­
action of the chloromethyl group in PCMS with the amino groups in
aminopyridine. PCMS (2 g) was placed in a three–necked flask with 30
mL of DMF and allowed to swell for 3 h at room temperature. Further,
15 mmol aminopyridine and 1 g NaHCO3 were added and refluxed at
60 ◦ C for 24 h. Then, the mixture was filtered and washed with DMF and
deionised water, and it obtained a solid phase immersed in 1 mol/L HCl
for 5 h. The product was washed several times with deionised water, and
vacuum dried at 60 ◦ C. A series of products were obtained, namely
2–AP/PCMS, 3–AP/PCMS, 4–AP/PCMS, 2–PA/PCMS, 3–PA/PCMS, and
4-PA/PCMS according to the type of pyridine. The N wt% values
determined using the oxygen/nitrogen/hydrogen analyser were 7.78 %,
14.40 %, 13.60 %, 11.80 %, 15.30 %, and 15.80 %, respectively.
2.3. Adsorption experiments
The adsorption experiments were conducted at room temperature,
except for the notes. The prepared adsorbent and pH–adjusted metal
ion–containing solution were added to a 100 mL Erlenmeyer flask and
absorbed for a certain time under mechanical stirring at a constant speed
of 250 rpm. The concentrations and components of the metal­
–ion–containing solutions were prepared according to the experimental
requirements using analytical reagent metal salts CuSO4, ZnSO4, MgSO4,
Fe(NO3)3, NiCl2, and CoCl2. The pH of the liquid was regulated using a
NaOH or HCl solution. Further, a KAuCl4 solution was prepared using
metal gold (≥99.99 %) via the aqua regia method. The adsorption rate
(R, %) and loading capacity (Q, mg/g) were calculated by Eqs. (1) and
(2) respectively.
c0 V0 − ct Vt
R= × 100% (1)
c0 V
c0 V0 − ct Vt
Q= (2)
m
Where, c0 and ct are the initial and t time ion concentration (mg/L). V0
and Vt are initial and t time adsorption solution volume (L) respectively.
m is the mass of adsorbent (g).
2.4. Characterization methods
The metal ion content was quantitatively analysed using atomic
absorption spectroscopy (AAS–300, PerkinElmer, USA) and inductively
coupled plasma–atomic emission spectrometry (ICAP7000, Thermo
Fisher Scientific, USA). The N content of the adsorbents were analysed
using an oxygen/nitrogen/hydrogen analyser (HORIBA EMGA–930,
Japan). FT–IR spectra were recorded in range of 4000–400 cm− 1 using
Nicolet iS10 (Thermo Fisher Scientific, USA). SEM and EDS were per­
formed using Phenom Prox (FEI Co., USA); XPS were obtained under Al
Kα X–ray radiation using K–Alpha (Thermo Fisher Scientific, USA). The
specific surface areas and pore structures were measured via N2
adsorption at 77 K (Beishide Instruments, China). Zeta potential data
were obtained using a zeta potential analyser (Anton Paar, Litesizer500,
Austria).
2.5. Quantum chemistry calculations
All structural model construction and quantum chemistry calcula­
tions were performed using GaussView 5.0 and Gaussian 09 W pro­
grams, respectively [18]. The density functional theory (DFT) of B3LYP
[19] functional was adopted for optimizing the structure using a mixed
basis set, LANL2DZ for gold and 6–311 + g(d, p) for other elements.
Multiwfn [20] and VMD [21] programs were used for the visual analysis.
The basis set superposition error (BSSE) for interaction energy was
considered as Eq. (3).
S. Chen et al.
Einteraction = EAB − EA − EB + EBSSE (3)
3. Results and discussion
3.1. Characterization of pyridine polymers
The nucleophilic substitution reaction of aminopyridine on the
PCMS was characterised by FT–IR spectroscopy. The spectra of PCMS,
4–AP, and 4–AP/PCMS are presented in Fig. 1, and those of the other
pyridine polymers are shown in Fig. S1. The peak at 674 cm− 1 indicates
the characteristic absorption of the C–Cl bond stretching vibration in
PCMS [22], which almost disappeared in 4–AP/PCMS. Peaks at ~ 1208,
1328, and 1650 cm− 1 were attributed to the C–N and C = N stretching
vibrations of the pyridine ring and the N–H bending vibration of primary
ammonia derived from 4–AP [23]. A new peak at 1538 cm− 1, which
contributed to –NH/–NH2, appeared in 4–AP/PCMS [24,25]. 4–AP
attached to the PCMS through the chemical reaction of chloromethyl
with the primary amine. The FT–IR spectra obtained from the experi­
ments were compared with those calculated using DFT to further vali­
date the structure of 4–AP/PCMS. As depicted in Fig. S2, major peak
positions exhibit a close resemblance between the two sets of data,
thereby providing additional support for the aforementioned
conclusions.
The N2 adsorption–desorption isotherms of 2–AP/PCMS, 3–AP/
PCMS, 4–AP/PCMS, 2–PA/PCMS, 3–PA/PCMS, and 4–PA/PCMS were
recorded at 77 K to measure the specific surface area, pore volume, and
pore diameter. Fig. 2 shows isotherms and proposed structures of the
cationic pyridine polymers; the isotherms of all polymers belong to type
IV, which indicate mesoporous structural features based on the IUPAC
classification [26]. Further, an H3 hysteresis loop was formed during the
adsorption and desorption processes, which is characteristic of meso­
porous materials. Table 1 summarises the specific surface areas, porosity
characteristic parameters, and N contents of the polymers. Both the
specific surface area and pore volume exhibited varying degrees of
reduction after the substitution reaction, which was potentially attrib­
uted to the collapse of certain micropores, thereby resulting in a minimal
or slight enlargement of the pore size. The N content in the polymer was
dependent on the pyridine content, and there appeared to be no direct
correlation with the specific surface area based on the measured N
content.
The SEM and EDS results for PCMS, 4–AP/PCMS, and 4–AP/
PCMS@Au (gold–loaded 4–AP/PCMS) (Figs. S3 and S4) show that the
surface of the material became smoother after substitution. This
Fig. 1. FT–IR of PCMS, 4–AP, and 4–AP/PCMS.
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Chemical Engineering Journal 483 (2024) 149325
indicates that 4–AP was attached to the surface because of the substi­
tution reaction occurring in the PCMS; therefore, there is an obvious
nitrogen peak in the corresponding EDS results. The shape of the mi­
crospheres did not change after the substitution reaction, thereby indi­
cating the excellent stability of the pyridine polymer.
Fig. 3 shows the XPS results for PCMS and 4–AP/PCMS. A wide–scan
survey of 4–AP/PCMS revealed more prominent N 1s peaks than those of
PCMS, which indicates that N was introduced into the polymer. The
high–resolution N 1s spectrum of 4–AP/PCMS in Fig. 3c was divided into
C = N, C–NH, and nitrogen oxide peaks at 398.98 (58.9 %), 400.68
(32.3 %), and 405.38 (8.8 %) eV, respectively [27]. These results suggest
that the configuration of the 4–AP graft on the material underwent slight
changes, with a portion of the nitrogen in pyridine oxidised during the
nucleophilic substitution reaction [28]. The high resolution spectrum of
Cl 2p before and after reaction were analysed, and the peak of Cl 2p3/2 at
199.53 eV (Fig. 3b) and 196.68 eV (Fig. 3d) were attributed to CH2–Cl
[29] and inorganic chlorine [30]. This implies that almost all the chlo­
rine on the chloromethyl of PCMS was replaced by an amino group of
4–AP in the substitution reaction, followed by the electrostatic adsorp­
tion of inorganic chlorine onto the polymer surface during subsequent
acidification.
3.2. Selectivity of cationic pyridine polymers
3.2.1. Binary component adsorption
High adsorbent selectivity is crucial for the recovery of high–purity
Au from practical hydrometallurgical solutions. The selectivity of
cationic pyridine polymers was evaluated through batch experiments at
room temperature. Fig. 4a and b plotted the Au(III) and Mn+ (Cu(II), Ni
(II), Co(II), Zn(II), Fe(III), Cd(II), and Mg(II)) adsorption rates of the
different pyridine polymers in binary solutions. Experiments were per­
formed using equal metal ion concentrations. All pyridine polymers
exhibited exclusive adsorption of gold over Mn+ in their binary com­
ponents. The uptake of pyridine polymers by Au(III) exhibited a signif­
icantly higher affinity than those of the other metal ions, with an
adsorption rate exceeding 98 %, except for 2–AP/PMCS. The decrease in
the Fe(III) content of the solution could be related to the hydrolysis of Fe
(III). Therefore, the effect of Fe(III) on Au(III) adsorption was investi­
gated in the absence of Fe(III) hydrolysis (pH < 2.2). Fe(III) had almost
no effect on Au(III) adsorption. The results indicated that pyridine
polymers have outstanding selectivity for Au(III) in binary solutions
containing interfering ions such as Cu(II), Ni(II), Co(II), Zn(II), Fe(III),
Cd(II), and Mg(II).
3.2.2. Multiple component adsorption
Five cationic pyridine polymers exhibited good selectivity for binary
solutions. The selectivity of pyridine polymers for Au(III) was evaluated
in a multicomponent solution of Au(III), Cu(II), Ni(II), Co(II), Zn(II), Fe
(III), Cd(II), and Mg(II) at the same initial concentration. Fig. 5 shows
that the adsorption rate of the pyridine polymers for Au(III) was
significantly higher than that for the other metal ions. In addition to
2–AP/PCMS, the adsorption rate of alternative gold materials was nearly
100 %, whereas it showed negligible affinity toward the other metal
ions. The distribution coefficient (kd) of 4–AP/PCMS for various metal
ions was calculated to determine material selectivity [31]. Table 2
shows that the Kd value toward Au(III) reached 5.35 × 105, further
demonstrating the good selectivity of pyridine polymers for separating
Au(III) from the multiple–component solution.
3.2.3. Zero–point charge pH measurement
The surface zeta potential of 4–AP/PCMS was monitored at different
pH values in Fig. 6. The point of zero charge (PZC) of 4–AP/PCMS
occurred at pH 6.58, which indicates that the surface of 4–AP/PCMS
displays a positive charge at a pH below 6.58 and a negative charge at a
pH above this threshold. Pyridine polymers with an antielectric skeleton
benefit from the electrostatic attraction to target ions. The acidic
S. Chen et al. Chemical Engineering Journal 483 (2024) 149325

Fig. 2. The N2 adsorption–desorption isotherm at 77 K. a) 2–AP/PCMS, b) 3–AP/PCMS, c) 4–AP/PCMS, d) 2–PA/PCMS, e) 3–PA/PCMS, and f) 4–PA/PCMS.

of the blue and red areas represent the magnitudes of negative and
Table 1
positive electrostatic potentials, respectively. The energies are presented
Surface area, porosity characteristics and N element content of PCMS, 2–AP/
in Table S1. Further, the energy of the pyridine polymers decreased after
PCMS, 3–AP/PCMS, 4–AP/PCMS, 2–PA/PCMS, 3–PA/PCMS, and 3–PA/PCMS.
the protonation of the amino group at different positions, thereby
Surface area Pore volume Pore diameter N wt
indicating that protonation conferred enhanced stability to the adsor­
(m2/g) (cm3/g) (nm) %
bents. Moreover, pyridine polymers exhibit a higher propensity for ring
PCMS 36.3390 0.3554 39.12 – protonation based on the observed energy drop, whereas 2–PA/PCMS
2–AP/ 31.9741 0.3200 40.03 7.78
PCMS
exhibits a greater tendency for chain protonation. Unprotonated ami­
3–AP/ 27.6501 0.2392 34.60 14.40 nopyridine substances have obvious electronegativity at the N atom
PCMS because of the presence of lone–pair electrons in nitrogen (the sur­
4–AP/ 19.2594 0.2123 44.09 13.60 rounding blue area represents a negative electrostatic potential).
PCMS
Therefore, pyridine substances exhibit a strong complexing ability with
2–PA/ 34.7953 0.3010 34.60 11.80
PCMS metal cations, making it difficult to selectively recover gold from the
3–PA/ 33.3758 0.2894 34.68 15.30 leaching solution. Upon protonation, the entire pyridine polymer skel­
PCMS eton becomes positively charged through the conjugation of the pyridine
4–PA/ 32.1691 0.2740 34.07 15.80 ring (surrounding red area), thereby forming a cationic adsorbent
PCMS
framework that enables the effective separation of anions and cations in
multicomponent solutions. Unlike other metallic elements, only gold
hydrometallurgy of WPCBs is performed in an acidic solution, wherein ions exist as AuCl–4 and can be selectively recovered by cationic pyridine
pyridine polymers enable the selective separation of AuCl−4 from the polymers via electrostatic interactions from solutions containing mul­
metal cation–containing leaching solution of acidic WPCBs. tiple metal ions.

3.2.4. DFT calculation 3.3. Effect of solution acidity

The nucleophilic reaction between aminopyridine and PCMS
occurred at the amino position, thereby forming a structure with an
amino group (secondary amine after the reaction) acting as a suspension
arm and a pyridine ring as the suspension. The nitrogen atom in the
amino group possesses a pair of lone electrons, which makes it suscep­
tible to protonation under acidic conditions. Density functional theory
(DFT) calculations were conducted for investigating the energy differ­
ence and ESP before and after protonating the amino group at various
positions within the five pyridine polymers. Fig. 7 shows that the depths
The hydrometallurgy of gold–containing WPCBs is performed in
highly acidic solutions such as aqua regia; therefore, the effect of solu­
tion acidity on the gold loading capacity of pyridine polymers was
investigated at pH values of 1, 3, and 5 % aqua regia solutions. Fig. 8
shows that all five pyridine polymers maintained a certain adsorption
capacity for gold in the acidic test solution, thereby indicating that
pyridine polymers worked well under highly acidic conditions. The gold
loading capacity was higher at pH 1, and this can be related to the degree

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S. Chen et al. Chemical Engineering Journal 483 (2024) 149325

Fig. 3. XPS results of PCMS and 4–AP/PCMS. a) Full spectrum, b) Cl 2p peak spectrum of PCMS, c) N 1s peak spectrum of 4–AP/PCMS, and d) Cl 2p peak spectrum of
4–AP/PCMS.

Fig. 4. The adsorption rate of 2–AP/PCMS, 3–AP/PCMS, 4–AP/PCMS, 2–PA/PCMS, 3–PA/PCMS, and 2–PA/PCMS in binary solutions. a) Au(III) adsorption rate, b)
Mn+ adsorption rate. (CAu(III) = 20 mg/L, Cn+
M = 20 mg/L, t = 24 h, m = 20 mg, V = 50 mL, pH = 3).

of the protonation of the amino groups on the surface of the material.
Even in a 5 % aqua regia solution, the adsorption of pyridine polymers
for gold was maintained at a satisfactory capacity, which showed the
excellent performance of the pyridine polymers for gold recovery in acid
leaching solutions.
The effect of acidity on gold adsorption of 4-AP/PCMS has been
comprehensively investigated, as illustrated in Figs. S5 and S6. A
decrease in gold adsorption capacity is observed with increasing pH
when the solution pH ranges from 1 to 6. The presence of a high con­
centration of aqua regia solution impedes the process of gold adsorption.
The stability of 4-AP/PCMS after adsorption gold at different pH values
and aqua regia were studied through FT-IR spectrum and shown in

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S. Chen et al. Chemical Engineering Journal 483 (2024) 149325

Fig. 5. Metal ions adsorption rate of 2–AP/PCMS, 3–AP/PCMS, 4–AP/PCMS, 2–PA/PCMS, 3–PA/PCMS, and 4–PA/PCMS in multiple solutions. (CAu(III) = 20 mg/L,
Cn+
M = 20 mg/L, t = 24 h, m = 20 mg, V = 50 mL, pH = 2).

mg/L). Adsorption models of Langmuir and Freundlich [32] were used

Table 2
to fit the isothermal adsorption of Au(III) on 4–AP/PCMS at 298 K,
Selective adsorption parameters of 4–AP/PCMS toward seven ions.
which can be expressed with the Eqs. (4) and (5).
Mixed ions Mn+ adsorption (%) Kd (mL/g)
kL ce
Au(III) 99.53 5.35 × 105 Qe = Qmax × (4)
Cu(II) 0.35 8.72
1 + kL ce
Ni(II) 0.35 8.66
Co(II) 0.09 2.35 Qe = kF c1/n
e (5)
Zn(II) 0.39 9.77
Fe(II) 1.28 32.53 Where, Qe and Qmax are Au(III) equilibrium and theoretical maximum
Cd(II) 0.29 7.20
loading capacity (mg/g), respectively, ce is equilibrium Au(III) concen­
Mg(II) 0.21 5.24
tration in the solution (mg/L), KL is the Langmuir isotherm constant (L/
mg), KF is Freundlich isotherm constants, and 1/n is adsorption
exponent.
Fig. 9 and Table 3 present the fitting plots and related parameters of
the Langmuir and Freundlich isotherm models for Au(III) adsorption.
Comparison with experimental data reveals that the Langmuir isotherm
model demonstrates better consistency with the adsorption of Au(III) by
4–AP/PCMS, as evidenced by the higher correlation coefficient (R2 =
0.9890) than that of the Freundlich isotherm model (R2 = 0.8700).
Therefore, the adsorption of Au(III) onto 4–AP/PCMS is a dynamic
equilibrium process, and the gold monolayer is uniformly distributed on
the 4–AP/PCMS surface. The theoretical maximum adsorption capacity
calculated using the Langmuir model was 437.68 mg/g, which is close to
the experimental data. The Au(III) adsorption capacities of 4–AP/PCMS,
commercially available coir activated carbon (AC), D301 anion ex­
change resin, and other relevant materials reported in literature were
compared (Table 4 and Fig. S9). The loading capacity of Au(III) by
4–AP/PCMS was considerably higher than that most of other studies,
which indicated that 4–AP/PCMS is a promising material for Au (III)
recovery.

3.5. Adsorption kinetics

Fig. 6. Zeta potential of 4–AP/PCMS at different pH.
Two classical kinetic models were employed to fit the relationship
between the adsorption time and loading capacity at initial gold con­
Figs. S7 and S8. The peak position of 4-AP/PCMS has remained virtually
centrations of 160 and 200 mg/L to examine the gold adsorption process
unchanged. In other words, 4-AP/PCMS exhibits excellent stability in
on 4–AP/PCMS. The pseudo–first–order and pseudo–second–order
aqua regia solution at various pH values, without any significant alter­
models are described as Eqs. (6) and (7).
ation to its main functional groups.
log(Qe − Qt ) = logQe − k1 t (6)

3.4. Adsorption isotherms t 1 t

= + (7)
Qt k2 Q2e Qe
The adsorption mechanism of the adsorbent toward gold ions was
determined by investigating the adsorption isotherm of the gold­ Where Qe and Qt (mg/g) were the loading capacity of equilibrium and
–adsorption system. The isotherm of Au(III) adsorbed on 4–AP/PCMS is time t (h), k1 (min− 1) and k2 (min− 1) were the pseudo–first–order and
shown in Fig. 9, which indicates that the loading capacity of Au(III) pseudo–second–order constant, respectively.
increased with initial Au(III) concentration (ranging from 160 to 400 Fig. 10 and Table 5 present the fitting graphs and related parameters

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S. Chen et al. Chemical Engineering Journal 483 (2024) 149325

Fig. 7. Energy difference and ESP before and after the protonation of amino at different positions of pyridine polymers. a) 2–AP/PCMS, b) 3–AP/PCMS, c) 4–AP/
PCMS, d) 2–PA/PCMS, e) 3–PA/PCMS, and f) 4–PA/PCMS.

Table 3
Parameters for the Langmuir and Freundlich isotherm models.
Langmuir Freundlich
2
Qmax (mg/ KL (L/ R KF n R2
g) mg)

4–AP/ 437.68 1.7922 0.9890 333.64 17.2117 0.8700

PCMS

Table 4
Comparison of the gold adsorption capacity of 4–AP/PCMS with the recently
reported adsorbents (25 ℃).
Materials Qmax (mg g− 1) Ref.

cellulose acetate fibers (CAF) 110 [33]

Cr-based MOF 357 [34]
UiO–66–ATU 227.68 [35]
Amberlite XAD-16 33.48 [36]
TRIS polymer beads. 173.18 [37]
4–AP/PCMS 437.68 This work.
ArgR 396.8 [38]
HisR 636.9
Fig. 8. Effect of solution acidity on gold adsorption. (CAu(III) = 200 mg/L, t =
MetR 549.5
24 h, m = 20 mg, V = 40 mL). CysR 769.2

of the pseudo–first– and second–order models for 4–AP/PCMS adsorp­

tion of Au(III) at initial gold concentrations of 160 and 200 mg/L,
respectively. The correlation coefficient (R2) of the pseudo–second–­
order kinetic model is higher (0.9984) than that of the pseudo–first–­
order kinetic model (R2 = 0.9739). In addition, the difference between
the equilibrium and actual load capacities was smaller when the pseu­
do–second–order kinetic model was used, which indicates its suitability
for describing the adsorption process of gold by 4–AP/PCMS. This im­
plies that Au(III) adsorption onto 4–AP/PCMS is a chemisorption pro­
cess, which is possibly induced by the electrostatic–force ion exchange.
The rate constant K2 for the adsorption of Au(III) at low concentrations
was significantly higher compared to that at high concentrations, sug­
gesting a greater ease in achieving adsorption equilibrium at lower
concentrations.
The Weber and Morris models were employed to ascertain whether
the control step of gold adsorption involved membrane diffusion or pore
diffusion, which can be expressed by observed adsorption time and
loading capacity as expressed in Eq. (8).

Fig. 9. Langmuir and Freundlich isotherm fitting plots of Au(III) adsorption on Qt = Ki t1/2 + C (8)
4–AP/PCMS. (m = 20 mg, V = 40 mL, pH = 1, t = 48 h).
Where Qt (mg/g) was the loading capacity at time t. C was the constant

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S. Chen et al. Chemical Engineering Journal 483 (2024) 149325

Fig. 10. Pseudo–first–order and pseudo–second–order models fitting plots of Au(III) adsorption of 4–AP/PCMS. a) CAu(III) = 160 mg/L, b) CAu(III) = 200 mg/L. (m =
20 mg, V = 40 mL, pH = 1).

reduced to zero–valence gold by the pyridine ring of the material; then,

Table 5
Parameters of pseudo–first–order and pseudo–second–order models.
Model Parameter Initial gold(III) concentration
(mg/L)
160 200
Pseudo–first–order kinetic model Qe (mg/g) 301.88 357.52
K1 0.2761 0.1917
R2 0.9739 0.9741
Pseudo–second–order kinetic Qe (mg/g) 336.52 400.02
model K2 1.12 × 10–3 6.90 × 10–4
R2 0.9984 0.9978
relative to the thickness of the liquid film, and Ki (mg⋅g− 1⋅h1/2) was the
diffusion rate constant.
The intraparticle diffusion adsorption kinetic process can be divided
into three stages at the initial gold concentrations of 160 and 200 mg/L
(Fig. S10 and Table S2), with the diffusion rate constants follow the
order: Ki, 1 > Ki, 2 > Ki, 3. During the initial 4 h, a rapid increase in
loading capacity was observed due to the abundant availability of
adsorption sites on 4-AP/PCMS. Subsequently, from 4 to 13 h, the
adsorption rate declined gradually owing to the progressive reduction of
available adsorption sites. In stage III (13–48 h), saturation of sites
occurred leading to equilibrium in adsorption. The results demonstrate
that the adsorption process of gold on 4-AP/PCMS is an intricate process
controlled by external surface adsorption and internal diffusion.
3.6. Adsorption mechanism
The chemical changes during Au(III) adsorption on 4–AP/PCMS
were analysed using XPS (Fig. 11). The full spectrum of 4–AP/
PCMS@Au in Fig. 3a exhibits a distinct characteristic peak corre­
sponding to Au, which indicates that the material successfully adsorbed
Au from the solution. The Cl 2p3/2 peaks of 4–AP/PCMS@Au in Fig. 11c
are resolved into two components at 196.83 and 198.08 eV, attributed to
the binding chlorine with cationic pyridine ring and Au(III), respec­
tively. The nitrogen in 4–AP/PCMS@Au appeared in the form of C = N
(399.18 eV), C–N (400.78 eV), and nitrogen oxide (405.78 eV), with
corresponding atomic distributions of 46.7 %, 36.9 %, and 16.4 %,
respectively, based on the N 1 s spectrum in Fig. 11b. Compared to
4–AP/PCMS, slight changes in the binding energy contributed to gold
chemisorption, and the ratio of C = N decreased significantly, gradually
transforming into nitrogen oxide. In addition, gold exists in the Au0 state
[39] (4f7/2 at 84.18 eV and 4f5/2 at 87.85 eV) and the Au(III) state [40]
(4f7/2 at 84.68 eV and 4f5/2 at 88.35 eV) on 4–AP/PCMS@Au. Therefore,
gold in the solution (as AuCl–4) adsorbed on 4–AP/PCMS were partially
aminopyridine was oxidised to aminopyridine oxide [41].
The adsorption mode of Au on 4–AP/PCMS was identified by DFT
using quantum chemistry calculations. The repetitive styrene structure
of PCMS was employed as a substitute for the PCMS in the modelling
procedure to simplify the calculation process. The binding energies of
4–AP/PCMS before and after protonation with AuCl–4 were calculated
using Eq. (9).
ΔEads = Etotal − Eadsorbate − Eadsorbent + EBSSE (9)
Where Etotal, Eadsorbate and Eadsorbent represent the total energy of the
adsorption system, energy of the adsorbates, and energy of the adsor­
bents, respectively. The theoretical models and energies are shown in
Fig. S11 and Table S3. The binding energies of 4–AP/PCMS before and
after protonation with AuCl−4 were − 0.0192 and − 0.1334 a.u.
respectively, which indicate that adsorption was feasible for 4–AP/
PCMS to adsorb gold; the protonated 4–AP/PCMS was more stable. In
other words, 4–AP/PCMS was suitable for recovering gold from the
WPCBs leaching solutions commonly applied under acidic conditions
with concentrated HCl.
The reduced density gradient [42] (RDG) of 4–AP/PCMS@Au was
analysed to further understand the driving force of gold adsorption in
pyridine polymers, wherein (λ2)ρ indicates a strong attractive Van der
Waals interaction and strong repulsion. The RDG colour contour plot
and scatter plot results (Fig. 12) indicate a predominant presence of the
strong repulsion between Cl− and Au(III) in the AuCl−4 complex. The Cl−
in AuCl−4 and H atom in protonated 4–AP/PCMS is dominated by Van der
Waals interaction which conforms to the designed purpose of electro­
static force between cationic framework and aimed anion.
The gold–loading capacities of the five cationic pyridine polymers
with amino groups at different relative locations are tested as shown in
Fig. S12. Several materials have an adsorption ability on Au(III); the
order of loading capacity for gold is 4–AP/PCMS > 3–PA/PCMS≈2–PA/
PCMS > 4–PA/PCMS > 3–AP/PCMS > 2–AP/PCMS. Indeed, there is no
direct relationship between the surface area, pore size distribution, and
adsorption properties of the pyridine polymers for Au(III), as summar­
ised in Table 1. The results show that the adsorption of Au(III) does not
depend on the surface area and pore size distribution, but on the binding
site on the pyridine polymer surface for producing a chemically specific
adsorption of Au(III).
The ESP of Au(III)–loaded cationic pyridine polymers were calcu­
lated using the DFT method and visualised using the VMD program for
clarifying the correlation between the pyridine polymer configuration
and adsorption properties. Fig. 13 shows the AuCl−4 plane, the vertical
plane configurations of 2–AP/PCMS@Au, 3–AP/PCMS@Au, 4–AP/
PCMS@Au, 2–PA/PCMS@Au, 3–PA/PCMS@Au, 4–PA/PCMS@Au and

8
S. Chen et al. Chemical Engineering Journal 483 (2024) 149325

Fig. 11. XPS results of 4–AP/PCMS@Au. a) C 1 s peak spectrum, b) N 1 s peak spectrum, Cl 2p peak spectrum, and d) Au 4f peak spectrum.

Fig. 12. RDG color contour plot and scatter plot of 4–AP/PCMS@Au.

the corresponding ESP diagrams. The interaction between cationic
pyridine polymers and AuCl−4 is governed by electrostatic attraction.
From the position of action, 2–AP/PCMS, 3–AP/PCMS, 2–PA/PCMS, and
4–PA/PCMS exhibited interactions involving the entire pyridine surface
with AuCl−4 , while for 4–AP/PCMS, it primarily relied on the protons of
the protonated pyridine ring. In contrast, 3–PA/PCMS demonstrated
attractive forces toward both the protons of the protonated pyridine ring
and cationised PCMS skeleton. The positive charge of cationic pyridine
was neutralised upon contact with the negative adsorbate, and the
neutralisation effect was enhanced by the surface contact compared to
the point contact. Further, multipoint contact leads to a greater neu­
tralisation effect than the single–point contact. The extent of the cationic
neutralisation of an adsorption material determines its capacity for
anion adsorption, which explains why 4–AP/PCMS exhibited a higher
gold–loading capacity than the other cationic pyridine polymers. Thus,
employing single–point interactions is an effective strategy for
enhancing the Au adsorption capacity of electrostatically interacting
adsorbents. The gold loading capacity of 4-PA/PCMS is worse than that
of 4-AP/PCMS, the reason is that 4-PA has a longer branched chain, the
presence of methylene allows the pyridine ring to rotate at a certain
angle, which causes the AuCl-4 to interact with the pyridine ring by
surface adsorption. However, 4-AP has a large steric hindrance, the
structure internal rotation is more difficult, so it is combined with gold
by point contact. The advantage of point contact over surface contact

9
S. Chen et al.
Fig. 13. AuCl−4 and the vertical plane configurations of 2–AP/PCMS@Au, 3–AP/PCMS@Au, 4–AP/PCMS@Au, 2–PA/PCMS@Au, 3–PA/PCMS@Au, 4–PA/PCMS@Au
and the corresponding ESP diagrams.
leads to an increased loading capacity of 4-AP/PCMS.
3.7. Reusability and actual sample adsorption test
The desorption method and adsorption/desorption cycle perfor­
mance of 4–AP/PCMS were investigated as shown in Fig. 14. An aqueous
solution of thiourea (1 % thiourea and 1 mol/L HCl) was used as the
desorption solution to elute gold from 4–AP/PCMS@Au, and the gold on
4–AP/PCM was almost completely desorbed under the experimental
conditions. Furthermore, the adsorption rate remained consistently
above 99 % even after five recycling cycles, and the gold desorption rate
of the acid thiourea aqueous solution exceeded 95 %. These results
demonstrate the excellent reusability of 4–AP/PCMS for Au(III)
recovery.
A gold adsorption experiment was conducted in an actual leaching
solution of WPCB to verify the practical application of 4–AP/PCMS.
Fig. 15 show an initial, straightforward process for the recovery of gold.
The WPCBs were slowly mixed with a 50 % aqua regia solution, and
after 24 h, the leaching solution was filtered and diluted twice with
water. The concentration of Au (III) in the leaching solution is deter­
mined to be 14.7 mg/L, whereas the concentrations of the other metal
Fig. 14. The adsorption/desorption cycle performance of 4–AP/PCMS.
Adsorption condition: CAu = 20 mg/L, pH = 1, V = 150 mL, m = 0.1 g.
Desorption condition: V = 50 mL, m = 0.1 g.
10
Chemical Engineering Journal 483 (2024) 149325
ions are measured using ICP–OES, as presented in Table S4. The Fe (II),
Cu (II), and Ni (II) contents in the solution were dozens or even hundreds
of times that of Au(III). In brief, 50 mg of 4–AP/PCMS were used to
recover gold from 50 mL of the WPCBs leaching solution. The mixture
was agitated at 200 rpm for 24 h at room temperature. The experiment
results are presented in Table S4; the recovery rate of 4–AP/PCMS to­
ward Au(III) is 92.24 %, despite the higher ions concentration of the
co–leaching metal, which demonstrates obvious selectivity for gold
related to the effects of the cationic skeleton on 4–AP/PCMS. 4–AP/
PCMS barely captured any of the common metals. The gold recovery
results from actual leaching proved that 4–AP/PCMS is practical for gold
recovery.
4. Conclusion
A series of aminopyridine–based polychloromethylstyrene polymers
were designed and synthesised by nucleophilic substitution. The struc­
ture and morphology of pyridine polymers, represented by 4–AP/PCMS,
were characterised by FT–IR spectroscopy, N2 adsorption–desorption
isotherms, SEM–EDS, and XPS; the gold adsorption performance was
also tested. 4–AP/PCMS is a polymer rich in amino and pyridine rings
with a nitrogen content of 13.60 %, which exhibits excellent adsorption
capabilities towards gold. The Langmuir and pseudo–second–order
models more accurately described the isotherm adsorption and kinetics
of 4–AP/PCMS gold adsorption, with a maximum gold loading capacity
of 437.68 mg/g. The adsorption of gold onto 4–AP/PCMS was slightly
affected by acid, even in a 5 % aqua regia solution. The acid thiourea
aqueous solution effectively desorbed gold from 4–AP/PCMS@Au while
maintaining high reusability over five cycles of adsorption–desorption
tests. The selectivity of the five pyridine polymers and pyridine and the
relative location of the amino group for the gold loading capacity were
also discussed. In the binary and multiple–component solutions (con­
taining Au(III), Cu(II), Ni(II), Co(II), Zn(II), Fe(III), Cd(II), and Mg(II)
ions), the pyridine polymers exhibited excellent selectivity for Au(III),
which benefited from the cationic skeleton of the adsorbent. Further, it
exhibited good selectivity in the actual leaching solution, even when the
concentration difference was dozens or hundreds of times greater. The
contact patterns of the cation skeleton with AuCl–4 play a major role in
gold loading capacity, where a smaller contact area is favourable for
gold adsorption. Overall, pyridine polymers are promising candidates
for the selective recovery of high–purity Au from WPCBs.
CRediT authorship contribution statement
Shuliang Chen: Writing – original draft, Validation, Investigation,
S. Chen et al.
Fig. 15. Flowsheet presenting the selective recovery of gold from WPCBs.
Data curation. Li Zhao: Formal analysis, Data curation. Xinrong Li:
Project administration, Investigation. Zhen Chen: Project administra­
tion, Data curation. Xianzhi Hu: Conceptualization. Futing Zi: Funding
acquisition, Validation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China (51674128, 52264031) and the Yunnan Provincial
Key Laboratory of Chemical Separation and Enrichment in China
(KKPH201907003).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2024.149325.
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