Advanced Powder Technology 31 (2020) 4018–4030

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Advanced Powder Technology

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

Original Research Paper

Efficient removal of Cr (VI) from aqueous solution by halloysite/poly

(amidoamine) dendritic nano-hybrid materials: kinetic, isotherm and
thermodynamic studies
Mohammad Hassan Kanani-Jazi, Somaye Akbari ⇑, Mohammad Haghighat Kish
School of Materials and Advanced Processes Engineering, Amirkabir University of Technology (Tehran Polytechnic), Tehran, Iran

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

Article history: This paper demonstrates functionalization of a new hybrid nanoclay for effective adsorption of
Received 23 April 2020 chromium(VI) ions from wastewater. Halloysite nanotubes (HNTs) were functionalized by
Received in revised form 4 August 2020 poly(amidoamine) dendritic polymers (HNTs-(DEN-NH2)) via a convergent synthetic route by carboxylic
Accepted 6 August 2020
acid as a linkage. Various characterization methods confirm that poly(amidoamine) dendritic groups
Available online 30 August 2020
were effectively grafted onto the surface of HNTs that found a high specific surface area of 75 m2/g, as
measured by micrometric BET analyzer. Moreover, the adsorption activity of HNTs-(DEN-NH2) for Cr
Keywords:
(VI) was systematically investigated using a batch solution that reveals the removal efficiency of 98%
Halloysite
Poly(amidoamine) dendritic polymer
for HNTs-(DEN-NH2) comparing to 23% for pristine HNTs, at optimum conditions. The enhancement of
Chromium (VI) Cr(VI) removal for HNTs-(DEN-NH2) comparing to HNTs was mainly ascribed to be due to the electro-
Functionalization static interaction, that was confirmed by the results of Fourier transform infrared (FTIR) and X-ray
Adsorption mechanism photoelectron spectroscopy (XPS). Moreover, regeneration studies display that HNTs-(DEN-NH2) can
maintain removal Cr(VI) with high efficiency after four consecutive cycles.
Ó 2020 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction stable, and cost-effective features [13–15]. Also, natural adsorbents

The water pollution due to the discharge of hazardous material
into the surface water that might be used for drinking or irrigation
is a serious environmental concern [1,2]. The discharge of heavy
metals and hazardous materials without any treatment causes
blocking the penetration of light, interruption of the photosyn-
thetic activity, and microorganism actions [3–5]. Chromium is a
toxic heavy metal, which is widely used in industries such as
leather tanning, electroplating, textile, metallurgy, steel fabrica-
tion, nuclear power plants, and photography [6,7]. Chromium nat-
urally exists in two states, Cr(VI) and Cr(III) [8]. Due to the high
solubility of chromium (VI), its bioavailability and persistence to
remain in the environment are severe environmental concerns
[9,10]. These materials affect human health, it causes diseases such
as cancer, allergies, and disorder of human nervous systems etc.
[11]. Accordingly, wastewater treatment plays a vital role [12].
Among many biological, chemical and physical processes, adsorp-
tion has received a lot of positive attention as an effective way to
remove Cr(VI) from wastewater because of its facile, simplicity,
⇑ Corresponding author.
E-mail address: akbari_s@aut.ac.ir (S. Akbari).
for treating colored wastewater, heavy metals and hazardous
materials attracted the attentions, probably it is due to the avail-
ability in massive amounts, and easy modification [16].
Halloysite (Al2Si2O5 (OH)4
nH2O) is an abundant natural min-
eral clay that exists in various morphologies including platy, spher-
oidal, and tubular with the tubular morphology being the
dominant one [17]. Halloysite is found in many countries such as
the United States, France, Brazil, China, Poland, and Australia. The
morphological parameters of halloysite such as length, internal/ex-
ternal diameter ratio, and thickness depend on crystallization con-
ditions and geological events, which lead to several morphological
properties. Halloysite consists of a hollow tubular structure formed
by multiple rolled layers [18–20]. HNTs are unique because of their
modifiability, hollow tubular shape, high specific surface area, nat-
ural origin, and low cost [21,22]. HNTs have many hydroxyl groups
on their surface and interlayer space, which reveals a significant
tendency to adsorb a variety of pollutants [23].
The literature reports the modification of pristine HNTs for
improving adsorption efficiency [19,24–25]. Acid treatment can
lead to an increased halloysite surface area [24]. The functionaliza-
tion of halloysite mainly begins with the silanization reaction of
hydroxyl groups to primary amine groups by c-aminopropyltrie

https://doi.org/10.1016/j.apt.2020.08.004
0921-8831/Ó 2020 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030
thoxysilane (APTES) [26]. Based on researchers’ reports, the
organosilane modification of halloysite leads to a versatile host
for loading different functional groups [19]. For instance, HNTs
have been modified with a hexadecyltrimethylammonium bro-
mide (HDTMA). Modified HNTs were capable of approaching 90%
of their maximum adsorption capacity and show an increased
adsorption rate of chromate [27]. In another work, the functional
groups of clays were modified from amine groups (HNTs-NH2) to
a carboxylic acid (HNTs-COOH) [28]. Polyethyleneimine (PEI) was
grafted on modified HNTs with APTES. The modified adsorbent
exhibited an acceptable performance to remove Cr(VI) [29]. Among
various functionalizations, growing dendritic structures on HNTs is
found to have a synergetic effect on adsorption capacity [30]; this
may be due to the free space between branches as well as abun-
dant functional groups at the exterior of dendritic structures. Dif-
ferent generations of amine-terminated dendrimer have been
applied onto the surface of HNTs via a divergent synthesis route
to improve the removal capacity of anionic dye molecules and
heavy metal ions [24,31]. However, a lengthy procedure for func-
tionalization causes difficulties for commercial applications. As a
result, a convergent synthesis route is preferred over divergent
synthesis due to being efficient, fast, and cost-effective. It appears
that in this route, macromolecules are attached onto the surface of
HNTs, similar to the grafting-to mechanism [25].
There are two general methods for the synthesis of dendrimers:
divergent route and convergent route. In the convergent route,
dendrons are individually synthesized, which are subsequently
attached to the central core. In the divergent route, branches grow
on the central core step by step. Each step leads to a rise in the gen-
eration of dendrimers [32,33]. Dendritic polymers by their unique
structure, i.e., high specific surface area and a large number of
active sites are suitable compounds to separate pollutants
[34,35]. On the other hand, among all investigated dendritic struc-
tures, including random hyperbranched polymers, dendrimers,
dendrigrafts, and dendrons, hyperbranched polymers have gained
more attention due to their low price and easy production [36].
By increasing the generation of dendritic polymers, the chain ends
start to back fold into the interior of dendritic polymers, and their
growth will not be limited to the surface [36,37]. Moreover, the
interaction between terminated groups leads to a compact struc-
ture surrounded by a dense shell, as explained by the de Gennes
dense-packed state [38]. As a result, functionalized HNTs can be a
relevant candidate for the removal of Cr (VI).
In this study, acid-washed HNTs-OH was reacted through
silanization reaction via APTES to produce HNTs-NH2. Then,
HNTs-NH2 was reacted with succinic anhydride to create the car-
boxylic acid functional group on the halloysite (HNTs-COOH).
Finally, the Poly(amidoamine) dendritic polymer was grown on
the HNTs-COOH through a convergent synthesis route. The modi-
fied hybrid nanoclays were characterized by different techniques.
Moreover, the practical adsorption factors with the best reaction
conditions of chromate and the mechanism of adsorption were
examined. Finally, three different models were adopted to specify
the maximum capacity of Cr(VI) adsorption on functionalized
HNTs.
2. Experimental
2.1. Materials
HNTs as the sorbent were from the Dunin Mine in Legnica,
Poland, and were purchased from the Intermark Company, Poland.
c-aminopropyltriethoxysilane (APTES), Dimethylformamide
(DMF), and succinic anhydride were supplied from Sigma-
Aldrich. Poly(amidoamine) dendritic polymer equal to second gen-
4019
eration of Poly(amidoamine) dendrimer was obtained by the
Delta-Innovative Company, Poland. Potassium dichromate
(K2Cr2O7) with ultra-pure water was purchased from Merck,
Germany.
2.2. Synthesis of HNTs-(DEN-NH2) via the convergent synthesis route
At the first, pristine HNTs were reacted with HCl (35%) at 25 °C
for 24 h under constant stirring to produce (HNTs-OH) and mean-
while to eliminate mineral impurities. Then, 5 g of dried HNTs-OH
was added to toluene (100 mL) containing 10 mL of APTES. The
suspension was refluxed at 80 °C for 12 h under constant stirring.
Next, the solid phase was separated and washed three times with
ethanol and methanol using Buchner funnel to remove the excess
organosilanes. Afterwards, 1 g of dried HNTs-NH2 was mixed with
50 mL of DMF and sonicated for 5 min. Subsequently, 1.2 g of suc-
cinic anhydride was added to the solution, which was then
refluxed and stirred at 95 °C for 20 h. Then, the solid phase was
separated and washed three times with DMF using a Buchner fun-
nel. The prepared HNTs-COOH was then dried at 60 °C for 8 h.
Finally, 1 g of HNTs-COOH was added to 250 mL of an aqueous
solution of poly(amidoamine) with a concentration of 500 mg/l.
This solution was placed for 24 h under stirring, and then the solid
phase was separated and washed with distilled water to remove
the excess poly(amidoamine). The solid adsorbent (HNTs-(DEN-
NH2)) was dried at 60 °C for 5 h.
2.3. Adsorption experiment
A chromium stock solution with a concentration of 100 mg/L
was prepared by dissolving a certain amount of K2Cr2O7 in deion-
ized water. A chromium solution with the required initial concen-
tration was obtained by diluting the chromium stock solution with
deionized water. The adsorption process was performed by adding
different adsorbent doses of 0.4, 0.6, 0.8, 1.0 and 1.2 g/L in the Cr
(VI) solution at various pH in the range of 2–7 for 60 min. For
the separation of the adsorbent, the solution was centrifuged by
Hettich EBA20 at 5000 rpm for 10 min. The standard colorimetric
method with the 1, 5-diphenylcarbazide was employed for the
absorbance measurement at the wavelength of 540 nm [39]. The
solution was then analyzed with a UV–Visible spectrophotometer
(UNICO 2100). The removal efficiency and adsorption capacity of
modified HNTs were calculated using the initial Cr(VI) concentra-
tion, C0, the Cr(VI) concentration at the time t, Ct, the mass of the
adsorbent, M (g), and the solution volume, V (L), Eqs. (1) and (2):
C0  Ct
Cr ðVIÞ Remov al ¼  100 ð1Þ
C0
ðC 0  C t ÞV
qe ¼ ð2Þ
M
2.4. Regeneration of the used HNTs-(DEN-NH2)
The reusability of HNTs-(DEN-NH2) as adsorbent were tested by
the following steps: (1) after adsorption of Cr(VI) in optimum con-
dition (pH = 3, T = 25 ◦C, adsorbent dosage 1.0 g/L), the HNTs-(DEN-
NH2) were separated from solution by a centrifuge, (2) to regener-
ate the adsorption sites, the Cr(VI) loaded onto the adsorbent
washed with ethanol for two times, (3) the washed adsorbent
was dried at room temperature, (4) the adsorption experiment
was carried out according to the section 2.3. These steps were
repeated four times.
4020 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030
2.5. Adsorbent characterizations
The transmission electron microscope (TEM) images of HNTs
were obtained with Philips CM30. A bright-field photomicrograph
was prepared to observe the morphology and determine the size of
HNTs. The surface morphology of HNTs-OH and HNTs-(DEN-NH2)
were observed with a field emission scanning electron microscope
(FE-SEM, MIRA 3-XMU). The Image J software was used to measure
the inner and outer diameter of pristine HNTs on various images.
The functional groups of pristine and functionalized HNTs were
examined by FTIR spectroscopy. The FTIR spectra of adsorbents
were measured with a Nicolet 360 spectrometer using the KBr pel-
let technique in the interval of 4000 to 400 cm1. The OMNIC soft-
ware was used to normalize all FTIR spectra. All spectra were
normalized by the Al-O-Si peak at 538 cm1 [24]. Also, the X-ray
diffraction (XRD) analysis was measured using Inel (France) with
a wavelength of 1.5418 °A, Cu-Ka radiation. The specific surface
area of adsorbents was measured with a Micromeritics BET instru-
ment (Quantachrome Autosorb iQ, USA). The mass loss of the sam-
ples was examined by thermogravimetric analysis (TGA, TA
Instruments Ltd, USA). All modified HNTs were heated from
30 °C to 800 °C at the heating rate of 10 °C/min under nitrogen
atmosphere. The f-potential charge of samples was measured
using Zetasizer (ZEN3600, Malvern, England). The XPS (the Kratos
Axis UltraDLD, USA) was used to analyze the chemical state of
the chromium element loaded onto HNTs-(DEN-NH2) after adsorp-
tion process at pH = 3 (the monochromated aluminum-Ka X rays
source at the power of 140 W). In this article, the XPS spectra were
analyzed utilizing CasaXPS software. The XPS spectra calibration
was employed using C 1s (C–C component) photoelectron with
binding energy values of 284 eV. The standard Shirley background
and Gaussian (Y%)-Lorentzian (X%) defined as GL(X), were per-
formed for background subtraction peak and de-convoluted XPS
spectra, respectively.
3. Results and discussion
3.1. Structure and morphology of unmodified and modified HNTs
The synthesis process and the structure of HNTs-(DEN-NH2) are
depicted in Scheme 1. First, pristine HNTs (washed with HCl) were
reacted through silanization via APTES to produce HNTs-NH2. Next,
HNTs-NH2 were reacted with succinic anhydride to create a car-
boxylic acid functional group on HNTs. Finally, poly(amidoamine)
dendritic polymer was attached onto HNTs-COOH through conver-
gent synthesis route. Scheme 1 is presented based on the following
observation and arguments.
The TEM and FE-SEM images of pristine HNTs and functional-
ized HNTs are depicted in Fig. 1. Pristine HNTs had a cylindrical
shape with a hollow open-ended tubular structure, which is
observable in the TEM image. The internal and external diameter
of pristine HNTs was in the range of 20–30 nm and 100–120 nm,
respectively. The FE-SEM image of HNTs-(DEN-NH2) compared to
that of pristine HNTs showed that the morphology of functional-
ized HNTs did not change significantly.
The FTIR spectra of modified samples are displayed in Fig. 2a.
The bands at 3697 and 3625 cm1 were ascribed to –OH stretching
vibration [40]. The peak at 913 cm1 was attributed to the stretch-
ing vibration of Al-OH [41]. The bending vibration peak at 468, 536,
1030 cm1 was related to Si-O-Si and Al-O-Si, Si-O stretching
vibration, respectively [24]. After the modification of HNTs with
APTES, some new FTIR peaks appeared at 2930, 1560, and
1490 cm1 related to the stretching vibration of –CH2, the bending
vibration of –NH2, and the bending vibration of –CH2, respectively.
The broad peak of the –OH band of water led to overlap with –OH
and –NH2 stretching vibration at 3360 cm1[26]. In the FTIR spec-
trum of HNTs-COOH, three new strong bands located at1410, 1650
and 1698 cm1 were related to stretching vibration of C-O, amide
and carboxylic acid groups, respectively. HNTs-(DEN-NH2)
revealed some new peaks in FTIR spectra. The bands at
1653 cm1 and 1560 cm1 were assigned to amide and bending
secondary amine-terminated groups, respectively [24,26]. Based
on these results, poly(amidoamine) dendritic polymer were syn-
thesized on the HNTs surface successfully.
The surface area of adsorbents is an important parameter that
influenced on adsorption process [42]. The specific surface areas
of HNTs and HNTs-(DEN-NH2) were 70 m2/g and 75 m2/g, respec-
tively. The presence of the hollow interior dendritic polymer
between branches in poly(amidoamine) could lead to an increase
in the specific surface area, indicating that the dendritic structure
was loaded at the external surface of HNTs.
The TGA curves of modified samples are shown in Fig. 2b. The
HNTs-OH curve reveals mass loss in two temperature regions.
The first region in the range of 50–150 °C is related to the physical
removal of adsorbed water from the structure of HNTs [20]. The
second region of mass loss occurring in the range of 400–600 °C
is related to the dehydroxylation of Al-OH groups on the external
and internal surface of HNTs [26]. According to the FTIR spectra
shown in Fig. 2a, the presence of water was confirmed in the hal-
loysite structure. For samples modified with APTES (HNTs-NH2),
the mass loss region in the range of 250–350 °C corresponding to
the thermal decomposition of silane bonded or silane groups
oligomerized with Al-OH and Si-OH. The modified sample with
APTES in the temperature range of 600–800 °C has a higher mass
loss than HNTs-OH, which indicated the replacement of hydroxyl
groups with ethoxy groups of APTES. The increasing weight loss
percentage of HNTs-COOH compared to HNTs-NH2 indicate the
reaction of the silane groups with carboxylic acid groups [43].
The gradual thermal decomposition of HNTs-(DEN-NH2) in a wide
range indicates various types of organic chemicals on the surface of
HNTs. The increasing weight loss percentage of HNTs-(DEN-NH2)
compared to HNTs-OH indicates the reaction of the dendritic poly-
mer with an active group on the surface of HNTs. Analysis of TGA
curve HNTs-(DEN-NH2) illustrates that an increase in the weight
loss of the functionalized HNTs-(DEN-NH2) may be related to the
remainder of the dendritic structure burnt residue. Also, after func-
tionalization HNTs via dendritic structure, the thermal stability of
HNTs-(DEN-NH2) was increased, this result is in agreement with
another report [44].
The main reflection of HNTs at 2h = 12.5°in the XRD pattern cor-
responds to an interlayer distance of 7.04 Å (dehydrated form)
(Fig. 2c.) [30]. Compared to the diffraction pattern of HNTs-(DEN-
NH2), the diffraction peak at 2h = 12.5° indicates that the interlayer
distance does not change after the functionalization of HNTs by
organic materials (7.07 Å). The result shows that the XRD patterns
of all the adsorbents are very similar. The functionalization of hal-
loysite by poly(amidoamine) does not affect its crystalline struc-
ture. According to the result, the active sites between interlayer
spaces for grafting organic material were unavailable because of
the hydrogen bonds between the interlayers [45].
The surface charges of absorbent are a very important issue in
adsorption efficiency. The f-potential charge of HNTs-OH, HNTs-
NH2, HNTs-COOH and HNTs-(DEN-NH2) at pH = 6.8 are illustrated
in Fig. 2d. The f-potential for HNTs-OH was about 8 mV due to
the outer hydroxyl groups and siloxane groups located at the sur-
face of HNTs. The f-potential for HNTs-NH2, HNTs-COOH and
HNTs-(DEN-NH2) with measured values of 3.58, 27.13, and
4.52 mV in this pH.
The wide scan XPS spectra of HNTs-OH, HNTs-NH2, HNTs-
COOH, and HNTs-(DEN-NH2) are shown in Fig. 3 a. In the survey
XPS spectrum of HNTs-OH, the index peaks of aluminum, silicon,
 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030 4021

Scheme 1. The possible synthesis routes of HNTs-(DEN-NH2).

Fig 1. (a) The TEM image of pristine HNTs; the FE-SEM image of (b) pristine HNTs, (c) HNTs-(DEN-NH2).

and oxygen were appeared based on the chemical structure of
HNTs. The peaks of nitrogen and carbon were also detected that
considered as contaminations which occur during sample prepara-
tion [46]. As can be seen, the intensity peak of nitrogen increases
during functionalization HNTs with poly(amidoamine) dendritic
groups. The atomic concentration percentages of modified samples
are shown in Fig. 3b. The results show that after the functionaliza-
tion of HNTs by silane coupling agent, the Si/Al ratio increased
from 1.47 to 2.06 in comparison to HNTs-OH. Also, the elemental
percentage of nitrogen and carbon increases while oxygen
decreases during this functionalization, which is an indication
the surface of HNTs fully covered with silane agent. The oxygen
and carbon concentration in the HNTs-COOH increases, because
of the grafting carboxylic acid onto the HNTs-NH2. The C/N ratio
was determined to be 7.6, 13.68, and 6.59 for HNTs-NH2, HNTs-
COOH, and HNTs-(DEN-NH2) samples, respectively. As a result,
more amine-terminated dendritic groups from poly(amidoamine)
grafted onto the surface of HNTs. In the O 1s spectra of HNTs-OH
(Fig. 3 c.), two chemical states of oxygen were founded. The peaks
at a binding energy of 530.78 and 533.22 eV correspond to Al-O
and Si-O species related to the HNTs structure. The O 1s spectra
of the HNTs-COOH (Fig. 3 d.), were fitted into three components
at 530.14, 533.40, and 534.17 eV, which were related to O-C=O,
C=O, and C-OH, respectively. The O 1s spectra of the HNTs-(DEN-
NH2) (Fig. 3e.) were fitted into two species. The peaks at the bind-
ing energy of 530.14 and 532.40 eV related to O-C=O, C=O spices
[4]. There is an O-C=O peak in the O 1s of spectra HNTs-(DEN-
NH2) that displays a lower fraction of unreacted carboxylic acid.
The XPS C 1s spectra of the HNTs-COOH (Fig. 3f.) showed peaks
at 282.95, 284.00, 286.50 and 288.9 eV, which are corresponded
to the C-Si, C-C, C-O, and O-C=O, respectively. The C 1s spectra of
HNTs-(DEN-NH2) (Fig. 3 g.) can be fitted into three components
at the binding energy of 284, 285.24, and 287.21 eV corresponded
to the C-C, C-N, and C=O, which were ascribed to the grafting poly
(amidoamine) onto the surface of HNTs. The N1s spectra of HNTs-
(DEN-NH2) (Fig. 3h.) display three chemical state of nitrogen onto
the surface of HNTs consistent with the result of C 1s and O 1s. The
peaks at the binding energy of 398.90, 400.20 and 401.40 eV orig-
inated from poly(amidoamine) structure. The –NH2/NH+3 peak is
related to either reaction of amine end groups that lead to the
4022 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030
Fig 2. (a) The FTIR spectra, (b) the TGA curves, (c) XRD pattern, and (d) the f-potential diagram of HNTs-OH, HNTs-NH2, HNTs-COOH and HNTs-(DEN-NH2).
hydrogen-bonded and subsequently closed geometric structure
[47]. The obtained results from FTIR, TGA, f-potential and XPS
strongly prove the successful grafting of silane agent, carboxylic
groups and amine-terminated dendritic polymer onto the surface
of HNTs.
3.2. Adsorption process
3.2.1. The influence of pH on adsorption
The pH of the initial solution affects the specification of the Cr
(VI) ion, surface charge, and the amount of protonation/deprotona-
tion of functional groups on the amine-terminated dendritic struc-
ture [48–50]. The effect of pH on Cr(VI) ion removal was
investigated at four pH (2, 3, 5, and 7) with the constant concentra-
tion (5 mg/L), constant adsorbent dosage (0.8 g/L). Other factors,
such as contact time and temperature, were kept fixed. Moreover,
chromate has many forms at different pH such as H2CrO4, HCrO 4,
CrO4 2, and Cr2O2 7 [51]. For pH in the range of 2 to 6, the species
are HCrO 2-
4 (major form) and Cr2O7 in equilibrium. By increasing
pH, the species cause shifting to CrO2 4 . When pH is below two,
HCrO4 and Cr2O2 7 can change into H2Cr2O7, which in turn, can
reduce electrostatic interaction [52]. When the pH of the aqueous
solution is changed, the existing prevailing forms of Cr(VI) have an
impact on the amount of the Cr(VI) uptake [53]. Not only chro-
mium ions differ in various pH, but also the poly(amidoamine) is
sensitive to change in pH. When pH is below four, amine groups
of HNTs-(DEN-NH2) are protonated. At pH values over four, an
increase occurs in the electron density by deprotonation of tertiary
and primary amine functional groups [54,55]. The result of the pH
effect on Cr(VI) removal is shown in Fig. 4 a. The high removal effi-
ciency about 90% was obtained for modified HNTs with the poly
(amidoamine) at pH = 3. At this pH, the amino groups of
HNTs-(DEN-NH2) and HNTs-NH2 were protonated via cationic
forms (–NH3+). As a result of this protonation, more interaction
occurred between HCrO-4 and amine groups. At pH below three,
CrO2- 2
4 and Cr2O7 ions can be converted to H2Cr2O7 [51]. According
to the zeta potential values, HNTs-(DEN-NH2) is positively charged
at natural pH value, whereas HNTs-COOH is negatively charged at
this pH. Accordingly, the electrostatic forces between the adsor-
bent and Cr(VI) decrease, which leads to low Cr(VI) adsorption
by HNTs-(DEN-NH2). With the increase of pH and the subsequent
increase in the concentration of OH– ions, the competition of OH–
ions with the CrO2-4 ion increases for adsorption onto the adsorbent
surface. This leads to a decrease in Cr(VI) adsorption at higher pH.
Finally, the repulsion force between the major form of Cr(VI) and
HNTs-COOH leads to a decrease in the percent removal of Cr(VI),
at lower pH. All of the above results were in agreement with the
zeta potential results.
3.2.2. The impact of contact time on adsorption
The kinetic curve for Cr(VI) reveals that the adsorption rate is
fast, and reach a plateau or adsorption equilibrium time after
10 min (Fig. 4 b.). At the initial stage of contact time, there are
more functional groups available, and then by increasing adsorp-
tion time, the vacant adsorption sites will be less accessible. This
is because the vacant adsorption sites were covered with Cr(VI)
during contact time. The high specific surface areas of HNTs-
(DEN-NH2) are generally correlated to a large number of adsorp-
tion sites and subsequently more adsorption capacity. Thus, the
enhancement removal for HNTs-(DEN-NH2) is partially related to
higher specific surface areas due to the presence of the hollow inte-
rior dendritic polymer between branches. On the other hand, the
 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030 4023

Fig 3. (a) The wide scan XPS spectra of HNTs-OH, HNTs-NH2, HNTs-COOH and HNTs-(DEN-NH2), (b) atomic concentration percentages of modified samples, (c) O 1s spectra of
HNTs-OH, (d) O 1s spectra of HNTs-COOH, (e) O 1s spectra of HNTs-(DEN-NH2), (f) C 1s spectra of HNTs-COOH, (g) C 1s spectra of HNTs-(DEN-NH2), and (h) N 1s spectra of
HNTs-(DEN-NH2).
4024 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030
Fig 4. (a) The effect of pH for Cr(VI) removal on modified adsorbents, (b) the effect of contact time on adsorption Cr(VI) with HNTs-(DEN-NH2), (c) the effect of HNTs-(DEN-
NH2) adsorbent dosage, and (d) the effect of initial concentration on HNTs-(DEN-NH2).
better removal efficiency for HNTs-(DEN-NH2) is related to the
higher zeta potential and specific surface areas, which leads to
the better interaction between HNTs-(DEN-NH2) and Cr(VI).
3.2.3. The effect of adsorbent dosage on adsorption
The amount of adsorbent is a vital parameter in the adsorption
process that influences the determination of the amount of pollu-
tant removal and adsorbent capacity. The effect of the adsorbent
dosage on the removal of Cr(VI) and the adsorbent capacity (qe)
is illustrated in Fig. 4 c. The results revealed that the removal of
Cr(VI) increased from 84% to 98% by increasing the concentration
of the adsorbent from 0.4 g/L to 1.2 g/L, while the adsorbent capac-
ity was reduced from 25.8 mg/g to 10.3 mg/g. This could be related
to an increase in accessible adsorption sites (number of available
amine-terminated groups), leading to an increase in removal. Since
all adsorption sites are saturated, the adsorbent capacity is reduced
gradually. It is worth mentioning that the percentage of Cr(VI) ion
removal for un-functionalized HNTs (HNTs-OH) was only 23% at
optimum conditions, while it increased to 98% for HNTs-(DEN-
NH2). Based on experimental results, the optimum adsorbent
dosage was determined as 1 g/L for adsorption Cr(VI) ion by the
HNTs-(DEN-NH2).
3.2.4. The effect of initial Cr(VI) concentration
The initial concentration of Cr(VI) is another factor affecting
adsorption capacity. The amount of Cr(VI) adsorption onto
HNTs-(DEN-NH2) in various concentrations of chromium ranging
from 3 to 11 mg/L at pH = 3 was examined while keeping all other
factors constant. The effect of the Cr(VI) concentration on the
removal efficiency and the adsorbent capacity is indicated in
Fig. 4 d. The removal efficiency and adsorbent capacity of
HNTs-(DEN-NH2) were calculated using Eqs. (1) and (2), respec-
tively. As the chromium concentration increased from 3 to
11 mg/L, the removal of HNTs-(DEN-NH2) decreased from 98.8%
to 60.5%. By increasing the chromium ion concentration, the
amount of chromium adsorbed per unit mass of the adsorbent sur-
face increased. This phenomenon can be described as the driving
force required to transfer the mass between the solution and the
adsorbent surface increases at higher chromium ion concentration,
which subsequently leads to an increase in the adsorbent capacity.
3.2.5. Mechanisms of Cr(VI) removal
The XPS analysis of HNTs-(DEN-NH2) after Cr(VI) adsorption
was performed for a better understanding of the Cr(VI) removal
mechanism. The XPS spectrum of Cr 2p (Fig. 5 a.) is used to specify
the chemical state of the chromium element. The specific binding
energy peak position of Cr 2p was fitted into two species at
580.8 and 589.5 eV, which are attributed to Cr(VI) [56]. This result
indicates that the primary adsorption mechanism for Cr(VI) is
based on electrostatic attraction among negatively charged HCrO-4

(a dominant form of chromium at pH = 3) and protonated amine
end groups.
The FTIR spectrum of HNTs-(DEN-NH2) after Cr(VI) adsorption
is shown in Fig. 4 b. The poly(amidoamine) dendritic polymer onto
the adsorbent surface is the critical parameter to realize the com-
plexation of functional groups (amine-terminated) with metal ions
[57]. The vibration peak of carbonyl was weakened and changed
from 1698 cm1 to 1696 cm1. The peak at 1547 cm1 was
assigned to the bending vibration of –NH2, which slightly shifted
from 1547 to 1553 cm1. After Cr(VI) adsorption, the peak at
1647 cm1, corresponding to amide groups, was shifted to
1653 cm1. This shift may be assigned to the interaction of
 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030 4025

Fig 5. (a) The high-resolution XPS of adsorbed Cr(VI) on HNTs-(DEN-NH2); (b) the FTIR spectrum of HNTs-(DEN-NH2) after Cr(VI) adsorption.

nitrogen from amine terminated dendritic groups and Cr(VI)
through electron sharing between amine groups in poly(ami-
doamine) dendritic polymer and Cr(VI) [57]. The synthesis of
poly(amidoamine) onto the surface of HNTs provides active sites
for Cr(VI) adsorption due to the complexation of –NH2 with Cr
(VI). Scheme 2 shows the mechanism for the removal of Cr(VI)
by HNTs-(DEN-NH2).
3.2.6. Comparison with other adsorbents
The results of the comparison between our modified halloysite
with other modified and unmodified mineral clay for Cr(VI)
adsorption are shown in Table 1. According to Table 1, the values
of the maximum adsorption capacity differ from 0.1 to 30 mg/g,
and our functionalization is in this range. HNTs-(DEN-NH2) has
excellent adsorption capacity compared to other adsorbents such
as boehmite, acid-activated kaolinite, HNTs-HDTMA, and Micelle-
Clay.
3.3. Adsorption isotherm
The equilibrium analysis by various models such as Langmuir,
Freundlich, and Temkin is determined to describe Cr(VI) adsorp-
tion onto HNTs-(DEN-NH2). The monolayer adsorption defines
the Langmuir adsorption, and all adsorption sites have equal
energy for adsorption [63]. The adsorption isotherm constants
are determined from corresponding parameters of the linear
regression equation. The constants and the correlation coefficient
are shown in Table 2. The high correlation coefficient demonstrates
that Cr(VI) adsorption onto HNTs-(DEN-NH2) follows the Langmuir
model (Fig. 6 a.). Here, Qm represents the adsorption capacity. The

Scheme 2. The Cr(VI) removal mechanism by HNTs-(DEN-NH2) at different pH.

4026 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030

Table 1
The comparison between our modified halloysite and other methods for Cr(VI) removal.

Adsorbent Adsorption capacity, Qm (mg/g) Initial concentration (mg/L) Optimum pH ref

Fe3O4/HNTs@C 30 25 2 [58]
Mt (DA-Al-Mt) 1.6 20 6 [59]
Micelle-Clay 9.43 50 2 [60]
HNTs-HDTMA 2.5 25 3 [27]
Boehmite 0.214 – 5.5 [61]
Acid activated kaolinite 13.9 50 4.6 [62]
HNTs-(DEN-NH2) 23.64 11 3 present work

Table 2
Isotherm parameters for Cr(VI) adsorption onto HNTs-(DEN-NH2).

Meaning of the parameters Parameters Linear equation Adsorption

isotherm
models
qt and qe(mg/g): adsorption quantity toward Cr(VI) at time t and equilibrium.Qm: maximum Qm (mg/g)23.64KL (L/mg) Ce
¼ K L1Q m þ QCme RL ¼ 1þK1L C 0 Langmuir
qe
capacity of adsorbents.C0 (mg): initial concentration of Cr(VI).Ct and Ce (mg/L): 3.22RL0.0938–0.0274R20.999
concentration of Cr(VI) at time t and equilibrium. KF (mg11/n
L1/n
g1) logqe ¼ logK F þ log 1n C e Freundlich
16.33n3.78R20.861
B3.68KT(L/mg)1.31R20.915 qe ¼ BlnK T þ BlnC e Temkin
Adsorption Linear equation Parameters Meaning of the parameters
isotherm
models
Langmuir Ce
¼ K L1Q m þ QCme RL ¼ 1þK1L C 0 Qm (mg/g)23.64KL (L/mg) qt and qe(mg/g): adsorption quantity toward Cr(VI) at time t and equilibrium.Qm: maximum
qe
3.22RL0.0938–0.0274R20.999 capacity of adsorbents.C0 (mg): initial concentration of Cr(VI).Ct and Ce (mg/L): concentration
Freundlich logqe ¼ logK F þ log 1n C e KF (mg11/n
L1/n
g1) of Cr(VI) at time t and equilibrium.
16.33n3.78R20.861
Temkin qe ¼ BlnK T þ BlnC e B3.68KT(L/mg)1.31R20.915

Fig 6. (a) Adsorption isotherm of Cr(VI) onto HNTs- (DEN-NH2), (b) pseudo-second-order adsorption kinetics of Cr(VI) onto HNTs- (DEN-NH2).

maximum adsorption capacity (Qm) of HNTs-(DEN-NH2) is 23.64.
The result shows that the Cr(VI) adsorption onto HNTs-(DEN-
NH2) follows the monolayer adsorption format. Although the num-
ber of available amine groups located at the surface of HNTs is
high, the strong electrostatic force is needed to overcome dendritic
boxes in the de Gennes dense-packed state [38]. Therefore, Cr(VI)
adsorption onto HNTs-(DEN-NH2) follows the Langmuir model.
Moreover, the dimensionless constant (RL) was calculated to con-
firm the favorability of the Cr(VI) adsorption process. Table 2 also
demonstrates the values of RL between 0.0938 and 0.0274 for Cr
(VI) adsorption onto HNTs-(DEN-NH2), which represent favorable
adsorption.
The correlation coefficient (R2 value) of the Freundlich model
for Cr(VI) adsorption was 0.861, indicating that the adsorption of
HNTs-(DEN-NH2) is not well fitted to the Freundlich equation.
The results demonstrate that the adsorption of HNTs-(DEN-NH2)
does not well fit the Temkin model with R2 of 0.915. The values
of Temkin constants are given in Table 2.
Moreover, the results show that Cr(VI) adsorption onto HNTs-
(DEN-NH2) with the highest R2 follows the Langmuir model. It
was expected that Cr(VI) adsorption, due to the presence of free
space between branches of poly(amidoamine) (heterogeneous sur-
face), would follow Freundlich isotherm. In amine-terminated den-
dritic polymers, the hydrogen bonds were found in low and high
generation dendrimer, which lead to the intermolecular back fold-
ing for each generation. In the lower generations, the back folding
phenomenon cannot be ignored, but the dendrimer structure is
certainly open and allows significant penetration of host–guest
molecules into the interior branches (heterogeneous surface). At
the higher generations, back folding can have more influence on
the structure of dendrimer and lead to barrier penetration of
host–guest molecules [64]. According to the N 1s XPS results, the
 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030 4027

Table 3
Kinetic parameters for adsorption Cr(VI) onto HNTs-(DEN-NH2).

qe,Exp(mg/g) Pseudo-first order kinetic Pseudo-second order kinetic

k1
logðqe  qt Þ ¼ logqe  2:303 t t
qt¼ k 1q2 þ q1 t
2 e e

C0(mg/L) qe(mg/g) K1(min1) R2 qe(mg/g) K2(g/mg min) R2

Cr (VI) 3 9.92 1.52 0.1312 0.958 11.23 0.0890 0.999
5 15.17 1.09 0.2111 0.874 15.69 0.2760 0.986
7 19.76 1.04 0.5359 0.822 19.80 0.4554 1.000
9 20.87 1.15 0.8030 0.941 21.37 0. 4056 1.000
11 22.09 1.12 0.1254 0.926 22.27 0.1055 0.999

Fig 7. (a) The effect of temperature on adsorption Cr(VI) with HNTs-(DEN-NH2), (b) Van’t Hoff plots of adsorption Cr(VI) onto HNTs-(DEN-NH2).

observation –NH2/NH+3 peak is related to either reaction of amine
end groups that lead to the hydrogen-bonded and subsequently
closed geometric structure. On the other hand, the interaction
between terminated groups leads to dense shell around of den-
drimer structure, as explained by the de Gennes dense-packed state.
According to the results, the formation of dense shells around
abounded poly(amidoamine) causes the Cr(VI) adsorption onto
HNTs-(DEN-NH2) to follow the monolayer adsorption fitted by
the Langmuir model.
Hence, the pseudo-second-order model was appropriate for
adsorption Cr(VI) by HNTs-(DEN-NH2). The results suggest that
the rate-limiting factor is controlled by chemical adsorption
through electron sharing or transfer between amine groups in
poly(amidoamine) dendritic polymer and Cr(VI). The increase of
initial chromium ion concentration results in the rise of adsorption
capacity (qe), indicating the strong driving force and mass transfer
between the solution and the adsorbent surface at higher chro-
mium ion concentration.

3.4. Adsorption kinetics

The adsorption kinetics were performed to describe the
adsorption mechanism and the adsorption rate of Cr(VI) by the
HNTs-(DEN-NH2). In our work, the kinetics models at different
adsorption stages were investigated in terms of the pseudo-first-
order and pseudo-second-order model. The pseudo-first-order
kinetic model is based on the assumption as follows: the occupa-
tion of the majority of the active sites is proportional to the num-
ber of unoccupied active sites [65]. Pseudo-second-order kinetic
model shows that the rate-limiting factor is controlled by chemical
adsorption, which includes valence forces through electron sharing
or transfer between adsorbate and adsorbent [66]. The applicabil-
ity of models with the fitted plots and parameters of each model
for Cr(VI) and the Equations of both models are presented in
Table 3. Fig. 6 b. shows that at different adsorption stages, the
pseudo-second-order model well better fitted with experiment
adsorption data due to the higher correlation coefficients (R2) val-
ues. The adsorption capacity value (qe), which is determined the
adsorption quantity at equilibrium time. Moreover, the experimen-
tal adsorbent capacity value (qe,Exp) is in better agreement with
the adsorbent capacity value (qe) acquired by the pseudo-
second-order model than those of the pseudo-first-order model.
3.5. Thermodynamic studies
The spontaneity nature and inherent energy change of the
adsorption process were investigated by adsorption thermody-
namics. The adsorption thermodynamic experiments were carried
out at 25 ◦C, 35 ◦C, 45 ◦C and 55 ◦C to investigate the temperature
effect on Cr(VI) removal (Fig. 7 a.). According to the results by
increasing temperature from 25 ◦C to 55 ◦C adsorption Cr(VI) onto
HNTs-(DEN-NH2) decreased from 92% to 70%. The thermodynamic
parameters of adsorption Cr(VI) are presented in Table 4. Thermo-
dynamic constants comprising standard Gibbs free energy (DG°),
standard enthalpy (DH°), and standard entropy (DS°) were calcu-
lated by the van’t Hoff equation (Fig. 7b.). The DG° value changed
2.18 to 3.18 with increasing temperature from 25 ◦C to 55 ◦C.
The negative value of DG° shows that the adsorption Cr(VI) by
HNTs-(DEN-NH2) is spontaneous. The negative values of DH° and
DS° confirm that the adsorption process of Cr(VI) onto HNTs-
(DEN-NH2) were exothermic nature and the decreased randomness
during the adsorption process. The results of adsorption Cr(VI) by
HNTs-(DEN-NH2) confirmed that the amine-terminated dendritic
groups are well located onto the surface of the adsorbent, which
confirms the results of other parts.
4028 M.H. Kanani-Jazi et al. / Advanced Powder Technology 31 (2020) 4018–4030
Table 4
Thermodynamic parameters of adsorption Cr(VI) onto HNTs-(DEN-NH2).
Linear equation T (K)
   
Cr(VI) DS
log Cqee ¼ 2:303R DH
þ 2:303RT 298
  
DG ¼ DH  T DS 308
318
328
Fig. 8. The regeneration ability of HNTs-(DEN-NH2) in four-cycle adsorption.
3.6. Regeneration of HNTs-(DEN-NH2)
The removal efficiency of Cr(VI) with HNTs-(DEN-NH2) after
four adsorption–desorption cycles are illustrated in Fig. 8. After
the first adsorption process cycle, the removal efficiency was about
99%. The HNTs-(DEN-NH2) can maintain removal Cr(VI) about 82%
after three consecutive cycles. This value decreased to 63% after,
the fourth cycle adsorption. The decreased in Cr(VI) removal effi-
ciency may be related to the blocked active site that presence in
the surface of HNTs during the adsorption process. The new hybrid
nanomaterial is applicable for effective adsorption of Cr(VI) and
regeneration for reused.
4. Conclusions
Amine-terminated functionalized HNTs with a carboxylic acid
group (HNTs-COOH) as a linkage between halloysite and poly(ami-
doamine) dendritic materials via a convergent route were success-
fully employed as the sorbent for Cr(VI) ions. Moreover, the
adsorption ability of the new adsorbent (HNTs-(DEN-NH2)) was
studied at optimum conditions. The results were summarized as
follows:
(I) The FTIR, TGA, XRD, and XPS results confirmed the presence
of the carboxylic acid group and amine-terminated dendritic
structure functionalization in the structure of HNTs.
(II) After functionalization HNTs by poly(amidoamine) dendritic
groups, the specific surface area (75 m2/g) and f-potential
charge (4.52 mV) were enhancement due to the presence
of the hollow interior dendritic polymer between branches
and increase number of amino groups onto the surface,
respectively.
DG(kJ mol1) DH(kJ mol1) DS(kJ mol1 K1)
2.89 46.650 0.152
2.99
3.09
3.18
(III) The adsorption isotherm study of functionalized HNTs-
(DEN-NH2) was fitted to the Langmuir isotherm due to the
formation of dendritic boxes explained by de Gennes dense-
packed state, leading to the monolayer adsorption.
(IV) The adsorption ability of amino terminated dendritic
polymer-functionalized HNTs-(DEN-NH2) toward Cr(VI)
was significantly higher than that of pristine HNTs and other
functionalized HNTs reported in this work. Moreover, the
improvement in Cr(VI) removal from 23% for pristine hal-
loysite to 98% for the amine-terminated dendritic polymer
was revealed at pH = 3.
(V) The Cr(VI) removal mechanism over HNTs-(DEN-NH2) by
XPS and FTIR was properly investigated. The results indi-
cated that the poly(amidoamine) structure synthesis onto
the surface of HNTs provided active sites to Cr(VI) adsorp-
tion by the electrostatic attraction between negatively
charged HCrO 4 and the protonated amino groups.
(VI) According to the regeneration studies, the new hybrid nan-
oclay can maintain removal Cr(VI) with high efficiency after
four consecutive cycles. Thus, the modified adsorbent has
excellent potential for application in real wastewater for
low concentrations of heavy metal ions.
Declaration of Competing Interest
The authors declared that there is no conflict of interest.
Acknowledgements
We gratefully acknowledge Functional Fibrous Structures &
Environmental Enhancement Excellence (FFSEE) Center, Amirkabir
University of Technology, Textile Engineering Department for the
partial financial support. Many thanks to Dr. E. Pajootan for her
cooperation in functionalization of HNTs.
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