Chemical Engineering Journal 203 (2012) 251–258

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Chemical Engineering Journal

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A novel adsorbent based on functionalized three-dimensionally ordered

macroporous cross-linked polystyrene for removal of salicylic acid from aqueous
solution
Xiaomei Wang, Yanning Wang, Lei Feng, Pange Liu, Xu Zhang ⇑
Department of Polymer Science and Engineering, Hebei University of Technology, Tianjin 300130, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" A novel polymeric adsorbent with A novel polymeric adsorbent with three-dimensionally ordered macroporous (3DOM) structure was pre-
three-dimensionally ordered pared to removal of salicylic acid from aqueous solution. This adsorbent exhibits a high adsorption
macroporous (3DOM) structure. capacity.
" Poly(2-hydroxyethyl methacrylate)
controllable graft polymerization
from the pore wall of 3DOM cross-
linked polystyrene.
" When the grafted amount is 22.1%,
the 3DOM CLPS-g-PHEMA exhibits
the optimum adsorption capacity for
salicylic acid.
" The 3DOM CLPS-g-PHEMA exhibits a
high adsorption capacity as well as a
fast rate of adsorption.

a r t i c l e i n f o a b s t r a c t

Article history: A novel polymeric adsorbent with three-dimensionally ordered macroporous (3DOM) structure was pre-
Received 20 May 2012 pared. Poly(2-hydroxyethyl methacrylate) (PHEMA) was controllably grafted from the pore wall of 3DOM
Received in revised form 6 July 2012 cross-linked polystyrene (3DOM CLPS-g-PHEMA) by surface-initiated atom-transfer radical polymeriza-
Accepted 6 July 2012
tion (SI-ATRP) technique. Batch adsorption runs of salicylic acid from aqueous solution onto 3DOM
Available online 15 July 2012
CLPS-g-PHEMA were investigated as well as the relationship of the grafted amount with the adsorption
capacity. When the grafted amount was 22.1%, the 3DOM CLPS-g-PHEMA exhibited the optimum adsorp-
Keywords:
tion capacity. Commercial macroporous resin XAD-4 was chosen as the comparison. Adsorption isotherm
Three-dimensionally ordered macroporous
polymer adsorbent
experimental results indicated that isotherms of salicylic acid adsorption onto 3DOM CLPS-g-PHEMA
Poly(2-hydroxyethyl methacrylate) adsorbent could be represented by Langmuir and Freundlich models and the Freundlich model was
Surface-initiated atom-transfer radical shown to be the most suitable. The 3DOM CLPS-g-PHEMA exhibited a much higher adsorption capacity
polymerization of salicylic acid than that of XAD-4, attributing to the special structure of 3DOM polymer and the grafted
Salicylic acid polymeric chains on the pore walls. The adsorption capacities increased with temperature increasing, and
Adsorption the isosteric enthalpy changes were calculated with a derivative Van’t Hoff equation. Kinetics studies
showed that the salicylic acid uptake onto 3DOM CLPS-g-PHEMA followed the pseudo-second order
model. In addition, the spent 3DOM CLPS-g-PHEMA could be regenerated by extracted with ethanol,
the regenerated 3DOM CLPS-g-PHEMA also exhibited the high adsorption capacity. We envision that
the novel 3DOM polymeric adsorption will play a significant role in developing a new generation
adsorbent.
Ó 2012 Elsevier B.V. All rights reserved.

⇑ Corresponding author. Fax: +86 022 60200443.

E-mail address: xuzhang@hebut.edu.cn (X. Zhang).

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.07.034
252 X. Wang et al. / Chemical Engineering Journal 203 (2012) 251–258
1. Introduction
Salicylic acid is a typical derivative of phenol, and its containing
wastewater presents a serious environmental problem due to its
high toxicity and accumulation in the environment [1–3]. Many
methods and technical processes have been developed to reduce
the pollution, such as biodegradation, catalytic oxidation, solvent
extraction, and adsorption [4–9]. Adsorption is proven to be one
of the most attractive and effective techniques for purification
and separation in wastewater treatment due to the high concen-
trating ability and reusability of adsorbent. Adsorption based on
polymeric adsorbents is shown to be effective because of its favor-
able physicochemical stability, large adsorption capacity.
At present, the cross-linked (or hypercrosslinked) polystyrene
adsorbents are the most widely used adsorbent. For example, Hu
et al. prepared a series of bisphenol modified hypercrosslinked
polystyrenes for adsorptive removal of salicylic acid [10]. Huang
et al. synthesized a series of novel b-naphthol modified hyper-
crosslinked poly(styrene-co-divinylbenzene) resins and studied
their adsorption characteristics for salicylic acid in aqueous solu-
tion [11]. Otero et al. compared the polymeric resins Amberlite
XAD-16 (Rohm and Hass) and Duolite S861 (Auchtel Products
Ltd.) as the adsorbent for salicylic acid [12]. However, the pore
structure of this traditional adsorbent is generally the random
microporous (less than 2 nm) and mesoporous (less than 50 nm)
structures, and the connectivity between the pores is poor. On
the one hand, this micro- and mesoporous structures make it diffi-
cult to introduce the long chain with functional adsorbent groups
in the hole, limiting to the adsorption capacity of the polymeric
resins. On the other hand, the pore structure affects the mass dif-
fusion in the absorbents, which results in the low adsorption
capacity in spite of the high specific surface area.
Three-dimensionally ordered macroporous (3DOM) materials
with diverse compositions, including metal oxides, metals, poly-
mers, and hybrid materials have been fabricated by variation of
the colloidal crystal templating techniques [13]. The 3DOM mate-
rials have relatively large and uniformly distributed pore size, and
the large pores are interconnected by twelve small ‘‘windows’’.
Although, the specific surface area of 3DOM material is typically
lower than that of mesoporous or microporous material, but the
large interconnected cavities enhance accessibility to the active
sites and the short diffusion path of the thin pore walls accelerates
material exchange [14]. In the current reports, 3DOM materials
have been applied as a promising candidate for heavy metal ion re-
moval, which were fabricated with inorganic materials. For exam-
ple, Srinivasan et al. [14d] studied the capability of 3DOM
hydroxyapatite, Ca10(PO4)6(OH)2 (HAp), to capture cadmium and
lead ions from their respective salt solutions. The sorption ability
of 3DOM material to Cd/Pb ion was benchmarked against HAp
powder prepared via the same route without the template.
Schroden et al. [14f] prepared 3DOM titania and zirconia with thiol
functional groups attached to frameworks by colloidal crystal tem-
plating technique as heavy metal ion adsorbents for mercury (II)
and lead (II) ions. We speculate that the special structure of
3DOM materials may be more advantageous to adsorption of or-
ganic molecules. In order to make up for the deficiency of surface
areas, the polymeric chain with functional groups can be intro-
duced to the pore walls of 3DOM resins by the method of ‘‘graft
from’’. To the best of our knowledge, this 3DOM polymer with
functional grafted chain using as an absorbent has not been re-
ported in the literatures yet.
Based on above idea, in this report, the salicylic acid was chosen
as the model absorbate, which has been well studied as a sample of
model organic, with an aromatic ring and polar functional groups
(carboxylic acid and phenol). The 3DOM cross-linked polystyrenes
(3DOM CLPS) were fabricated by the colloidal crystal templating
techniques. The poly(2-hydroxyethyl methacrylate) (PHEMA) with
different grafted amounts were introduced to the pore wall of
3DOM CLPS (3DOM CLPS-g-PHEMA) by surface-initiated atom-
transfer radical polymerization (SI-ATRP) technique. The hydro-
philic PHEMA possesses excellent biocompatibility and physical
properties similar to those of living tissues [15]. The 3DOM
CLPS-g-PHEMA can be easily wetted by water and has a higher
adsorption capacity for salicylic acid.
2. Experimental
2.1. Materials
Chloromethyl methyl ether (CME, Tianjin Youlong
Chemical-technical Factory, 96%) was removed water by anhy-
drous magnesium sulfate. HEMA was obtained from Tianjin Chem-
ical Reagent Factory and was dried over calcium hydride overnight,
distilled under reduced pressure, then stored under argon at
10 °C to use. CuCl was purchased from the Shanghai Zhenxin
Chemical Reagent Factory and purified according to the published
procedure [16]. Cyclohexanone (99%) was purchased from Tianjin
Chemical Reagent Factory and dried over molecular sieves (4 Å).
Tetrahydrofuran (THF, Tianjin Chemical Reagent Factory, 99%),
N,N0 ,N0 ,N00 ,N00 -pentamethyldiethylenetriamine (PMDETA, Fluka,
98%), and ZnCl2 (Tianjin Chemical Reagent Factory, 99%) were used
as received. Salicylic acid (P99.5%, SA) was obtained from Tianjin
Chemical Reagent Factory and used without further purification.
Amberlite XAD-4 was purchased from Rohm Haas (Philadelphia,
PA, USA) and extracted with acetone for 8 h and then dried for
2 h under vacuum at 60 °C before use.
2.2. Preparation and characterization of 3DOM CLPS-g-PHEMA
adsorbent
2.2.1. Preparation of 3DOM CLPS
The 3DOM CLPS with pore size of 200 nm was prepared accord-
ing to our previous works [17]. The difference of the procedure is
that the silica colloidal crystal template was fabricated by centrif-
ugalization of the silica latex with 3000 rpm.
2.2.2. Chloromethylation of 3DOM CLPS
The halogen atom as initiator of SI-ATRP was immobilized onto
the pore wall of 3DOM CLPS by chloromethylation (3DOM CLPS-
CH2Cl) according to our previous works [17]. The 3DOM CLPS
(0.1 g) was placed into a 50 mL two-necked flask and vacuumized
at 35 °C. Anhydrous ZnCl2 (0.1 g) was dissolved in CME (2 mL) and
the solution was injected into the flask under the vacuum condi-
tion and sonicated for 10 min. After the reaction was carried out
at 35 °C for 24 h, the product of chloromethylated 3DOM CLPS
was extracted with ethanol for 12 h and dried at 80 °C under vac-
uum. The relative content of benzyl chloride is 3.69 mmol/g.
2.2.3. Grafted polymerization of HEMA from pore wall of 3DOM CLPS
All the operations were carried out under the argon protection.
A representative example is described as follows: a glass tube with
a magnetic bar was loaded with chloromethylated 3DOM CLPS
(0.5 g) and vacuum pumped for 2 h at 70 °C. HEMA (15 mL), CuCl
(0.2463 g), PMDETA (0.52 mL), and cyclohexanone (75 mL) were
mixed under argon atmosphere and stirred until a homogeneous
solution formed. The solution was then quickly injected into the
tube containing chloromethylated 3DOM CLPS under vacuum at
70 °C. The magnetic mixer was switched on, stirred slowly, and
the graft polymerization was carried out. The grafted amounts
 X. Wang et al. / Chemical Engineering Journal 203 (2012) 251–258 253

were controlled by changing of the reaction time. After polymeri-
zation, in order to remove ungrafted efficiently, physically ad-
sorbed (free) polymers, the final products were washed by
ultrasonication in THF for 20 min, and then extracted with THF
for 12 h. Finally, the products were dried at 80 °C under vacuum.
2.2.4. Characterization
FT-IR spectra were recorded on a Bruker VECTOR-22 at room
temperature with KBr pellet. The 3DOM polymer samples were
fractured and sputtered with gold in vacuum for scanning electron
microscopy (SEM, Hitachi S-4800) characterization. The contents of
oxygen in grafted chains were determined by the EA 1112 Element
Analyzer. The grafted amount was quantitatively characterized by
increased weight percent after graft polymerization. The concen-
tration of SA in solution, before and after the sorption process,
was determined using a UV–Vis spectroscopy (Cary 300, Varian)
at a wavelength of 296 nm. A linear relationship between the
absorbency and the SA concentration was obtained in the range
of 4–100 mg/L.
vibrating of mono-substituted benzene signals are observed at
758 and 698 cm1. On the chloromethylated 3DOM CLPS spectrum
(Fig. 1b), it appears a band at 675 cm1, which is characteristic of
C–Cl stretching vibration. Moreover, the characteristic peak of –
CH2 of chloromethyl group is found at 1421 cm1, indicating that
chloromethyl groups had been successfully immobilized onto the
pore wall of the 3DOM CLPS. Furthermore, the bands at about
822 cm1 and 1265 cm1 are characteristic of para-disubstituted
benzene, suggesting that the chloromethyl must be predominantly
at the para position [18]. Fig. 1c depicts the spectrum of PHEMA-
grafted 3DOM CLPS. The strong bands at 1724 cm1 are stretching
vibration of carbonyl groups, the bands at 3400–3300 cm1 and
1267–1080 cm1 are corresponding to stretching vibration of hy-
droxyl groups and alkoxy groups, respectively. These results indi-
cate that PHEMA have been successfully grafted from the pore
wall of 3DOM CLPS.

2.3. Adsorption characteristics

2.3.1. Adsorption isotherms

The accurately weighted dry 3DOM CLPS-g-PHEMA (about
0.1 g) was taken into several 250 mL sealed flasks directly. A
100 mL aqueous solution containing different concentration of SA
(ranging from 100 to 500 mg/L) was added into each flask. After
shaking during 24 h at different temperatures (293, 303 and
313 K), the suspension was filtered. The equilibrium concentration
(Ce) of the SA was measured by UV-spectrophotometer. The equi-
librium adsorption capacity Qe (mg/g) was calculated with the fol-
lowing equation:

ðC 0  C e ÞV
Qe ¼ ð1Þ
W
where C0 and Ce are the initial and equilibrium liquid-phase concen-
tration of SA, respectively (mg/L); V is the volume of the solution
(L); W is the weight of the dry corresponding adsorbent (g).
Fig. 1. FT-IR spectra of (a) 3DOM CLPS, (b) 3DOM CLPS-CH2Cl, and (c) 3DOM CLPS-
2.3.2. Kinetic adsorption g-PHEMA.
The accurately weighted dry 3DOM CLPS-g-PHEMA (about
0.2 g) and 200 mL of SA solution with an initial concentration of
around 100 mg/L were introduced into a cone-shaped flask and
continuously shaken. The aqueous samples were taken from the
shaker mixer at pre-set time intervals, and the concentration of
SA was measured. Three sets of kinetic experiments (at 293, 303
and 313 K) were also conducted for each adsorbent-SA system
starting with initial concentration of SA in solution around
100 mg/L.

2.3.3. The regeneration of 3DOM CLPS-g-PHEMA

In order to determine the reusability of the 3DOM CLPS-g-PHE-
MA, consecutive adsorption–desorption cycles were repeated five
times using the same sorbent. After adsorption of SA every time,
the 3DOM CLPS-g-PHEMA was extracted by Soxhletextractor with
ethanol for 24 h.

3. Results and discussion

3.1. FT-IR analysis

The 3DOM CLPS, 3DOM CLPS-CH2Cl, and 3DOM CLPS-g-PHEMA

infrared spectra are shown in Fig. 1. Fig. 1a shows that the 3DOM
CLPS FT-IR display bands at 3085, 3060, and 3026 cm1 indicating
the C–H stretching of the benzene ring. Moreover, the C–H Fig. 2. The relationship between grafted amount and the graft polymerization time.
254 X. Wang et al. / Chemical Engineering Journal 203 (2012) 251–258
3.2. The grafted amount effect on SA sorption
The 3DOM materials have relatively large and uniformly dis-
tributed pore size (the pore size P 50 nm). The large pores are
interconnected by twelve small ‘‘windows’’, which provide a possi-
bility for introduction of longer polymer chains onto pore walls,
and the loaded polymer chains do not plug the channels. SI-ATRP
has been proven to be a practicable living/controlled free radical
polymerization and has been used to surface modify and function-
alize many kinds of materials [19]. This technique is an effective
route to accurately control the chain length (the thickness of
grafted layer) by controlling the monomer conversion (such as
changing the graft polymerization time), and it also affords excep-
tionally high grafting densities. In order to investigate the relation-
ship of the grafted amount and the adsorption capacity, the SI-
ATRP was carried out to control the different degrees of grafting
by changing the graft polymerization time. However, we are un-
able to characterize the length of the grafted polymer chain
(molecular weight) and molecular weight distributions of the
grafted chains, because detaching grafted layers from the pore
walls is difficult due to the stability of C–C bond tethered to the
3DOM CLPS skeleton. In this study, the grafted amount was used
to characterize the length of the grafted polymer chain. Fig. 2 dis-
plays the relationship between the grafted amount and the graft
polymerization time. The grafted amount was controlled by simply
changing the SI-ATRP reaction time at constant catalyst
concentration.
The PHEMA chains were tethered on the pore-walls of 3DOM
CLPS with covalent bond. The grafted PHEMA chains contain oxy-
gen atoms of the pendent ester and hydroxyl groups, which can
be used as the hydrogen bonding acceptors and interact with SA
through strong hydrogen bonding. Therefore, theoretically, the
longer the grafted polymer chains, the more the adsorption sites
will be, which should result in the adsorption capacity increasing
with the amount of grafted PHEMA. However, the experimental re-
sult is not the case. The effect of grafted amount on SA sorption is
shown in Fig. 3. The initial concentrations of SA are around
1000 mg/L and 500 mg/L, respectively. The adsorption temperature
is 303 K. In Fig. 3, it can be seen that the adsorption capacities
firstly increase and then decrease with the increasing of the grafted
PHEMA amount. The maximum adsorption capacities are 300 mg/g
and 269.9 mg/g, respectively, when the amount of grafted PHEMA
is 22.1%. In order to explore the adsorption mechanism, the
Fig. 3. Effect of the grafted amount on the SA and Phenol adsorption capacity at
303 K.
Table 1
Characteristic properties of 3DOM CLPS-g-PHEMA and XAD-4.
Property XAD-4 3DOM CLPS-g-PHEMA
Chemistry Aromatic, PHEMA grafted from CLPS
Polystyrene
Matrix Random 3DOM structure
pore
structure
Polarity Nonpolar Moderate polar
Surface area (m2/g) 750 63.9
Average pore diameter 5.8 200 (the size of macropore), the size
(nm) of connected windows is about
25 nm.
Morphology and size Particle, Granule, 1–5
(mm) 0.4–0.6
Pore volume (mL/g) 1.0 2.4
Oxygen content (%) – 8.07
Color White White
adsorption of 3DOM CLPS without grafted PHEMA towards SA is
investigated. No SA was adsorbed from aqueous onto 3DOM CLPS
at 303 K (the initial concentration is 499.52 mg/L), which means
that there is little hydrophobic interaction between the 3DOM
adsorbent and SA. It possibly attributes to the small specific surface
area (the specific surface area of the 3DOM CLPS-g-PHEMA is
63.9 m2/g, see Table 1) [20]. Therefore, we reasoned that the
hydrogen bonding between the grafted PHEMA chains and SA plays
a predominant role in adsorption of SA in aqueous solution. The
pendent groups in the grafted PHEMA chains contain ester and hy-
droxyl groups, which can form various hydrogen bonds with hy-
droxyl and carboxyl groups in SA molecule [21]. In the
subsequent discusses, the enthalpy changes of adsorption also con-
firm that hydrogen bonding is the main interaction mechanism for
the adsorption. Therefore, the adsorption capacity of 3DOM CLPS-
g-PHEMA is in direct correlation with the pendent groups in the
grafted PHEMA chains. However, the grafted PHEMA chains are
prone to curl or intertwist due to increasing of the length of grafted
chains, which results in the functional groups intramolecular or
intermolecular hydrogen bond forming. It is a possible reason,
leading to the adsorption capacities firstly increasing and then
decreasing with the increase of the grafted PHEMA amount. Above
experiment data show that the hydrophobic interaction is little
and the hydrogen bonding is dominated even in the aqueous solu-
tion. It is essential to selectively bind solutes through only a single
type of mechanistic interaction [22]. Hydrogen bonding is a specif-
ically intramolecular or intermolecular interaction. It is also a very
useful adsorption mechanism because the low energy of this bond
ensures reversibility. Especially, the directionality and the short
range of this bond confer its selectivity, which is utilized to develop
high selective adsorbents [23,24]. The adsorptions of phenol on
3DOM CLPS-g-PHEMA with different grafted amounts were also
investigated, the results are shown in the Fig. 3. It can be seen that
the 3DOM CLPS-g-PHEMA have poor adsorption capacities toward
phenol relative to SA. Compared to SA, there is not carboxyl group
in the phenol molecule, which results in the hydrogen bonding be-
tween grafted PHEMA chains and phenol molecules weakening.
This result also further indicates that the hydrogen bonding is
the dominated driving force for the adsorption of SA onto 3DOM
CLPS-g-PHEMA in the aqueous solution.
3.3. SEM characterization
Fig. 4a and b displays the morphologies of 3DOM CLPS before
(3DOM CLPS-CH2Cl) and after graft polymerization via SI-ATRP
(3DOM CLPS-g-PHEMA), the macropore size is around 200 nm. It
can be seen that all the 3DOM CLPS has a close-packed ordering
structure and each macropores is connected to its twelve
 X. Wang et al. / Chemical Engineering Journal 203 (2012) 251–258 255

Fig. 4. SEM images of 3DOM samples: (a) 3DOM CLPS-CH2Cl, (b) 3DOM CLPS-g-PHEMA with the grafted amount of 22.1%, (c) the 3DOM CLPS-g-PHEMA after adsorption of SA.

neighbors by small ‘‘windows’’. These windows are access channels

between the adjacent macropores, and are crucial for substance
diffusion between the macropores, which make it possible to func-
tionalize the frameworks of 3DOM CLPS and provide convenient
diffusion channels for adsorbate into the interior of 3DOM CLPS.
In Fig. 4b, the SEM image of PHEMA grafted 3DOM CLPS shows that
the ordered structure is well preserved after graft reactions and the
‘‘windows’’ still exist among the adjacent large pores. In addition,
Fig. 4c demonstrates the morphology of 3DOM CLPS-g-PHEMA
after adsorption of SA, the ordered structure is still preserved.

3.4. Adsorption isotherms

The 3DOM CLPS-g-PHEMA with the grafted amount of 22.1%

was chosen to study the adsorption properties due to the maxi-
mum adsorption capacity for SA. Moreover, a well-known adsor-
bent Amberlite XAD-4 was used as a reference, which is one of
the polystyrene based adsorbents with a high surface area [25]. It
has been referred to the best polymeric adsorbent for the removal
of phenol from phenol-contaminated aqueous solutions [26,27].
Table 1 lists some characteristic properties of two polymeric absor-
bents, the 3DOM CLPS-g-PHEMA with the grafted amount of 22.1%
and Amberlite XAD-4. The two polymeric adsorbents have quite
different in the pore properties. Although, the surface area of
3DOM CLPS-g-PHEMA is much less than that of XAD-4. However,
the adsorption properties of 3DOM CLPS-g-PHEMA are much better
than those of XAD-4, the reasons and the adsorption properties of
3DOM CLPS-g-PHEMA will be described in the following.
Fig. 5 shows the equilibrium adsorption isotherms of SA on
3DOM CLPS-g-PHEMA (Fig. 5a) and XAD-4 (Fig. 5b) at 293, 303
and 313 K respectively. Data fittings to the Langmuir (Eq. (2))
and Freundlich (Eq. (3)) models are shown together with the
experimental points.
Ce Ce 1
¼ þ ð2Þ
Q e Q m Q mKL

1
log Q e ¼ log K F þ log C e ð3Þ
n
Fig. 5. Equilibrium adsorption isotherms at 297 K, 303 K, and 313 K for SA on (a)
where Qm is the maximum adsorption capacity (mg/g); KL is a 3DOM CLPS-g-PHEMA and (b) Amberlite XAD-4. Fitted to Langmuir and Freundlich
constant related to the affinity of the binding sites (L/mg) [28]. KF models are shown together with these experimental data points.
256 X. Wang et al. / Chemical Engineering Journal 203 (2012) 251–258

Table 2
Correlated parameters of the equilibrium data for the adsorption of SA on 3DOM CLPS-g-PHEMA and XAD-4 from aqueous solution according to Langmuir and Freundlich
equations at 293, 303 and 313 K.

Absorbent T (K) Langmuir equation Freundlich equation

KL (L/mg) Qm (mg/g) R2 KF ([(mg/g)(L/mg)1/n]) n R2
3DOM CLPS-g-PHEMA 293 0.0403 238.1 0.9883 73.33 5.157 0.9905
303 0.0600 285.7 0.9890 79.09 4.357 0.9997
313 0.0622 324.7 0.9892 79.56 3.922 0.9965
XAD-4 293 0.0026 142.0 0.9923 1.6959 1.596 0.9977
303 0.0034 104.3 0.9996 2.0846 1.776 0.9839
313 0.0043 80.24 0.9950 2.3702 1.954 0.9708

Fig. 6. Determination of the isosteric enthalpy changes of the adsorption of SA onto

the 3DOM CLPS-g-PHEMA (log Ce vs. 1/T).

[(mg/g)(L/mg)1/n], and n are the corresponding characteristic con-

stant. In particular, KF is an indicator of the adsorption capacity
and n is related to the favorableness of the system [29–31]. The typ-
ical parameters and the correlation coefficients R2 are listed in Table
2. It is seen that the isotherm data can be fitted by Langmuir and
Freundlich models since R2 > 0.98 and Freundlich model is more
suitable for the adsorption. From Table 2, it can be seen that the
maximum adsorption capacities of 3DOM CLPS-g-PHEMA are much
higher that those of the XAD-4. In addition, the 3DOM CLPS-g-PHE-
MA has a large adsorption capacity toward SA, even if the initial
concentration of SA is low. When the initial concentration of SA is
100 mg/L, at 303 K, the adsorption capacity and adsorption rate
are 97.75 mg/g and 97.0%, respectively. To the best of our knowl-
edge, the adsorption results of 3DOM CLPS-g-PHEMA are also supe-
rior to some reported adsorbents towards SA, including polymeric
adsorbents [10,11,32,33] and other adsorbents [34]. The maximum
adsorption capacity is close to that of the activated carbon [12]. The Fig. 7. Kinetic adsorption curve of adsorbents for SA at different temperatures: (a)
3DOM CLPS-g-PHEMA and (b) XAD-4.
high adsorption capacity of 3DOM CLPS-g-PHEMA should be as-
cribed to two reasons. First, the 3DOM materials have relatively 3.5. Isosteric enthalpies
large and uniformly distributed pore size, and the large pores are
interconnected by twelve small ‘‘windows’’, which facilitate acces- In Fig. 5, it can be seen that the adsorption capacities signifi-
sibility to the active sites and the short diffusion path of the thin cantly increase with the temperature in the range of 293–313 K,
pore walls accelerates material exchange [14]. Second, the special meaning that higher temperature is in favor of the adsorption.
structure is in favor of introducing the functional polymer chains The isosteric enthalpy changes of adsorption were calculated with
to improve the adsorption, and the adsorption capacity will be very a derivative Van’t Hoff equation (Eq. (4)) [34].
high if those functional groups can be used sufficiently. The special
structure of 3DOM material enhances the use ratio of the functional DH
groups. This encouraging result suggests that the new polymer log C e ¼  log K 0 þ ð4Þ
2:303RT
adsorbent based on the 3DOM structure being developed in our
team group is promising to develop a series of new adsorbents with where DH is the isosteric enthalpy change of adsorption (kJ/mol), R is
superior performances. the gas constant (8.314 J/mol K) and K0 is a constant. Ce was obtained
 X. Wang et al. / Chemical Engineering Journal 203 (2012) 251–258 257

Table 3
Kinetic parameters of SA adsorption onto 3DOM CLPS-g-PHEMA and XAD-4 at different temperatures.

Adsorbent T (K) Pseudo-first order model Pseudo-second order model

2
Qe (cal.) (mg/g) k1 (min 1
) R k2  104 (g/mg min) Qe (cal.) (mg/g) R2
3DOM CLPS-g-PHEMA 313 82.0 0.0603 0.9982 12.8 100.9 0.9983
303 69.1 0.0359 0.9501 8.5 97.4 0.9987
293 69.9 0.0334 0.9769 7.9 96.4 0.9989
XAD-4 313 16.4 0.0198 0.9943 13.9 19.0 0.9966
303 20.4 0.0082 0.9923 2.6 26.9 0.9973
293 26.4 0.0161 0.9964 5.1 31.5 0.9898

pseudo-first order rate constant (min1), and k2 is the pseudo-sec-

ond order rate constant (g/mg min). The kinetic parameters are
determined and listed in Table 3. Results indicate that SA adsorp-
tion kinetic on 3DOM CLPS-g-PHEMA is better fitted by the pseu-
do-second order model, because the higher R2 values obtained
with the pseudo-second order model and the calculated Qe (cal.)
values are closer to the experimental data than the calculated val-
ues of pseudo-first order model. For the same reason, as shown in
Table 3, SA adsorption kinetic on XAD-4 is better fitted by the pseu-
do-first order model.

3.7. The regeneration of 3DOM CLPS-g-PHEMA

The SA loaded 3DOM adsorbent was extracted by Soxhletex-

Fig. 8. Adsorption–desorption cycle of 3DOM CLPS-g-PHEMA.
from the Freundlich isotherms at a definite Qe value (100 mg/g) at dif-
ferent temperatures (293, 303 and 313 K). DH was determined by
plotting log Ce vs. 1/T, the fitting result is shown in Fig. 6. The value
of DH from slope is 26.87 kJ/mol. The positive value indicates that
the adsorption of 3DOM CLPS-g-PHEMA towards SA is favored with
increasing the adsorption temperature at the current range of
adsorption temperatures. In addition, this value of DH is in the range
of hydrogen bonding [35,36], which deduces that hydrogen bonding
is the main interaction mechanism for the adsorption.
3.6. Adsorption dynamics of SA in aqueous solution
The time evolution of SA uptake by 3DOM CLPS-g-PHEMA at
different temperatures is shown in Fig. 7a. The initial concentration
of SA is around 100 mg/L. In comparison, the adsorption dynamic
curves for XAD-4 (dry resin) were also described in Fig. 7b under
the same test condition. Fig. 7a displays that the required time
from the beginning to the equilibrium is about 60 min for 3DOM
CLPS-g-PHEMA, much shorter than that of the XAD-4 (Fig. 7b). This
should be attributed to the interconnected macroporous structure,
which improves accessibility to the active sites and the short diffu-
sion path of the thin pore walls accelerates material exchange.
The Lagergren pseudo-first order (Eq. (5)) and pseudo-second
order models (Eq. (6)) were employed to fit the data [37,38].
k1 t
pseudo-first order model : log ðQ e  Q t Þ ¼ log Q e 
2:303
t 1 t
pseudo-second order model : ¼ þ
Q t k2 Q 2e Q e
tractor with ethanol for 24 h to remove the SA. In order to show
the reusability of the 3DOM CLPS-g-PHEMA, an adsorption–
desorption cycle of SA was repeated five times using the same
deabsorption method. The results are shown in Fig. 8. All the
adsorption–desorption cycle maintained around 90% of the original
SA loading capacity, meaning that the 3DOM CLPS-g-PHEMA can
be reused for SA cleanup.
4. Conclusion
A new adsorbent with 3DOM structure was prepared to adsorb
SA from aqueous solution. The PHEMA chains were controllably
grafted from the 3DOM CLPS via SI-ATRP. The interconnected mac-
roporous structure improves accessibility to the active sites, and
the short diffusion path of the thin pore walls accelerates material
exchange. When the grafted amount was 22.1%, the 3DOM CLPS-g-
PHEMA exhibited the optimum adsorption capacity. The adsorp-
tion capacity of 3DOM CLPS without grafted PHEMA toward SA is
little, the hydrogen bonding maybe play a predominant role in
3DOM CLPS-g-PHEMA adsorption toward SA in aqueous solution.
Adsorption isotherm experimental results indicated that isotherms
of SA adsorption onto 3DOM CLPS-g-PHEMA adsorbent could be
represented by Langmuir and Freundlich models and the Freund-
lich model was shown to be the most suitable. The adsorption
capacities increased with the temperature increasing in the tem-
perature range of 293–313 K. The kinetics studies indicated that
the adsorption process of SA onto the 3DOM CLPS-g-PHEMA fol-
lowed the pseudo-second order model. In addition, the regenera-
tion experiments were carried out. The spent 3DOM CLPS-g-
PHEMA adsorbent could be regenerated by simply extracted with
ethanol. The regenerated 3DOM CLPS-g-PHEMA also exhibited
ð5Þ the high adsorption capacity. All the results suggested that the
3DOM CLPS-g-PHEMA is a well potential candidate for treatment
of chemical effluent containing SA pollutants.
ð6Þ Acknowledgements

where Qe and Qt are the amounts of SA adsorbed onto adsorbents at This work was supported by National Science Funds for Young
equilibrium and at contact time t, respectively (mg/g), k1 is the Scholar (No. 50903027); Natural Science Foundation of Tianjin City
258 X. Wang et al. / Chemical Engineering Journal 203 (2012) 251–258
(No. 11JCYBJC02200); the Natural Science Foundation of Hebei
Province (No. E2010000058).
References
[1] A. Monique, K.K. Ravi, B. Stephen, Adsorption of phenol and chlorinated
phenols from aqueous solution by tetramethyl ammonium and tetramethyl
phosphonium exchanged montmorillonite, Appl. Clay Sci. 13 (1998) 13–20.
[2] S.H. Lin, M.J. Cheng, Adsorption of phenol and m-chlorophenol on
organobentonites and repeated thermal regeneration, Waste Manage. 22
(2002) 595–603.
[3] Y. Ku, K.C. Lee, Removal of phenols from aqueous solution by XAD-4 resin, J.
Hazard. Mater. B80 (2000) 59–68.
[4] F. Stuber, J. Font, A. Eftaxias, Chemicalwet oxidation for the abatement of
refractory non-biodegradable organic wastewater pollutants, Process Saf.
Environ. Prot. 4 (2005) 371–380.
[5] S.Y. Tsai, R.S. Juang, Biodegradation of phenol and sodium salicylate mixtures
by suspended Pseudomonas putida CCRC 14365, J. Hazard. Mater. B138 (2006)
125–132.
[6] C.F. Yang, Q. Yu, L.J. Zhang, J.Z. Feng, Solvent extraction process development
and on-site trial-plant for phenol removal from industrial coal-gasification
wastewater, Chem. Eng. J. 117 (2006) 179–185.
[7] V.V. Azanova, J. Hradil, Sorption properties of macroporous and
hypercrosslinked copolymers, React. Funct. Polym. 41 (1999) 163–175.
[8] M.S. Bilgili, Adsorption of 4-chlorophenol from aqueous solutions by XAD-4
resin: isotherm, kinetic, and thermodynamic analysis, J. Hazard. Mater. B137
(2006) 157–164.
[9] J.A. Stephen, G. Quan, M. Ronan, A.J. Pauline, Mass transfer processes in the
adsorption of basic dyes by Peanut Hulls, Ind. Eng. Chem. Res. 44 (2005) 1942–
1949.
[10] H. Hu, X. Wang, S. Li, J. Huang, S. Deng, Bisphenol-A modified hyper-cross-
linked polystyrene resin for salicylic acid removal from aqueous solution:
Adsorption equilibrium, kinetics and breakthrough studies, J. Colloid Interf.
Sci. 372 (2012) 108–112.
[11] J.H. Huang, G. Wang, K.L. Huang, Enhanced adsorption of salicylic acid onto a
b-naphthol-modified hyper-cross-linked poly(styrene-co-divinylbenzene)
resin from aqueous solution, Chem. Eng. J. 168 (2011) 715–721.
[12] M. Otero, C.A. Grande, A.E. Rodrigues, Adsorption of salicylic acid onto
polymeric adsorbents and activated charcoal, React. Funct. Polym. 60 (2004)
203–213.
[13] (a) O.D. Velev, P.M. Tessier, A.M. Lenhoff, E.W. Kaler, A class of porous metallic
nanostructures, Nature 401 (1999) 548;
(b) L.Y. Yang, W.B. Liau, Optical responses of polyaniline inverse opals to
chemicals, Synth. Met. 160 (2010) 1809–1814;
(c) X.S. Qu, H.W. Song, X. Bai, G.H. Pan, B. Dong, H.F. Zhao, F. Wang, R.F. Qin,
Preparation and upconversion luminescence of three-dimensionally ordered
macroporous ZrO2: Er3+, Yb3+, Inorg. Chem. 47 (2008) 9654–9659;
(d) J.S. Yu, S. Kang, S.B. Yoon, G. Chai, Fabrication of ordered uniform porous
carbon networks and their application to a catalyst supporter, J. Am. Chem.
Soc. 124 (2002) 9382–9383;
(e) H.T. Bu, J.H. Rong, Z.Z. Yang, Template synthesis of polyacrylonitrile-based
ordered macroporous materials and their derivatives, Macromol. Rapid
Commun. 23 (2002) 460–464.
[14] (a) B.T. Holland, C.F. Blanford, A. Stein, Synthesis of macroporous minerals
with highly ordered three-dimensional arrays voids, Science 281 (1998) 538–
539;
(b) A. Stein, Sphere templating methods for periodic porous solids,
Microporous Mesoporous Mater. 44–45 (2001) 227–229;
(c) B.J. Melde, A. Stein, Periodic macroporous hydroxyapatite-containing
calcium phosphates, Chem. Mater. 14 (2002) 3326–3331;
(d) M. Srinivasan, C. Ferraris, T. White, Cadmium and lead ion capture with
three dimensionally ordered macroporous hydroxyapatite, Environ. Sci.
Technol. 40 (2006) 7054–7059;
(e) J.P. Bosco, K. Sasaki, M. Sadakane, W. Ueda, J.G. Chen, Synthesis and
characterization of three-dimensionally ordered macroporous (3DOM)
tungsten carbide: application to direct methanol fuel cells, Chem. Mater. 22
(2010) 966–973;
(f) R.C. Schroden, M. Al-Daous, S. Sokolov, B.J. Melde, J.C. Lytle, A. Stein, M.C.
Carbajo, J.T. Fernandez, E.E. Rodriguez, Hybrid macropous materials for heavy
metal ion adsorption, J. Mater. Chem. 12 (2002) 3261–3267;
(g) X.M. Wang, X. Zhang, H.F. Guo, L.X. Yuan, P.G. Liu, Three-dimensionally
ordered macroporous cross-linked polystyrene incorporating functional
groups via hydrophilic spacer arms: application for heavy metal ion
adsorption, Polym. Eng. Sci. 52 (2011) 972–978.
[15] S. Brahim, D. Narinesingh, A.G. Elie, Synthesis and hydration properties of pH-
sensitive p(HEMA)-based hydrogels containing 3-(trimethoxysilyl)propyl
methacrylate, Biomacromolecules 4 (2003) 497–503.
[16] R.N. Keller, H.D. Wycoff, L.E. Marchi, Copper(I) chloride, in: W.C. Fernelius
(Ed.), Inorganic Synthese, John Wiley & Sons Inc., Hoboken, 1946, pp. 1–4.
[17] X. Zhang, W. Yan, H. Yang, B. Liu, P. Liu, Graft polymerization from pore wall of
three-dimensionally ordered macroporous cross-linked polystyrene via atom
transfer radical polymerization, Euro. Polym. J. 45 (2009) 1359–1366.
[18] G. Socrates, Infrared Characteristic Group Frequencies, Wiley, New York, 1980.
pp. 254.
[19] (a) K. Matyjaszewski, J. Xia, Atom transfer radical polymerization, J. Chem.
Rev. 101 (2001) 2921–2990;
(b) M. Kamigaito, T. Ando, M. Sawamoto, Metal-catalyzed living radical
polymerization, Chem. Rev. 101 (2001) 3689–3746;
(c) K. Matyjaszewski, P.J. Miller, N. Shukla, B. Immaraporn, A. Gelman, B.B.
Luokala, T.M. Siclovan, G. Kickelbick, T. Vallant, H. Hoffmann, T. Pakula,
Polymers at interfaces: using atom transfer radical polymerization in the
controlled growth of homopolymers and block copolymers from silicon
surfaces in the absence of untethered sacrificial initiator, Macromolecules 32
(1999) 8716–8724;
(d) W. Huang, J.B. Kim, M.L. Bruening, G.L. Baker, Functionalization of surfaces
by water-accelerated atom-transfer radical polymerization of hydroxyethyl
methacrylate and subsequent derivatization, Macromolecules 35 (2002)
1175–1179;
(e) A. Carlmark, E. Malmström, Atom transfer adical polymerization from
cellulose fibers at ambient temperature, J. Am. Chem. Soc. 124 (2002) 900–
901.
[20] B.C. Pan, X. Zhang, W.M. Zhang, J.Z. Zheng, B.J. Pan, J.L. Chen, Q.X. Zhang,
Adsorption of phenolic compounds from aqueous solution onto a macroporous
polymer and its aminated derivative: isotherm analysis, J. Hazard. Mater. B121
(2005) 233–241.
[21] F.Q. An, B.J. Gao, X.Q. Feng, Adsorption mechanism and property of novel
composite material PMAA/SiO2 towards phenol, Chem. Eng. J. 153 (2009) 108–
113.
[22] F.P. Gregory, N. Yuko, Selective adsorption of solutes based on hydrogen
bonding, Sep. Sci. Technol. 25 (1990) 1117–1129.
[23] J.H. Huang, K.L. Huang, S.Q. Liu, Q. Luo, S.Y. Shi, Synthesis, characterization, and
adsorption behavior of aniline modified polystyrene resin for phenol in hexane
and in aqueous solution, J. Colloid Interf. Sci. 317 (2008) 434–441.
[24] J.G. Amy, A.K. Jeffrey, J.B. Brian, F.P. Gregory, Ind. Eng. Chem. Res. 37 (9) (1998)
3685–3690.
[25] R. Kunin, The use of macroreticular polymeric adsorbents for the treatment of
waste effluents, Pure Appl. Chem. 46 (1976) 205–211.
[26] B.L. He, W.Q. Huang, Ion Exchange and Adsorption Resins, first ed., The Science
and Education Press of Shanghai Press, Shanghai, 1992.
[27] K. Young, K. Lee, Removal of phenols from aqueous solution by XAD-4 resin, J.
Hazard. Mater. B80 (2000) 59–68.
[28] C.K. Lee, K.S. Low, P.Y. Gan, Removal of some organic dyes by acid treated spent
bleaching earth, Environ. Technol. 20 (1999) 99–104.
[29] J.H. Huang, K.L. Huang, S.Q. Liu, Q. Luo, M.C. Xu, Adsorption properties of tea
polyphenols onto three polymeric adsorbents with amide group, J. Colloid
Interf. Sci. 315 (2007) 407–414.
[30] J.H. Huang, K.L. Huang, S.Q. Liu, Q. Luo, M.C. Xu, Adsorption behavior,
thermodynamics, and mechanism of phenol on polymeric adsorbents with
amide group in cyclohexane, J. Colloid Interf. Sci. 316 (2007) 10–18.
[31] N.K. Hamadi, X.D. Chen, M.M. Farid, M.G.Q. Lu, Adsorption kinetics for the
removal of chromium(VI) from aqueous solution by adsorbents derived from
used tyres and sawdust, Chem. Eng. J. 84 (2001) 95–105.
[32] M. Otero, M. Zabkova, A.E. Rodrigues, Comparative study of the adsorption of
phenol and salicylic acid from aqueous solution onto nonionic polymeric
resins, Sep. Purif. Technol. 45 (2005) 86–95.
[33] S.P. Deosarkar, V.G. Pangarkar, Adsorptive separation and recovery of organics
from PHBA and SA plant effluents, Sep. Purif. Technol. 38 (2004) 241–254.
[34] (a) F.P. Bonina, M.L. Giannossi, L. Medici, C. Puglia, V. Summa, F. Tateo,
Adsorption of salicylic acid on bentonite and kaolin and release experiments,
Appl. Clay Sci. 36 (2007) 77–85;
(b) D. Kovačević, N. Kallay, I. Antol, A. Pohlmeier, H. Lewandowski, H.D.
Narres, The use of electrokinetic potential in the interpretation of adsorption
phenomena: adsorption of salicylic acid on hematite, Colloids Surf. A 140
(1998) 261–267;
(c) J.E. Thomas, M.J. Kelley, The adsorption of salicylic acid onto Fourier
transform spectroscopy (DRIFT), J. Colloid Interface Sci. 338 (2009) 389–394;
(d) M. Ukrainczyk, M. Gredičak, I. Jerić, D. Kralj, Interactions of salicylic acid
derivatives with calcite crystals, J. Colloid Interf. Sci. 365 (2012) 296–307.
[35] N. Maity, G.F. Payne, Adsorption from aqueous solutions based on a
combination of hydrogen bonding and hydrophobic interactions, Langmuir 7
(1991) 1241–1254.
[36] J.H. Huang, K.L. Huang, A.T. Wang, Q. Yang, Adsorption characteristics of
poly(styrene-co-divinylbenzene) resin functionalized with methoxy and
phenoxy groups for phenol, J. Colloid Interf. Sci. 327 (2008) 302–307.
[37] S. Lagergren, Zur theorie der sogenannten adsorption gelöster stoffe, K. Sven.
Vetenskapsakad. Handl. 24 (1898) 1–39.
[38] Y.S. Ho, G. Mckay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (1999) 451–465.