Dithiocarbamate functionalized Al(OH)3-polyacrylamide adsorbent for

rapid and efficient removal of Cu(II) and Pb (II)

Ya Liu,1,2 Peng Qian,1 Yang Yu,3 Li Xiao,1,2 Yongliang Wang,1 Shufeng Ye ,1 Yunfa Chen1
1
State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, P.O. Box
353, Beijing 100190, China
2
University of Chinese Academy of Sciences, Beijing 100049, China
3
Lakehead University, Thunder Bay Ontario P7B 5E1, Canada
Correspondence to: S. Ye (E - mail: sfye@ipe.ac.cn)

ABSTRACT: Heavy metal ions such as Cu21 and Pb21 impose a significant risk to the environment and human health due to their
high toxicity and non-degradable characteristics. Herein, Al(OH)3-polyacrylamide chemically modified with dithiocarbamates (Al-
PAM-DTCs) was synthesized using formaldehyde, diethylenetriamine, carbon disulfide, and sodium hydroxide for rapid and efficient
removal of Cu21 and Pb21. The synthesized adsorbent was characterized by Fourier transform infrared (FTIR) spectroscopy, ther-
mogravimetric analysis, scanning electron microscopyenergy dispersive X-ray spectroscopy analysis, and transmission electron micro-
scope measurements. Al-PAM-DTCs showed rapid removal of Cu21 (<30 min) and Pb21 (<15 min) with high adsorption capacities
of 416.959 mg/g and 892.505 mg/g for Cu21 and Pb21 respectively. Al-PAM-DTCs also had high capacities in removing suspended
solids and metal ions simultaneously in turbid bauxite suspensions. FTIR, thermodynamic study, and elemental mapping were used
to determine the adsorption mechanism. The rapid, convenient, and effective adsorption of Cu21 and Pb21 indicated that Al-PAM-
DTCs has great potential for practical applications in purification of other heavy metal ions from aquatic systems. V
C 2017 Wiley Period-

icals, Inc. J. Appl. Polym. Sci. 2017, 134, 45431.

KEYWORDS: adsorption; applications; functionalization of polymers

Received 28 March 2017; accepted 16 June 2017

DOI: 10.1002/app.45431

INTRODUCTION removal due to their strong binding with metal ions.1820

Owing to the excellent effect and low cost, DTC has been
Water contamination with heavy metal ions such as Cu21 and
converted to a variety of different materials including micro-
Pb21 is an increasing concern for public health in many areas,
molecules with single and multiple DTC groups, and macromo-
due to their high toxicity and non-degradable characteristic.13
lecules with multiple DTC groups. Fu et al. compared diethyldi-
Moreover, they accumulate in living organisms and may cause
thiocarbamate (DDTC) and N,N0 -bis-(diethylcarboxyl)
several diseases and death.46 The toxic heavy metal ions are
piperazine (BDP) in the treatment of wastewater containing
usually released into the aquatic environment from mineral
Cu21, and the results showed that both DDTC and BDP were
processing, metallurgy engineering, metal electroplating, battery
able to reduce Cu21 significantly to satisfy the standard for
manufacturing, etc.710 Several removal methods and separation
heavy metal discharging,21 while BDP-chelated precipitates had
technologies have been explored and developed to minimize the
a much higher settling rate than DDTC chelated ones. There-
amount of heavy metals ions discharged into environment,
fore, although micro-molecule with single DTC group demon-
including chemical precipitation, chelation-precipitation, mem-
strates strong chelating abilities because of the abundant
brane separation, ferric methods, ion exchange, adsorption, and
functional groups, the formed floccules are small, leading to
electrodialysis.1115 Among all of them, chelation-precipitation
poor separation of floccules and the treated water. Micro-
has been regarded as a simple, rapid, and low cost method
molecular chelants with multiple DTC group such as sodium
capable of large-scale removal of heavy metal ions with high
1,3,5-hexahydrotriazinedithiocarbamate form larger floccules
efficiency.16,17
through chelation between the same metal ion and more func-
Chelating agents, such as dithiocarbamates (DTCs), are widely tional groups on different molecules, enhancing settling perfor-
used as extractive reagents for effective heavy metal ions mance.22 Whats more, macromolecular chelants are found to

C 2017 Wiley Periodicals, Inc.

V

WWW.MATERIALSVIEWS.COM 45431 (1 of 11) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431

ARTICLE WILEYONLINELIBRARY.COM/APP
be even more efficient than micromolecules in precipitating
heavy metal ions, which attributes to their strong metal chelat-
ing abilities and excellent flocculation properties. However,
during the chelation process of macro-molecular chelants con-
taining multiple DTC groups, especially those materials
obtained by introducing functional groups into linear polymers,
some of the functional groups are prevented from chelating
with metal ions due to steric hindrance and spatial mismatches.
As a result, the loose floccules with excess negative charges are
formed, which inhibits them from further growth and rapid
settlement.2023
In the past few years, attempts have been made to introduce
positively charged groups into chelating absorbents such as pol-
y(dimethyldiallylammonium chloride-co-acrylamide)-graft-trie-
thylenetetramine-DTC (PDCATD) to neutralize the excess
negative charges of floccules so as to improve the settling per-
formance.16,17,20 However, this still cannot make full use of
active adsorption sites because of steric hindrance and spatial
mismatches. From a molecular structure point of view, a star-
like structure is more beneficial for the adsorption process
compared to linear chain molecules, due to easy accessibility of
DTC functional groups in the stretched polymer chains sur-
rounding Al(OH)3 core to metal ions. Meanwhile, much more
cation metal ions are adsorbed on each adsorbent molecule,
which could reduce the excess negative charges of formed floc-
cules that negative DTC groups contribute. To our knowledge,
no research has been carried out to extend the graft of DTC
onto a star-like inorganicorganic hybrid polymer for effective
utilization of functional groups, which could enhance chelating
adsorption capacity of the material and reduce negative charges
of floccules which may lead to rapid settlement as well.
Al(OH)3-polyacrylamide (Al-PAM) has a star-like structure,
in which Al(OH)3 colloids acts as cores connecting PAM chains
as arms. The material has been confirmed to be an excellent
flocculant due to its charge neutralization capacity by Al(OH)3
as well as its easy accessibility of PAM chains in the star-like
structure for bridging flocculation.2426 Therefore, the cationic
Al-PAM was selected as the model skeleton to be functionalized
through the reaction between amino groups in PAM with DTC
groups (Al-PAM-DTCs) and serve as a polymeric chelating-
adsorbent in aquatic system. We evaluated the adsorption
capacity of Al-PAM-DTCs to Cu21 and Pb21 with different ini-
tial concentrations and studied the adsorption kinetics, iso-
therms as well as the adsorption mechanism. In addition, the
flocculation and chelation performance of Al-PAM-DTCs for
removal of particles and metal ions were also investigated in
turbid suspensions.
EXPERIMENTAL
Chemicals
Acrylamide (AM), diethylenetriamine (DETA), and carbon
disulfide (CS2) were purchased from Aladdin (Shanghai/China).
Aluminum chloride, ammonium carbonate, ammonium pursul-
fate, sodium sulfite, sodium hydroxide, formaldehyde, copper
sulfate, and lead nitrate were purchased from Xilong chemical
Co. Ltd (Shantou/China). All reagents were used as received,
without further purification. Milli-Q water with a resistivity of
WWW.MATERIALSVIEWS.COM 45431 (2 of 11)
18 MX .cm were used to prepare all solutions in this study
unless otherwise stated.
Preparation of Al-PAM-DTCs
Al-PAM was prepared by polymerization of AM on the surface
of Al(OH)3 colloid with ionic bonds. The Mannich reaction
took place at the amino groups in the side chains of PAM to
produce an iminium ion immediate through aminomethylation
reaction with HCHO, and Al-PAM-DETA was generated
through the nucleophilic reaction of DETA with the immediate.
The secondary DTC is more stable than the primary DTC, and
the negative surface charges of the secondary nitrogen are more
than those of the primary nitrogen,16 so CS2 was easily and
mainly reacted with the secondary amino group in the presence
of NaOH to generate the crosslinked product Al-PAM-DTCs.
Synthesis of Al(OH)3-Polyacrylamide. The synthesis of Al-
PAM was based on solution polymerization.25,26 In general, Al-
PAM was synthesized by polymerization in aluminum hydroxide
colloidal suspensions under the initiation of ammonium persul-
fate/sodium sulfite. Al(OH)3 colloidal suspensions was obtained
by dripping 9 mL of 15 wt % ammonium carbonate solution
into 20 mL of 8 wt % aluminum chloride solution under vigor-
ous stirring, which exhibited obvious Tyndall phenomenon after
preparation. With the addition of 4.5 g of AM into the
Al(OH)3 colloidal suspensions, the mixture was being agitated
and heated concurrently in a water bath at 40 8C under the
nitrogen gas flow for half an hour. To initiate the reaction,
2 mL of 0.05 wt % (NH4)2S2O8 and 0.025 wt % NaHSO3 mix-
ture was dripped slowly into the as-prepared Al(OH)3 colloidal
suspensions containing AM monomers. The reaction was con-
tinued for 12 h in the absence of air. The resulted gel was dis-
solved in Milli-Q water and purified by acetone precipitation to
get the product Al-PAM. The product was dried at 55 8C under
vacuum until no change in weight.
Synthesis of Al-PAM-DETA. In order to introduce xanthogenic
acid into PAM polymer chains, DETA was grafted onto the side
chains of PAM through the Mannich reaction of DETA and
formaldehyde with Al-PAM,16 in which Al-PAM (1 g) solution
was prepared at 1 wt % with milli-Q water, adjusting the pH to
78 using 5 wt % NaOH solution, followed by the slow addi-
tion of 1.4 mL of formaldehyde. Reaction was allowed to occur
for 1 h in a water bath at 50 8C. About 1.5 mL of DETA was
added to the mixture to react for another 3 h. The obtained Al-
PAM-graft-DETA was cooled to room temperature for later use.
Synthesis of Al-PAM-DTCs. The Al(OH)3-PAM-graft-DETA-
dithiocarbamate (Al-PAM-DTCs) was synthesized from Al-
PAM-graft-DETA, NaOH, and CS2 through the nucleophilic
addition reaction, in which 5 mL of 27.5 wt % NaOH was
added to the Al-PAM-graft-DETA solution, followed by slow
dripping of 3 mL of CS2 into the reaction mixture at room
temperature to react for 4 h. Then the temperature was raised
to 55 8C to continue the reaction for another 1.5 h until a yel-
lowish or yellow solution was generated. The resulting solution
was precipitated in acetone, and the precipitates were washed
with ethanol for three or more times. The final product was
dried at 55 8C under vacuum to a constant weight.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431
ARTICLE WILEYONLINELIBRARY.COM/APP
Analytical Methods of Al-PAM-DTCs
The FTIR spectra were recorded in the 4000400 cm21 region
with a resolution of 4 cm21 using a FTIR spectrometer (Spec-
trum GX, USA) to qualitatively identify the functional groups
of the prepared Al-PAM-DTC. Sample powders were stirred and
pressed in a mixture with KBr (1:100, wt/wt). The thermal deg-
radation test was conducted in a thermogravimetric analysis
device (STA449 F3, Germany) with a maximum weight of 35 g.
The heating rate was 10 8C/min from 35 8C to 900 8C under an
air flow of 100 mL/min. The morphology and component of
the Al-PAM-DTCs were analyzed with scanning electron
microscopy (SEM) observations and energy dispersive X-ray
spectroscopy analysis (EDX) simultaneously with thermal field
emission scanning electron microscope operated at 15 kV (FE-
SEM, JSM-7001F, Japan). The microstructure of Al-PAM-DTCs
was investigated using transmission electron microscope (TEM,
JEM-2100, Japan) with an accelerating voltage of 200 kV. TEM
micrograph was obtained on carbon-coated copper grids.
Adsorption Experiments of Cu21 and Pb21
To determine the capacity of Al-PAM-DTCs for adsorbing the
heavy metals of Cu21 and Pb21, all adsorption experiments
were performed by adding 10 mg Al-PAM-DTCs to 50 mL of
metal solution with concentrations ranging from 10 mg/L to
200 mg/L. The adsorption kinetic was studied at a metal con-
centration of 50 mg/L. At a designated contact time of the
adsorbent with the heavy metals under agitation of 200 rpm,
the adsorbent was separated from solution using 0.45 lm poly-
propylene syringe filters. The residual metal concentration in
supernatant was measured by an inductively coupled plasma
optical atomic emission spectrometry (iCAP 6300, Thermo Sci-
entific). All experiments were conducted in triplicate. The
adsorption thermodynamics of Cu21 and Pb21 on Al-PAM-
DTCs were investigated to determine the adsorption nature.
The influence of temperature on adsorption was studied at 298,
308, 318 K with an initial concentration of 64 mg/L (1 mmol/L)
Cu21 and 207 mg/L (1 mmol/L) Pb21.
Analysis of Adsorption Data
Metal removal efficiency [eq. (1)] and the adsorption capacity
qe (mg/g) [eq. (2)] of the Al-PAM-DTCs were calculated as27,28:
C0 2Ct
Removal efficiency5 3100% (1)
C0
C0 2Ct 3V
Adsorption capacity5qe 5 (2)
m min. Time was recorded as zero when the suspension was just
where C0 and Ct (mg/L) are the initial and residual concentra-
tions of metal ions, V (L) and m (g) are the volume of metal
solution and the mass of Al-PAM-DTCs, respectively.
Pseudo-first-order [eq. (3)] and pseudo-second-order [eq. (4)]
kinetic models were employed to evaluate the kinetic data of
metals.29,30
ln qe 2qt 5ln qe 2k1 t (3)
t 1 1
5 1 t (4)
qt k2 qe2 qe
where k1 (min21) and k2 (g/mg min) are the adsorption rate
constants of the two kinetics.
WWW.MATERIALSVIEWS.COM 45431 (3 of 11)
The Cu21 and Pb21 equilibrium adsorption was fitted with
Langmuir and Sips (LangmuirFreundlich) isotherm adsorption
models. The Langmuir isotherm [eq. (5)] is on the base of
homogeneous adsorption:
qm KL Ce
qe 5 (5)
11KL Ce
The Sips model [eq. (6)] is modified by the Langmuir and
Freundlich models which takes heterogeneity into
consideration.31,32
qm KS Ce 1=ns
qe 5 (6)
11KS Ce 1=ns
where Ce (mg/L) and qe (mg/g) are the metal solution concen-
tration and adsorption capacity of adsorbent at equilibrium,
whereas qm (mg/g), KL/KS (L/mg), and ns represent the satura-
tion adsorption capacity, the Langmuir and Sips adsorption
equilibrium constants, and the heterogeneity factor obtained
after nonlinear fitting, respectively.
The enthalpy changes in adsorption process were calculated by
Vant Hoff equations:2,32
qe
KC 5 (7)
Ce
DG52RT ln KC (8)
DH DS
ln KC 52 1 (9)
RT R
where KC is the separation constant between solid and liquid
phase in adsorption process, R is the gas constant (R 5 8.314 J/
mol K), T (K) is the absolute temperature.
Flocculation Test
Synthetic turbid solution containing 50 mg/L Cu21 and Pb21
was prepared with copper sulfate pentahydrate and lead nitrate
with bauxite turbid suspensions as stock solution. Al-PAM-
DTCs was mixed with 500 mL of the synthetic solution in a
beaker to a final concentration of 0.2 g/L to evaluate its floccu-
lation on suspended solids with an average particles size of 1
lm as well as its adsorption capacity on metal ions of Cu21
and Pb21. The resulting mixture was immediately stirred at
200 rpm for 2 min, followed by 100 rpm for 8 min and 50 rpm
for 20 min to avoid breaking the formed floccules and guaran-
tee the saturated adsorption for metal ions. The suspensions
were transferred to 500 mL measuring cylinder to settle for 20
transferred to the measuring cylinder and the height of the clear
supernatant was recorded at specific times in a period of 20
min for settling of the formed floccules. The supernatant 2 cm
below the surface was taken to measure the turbidity using a
photoelectric turbidimeter (WZT-3, China). The residual Cu21
and Pb21 concentrations were measured under conditions simi-
lar with the above described adsorption experiments.
RESULTS AND DISCUSSION
Al-PAM-DTCs Characterization
SEM and TEM Imaging. SEM enables the direct observation of
surface morphology of Al-PAM-DTCs. As can be seen in Figure
1(A), the Al-PAM-DTCs was in the form of flocks and each
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431
ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 1. (A) SEM and (B) TEM micrograph of Al-PAM-DTCs.

plane surface seemed to be relatively smooth. In the high reso-
lution of TEM image [Figure 1(B)], the black spots were seen
to well distribute on the surface which were attributed to
Al(OH)3 colloidal particles. The Al(OH)3 colloids with an aver-
age size of about 10 nm were surrounded by polymer chains
and acted as cores connecting the chains. As schematically
described in Figure 2, one Al(OH)3 acted as core connecting
several PAM side chains as arms, exhibiting a star-like struc-
ture.24,26 The DTCs functional reaction occurred at the side
chains of PAM maintaining the star-like structure which was
more beneficial for the adsorption process compared to the lin-
ear chain molecules because of the easy access of the active
adsorption sites in PAM-DTCs chains by metal ions.
FTIR Analysis. In Figure 3(a), the broad absorption band
observed at 3442.69 cm21 was attributed to the stretching vibra-
tions of NAH group in AM monomer unit and the OAH in
the absorbed water of Al-PAM from air during pellet-making.
The peaks at 1645.17 cm21 and 1440.36 cm21 can be assigned
to the C@O and the CAN stretching vibrations in the
ACONH2 group, respectively.33 The peak at 2922.75 cm21 is
due to the stretching vibration of CAH of ACH2A, while the
deformation vibration is at 1323.18 cm21.20 The absorbance at
1033.0 cm21 and 736.12 cm21 can be assigned to the deforma-
tion vibrations of AOH and stretching vibrations of AlAO in
Al(OH)3 respectively.25 The Figure 3(b) showed the similar
absorption peaks with Figure 3(a) but a small shift in wave
numbers. Besides, the peak observed at 789.73 cm21 is the rock-
ing vibrations of ACH2A of grafted DETA. The obvious
absorption peak at 869.23 cm21 can be assigned to the defor-
mation vibration of ACSS and the peak at 671.27 cm21 can be
attributed to the stretching vibration of CAS. The peak at
1454.36 cm21 is attributed to the stretching vibrations of CAN
group in the NACSS.16 The peak at 1040 cm21 can be attrib-
uted to the stretching vibration of C@S, which may overlap
with the deformation vibrations of AOH in Al(OH)3.Therefore,
the ACSS has been successfully introduced to molecular chains
of Al-PAM-DTCs.

Figure 2. Schematic representation of Al-PAM-DTCs synthesis and structure. [Color figure can be viewed at wileyonlinelibrary.com]

WWW.MATERIALSVIEWS.COM 45431 (4 of 11) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431

ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 3. FTIR spectra of (a) Al-PAM (b) Al-PAM-DTCs. [Color figure Figure 5. Effect of contact time on adsorption of Cu21 by (a) PAM-DTCs
can be viewed at wileyonlinelibrary.com] (c) Al-PAM-DTCs and Pb21 by (b) PAM-DTCs (d) Al-PAM-DTCs.
[Color figure can be viewed at wileyonlinelibrary.com]
Thermogravimetric Analysis. The thermogravimetric analysis
(TGA) curves of the as-synthesized Al-PAM and Al-PAM-DTCs
(Figure 4) showed four thermal degradation steps. In the first step,
about 10% weight lost started from 40 to 150 8C, owing to the
evaporation of absorbed moisture.34 The degradation of structure
units in PAM or PAM-DTCs chains and decomposition of alumi-
num hydroxide began at 230 8C, which caused the slight drop in
the second step of the TGA curves.35 Another drop occurred at the
third step from 350 8C, which was probably ascribed to thermal
process containing the thorough decomposition of aluminum
hydroxide and cleavage of the weak and unstable linkages, such as
the side chain of acylamino producing NH3. Further increase of
temperature to 400 8C led to the fourth step, in which the polymer
backbone broke down completely to generate low molecular gases,
i.e., CO2 and H2O, leading to rapid weight loss.36 The weight of Al-
PAM tended to be constant when the temperature exceeded 600 8C,
and there was about 8 wt % of residual mass which could be
Al2O3. About 30 wt % of weight was retained in the thermal degra-
dation of Al-PAM-DTCs above 500 8C, which possibly attributed
to the mixture of Al2O3 and Na2SO4.

Figure 4. TGA curves of (a) Al-PAM and (b) Al-PAM-DTCs. [Color fig- Figure 6. Cu21 and Pb21 adsorption kinetics by pseudo-first order and
ure can be viewed at wileyonlinelibrary.com] pseudo-second order. [Color figure can be viewed at wileyonlinelibrary.com]

WWW.MATERIALSVIEWS.COM 45431 (5 of 11) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431

ARTICLE WILEYONLINELIBRARY.COM/APP

Table I. Kinetic Parameters for Adsorption of Cu21 and Pb21 on Al-PAM-DTCs

Pseudo-first order Pseudo-second order

Metal ions qe,exp (mg/g) qe (mg/g) K1 (min 21
) R21 qe (mg/g) K2 (g/min mg) R22
Cu21 247.505 60.566 0.092 0.951 248.756 0.005 0.999
Pb21 249.526 15.495 0.120 0.962 250.000 0.030 1.000

Adsorption Kinetics of Cu21 and Pb21
Time-dependent removal of Cu21 and Pb21 (initial concentra-
tion is 50 mg/L) by Al-PAM-DTCs showed rapid adsorption in
the first 30 min (above 97% removal efficiency), and then the
adsorption rate tend to be zero gradually (Figure 5). The
adsorption of Cu21 achieved an equilibrium with no obvious
change in removal efficiency of 97% at 30 min, while the equi-
librium for Pb21 was attained much faster at 15 min than Cu21
with above 99% of removal efficiency. The Al-PAM-DTCs
exhibited an extremely rapid adsorption, as the contact time of
each experiment was 2 h, which was significant in comparison
with other adsorption materials required for routinely ranging
from 12 h to as much as 48 h.27,32,37 In contrast, the PAM-
Figure 7. Cu21 and Pb21 adsorption isotherms fitted by Langmuir and
Sips model. [Color figure can be viewed at wileyonlinelibrary.com]
DTCs showed much slower and poorer adsorption for Cu21
and Pb21. The fast and effective adsorption of Al-PAM-DTCs is
due to the easy access and complete contact of metal ions with
the evenly distributed DTCs in its star-like structure.26
The kinetic data were fitted with the pseudo-first-order and
pseudo-second-order kinetic models to investigate the adsorp-
tion rate of Cu21 and Pb21 onto Al-PAM-DTCs (Figure 6). The
pseudo-second-order model demonstrated perfect application
for the adsorption kinetics of Al-PAM-DTCs toward metal ions
(R22 > 0.999) and wonderful consistency between the experimen-
tal and calculated qe (Table I). However, the pseudo-first order
showed relatively high correlation coefficient factor of
R12 > 0.951 but poor matching between the experimental qe with
that of calculated. The results suggested that the pseudo-
second-order model was better than pseudo-first-order model
to describe the adsorption kinetic characteristic of metal ions
on the Al-PAM-DTCs surface.
Adsorption Isotherms of Cu21 and Pb21
The isotherm adsorption data of Cu21 and Pb21 were fitted
using Langmuir and Sips adsorption isotherm models (Figure
7). The high values of the correlation coefficients of R2, the con-
sistency of the experimental and calculated qm values, as well as
the isotherm adsorption curves fitting well with experimental
data of Cu21 and Pb21 indicated the Sips model fitted better
for the adsorption of Cu21, while the Langmuir model could
describe better the adsorption of Pb21. So this phenomenon
might suggest heterogeneous distribution of adsorption active
sites for Cu21 and homogeneous distribution of adsorption
active sites for Pb21. In addition, the relatively high values of
R2 (>0.95) and contiguous numerical value of qm obtained by
Sips model indicated that heterogeneous active sites for Pb21
might exist. One kind of active sites plays a predominant role
and the other ones play a minor role in the adsorption of
metal.32 Results of Table II indicated that the saturated adsorp-
tion capacities of Al-PAM-DTCs were 416.959 mg/g (6.515
mmol/g) for Cu21 and 892.505 mg/g (4.312 mmol/g) for Pb21.
The adsorption affinity (KL/KS) suggested that the adsorbent
seemed to exhibit stronger affinity to Pb21, as compared with
Cu21.4,32 Table III summarizes the maximum adsorption capac-
ity of the commonly used adsorbents in contrast to the data of
as-prepared Al-PAM-DTCs in this study. Evidently, the much
higher qm indicated that Al-PAM-DTCs is an effective adsorbent
for the removal of Cu21 and Pb21 or other heavy metals in
wastewater systems.20,23
Flocculation Study
Figure 8 shows how the supernatant turbidity, the clarified
height, and the removal efficiency of metal ions varies over time

WWW.MATERIALSVIEWS.COM 45431 (6 of 11) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431

ARTICLE WILEYONLINELIBRARY.COM/APP

Table II. Isotherm Parameters for Adsorption of Cu21 and Pb21 on Al-PAM-DTCs

Langmuir model Sips model

2
Metal ions qm,exp (mg/g) qm (mg/g) KL (L/mg) R qe (mg/g) KS (L/mg) 1/ns R2
Cu21 440 429.067 0.682 0.923 416.959 0.770 1.932 0.972
Pb21 882.5 892.505 1.217 0.973 839.040 1.413 1.970 0.970

Table III. Comparison of the Maximum Adsorption Capacities of Metals by Different Adsorbents

Maximum metal adsorption

capacity (mmol/g)
Adsorbents Cu21 Pb21 Isothermal adsorption model Refs.
Fe2O3-APTES-EDTA 0.484 Langmuir 27
EPI-b-CD 0.369 N/A 32
EDTA-b-CD 1.242 Langmuir 32
g-CA-TA-NMOa 0.951 Langmuir 38
Fe3O4@SiO2@TiO2 1.953 0.773 Langmuir 39
A-CMK-3b 0.672 1.184 Langmuir 40
c
SBA-15 1.408 Langmuir 41
Pb-ICBd 0.858 Langmuir 42
GO-SHe 1.550 Langmuir 37
GO-Nf 1.614 Langmuir 37
Al-PAM-DTCs 6.515 4.312 Langmuir This study
a
g-CA-TA-NMO: triethylenetetramine functionalized cellulose acetate grafted with the copolymer-manganese dioxide composite.
b
A-CMK-3: Amine-functionalization ordered mesoporous carbon.
c
SBA-15: 1,2-diaminocyclohexane-functionalized SBA-15 silica sorbent.
d
Pb-ICB: Pb(II)-imprinted chitosan beads.
e
GO-SH: 4-aminothiophenol modified GO.
f
GO-N: 3-aminopropyltriethoxysilane modified GO.

in bauxite turbid suspensions with 50 mg/L of Cu21 and Pb21
treated by Al-PAM-DTCs of 0.2 g/L. The formed floccules
completely settle within 5 min after addition of Al-PAM-DTCs,
and the turbidity of supernatant sharply reduced from 324.3
NTU without Al-PAM-DTCs to about 5 Nephelometric Turbid-
ity Unit (NTU) which indicated an efficient removal of sus-
pended solid in bauxite turbid suspensions. Whats more, the
Figure 8. Removal of metal ions and suspended solids in bauxite turbid suspen-
sions by Al-PAM-DTCs. [Color figure can be viewed at wileyonlinelibrary.com]
removal efficiency of Cu21 and Pb21 acquired high values of
above 97% and 99% respectively, which agreed with the results
in Figure 5 without bauxite suspended particles. This phenome-
non indicated that there are specific and different adsorption
active sites for solid particles and metal ions, the presence of
solid particles does not affect the chelation of Al-PAM-DTCs to
metal ions. The Al-PAM has been confirmed as an effective floc-
culant in treating turbid wastewater or mineral suspensions by
neutralization of Al(OH)3 to negative charges and bridge
adsorption of PAM to particles in the suspensions,24,25 which
perfectly interpreted the high removal of turbidity in the baux-
ite suspension. Meanwhile, the functional group such as
NACSS grafted on Al-PAM in Al-PAM-DTCs chelated with
Cu21 and Pb21, thus achieving the high removal of metal ions
in suspensions.
Adsorption Mechanism
The morphology and element distribution for Al-PAM-DTCs
after adsorption of Cu21 and Pb21 are demonstrated in Figure 9.
The surface of adsorbent becomes rough compared with that
before adsorption. The well dispersion of bright signal spots [Fig-
ure 9(A,B)] showed that sulfur and nitrogen was well dispersed
on the surface of Al-PAM-DTCs, which indicated that the func-
tional groups were uniformly grafted onto the side chains of Al-
PAM, resulting in the well-distributed active adsorption sites. As

WWW.MATERIALSVIEWS.COM 45431 (7 of 11) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431

ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 9. SEM, the elemental distribution mapping, and the EDX spectrum of Al-PAM-DTCs after adsorption of (A) Cu21 and (B) Pb21. [Color figure
can be viewed at wileyonlinelibrary.com]

WWW.MATERIALSVIEWS.COM 45431 (8 of 11) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431

ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 10. Vant Hoff graph for Cu21 and Pb21 adsorption on Al-PAM-
DTCs. [Color figure can be viewed at wileyonlinelibrary.com]
expected, the Cu [Figure 9(A)] and Pb [Figure 9(B)] were suc-
cessfully adsorbed and spread over the whole surface of Al-PAM-
DTCs. The EDX spectra gave further evidence on the above result.
The high contents of Cu and Pb are in good agreement with the
results of high adsorption capacities of Al-PAM-DTCs.
The thermodynamic parameters were obtained from the plots
of ln KC versus 1/T (Figure 10), and the results are listed in
Table IV. The negative values of DG for both Cu21 and Pb21 at
all investigated temperatures indicated the spontaneous charac-
teristic of these two metal ions in adsorption by Al-PAM-DTCs.
In addition, the values of DH for both Cu21 and Pb21 were
positive, suggesting the endothermic process for adsorption of
the two metal ions onto Al-PAM-DTCs, and the adsorption
would be enhanced with the increase of temperature. This also
indicated that it is mainly chemisorption between Cu21 and
Pb21 with Al-PAM-DTCs, which could possibly attributed to
chelation of xanthate and nitrogen-containing groups with
metal ions.43,44 The increasing randomness at solidliquid inter-
face in the adsorption process of Cu21 and Pb21 were well illus-
trated by the positive DS values for these two metal ions.
In order to further verify the adsorption mechanism, the FITR
spectra of Al-PAM-DTCs before and after Cu21 and Pb21
adsorption were compared and demonstrated in Figure 11.
Compared to the control, the peak at 869.23 cm21 corre-
sponding to the deformation vibration of ACSS disappeared,
the FTIR spectrum of Cu21 chelates shifted obviously to
612.45 cm21 from 671.27 cm21 ascribed to the stretching
Table IV. Thermodynamic Parameters for Adsorption of Cu21 and Pb21 on Al-PAM-DTCs
DG (kJ/mol) at T
Metal ions 298 K 308 K 318 K
Cu21 212.605 213.597 214.683
Pb21 26.759 27.421 28.156
WWW.MATERIALSVIEWS.COM 45431 (9 of 11)
Figure 11. FTIR spectra of Al-PAM-DTCs before and after adsorption of
Cu21 and Pb21: (a) Al-PAM-DTCs, (b) Al-PAM-DTCs-Cu, (c) Al-PAM-
DTCs-Pb. [Color figure can be viewed at wileyonlinelibrary.com]
vibration of CAS and the stretching vibration of C@S at
1040.16 cm21 slightly shifted to 1046.52 cm21, indicating the
interaction between DTCs xanthate groups and Cu21. In addi-
tion, the stretching vibrations of CAN group in the NACSS at
1454.36 cm21 shifted to 1436.08 cm21, reflecting the synergic
effect of nitrogen-containing groups which has been reported to
be able to complex metals.17,20 Similar shift of Pb21 chelates in
FTIR spectrum was also observed in Figure 11, suggesting the
coordination action of the functional xanthate and the
nitrogen-containing groups in Al-PAM-DTCs to the adsorption
of metal ions.
According to the EDX, thermodynamics, and FTIR analysis, as
well as the adsorption and flocculation results, the synergetic
mechanism for the simultaneous removal of suspended bauxite
and metal ions is proposed. The Al-PAM demonstrated func-
tions not only as star-like model for grafted DTCs but also as
adsorption sites for solid particles. The star-like structure of
Al-PAM-DTCs make the xanthate and nitrogen-containing
functional groups fully expose to the metal ions for chelation.
The charge neutralization of Al(OH)3 colloids and the bridging
adsorption of extended PAM chains contribute to the effective
flocculation of solid particles. The presence of solid particles did
not prevent the metal ions from chelation in binary system of
heavy metal ions and particles. Moreover, the large floccules
formed by the simultaneous adsorption of solid particles and
chelation of metal ions onto Al-PAM-DTCs led to more rapid
DH (kJ/mol) DS (J/mol K) R2
18.307 103.79 0.996
14.056 69.804 0.996
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431
ARTICLE WILEYONLINELIBRARY.COM/APP
settlement of both in contrast to metal ions chelates in single
system.16,17,2426
CONCLUSIONS
The star-like Al-PAM-DTCs was successfully synthesized and
demonstrated significant removal of Cu21 and Pb21. It took 15
min and 30 min respectively to remove above 97% of Cu21 and
99% of Pb21 from 50 mL of metal solution with a concentration of
50 mg/L. The kinetic studies indicated the Al-PAM-DTCs adsorp-
tion of Cu21 and Pb21 could be well described by kinetic second
order. The adsorption equilibrium isotherm of Cu21 showed a
good fit to the Sips model, while Pb21 adsorption was better
described by the Langmuir model. The maximum adsorption
capacities for Cu21 and Pb21 were 416.959 mg/g and 892.505 mg/
g, respectively. Al-PAM-DTCs was able to remove suspended solids,
Cu21 and Pb21 simultaneously through flocculation and chelation
in bauxite turbid suspensions. The coexisting suspended solids had
no influence on removal of Cu21 and Pb21 ions. Chemisorption
was the major mechanism of the Al-PAM-DTCs adsorption for
Cu21 and Pb21, which was attributed to the chelation of xanthate
and nitrogen-containing functional groups with metal ions. The
star-like structure of Al-PAM-DTCs makes the active adsorption
sites fully expose to the metal ions for chelation, which make the
removal of the metal ions significantly effective. Therefore, Al-
PAM-DTCs is an excellent adsorbent for rapid, convenient, and
highly efficient removal of Cu21 and Pb21 in aquatic system. Cur-
rently, studies are being carried out to use Al-PAM-DTCs to treat
water contaminated with other types of metal ions. It is prospected
that Al-PAM-DTCs has great potential in industrial application.
ACKNOWLEDGMENTS
The financial support for this work from 863 Projects
(2011AA06A104) and (2013AA065703) in the National Science &
Technology Pillar Program are gratefully acknowledged. The
authors thank all the members at the Material Chemistry and Engi-
neering Group in Institute of Process Engineering, CAS.
REFERENCES
1. Schwarzenbach, R. P.; Escher, B. I.; Fenner, K.; Hofstetter, T.
B.; Johnson, C. A.; Gunten, U. V.; Wehrli, B. Science 2006,
313, 1072.
2. Luo, S. L.; Xu, X. L.; Zhou, G. Y.; Liu, C. B.; Tang, Y. H.;
Liu, Y. T. J. Hazard. Mater. 2014, 274, 145.
3. Loiacono, S.; Morin-Crini, N.; Cosentino, C.; Torri, G.;
Chanet, G.; Winterton, P.; Crini, G. J. Appl. Polym. Sci.
2017, 134, DOI: 10.1002/app.44422.
4. Tzu, T. W. J. Environ. Prot. 2013, 4, 51.
5. Moreira, H.; Pereira, S. I. A.; Marques, A. P. G. C.; Rangel,
A. O. S. S.; Castro, P. M. L. Geoderma 2016, 278, 1.
6. Jarup, L. Br. Med. Bull. 2003, 68, 167.
7. Argane, R.; El Adnani, M.; Benzaazoua, M.; Bouzahzah, H.;
Khalil, A.; Hakkou, R.; Taha, Y. Environ. Sci. Pollut. Res.
2016, 23, 598.
WWW.MATERIALSVIEWS.COM 45431 (10 of 11)
8. Onditi, M.; Adelodun, A. A.; Changamu, E. O.; Ngila, J. C.
J. Appl. Polym. Sci. 2017, 134, DOI: 10.1002/app.44422.
9. Mohan, D.; Pittman, C. U., Jr. J. Hazard. Mater. 2006, 137, 762.
10. Gupta, V. K.; Nayak, A. Chem. Eng. J. 2012, 180, 81.
11. Bailey, S. E.; Olin, T. J.; Bricka, R. M.; Adrian, D. D. Water
Res. 1999, 33, 2469.
12. Fu, F. L.; Wang, Q. J. Environ. Manage. 2011, 92, 407.
13. Crini, G. Prog. Polym. Sci. 2005, 30, 38.
14. Dabrowski, A.; Hubicki, Z.; Podkoscielny, P.; Robens, E.
Chemosphere 2004, 56, 91.
15. Raval, N. P.; Shah, P. U.; Shah, N. K. J. Environ. Manage.
2016, 179, 1.
16. Liu, L. H.; Wu, J.; Ling, Y. L.; Li, X.; Zeng, R. J. J. Appl.
Polym. Sci. 2013, 127, 2082.
17. Liu, L. H.; Li, Y. H.; Liu, X.; Zhou, Z. H.; Ling, Y. L. Spec-
trochim. Acta 2014, 118, 765.
18. Tiwari, S.; Bajpai, A. React. Funct. Polym. 2005, 64, 47.
19. Fu, F. L.; Chen, R. M.; Xiong, Y. J. Hazard. Mater. 2007,
142, 437.
20. Liu, L. H.; Wu, J.; Li, X.; Ling, Y. L. Sep. Purif. Technol.
2013, 103, 92.
21. Fu, F. L.; Chen, R. M.; Xiong, Y. Sep. Purif. Technol. 2006, 52, 388.
22. Fu, F. L.; Zeng, H. Y.; Cai, Q. H.; Qiu, R. L.; Yu, J.; Xiong,
Y. Chemosphere 2007, 69, 1783.
23. Li, Z. L. J. Ind. Eng. Chem. 2014, 20, 586.
24. Alagha, L.; Wang, S. Q.; Yan, L. J.; Xu, Z. H.; Masliyah, J.
Langmuir 2013, 29, 3989.
25. Liu, Y.; Lv, C. C.; Ding, J.; Qian, P.; Zhang, X. M.; Yu, Y.;
Ye, S. F.; Chen, Y. F. Miner. Eng. 2016, 89, 108.
26. Sun, W.; Long, J.; Xu, Z. H.; Masliyah, J. H. Langmuir 2008,
24, 14015.
27. Huang, Y.; Keller, A. A. Water Res. 2015, 80, 159.
28. Erdem, E.; Karapinar, N.; Donat, R. J. Colloid Interface Sci.
2004, 280, 309.
29. Reddad, Z.; Gerente, C.; Andres, Y.; Cloirec, P. L. Environ.
Sci. Technol. 2002, 36, 2067.
30. Taty-Costodes, V. C.; Fauduet, H.; Porte, C.; Delacroix, A. J.
Hazard. Mater. 2003, 105, 121.
31. Abney, C. W.; Gilhula, J. C.; Lu, K.; Lin, W. Adv. Mater.
2014, 26, 7993.
32. Zhao, F.; Repo, E.; Yin, D. L.; Meng, Y.; Jafari, S.; Sillanpaa,
M. Environ. Sci. Technol. 2015, 49, 10570.
33. Kutsevol, N.; Bezugla, T.; Bezuglyi, M.; Rawiso, M. Macro-
mol. Symp. 2012, 317318, 82.
34. Sato, T.; Sato, K. J. Ceram. Soc. Jpn. 1996, 104, 377.
35. Cao, L. Y.; Fei, X. N.; Zhao, H. B.; Gu, Y. C. Dyes Pigm.
2015, 119, 75.
36. Tang, Q. L.; Wang, K. W.; Zhu, Y. J.; Chen, F. Mater. Lett.
2009, 63, 1332.
37. Chen, D.; Zhang, H. N.; Yang, K.; Wang, H. J. Hazard.
Mater. 2016, 310, 179.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431
ARTICLE WILEYONLINELIBRARY.COM/APP

38. Yakout, A. A.; El-Sokkary, R. H.; Shreadah, M. A.; Abdel
Hamid, O. G. A. Carbohydr. Polym. 2016, 148, 406.
39. Habila, M. A.; Alothman, Z. A.; El-Toni, A. M.; Labis, J. P.;
Soylak, M. Talanta 2016, 154, 539.
40. Barczak, M.; Michalak-Zwierz, K.; Gdula, K.; Tyszczuk-
Rotko, K.; Dobrowolski, R.; Dabrowski, A. Micropor. Meso-
por. Mater. 2015, 211, 162.
41. Sreenu, B.; Sharma, P.; Seshaiah, K.; Singh, A. P. Desalin.
Water Treat. 2016, 57, 15397.
42. Jing, Y. J.; Yin, N. N.; Yu, X. Q. Desalin. Water Treat. 2015,
57, 1.
43. Saenger, W. Angew. Chem. Int. Ed. Engl. 1980, 19, 344.
44. Tolani, S.; Mugweru, A.; Craig, M.; Wanekaya, A. K. J. Appl.
Polym. Sci. 2010, 116, 308.

WWW.MATERIALSVIEWS.COM 45431 (11 of 11) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45431