Polymer 175 (2019) 71–80

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Single-step fabrication of recyclable microporous hyperbranched T

polyethyleneimine adsorbent with highly efficient and selective removal of
lead ions
Jie Chen, Xu Liu, Shi Wang, Ailian Wang, Zhinan Wang, Qinghui Zeng, Zengxi Li∗∗,
Liaoyun Zhang∗
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China

H I GH L IG H T S

• ATheporous hyperbranched adsorbent has been prepared by single-step crosslinking method.

• The removal efficiency of Pb 2+
ions onto adsorbent can reach 99.2%.
• Regeneration
obtained adsorbent shows a adsorption capacity of 252.4 mg/g for Pb 2+
in aqueous solution.
• experiments show that the removal capacity remains above 88%within eight cycles.

A R T I C LE I N FO A B S T R A C T

Keywords: A novel recyclable hyperbranched adsorbent for selective adsorption of Pb2+ ions is fabricated by a facile single-
Hyperbranched polyethylenimine step crosslinking reaction. The as-synthesized adsorbent has porous structure and large of amino groups which
Crosslinking structure beneficial for the removal of Pb2+ ions in aqueous solution and the removal efficiency is 99.2%. The result also
Adsorption capacity indicates that adsorption ability of the obtained adsorbent increased with the increase of pH from 1 to 6 and
Selectivity
temperature from 278 K to 308 K, respectively. The adsorption process of Pb2+ ions onto PPEI-2-AG followed the
Recyclability
Langmuir isotherm model, and a kinetic study indicates that the process fitted pseudo-second order model well.
The removal of Pb2+ ions by PPEI-2-AG is mainly controlled by the specific interactions between Pb2+ ions and
amino functional groups, which could be further confirmed by X-ray photoelectron spectroscopy (XPS). The
results demonstrate that PPEI-2-AG holds high potential in environmental remediation.

1. Introduction
With the rapid development of agriculture and industry, water
pollution becomes a worldwide issue that concerns billions of people
[1–3]. Moreover, improper discharge of sewage containing heavy metal
ions further exacerbates the water crisis [4]. Unlike biodegradable
pollutants such as organic dyes and physical pollutants which influence
the physical properties of water. Heavy metal ions are resistant to
weathering, they are accumulated in water, soil and food chain then
alter to human physiology [5]. Lead is one of the most common used
metal in the fields of lead-acid batteries, pesticides, glassware, pigments
and so on [6,7]. Lead ions in water can cause sever dysfunction in the
kidneys, liver and reproductive system, or even death [8]. In addition,
other metal ions such as Cu ions, Ni ions, and Fe ions are also used in
batteries, alloys, computer components, catalysts and so on, they can
cause stomach cramps, lung and kidney problems [9]. Therefore, it is of
urge need to develop cost-effective technologies to solve the severe
environment issues.
Till now, many methods including ion exchange [10,11], chemical
precipitation [12], adsorption [13], electrochemical [14] and mem-
brane separation methods [15] have been developed to separate heavy
metal ions from contaminated water. Among them, adsorption is the
conventional option due to its low investment, and potential of re-
generation and recyclability of materials. The extensively used or newly
designed adsorbents such as clay [16,17], waste biomass [18,19], metal
organic frameworks (MOFs) [20] and layered doubled hydroxides [21]
show a poor selectivity towards targeted heavy metal ions, which
hinders the deep removal of targeted metal ions from wastewaters.

∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: lizengxi@ucas.ac.cn (Z. Li), zhangly@ucas.ac.cn (L. Zhang).

https://doi.org/10.1016/j.polymer.2019.04.068
Received 28 January 2019; Received in revised form 2 April 2019; Accepted 28 April 2019
Available online 30 April 2019
0032-3861/ © 2019 Elsevier Ltd. All rights reserved.
J. Chen, et al.
Furthermore, the adsorption capacity, removal efficiency, and recycl-
ability are also need to be optimized to satisfy the increasingly strict
standards.
In order to synthesize a cost-effective adsorbent with advanced
adsorptive properties, one of the effective methods is to develop ad-
sorbents with high selectivity by incorporating various functional
groups which can provide specific interactions with heavy metal ions.
Hyperbranched polyethylenimine (PEI) which contains large amounts
of the primary amine (-NH2) and secondary amine (-NH) [22,23] is an
idea adsorbent materials due to outstanding complexation of nitrogen
atoms and toxic metal ions. However, the water-solubility of PEI limits
its application as an adsorbent in wastewater treatment. Crosslinking is
often adopted to fabricate the water-insoluble PEI for removing toxic
metal ions. For example, PEI was crosslinked with biomass [24,25],
lignin [26,27] and synthetic linear polymers [28,29] respectively to
obtain water-insoluble adsorbents. But these materials which were
crosslinked with PEI hardly provide enough functional groups for re-
moval of heavy metal ions. Moreover, PEI also inevitably sacrificed the
amounts of amino functional groups, so it is a challenge to develop a
facile approach to prepare stable three-dimensional network porous-
structured PEI adsorbent with large numbers of amino groups for im-
proving the adsorption capacity of heavy metal ions.
In this study, we put forward a one-step method of self-crosslink of
hyperbranched PEI by using Glutaraldehyde (GLA) as cross-linking
agent to achieve a new adsorbent for removal of Pb2+ ions from water
solution. This type of adsorbent can show excellent selectivity and high
adsorption efficiency for Pb2+ ions by adjusting the proportion of GLA.
Moreover, both the formed microporous structure and functional
groups of adsorbent can also significantly enhance the adsorption
ability of adsorbents towards Pb2+ ions. Thus, the as-prepared new
adsorbent with rapid preparation, superior selectivity, high adsorption
efficiency and recyclability has the potential application in wastewater
treatment.
2. Experimental
2.1. Materials
The hyperbranched polyethyleneimine (PEI, Mw = 2.5 × 104 g/
mol，Mn = 1 × 104 g/mol) in was purchased from Sigma-Aldrich
(Shanghai, China). Glutaraldehyde solution (GLA, 50%) was purchased
from Sinopharm Chemical Regent Co., Ltd., China. Other chemicals
such as methyl alcohol, Pb(NO3)2, Cu(NO3)2·3H2O, Ni(NO3)2·6H2O, Fe
(NO3)2·9H2O are of analytical grade, were purchased from Chinese
manufactures. All above-mentioned reagents were used without further
purification.
2.2. Characterization
A Thermo Nicolet AVATAR 360 infrared instrument was adopted to
record the Fourier transform infrared (FT-IR) spectra using the atte-
nuated reflectance technique with the wavenumber range from 4000 to
500 cm−1. Nitrogen adsorption and desorption isotherms were con-
ducted at 77 K on a Micromeritics ASAP2400 instrument. The specific
surface areas were detected by Brunauer-Emmett-Teller (BET) ap-
proach. The morphologies of PPEI-2-AG were acquired using a SU8010
field emission scanning electron microscope (SEM), Hitachi. pH mea-
surement was performed using a STARTER2100 pH meter, OHAUS. The
concentration of each metal ions was detected by inductively coupled
plasma atomic emission spectrometer (ICP-OES) Analytikjena PQ9000
after filtered. X-ray photoelectron spectra (XPS) were recorded on a
Thermo Scientific ESCA Lab 250Xi X-ray photoelectron spectrometer
with an Al Kα X-ray radistion before and after adsorption.
72
Polymer 175 (2019) 71–80
2.3. Synthesis of cross-linking hyperbranched polymer adsorbent PPEI
PPEI was synthesized by using hyperbranched PEI and GLA to form
an insoluble cross-linking product. And detailed reaction processes can
be summarized as follows: (1) 3.6 g (43.61 mmol) of PEI was added into
a 50 ml round-bottom flask, using 20 ml methyl alcohol as solvent, and
the mixture was stirred at room temperature for 30 min to form a clear
and transparent solution. (2) Several portions of GLA was cautiously
added dropwise into the as-prepared solution, and vigorously stirred at
R.T. for 10 min to ensure the equilibrium reaction. A yellowish-brown
precipitation could be obtained. The amount of adding GLA solution
was as follows: 1.8 ml (17.03 mmol), 3.6 ml (34.06 mmol), 5.4 ml
(51.09 mmol), 7.2 ml (68.12 mmol). The corresponding products were
named as PPEI-1, PPEI-2, PPEI-3 and PPEI-4, respectively. (3) The re-
action degree of PPEI-2-AG was calculated as 0.282, indicating that
most of the amine groups were remained during the forming process of
water insoluble PPEI-2-AG（see the detailed information in the
Supporting information）. After being filtered, the solid rinsed thor-
oughly with ultrapure water for 5 times to remove unreacted regents,
then they were dried under vacuum condition at 80 °C overnight. The
washed PPEI-2 was also dehydrated by putting in a freeze dryer for 2
days and we obtained the aerogel-like PEI-immobilized adsorbent PPEI-
2-AG (yield = 65%).
2.4. Batch adsorption experiments
The adsorption experiments were conducted in 10 ml centrifuge
tubes by mixing adsorbent with target metal ion solution. The con-
centration of the adsorbent or the metal ions were adjusted whenever it
was necessary. A 1.0 M HNO3 or NaOH was adopted to adjust the
acidity of metal ions. The centrifuge tubes were then located in a
thermostatic oscillator at 30 °C and vibrated at 180 rpm for desired time
to accomplish equilibrium adsorption. The kinetic experiments sug-
gested that 4 h was adequate to reach adsorption equilibrium. The
concentration of each metal ions was detected by inductively coupled
plasma atomic emission spectrometer (ICP-OES) and the quantities of
these metal ions trapped by PPEI were calculated based on mass bal-
ance before and after the test. The detection limits of ICP-OES for Pb2+
ions, Cu2+ ions, Ni2+ ions, and Fe3+ ions are 0.01 mg/L, 0.005 mg/L,
0.001 mg/L, 0.01 mg/L, respectively.
For the determination of kinetic experiments, 100 ml of metal ions
solution with initial concentration of 1000 mg/L was prepared, and the
proper amount of mother liquor was transferred by pipettor into 10 ml
centrifuge tubes to obtain metal ions solution with desired concentra-
tion. And a certain amount of adsorbent was added subsequently, then
1 ml solution at different time intervals was sampled from centrifuge
tubes, the adsorbent was filtered out and the residual concentration of
metal ions in each solution was measured by ICP-OES. In the adsorption
isotherm experiment, the initial metal ions concentrations were range
from 1 to 400 mg/L at pH 6, and the mixtures were shaken for 720 min.
The original pH of the solution was ranged from 1 to 9 to study the
relationship between solution acidity and adsorption efficiency.
Meanwhile, the adsorption efficiency was investigated as the existence
of interfering ions, we choose the most effective ones including Pb2+
and Cu2+ as object of study.
2.5. Desorption and recycling
The experiment showed that the interaction between metal ions and
adsorbent was very weak in strong acidic solution. So, the metal ions
loaded PPEI-2-AG was rinsed in 0.1 M HNO3 solution and then washed
with 0.1 M NaOH to adjust the pH. The recycling experiment of the
regenerated PPEI-2-AG was conducted for eight times.
J. Chen, et al.
Scheme 1. Schematic for the synthesis of PPEI.
3. Results and discussion
3.1. Preparation and characterization
A series of cross-linked hyperbranched polyethylenimine (PPEI) was
fabricated (see Fig. S1) by a facile one-pot method as shown in Scheme
1. The hyperbranched PEI was chosen due to existence of multitudinous
primary, secondary, and ternary amine functional groups which can
interact with heavy metal ions. Glutaraldehyde (GLA) was served as a
cross-linking agent. The reaction of PEI and GLA was very fast, which
could save preparation time.
FT-IR technique was adopted for structural characterization of
prepared adsorbent. As shown in Fig. 1, the spectrum of PPEI-2-AG
exhibited several differences and significant signals. Compared with
PEI, the peak at 3270 cm−1 which concerns the stretching vibration of
N–H intensity decreases, indicating occurrence of the crosslinking re-
action between primary or secondary amine with GLA. The appearance
of absorption peak at 1650 cm−1 which belongs to characteristic ad-
sorption bond of C=N further provides evidence for the successful
Schiff's base reaction between amine groups of PEI and aldehyde groups
of GLA (see Scheme 1). And from the insert Fig. 1, it can be found that
the peak intensity of C=N bonds at 1650 cm−1 becomes stronger from
PPEI-1 to PPEI-4, which reveals the more formation of C=N bonds with
more adding amount of GLA (PEI unchanged). The information
Fig. 1. FT-IR spectra of PEI and PPEI.
73
Polymer 175 (2019) 71–80
together suggests the successful crosslinking reaction of PEI and GLA.
In addition, the morphology of the prepared adsorbent was studies
by scanning electron microscope. It is observed from Fig. 2(a) and (b),
the obtained cross-linked adsorbent PPEI-2-AG possess microporous
structure, which is beneficial to enhance the adsorption of PPEI-2-AG
for heavy metal ions.
3.2. Adsorbent dosage
The adsorbent amount is a crucial factor in controlling the ad-
sorbent capacity for a certain amount of an adsorbent at operating
conditions. The heavy metal ions removal efficiency increases as the
adsorbent amount increases. In other words, the sorption sites at the
adsorbent surface increase by increasing the amount of the adsorbent,
so it is hoped that the minimum amount of the adsorbent is used to
achieve high adsorption capacity for heavy metal ion. In quest of the
uttermost utilization of the adsorbents, it is essential to study adsorbent
dosage. It can be found from Fig. 3(a) that the removal efficiency for
Pb2+ ions firstly increases with the increase of adsorbent dosage, then
the removal efficiency trends to stabilize. The results also indicate that
as the amount of GLA increases in the course of preparation, the effi-
ciency sequences of the obtained adsorbent are as follows: PPEI-
2 > PPEI-3 > PPEI-1 > PPEI-4. Thus, it is clear that adsorbent PPEI-
2 had the highest removal efficiency for Pb2+ ions than the others,
which may be attributed to easily form an insoluble porous structure
(see Fig. S2a) and more adsorption sites of amino groups on PPEI.
Therefore, too high concentration of GLA used in the preparation of the
adsorbent PPEI is not beneficial to achieving high removal efficiency. In
addition, it can also be seen from Fig. 3(b) that the removal efficiency of
Pb2+ ions onto the aerogel-like PPEI-2-AG adsorbent obtained by a
freeze dry method firstly increases with increasing the concentration of
PPEI-2-AG, which is owing to the increase of free sorption sites as the
dosage of PPEI-2-AG increases. Then, the maximum data are gotten and
kept. Interestingly, compared with the adsorbent PPEI, aerogel-like
PPEI-2-AG adsorbent has a higher removal efficiency than PPEI-2,
which can be verified by BET test. As shown in Fig. 4(a) and (d), the
surface area of the PPEI-2-AG adsorbent can reach 169.45 m2/g, while
the surface area of PPEI-2 is only 14.91 m2/g. Obviously, the surface
area of the PPEI-2-AG adsorbent is much larger than that of the PPEI.
Moreover, the Fig. 4(c) and (d) demonstrate that the PPEI-2-AG mainly
has microporous structure, while PPEI-2 possesses mesoporous struc-
ture. Compared with PPEI-2, it is found that the higher adsorption
ability of the PPEI-2-AG can be attributed to the higher porosity and
larger surface area (see Table 1). Thus, both larger surface area and
porous structure gives PPEI-2-AG higher removal efficiency for Pb2+
J. Chen, et al.
Fig. 2. (a) and (b) are the SEM images of PPEI-2-AG at different magnifications.
ions. As a result, more than 99% of Pb2+ ions can be eliminated by
PPEI-2-AG when the concentration of the dosage is 1 g/L, revealing that
the PPEI-2-AG adsorbent possesses superior adsorption capacity for
Pb2+ ions.
2+
3.3. Effect of pH on Pb ions adsorption by PPEI-2-AG
The initial pH of the aqueous solution can exert an important in-
fluence on the adsorption process, it not only may affect the surface
properties of adsorbent, but also can influence the ionization degree of
amino groups as sorption sites. In this work, the pH of the Pb2+ ions
solution is varied from 1 to 9 to study the influence of solution acidity
on the removal efficiency of Pb2+ ions onto the PPEI-2-AG. It is ob-
viously found from Fig. 5(a) that the removal efficiency turns sharply
from 22.3% to 99.1% with variation of the pH ranges from 1 to 6. As is
known, lead (II) species can exist in several forms including Pb2+, Pb
(OH)2 in aqueous solution with different pH [30]. When the pH of so-
lution is lower 6, the main form of existence is Pb2+ ion. At very low
pH, a tiny portion of Pb2+ ions can interaction with the amino groups of
PPEI-2-AG, this is probably due to the sorption sites’ protonation of the
PPEI-2-AG, which exerts a repulsive force to Pb2+. Meanwhile, the
competitive adsorption of the PPEI-2-AG for Pb2+ and protonated
sorption sites (NH3+) cannot be neglected. These together give PPEI-2-
AG a poor adsorption capacity at pH below 4. As increasing pH, the
removal efficiency reaches maximum value of 99.1% at pH 6, this may
be attributed to the weak protonation of the PPEI-2-AG and the re-
duction of H+. When pH is over 6, the removal efficiency of the PPEI-2-
AG for Pb2+ ions begins decrease and then dropped rapidly. It may be
Fig. 3. (a) Removal efficiency of the as-prepared adsorbents with different amount of cross-linking agent for Pb2+ ions. (b) Removal efficiency of PPEI-2 and PPEI-2-
AG adsorbents for Pb2+ ions, respectively (initial Pb2+ ions concentration 10 mg/L).
74
Polymer 175 (2019) 71–80
because that formed lead hydroxide precipitation at high pH can dis-
turb adsorption of the sorption sites. Therefore, we chose pH 6 to
conduct the following experiments.
3.4. Thermodynamic parameters
Temperature is a significant parameter that influences the practical
adsorption efficiency of the adsorbent. The research was conducted at
278, 288, 298, 308 K to study the effect of temperature on the ad-
sorption efficiency of the PPEI-2-AG adsorbent for Pb2+ ions. It can be
seen that with the temperature rises, the adsorption efficiency increases
from 81.5% at 278 K to over 99% at 298 K, which indicates that the
adsorption of PPEI-2-AG for Pb2+ ions is endothermic process. The
standard Gibbs free energy change ΔG°, standard enthalpy change ΔH°,
and standard entropy change ΔS° can be calculated by the following
equations:
ΔG° = −RT ln K (1)
ln K = −ΔH °/RT + ΔS°/R (2)
−1 −1
where R is the gas constant (8.314 J mol K ), T (K) is Fahrenheit
temperature, K is the thermodynamic equilibrium constant calculated
at various temperature by Qe /Ce .
Therefore, ΔH ° and ΔS° can be obtained by the slope and intercept
of the plot of ln K vs. 1/T, respectively (see Fig. S3), as shown in
Table 2. It is found that all ΔG° at 278, 288, 298, 308 K were negative,
indicating that adsorption process of Pb2+ ions onto PPEI-2-AG is
spontaneous. Meanwhile, the overall values of the ΔH0 were positive,
suggesting the endothermic process of the adsorption [26], it can be
J. Chen, et al. Polymer 175 (2019) 71–80

Fig. 4. The nitrogen adsorption-desorption isotherms of PPEI-2 (a) and PPEI-2-AG (b). (c) and (d) present the pore diameter distribution of PPEI-2 and PPEI-2-AG,
respectively.

Table 1 Table 2
Pore properties of PPEI-2 and PPEI-2-AG. Thermodynamic parameters of Pb2+ ions adsorption onto PPEI-2-AG at tem-
perature range from 278 K to 308 K.
Pore Size Pore Volume Porosity (%) BET Surface Area
（nm） （cm³/g） (m [2]/g) T (K) ΔG° (kJ mol−1) ΔH° (kJ mol−1) ΔS° (J mol−1 K−1)

PPEI-2 5.118 0.087 49.932 14.910 278 −3.71

PPEI-2-AG 1.698 0.724 95.586 169.450 288 −6.63
298 −10.65 80.13 302.1
308 −11.49

Fig. 5. (a) Effect of solution pH on Pb2+ uptake. (b) Effect of temperature on Pb2+ uptake. (Conditions: contact time, 12 h; adsorbent dosage, 1 g/L; concentration,
10 mg/L; pH, 6).

75
J. Chen, et al. Polymer 175 (2019) 71–80

Fig. 6. (a) Effect of contact time on Pb2+ ions removal efficiency by PPEI-2-AG. (b) Pseudo-first-order model. (c) Pseudo-second-order model. (d) Intraparticle
diffusion model.

further conformed by the fact that the adsorption of the adsorbent PPEI-
2-AG for Pb2+ increases with the rise of temperature, showing that
chemisorption process is the rate-determining step [31]. The larger
positive value of ΔS° demonstrates a drastically increase of randomness
at the solid-liquid interface during the adsorption of Pb2+ ions on the
PPEI-2-AG [26].
3.5. Adsorption kinetics
Adsorption kinetics is an important method to describe adsorption
efficiency and evaluates the adsorption process. Kinetics experiments
were conducted to illustrate Pb2+ ions adsorption onto PPEI-2-AG. As is
known, the contact time is an important parameter to help identify the
speed of complexation and the removal of the Pb2+ ions. In this work,
10 mg of PPEI-2-AG was added into 10 ml solution which contained 10
mg L-1 of Pb2+ with contact time from 1 to 240 min. As shown in
Fig. 6(a), in the first 5 min, the adsorption efficiency rose rapidly and
over 50% of the Pb2+ ions were adsorbed, then followed by a relatively
slow process with prolonging contact time. After 240 min, over 99% of
the Pb2+ ions were adsorbed by the PPEI-2-AG, the residual hazardous
pollutants decreased to 0.9 mg L-1, which is far below the provisional
maximum tolerable daily intake standard (10 mg L-1) [32]. It is also
found that the adsorption capacity increases with lasting contact time
to reach the optimum time, then the adsorption efficiency remains al-
most constant thereafter. Thus, this superior adsorption efficiency im-
plies that the PPEI-2-AG is of great value and potential in practical
application.
To further understand the adsorption process, the Lagergren
pseudo-first-order, pseudo-second-order [33], Elovich [34] and intra-
particle diffusion [35] kinetics models were employed to analyze the
experiment results. These two models can be expressed in the following
equations, respectively.
K1
log(Qe − Qt ) = log Qe − t
2.303 (3)
t 1 t
= +
Qt k2Qe2 Qe (4)
where Qe is the amount of lead ions adsorbed in equilibrium, Qt is the
adsorption capacity of adsorbent at various time, k1 and k2 are the rate
constant of pseudo-first-order and pseudo-second-order, respectively.
As depicted in Fig. 6(c) and Table 3, it is found that the pseudo-second
order model is the more consistent kinetics model to describe the ad-
sorption of Pb2+ ions on PPEI-2-AG with a better correlation (R

Table 3
Adsorption kinetics fitting results for Pb2+ ions on PPEI-2-AG.
Pseudo-first-order Pseudo-second-order

Qe, exp (mg g−1) K1 (min−1) Qm (mg g−1) R [2] K2 (g mg−1h−1) Qe, cal (mg g−1) R [2]
9.89 0.02303 21.518 0.9467 0.09948 10.05 0.9999

76
J. Chen, et al. Polymer 175 (2019) 71–80

[2] = 0.9999), indicating that the kinetics of adsorption Pb2+ ions onto Table 4
PPEI-2-AG is controlled by chemisorption [36]. Adsorption isotherms kinetics fitting results for Pb2+ ions on PPEI-2-AG.
It can be seen from Fig. 6(d) that the adsorption of Pb2+ ions on to Langmuir model Freundlich model
PPEI-2-AG can be divided into three stages: Firstly, the Pb2+ ions were
−1 −1
captured by the sorption site on the surface of PPEI-2-AG, which is KL (L mg ) Qm (mg g ) R [2] n KF (mg g−1) R [2]
0.1981 252.4 0.978 1.69 15.4882 0.966
called diffusion model; Secondly, the adsorbent pores were occupied by
Pb2+ ions, that is intraparticle diffusion; and then reached adsorption
equilibrium. All these together suggest that the adsorption of PPEI-2-AG
were also studied. The initial concentrations of four metal ions in-
towards Pb2+ ions not only was chemisorption process, but also was
cluding Pb2+, Cu2+, Ni2+ and Fe3+ varies from 1 mg/L to 400 mg/L, as
controlled by intraparticle diffusion.
shown in Fig. 8. At lower initial concentration, the remove efficiency of
the PPEI-2-AG towards Fe3+ ions was the highest, then drops rapidly to
3.6. Adsorption isotherms below 20% when the initial concentration was over 300 mg/L, re-
vealing the relatively lower adsorption capacity of the PPEI-2-AG for
In order to understand the mechanism of Pb2+ ions on PPEI-2-AG, Fe3+ ions compared with for Pb2+. The removal capacity towards PPEI-
the adsorption data obtained in our research were fitted by Langmuir 2-AG on Pb2+ is 252.4 mg/g, manifesting that Pb2+ ions is more easily
[37] and Freundlich [38] isothermal models. These two models can be absorbed onto PPEI-2-AG than other three types of ions.
expressed as the following equations, respectively. In order to investigate the surface state of samples before and after
1 the adsorption, XPS, SEM and EDS analysis methods were used in the
logQe = logKF + logCe
n (5) present work. The XPS spectra of PPEI-2-AG after adsorption reaction
with different heavy metal (Pb2+, Cu2+, Ni2+, Fe3+) are shown in
Ce C 1 Fig. 10. The Pb4f spectrum (Fig. 9(a)) presents two characteristic peaks
= e +
Qe Qm Qm KL (6) of Pb4f (∼138.4 eV) and of PbCO3 (∼139.2 eV), indicating the strong
interaction of Pb2+ ions and PPEI-2-AG. Besides, the other relatively
where Ce is the Pb2+ ions equilibrium concentration, Qe denotes the
weak peaks at ∼143.3 eV and 144.0 eV are the satellite peaks of PbCO3
amount of lead adsorbed in equilibrium, Qm is the maximum amount of
[39]. In the Cu2p spectra (Fig. 9(b)), the peak at 932.3 eV corresponds
Pb2+ ions adsorbed and KL denotes the Langmuir adsorption constant.
to the binding energy (BE) of Cu2p3/2, along with a satellite peak lo-
KF is Freundlich constant indicating adsorption capacity and n is an
cates at 942.4 eV. The peak at 953.1 eV belongs to the Cu2p1/2. These
empirical parameter of Freundlich model, they can be obtained from
observations suggest the existence of copper with high oxidation states
the intercept and slope of the linear graph of logQe and logCe , respec-
(Cu2+) [40]. The Ni2p spectrum (Fig. 9(c)) can be resolved into three
tively (see Fig. 7(c)). The initial concentration of heavy metal ions is an
peaks, two peaks are located at 872.7 eV (Ni2p1/2) and 854.9 eV
important parameter on the adsorption rate to describe the adsorption
(Ni2p3/2), indicating the binding energy of Ni2+. Another peak
process [8]. As shown in Fig. 7(a), the adsorption amount of Pb2+ ions
(861.0 eV) is assigned to NiO, which implies the existence of surface
increases gradually with the increase of initial concentrations, then
oxidation on PPEI-2-AG-Ni after adsorption the Ni2+. Peaks of Fe2p are
reaches the plateau. The obtained parameters using these models from
observed when Fe ions was adsorbed via PPEI-2-AG (Fig. 9(d)) [41].
the nonlinear regression are listed in Table .4. In general, Langmuir
The Fe2p3/2 (710.3 eV) and Fe2p1/2 (712.2 eV) main peaks are clearly
isotherm demonstrates a monolayer adsorption process which occurs on
accompanied by satellites on their higher BE sides. The peaks at
the homogeneous surface of the PPEI-2-AG, while the Freundlich iso-
724.3 eV that arise from the Fe2p1/2 spectrum are assigned to the Fe3+
therm describes the adsorption on the heterogeneous surface. This
bond with O2− in the grain surface, while the other peaks at lower
suggests that the adsorption of Pb2+ ions on PPEI-2-AG can be ex-
bonding (717.9 and 732.5 eV) are attributed to trace Fe3+ in PPEI-2-
plained by the monolayer and multilayer synergistic adsorption iso-
AG-Fe.42 The corresponding of SEM images and element mapping are
therm, and the Qm of PPEI-2-AG for Pb2+ ions is 252.4 mg/g. The ad-
shown in Fig. 9(e). Obviously, when PPEI-2-AG adsorbs heavy metal
sorption capacity of Pb2+ ions onto PPEI-2-AG is superior to some of
ions (Pb2+, Cu2+, Ni2+, Fe3+), small particles are generated on the
the newly published literature, indicating that PPEI-2-AG has a poten-
surface and the surface becomes rough. Meanwhile, EDS images show
tial as a high-efficient adsorbent for removing Pb2+ ions from waste-
that heavy metal elements are evenly distributed on the surface of the
water.
PPEI-2-AG.

3.7. The removal efficiency and ability towards Cu2+, Ni2+ and Fe3+ at
various initial concentration 3.8. Selectivity and competitive adsorption behaviors of heavy metal ions

In order to make the best use of the PPEI-2-AG, the adsorption ef- Fig. 10(a) shows that the adsorption capacity of PPEI-2-AG toward
ficiency and capacity of others metals ions such as Cu2+, Ni2+ and Fe3+ Pb2+ ions can reach 252.4 mg/g in a single metal ions solution, which

Fig. 7. (a) Adsorption isotherm for Pb2+ ions on PPEI-2-AG; (b) Plot of Langmuir adsorption isotherm; (c) Plot of Frundlich adsorption isotherm.

77
J. Chen, et al. Polymer 175 (2019) 71–80

Fig. 8. Removal efficiency towards the as-prepared adsorbents on (a) Pb2+, (b) Cu2+, (c) Ni2+and (d) Fe3+, respectively.

Fig. 9. High-resolution XPS spectra of (a) Pb4f, (b) Cu2p, (c) Ni2p and (d) Fe2p of PPEI-2-AG adsorption of different heavy metal ions. (e) The corresponding of SEM
images and element mapping of PPEI-2-AG with different metal ions, indicating the homogeneous distribution of heavy metal ions, the scale bar is 8 μm.

78
J. Chen, et al.
Fig. 10. Selectivity adsorption behaviors of heavy metal ions, (a) single ions, (b) mixed ions.
Fig. 11. Removal efficiency towards the adsorption-sorption recycling rounds.
is much higher than the others. It is found that an order of adsorption
ability among various metal ions is as follows：Pb2+ ＞ Cu2+ ＞ Ni2+
＞ Fe3+, indicating that the PPEI-2-AG has a better adsorption capacity
towards Pb2+ ions. Further experiment (Fig. 10(b)) shows that the
PPEI-2-AG still exhibits extraordinary adsorption capacity towards
Pb2+ in mixed solutions, and the adsorption capacity are 162.3 mg/g,
85.4 mg/g, 54.2 mg/g and 30.2 mg/g for Pb2+, Cu2+, Ni2+ and Fe3+
ions, respectively. So it is obvious that there is a selective adsorption
between Pb2+ ions and other mixed ions onto the PPEI-2-AG.
3.9. Regeneration and reuse of PPEI-2-AG
Separating metal ions from adsorbents is vital to the reuse of the
adsorbent. It can be known from above study that the pH of solution has
significant influence on adsorption capacity of PPEI-2-AG, so the Pb2+
ions loaded PPEI-2-AG can be desorbed in 0.1 M HNO3 solution.
Regeneration study (Fig. 11) illustrates that PPEI-2-AG can be reused
more than eight adsorption-desorption cycles without obvious decrease
in the removal efficiency, remained more than 88.1%. It is indicated
that PPEI-2-AG absorbent exhibits relatively good recyclability, sug-
gesting a great potential in practical application.
4. Conclusion
A cross-linking hyperbranched PEI functionalized porous adsorbent
has been successfully prepared by a single-step method. The as-pre-
pared PPEI-2-AG shows a satisfying adsorption capacity for Pb2+
(252.4 mg/g) in water solution, the removal efficiency reaches 99.2%
when the initial concentration of Pb2+ ions is at 10 mg/L, which is
superior to some of other adsorbents in published literature. The result
shows that the adsorption capacity of Pb2+ ions onto adsorbent
79
Polymer 175 (2019) 71–80
depends on pore size and distribution, adsorbent dosage, pH, tem-
perature, sorbents concentration and contact time. Importantly, even in
presence of high concentration of competing metal ions such as Cu2+,
Ni2+, and Fe3+, effective Pb2+ removal can be achieved. In particular,
regeneration experiments show that the removal capacity remains high
within eight cycles. Given all these advantages, it suggests that the self-
crosslinking hyperbranched polyethyleneimine has a promising poten-
tial application as an adsorbent in environmental remediation.
Declarations
None.
Acknowledgments
The authors express thanks for the analysis and test center of
University of Chinese Academy of Science. We thanks to the supports of
the National Natural Science Foundation of China (No.51073170), the
NSFC-Key Projects of Shanxi Coal Based Low Carbon Joint Foundation
(no. U1610222) and the Innovation Program of CAS Combination of
Molecular Science and Education.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.polymer.2019.04.068.
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