Environmental Technology

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Adsorption of cadmium by a high-capacity

adsorbent composed of silicate-titanate
nanotubes embedded in hydrogel chitosan beads

Roxana Quiroga-Flores, Asma Noshad, Reine Wallenberg & Linda Önnby

To cite this article: Roxana Quiroga-Flores, Asma Noshad, Reine Wallenberg & Linda Önnby
(2020) Adsorption of cadmium by a high-capacity adsorbent composed of silicate-titanate
nanotubes embedded in hydrogel chitosan beads, Environmental Technology, 41:23, 3043-3054,
DOI: 10.1080/09593330.2019.1596167

To link to this article: https://doi.org/10.1080/09593330.2019.1596167

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ENVIRONMENTAL TECHNOLOGY
2020, VOL. 41, NO. 23, 3043–3054
https://doi.org/10.1080/09593330.2019.1596167

Adsorption of cadmium by a high-capacity adsorbent composed of silicate-

titanate nanotubes embedded in hydrogel chitosan beads
a,b
Roxana Quiroga-Flores , Asma Noshadc, Reine Wallenberg c,d
and Linda Önnby c

a
Division of Biotechnology, Department of Chemistry, Lund University, Lund, Sweden; bInstituto de Investigaciones Fármaco Bioquímicas,
Universidad Mayor de San Andrés, La Paz, Bolivia; cCentre for Analysis and Synthesis, Department of Chemistry, Lund University, Lund, Sweden;
d
National Centre for High Resolution Electron Microscopy, Lund University, Lund, Sweden

ABSTRACT ARTICLE HISTORY

In this study, we developed a nanoparticle-based mesoporous composite that consisted of silicate- Received 21 November 2018
titanate nanotubes (STNTs) supported in hydrogel chitosan beads (STNTs-Ch beads) and was Accepted 12 March 2019
studied for Cd2+ adsorption. By using Fourier-transform infrared spectroscopy, transmission and
KEYWORDS
scanning electron microscopy coupled to an energy-dispersive X-ray spectrometer, we could Silicate-titanate nanotubes;
determine that the hollow STNTs were highly dispersed in the walls of the hollow beads. The chitosan beads; cadmium;
dispersion was attributed to the effect of pH when the composite was prepared and we adsorption; reuse
observed a non-interaction between STNTs and chitosan. The adsorption studies of Cd2+ showed
that the kinetic rate (k2) increased 3-fold and that the diffusion rate (Kd) increased 2-fold after
the embedment. Moreover, the maximum capacity of adsorption of STNTs-Ch beads was 2.3
times higher than that of STNTs alone. The treatment of a synthetic Cd2+ solution and a real
leachate in continuous mode showed two phases in which it was observed higher removed
fractions of transition metal ions (Cd2+, Co2+, Ni2+, Zn2+ and Cu2+) and the post-transition metal
ion Pb2+, in comparison to the removed fractions of alkali and alkali-earth metal ions (Ca2+, K+,
Mg2+). The composite was successfully reused four times when adsorbing Cd2+, saving three
times the needed amounts of TiO2, SiO2 and chitosan for the production of the material. This
composite was produced in a simple way and shows the potential for wastewater treatment.

1. Introduction By preparing adsorbents from nanoparticles (NPs),

Waters contaminated with cadmium (Cd2+) can cause
adverse effects on living organisms [1] and need to be
treated. Adsorption is a treatment technique that offers
simple operation, cost-effectiveness and a sludge-free
process [2,3]. An ideal adsorbent should have a strong
affinity to the target ion(s), large surface area, reusability
potential and be economically feasible [2,4].
many of the desired characteristics of an adsorbent can
be addressed: the nanoscale level can, for instance,
offer a large surface area. Among the NPs produced for
heavy metals adsorption, the literature reports about
the use of (i) titanium-based NPs (titanate nanotubes,
TNTs) used for adsorbing e.g. Pb2+, Cd2+, Cu2+, Cr3+
and Ni2+ [5–9] and (ii) silicon-based NPs (silica nano-
tubes, SNTs) and a functionalized form (sym-

CONTACT Linda Önnby linda.onnby@chem.lu.se Centre for analysis and synthesis, Department of Chemistry, Lund University, P.O. Box 124, SE-223 62
Lund, Sweden
Supplemental data for this article can be accessed at https://doi.org/10.1080/09593330.2019.1596167
© 2019 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group
This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License (http://creativecommons.org/licenses/by-nc-nd/
4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited, and is not altered, transformed, or built upon in
any way.
3044 R. QUIROGA-FLORES ET AL.
diphenylcarbazide-SNTs) for adsorbing Pb2+, Cd2+ and
Co2+ [10–12]. In order to meet an economically feasible
process, the TNTs have previously been regenerated
and reused [7,9]. However, bare NPs are not readily
applied in water treatment as the treatment would
require a necessary solid–liquid separation step [13,14]
for avoiding the loss of NPs into the water [15].
Another well-known drawback of NPs is aggregation
[16], which makes the application of NPs still limited.
The above-mentioned challenges have led to the
development of different types of composites where
NPs are embedded or coated onto other materials, e.g.
chitosan [13–21]. The resulting physico-chemical proper-
ties of the chitosan-based composites depend on the
interaction of the components involved and can
further define the distribution of the NPs in the chitosan
shell [13]. For a chitosan goethite bionanocomposite, the
distribution of iron was shown to have a vascular nature
inside chitosan beads [20], which resulted in a higher
concentration of the arsenic species at the edge of the
beads and decreasing concentrations towards the
centre, a process controlled by diffusion [20]. Given
that the number of combinations of composites can be
very high, the resulting distribution of the NPs inside
has to be investigated for each case.
For applying adsorbents as a treatment option, the
complexity of the water and the challenge that the
matrix represents for the treatment need to be con-
sidered. For example, for treating wastewater such as
leachate [22], the adsorbent would have to target a
broad spectrum of toxic metal ions such as Cd2+, Cu2+,
Pb2+ and show a poor adsorption for nontoxic ions
(e.g. Na+, K+, Mg2+ and Ca2+), which are of higher con-
centration than the toxic ions [2]. From such an appli-
cation, the discharged water would be secure and
could be further used for downstream processing in
the industry.
In this study, we have produced a composite made
of titanium-silicon nanotubes (STNTs) and chitosan
that were produced in the form of hydrogel beads
(STNTs-Ch beads). The composite was further character-
ized by studying the crystal phases and textural proper-
ties along with the interaction of the two components
by Fourier-transform infrared spectroscopy (FTIR), trans-
mission electron microscopy (TEM) and scanning elec-
tron microscopy, both coupled to energy X-ray
dispersive spectrometer (XEDS). The composite was
used for Cd2+ adsorption in batch solutions and to
treat real leachate by using packed columns. Finally,
we studied the recycling and the reuse of the compo-
site, in parallel with an assessment of the saved
amount of consumed chemicals involved in the
process.
2. Material and methods
2.1 Chemicals and solutions
Nanopowder of titanium dioxide (TiO2, particle size <
25 nm), powder of silicon dioxide (SiO2, 0.2–0.3 µm
average particle size, aggregate), cadmium chloride
(CdCl2, >99%), nickel chloride hexahydrate (NiCl2·6H2-
O), lead nitrate (Pb(NO3)2, >99%), sodium hydroxide
pellets (NaOH) and hydrochloric acid (HCl) were
bought from Sigma Aldrich, Sweden. Chitosan (70%
degree of deacetylation) was purchased from Heppe
Medical Chitosan GmbH, Germany. Stock standard
solutions of Cd (1000 mg Cd2+·L−1) and ammonium
phosphate ((NH4)2HPO4, matrix modifier solution,
40%) were purchased from Analytical Standards,
Sweden.
Membrane-filtered deionized water was obtained
from a Millipore system (18.2 MΩ · cm−1, Millipore,
France) and will be denoted as ultrapure water. Real lea-
chate from anaerobically acid-digested seaweed was
obtained from an anaerobic digester in Trelleborg,
south of Sweden in November 2014. The composition
of the leachate can be found in Table S1 in the sup-
plementary information (SI).
2.2 Synthesis of silicate-titanate nanotubes
Titanate nanotubes (TNTs) have previously been
obtained by alkaline hydrothermal treatment of TiO2
powder [23,24]. The procedure involved dissolving 2
M of TiO2 in 10 M NaOH in a Teflon reaction vessel
that was heated to 150°C and kept at a constant temp-
erature during 48 h. After the reaction finished, the
powder was washed repeatedly with ultrapure water
until the filtrate reached a neutral pH. In this work, we
performed the reaction in a gas tight reaction vessel
of glass (Pyrex), on which an opaque surface was
observed after the reaction. We thereafter confirmed
the presence of Si in the product; possibly resulting
from the dissolution of silica from the Pyrex vessel.
The molar ratio of Ti to Si was 1.0:1.1 (Table S2). Based
on the molar ratio of Ti-Si in the powder, an attempt
to produce an identical nanoparticle was done by carry-
ing out the same reaction in a glass-free reaction vessel
(Teflon tube) using equimolar amounts (2 M) of TiO2
and SiO2, respectively. The obtained nanoparticle had
a Ti to Si molar ratio of 1.0:0.3 (Table S2), suggesting
that the reaction needed further optimization. We will
report on the reaction details for silicate-titanate nano-
tubes (STNTs) in a second study and the results
obtained from the as-produced STNTs are reported in
this study.

2.3 Preparation of hydrogel STNTs-Ch beads
A solution of chitosan was prepared (1.7 g chitosan·100
mL−1 of 0.1 M HCl) as reported previously [17].
Different amounts of STNTs were added into the sol-
ution of chitosan, resulting in STNTs-Ch beads with
different dosages (expressed as g STNTs·g−1 chitosan):
0.14, 0.28, 0.42 and 0.56. Once homogeneous, the
STNTs-chitosan solution was added drop wise into a
0.1 M NaOH solution. The formed hydrogel beads
were rinsed with ultrapure water until the pH of the
filtrate was neutral. The STNTs-Ch beads were not
dried but kept as hydrogel beads in order to avoid
the changes in the pore structure of chitosan caused
by normal drying [25].
2.4 Characterization of STNTs and STNTs-Ch
beads
For determining the morphology and size of STNTs, the
powder of STNTs was analysed by a JEM 2200FS trans-
mission electron microscope (TEM) working at 200 kV.
The image data were analysed by the Digital Micrograph
suite (DM) software (Gatan Inc., USA). A TEM sample of
STNTs was also analysed by an energy-dispersive X-ray
spectrometer (TEM-XEDS). The quantification was made
using the Oxford INCA software.
The distribution and the elemental composition of
STNTs in the STNTs-Ch beads were studied by a Jeol
6700F-Scanning EM coupled to the Oxford Instruments
energy-dispersive X-ray spectrometer (SEM-XEDS). The
acceleration voltage was 5–15 kV. The sample was
freeze-dried and coated with carbon to allow collection
of data and images from a cross-section of the STNTs-
Ch beads.
Stretch band vibrations corresponding to functional
groups in STNTs, chitosan beads and STNTs-Ch beads
were studied from freeze-dried samples by using an
ALPHA Fourier transformed infrared spectrometer
(FTIR), the data were treated by the Opus software,
Bruker, USA.
The identification of crystal phases of STNTs, chitosan
and STNTs-Ch beads was analysed by a Stadi MP Powder
X-ray diffractometer (Stoe, Germany) with a copper tube
working at 40 mA and 40 kV. The scanning was per-
formed over a range of 2θ from 9° to 80° with a step
size of 0.013. The data were processed by the MATCH!
and JANA2006 software [26]. More details of the pro-
cedure are described in Text S1.
For determining textural properties, the Brunauer–
Emmett–Teller (BET) surface area of STNTs and STNT-Ch
beads were determined from N2 adsorption–desorption
isotherms were measured using a 3Flex Micromeritics
ENVIRONMENTAL TECHNOLOGY 3045
instrument (USA). The pore size distribution of STNTs-
Ch beads was calculated by the Barret–Joyner–Halenda
(BJH) model. The samples were degassed at 30°C for
24 h and the data were collected at a relative pressure
P/Po between 0.0025 and 0.99. The data were processed
by the 3Flex Software version 4.01.
2.5 Batch adsorption studies of STNTs and STNTs-
Ch beads
All batch experiments were carried out using a synthetic
Cd2+ solution (10 mg · L−1 (89 µM), pH = 6.5 ± 0.2) unless
otherwise mentioned. The experiments were performed
in duplicates at room temperature (T = 22°C) in polyethy-
lene tubes (volume = 10 mL) under constant agitation
using a rocking table from VWR, USA. Adsorption of
Cd2+ by the polyethylene tube was found to be negli-
gible (data is shown in Table S3).
2.5.1 Adsorption kinetics
For studying adsorption kinetics and the diffusion behav-
iour, kinetic experiments were carried out first for (i)
0.24 g STNTs · L−1, (ii) 15 chitosan beads (0 g STNTs ·
L−1) and (iii) 15 STNTs-Ch beads·L−1 (0.28 g STNTs · g−1
chitosan). Samples were collected between 0 and
2880 min and analysed for Cd2+. The pseudo-first order
[27], pseudo-second order model [28] and the intraparti-
cle diffusion model [29] were used to fit our kinetic data.
Thereafter, to determine the optimal dosage, the second
batch of kinetics experiments was carried out testing the
following dosages: 0.14, 0.42 and 0.56 g STNTs·g−1
chitosan.
2.5.2 Adsorption isotherms
Adsorption isotherms were evaluated using Cd2+ sol-
utions ranging from 0.1 to 400 mg · L−1. Samples were
collected at equilibrium. The Langmuir [30] and the
Freundlich [31] adsorption models were used to fit
the data of the adsorption isotherms. For calculating
the capacities of adsorption at equilibrium, the mass
of the adsorbent was equal to the mass of the STNTs in
the STNTs-Ch beads.
2.5.3 Metal ions competition
Metal ions competition between Cd2+, Ni2+ and Pb2+ was
evaluated by studying adsorption from solutions of
89 µM of each metal respectively. Three conditions
were established: (i) single metal ion solution, (ii) bisolute
metal ion solution containing Cd2+ and Pb2+ and (iii) tri-
solute metal ion solution.
3046 R. QUIROGA-FLORES ET AL.
2.6 Adsorption in continuous mode by STNTs-Ch
beads
A glass column (9 × 170 mm) was packed with 350
STNTs-Ch beads with a bed volume of 6 mL. In continu-
ous mode, the column was used to treat (i) a synthetic
Cd2+ solution (1400 mL or 233 bed volumes of 0.5 mg
Cd2+·L−1) and (ii) real leachate (210 mL or 35 bed
volumes of 0.034 mg Cd2+ · L−1) with an upward flow
rate of 0.32 mL · min−1. Both experiments were con-
ducted in duplicates at 22°C. Samples of 15 mL (interval
of 46.8 min) were collected using a fraction collector
FC204, Gilson, USA.
2.7 Recycling and reuse of STNTs-Ch beads
The STNTs-Ch beads were recycled and reused in batch
experiments. The recycling procedure consisted of deso-
rption and regeneration. The conditions for desorption
were optimized by comparing two acids (HCl and
H2SO4) as desorbing agents. The dosage for desorption
and regeneration was the same used in a previous
study for TNTs (i.e. 0.08 g TNTs·100 mL−1) [32]. The
optimal desorbing agent was selected according to Cd2
+
desorption efficiency (%) and weight loss quantification
(% mass loss). Once selected the desorbing agent, deso-
rption was performed by immersing 15 STNTs-Ch beads
in 3 mL of the desorbing agent for 3 h. For regeneration,
the 15 Cd2+-desorbed STNTs-Ch beads were immersed in
3 mL of 0.2 M NaOH for 3 h, thereafter the beads were
rinsed 3 times with 1 mL of ultrapure water. The recycled
STNTs-Ch beads were then reused under the same con-
ditions as virgin beads. Recycling was carried out 7 times
following the above-mentioned steps. For every cycle,
adsorption capacity at equilibrium (Qe) was measured.
With the newly Qe measured in every cycle, Qe recovery
(%) was calculated as the ratio between the Qe of each
cycle and Qe of virgin beads.
2.8 Analytical methods
The concentration of Cd2+ was determined by a Zeenit
700 P graphite furnace atomic absorption spectrometer
(GFAAS) on an Analytik Jena Zeenit 700, Germany.
Samples were acidified with concentrated HNO3. The
modifier (NH4)2HPO4 (1% w · v−1) was added to reduce
the matrix effect. The range of the calibration curve
was 1.0–5.0 µg Cd2+ · L−1 with a limit of detection of
0.20 µg Cd2+ · L−1. The processed data had residual stan-
dard deviations (RSD) <5%.
Total Ca, Pb, Ni, K, Mg, Zn, Co and Cu of the leachate
were analysed using an Optima 8300 ion coupled plasma
atomic emission spectroscopy (ICP-OES), Perkin Elmer,
USA. The data were treated by the WinLab32 software
and reported RSD values were <10%. The limits of detec-
tion can be found in Table S4.
Ammonium (NH+4 , LCK303), nitrate (NO− 3 , LCK339), sul-
phate (SO4 , LCK153) and phosphate (PO3−
2−
4 , LCK049)
were analysed using analytical kits from Dr. Hach
Lange (Sweden). Presented data are average values
from 3 measurements with an RSD <5%. The limits of
detection were 1.0 mg · L−1 for NO− 3 , 2.5 mg · L
−1
for
NH4+, 5 mg · L−1 for PO3−
4 , and 40 mg · L
−1
for SO2−
4 .
3. Results and discussion
3.1 Characterization of STNTs, STNTs-Ch beads
and effects of pH on STNTs dispersion
3.1.1 STNTs and STNTs-Ch beads characterization
Figure 1(a)–(c) depicts TEM images of STNTs showing
hollow nanotubes and the elemental analysis obtained
by EDS. The diameter of the nanotubes was approxi-
mately 6–8 nm with 3–4 layers in the walls. The multi-
walls had an interplanar distance of approximately
0.7 nm. Figure 1(c) shows the co-existence of Si and Ti
in the nanotubes determined by TEM-XEDS analysis of
a pair of nanotubes where the quantification showed a
Ti:Si molar ratio of 1.04:1.
Figures S1(a)–(c) show the infrared spectra of STNTs,
chitosan beads and STNTs-Ch beads, respectively. In
Figure S1(a) the observed bands for STNTs at 411 cm−1
Figure 1. High-resolution TEM images of the STNTs showing the
silicate-titanate nanotubes. In (a) two nanotubes viewed edge-
on. In (b) the profile view of the STNTs where the interplanar dis-
tance between the multi-walls is observed. In (c) a TEM micro-
graph showing the hollow nanotubes where XEDS analysis was
performed (circled area) and the corresponding spectrum with
Ti and Si respectively is shown to the right (The element Cu
comes from the grid used during sample analysis and the grid
can also contribute to the C signal).

and 905 cm−1 were assigned to the TiO6 octahedron and
to the four-coordinated Ti–O of (TiO(OH)2) respectively.
Both bands have been reported in studies for TNTs
before [7,8,33]. The absorption band at 1033 cm−1 was
assigned to Si–O–Si. The same band has been previously
ascribed to Si–O3–Si in the case of polygorskite
embedded in chitosan beads [21,34]. The two remaining
bands observed at 1634 cm−1 and 3345 cm−1 were
attributed to the O–H and H–O–H binding vibrations,
respectively. Overall, the infrared results confirmed the
presence of –OH, the TiO6 octahedron and the Si–O–Si
bond in STNTs. Figure S1(b) shows bands observed in
chitosan beads. The bands in the range from 989 cm−1
to 1148 cm−1 were assigned to the C–O and C–N
bonds. The bands in the range from 1561 cm−1 to
1649 cm−1 corresponded to the secondary amide and
primary amide of the N-acetylated group [35,36]. The
bands in the range from 3285 cm−1 to 3362 cm−1,
Figure 2. (a) XRD spectra of STNTs, chitosan beads and STNTs-Ch
beads. (b) Nitrogen adsorption–desorption isotherms of STNTs-
Ch beads. (c) Pore size distribution of STNTs-Ch beads.
ENVIRONMENTAL TECHNOLOGY 3047
corresponded to O–H and N–H stretching [36]. Finally,
Figure S1(c) shows that STNTs-Ch beads exhibited the
same bands observed in the other two spectra (Figure
S1(a)–(b). The absence of new bands in STNTs-Ch
beads suggests that STNTs and chitosan did not form
new chemical bonds.
Figure 2(a) shows the XRD spectra of STNTs, chitosan
beads and STNTs-Ch beads. The spectrum of STNTs
exhibited diffraction peaks at 2θ value of 10°, 24° and
48° corresponding to the planes (0 2 0), (1 1 0) and (2
0 0) respectively indicating the presence of nanotubes.
The obtained spectrum clarified the low intensity
peaks, proposing a low crystalline nature of the STNTs
particles. The spectrum of chitosan beads displayed
one weak diffraction peaks at 2θ value of 20° indexed
with (1 0 0) plane which is consistent with the reports
for chitosan [37]. The possible reason behind could be
the presence of inter and intra-molecular H-bonding
which has been reported earlier [38]. This is consistent
with our discussed observations from the FTIR spectrum
(Figure S1(b)). In the STNTs-Ch beads spectrum, some
interesting differences have been observed such as (i) a
location shift at 2θ value of 20° towards a higher value
of intensity indicating high quantity of chitosan beads
and (ii) all the characteristic peaks of STNTs disappeared
in the STNTs-Ch beads spectrum which could be due to
the dominating existence of a high quantity of chitosan
and a weak crystalline nature of STNTs.
The BET surface area of STNTs and STNTs-Ch beads
was calculated to be 216.7 ± 0.7 and 12.9 ± 0.02 m2 · g−1,
respectively. The high surface area of STNTs and similar
materials, e.g. between 240 and 302 m2 · g−1 for TNTs
[6–9] and 411 m2 · g−1 for SNTs [10] could be attributed
to its small inner diameters and multilayer morphology
as observed by TEM in Figure 1(a). In contrast, the
surface of the STNTs-Ch beads was 16 times lower as com-
pared to the STNTs-Ch beads, which was probably due to
the relatively low load of STNTs in the STNTs-Ch beads,
which was 22% of the total mass. A higher load of particles
would increase the surface area of the composite as
observed when the load of TNTs was increased to γ-
Fe2O3/TNTs [9].
The pore size and pore volume STNTs-Ch beads were
calculated to be 11.6 nm and 0.0035 cm3 · g−1. Figure 2
(b) shows the nitrogen adsorption–desorption isotherms
and it is seen that the isotherm exhibited an IV-type iso-
therm indicative of capillary condensation occurring in a
mesoporous adsorbent [39,40]. The H3-type hysteresis
loop indicates that it does not exhibit limiting adsorption
while approaching P/Po = 1 and is often seen in aggre-
gates of materials with flat- or slit-shaped pores [39].
The pore size distribution showed in Figure 2(c) shows
a bimodal distribution. The small pores (2–3 nm) may
3048 R. QUIROGA-FLORES ET AL.

Figure 3. SEM images and SEM-XEDS mapping of STNTs-Ch beads, respectively. In (a) the cross-section of a STNTs-Ch bead shows both
the inner and outer part of the bead. The selected area is magnified in (b) and a group of white aggregates are shown in (c). The SEM-
XEDS mapping of a STNTs aggregate from the outer part is shown in (d), and from the cross-section is shown in (e). Both mapped areas
in (d,e) showed the presence of Na, Si, Ti and O in the aggregates.

correspond to the pores of STNTs; similar values are for –OH groups present in the STNTs have been reported
reported for TNTs [9,41] and the larger pores (10– to be in the range from 9.5 to 13 [43,44]. Thus, for the
12 nm) might correspond to sites with higher aggrega- prepared chitosan-STNTs suspension at pH = 1 (cf.
tion degree [8,9] of STNTs or probably correspond to Section 2.3), both the –NH2 and –OH groups present in
chitosan pores. chitosan and STNTs respectively would be protonated.
This, in turn, would yield highly dispersed STNTs in the
produced STNTs-Ch beads as similar charges result in
3.1.2 STNTs dispersion in STNTs-Ch beads and
repulsion and hence absent interaction between STNTs
effects from pH
and chitosan. Our results are supported with previous
Figure 3(a)–(f) shows the SEM imaging and the elemental
mapping of the STNTs-Ch beads obtained by SEM-XEDS.
Figure 3(a) shows the cross-section of an STNTs-Ch bead Table 1. Obtained model constants from the pseudo-second
and its hollow inner area. The magnification of the order model and the intraparticle diffusion model for STNTs
and STNTs-Ch beads, respectively.
selected area in Figure 3(a) is shown in Figure 3(b),
Kinetic model STNTs STNTs-Ch beads
which shows white aggregates in the outer and inner
Pseudo-second order
wall of the bead. Higher magnification of a group of Qe (mg · g−1) 31.4 ± 1.2 38.8 ± 1.6
aggregates is shown in Figure 3(c). Figure 3(d,e) shows k2 × 10−3 (g · mg−1 · min−1) 2.5 ± 0.6 0.8 ± 0.2
h (mg · g−1 · min−1) 2.5 ± 0.2 1.2 ± 0.1
the SEM-XEDS mapping of two aggregates; one of t1/2 (min) 12.7 ± 0.5 32.2 ± 1.3
them was from the cross-section and the other one R2 0.9224 0.9604
Intraparticle diffusion
from the outer wall. Both selected sites (Figure 3(d,e))
Kd1 (mg · g−1 · min−0.5) 3.4 ± 0.7 3.4 ± 0.5
showed the presence of Na, Si and Ti, confirming that C1 (mg · g−1) 3.9 ± 3.0 0.8 ± 2.1
the aggregates were indeed STNTs. R21 0.9550 0.9772
Kd2 (mg · g−1 · min−0.5) 0.9 ± 0.0 1.8 ± 0.5
The degree of protonation could affect the distri- C2 (mg · g−1) 16.3 ± 0.2 9.5 ± 5.0
bution of the particles inside the chitosan bead. The R22 0.9996 0.9237
Kd3 (mg · g−1 · min−0.5) 0.2 ± 0.0 0.3 ± 0.1
pKa of chitosan ranges from 6.17 to 6.54 for a degree C3 (mg · g−1) 28.0 ± 0.9 28.7 ± 2.3
of deacetylation from 94% to 73% [42]. In our study, R23 0.9560 0.9280
the degree of deacetylation was 70%. The pKa values Note: Numbers were rounded off to one decimal.
 ENVIRONMENTAL TECHNOLOGY 3049

observations done for TNTs where a higher degree of layer, were higher for the first and second region of
reorganization of aggregates followed by an increased STNTs than that of STNTs-Ch beads. This can be corre-
surface area was observed in an acidic environment [45]. lated with the higher diffusion resistance observed for
STNTs. Overall, STNTs-Ch beads showed improved
diffusion than the STNTs alone.
3.2 Adsorption studies
3.2.1 Kinetic modelling of Cd2+ adsorption
3.2.2 Optimization of the dosage of STNTs in STNTs-
The kinetic data were best described by the pseudo-
Ch beads
second order and intraparticle diffusion models. Both
For a batch adsorption process, the overall removal can
models are described in Text S2. Table 1 shows the con-
be a guiding tool for the selection of optimal dosage,
stants obtained from modelling. The highest Qe was
whereas the kinetic parameters are those directing for
obtained for STNTs-Ch beads (38.8 mg · g−1), followed
a continuous process. We studied three additional
by STNTs (31.4 mg · g−1). The kinetic data of chitosan
dosages of STNTs in our STNTs-Ch beads (g STNTs ·
did not fit to any of the studied models (Table S5). For
g−1 chitosan): 0.14, 0.42 and 0.56, that were compared
that reason, we only calculated the experimental Qe
with the dosage of 0.28. The kinetic data were studied
using Equation S4, and was found to be low (Qe =
by using the pseudo-second order model. The model
5.21 mg · g−1). The higher Qe found for STNTs-Ch beads
constants are listed in Table S6. Figures 4(a)–(b)
is hypothesized to be due to (i) the chelation of Cd2+
depict the changes of k2, h, Qe, Cd2+ removal (%) and
by the duplet of electrons on nitrogen atoms present
t1/2 with increasing STNTs dosage. Figure 4(a) shows
in chitosan, and (ii) the dispersion of STNTs in the compo-
the low variation of h, which indicates that the adsorp-
site as confirmed by SEM-XEDS (cf. Figure 3(d)–(e), and
tion at the initial stage was independent of the dosage.
Section 3.1.2). Overall, the STNTs were shown to be the
In contrast, k2 showed an increasing trend due to the
main component involved in the adsorption of Cd2+ by
availability of more adsorption sites for Cd2+ as the
STNTs-Ch beads.
In Table 1, the initial adsorption rate (h) indicates that
adsorption of Cd2+ by STNTs was faster than STNTs-Ch
beads (2.5 versus 1.2 mg g−1 · min−1). In contrast, the
chemical rate (k2) for STNTs was slower as compared
with STNTs-Ch beads (2.5 × 10−3 versus 0.8 × 10−3 g
mg−1 min−1), which explains the higher resulting Qe for
STNTs-Ch beads. The advantage of a faster k2 and
higher Qe of STNTs-Ch beads indicates an improvement
in kinetics adsorption for STNTs-Ch beads.
Table 1 shows the Kd rates and C values from the
linear regressions of the intraparticle diffusion model.
The linear regressions (c.f. Figure S2) of the three com-
pared adsorbents: STNTs, chitosan beads and STNTs-Ch
beads, showed three regions that did not pass through
the origin, which means that diffusion is not the only
rate-liming step. The Kd rates and C values for each adsor-
bent were ranked as follows: Kd1 > Kd2 > Kd3 and C3 > C2 >
C1. As described by Weber [46], the first region is associ-
ated with the transport of Cd2+ ions towards the surface
of the adsorbent. Both STNTs and STNTs-Ch beads had
equal Kd1 indicating an identical pace. The second Figure 4. Relation between dosage of STNTs (g STNTs·g−1 chit-
region is associated with the diffusion of Cd2+ ions osan) present in STNTs-Ch beads and kinetic constants k2, h, t1/
through the pores of the adsorbent. The Kd2 of STNTs- 2 and Qe obtained from pseudo-second order kinetic modelling
Ch beads was twice the value of Kd2 of STNTs, indicating and total Cd2+ removal (%). In (a) k2 (g · mg−1 · min−1) and h
on a higher diffusion resistance for STNTs. Finally, the (mg · g−1 · min−1). In (b) Qe (mg · g−1), total Cd2+ removal (%)
and t1/2 (min) as a function of the STNTs dosage in STNTs-Ch
third region that is associated with the final equilibrium
beads. The dashed lines show the trends for each constant
stage showed the lowest and similar Kd3 values for with increased STNTs dosage. The experimental conditions
both adsorbents. One the other hand, C values, which were: pH = 6.5 ± 0.2, T = 22°C, Ci = 10 mg Cd2+ · L−1. Kinetic
are associated with the thickness of the boundary modelling was done with Graphpad prism®.
3050 R. QUIROGA-FLORES ET AL.

STNTs dosage increased. The changes in k2 influenced
the resulting Qe that gradually decreased with increas-
ing dosage of STNTs. In another study, similar
changes in Qe were observed for an increased dosage
of TNTs used for adsorption of Pb2+ [8]. Finally, the
highest overall removal (82–87%) was obtained by the
dosages from 0.28 to 0.56. We chose 0.28 as the
optimal dosage due to the small-observed variations
in this interval.
to the single solute solutions. Nevertheless, the overall
removal did not change and was ranked as: Pb2+ > Cd2
+
>> Ni2+ for all cases. Similar removal ranking was
observed for TNTs when Cd2+, Pb2+, Ni2+ and Cr3+ were
together in solution [5,8,33]. As there were differences
in the kinetics constants, we can hypothesize that the
differences in the total removal would be larger if a
higher concentration of metals close to a limiting
threshold had been evaluated.

3.2.3 Metal ions competition

The competition of metal ions was evaluated by studying 3.2.4 Modelling of the adsorption isotherms
the kinetics of metals in single, bisolute and trisolute The best fit of the experimental data was found for the
equimolar metal solutions. The kinetic plots and the Langmuir model; the fitting to the Freundlich model is
pseudo-second order model constants for the metal shown in Table S8. Both models are described in Text
ions in the respective solutions are shown in Figure S3 S3. Figure S4 shows the modelling of adsorption iso-
and Table S7, respectively. We observed differences in therms of STNTs, chitosan beads and STNTs-Ch beads.
kinetics in the bisolute and trisolute solutions compared The constants obtained by the model are listed in
Table 2 along with other Ti- and Si-based nanotube
Table 2. Langmuir constants (Qm, KL and R 2) of our studied adsorbents reported before. The Qm of STNTs-Ch beads
adsorbents and other reported Ti- and Si-based adsorbents for was found to be 2.3 times higher than that of STNTs
Cd2+ adsorption, including conditions used, adsorbent dosage (656 versus 286 mg · g−1, Table 2). The Qm of chitosan
and reference. beads was the lowest (172.4 mg · g−1) but not negligible,
Adsorbent
Langmuir Temperature dosage indicating that a fraction of Cd2+ ions was adsorbed to
Adsorbent constants (°C) and pH (g L−1) Reference chitosan, and is in line with our observations from kin-
Qm (mg g−1), etics (section 3.2.1). The RL values for STNTs and STNTs-
KL (L mg−1)
and R 2 Ch beads were found to be between 0 and 1, indicating
STNTs Qem= 286 ± 32 22°C, pH=6.8 0.24 This study that adsorption was favourable, reversible and linear at
KL = 0.07 ± lower concentrations.
0.03
R 2= 0.966 Table 2 shows that Qm of STNTs was higher than the
Chitosan Qem= 172 ± 37 22°C, pH=6.8 0.83 This study highest Qm previously reported for any of the Ti- and
beads KL = 0.02 ±
0.01 Si-based adsorbents. The highest previously reported
R 2 = 0.919 value for TNTs was 240 mg · g−1. SNTs functionalized
STNTs-Ch Qem= 656 ± 27 22°C, pH = 6.8 0.24 This study
beads KL= 0.039 ± with sym-diphenylcarbazide (SD) exhibited a Qm of
0.005 111.2 mg · g−1 for Cd2+, which was still lower than the
R 2 = 0.989 Qm found for STNTs-Ch beads in this study. These com-
TNT-cryoa Qm= 156 22°C, pH = 7.2 1.00 [22]
R 2 = 0.968 parisons indicate that the embedment of STNTs in chito-
b
TNTs Qm= 157 22°C, pH = 7.2 1.00 [22] san had a synergist effect on Cd2+ adsorption.
R 2 = 0.987
TNTsb Qm= 240 25°C, pH = 5 0.20 [7] The comparison of STNTs-Ch beads with other
R 2 = 0.999 recently developed adsorbents targeting Cd and shows
b
TNTs Qm= 240 25°C, pH = 5 0.20 [5]
R 2 = 0.999 that STNTs-Ch beads exhibit a higher capacity of adsorp-
TNMsb Qm= 216 25°C, pH = 5 0.20 [41] tion than that of other nano-based adsorbents, e.g.
R 2 = 0.999
TNs b
Qm= 239 20°C, pH = 5.0– 0.20 [8]
sulphur functionalized graphene oxide nanosheets (Qm
R 2 = 0.999 6.0 = 384 mg · g−1) [47], nano-KFeP2O7 implanted on silica
SNTsc Qm= 81
R 2 = 0.991
30°C, pH = 7.0 0.25 [10]
gel beads (Qm = 5.08 mg · g−1) [48] or thiol-functiona-
SD-SNTs d
Qm= 111 30°C, pH = 7.0 0.25 [10] lized nano-Fe3O4 (Qm = 73.8 mg · g−1) [49]. The difference
R 2 = 0.991 with our reported Qm is considerable, even though all
Note: Values are rounded to significant digits.
a
TNTs, TNMs and TNs stand for titanate nanotubes, titanate nanomaterials and
mentioned adsorbents show higher surfaces areas
titanate nanotubes respectively. (168–208 m2 · g−1) than the studied STNTs-Ch beads
b
TNTs were supported in cryogels. (see Section 3.1.1). Overall, nanotube-based adsorbents
c
Silica nanotubes.
d
SD-SNTs, silica nanotubes functionalized with sym-diphenylcarbazide (SD). seem to have a natural affinity to adsorb Cd2+ which
e
Qm values were obtained by non-linear regression using Graphpad Prism®. could explain higher adsorption capacities.
 ENVIRONMENTAL TECHNOLOGY 3051

3.3 Continuous removal of metal ions present in
synthetic and real leachate
We treated a synthetic Cd2+ solution (500 µg Cd2+·L−1)
and real wastewater leachate by STNTs-Ch beads
packed in columns. Figure S5 shows the fractions of
Cd2+ removed (expressed as 1 − (C·C−1o )) from the syn-
thetic solution as a function of bed volumes. Two
phases were observed during the treatment, phase I
comprised 0 < bed volumes <15 and phase II comprised
15 < bed volumes <275. During phase I, an outlier value
(1 − (C·C−1
o ) = 0.76) was observed at 7.5 bed volumes,
indicating that poor adsorption occurred. Figure 3(a)
showed the beads were hollow, which means that
water could have occupied the core of the beads. The
longitudinal diffusion rates of water molecules inside
the bead could have affected the Cd2+ adsorption
during phase I. Phase II showed that Cd2+ adsorption
maintained a threshold of 0.9 for the removed fractions
until 107 bed volumes.
Figure 5(a)–(c) shows the fractions (1 − (C·C−1 o )) of
removed metals from the real leachate as a function of
bed volumes. We divided the column run in phase I
and II, based on the observations done for Cd2+ adsorp-
tion in Figure S5. Figure 5(a,b) shows metals that were
removed during phase I. Figure 5(a) shows that alkali
and alkali-earth metals such as Mg2+, Ca2+and K+ are
removed up to 1 − (C·C−1 o ) < 0.5. Figure 5(b) shows that
transition metal ions such as Zn2+, Co2+, Ni2+ and Cu2+
are removed up to 1 − (C·C−1 o ) > 0.5. During phase II,
Figure 5(c) shows the removal of Cd2+ (transition
metal) and Pb2+ (post-transition metal) and their respect-
ive removed fractions that were found in the range of 1
− (C·C−1
o ) > 0.5.
In order to study the ranking of the fractions removed
in both phases, we plotted the data of the fractions
removed versus the ionic radii, hydrated radii, hydration
energy and electronegativity, respectively (the theoreti-
cal values are listed in Table S9). From our comparisons,
we found that R 2 values ≥ 0.7 occurs only for post-tran-
sition and transition metal ions plotted versus ionic
radii and hydration energy. The graphs can be found in
Figures S6a-d. Similar accordance between hydration
energy and adsorption capacities for Pb2+, Cd2+, Cu2+
and Cr3+ has been found for TNTs in batch experiments
[5,6]. The fractions removed of other ionic compounds
−
such as SO2− 3− +
4 , PO4 , NH4 and NO3 are shown in Figure S7.

Table 3. Repeated adsorption of Cd2+ using recycled STNTs-Ch

beads showing the obtained equilibrium capacity (Qe′ ), the
recovered Qe (Qe, recov, %) and the total removal and
desorption of Cd2+ (%) Experimental conditions: Cai
= 10 mg Cd2+ · L−1, T = 22°C, pH = 6.5 ± 0.2.
Removal Desorption
Number of efficiency of efficiency of Cd2+
cycles Qe′ (mg·g−1)b Qe recov (%) Cd2+ (%) (%)
c
1 38.6 ± 0.1 Na.d 99 69
2 36.8 ± 0.5 95 94 75
3 33.2 ± 0.6 86 85 89
4 33.3 ± 2.1 86 85 72
5 26.5 ± 2.3 69 68 71
6 24.7 ± 1.1 64 63 56
7 21.0 ± 0.6 54 54 52
a
Note that the initial concentration of Cd2+ could influence the number of
Figure 5. Fractions of ions adsorbed during the column run of b
cycles the adsorbent can be reused.
The precipitation of Cd(OH)2 inside the beads after the use of NaOH could
leachate expressed as 1 − (C·Co−1). In (a) adsorbed ions with 1 limit the number of times the adsorbent can be recycled with an
− (C·Co−1) < 0.5, in (b) ions with 1 − (C·Co−1) > 0.5 and in (c) unchanged Qe′ .
c
ions adsorbed after 12.5 bed volumes. Experimental conditions: The 1st cycle corresponds to virgin STNTs-Ch beads.
pH = 5.7 ± 0.3, T = 22°C, Ci = 34 μg Cd2+·L−1.
d
Na, not applicable.
3052 R. QUIROGA-FLORES ET AL.

Figure 6. Scheme of STNTs-Ch beads production from synthesis of STNTs to waste disposal without (upper area) or with (lower area)
recycling. The non-recycling balance shows single use to solid waste shown as steps 1 to 3 for 4 times of STNTs-Ch beads use. The
recycling process includes steps 1 to 7 where recycling of STNTs-Ch beads was performed three times. The pre-treatment was only
conducted for the 1st cycle.

3.4 Recycle and reuse of STNTs-Ch beads for the production of virgin beads. The additional
inputs for recycling were H2SO4 (step 5) and NaOH
The recycle of STNTs-Ch beads was composed of deso-
(steps 4 and 6). As a result, 1.9 times more of NaOH is
rption of Cd2+ and regeneration of the STNTs. The data
needed for a recycling process of 4 cycles as compared
for the optimization of desorption conditions can be
to 4 times of single use of STNTs-Ch beads.
found in Table S10. The results showed that a pre-treat-
To further reduce the amount of NaOH needed during
ment of STNTs-Ch beads with 0.1 M NaOH prior deso-
recycling, the optimization of the NaOH dosage needed
rption with H2SO4 increased the tolerance of the beads
in Steps 4 and 6 is more advantageous than the reuse of
from 0.01 M to 0.5 M H2SO4. The highest desorption
the supernatant in Step 1; the latter would only save
efficiencies were 71% and 75% for 0.1 and 0.5 M
3.3% of the total amount of NaOH. Note that the optim-
H2SO4, respectively. Hence, 0.1 M H2SO4 was selected
ization will be restricted by the alkalinity needed for
as a desorbing agent.
forming round-shaped chitosan beads and the amount
Table 3 shows the total removal (%) and desorption of
2+ of Na+ and OH− that needs to be replenished in regener-
Cd (%), the equilibrium capacity for each adsorption
ation [50,51].
cycle (Qe′ ) and the recovered capacity (Qe,recov, %). The
Recycling has advantages over a non-recycling
quantified mass loss was measured on dried beads and
process in terms of both consumed chemicals and the
found to be negligible. Satisfactory values of Qe,recov
lifespan of the adsorbent. To give an example, 89
(>86%) were obtained for up to four cycles with more
columns would be able to perform 445 treatments if
than 85% of Cd2+ removed. However, it was not possible
the adsorbent is recycled 4 times.
to desorb all Cd2+ in each desorption step; only 69% was
desorbed during the 1st cycle.

3.4.1 Comparison and balance of the consumed
chemicals for recycled STNTs
Figure 6 shows the different steps from STNTs-Ch bead
production followed by (i) single use or (ii) four times
reuse. Steps 1–3 comprise the synthesis of STNTs till
the use of STNTs-Ch beads for adsorbing Cd2+, which
thereafter go to waste disposal. Steps 1–7 include a
four-times repeated use of recycled STNTs-Ch beads.
The detailed calculations for the respective scenarios
are shown in Table S11. Thus, for four times recycled
STNTs-Ch beads, the amount saved for TiO2, SiO2, chito-
san and HCl was three times the initial amount needed
4. Conclusion
For the sake of obtaining more secure water, the technol-
ogies for treating complex waters need to be highly selec-
tive, but preferably also affordable and feasible. Although
some adsorbents have shown to be highly selective; there
is still a notable gap between lab research and pilot appli-
cations. In this study, we have chosen to work with a com-
posite made of a silicate-titanate nanotube that was
embedded in a biodegradable hydrogel polymer (chito-
san). The adsorbent was used for adsorbing Cd2+ from
synthetic water and real leachate. By dispersing the
STNTs in chitosan beads, the BET surface area decreased

but a reduced degree of aggregation could be achieved,
and resulted in improved adsorption characteristics as
opposed to when the STNTs were applied without any
supporting material. The pore size distribution results cor-
roborate this outcome because even after the embed-
ment the pores of the STNTs were available for
adsorption in the STNTs-Ch beads. During the treatment
of real leachate from a biogas plant, we found a higher
degree of removal for transition and post-transition
metals than for alkali and alkali-earth metal ions. The recy-
cling of the composite was successful and the amount of
materials needed for production was reduced, which also
implied reduced amounts of waste after adsorption. By
working with hydrogel beads the cost of production can
be reduced (i.e. energy needed for freeze-drying).
However, the mechanical strength can be compromised
and needs further improvement. Overall, the composite
was produced in a simple way and shows potential in
wastewater treatment. Thus, the adsorbent enables
more secure discharged water and could be used in a
downstream process where metals-free water is desirable.
Acknowledgements
LÖ and RQF also would like to acknowledge Prof. Ola Wendt
from the Centre for Analysis and Synthesis, Lund University
for his comments on the material description of the STNTs.
We acknowledge Dr. Anna Carnerup at the national centre for
high-resolution electron microscopy (nCHREM) for TEM images.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
LÖ would like to acknowledge the Swedish Research Council
[grant number 2014-6839] for funding as well as Region
Skane. RQF gratefully acknowledges SIDA (Swedish Inter-
national Development Cooperation Agency) for supporting
Sweden-Bolivia cooperation project (No. 75000553-04). RW
acknowledges the Knut and Alice Wallenberg Foundation and
NanoLund for support to nCHREM.
ORCID
Roxana Quiroga-Flores http://orcid.org/0000-0002-1322-
9395
Reine Wallenberg http://orcid.org/0000-0002-0850-0398
Linda Önnby http://orcid.org/0000-0002-5592-0539
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