Chemosphere 308 (2022) 136267

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Hydrothermal synthesis temperature induces sponge-like loose silica

structure: A potential support for Fe2O3-based adsorbent in treating As
(V)-contaminated water
Thanapha Numpilai a, 1, Kim Hoong Ng b, 1, Nutkamaithorn Polsomboon c, d, Chin Kui Cheng e,
Waleeporn Donphai c, d, Metta Chareonpanich c, d, Thongthai Witoon c, d, *
a
Department of Environmental Science, Faculty of Science and Technology, Thammasat University, Pathum Thani, 12120, Thailand
b
Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City, 24301, Taiwan, ROC
c
Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok, 10900,
Thailand
d
Center for Advanced Studies in Nanotechnology for Chemical, Food and Agricultural Industries, KU Institute for Advanced Studies, Kasetsart University, Bangkok,
10900, Thailand
e
Center for Catalysis and Separation (CeCaS), Department of Chemical Engineering, College of Engineering, Khalifa University, P.O. Box 127788, Abu Dhabi, United
Arab Emirates

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Pore sizes increased with increasing

hydrothermal synthesis temperature.
• SiO2 with close-packed structure ob­
tained at 60–100 ◦ C.
• SiO2 with sponge-like loose structure
formed at 140–180 ◦ C.
• Structures of SiO2 were more dominant
in As(V) adsorption compared to pore
sizes.
• Fe2O3/SiO2 with sponge-like structure
had the highest As uptake of 7.4 mg g− 1.

A R T I C L E I N F O A B S T R A C T

Handling editor: Fateme Karimi Low cost Fe2O3-based sorbents with an exceptional selectivity toward the targeted As(V) pollutant have gained
extensive attention in water treatment. However, their structural features often influence removal performance.
Keywords: In this respect, we present herein a rational design of silica-supported Fe2O3 sorbents with an enhanced
Porous silica materials morphological structure based on a simple temperature-induced process. Low-hydrothermal temperature syn­
Hydrothermal treatment temperature
thesis (60 and 100 ◦ C) provided a large silica-cluster size with a close packed structure (S-60 and S-100),
Adsorption
contributing to an increase in mass transport resistance. Fe2O3/S-60 with 6.2-nm pore width silica achieved a
Arsenic removal
Sponge-like structure maximum As(V) uptake capacity (qm) of only 3.5 mg g− 1. Supporting Fe2O3 on S-100 with an approximately two-
fold increase in the pore size (13 nm) did not lead to any evident enhancement in qe (3.7 mg g− 1). However,
expanding the pore window up to 22.6 nm (S-140) and 39.5 nm (S-180), along with changing from close-packed

* Corresponding author. Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty of Engineering, Kasetsart
University, Bangkok, 10900, Thailand.
E-mail address: fengttwi@ku.ac.th (T. Witoon).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.chemosphere.2022.136267
Received 6 June 2022; Received in revised form 3 August 2022; Accepted 27 August 2022
Available online 30 August 2022
0045-6535/© 2022 Elsevier Ltd. All rights reserved.
T. Numpilai et al.
to sponge-like loose structures induced by high-temperature synthesis (140 ◦ C and 180 ◦ C), resulted in sub­
stantial increases in qm. Fe2O3/S-140 had 1.7 and 1.6 times higher qm (5.9 mg g− 1) than Fe2O3/S-100 and Fe2O3/
S-60, respectively. The highest qm (7.4 mg g− 1) was achieved for Fe2O3/S-180, which was attributed to its
relatively small-sized silica cluster and the largest cavities that facilitated easier access by As(V) to adsorbing
sites.
1. Introduction
Environmental disturbance by widespread arsenic (As) contamina­
tion, particularly in water supplies, requires immediate action because
arsenic is lethal and has cancer-causing properties (Ahmad and Bhat­
tacharya, 2019; Shahid et al., 2018). arsenic originates naturally but
cannot be degraded by bioprocessing so that it remains permanently in
surroundings and ultimately transfers to food chains, causing ill effects
to living species. Typically, arsenic is emitted and dispersed into the
environment through geological events (erosion of rocks/minerals and
volcanic eruptions) as well as industrial and agricultural activities
(mining operations, burning of fossil fuels and the use of chemicals to
destroy insect pests and weeds for preserving wood) (Ahmed et al.,
2022; Yadav et al., 2021). People may come in contact with arsenic by
inhalation of polluted air or dermal exposure, but mostly following the
ingestion of contaminated water. A massive intake of arsenic, even for a
short period, can result in severe or even fatal symptoms due to car­
diovascular collapse and hypovolemic shock. Prolonged exposure to
low-level arsenic contributes to dermatological changes, liver and kid­
ney damage, neurological function disorder and several malignancies
(Monteiro De Oliveira et al., 2021; Rahman et al., 2018). As it is difficult
to heal chronic poisoning without side effects and specific treatments are
not yet available, a reduction in arsenic-induced disease risk is best
advanced by reducing the level of arsenic in the environment and spe­
cifically in water.
Several technologies based on physical, chemical and biological
processes have been developed for treating arsenic-polluted water,
including precipitation (Du et al., 2016; Li et al., 2022b),
flocculation-coagulation (Goren and Kobya, 2021), adsorption (Sherlala
et al., 2019), ion exchange (Chen et al., 2020) and membrane-assisted
separation (reverse osmosis, nanofiltration and electrodialysis) (Mor­
eira et al., 2021; Ortega et al., 2017; Qiu et al., 2022). Compared to other
methods, the adsorption process is of particular interest because it has
lower cost and energy requirements, is easier to operate and provides
greater efficiency with less waste generated (Karimi et al., 2022).
Iron-based adsorbents, have specific affinity toward arsenic, are cheap
and environmentally safe; consequently, they have been applied
extensively for arsenic sorption (Gong et al., 2020; Lin et al., 2022).
Effective efficacy in water decontamination often relies on the small
particle size of iron oxides that provide abundant adsorptive sites for
adsorbate molecules and contribute greatly to optimizing uptake ca­
pacity (Faria et al., 2014; Yavuz et al., 2006). The iron oxide hydroxide
(FeOOH) with a smaller particle size had 2.5-fold and 3-fold greater
adsorption capacity for As(III) and As(V), respectively, compared to
larger particles (Usman et al., 2018).
Immobilizing iron nanoparticles on support materials, such as silica
(Jamasbi et al., 2022; Song et al., 2022; Zhou et al., 2020), carbon (Islam
et al., 2021; Vazquez-Jaime et al., 2020), zeolite (Li et al., 2022a) and
alumina (Inchaurrondo et al., 2019), can promote iron species growth in
the form of small particles and enhance resistance to their clumping
simultaneously, which is beneficial for applying in the continuous
operation of a column-filtration system. However, the structure of the
matter exerts considerable influence on molecular diffusion, leading to
an improvement or lag in the adsorption rate. A relatively large particle
size results in high internal transfer resistance, delaying the moving of
molecule towards active sites (Numpilai et al., 2022). Likewise, diffu­
sion resistance is more intense inside the finite pore, thereby resulting in
lower sorbent effectiveness (Dai et al., 2016; Ge et al., 2018). Therefore,
2
Chemosphere 308 (2022) 136267
it is very attractive but challenging to enhance the adsorption perfor­
mance of arsenic using iron oxide nanoparticles embedded in a support
without a mass transfer effect. Designing materials with a multiple pore
structure or extraordinary morphology is one of the most promising
strategies (Chen et al., 2020; Yang et al., 2020). Hasan et al. (2019)
disclosed that the silica nanosphere (KCC-1) with a fibrous morphology
exhibited a good potential and reusability in eliminating Pb(II) from
aqueous solution with the percentage removal of 75%. Graphene oxi­
de/hollow mesoporous silica composite also showed superior adsorp­
tion performance for methylene blue (Yilmaz, 2022).
Much attention has been paid to fabricating porous silica owing to its
outstanding features regarding a facile tunable pore size, exceptional
surface area and easily modified surface based on mass production.
Typically, various swelling agents, such as 1,3,5-trimethylbenzene
(TMB), 1,3,5-triisopropylbenzene (TIPB) and C6–C10 alkanes have
been applied to expand the pore diameter of mesoporous silica-based
materials (Awoke et al., 2020; Santos et al., 2016; Zhou et al., 2019).
These molecules can be incorporated into the core of surfactant micelles
and are involved in enlarging their size, resulting in an increase in pore
space after eradicating the template. Mesoporous silica, with a pore
diameter of up to 20 nm, can be created using a pluronic F127 triblock
copolymer as a structural-directing component and TMB as a pore
expander, to fabricate an excellent carrier for delivering protein (Ban­
che-Niclot et al., 2021). Nevertheless, these chemicals suffer from high
cost and in combination with a solubility enhancer, such as ammonium
fluoride (NH4F), can pose toxicity issues to the environment. In addition,
high temperature is required to eliminate the template, making the
procedure less attractive for silica production, especially in a large-scale
system, and thus a green method to access the large-size pore structure is
highly desirable.
Hence, we focused on an uncomplicated and low-cost approach for
efficient manufacturing a pore size-adjustable silica substance through
hydrothermal restructuring in the absence of a pore extender. As far as
we know, there has been no investigation to date supporting Fe2O3 on
silica materials prepared using a temperature-induced process and
applying them as adsorbents for trapping As(V) from water. In this work,
the silica supports were synthesized at different hydrothermal treatment
temperatures (60, 100, 140 and 180 ◦ C) from sodium silicate, an inex­
pensive and environmental-friendly precursor, followed by the system­
atic evaluation of the influence of the structure of silica-supported Fe2O3
adsorbents on water purifying efficiency.
2. Experimental
2.1. Synthesis protocol for porous silica materials
Porous silica supports were fabricated using a hydrothermal-assisted
technique. Initially, sodium silicate solution was poured into a 100:1
mixture of DI water and acetic acid while agitating at 40 ◦ C. Then, the
pH was adjusted to 6 using 2 M HCl. After aging the solution for 3 h at
40 ◦ C, it was hydrothermally treated at different temperatures (60, 100,
140 or 180 ◦ C) in a tightly closed autoclave for 24 additional hours. The
resulting products were filtered to separate the solid from the solution,
followed by consecutive steps of washing, drying (100 ◦ C, 12 h) and
calcining (600 ◦ C, 4 h). The obtained materials were denoted as S-X,
where X corresponded to the hydrothermal treatment temperature
expressed in degrees Celsius.
T. Numpilai et al. Chemosphere 308 (2022) 136267

2.2. Synthesis protocol for silica-supported Fe2O3 sorbents

An impregnation method was used to deposit Fe2O3 (10 wt%) onto
silica materials. The desired amount of Fe(NO3)3⋅9H2O was dissolved in
DI water to form a clear solution and then silica (1 g) was added. The
resulting mixture was heated at 60 ◦ C under stirring until the liquid had
been completely evaporated. Afterward, the collected solid was dried at
100 ◦ C for 24 h, followed by calcination at 400 ◦ C for 4 h.
2.3. Adsorption experiments
Batch experiment of As(V) adsorption was carried out by adding
adsorbent (0.1 g) into As(V) solution (100 mL) with the desired initial
concentration. The mixture was maintained at 35 ◦ C under shaking (250
rpm) for 36 h to reach equilibrium. After a predetermined interval, the
suspension was taken out for analysis of residual As(V) using a UV–Vis
spectrophotometer (Thermo Scientific, Genesys 10S) based on the
molybdate method according to Verma and Singh (2019). The adsorbed
amount of As(V) per adsorbent mass (qt) and As(V) removal efficiency
were calculated using the following equations:
V(C0 − Ct )
qt = (1)
m
(C0 − Ct )
Removal efficiency (%) = × 100 (2)
C0
where V represents the solution volume of As(V) (L), C0 is the initial As
(V) concentration (mg L− 1), Ct is the residual As(V) concentration at
time t (mg L− 1) and m is the weight of adsorbent (g). All experiments
were repeated in triplicate to ensure the reliability of results, and the
average value was reported. The spent adsorbents were regenerated
after each test using 0.1 M NaOH for 6 h and washed with deionized
water for reutilization (Liu et al., 2018). Information on the character­
ization methods and the equations in the isotherm and kinetic models
for data fitting are provided in the supplementary information.

Fig. 1. N2 sorption isotherms and pore size distributions of different silica supports and Fe2O3-loaded silica materials: S-60 and Fe2O3/S-60 (a), S-100 and Fe2O3/S-
100 (b), S-140 and Fe2O3/S-140 (c) and S-180 and Fe2O3/S-180 (d).

3
T. Numpilai et al. Chemosphere 308 (2022) 136267

3. Results and discussion void spaces.

The TEM and HRTEM images of Fe2O3 and Fe2O3 supported on silica
3.1. Structural properties of prepared materials materials prepared with different hydrothermal temperatures are shown
in Fig. 3. As shown in Fig. 3a, primary Fe2O3 nanoparticles with about
Porosimetry analysis, based on the N2 adsorption-desorption iso­ 20 nm in size were stuck tightly to neighboring nanoparticles, forming
therms and the BJH pore size distribution of the silica substances hy­ sub-micrometer-sized particles. The samples subjected to hydrothermal
drothermally treated at different temperatures (60 ◦ C, 100 ◦ C, 140 ◦ C or treatment at 60 ◦ C and 100 ◦ C displayed close-contact nanoparticle
180 ◦ C) are illustrated in Fig. 1. The isotherms of all samples resembled aggregates without macrovoids (Fig. 3b and c). Cleary, increasing the
type IV, revealing their dominant pore dimension at the meso-scale. The hydrothermal temperature from the low-temperature region (60 ◦ C and
silica support synthesized at the low hydrothermal temperature of 60 ◦ C 100 ◦ C) to the high temperature of 140 ◦ C caused a notable change in the
(S-60) exhibited a H2 hysteresis loop, encountered for material with structural appearance to a foam-like network morphology with large
holes with a cramped entrance and large cage (Fig. 1a). The pore width cavities (Fig. 3d). This structure was still well-preserved and enlarged
distribution diagram had one narrow peak centered at 6.2 nm, repre­ gaps resulted when the treatment temperature increased to 180 ◦ C
senting the pore throat size (inset in Fig. 1a). As the temperature of the (Fig. 3e). It was noteworthy that a substantial decrease in the Fe2O3
hydrothermal treatment increased to 100 ◦ C, the adsorption-desorption particle size to ~4–5 nm was observed whether applying a dense or
cycle changed from the H2 to H1 type, displaying two parallel ascending loose silica structure (Fig. 3b–e).
and descending branches, evidencing a columnar-like pore structure in
the S-100 sample (Fig. 1b). The pore diameter was distributed over a 3.2. As(V) adsorption performances
relatively narrow range, with an average value of 13 nm, corresponding
to space among the stacked particles with a fairly uniform size (inset in Fig. 4a and b shows the percentage removal of As(V) at different
Fig. 1b). With further increases in the hydrothermal temperature to intervals for the Fe2O3 and silica-supported Fe2O3 sorbents evaluated
140 ◦ C and 180 ◦ C, the hysteresis loop feature was not perturbed to a under identical conditions of 35 ◦ C, pH 5, 5 mg L− 1 As(V) concentration
great extent but an abrupt upturn of capillary condensation phenome­ and 1 g L− 1 sorbent dosage. All sorbents were capable of efficiently
non occurred at high relative pressure (P/P0) approaching 1, demon­ decreasing the level of As(V) in water. As(V) was eliminated rapidly in
strating an enlargement of the pore width to 22.6 nm (Figs. 1c) and 39.5 the early stage and then slowed down, reaching a nearly constant value.
nm (Fig. 1d), respectively. As shown in Fig. 1a, the N2 isotherm of Fe2O3 As shown in Fig. 4b, removal percentages of 10.9%, 11.9%, 32.7 and
alone displayed a type-IV curve with a quite low amount of gas adsor­ 42.6% were reached within 5 min contact time for Fe2O3/S-60, Fe2O3/S-
bed, suggesting that it was also made up of mesopores (11.2 nm) but had 100, Fe2O3/S-140 and Fe2O3/S-180, respectively, which were higher
a low surface area and pore volume. Decorating Fe2O3 on the silica than for bulk Fe2O3 (6%). Increasing the adsorption time was conducive
supports brought lower N2 adsorption capacity, given the pore filling by to an improvement in As(V) removal efficiency. At 1 h, Fe2O3 supported
Fe2O3 particles. All parameters of textural properties (BET surface area, on S-60 and S-100 provided trapping performance levels of 27.5%
pore volume and BJH pore size) of all samples are summarized in (Fe2O3/S-60) and 32.2% (Fe2O3/S-100), which were slightly lower
Table 1. The surface area of the silica materials progressively decreased, compared to Fe2O3 alone (34.2%) because of the relatively large cluster
while the pore volume and pore size increased with increasing treatment sizes with compacted structures for S-60 and S-100 (Fig. 2) that
temperatures. contributed to an increase in internal resistance to mass transfer, thus
Fig. 2 illustrates SEM micrographs of the porous silica materials delaying the mobility of As(V) to the adsorptive sites. Exceeding 70%
prepared using different hydrothermal temperatures. The SEM image of removal percentage for As(V) was accomplished over Fe2O3/S-140 and
S-60 revealed the close-packed structure of globule-like particles with Fe2O3/S-180. Nevertheless, prolonged contact time beyond 1.5 h and 2 h
sub-100 nm size. Upon applying an elevated temperature of 100 ◦ C led to an increase in the removal performance for Fe2O3/S-60 and
during the thermal treatment process (S-100), a rather dense clump Fe2O3/S-100 which could dispose of more As(V) than did Fe2O3. At
could be observed but some void spaces were apparent. Raising the equilibrium, the As(V) removal efficiency levels by Fe2O3 decorated on
hydrothermal temperature to 140 ◦ C led to a clear change in morpho­ silica supports prepared at high hydrothermal temperatures were much
logical features from tight to loose agglomerates (S-140), reflecting the greater than from low-temperature synthesis and unsupported Fe2O3, in
influence of temperature-induced restructuring. The 180 ◦ C processing the following order: Fe2O3/S-180 (97.6%) > Fe2O3/S-140 (96.9%) >
temperature clearly modified the structure of silica, resulting in a more Fe2O3/S-100 (72.7%) > Fe2O3/S-60 (68.2%) > Fe2O3 (57.8%). The
sponge-like feature. The nanoparticles were attached to each other but factors affecting the effectiveness of sorbents were examined using the
not as much as in S-140, forming a small cluster size with relatively large correlation between As(V) saturated uptake capacity (qe) and Fe2O3
crystallite size (Fig. 4c) as well as silica support pore size (Fig. 4d). In
this work, actual equilibrium adsorption capacity of As(V) (qe) was
Table 1
obtained by varying the initial concentration of As(V) in the range 1–35
Textural properties of different silica materials, bare Fe2O3 and Fe2O3-loaded
mg L− 1. As shown in Fig. 4c, the relatively smaller particle size of Fe2O3
silica materials and Fe2O3 crystallite sizes.
loaded on silica materials (4–5 nm) was profoundly beneficial to scav­
Sample BET surface Pore volume BJH pore Fe2O3 crystallite enging As(V) from water, providing 1.2–2.5 times higher qe than for the
area (m2 g− 1) (cm3 g− 1) diameter (nm) size (nm)a
ultra-large size of unsupported Fe2O3 (20 nm). However, the qe value
S-60 446 0.71 6.2 – was not directly correlated with the Fe2O3 crystallite size upon
S100 274 0.9 13 –
dispersing the Fe2O3 on the silica supports. The smallest Fe2O3 particle
S140 236 1.22 22.6 –
S180 152 1.43 39.5 – size of 4 nm (Fe2O3/S-60) could achieve adsorption ability of only 3.5
Fe2O3 49 0.24 11.2 20 mg g− 1 which was quite similar to 3.7 mg g− 1 for the Fe2O3/S-100 but
Fe2O3/S- 378 0.57 6.3 4 was much lower than for sorbents with a slightly larger Fe2O3 size (5
60 nm). In addition, although the Fe2O3 sizes of Fe2O3/S-140 and Fe2O3/S-
Fe2O3/S- 272 0.79 11.6 4
100
180 were both 5 nm, supporting Fe2O3 on S-180 produced the highest qe
Fe2O3/S- 221 0.96 22.5 5 value of 7.4 mg g− 1, while Fe2O3/S-140 had a saturation uptake capacity
140 of 5.9 mg g− 1 for As(V). The positive impact of the silica-supported
Fe2O3/S- 142 1.05 40.4 5 Fe2O3 sorbents on As(V) removal performance seemed to be depen­
180
dent on the pore size of the silica materials (Fig. 4d). The enhancement
a
From TEM analysis. in qe as the pore diameter increased from 6.2 nm to 39.5 nm affirmed

4
T. Numpilai et al.
Fig. 2. SEM micrographs of porous silica materials prepared at hydrothermal temperatures of 60 ◦ C (S-60), 100 ◦ C (S-100), 140 ◦ C (S-140) and 180 ◦ C (S-180).
that the existence of a large cavity in the structure enhanced the
accessibility of As(V) to adsorbing sites, which was beneficial for
reducing the level of As(V) pollution. However, it was noteworthy that
the difference in pore channels of 6.2 nm (S-60) and 13 nm (S-100) did
not produce any evident difference in qe values, while a predominant
increase in qe was observed by extending the pore scale from 13 nm to
22.6 nm (S-140). This was attributed to an alteration in the morpho­
logical structure of the silica material from the compacted structure for
S-100 (13 nm size pore) to the sponge-like structure with relatively
lower cluster size for S-140 (22.6 nm size pore), which could facilitate
the diffusion of As(V) into active sites. Furthermore, increasing the pore
width to 39.5 nm (S-180) increased qe to a maximum value of 7.4 mg
g− 1. To verify the binding of As(V) on sorbent surface, FTIR spectra of
Fe2O3/S-180 before and after As(V) adsorption were examined and the
results are shown in Figure S1. Before adsorption of As(V), IR spectra of
Fe2O3/S-180 showed a broad band centered at ~3450 cm− 1 which was
attributed to –OH stretching vibrations (ν-OH) of silanol groups and
adsorbed H2O. A band at ~1632 cm− 1 signified –OH bending (δ-OH) of
H2O molecules. The characteristic peaks of silica including bending
Si–O–Si mode, and symmetric and asymmetric stretching Si–O–Si vi­
brations appeared at ~470, 810 and 1110 cm− 1, respectively. There was
no significant change in the spectra of Fe2O3/S-180 after As(V)
adsorption (Fe2O3/S-180-As(V)), and no bands associated with arsenic
species were identified because of the low amount of arsenic in the
sorbent. However, an effective trapping of As(V) by Fe2O3/S-180 was
confirmed by SEM-EDX mapping analysis, as shown in Figure S2.
Observably, As(V) was uniformly distributed over Fe2O3/S-180 surface,
which exhibited excellent structural stability after adsorption. Overall,
these results implied that both the pore diameter and textural
morphology of the silica material contributed to determining the
adsorption capability of silica-supported Fe2O3 sorbents, where the
morphological structure was more dominant.
3.3. Adsorption isotherms of various sorbents for As(V)
In order to understand the adsorption behavior of As(V) on the silica-
supported Fe2O3 sorbents and to assess the potential use of these sor­
bents, two prevalent used isotherm models, Langmuir and Freundlich
5
Chemosphere 308 (2022) 136267
were applied in simulating the experimental adsorption data. These
models were simple to interpret and relatively accurate for dis­
tinguishing between physical and chemical adsorption process, and also
provided valuable information for an improvement of adsorbent mate­
rials and effective design of adsorption system. Typically, the adsorption
of pollutants on almost all sorbent materials often followed Langmuir or
Freundlich isotherm (Rangabhashiyam et al., 2014). Langmuir model
dealt with monolayer adsorption in which each identical sorption site
could accommodate only one sorbate molecule, and no interaction took
place between the adsorbed molecules. Therefore, it considered the
adsorption to be a chemisorption process. While, Freundlich model took
into account the multilayer adsorption on heterogeneous surface of
adsorbent, which represented a physical adsorption. Fig. 5a illustrates
the fitted experimental data, evaluated at different initial concentrations
(1, 2.5, 5, 15, 25 and 35 mg L− 1), with Langmuir and Freundlich
isotherm models (model equations are provided in the Supplementary
Information). The corresponding linear fits are given in Fig. 5b and c,
respectively, and the calculated adsorption isotherm parameters are
summarized in Table S1. The results demonstrated that the adsorption of
the Fe2O3 and silica-supported Fe2O3 sorbents toward As(V) was more
validly described by the Langmuir equation (R2 = 0.9946–0.9995)
compared to the Freundlich equation (R2 = 0.7254–0.8091), indicating
that As(V) could only adhere to adsorptive site homogeneously distrib­
uted throughout the adsorbent surface one-by-one, forming a
single-molecule thick layer known as monolayer coverage. According to
the Langmuir results, Fe2O3 loaded on silica material prepared at the
highest hydrothermal temperature (Fe2O3/S-180) outperformed the
others in terms of maximum mass of As(V) adsorbed per equivalent
sorbent dosage (qm), as follows: Fe2O3/S-180 > Fe2O3/S-140 >
Fe2O3/S-100 > Fe2O3/S-60. The dimensionless equilibrium parameter
(RL) was determined at the given As(V) concentration range (1–35 mg
L− 1). The calculated RL values ranging from 0.003 to 0.067 (0<RL < 1)
implied that the adsorption process was favorable under the designed
conditions.
3.4. Adsorption kinetics of various sorbents for As(V)
The kinetic models are used to describe the adsorption rate of
T. Numpilai et al.
Fig. 3. TEM and HRTEM images of Fe2O3 (a), Fe2O3/S-60 (b), Fe2O3/S-100 (c), Fe2O3/S-140 (d) and Fe2O3/S-180 (e).
adsorbate at the solid surface which was related to the design and
development of adsorbents in industrial scale. The overall rate of the
adsorption is generally controlled by diffusion through a boundary
liquid film (physical adsorption) and chemical adsorption. In order to
predict whether the adsorption of As(V) on Fe2O3 supported modified
SiO2 materials was governed by the diffusion through a boundary liquid
film or chemical adsorption (Agbovi and Wilson, 2021; Ho and McKay,
1999), two models, namely pseudo-first order and pseudo-second order
rate laws (model equations are provided in the Supplementary Infor­
mation), were applied to interpret the adsorption characteristics. In
addition, the Intra-particle diffusion model was used to describe the
effect of the closed-packed and sponge-like structures of adsorbents on
As(V) adsorption.
Non-linear and linear fitting curves of the pseudo-first order and
6
Chemosphere 308 (2022) 136267
pseudo-second order dynamic models are shown in Fig. 6. As can be seen
in Table S2, the higher R2 value (0.9956–1) and the closeness of the
adsorption equilibrium quantity (qe) of the calculated (qe,cal) and
experimental (qe,exp) data for the pseudo-second order model indicated
that the adsorption of As(V) on all sorbents followed a chemisorption
mechanism corresponding to binding of As(V) to the surface of Fe2O3. It
was observed from the model-predicted values that Fe2O3/S-180 had
slightly superior equilibrium adsorption capacity (qe,cal = 4.9 mg g− 1)
and an ultra-fast removal rate for As(V) (k2 = 0.0243 g mg− 1 min− 1)
with respect to Fe2O3/S-140 (qe,cal = 4.8 mg g− 1, k2 = 0.0118), and even
greater than Fe2O3 supported on S-100 (qe,cal = 3.7 mg g− 1, k2 = 0.0038)
and S-60 (qe,cal = 3.5 mg g− 1, k2 = 0.0035), as well as on unsupported
Fe2O3 (qe,cal = 2.9 mg g− 1, k2 = 0.0066). Intra-particle diffusion model
analysis for Fe2O3 and Fe2O3 decorated on S-60 and S-100 (Fig. 6d)
T. Numpilai et al. Chemosphere 308 (2022) 136267

Fig. 4. Adsorption performance of As(V) on different sorbents (a) and (b), qe versus Fe2O3 crystallite size plot (c) and qe versus pore size plot (d) of all sorbents.
Conditions: C0 = 5 mg L− 1, 35 ◦ C, pH = 5 and ratio of sorbent mass to solution volume of As(V) = 1 g L− 1.

Fig. 5. Adsorption isotherms (a) and linear fitting of Langmuir (b) and Freundlich (c) isotherms for Fe2O3 and different silica-supported Fe2O3 adsorbents. Con­
ditions: 35 ◦ C, pH = 5 and the ratio of sorbent mass to solution volume of As(V) = 1 g L− 1.

7
T. Numpilai et al.
Fig. 6. Experimental data fitted with pseudo-first order and pseudo-second order kinetic models (a), linear fitting of pseudo-first order (b) pseudo-second order (c)
and intraparticle diffusion (d) kinetic models for As(V) adsorption on Fe2O3 and different silica-supported Fe2O3 sorbents. Conditions: C0 = 5 mg L− 1, 35 ◦ C, pH = 5
and the ratio of sorbent mass to solution volume of As(V) = 1 g L− 1.
showed three-segmented straight lines with different slopes, represent­
ing that three diffusion steps controlled the rate of As(V) binding to the
adsorbent surface: (I) external diffusion across the film layer (II) diffu­
sion within the internal structure and (III) diffusion to saturated
adsorptive sites. The second stage was not apparent in the plot of qt
against t1/2 for both Fe2O3/S-140 and Fe2O3/S-180, suggesting that
transportation inside particles did not influence the rate of As(V)
adsorption. In other words, mass transfer from the outer to the inner
structure of the adsorbents occurred easily and rapidly due to the
absence of internal mass transfer resistance. Taking the large-size pore
and small-size cluster in S-140 and S-180 into consideration, it could be
concluded that a short transport distance and an internal mass transfer-
resistance-free structure were more favorable to boosting the adsorption
performance of the silica-supported Fe2O3 sorbent.
3.5. Reusability study
The reusability of Fe2O3/S-180 was investigated over five successive
runs of adsorption-desorption cycles. It can be seen that there was a
slight decrease in As(V) removal efficiency over the cycles. At the end of
the fifth cycle, the removal efficiency was 92.4% which was negligibly
lower compared to 97.6% in the first cycle (Figure S3). This result
indicated that Fe2O3/S-180 had an excellent reusability with great po­
tential for industrial-scale applications. For the management of the spent
8
Chemosphere 308 (2022) 136267
adsorbents, the As(V) and Fe2O3 can be removed from the surface of
silica materials and the bare porous silica materials can be reused in
many applications such as catalyst supports and insulator materials
(Baskar et al., 2022; Rial and Ferreira, 2022). In addition, at the
end-of-life stage they can be thermally treated and disposed in a landfill
(Baskar et al., 2022; Kasiuliene et al., 2020).
4. Conclusions
The hydrothermal treatment process could effectively enhance the
structural morphology of silica-supported Fe2O3 sorbents. High treat­
ment temperatures (140 ◦ C and 180 ◦ C) induced the formation of large
void spaces up to 22.6 nm (S-140) and 39.5 nm (S-180) as well as pro­
moting a structural change to a foam-like structure, which were crucial
to achieving superior maximum As(V) adsorption capacity (qm). Fe2O3/
S-180 achieved the best qm of 7.4 mg g− 1, which was 1.3-fold higher
than for Fe2O3/S-140 (5.9 mg g− 1) that had the same morphology.
Synthesis at low temperatures (60 ◦ C and 100 ◦ C) not only resulted in
smaller pore diameters of 6.2 nm (S-60) and 13 nm (S-100) compared to
high-temperatures synthesis, but also provided relatively large cluster
sizes with a compacted structure, leading to a lower qm of 3.5 mg g− 1
(Fe2O3/S-60) and 3.7 mg g− 1 (Fe2O3/S-100). Lastly, the best sorbent
(Fe2O3/S-180) provided a high As(V) uptake capacity, which could
competitive to the other Fe-based adsorbents and showed favorable
T. Numpilai et al.
stability after five sorption-regeneration repetitions. Importantly, the
design of a low-cost manufacturing process using the inexpensive and
environmental-friendly raw material, and applying easy and uncom­
plicated method for the synthesis made Fe2O3/S-180 a promising sor­
bent for practical applications in an industry.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This project was funded by: the Kasetsart University Research and
Development Institute (KURDI), FF(KU)2.65 and the National Research
Council of Thailand (N42A640324). C.K. Cheng would like to
acknowledge the Khalifa University (RC2-2018-024) Phase 2 fund
(project reference number 8474000133).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.chemosphere.2022.136267.
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