Microporous and Mesoporous Materials 207 (2015) 46e52

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Microporous and Mesoporous Materials

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

Polyethylenimine functionalized halloysite nanotubes for efficient

removal and fixation of Cr (VI)
Xike Tian a, Weiwei Wang a, Yanxin Wang b, Sridhar Komarneni c, *, Chao Yang a, c, **
a
Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074, PR China
b
School of Environmental Studies, China University of Geosciences, Wuhan 430074, PR China
c
Materials Research Laboratory, Materials Research Institute and Department of Ecosystem Science and Management, The Pennsylvania State University,
University Park, PA 16802, USA

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

Article history: A typical nanoporous-geomaterial (halloysite nanotubes, HNTs) was functionalized by polyethyleneimine
Received 21 July 2014 (PEI) grafting and the functionalized halloysite (PEI-HNTs) exhibited excellent performance for Cr (VI)
Received in revised form removal from aqueous solution and immobilization by reduction. After PEI modification, the Cr (VI)
24 December 2014
uptake capacity of PEI-HNTs was about 64 times higher than that of the original HNTs and the maximum
Accepted 28 December 2014
Available online 13 January 2015
equilibrium removal capacity was found to be 102.5 mg g
1 at 328 K. Part of Cr (VI) was reduced to Cr (III)
and then precipitated on the surface of adsorbent during the sorption process as determined by X-ray
photoelectron spectroscopic analysis, suggesting that the PEI-HNTs are not only useful for Cr (VI)
Keywords:
Nano-geomaterial
immobilization but also good for its reduction. The adsorption of Cr (VI) by the PEI-HNTs was fitted to
Halloysite Langmuir model and the kinetics of uptake could be described by a pseudo-second-order rate model very
Functionalized halloysite well. The results also demonstrated that PEI-HNTs could detoxify Cr (VI) at low pH value. The mechanism
Cr (VI) reduction of uptake of Cr (VI) was postulated to be electrostatic interaction followed by its immobilization through
Cr immobilization reduction. The functionalized nano-geomaterial synthesized here could be a promising candidate of low
cost for highly efficient Cr (VI) removal followed by its immobilization.
© 2015 Elsevier Inc. All rights reserved.

1. Introduction consumption of reagents and a massive amount of toxic sludge

Cr (VI) is a highly toxic, mutagenic, and carcinogenic species and
has been one of the most frequently detected in groundwater at
hazardous waste sites [1,2]. Therefore, low cost and highly effective
strategies for treating Cr (VI) containing wastes are in great demand
all over the world.
Considerable attention has been paid to the treatment of Cr (VI)-
containing wastewater over the past few decades, and different
treatment processes have been developed for the removal of Cr (VI)
from wastewater. Technologies including chemical reduction-
precipitation, [3,4] membrane separation [5] and ion-exchange
[6] have been mainly used for removing Cr (VI) from wastewater.
The primary drawbacks of reduction-precipitation are large
* Corresponding author. Tel.: þ1 8148651542; fax:þ1 8148652326.
** Corresponding author. Faculty of Material Science and Chemistry, China Uni-
versity of Geosciences, Wuhan 430074, PR China.
E-mail addresses: sxk7@psu.edu, 5177828@sohu.com (S. Komarneni), 5177828@
sohu.com (C. Yang).
production which could easily cause secondary pollution. On the
other hand, reverse osmosis and ion-exchange processes are costly
and complex. Recently, chromium immobilization using a reduc-
tionesorption process on a single solid adsorbent has been pro-
posed as a most effective technique, [7e9] in which Cr (VI) is
converted into Cr (III) as hydroxide with much lower toxicity and
limited solubility. However, there is a strong need to design a solid-
adsorbent, which is cost-effective and environmentally friendly
with strong ability for Cr (VI) removal.
Geomaterials for environmental remediation are much more
attractive compared to synthetic or commercial materials because
the former are ubiquitous and of low cost. Additionally, it is not
necessary to regenerate the inexpensive geomaterials because of
their environmental compatibility. Various geomaterials such as
montmorillonite, kaolinite, rectorite, hydrotalcite, bentonite, etc.,
[10e14] have been studied to remove heavy metals from waste-
water. Among the geomaterials, halloysite (Al2Si2O5(OH)4$nH2O) is
a special nano-geomaterial because of its tubular morphology, high
porosity and tunable surface chemistry which enabled it to be
utilized as a promising adsorbent for various organic pollutants and

http://dx.doi.org/10.1016/j.micromeso.2014.12.031
1387-1811/© 2015 Elsevier Inc. All rights reserved.
 X. Tian et al. / Microporous and Mesoporous Materials 207 (2015) 46e52
heavy metals [15e17]. This kind of nano-geomaterial is available in
abundance in China and many other countries [18]. However,
naturally occurring halloysite has little or no capacity for the
removal of heavy metal cations because there is little or no per-
manent negative or positive charge on the surfaces due to
isomorphous substitution unlike montmorillonite, which is nega-
tively charged. Therefore, it is highly desirable to develop effective
methods to modify the surface of halloysite. Recently, chemical
modification of halloysite nanotubes (HNTs) with cationic surfac-
tant was performed to increase the surface positive charge and
enhance the removal efficiency for Cr (VI) [19]. In another study, it
has been reported that amine-functionalized clay is effective in
removing anionic metal species [20] because the amine groups are
easily protonated and thus could remove anionic metal species via
electrostatic interaction or hydrogen binding.
Polyethyleneimine (PEI), a cationic polymer with the highest
cationic-charge density is well known for its outstanding adsorp-
tion ability for heavy metals due to the presence of a large number
of primary and secondary amine groups per molecule [21,22].
Several researchers have reported that PEI-modified adsorbents
exhibited high isoelectric point and good adsorption ability for Cr
(VI) from wastewater [23,24]. Herein, we fabricated a novel
adsorbent by grafting polyethyleneimine onto HNTs. The obtained
composites of PEI-HNTs were tested and found to be very useful for
Cr (VI) reduction and immobilization from aqueous solution. The
affinity of modified HNTs for Cr (VI) and the possible immobiliza-
tion mechanism of Cr (VI) on this material were investigated. The
obtained PEI-HNTs as an inexpensive solid-adsorbent exhibited
excellent performance for Cr (VI) decontamination and
immobilization.
2. Experimental section
Reagents and Instrumentation: All the reagents were of analytical
grade and purchased from the Sinopharm Chemical Reagent Co.
Ltd., (Shanghai, China). Ultra pure water was used in all prepara-
tions. Processed halloysite (HNT) was provided by Zhengzhou
Jinyangguang Chinaware Co. Ltd., (Henan, China). Prior to use, all of
the raw clay samples were purified by repeated sedimentation
processes to remove the quartz impurities followed by drying at
373 K for 24 h and grinding and sieving. A branched poly-
ethyleneimine (PEI, molecular weight of 25,000) was purchased
from SigmaeAldrich. A stock solution (1000 mg L
1) containing
potassium dichromate (K2Cr2O7) was prepared by dissolving
K2Cr2O7 with ultra pure water and a series of solutions used during
the experiment were prepared by diluting the stock solution to the
desired concentrations.
Characterization: The morphology of the samples was examined
by TEM (JEOL 2000 EX) operating at an accelerating voltage of
200 KV. Nitrogen adsorptionedesorption isotherms were
measured at
196  C using a Micromeritics ASAP2020 apparatus.
The FT-IR spectra were recorded with a NICOLET AVATAR 370 DTGS
instrument by diffuse reflectance scanning disc technique from
4000 to 400 cm
1 at room temperature. The X-ray powder
diffraction patterns of materials were obtained with a diffractom-
eter (Rigaku D/max-b B) using a Cu Ka radiation source
(l ¼ 0.15432 nm). X-ray photoelectron spectrometer (MULTI-
LAB2000) was used in the surface analysis of the as-prepared PEI-
HNTs material before and after Cr (VI) adsorption. The zeta po-
tential values were determined on a Zetasizer Nano (ZS90). The
element analysis of the product was measured on an Elementar
Vario EL cube (Germany). The concentration of Cr (VI) was detected
using the 1,5-diphenylcarbazide method, on an ultravioletevisible
TU-1800PC spectrophotometer analyzer at l ¼ 540 nm.
47
Synthesis of PEI functionalized HNTs: First, APTES-functionalized
halloysite (APTES-HNTs) were prepared according to the
following routes [25]. Briefly, 4 ml of 3-aminopropyltriethoxysilane
(APTES) was added drop wise into 50 ml of dry toluene. Then about
1.2 g of activated HNTs powder was dispersed into the mixture
mentioned above ultrasonically for 30 min. The mixture was
refluxed at 120  C for 24 h under a nitrogen atmosphere. Finally, the
APTES-functionalized halloysite solid was filtered out and washed
with fresh toluene to remove the excess APTES, and dried at 60  C
under vacuum for 12 h.
In a typical processing for preparing PEI-HNTs, 4 g APTES-
functionalized halloysite powder was immersed in 100 ml 2% (w/
v) PEI in methanol solution for 24 h under vigorous stirring. Then
the suspension was immediately transferred into 200 ml 1% (w/v)
glutaraldehyde solution for 30 min, followed by washing with ul-
trapure water several times until the suspension eventually became
clear. The PEI-HNTs were obtained by drying under vacuum at
60  C.
Batch experiments: Batch experiments were carried out in
250 ml conical flasks, each of which contained 50 ml Cr (VI)
aqueous solution prepared with K2Cr2O7. 55 mg of PEI-HNTs pow-
der was added to each flask and shaken at 150 rpm in a thermo-
static shaker. The initial pH of solution was adjusted by the addition
of 0.1 M NaOH or HCl solution. A series of adsorption experiments
were conducted for the investigation of pH, reaction time and
adsorption capacity. In order to investigate the effect of initial so-
lution pH, the solution pH with initial concentrations of 30 mg L
1
were controlled ranging from 1 to 8.
For the adsorption kinetic tests, 55 mg of adsorbent was added
into 50 ml of 30 and 50 mg L
1 Cr (VI) under stirring at a pH of 2,
and stirring continued for a specified time (0e37 h). And the
pseudo-first-order and pseudo-second-order kinetic models were
applied to fit experimental data obtained from batch experiments.
The isothermal adsorption experiments were conducted by varying
the concentration of Cr (VI) from 29.92 to 258.23 mg L
1 (pH ¼ 2).
The flasks were kept in an isothermal shaker for 36 h to reach
equilibrium of the solution with the solid mixture. Langmuir and
Freundlich isotherm models were used to fit the equilibrium data of
adsorption of Cr (VI) on the PEI-HNTs.
3. Results and discussion
3.1. Characterization of PEI-HNTs
Scheme 1 shows the synthesis process of PEI grafting of HNTs.
The HNTs were first treated with g-aminopropyltriethoxysilane,
which was selected as coupling agent to chemically link silica with
PEI. Subsequently, composites of the PEI-HNTs were synthesized
based on the cross-linking reaction between aldehydes in glutar-
aldehyde and amine groups anchored on the APTES-HNTs.
The XRD patterns of halloysite before and after pretreatment by
sedimentation processes are shown in Fig. S1. Both of them are in
good agreement with previously published patterns for halloysite
[26]. Before pretreatment, the XRD patterns showed mineral
Scheme 1. Schematic depiction of the grafting process of PEI on the HNTs.
48 X. Tian et al. / Microporous and Mesoporous Materials 207 (2015) 46e52
Fig. 1. FTIR spectra of (a) HNTs (b) PEI and (c) PEI-HNTs.
phases of quartz, gibbsite and feldspar as impurities (Fig. S1A). After
pretreatment by sedimentation processes, all the impurities were
removed and only pure halloysite remained (Fig. S1B). FT-IR spec-
troscopy was used to characterize the functional groups of the
different samples as shown in Fig. 1. Untreated HNTs show a band at
1045 cm
1, which corresponds to the vibration modes of the SieO
network (SieOeSi and OeSieO) (Fig. 1a). The broad band at
3400~ cm
1 arises from adsorbed water. The band at 3700~ cm
1 is
Fig. 2. TEM images: (A) and (B) HNTs; (C) and (D) PEI-HNTs.
attributed to SieOH hydroxyl stretching vibrations. The character-
istic bands at 3630~ cm
1 are attributed to AleOH stretching vi-
brations [27] (Fig. 1a). After modification of HNTs with PEI (Fig. 1b),
the spectrum of the PEI-HNTs (Fig. 1c) exhibit some changes. Two
new bands appeared at 2942 cm
1 and 1459 cm
1 in the PEI-HNTs
(Fig. 1c) and these are ascribed to the CeH asymmetric and defor-
mation stretching vibrations. The peak at 1656 cm
1 represents the
new eC]Ne cross-linking formed by the free amine NH2 on PEI
and the HC]O aldehyde group on the glutaraldehyde [28]. The
produced band at 1575 cm
1 is ascribed to the stretching vibration
absorption of CeN bond [21]. These two peaks (1656 and
1575 cm
1) also have overlapping contributions from the NeH and
NeH2 bending vibrations due to amines [29]. Similar peaks also
appear between 1500 and ~ 1600 cm
1 of PEI (Fig. 1b). The above
FT-IR results confirmed that the PEI had been successfully grafted
onto the HNTs. Furthermore, the introduction of PEI onto the HNTs
was also indicated by the elemental analysis of the samples with
nitrogen contents of 0.00%, 0.80% and 1.62% for HNTs, ATPES-HNTs
and PEI-HNTs, respectively. Lastly, an XPS study was used to
investigate the PEI modification. N1s peaks of PEI-HNTs from the
fine spectrum can be seen in Fig. S2. The binding energy at 399.7 eV
can be assigned to nitrogen in the NH (NH2)/CN. The binding en-
ergies at 398.6 eV can be assigned to the N in the tertiary amine
groups (>Ne), indicating that aldehyde groups of glutaraldehyde
reacted with amine groups of biomass and PEI. Thus, the glutaral-
dehyde actually serves as a bridge to graft the PEI onto the HNTs
surface [30].
The morphological features of the various samples were
observed by Transmission electron microscopy (TEM) as shown in
 X. Tian et al. / Microporous and Mesoporous Materials 207 (2015) 46e52
Table 1
Textural parameters of the HNTs and PEI-HNTs.
Property HNTs
BET surface area (m2 g
1) 42.3
Pore volume (cm3 g
1) 0.19
Pore diameter (nm) 18.1
Fig. 2. TEM images (Fig. 2A and B) revealed that halloysite is a
cylindrical-shaped tube with multilayer smooth walls and an open-
ended lumen along the nanotube. The tubes have an external
diameter of 40e60 nm and an inner diameter of 15e20 nm, while
the wall thickness is about 10e20 nm. Overall, the morphology
parameters of the present halloysite sample are identical to those
reported previously for other samples [31,32]. After modification
(see Fig. 2C and D), a prominent change in the modified nanotube
was a more uneven and rougher surface morphology compared to
the raw halloysite. The relevant textural parameters before and
after modification also support the above observation and they are
summarized in Table 1. The PEI-modified halloysite has a specific
surface area and pore size of 30.9 m2 g
1 and 15.3 nm, respectively
which are smaller than the specific surface area and pore size of
42.3 m2 g
1 and 18.1 nm, respectively for untreated halloysite (see
Fig. 3). These results are in agreement with the results of previously
published research [33,34].
3.2. Effect of pH
It is well known that the pH value of aqueous solution is one of
the key factors in the removal of metal ion contaminants because it
not only affects the charge density of adsorbent surface but also
determines the present state of the adsorbate in solution. To obtain
information about the surface charge of HNTs and PEI-HNTs, zeta
potential measurements were performed at various pH values and
the results are shown in Fig. 4. It can be seen from Fig. 4 that the
zeta potential values for the surface of PEI-HNTs became more
positive than those of HNTs in the whole pH range. The positive
charge in the former could be attributed to the PEI, which is a
cationic polyelectrolyte and is protonated at pH lower than 10. The
isoelectric point of PEI-HNTs is at pH ¼ 8 and this relatively high
Fig. 3. Nitrogen adsorptionedesorption isotherms of HNTs and PEI-HNTs and pore-
size distribution in the inset.
49
PEI-HNTs
30.9
0.12
15.3
Fig. 4. Zeta potential vs pH of (a) HNTs and (b) PEI-HNTs.
isoelectric point is favorable for adsorption of anionic contaminants
by electrostatic attraction.
The effect of the initial pH in the removal of Cr (VI) was
investigated in the pH range of 1e8 as shown in Fig. 5. It is evident
from Fig. 5 that the adsorption of Cr (VI) on PEI-HNTs is remark-
ably pH-dependent. Chromium removal decreased with
increasing pH and the maximum adsorption of Cr (VI) on PEI-
HNTs occurred at about pH ¼ 2.0. The increase in the adsorption
capacity at lower pH values could be attributed to the availability
of protonated amino groups as sites for adsorption of Cr(VI)
anionic species, HCrO
4.
3.3. Effect of PEI concentration used on the adsorption properties
Three different PEI concentrations (1, 2 and 4%) were used to
determine the optimum amount of PEI modification on HNTs.
Samples are numbered as HNTs/PEI(1), HNTs/PEI(2) and HNTs/
PEI(4). The introduction of PEI onto the HNTs was also indicated
by the elemental analysis of the samples with nitrogen contents
of 0.66%, 1.62% and 1.89% for HNTs/PEI(1), HNTs/PEI(2) and
HNTs/PEI(4) respectively. Chromium ion adsorption capacity of
these samples was investigated and the results are shown in
Fig. 6. The results confirmed that the Cr (VI) adsorption capacity
was enhanced after HNTs were modified by PEI. When the re-
action concentration of PEI was 2%, PEI-HNTs showed the
highest adsorption capacity for Cr (VI) of the tested adsorbents,
followed by a slight reduction in efficiency when the concen-
tration of PEI increased (Fig. 6). The adsorption capacity of Cr
(VI) on PEI (2%)-HNTs is 81.5 mg g
1, which is approximately
64 times as much as the adsorption capacity of Cr(VI) on un-
modified HNTs. This large increase in adsorption by the PEI
treated HNTs can be explained as follows: After coating the
cationic polyelectrolyte on to the HNTs, the positive charge
density and reactive sites (amino) on the HNTs increased, which
facilitated the adsorption of the negatively charged Cr(VI) spe-
cies by electrostatic interactions and hydrogen bonding. The
reduction of adsorption capacity when higher PEI concentration
was used may have resulted from reduced effective surface area
by the partial self cross-linking of PEI during the preparation
with higher PEI concentration.
50 X. Tian et al. / Microporous and Mesoporous Materials 207 (2015) 46e52
Fig. 5. Effect of initial solution pH on Cr (VI) adsorption by PEI-HNTs.
3.4. Adsorption kinetics and isotherms
To determine the time necessary to achieve equilibrium
adsorption, the effect of contact time on adsorption of Cr(VI) onto
PEI-HNTs was studied using initial concentrations of 30 and
50 mg L
1 Fig. 7 shows the effect of contact time on the adsorption
of Cr(VI) on PEI-HNTs. The adsorption capacity of Cr(VI) on PEI-
HNTs increased very rapidly within 4 h. Thereafter, it's continued
to increase at a slower rate and finally approached adsorption
equilibrium after 20 h. The pseudo-first-order and pseudo-second-
order kinetic models were fitted to the adsorption kinetic data. The
kinetic parameters and the correlation coefficients (R2) were
determined by linear regression (Supporting information, Fig. S3)
and were given in Table S1 (Supporting information, Table S1). The
calculated values qe,cal of the pseudo-second-order kinetic model
are close to the experimental ones qe,exp, and the plots show quite
good linearity with R2 values of 0.9998 and 0.9999, respectively.
Therefore, the adsorption kinetics follows the pseudo-second-
order model well, suggesting a chemisorption, process.
Fig. 8 shows the adsorption of Cr (VI) on the PEI-HNTs versus the
solution temperature at various equilibrium concentrations. The Cr
Fig. 6. Effect of PEI concentration on Cr (VI) adsorption by PEI-HNTs.
(VI) adsorption uptake was found to increase with increasing so-
lution temperature from 298 to 328 K for all initial concentrations,
indicating the endothermic nature of the adsorption reaction. The
increased uptake with increasing temperature may be due to
increased rate of diffusion of the adsorbate molecules across the
external boundary layer.
The linearized Langmuir and Freundlich plots are shown in
Fig. S4 (Supporting information, Fig. S4). All the correlation co-
efficients, R2 values and the constants obtained from the isotherm
models applied for adsorption of Cr (VI) at 298, 308 and 328 K on
the PEI-HNTs are summarized in Table S2 (Supporting information,
Table S2). It can be clearly seen from Table S2 that higher correla-
tion coefficients are obtained with the Langmuir model and hence
this model fits the data better than Freundlich model. The results
also revealed that the adsorption capacity increased from 64.4 to
102.5 mg g
1 when the temperature increased from 298 K to 328 K.
3.5. Adsorption mechanism
An electrochemical experiment was used to investigate the
standard electrode potential (298 K) of PEI-HNTs. According to the
Tafel curves (Supporting information, Fig. S5), we calculated the
standard electrode potential of PEI-HNTs is about
0.2462 V
(Saturated calomel electrode potential is 0.2438 V at 298 K). HCrO
4
is the major form of Cr (VI) at low pH (1 < pH < 4), which is a strong
oxidizing agent with E0 of 1.35 V [35]. This suggests that reduction
of Cr (VI) to Cr (III) can occur after the adsorption of Cr (VI) onto PEI-
HNTs.
The adsorption process was usually determined by the func-
tional groups on the adsorbent's surface. So the XPS study was used
to investigate the surface chemical composition of the as-prepared
PEI-HNTs before and after Cr (VI) adsorption (Fig. 9). Fig. 9c shows
the N1s spectra of PEI-HNTs and PEI-HNTs after adsorption of Cr
(VI). The new binding energy (BE) component at 401.0e402.0 eV
corresponds to a protonated amine group (eNHþ 3 ), and the change
of BE component at 399.7 eV is probably due to the state of the
amino groups being changed by the adsorption process [36].
Similar to the conventional amine family, the N atom of the hal-
loysite amine group is able to donate and share the lone electron
pair with the empty orbit of other cations, featuring thus with
weak-base characteristics. The protonation of amine groups is
Fig. 7. The variation of adsorption capacity with adsorption time at various initial
Cr(VI) concentrations.
 X. Tian et al. / Microporous and Mesoporous Materials 207 (2015) 46e52
Fig. 8. Adsorption isotherms of chromium with different Cr (VI) concentrations and
temperatures.
controlled by the pKa of the polymer (i.e., 9.5e11) [37]. Therefore,
when the solution pH is lower than the corresponding pKa, the
amine sites could be effectively protonated with a positive charge,
and an anion could thus be bound. The ratio [NH2]/[NHþ 3 ] increases
as the amine group of surface complexes is deprotonated.
The high-resolution XPS spectra of the Cr2p region are shown in
Fig. 9b. Cr1/2p and Cr3/2p line peaks are located at 586.9 and
577.2 eV, respectively. The broad peak of Cr3/2p can be fitted to two
peaks at binding energies of 578.5 eV and 576.8 eV, which are the
characteristic peaks of Cr (VI) and chromic hydroxide [38,39]. It is
Fig. 9. XPS spectra of the PEI-HNTs before and after Cr (VI) adsorption: (a) survey, (b) Cr2p, (c) N1s.
51
evident that both Cr(VI) and Cr(III) are present on the modified
surface over the pH range of 1.6e8.5, suggesting that chromium
was removed from solution mainly by reduction and subsequent
surface precipitation of phases [37]. The electrons for the reduction
of Cr(VI) to Cr(III) were probably from the aldehyde group of
glutaraldehyde [40] and amine group of PEI [8].
Taking into account the effect of pH value and the XPS results,
the possible mechanism of Cr (VI) adsorption on PEI-HNTs is pro-
posed as follows: (1) At lower pH, amino groups were strongly
protonated and Cr (VI) anions were adsorbed onto the surface of
PEI-HNTs via electrostatic attraction and hydrogen binding; (2) Cr
(VI) was reduced to Cr (III) and immobilized on the PEI-HNTs sur-
face by complex reaction with aldehyde and amine groups. Amine
groups have been shown to play an important role in the Cr (VI)
adsorption process.
4. Conclusions
In summary, a functionalized nano-geomaterial (PEI-HNTs) was
synthesized and the Cr (VI) uptake of modified nano-geomaterial
had been improved greatly. The as-obtained PEI-HNTs exhibited
superior functionality to capture Cr(VI) anions from solution with
the maximum adsorption capacities of 64.4 mg g
1 (298 K) and
102.5 mg g
1 (328 K). The pseudo-second-order model provided a
very good fitting (R2 > 0.9998) for kinetics of Cr(VI) adsorption. The
Langmuir model was applied to describe the equilibrium iso-
therms. In addition, XPS analysis results indicated that some of the
adsorbed Cr(VI) was reduced to Cr (III) during the removal process,
which suggested that PEI-HNTs could immobilize Cr(VI) by reduc-
tion. The results presented here have demonstrated the usefulness
of a novel functionalized nano-geomaterial as a highly efficient
candidate for Cr containing wastewater treatment and it is also a
potentially low-cost, high adsorption capacity and environmentally
friendly material.
52 X. Tian et al. / Microporous and Mesoporous Materials 207 (2015) 46e52
Acknowledgments
We are grateful to the National Basic Research Program of China
(Grant No. 2011CB933700) for the financial support. The project
was also supported by the National Natural Science Foundation of
China (Grant NO. 51371162 and NO. 51344007).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.micromeso.2014.12.031.
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