Journal of Molecular Liquids 360 (2022) 119407

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Journal of Molecular Liquids

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

Designing of hydroxyl terminated triazine-based dendritic polymer/

halloysite nanotube as an efficient nano-adsorbent for the rapid removal
of Pb(II) from aqueous media
Elham Zandi-Mehri a, Lobat Taghavi b, Farid Moeinpour c,⇑, Iman Khosravi d, Saber Ghasemi c,e
a
Department of Environment, Qeshm Branch, Islamic Azad University, Qeshm, Iran
b
Department of Natural Resources and Environment, Science and Research Branch, Islamic Azad University, Tehran, Iran
c
Department of Chemistry, Bandar Abbas Branch, Islamic Azad University, Bandar Abbas, Iran
d
Department of Chemistry, Qeshm Branch, Islamic Azad University, Qeshm, Iran
e
Marine Environmental Research Center, Bandar Abbas Branch, Islamic Azad University, Bandar Abbas, Iran

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

Article history: In the present study, the hydroxyl terminated triazine-based dendritic polymer was synthesized and
Received 13 March 2022 grown on the halloysite nanotubes surface (HNT-G2) to efficiently remove the Pb(II) ions from aqueous
Revised 4 May 2022 solution. The nano-adsorbent morphology and structure were determined through TEM (transmission
Accepted 13 May 2022
electron microscope), XRD (X-ray diffraction), FT-IR (Fourier transformation infra-red), TGA (thermo-
Available online 22 May 2022
gravimetry analysis), BET (Brunauer-Emmet-Teller) isotherm, and EDS (energy dispersive analysis
X-ray spectroscopy) methods. The adsorption of Pb(II) resulted a maximum of 75.2 mg/g at 298 K at opti-
Keywords:
mal pH 6 after only 10 min and 2 g/L of HNT-G2. The adsorption kinetic revealed that it followed the
Dendrimer
Halloysite
pseudo-second-order model while the adsorption isotherms corresponded the Langmuir model.
Adsorption Accordingly, it could be inferred that the Pb(II) was a single-layer adsorption occurring on the adsorbent
Pb(II) surface and further, the rate-controlling step was denoted chemical adsorption. Also, the thermodynamic
Triazine outcome indicated that the adsorption progress could happen spontaneously, and was of the exothermic
reaction types (DH =
79.99 kJ/mol and DG =
7.90 kJ/mol). Surprisingly, the adsorption and desorption
efficiency after four cycles was high, while the Pb(II) adsorption mechanism affecting the adsorbent was
basically via chelation through the O atoms. Hence, it can be concluded that the HNT-G2 was an effective
in efficiently elimination of Pb(II) from the aqueous solution, having high applicability significance.
Ó 2022 Elsevier B.V. All rights reserved.

1. Introduction
Heavy metals in minute amounts are vital for the overall cellu-
lar and development growth [1,2] while, in large amounts, they
could be hindering the normal growth and evolution of living spe-
cies [3,4]. As the consequence of the industrialization era, global
environmental changes have emerged, including contamination
problems [5] arising from textile, paint, and plastics industries’
wastewater as well as the spillage of petroleum-based products.
All such pollutants beside the application of pesticides, organic
pollutants, fertilizers, and heavy metals in agriculture will lead to
the adulteration of subsurface water resources [6–9]. The excess
amounts of such unwanted substances in the water will make it
inappropriate for potation, irrigation and other necessary uses
[10]. Heavy metals, owing to high mobility and toxicity, are the
⇑ Corresponding author.
E-mail address: fmoeinpour@iauba.ac.ir (F. Moeinpour).
major cause of water pollution [11–14], and because they are
non-degradable, they aggregate at various trophic levels of human
body and exhibit harmful effects, endangering human health [15–
16]. Lead and lead compounds are highly toxic and medically are
very carcinogenic [3,17]. As a naturally occurring metal, it can take
the form of a mineral such as PbS, PbCO3, etc., while pesticides, cell
phone batteries and petroleum-based products are the main
sources of lead. Also, lead contamination due to different industrial
activities such as: phosphate fertilizer, electronics, automobile
emissions, leaded glass, pigments, etc is considered as the main
cause and major source of worldwide concern in the last few dec-
ades [18,19]. The lead occurring in various oxidation forms includ-
ing Pb(0), Pb(I), Pb(II) and Pb(III), essentially impacts the
gastrointestinal tract, lungs, central nervous system and kidneys,
with implications differing based on the age of the individual
[20]. Thus, in case the Pb(II) concentration in potable water reaches
above 50 lg/L, the kids below six may be affected by brain damage,
reduced attention time period, hyperactivity and below normal IQ

https://doi.org/10.1016/j.molliq.2022.119407
0167-7322/Ó 2022 Elsevier B.V. All rights reserved.
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al.
[21]. Adults, however, may be subjected to decrease in fertility,
memory loss, brain tumor, insomnia and sometimes irritation
[22]. The World Health Organization has determined the max per-
missible amount of Pb(II) in potable water as equal to 10 lg/L [23].
Lead poisoned persons may develop encephalopathy leading to
abnormalities of various bodily organs and ultimately, death of
the person involved. Therefore, considering the harms and dangers
mentioned for heavy metals, it seems necessary to measure their
amounts and also to remove them from water sources [24,25].
Numerous strategies are nowadays utilized for removal of pollu-
tants from drinking water [26,27]. Adsorption, however, among
all such treatment methods, is broadly used because of its cost
effectiveness, high removal efficiency and ease of application
[28–30].
Zeolites are crystalline-hydrated aluminosilicates, which con-
tain silica, alumina, ferric oxide, magnesium, calcium, sodium
and potassium oxides. There are about 50 different types of zeolite
with various mineralogical compositions depending on their struc-
ture and Si/Al ratio [31]. Zeolites are characterized by a well-
developed specific surface area, greater than that of humus and
other fine-grain minerals known as particle or molecular sieves.
They are characterized by selective sorption properties, ion
exchanging ability and an optimal geometry of chambers and
canals within the crystals. Despite extant knowledge of the appli-
cation of zeolites in wastewater treatment, little is known about
other minerals that may enhance the process. One of them is hal-
loysite, a unique tubular nanoclay, which has attracted a growing
scientific interest [32]. Halloysite nanotube (HNT) can naturally
be found as aluminosilicate (Al2Si2O5(OH)4nH2O) rolled sheet clay
with water purification potential. The HNT inner and outer struc-
tural surface have different electro-chemical characteristics due
to their differing crystal structure [33]. The inner surface of HNT
has a greater number of –OH (Al-OH) groups with positive charge.
The outer surface, however, possesses lower number of hydroxyl
groups (Si-OH) with negative charges due to the presence of fewer
Si-OH groups (mostly Si-O-Si groups) on HNT. The O-atoms
electro-negativity thus has made the outer surface of HNT to adopt
a negative charge [34]. Due to fewer –OH groups’ concentration
and surface charging, the HNT exhibits excellent dispersibility for
binary or ternary hybrid amalgamation with polymers or some
other appropriate materials.
As large nanoscale molecules, dendrimers have a tree-like
structure, possessing many functional groups at their various ter-
minal branches [35]. Dendrimers have shown their special capabil-
ity in the treatment of cancer [36] drug delivery [37] and catalysis
operations [38].
According to the literature, using organosilanes for the HNTs
modification has proved to be an effective method of improving
the surface characteristics to load adaptable guests [39,40]. The
HNTs capability of selective surface alteration using covalent graft-
ing amine-terminated dendritic groups e.g., polymer to load or
eliminate pollutants via host-guest structure has attracted consid-
erable attention among various modification methods [41–44].
Generally, pristine HNTs can remove heavy metal ions from aque-
ous media through the mechanisms of site geometry, physical and/
or chemisorption and so on. However, application of these materi-
als as adsorbents of pollutants is limited by their low loading
capacity, less metal ion binding active-sites, and low selectivity
to specific metals. To enhance the loading capacity and the affinity
towards heavy metal ions, pristine HNTs can be functionalized
with some interesting nanomaterials and/or functional groups to
endow them with the extra mechanism of complexation [45]. Acid
treatment can lead to an increased halloysite surface area [46].
Among various functionalizations, growing dendritic structures
on HNTs is found to have a synergetic effect on adsorption capac-
ity; this may be due to the free space between branches as well as
2
Journal of Molecular Liquids 360 (2022) 119407
abundant functional groups at the exterior of dendritic structures.
Different 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 [47]. However, a lengthy procedure for function-
alization 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 [48].
In the present study, the HNTs-OH after acid-washing under-
went silinization reaction through APTES (c-aminopropyltriethoxy
silane) to yield HNTs-NH2. The obtained product was then synthe-
sized using cyanuric chloride to generate the triazine functional
group on the halloysite as the core of dendrimer construction.
Finally, the hydroxyl terminated triazine-based dendritic polymer
so produced was cultivated on the HNTs surface via a convergent
route of synthesis. The properties of altered hybrid nano clays were
identified through different methods. Additionally, the applicable
adsorption parameters together with quality Pb(II) reaction condi-
tions as well as the adsorption mechanism were considered. Ulti-
mately, three differing approaches were identified to adopt to
determine the maximum Pb(II) adsorption capacity on the func-
tionalized HNTs.
2. Experimental
2.1. Materials
HNT powder and all other materials were supplied by the US
Natural Nano Inc. and Sigma Co. respectively and deionized (D.I.)
water was used for the preparation of the reagents’ aqueous
solutions.
2.2. Synthesis of halloysite/triazine based dendrimer (HNT-G2)
Primarily, a reaction of pristine HNTs and HCl (35%) was
arranged at 25 °C for 24 h with continuous stirring to prepare
(HNTs-OH) and in the meantime the mineral impurities were
removed. Afterwards, dried HNTs-OH (5 g) and toluene (100 mL)
containing 10 mL of APTES were blended and the suspension so
prepared was refluxed at 80 °C for 12 h with continuous stirring.
Then, a separation of solid phase was made and rinsed with etha-
nol and methanol (3 times) through Buchner funnel to separate the
excess organosilanes. Next, 1.7 mL of diisopropyl ethylamine
(DIPEA) and 1.85 g cyanuric chloride, were introduced to 10 mL
THF, and 2 g of the preceding step product (HNT-APTES) was mixed
with this prepared solution and agitated for one night at room
temperature. Next, the produced solid (core) was separated
through filtration and washed with hot tetrahydrofuran and
extracted using Soxhelet device and dried via vacuuming at 50 °C
[49]. The produced solid (2 g) was mixed in bis(2-hydroxyethyl)
amine solution (0.04 mmol, 0.004 g) with 10 mL THF. The mixture
so produced was then refluxed for about 2 h and afterwards it got
cold, the solid product was filtered, rinsed with acetone and vac-
uum dried to yield generation 1(G1) dendrimer. As for producing
G1.5 dendrimer, an amount of 0.08 mmol (0.015 g) of 2,4,6-
trichloro-1,3,5-triazine was dissolved in 10 mL CH2Cl2 and kept
at 0–5 °C. Next a G1 (1 g) dendrimer mixture containing NaOH
(0.08 mmol, 0.003 g) in deionized water was introduced dropwise
to the previously made cyanuric chloride solution, while the addi-
tion was made in ice bath with continuous stirring. We agitated
the solution at the above temperature for 2 h and followed by
refluxing for another 6 h. Afterwards the filtration, a rinsing of
the solution was done using acetone and methanol and dried in
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al.
vacuum. In the end, in order to synthesize the G2 dendrimer, a
mixture of G1.5 (0.8 g) and bis(2-hydroxyethyl)amine (0.16 mmol,
0.030 g) was prepared and left to reflux for 2 h. When it was cold,
we spread it and washed it using acetone several times and this
way, G2 was obtained [50].
2.3. Adsorption studies
For the purpose of studying the adsorption of Pb(II) ions, the
batch adsorption experiments were performed via the application
of HNT-G2 nanocomposite. We kept all the factors constant, save
one, to achieve the optimum values throughout the adsorption
experiments. To do this, we put 0.2 g of HNT-G2 nanocomposite
into an Erlenmeyer 250 mL flask containing 100 mL of Pb(II) ion
solution, conc. 50 mg/L (with the exception of analyzing the
adsorption isotherm in which the C0 was maintained among 10–
600 mg/L and 50 mg/L to perform thermodynamic investigations)
for a 10 min. period (but as for the kinetic analyses, we changed
the time between 1 and 100 min.) keeping a pH 6 constant (as
for examining the pH effect, the pH was changed from 2 to 7)
and 298 K (while as for testing the temperature effect we changed
the it from 298 to 328 K). Afterwards the completion of the adsorp-
tion process, the Pb(II) ions remnant conc. in the medium solution
was specified by the use of atomic absorption spectroscopy (AAS).
The experiments were repeated 3 times and the mean values
determined. Also, the removal efficiency (%R) and the adsorption
capability of Pb(II) onto HNT-G2 nanocomposite (qe) were deter-
mined through the below calculations:
C0
Ce
% Removal ¼  100
C0
ðC0
Ce ÞV
qe ¼
m ous FT-IR spectra including core, HNT-G1, HNT-G1.5 and HNT-G2
where qe represents the equilibrium adsorption capability (mg/g);
C0 and Ce respectively denote the Pb(II) initial and equilibrium con-
centrations (mg/L) in solution; V and m respectively stand for the
solution volume (L) and adsorbing material mass (g).
The point of zero charge (pHpzc) of HNT-G2 was investigated to
determine the point where the density of electrical surface charge
of adsorbent is zero. The initial pH of 0.01 M NaCl aqueous solution
was adjusted to 3, 4, 5, 6, 7, 8, 9, 10 and 11. The initial pH (pHi) was
adjusted up to the desired value using HCl (0.1 N) and NaOH
(0.1 N) solutions. After that, 20 mg of HNT-G2 was added into
the flask containing 5 mL of aforementioned NaCl solution and
was kept it for shaking for 48 h in an air tight condition at
100 rpm and 25 °C. After 48 h of shaking, the mixture was filtered.
The final pH of decanted supernatant liquid was measured for each
set. The intersection point on the DpH curve versus pHi was con-
sidered for pHpzc determination [51].
Desorption investigations were performed using saturated
HNT-G2 nanocomposite with identical batch adsorption with the
following specifications: a 250 mL Erlenmeyer flask containing
100 mL Pb(II) ion solution (50 mg/L) was taken and 0.2 g of
HNT-G2 nanocomposite poured and shaken in it for 10 min at
298 K. The HNT-G2 was then filtered, rinsed with milli-Q water,
and dried at ambient temperature. A treatment was subsequently
made for the obtained product with 50 mL solution of 0.1 M
hydrochloric acid so as to wash Pb(II) ions from the HNT-G2
nanocomposite surface. The adsorption–desorption cycle was
repeated for 4 times to determine the HNT-G2 nanocomposite
reusability.
Journal of Molecular Liquids 360 (2022) 119407
2.4. Characterizations
A diffractometer of Philips model with Cu Ka (k = 1.54 Å) radi-
ation was used to scrutinize the nanocomposites’ crystalline phase.
Also, a TEM system equipped with a Germany made LEO 912AB
(120 kV) Zeiss electron microscope was used to describe the mor-
phologic structure of HNT-G2. The surveys of Nitrogen adsorption–
desorption isotherms were performed using a USA made Autosorb-
1 Quantachrome Sorptometer. To specify the effective surface
areas and pore size distribution, the BET procedure was imple-
mented. As for the confirmation of functionalization of the samples
as KBr pellets, the FT-IR spectra registration was made on a Bruker
spectrophotometer (model 470). The measurement of elemental
compositions was made using a 133 eV resolution EDS analysis
(model 7353, made by Oxford Instruments Co., UK). As for examin-
ing the TG, it was performed under nitrogen gas using a thermo-
gravimetric analyzer of model Netzsch- TGA 209 F1. The lead(II)
ions concentrations were determined using atomic absorption
spectrophotometer (Varian, model AA240FS). Statistical analyses
were performed using Data Analysis Toolpak Microsoft Excel for
Windows 10 with level of significance maintained at 95% for all
tests.
3. Results and discussion
3.1. HNT-G2 nano-adsorbent properties
HNT-G2 nanocomposite was fabricated using HNTs-OH, APTES,
cyanuric chloride and diethanolamine for which the Scheme 1
shows the schematic illustration.
Various structural analysis tests like FT-IR spectra, TGA, and
ð1Þ
XRD together with the morphological studies through TEM have
remarkable importance in identifying the characteristics of
nanocomposites. In this study, the favorable synthesis of HNT-G2
nanocomposite was tested using FT-IR spectra for which the vari-
ð2Þ
nanocomposites are shown in Fig. 1(a). The 911 cm
1 absorption
peak may be attributed to AlAOAOH vibration [52], whereas the
3695 and 3627 cm
1 peaks initiated via the stretch vibration of
inner-surface AlAOH groups prove the existence of HNT [53]. Also,
a definitive HNT in-plane stretching vibration seen at 1091 cm
1
and 1040 cm
1 indicated the existence of SiAOASi. Moreover,
the peaks seen at 1470 cm
1 can be ascribed to the presence of
SiAC group [54]. Also, the 3429, 2937, 795 and 687 cm
1 absorp-
tion bands could be due to AOH water stretching, ACH stretching
in methylene groups (CH2), CACl stretching and presence of
AlAOASi groups [8,50,55]. Another peak at 1630 cm
1 resulted
from the stretching of imine group (C@N), denoting the presence
of triazine ring [56]. Concerning HNT-G1, the 3400, 2960, 2853,
1645 and 1060 cm
1 absorption bands could be respectively
assigned to the stretching vibrations of OAH, ACH, C@N and
CAO chemical bonds [50]. Regarding FT-IR spectrum in HNT-
G1.5, the 2910, 1633, 1039 and 795 cm
1 absorption peaks may
be respectively ascribed to the CAH, C@N, CAO and CACl chemical
bonds’ stretching vibrations. As for HNT-G2, the comparison of
spectra of core, HNT-G1 and HNT-G1.5 and considering the
recorded peaks, the conclusion can be made that the OH, C@N,
CH and CAO bonds exist.
The TGA thermograms are represented in Fig. 1(b). The HNT-G1,
HNT-G1.5 and HNT-G2, the respective TGA plots denote a 2-step
thermal decomposition. The ignorable decrease in weight below
250 °C relates to the unwanted adsorbed water elimination, while
the major weight loss during the second step can be assigned to the
organic moieties’ removal of the surface [57]. The observed total
weight loss for HNT-G1, HNT-G1.5 and HNT-G2 are 25.28%,
3
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al.
Scheme 1. Schematic illustration of HNT-G2 nanocomposite fabrication.
44.03% and 80.17%, respectively. On the basis of these results, the
theoretical conversion is 74.2% for HNT-G1 ? HNT-G1.5 and
82.1% for HNT-G1.5 ? HNT-G2. The results are consistent with
previously published literature [58,59].
The extent of surface expanse (area) is of high importance from
the adsorption angle of view, as the higher area of surface would
cause higher capacity of adsorption. The researchers used N2
adsorption/desorption analysis method to investigate the HNT-
G2 porosity (Fig. 1(c)). As this figure illustrates, the specimen rep-
resents the H-type isotherm, denoting its mesoporous nature [60].
The area of BET surface was measured and a figure of about
85.21 m2/g was obtained. The relevant volume of pores, obtained
from the adsorption information shown in the inset of Fig. 1(c),
was about 22 nm. As an advantage, the variability of the composite
pore size and volume facilitates the HNT-G2 nanocomposite
adsorption activity.
The XRD patterns corresponding to HNTs-OH and HNT-G2 are
represented in Fig. 2a and 2b respectively. The HNTs-OH pattern
exhibiting reflections at 2h = 12.5°, 20.4°, 25.4°, 35.8°, 36.8°,
39.2° and 46.3° could best be respectively indexed to the (0 0 1),
(0 2 0), (0 0 2), (1 3 0), (1 3 1), (0 0 3) and (2 0 3), the results of which
are consistent with the JCPDS 29–1487 standard data. The main
HNTs-OH reflection of XRD pattern at 2h = 12.5° corresponds to
7.04 Å interlayer distance (dehydrated product form) [61]. The
diffraction peak at 2h = 12.5° compared with the HNT-G2 diffrac-
tion pattern, provides that the interlayer overall distance will not
vary after the HNTs-OH functionalization through organic materi-
als (7.07 Å). Hence, the halloysite functionalization via G2 will not
have any influence on its crystalline structure. The crystallite size
of the sample was estimated by the Scherrer and Williamson-
4
Journal of Molecular Liquids 360 (2022) 119407
Hull (W-H) equations. The Scherer equation is useful for the esti-
mation of the samples with a grain size below 100 nm. This equa-
tion and its parameters have illustrated in the literature [62]. The
information used for the estimation of the crystallite size for the
HNT-G2 by both models are summarized in Table S1 (see supple-
mentary data). As shown, the average size of 41.02 ± 3.8 nm was
estimated by the Scherrer equation for the composite. Eqs. (3)
and (4) show two formats for the W-H equation. This equation
shows the simultaneous effects of the size broadening and the
internal strain broadening (e or h) on the estimated crystallite size
from the XRD peaks. The first term in the right hand of this equa-
tion shows the Scherrer equation, and when no strain effect was
observed, this equation shows the pure Scherrer equation [63].
b cos h ¼ ðkk=dÞ þ ðg sin hÞ ð3Þ
b cos h k 4e sin h
¼ þ ð4Þ
k D k
The typical W-H plot for the composite is shown in Fig. 2c. From
the slope of this equation, the average crystallite size of 72 nm was
obtained for the composite. Generally, the W-H equation can eval-
uate the effects of both the crystallite size and lattice strain on the
peak broadening simultaneously. This ability causes the wide
application of this equation for the estimation of the size of crys-
tals. The width b in a diffraction peak can vary due to the change
in some instrumental factors, the crystal’s defects, the different
strains of different grains, and the crystallite size. In more cases,
there are simultaneous effects of both size and strain broadening
interactions, and hence the calculation should be done by the W-
H equation [64].
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al. Journal of Molecular Liquids 360 (2022) 119407

Fig. 1. (a) FT-IR spectra of the core, HNT-G1, HNT-G1.5 and HNT-G2, (b) TGA plot of the HNT-G1, HNT-G1.5 and HNT-G2 and (c) The N2 adsorption–desorption plot of HNT-
G2.

5
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al.
Fig. 2. XRD patterns of (a) HNTs-OH, (b) HNT-G2 and (c) the Williamson-Hall plot
constructed based on the XRD information for the estimation of the crystallite size
of HNT-G2 sample.
The pristine HNTs and HNT-G2 nanocomposite TEM illustra-
tions are provided respectively in Fig. 3a and 3b. Pristine HNTs
were observed to have a cylindrical form featuring the special
structure of a hollow open-ended tubular shape, as can be seen
in the respective TEM image. The pristine HNTs’ inner and outer
diameters lied respectively between the range 20–30 nm at mini-
mum and 100–120 nm at maximum. Also, by comparing the TEM
images of pristine HNTs and HNT-G2, it can be concluded that the
dendrimeric layer is well attached to HNT.
FESEM-EDS mapping of HNT-G2 and the relative structural ele-
ments are depicted in Fig. 4. The illustrations indicate that HNT-G2
nanocomposite possesses a uniform surface area with the elements
homogeneously distributed. On the other hand, the respective EDS
peaks of the composite’s structural elements (C, N, O, Al and Si) are
notably represented in the EDS spectra (Fig. 4).
3.2. Adsorption studies
One of the important factors for evaluating the adsorption char-
acteristics of the adsorbents is ‘adsorption equilibrium time’. In
6
Journal of Molecular Liquids 360 (2022) 119407
Fig. 3. TEM images of (a) pristine HNTs and (b) HNT-G2.
this study, the contact time impact concerning the Pb(II) ions
adsorption over the nanocomposite HNT-G2 was evaluated across
the range of 1–100 min. Fig. 5a obviously shows that the percent-
age of adsorption regarding the Pb(II) ions got better with the
increase in time from 1 to 10 min and afterwards it remained
invariable. Thus, a reaction time of 10 min will be considered for
the forthcoming experiments. In the initial 10 min, quick adsorp-
tion was observed, as the result of higher availability of functional
groups at the HNT-G2 nanocomposite surface, capable of binding
Pb(II) ions comfortably. The charge transferred on the solid–liquid
interface could be affected by the pH, and this impact could be
greater during the metal ions adsorption from an aqueous medium.
Fig. 5b shows that the Pb(II) adsorption percentage was improved
quickly from 29.8 to 99.7% by the increase of pH from 2 to 6, while
pH 6 yielded the maximum adsorption percentage. This is while
the further increase in pH (above 6) did not increase the removal
percentage. Therefore, the higher proton concentration within
the solution (with lower pH) prevents the adsorbent’s metal-
chelate complex formation. The increased adsorption with greater
pH values resulted from the increased negative charge at the HNT-
G2 nanocomposite surface, something useful for the Pb(II) adsorp-
tion due to the hydroxyl groups and nitrogen atoms that are able to
conveniently form complexes with Pb(II) ions because of the little
competition existing between the Pb(II) on the one hand and H+ on
the other hand at greater pH values. Metal hydroxide, however, can
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al. Journal of Molecular Liquids 360 (2022) 119407

Fig. 4. (a) EDS spectra of HNT-G2 and elemental mapping images of HNT-G2 for C (b), N (c), O (d), Al (e) and Si (f).

Fig. 5. Pb(II) removal utilizing HNT-G2 at various (a) times, (b) pHs, (c) HNT-G2 dosage, (d) temperatures and (e) initial concentrations of Pb(II).

be precipitated in the alkaline environment as the pH increases. At 6 preferably was selected as the optimum pH for the next experi-
pH values over 6, the adsorption investigation ceased due to Pb(II) mental tests. In order to confirm these results, the pHpzc of HNT-G2
precipitation like Pb(OH)2 or Pb(OH)-3. [65,66]. Accordingly, the pH was investigated. The pHpzc indicates the value of pH of the liquid

7
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al.
around adsorbent is zero, which the sum of surface positive and
negative charges of the adsorbent surface are balanced [67].
Fig. 5b shows the change surface charges of HNT-G2 with pHpzc
curve. The pHpzc of adsorbent was 7.2, which at this pH the surface
of adsorbent has net electrical neutrality. Accordingly, when the
pH of the solution is higher than pHpzc, the surface of adsorbent
becomes negative charge and electrostatic interaction is suitable
for adsorption of cations. On the other hand, the surface of adsorp-
tion can be neutralized when the pH value decreases from pHpzc
and the adsorption amount of cations decreases [68]. Depending
on the pH value of liquid phase, the functional groups can either
be protonated or dissociated. Accordingly, the competition
between metal ions and H+ decreases with an increase in the pH
and lead to an increase in adsorption capacity [69].
To optimize the HNT-G2 dosage, various experiments ranged
between 0.1 and 5 mg/L HNT-G2 dosages were carried out, as
depicted in the Fig. 5c. We observed during the adsorption
that by the increase in the HNT-G2 amount, the adsorption
percentage would increase as the result of greater number of
HNT-G2 binding sites the Pb(II) ion would have. As can be
seen from Fig. 5c, some 98.0% of Pb(II) ions were removed
via the use of only 2 g/L of HNT-G2; further increase of the
dosage was proved to produce no considerable effect on the
removal percentage of Pb(II) ions. According to the literature,
similar results have been reported regarding the Pb(II) ions
adsorption [30,70].
As a crucial factor, temperature plays a significant role in
adsorption chemical reactions. In this study, the researchers varied
the temperature in the range 298 K to 328 K via maintaining other
factors constant (i.e., Co
50 mg/L; pH-6; contacting time-10 mins
and the adsorbent dosage
2 g/L). As Fig. 5d illustrates, the Pb(II)
removal percentage by the use of HNT-G2 nano-adsorbent
decreased from 97.5 to 70.1% by the increase in the temperature
from 298 K to 328 K. Results showed that 298 K was the optimal
temperature, which was similar to the reports by other previously
undertaken studies [71,72].
The Pb(II) ions adsorption through HNT-G2 nano-adsorbent was
declined from 99.92 to 24.84% by the increase in the Pb(II) concen-
tration from 10 to 600 mg/L (Fig. 5e) which could be the result of
lower accessibility to the groups at the surface of HNT-G2 nano-
adsorbent at higher Pb(II) ions concentrations.
3.3. Adsorption modeling
In this study, the experimental equilibrium information for the
adsorption of lead by HNT-G2 nanocomposite were considered
through the implementation of Freundlich, Temkin and Langmuir
isotherms. The isotherms’ linear equations are presented in
Table S2. The above isotherms’ linear diagrams are illustrated in
(Figs. S1, S2, and S3 of Supplementary Information respectively).
Also, the isotherms respective variables concerning each model
can be obtained from the relative graphs as summarized in Table 1.
Moreover, the separation factor, (RL) can also be determined by the
Langmuir model, as the following [73]:
Table 1
Langmuir, Freundlich, and Temkin isotherms factors for adsorption of Pb(II) ions on HNT-G2.
Langmuir
T (K) qm (mg/g) KL (L/mg) RLa range
298 75.19 0.166 0.376–0.010
308 61.73 0.135 0.426–0.012
318 51.02 0.214 0.318–0.008
328 36.36 2.500 0.038–0.001
a
The range of initial concentrations of Pb(II) ions was 10–600 mg/L.
Journal of Molecular Liquids 360 (2022) 119407
1
RL ¼ ð5Þ
1 þ K LC0
where C0 represents the initial concentration of Pb(II) ions (mg/L)
and KL (L/mg) stands for the Langmuir constant. Hence, the uptake
process is considered to be favorable in case we have 0 < RL < 1.
The model applicability can be analyzed via comparison
between the correlation coefficient (R2) of the individual models.
The greater the R2, the more appropriate the model would be.
Through comparison between the results contained in Table 1, it
can be found that under various temperature conditions, the Lang-
muir model represents a higher R2 value compared with the Fre-
undlich and Temkin models. This reveals that the Langmuir
model is probably better describing the Pb(II) adsorption influence
on the HNT-G2. Additionally, it also indicates that the Pb(II)
adsorption effect on the HNT-G2 denotes a single-layer type
adsorption [74]. Firstly, the adsorbent superficial sites having the
highest amount of energy are occupied. A typical Langmuir iso-
therm is based on four following hypotheses: (i) the uniform sur-
face of the adsorbents, or equal all the adsorption sites; (ii)
adsorbed molecules do not interact; (iii) the same mechanism
involved adsorption and (iv) at the maximum adsorption, only a
monolayer is formed or molecules of adsorbate do not deposit on
other. The Langmuir isotherm shows monolayer adsorption on a
uniform surface with a finite number of adsorption sites. Once a
site is filled, no further adsorbates can be taken up at that site.
Hence, the surface reaches a saturation point where maximum
adsorption is achieved [75]. The maximum capacity of monolayer
Pb(II) adsorption for HNT-G2 nanocomposite was obtained to be
respectively equal to 75.19, 61.73, 51.02 and 36.36 mg/g at 298,
308, 318 and 328 K. Obviously, the Pb(II) adsorption amount was
decreased owing to the increase in temperature. The RL values lied
respectively in 0 and 1 range (0.376–0.010, 0.426–0.012, 0.318–
0.008 and 0.038–0.001), denoting the high favorability of the
uptake process (0 < RL < 1). The 1/n values were<1, denoting the
desirable Pb(II) adsorption over the HNT-G2 nanocomposite. The
temperature effect can also be observed in the reduction of the Fre-
undlich constant (KF) showing that the HNT-G2 capacity for
adsorbing Pb(II) was decreased by the increase in the reaction tem-
perature value.
3.4. Adsorption kinetics
For the purpose of examining the adsorption process, we used
the pseudo-first-order, pseudo-second order and Elovich models
(Table S3). The above kinetics’ linear diagrams are illustrated in
(Figs. S4, S5, and S6 of Supplementary Information respectively).
Table 2 contains the selected models’ kinetics parameters. The
most suitable kinetic model matching the experimental data can
be selected on the index of correlation (R2) basis as well as the cal-
culated uptake capacity (qe,cal). Based on the Table 2, it was deter-
mined that the pseudo-first- and pseudo-second order kinetic
models produced higher R2 values (respectively 0.907 and 1) com-
pared with the Elovich model (0.632). Also, the pseudo-second
Freundlich Temkin
R2
KF [(mg/g)(L/mg) 1/n
] 1/n R 2
AT (L/g) B (J/mol) R2
0.996 19.436 0.250 0.977 52.200 349.915 0.925
0.998 13.186 0.284 0.986 11.603 368.628 0.926
0.995 10.859 0.296 0.968 7.177 399.536 0.874
0.984 8.978 0.283 0.925 6.144 506.330 0.787
8
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al. Journal of Molecular Liquids 360 (2022) 119407

Table 2 the temperature of solution (K), and R represents gas constant

Kinetic models variables for Pb(II) ions adsorption on HNT-G2. (8.314 J/mol.K). Fig. 6 represents that the van’t Hoff plot of ln Kd
Kinetic model Parameters vs. 1/T provides a straight line with suitable correlation coefficient
Pseudo-first order qe,cal a (mg/g) k1 R2
(R2) for various studied concentrations of Pb(II). The DH and DS val-
19.572 0.856 0.907 ues may be specified from the intercept value and slope of the van’t
Pseudo-second order qe,cal (mg/g) k2 R2 Hoff plots respectively. The computed DH, DS, and DG values for Pb
24.938 0.383 1 (II) adsorption on the HNT-G2 nanocomposite at various solution
Elovich a b R2
temperatures are given in Table 3. The negative DH values revealed
3.25  108 0.922 0.632
that the process course of adsorption was inherently exothermic
a
is the experimental adsorption capacity at equilibrium (qe) which is equal to which is consistent with the previous results when the Pb(II) elim-
24.938 mg/g.
ination percentage through the use of phenylthiosemicarbazide-fu
nctionalized UiO-66-NH2 reduced along with the increase in the
order model compared with the pseudo- first-order model pos- solution temperature [79]. The DH value presents interesting infor-
sesses a qe,cal value duly equal to qe,exp value (Table 2). Then it mation on the adsorption process type. Regarding adsorbing the Pb
can be concluded that the kinetic info of Pb(II) adsorption on the (II) onto the HNT-G2, it was determined to be equal to
79.996 kJ/-
HNT-G2 nanocomposite are desirably matching with the quasi- mol as shown in the Table 3, denoting some chemical adsorption
second order model. Hence, the model signifies that the rate deter- percentage [80]. This is while the negative DG values gained
minant stage in the uptake process could be chemisorption, while revealed the spontaneous and feasible behavior of the adsorption
the overall results are confirmatory to and consistent with previ- process at the understudy temperatures range. Negative DG also
ous studies [76,77]. indicates that the binding energy of lead-adsorbent is stronger than
the lead-solvent, so this difference between energetic potentials of
the system components is the driving force of the Pb(II) cations
3.5. Adsorption thermodynamics
redistribution in the system and spontaneously adsorption of lead
on HNT-G2 [81]. Its noteworthy that the change in the free energy
To evaluate the various temperatures effect in the Pb(II) adsorp-
would increase in line with the temperature increase, exhibiting the
tion by HNT-G2, we studied the thermodynamic parameters (i.e.
reduction of adsorption along with the rise in the temperature [82].
the entropy (DS), enthalpy (DH), and Gibbs energy (DG) changes)
In the meantime, the entropy changes (DS) negative values show a
at four different temperatures of 298, 303, 318 and 328 K. In case of
reduced disorder at the solid/liquid interface in line with the Pb(II)
the increase in the adsorption capacity (qe) along with the
adsorption. With the increase in temperature, the Pb(II) ions mobil-
increases in the temperature, the process would be endothermic,
ity would increases, pushing the ions to migrate from the solid
otherwise, the process would be exothermic. On the other hand,
phase toward the liquid phase. Thus, the probability of greater
if a negative DG is reached, the adsorption process is deemed to
amount of Pb(II) ions adsorption would decrease [83]. In pure ion
be feasible and spontaneous. The formulas (6)–(8) below show
exchange process, the lead in solution could be replaced with a
the calculation procedure [78]:
divalent ion (such as Ca2+) or two monovalent ions (such as K+ or
  Na+) in adsorbent structure (positive or zero entropy change,
qe
DG
ln ðK d Þ ¼ ln ¼ ð6Þ respectively), but negative values of entropy change indicate that
Ce RT

DH DS
ln ðK d Þ ¼ þ ð7Þ Table 3
RT R Thermodynamical variables for the adsorption of Pb(II) on HNT-G2.

T (K) DG (kJ/mol) DH (kJ/mol) DS (kJ /mol K)

DG ¼ DH
T DS ð8Þ
298
7.895
79.996
0.244
where Kd (L/g) represents the thermodynamic equilibrium constant, 308
3.967
qe denotes the equilibrium adsorption capacity of Pb(II) (mg/g), Ce 318
2.231
328
0.433
stands for the equilibrium Pb(II) concentration (mg/L), T refers to

Fig. 6. Plot of ln Kd vs. 1/T for the Pb(II) adsorption on HNT-G2.

9
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al. Journal of Molecular Liquids 360 (2022) 119407

the adsorption of lead ion in solution occurs with low amount ion 3.6. Recycling adsorbent and desorption
replacement. Thus chemisorption due to complex formation are
dominant process in lead removal and ion exchange is less effective During the applied usage, it is crucial to know the adsorbent
in removing Pb(II) [84]. capability to reform and recoverability. The HCl (0.1 mol/L) solu-

Fig. 7. Recycling examination for HNT-G2 utilizing 0.1 M HCl solution.

Scheme 2. Probable adsorption mechanism of Pb2+ ions on HNT-G2.

10
E. Zandi-Mehri, L. Taghavi, F. Moeinpour et al.
Table 4
Comparison of max adsorption capabilities of Pb(II) ions utilizing different adsorbents.
Adsorbents Contact time (min.)
LDH/MOF a 120
Magnetic bentonite 90
CSt-ZnO b 120
UiO-66-EDTA 30
LDH-H 2880
Amino-functionalized Fe3O4 10
HNT 10
HNT-G2 10
a b
LDH/MOF = carboxylic acid-functionalized layered double hydroxide/metal–organic framework nanocomposite;
tion was able to reproduce the Pb(II)-loaded adsorbent in 10 min
so that the recovered adsorbent could be reused in 4 sequent
adsorption cycles. Fig. 7 shows the adsorption performance of
the adsorbents. The percentage of removal efficiency was reduced
about 5% in the initial adsorption-regeneration cycle. In the subse-
quent cycle however, this reduction was below 2%, indicating
agreeable adsorption capacity of the adsorbents recovered by acid
treatment.
Based on the results obtained emphasizing the chemical
adsorption, the adsorption of lead probably occurs via the follow-
ing course as shown in the Scheme 2. The removal of lead(II) ions
probably takes place through the complexes that are constructed
between the hydroxyl (–OH) moieties on HNT-G2 superficial layer
and the ions of lead(II). The probable adsorption mechanism can be
analyzed by using the Hard-Soft interaction theory. In general, the
hard acids/bases/cations (such as Fe(III), Cr(III), Mg(II), Mn(II), Cl-,
OH–, etc.) have a high charge density and their d-orbitals do not
participate in p-bond formation. These species have a high ten-
dency towards the electrostatic interactions and hence they have
a high affinity towards the hard-head groups of the ligands. In con-
trast, the soft acids/bases/cations (such as Hg(II), Pt(II), Pb(II), Rh
(III), Cd(II), I-, CN–, SCN-, etc.) have a low charge density and their
d-orbitals can participate in p-bond formation. These species com-
monly have the oxidation states of (I) and (II) and have a high ten-
dency to form the covalent bonds with the soft head groups of
ligands [85]. Based on the observed results, the interaction of hard
oxygen atoms of HNT-G2 with the soft Pb(II) cations does not seem
very favorable. But according to previous researches, lead ion has a
special coordination mode. Pb2+ behaves in its affinity towards O
donors just like Cu2+ which is relatively hard. However, more
important, provided a suitable primary binding site is available,
then Pb2+ shows a remarkable affinity for hydroxyl groups; this
is an important observation regarding nucleotides and nucleic
acids and other hydroxyl containing ligands [86,87].
The adsorption ability constitutes an important variable, imply-
ing the adsorbent performance. Table 4 contains a comparison
between the max HNT-G2 adsorptive capacity of and the various
other adsorbents for the Pb(II) adsorption. It is noteworthy that
the removal of Pb(II) in the presence of pristine HNT at the
obtained optimal conditions was also investigated. The results
show that the maximum adsorption capacity is much lower com-
pared to the HNT-G2. The result is shown in Table 4. Therefore, it
can be concluded that the correction of HNT with hydroxyl termi-
nated triazine-based dendritic polymer (G2) has increased its per-
formance in removing Pb(II).
4. Conclusions
This paper produced a dendritic polymer of hydroxyl based ter-
minated triazine, grown on the HNT-G2 in order to efficiently
removing Pb(II) ions from aqueous solution. Next, the TEM, XRD,
11
Journal of Molecular Liquids 360 (2022) 119407
Langmuir adsorption References
capacity qm (mg/g)
301.4 [72]
80.40 [88]
256.4 [30]
357.9 [89]
100 [90]
40.10 [91]
25.12 Present study
75.19 Present study
CSt-ZnO = starch based ZnO.
FT-IR, TGA, BET and EDS were utilized to determine the HNT-G2
properties. This work also performed experiments under various
pH (2–7), contact times (1–100 min) differing initial concentra-
tions (10–600 mg/L) and temperatures (298–328 K). Under
pH = 6 and 298 K conditions, the reaction attained the adsorption
equilibrium for a duration of 10 min, while a max adsorption
capacity equal to 75.2 mg/g was obtained. The Pb(II) adsorption
on HNT-G2 is consistent with the pseudo-second order kinetic as
well as the Langmuir isotherm model, showing the chemical
adsorption is by nature the speed control phase process and the
Pb(II) adsorption by HNT-G2 occurs as monolayer on a uniformly
constructed surface. The thermodynamic investigations revealed
that the adsorption procedure was exothermic, while it is undesir-
able in line with the temperature increase. At the same time, the
HNT-G2 nanocomposite still is having a high elimination rate after
four repeated cycles, showing its high recoverability. The Pb(II)
essentially constitutes chelation with the superficial HNT-G2 oxy-
gen atoms to attain adsorption effect.
CRediT authorship contribution statement
Elham Zandi-Mehri: Investigation, Methodology, Writing –
original draft. Lobat Taghavi: Conceptualization, Supervision,
Writing – review & editing. Farid Moeinpour: Conceptualization,
Supervision, Project administration, Writing – review & editing.
Iman Khosravi: Conceptualization, Writing – review & editing.
Saber Ghasemi: Conceptualization, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
The authors are grateful for the financial support of the Islamic
Azad University Qeshm Branch for this study.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molliq.2022.119407.
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