Chemical Engineering Journal 276 (2015) 349357

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Preparation and performance of polyacrylonitrile ber functionalized

with iminodiacetic acid under microwave irradiation for adsorption
of Cu(II) and Hg(II)
Sheng Deng a, Guangshan Zhang a, Xi Wang a, Tong Zheng a, Peng Wang a,b,
a
b

School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, PR China
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, PR China

h i g h l i g h t s
 Modied bers under microwave irradiation owns higher adsorption capacity.
 The maximum adsorption capacity toward Cu(II) and Hg(II) was 119.39 and 275.76 mg g

1

 Non-thermal effect of microwave irradiation showed same impact with thermal effect.

a r t i c l e

i n f o

Article history:
Received 21 February 2015
Received in revised form 7 April 2015
Accepted 8 April 2015
Available online 15 April 2015
Keywords:
Microwave irradiation
Polyacrylonitrile ber
Adsorption
Copper
Mercury
Non-thermal effect

a b s t r a c t
Polyacrylonitrile ber immobilized with iminodiacetic acid (IDA) was prepared under microwave irradiation and was used to adsorb Cu(II) and Hg(II) in aqueous solution. Synthesis conditions such as time, temperature and ratio of solvents were exploited systematically by orthogonal experiment and the properties
of this brous absorbent were characterized by fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), scanning electron microscopy (SEM). The adsorption performances, in both thermodynamic and kinetic conditions, were investigated strictly and the experimental data tted the Langmuir
model (R2 > 0.99) and pseudo-second-order equation very well. The effect of pH on the adsorption capacity of metal ions was discussed and the optimal value for Cu(II) and Hg(II) was found to be 5.0 and 2.0,
respectively. Thermodynamic parameters reveal the spontaneous and endothermic nature of the adsorption process, due to the negative value of standard free energy (DG) and the positive value of standard
enthalpy (DH). The adsorption capacities toward Cu(II) and Hg(II) on the modied polyacrylonitrile bers
under microwave irradiation are higher than those on other adsorbents through conventional heating.
The less consumed time and high grafting rate of the functional groups may be attributed to thermal
effect as well as non-thermal effect of microwave irradiation.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Heavy metal ions are highly toxic to human health, and the discharge to environment was mainly caused by anthropogenic
behavior and nature disaster [1]. With the rapid growth of population and industrialization in the world, the frequency of accidently heavy metal pollution boosted fast in recent years. Due to
its non-biodegradation and non-decomposing characters, metal
ions can be accumulated through food chain and then absorbed
by human-being [2]. Mercury is one of the most toxic metal ions,
especially when the metal is transferred into methyl mercury by
Corresponding author. Tel./fax: +86 451 86283557.
E-mail address: pwang73@vip.sina.com (P. Wang).
http://dx.doi.org/10.1016/j.cej.2015.04.043
1385-8947/ 2015 Elsevier B.V. All rights reserved.

anaerobic organism in the aqueous environment. Mostly, mercury

can enter into the environment through improper disposal of certain products including auto parts, batteries, uorescent bulbs,
medical products, thermometers and thermostats. When it comes
into human body, central nervous system damage, brain inefciency and liver disfunction may be caused [3]. Meanwhile, copper
has also been widely used in electrical engineering, machinery
manufactory and construction industry, leading to the risk of severe gastrointestinal irritation, muscular pain and possible necrotic
change in kidney [4]. Thus, how to remove heavy metal ions from
water environment has become a vital study, especially when sudden pollution accident happens.
Many techniques, including solvent extraction, membrane separation, electrochemical operation, adsorption, and ion exchange,

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S. Deng et al. / Chemical Engineering Journal 276 (2015) 349357

have been utilized to fulll the task [5]. Among these methods,
adsorption is expected to be an attractive way due to its removal
efciency as well as excellent reusability. Activated carbon [6],
oxide minerals [7], polymer materials [8], resins [9] and biosorbents [10] have been applied as absorbents to extract metal ions
from the aqueous solution. The efciency of the absorption process
depends on the capability of the absorbents, where immobilized
functional groups play a dominant role in it. It is widely acknowledged that chelating agents such as IDA exhibit good afnity with
metal ions. IDA is a typical type of aminopolycarboxylic acids that
contains two carboxyl groups bound to one nitrogen atom. The
high adsorption capacity of IDA absorbents may attributes to the
formation of stable metal-IDA chelates with multidentate interaction. Based on different raw materials such as silica gel, chitosan,
acrylonitrile-divinylbenzene (AN-DVB) and amino methyl polystyrene (AMPS), many IDA functionalized absorbents were successfully invented in recent years [1113]. The chelating brous
adsorbents have attracted considerable attention owing to their
large specic surface area and quick mass transfer velocity. At present, many researchers have explored the synthesis and modication of various chelating ber absorbents in an effort to enhance
the afnity of metal ions [14,15]. However, most of these methods
are accomplished by using conventional heating such as waterbath heating, oil-bath heating and electrical heating ask, which
are low efciency, high energy waste and low safety. Radiation
induced or electron-beam-induced technique is less universal
owing to its high price and unstability.
Microwave (MW) is electromagnetic waves with wavelengths
between 1 mm and 1 m (frequencies of 300 GHz to 300 MHz).
Contrasted with heat-transfer way of conventional heating, MW
irradiation can make dipolar molecules rotate and ions migrate
when penetrate into samples, then cause heating throughout the
volume of the product. The most common mechanism of MW heating is dipolar polarization which means a dipolar molecule such as
water tries to align itself within the electric eld of MW, and heating was caused by frictional resistance of molecular rotation. This
mechanism is utilized in the domestic MW oven where water acts
as the MW receptor. In addition, the non-thermal effects were also
believed to affect the reaction in some degree [16]. By using this
rapid in core volumetric heating, heating time can be up to three
orders of magnitude lower than that of conventional heating. Due

to its advantage of high-efciency, selectively heating and no pollution to environment, MW has been widely used in various elds,
such as food processing, pharmaceutical synthesis and organic synthesis reaction [1719]. Our group has done some researches on
the application of MW and many achievements have been
obtained [2024].
In the study, an IDA modied chelating ber based on polyacrylonitrile was synthesized in two steps through MW irradiation. The
reaction parameters such as time, temperature and ratio of solvents were optimized thoroughly. The adsorption performance of
Cu(II) and Hg(II) onto the IDA functionalized ber was studied.
The effect of various parameters including pH, initial concentration, contact time and temperature on the adsorption process were
deeply investigated. In addition, the equilibrium isotherms, kinetic
models and thermodynamic parameters were utilized and calculated for the adsorption of Cu(II) and Hg(II) on the modied ber.
2. Experimental
2.1. Materials
The polyacrylonitrile ber (PANF) made by 100% acrylonitrile
was purchased from Beijing Rongnai industry material company.
Diethylenetriamine, anhydrous ethanol, chloroacetate acid, and
sodium bicarbonate were all supplied by Aladdin Corporation of
China. The solution of Cu2+ and Hg2+ ions were prepared by dissolving weighted amounts of copper and mercury nitrates (Sinopharm
Chemical Reagent Co. Ltd) in deionized water.
2.2. Microwave-assisted preparation of polyacrylonitrile ber modied
by IDA
The PANF was dried in the oven overnight before use and cut
into 5 cm length, so that it wont get twined while stirring. The
synthetic reaction was carried out as in the following two steps
and shown in Scheme 1.
(1) The PAN ber was initially modied via amination reaction.
An orthogonal experiment design, described in Table 1, was
applied to conduct this synthetic procedure. In a typical synthesis, 1.0 g PANF, diethylenetriamine (DETA), and deionized

Scheme 1. The synthetic scheme of PANMW-IDA.

S. Deng et al. / Chemical Engineering Journal 276 (2015) 349357

351

The grafting percentage (GP) was calculated by gravimetry

through following equation:

Table 1
Investigated variables and their levels.
Levels of
each variables

A
Water/diethylenetriamine
ratio (V/V)

B
Temperature
(K)

C
Time
(min)

1
2
3

1:2
1:1
2:1

383
388
393

10
20
30

water were added into a 250 mL three neckask and the

solution was ultrasonicated for 5 min, followed by the addition of some zeolites. The ask was moved into the MW
reactor (COOLPEX-E with output power 1200 W, purchased
from PreeKem Scientic Instruments Co., Ltd., China) and
the parameters of time and temperature were set up. Fig. 1
shows the components of the MW reactor. As the volume
of the mixed solution was less than 100 mL, all experiments
were conducted at PMW = 500 W according to the instruction
of MW reactor.
The reaction was carried out under continuous stirring. After
it was nished, the mixture was cooled till room temperature. Then the ber was ltered, washed with anhydrous
ethanol and hot deionized water until neutral. Finally, the
product was dried in a vacuum oven at 343 K overnight.

GP

m1  m0
 100%
m0

where m0 and m1 are the weights of raw polyacrylonitrile

ber and amine grafted ber, respectively. The grafted PAN
ber was named as PANMW-DETA.
(2) The IDA modied ber was prepared by the action of above
PANMW-DETA ber with 100 mL chloroacetate acid (CAA).
The pH of the solution was then adjusted to 89 by adding
saturated sodium bicarbonate. The reaction was carried
out at 378 K in the MW reactor for 15 min. After the reaction
nished, the mixture was cooled at room temperature. The
ber was ltered and washed with anhydrous ethanol and
hot deionized water until neutral. Then the chelating ber
was dried in vacuum at 343 K overnight. The obtained ber
was named as PANMW-IDA.

2.3. Characterization of PANMW-IDA

FT-IR spectra was scanned in the region of 4004000 cm1 in
KBR pellets on PerkinElmer spectrum. The PAN and modied
bers were dried overnight at 343 K in vacuum oven.

Fig. 1. The chart of the MW reactor (PreeKem Scientic Instruments Co., Ltd.).

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S. Deng et al. / Chemical Engineering Journal 276 (2015) 349357

The elemental analysis (EA) of PAN, PANMW-DETA and

PANMW-IDA ber was obtained from a Perkin-Elmer 240 C
Elemental Analytical Instrument (Germany).
The surface morphologies of the raw and modied bers were
examined at FEI Quanta-200 scanning electron microscope (FEI
Company, The Netherlands). The samples were sputter-coated
with gold for 40s at 15 mA prior to the SEM observation.
2.4. Adsorption experiments
The adsorption properties of PANMW-IDA toward Cu(II) and
Hg(II) were determined under non-competitive conditions by adding the ber into a solution containing each one metal ion.
2.4.1. Effect of pH
The capacity of the chelating ber was affected by the pH of the
metal solution in a certain range. In order to determine the effect of
pH, 0.100 g PANMW-IDA ber was added into a series of 100 mL
(300 mg L1) of metal ion solution with different pH values
(16). The mixture was shaken in thermostatic water bath for
24 h at 293 K. Then the solution samples were taken out by syringe
and ltered with a 0.45 lm membrane to remove tiny ber fragments. These ltrates were used to measure the nal concentration
of metal ions by ultravioletvisible spectroscopy (UVVIS) and
inductively coupled plasma atomic emission spectroscopy (ICPAES). This procedure was repeated for three times, and the average
of results was obtained. The amount of the metal ions adsorbed
onto the chelating ber (q, mg g1) was calculated on the basis of
the following equation:

C 0  C e V
m

where C0 and Ce are the initial and the equilibrium concentration of

the metal ions in the test solution (mg L1), respectively, V is the
volume of the testing solution (L), and m is the weight of the adsorbent (g).
2.4.2. Adsorption kinetics
In kinetic adsorption experiments, an amount of 0.100 g of
PANMW-IDA ber was added into the 100 mL of metal ion solution
(300 mg L1) where the initial pH of the solution was adjusted to
5.0 and 2.0 for Cu(II) and Hg(II), respectively. The solution samples
were agitated at thermostatic water bath at 293 K and draw out at
regular intervals from 5 min to 240 min. The solutions were ltered with a 0.45 lm membrane and the remaining amounts of
metal ions were determined by UVVIS and ICP-AES.
2.4.3. Adsorption isotherms
Equilibrium adsorption of Cu(II) and Hg(II) were conducted as
follows: 0.100 g amount of PANMW-IDA ber was introduced into
250 mL asks respectively, and then 100 mL aqueous solutions
with different concentrations of certain metal ion were added into
those asks. Then the asks were completely sealed and placed in a
SHA-C model thermostatic water bath oscillator at different temperatures (283 K, 293 K, 303 K). The batch test ran continuously
for 24 h to ensure that the adsorption equilibrium has been
reached and the concentrations of heavy metal ions were
determined.
3. Results and discussion
3.1. Preparation of PANMW-IDA ber under MW irradiation
The introduction of microwave energy into a chemical reaction
which has at least one component that is capable of coupling

strongly with microwave can lead to much higher heating rates

than those which are achieved conventionally. The magnitude of
heating depends on the dielectric properties of the molecules
[25,26]. The dielectric constant of water and DETA is 81.5 and 4.1
at 23 C, respectively, which makes both of them suitable for the
reaction under MW irradiation. The ratio of solutions, temperature
and reaction time affect both the amination rate of bers and the
mechanical strength. Theoretically, raised temperature and
extended reaction time lead to high grafting rate, but the mechanical strength of ber dropped largely at the same time. So the
orthogonal experiments were conducted to optimize the best
condition.
The orthogonal results show that the main inuence factor is
time and the inuence order of different parameters is: C > B > A,
by evaluating the K(k) values of each factor listed in Table 2. The
optimum combination program was A2B3C3, in detail:
V(water):V(DETA) = 1:1; temperature at 120 C, reaction time for
30 min. In order to prove the optimized result with the largest
weight gain in Table 2, adsorption tests using PANMW-DETA were
performed three times. The results show that the optimum combination program was A2B3C3 with the highest adsorption capacity.
Compared to previous brous adsorbent studies [27,28], the temperature raised 1030 C under MW irradiation while the ber
would melt if conventional heating was applied in this condition.
The non-thermal effect of MW may attribute to the high grafting
rate in terms of a short duration of this process.
The parameters inuenced the formation of IDA functional
group such as temperature, time were also discussed. The results
revealed that when temperature was higher than 105 C, the synthesized ber was easily fractured while the weight gain increased
slightly. This may be caused by the effects of strong alkaline
solution and high energy of MW irradiation. Same results were
obtained when time increased more than 15 min. So in this step,
temperature and time were controlled at 105C and 15 min,
respectively. Under this condition, 2025% weight gain
PANMW-IDA ber was fabricated.
3.2. Characterization of PANMW-IDA
The FT-IR spectra of (a) PANF, (b) PANMW-DETA and (c)
PANMW-IDA were presented in Fig. 2. A sharp and distinct adsorption band at 2243 cm1 in PANF, PANMW-DETA, PANMW-IDA
attributed to CN group in the polyacrylonitrile ber. Although
the ber was claimed to be made of 100% acrylonitrile, the

Table 2
Orthogonal experimental arrangement and test result.
Experimental
number

Factors
A

GP (%)

1
2
3
4
5
6
7
8
9
K1
K2
K3
k1
k2
k3
R
Order
Optimal condition

1:2
1:2
1:2
1:1
1:1
1:1
2:1
2:1
2:1
25.4
61.0
59.4
8.47
20.3
19.8
11.8
C>B>A
A2B3C3

383
388
393
383
388
393
383
388
393
24.6
57.4
63.8
8.20
19.1
21.3
13.1

10
20
30
20
30
10
30
10
20
27.8
47.6
70.4
9.27
15.9
23.5
14.2

3.0
5.4
17
8.2
40
13
13
12
34

S. Deng et al. / Chemical Engineering Journal 276 (2015) 349357

353

Fig. 4. Effect of pH on the adsorption capacity of PANMW-IDA for Cu2+ and Hg2+ at
293 K.
Fig. 2. FT-IR spectra of (a) PANF, (b) PANMW-DETA and (c) PANMW-IDA.

Table 3
The dates of element analysis of PAN, PANMW-DETA and PANMW-IDA.
Sample

PAN
PANMW-DETA
PANMW-IDA

Element content (%)

C

65.48
56.39
51.43

26.52
23.94
18.78

2.59
12.82
23.61

C/N
(mole ratio)

C/O
(mole ratio)

2.88
2.75
3.2

25.21
4.4
2.18

adsorption peak at 1731 cm1 still conrmed the existence of

methyl acrylate. After DETA was attached onto the ber, the
adsorption intensity of both CN group and methyl acrylate
decreased but not omitted, and new peaks appeared at 1665 and
1600 cm1 corresponding to the banding vibration of NH2 group
and the stretching vibration band of C@O group [29], which
suggests the CN group was hydrolyzed into O@COH initially
before it further reacted with DETA (Fig. 2b). A broad peak at
16841543 cm1 occured after functionalized by CAA, which
attributed to C@O stretching vibration of carboxylic and carboxylate
groups (Fig. 2c). The board adsorption band at 34003100 cm1
corresponds to the combination of NH and O@COH groups [30,31].
The results of the elemental analysis of C, N, O of the bers were
given in Table 3. The C value of PANMW-DETA and PANMW-IDA
decreased after the grafting and modication, which mainly attribute to the lower carbon content of DETA and CAA. Due to the
hydrolysis of CN group into O@COH, the N value decline was
found in PANMW-DETA which coordinates to the result of FT-IR.
Higher oxygen content was observed in PANMW-IDA, indicates

the carbonyl was successfully attached in the ber. EA and FT-IR

spectrum results proved that the IDA functional group has been
immobilized in PANF.
The morphologies of (a) PANF, (b) PANMW-DETA and (c)
PANMW-IDA were observed by SEM and the results were shown
in Fig. 3. It can be seen that the surface of PANF is smooth and
has nearly no crack. After modication, the PANMW-IDA became
very rough and the crack on the surface of PANMW-IDA increased
obviously. Compared with PANF, PANMW-IDA showed an observed
increase in diameter which may be due to the insertion of the DETA
chains onto the PAN ber surface and the conversion of amine
groups into IDA groups in grafted chains [32]. As the reaction
proceeded, the ber swelled up and its color changed from faint
yellow to brown yellow. Therefore, the introduction of amine,
amino and carboxyl groups was expected to change the properties
of the original ber and then affect metal ion adsorption.
3.3. Adsorption performance of PANMW-IDA
3.3.1. Effect of pH
The pH of the adsorbate solution not only affects metal species
in solution, but also inuences the surface properties of the adsorbents in terms of dissociation of functional groups and surface
charges. For that, the adsorption of Cu(II) and Hg(II) were studied
in the range of 16, and Fig. 4 shows the uptake of the metal ions
with an initial concentration of 300 mg L1. It is seen that the
adsorption of copper ascended when the pH increased from 1.0
to 5.0. This phenomenon can be attributed to the protonation of
the active groups and the competition of H+ with metal ions on
adsorption sites [33]. Similar result was obtained for mercury
when the pH increased from 1.0 to 2.0. However, as the pH

Fig. 3. SEM characterization of (a) PANF, (b) PANMW-DETA and (c) PANMW-IDA.

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S. Deng et al. / Chemical Engineering Journal 276 (2015) 349357

Fig. 5. Adsorption kinetics of Cu2+ and Hg2+ at 293 K.

continued to increase, the adsorption shows substantial descending, which is probably due to the formation of Cu(OH)2 and
Hg(OH)2 [34]. Our results in this study are consistent with the
observation of Jie chen et al. [35] and Zhang yu et al. [36].
Furthermore, it should be noted that PANMW-IDA showed a relative
high adsorption capacity for Hg(II) even under strong acidic condition (pH = 2.0), which could be signicant for Hg(II) recovery from
strong acidic aquatic system like mining efuents [37].
3.3.2. Effect of contact time and adsorption kinetics
The time-dependent adsorption performances of PANMW-IDA
were investigated to determine the capacity with two metal ions.
Fig. 5 showed the adsorption kinetic curves of PANF and
PANMW-IDA of two metal ions at optimum pH. The chelating ber
has reached half saturated in less than 20 min and nearly saturated
in 2 h toward both Cu(II) and Hg(II), indicating that the modied
ber has a rapid capture ability at metal ions. At the initial stage,
the fast rate of adsorption was mainly due to the high collision
possibility with chelate groups which was controlled by the diffusion and migration process of metal ions in the solution to the
active site on the surface of functionalized ber [38]. As time went
on, the concentration of Cu(II) and the active site decreased and the
adsorption rate slowed down.
Lagrange kinetic models were used to describe the mechanism
of adsorption process. The equation of pseudo-rst-order and
pseudo-second-order can be written as follows:

lnqe  qt ln qe  k1

t
1
t

qt k2 q2e qe

where qe and qt are the amounts of metal ions adsorbed on the

adsorbent (mg g1) at equilibrium and at time t, respectively; k1
and k2 are the rate constant of the rst-order adsorption in min1
and the second-order adsorption in (g mg1 min1), respectively.

Fig. 6. Adsorption isotherm of metal ions on PANMW-IDA at 283 K, 293 K and 303 K.

The calculated kinetics parameters for adsorption of Cu(II) and

Hg(II) onto the modied ber were tabulated in Table 4. As can
be observed, the pseudo-second-order equation, correlation coefcient (R2) of Cu(II) and Hg(II) are both 0.999, appeared to be the
better tting model than the pseudo-rst-order. Pseudo-rst-order
believes that the mass transfer resistance is the restriction factor of
adsorption, while pseudo-second-order considers that the adsorption mechanism affects instead [39]. The adsorption of the metals
ions onto the chelating ber is controlled by chemisorption
through chelation interaction, coordinated to the result of
pseudo-second-order.
3.3.3. Adsorption isotherms
The adsorption behavior of the chelating ber at different temperature was investigated. As can be observed in Fig. 6, the equilibrium adsorption uptake of the PANMW-IDA increased with
increasing the initial concentration of heavy metal ions and the
adsorption capacity of PANMW-IDA increased with increasing temperature, indicating that the adsorption was an endothermic process. Langmuir and Freundlich adsorption isotherm models were
widely used to describe the adsorption progress [40].The
Langmuir and Freundlich equations can be written as follows:

Table 4
Kinetic parameters for the adsorption of Cu2+ and Hg2+.
Metal

Cu2+
Hg2+

Pseudo-rst-order model

Pseudo-second-order model

k1
(min1)

qe
(mg g1)

R2

k2
(103 g mg1 min1)

qe
(mg g1)

R2

0.018
0.023

55.84
128.32

0.9724
0.9846

0.697
0.29

114.56
258.37

0.9991
0.9992

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S. Deng et al. / Chemical Engineering Journal 276 (2015) 349357

Table 5
Thermodynamic parameters for the adsorption of Cu2+ and Hg2+ on PANMW-IDA.
Metal ions

DH
(kJ mol1)

DS
(Jmol1 k)

DG (kJ mol1)
283 K

293 K

303 K

Cu2+
Hg2+

21.48
20.06

89
72

3.58
0.34

4.47
1.06

5.35
1.78

qe

qm K l C e
1 K lCe

3.4. Comparison between PANMW-IDA and other adsorbents

qe K f C ne

where qe is the amount of metal ion adsorbed at equilibrium by the

adsorbent (mg g1), Ce is the equilibrium concentration (mg L1), qm
is theoretical saturation adsorption capacity (mg g1), Kl is the equilibrium Langmuir constant, Kf and n are constants representing the
adsorption capacity and intensity of adsorption.
As presented, the equilibrium data of both Cu(II) and Hg(II) ions
were well described by Langmuir isotherm model (R2 > 0.99)
compared with Freundlich isotherm model. This indicated the
presence of monolayer sorption phenomenon for copper and mercury ions sorption by the PANMW-IDA adsorbent. The monolayer
saturation adsorption values were 119.39 and 275.76 mg g1 for
Cu(II) and Hg(II) ions (293 K), which are well agreed with the
experimentally obtained values, respectively. As shown in Fig. 6,
the maximum uptake on PANMW-IDA notes the order of Cu
(1.88 mmol g1) > Hg (1.37 mmol g1), while the surface of the
ber is predominantly positive at this pH range, which means
the chelation force favor the interaction between adsorbent and
metal ions instead of Coulombic forces [9,41,42].
3.3.4. Adsorption thermodynamics parameters
The thermodynamic qualities such as Gibbs free energy change
(DG), entropy (DH) and enthalpy (DS) for the adsorption of copper
and mercury ions using PANMW-IDA bers were determined by the
following equations:

DG RTLnk
Lnk

increased randomness at the solidliquid interface, which demonstrated that the adsorption process was favorable at higher temperature and that the spontaneity of adsorption was a
consequence of the increase in entropy. It is assumed that adsorption heats between 20.9 and 418.4 kJ mol1 are the heats of chemical reactions which represents the chemical adsorption process
[36,43]. The DH value for Cu(II) and Hg(II) are 21.48 and
20.06 kJ mol1, respectively, suggesting that the adsorption of the
two metal ion on the PANMW-IDA ber was mainly chemically
reactive adsorption.

DS DH

R
RT

where K is the adsorption equilibrium constant, R is the universal

gas constant (8.314 J mol1 K1), T is the temperature (K). The values of DH and DS could be obtained as the slope and intercept from
a linear plot between Lnk versus 1/T.
The obtained thermodynamic parameters for the adsorption
process are given in Table 5. The negative values of DG indicated
the spontaneous behavior of the adsorption process, and the positive values of DH and DS for the adsorption of Cu(II) and Hg(II) suggested the endothermic behavior of this process, couple with an

The comparison of PANMW-IDA ber synthesized through MW

irradiation with various IDA functionalized adsorbents fabricated
under conventional heating in terms of time and adsorption
capacities for Cu(II) and Hg(II) is given in Table 6.
The duration of functionalization process decreased remarkably
by using microwave irradiation compare to conventional heating
method, more specically, the consumed time declined from
5-30 h to 0.75 h. Although PANMW-IDA ber has lower adsorption
capacity for Cu(II) than IDA modied amino methyl polystyrene,
it has a comparative adsorption capacity of copper ion with other
IDA modied adsorbents, as well as a much better binding ability
toward mercury ion. The higher capacity may attribute to the high
transferring rate of cyano group to amine group and then take
effects in the adsorption process.
The effect of microwave irradiation in chemical reactions is a
combination of the thermal effect and non-thermal effect.
Thermal effects were initiated by transforming electromagnetic
energy to heat, which is contract to conduction and convection
processes observed in conventional heating. In particularly, the
high yield of PANMW-DETA was proved by experiments owing to
the ability of water to transmit energy by dielectric losses. The
experimental results show that almost no grafting rate was
observed if DETA was applied as solvent solely.
In the meanwhile, the non-thermal effects, especially overheating make considerable differences in these two synthesis process
compared to previous researches. Nearly all brous adsorbents
were fabricated under 373 K in former studies, which is the boiling
point of water, for sake of maintaining its crystallinity in such a
long period. While in this study, as the consequence of the much
shorter interval of the reaction, temperature is higher than the
boiling point of water which cause overheating effect in the solution and then accelerate the reaction process spectacularly.
4. Conclusions
The IDA group was rapidly grafted onto polyacrylonitrile ber
by using MW irradiation through two-step modication: amination and carboxymethylation. Compared to conventional heating,
MW irradiation exhibits excellent advances such as high grafting

Table 6
Comparison PANMW-IDA ber adsorption capacities with other IDA functionalized adsorbents.
Adsorbents

Glycidyl methacrylate
Silica gel
Fe3O4-glycidyl methacrylate-iminodiacetic
acid-styrene-divinyl benzene resin
Polybenzylamine
Amino methyl polystyrene
Nature wool ber
Buckwheat hulls
PANMW-IDA ber

Reaction time
(h)

Adsorption capacity
(mg g1)

Reference

Cu2+

Hg2+

18
12

27.32
78.17
55.92

[44]
[45]
[46]

30
22
5

0.75

109.31
144.25
110.49

119.39

154.32
116.34
275.76

[47]
[42]
[48]
[49]
Present study

356

S. Deng et al. / Chemical Engineering Journal 276 (2015) 349357

rate and spectacularly acceleration of reaction process due to the

combination of thermal effect and non-thermal effect. Through
the orthogonal experiment, the optimal conditions for the maximum rate of amination were found at V(water):V(DETA) = 1:1,
temperature at 120 C and reaction time for 30 min. FT-IR spectra
were used to conrm the formation of IDA group onto the bers.
At the optimum pH condition, the PANMW-IDA exhibited high
efciency of Cu(II) and Hg(II) capacity. The adsorption kinetic
was explained by Pseudo-second-order equation, which was
proved to be chemical reaction. The adsorption followed the
Langmuir isotherm, indicating that the binding process took place
at monolayer within the adsorbent, and the calculation results
about DG, DH and DS indicated that the process was spontaneous
and endothermic. The adsorption of both Cu(II) and Hg(II) metals
onto the PANMW-IDA are higher than those IDA adsorbents in
previous studies.
Acknowledgments
The work was supported by State Key Laboratory of Urban
Water Resource and Environment (Harbin Institute of
Technology) (2015D03) and the National Water Pollution Control
and Management Technology Major Projects (2012ZX07205-005).
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