Journal of Environmental Chemical Engineering 3 (2015) 2727–2737

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Journal of Environmental Chemical Engineering

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

Mesoporous titania spheres derived from sodium alginate-gum acacia

composite beads: Efficient adsorbent for “Reactive blue H5G” dye
V. Singh* , Preeti
Department of Chemistry, University of Allahabad, Allahabad 211002, India

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

Article history: Dye sorbing mesoporous titania spheres (TS) are being reported in the present communication. TS were
Available online 30 September 2015 fabricated by polymerizing titanium (IV) isopropoxide under the templating and structure directing
influence of sodium alginate-gum acacia composite beads. The TS synthesis was optimized by varying the
reaction parameters while targeting the removal of reactive blue H5G dye from aqueous solutions, which
Keywords: was chosen as model reactive azo dye for the study. The optimum performance TS (TSAA11) sample has
Titania spheres
been extensively characterized using Fourier transform infrared spectroscopy, X-ray diffraction study,
Alginate-gum acacia composite beads
scanning electron microscopy, and Brunauer–Emmett–Teller analysis. Under the optimized conditions
Reactive blue dye
Adsorption
TSAA11 was capable of capturing 92% dye from 100 mg/l dye solution. The adsorption equilibrium data
indicated that the TSAA11 has high Q0 (100) mg/g and heterogeneous surface sites for the adsorption. A
linear plot of t/(qt) vs. t indicated that the dye sorption followed pseudo-second-order kinetics which
supported chemisorption. The rate constants at 100, 150, 200 mg/l initial dye concentrations were
1.48
103, 2.65
103, and 10.6
102 g/mg min respectively. The used TSAA11 was recovered with 1 M
NaOH and used for three consecutive cycles where it was possible to remove 87% dye even in the third
cycle. Photocatalytic study indicated that TSAA11 is capable of degrading 86% dye from 100 mg/l dye
solution under the exposure to sunlight for 5 h. This study indicates that TSAA11 may be utilized as
promising adsorbent for reactive anionic azo dyes.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction technique of water remediation due to its low initial cost,

The minimization of water contamination is the emerging area
of research in the developing countries due to strict environmental
regulations over the world [1]. The effluents from industries such
as leather tanning, paper production, food technology, printing,
textile, and coloring carry many toxic dyes [2,3] to water bodies by
virtue of which water becomes colored and unacceptable for
consumption [4,5]. The removal of synthetic dyes from the
industrial effluents is necessary as they are mutagenic and
carcinogenic besides being genotoxic and resistant to natural
degradation [6–8]. Reactive dyes are known for their brilliant and
broad range of color shades. The most common reactive dyes are
anthraquinone, phthalocyanine, and azo dyes [9] which are
enormously discharged to water systems by industries [3]. The
conventional treatment processes together with chemical oxida-
tion, physical separation, and biological degradation are not always
effective and economic where the contaminant’s concentrations
are very low [10]. Adsorption is an effective, versatile and reliable
* Corresponding author: Tel.: +91 9415310942.
E-mail address: vschemau@gmail.com (V. Singh).
simplicity of design, ease of operation and insensitivity to toxic
substances [11]. A voluminous literature is available on the dye
adsorption by activated carbon [12,13], zeolite [14], fly ash [15],
chitosan [16], biological materials [17] composites [18,19], and
metal oxide nano adsorbents [20].
TiO2 spheres having 3D nanostructure perform as competitive
adsorbent [21] due to their high surface area and good mechanical
robustness. Solvothermal synthesis of titanium hollow spheres is
reported where combined templation of Tween 20 and polyethyl-
ene glycol 1000 vesicles have been used [22]. These spheres have
shown admirable properties such as great internal space, high
mechanical & thermal stability, surface area, crystalline frame-
work, and low density. The adsorptive and photocatalytic property
of such materials have been used for the adsorption and
degradation of methylene blue dye. However the synthetic
polymer and surfactant used for synthesizing such spheres may
have environmental implications.
Polysaccharide templates are considered superior over the
synthetic polymers as they are natural, renewable, cheap and
abundant. Mesoporous titania beads with high surface area and
uniform size have been reported for the removal heavy metal ions

http://dx.doi.org/10.1016/j.jece.2015.09.021
2213-3437/ ã 2015 Elsevier Ltd. All rights reserved.
2728 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737

from simulated wastewater [23]. Very recently we designed
mesoporous titania spheres suitable for Hg(II) adsorption [24]
from sodium alginate-guar gum composite bead templated
polymerization of titanium (IV) isopropoxide. The ratio of alginate
(anionic polysaccharide) and guar gum (nonionic polysaccharide)
in the beads showed significant impact on the final characteristics
and performance of the spheres.
Based on our past experience with alginate-guar gum
templated titania spheres, in the present study we have planned
to design titania spheres using composite beads constituted of
sodium alginate and gum acacia. The adsorptive caliber of the
synthesized titania spheres have been evaluated for dye removal
using reactive blue H5G (RBH5G) as the model dye. Alginate [25] is a
polysaccharide, extracted from brown seaweed. It is constituted of
mannuronic and guluronic acid residues. Gum acacia is a natural
multifunctional acidic polysaccharide [26]. Incorporation of gum
acacia within alginate beads is likely to have significant influence
on the final characteristics of the beads and eventually on their
templating behavior.
Removal of reactive blue dye and adsorption activity of
alginate-gum acacia hybrid bead templated mesoporous titania
spheres are being reported for the first time. This study is
important as mesoporous titania spheres have been synthesized
using composite polysaccharide beads instead of using any
synthetic polymer and/or surfactant as template. Nevertheless
the removal of reactive azo dye using titania spheres has not been
previously studied.
2. Materials and methods
2.1. Chemicals and equipments
Titanium(IV) isopropoxide (97% purity) and 2-propanol (99%
purity) were purchased from Aldrich and Merck, India, respective-
ly. Absolute ethanol 99.9% (AR) was purchased from Changshu
Yangyuan Chemical, China. Sodium alginate (Food grade) was from
Loba Chemie. Calcium chloride (fused) and gum acacia sourced
from Acacia Senegal, were purchased from Merck, India. Double
distilled water was used in all the procedures. The pH values were
adjusted with the help of 5 M HCl (GR, Merck, 35%); or 1 M NaOH
(Merck). The dye was a gift from dye manufacturing company
where the usage of this dye was high. EUTECH Instruments pH
meter (model 510) was used for the pH measurements. Tempera-
ture treatment of the composite TiO2 spheres was done (in air) in
microprocessor controlled electric muffle furnace, Metrex Scien-
tific Instruments (P) Ltd., New Delhi, India. Orbital shaker
Incubator, Metrex Scientific Instruments (P) Ltd., New Delhi was
used. Brunauer–Emmett–Teller (BET) surface area and porosity of
the TS were determined by N2 adsorption–desorption isotherms
using a Quantachrome Instruments Autosorb 1C surface area
analyzer at 77 K. XRD was performed on Rigaku D/max-2200 PC
diffractometer operated at 40 kV/20 mA, using CuKa1 radiation
with wavelength of 1.54 Å in the wide angle region from 10 to 70 on
2-theta scale. The crystallite size was calculated from the full width
at half maximum of the major XRD peaks using Scherrer’s formula.
FTIR was done on PerkinElmer FTIR spectrophotometer. Scanning
electron microscopy (SEM) was done using FEG-SEM (JSM-7600F)
to examine microscopic morphology of the TiO2 spheres. The
samples were gold coated to avoid charging. Labtronics visible
Spectrophotometer model LT 39 was used to determine the dye
concentrations in the solution.
2.2. Synthesis of alginate-gum acacia hybrid beads
Mixed polysaccharide solutions were prepared [24] by dissolv-
ing known amounts of sodium alginate (0.1–0.5 g) and gum acacia
(0.0–0.4 g) in 25 ml water under continuous stirring at room
temperature so that the final concentration of mixed polysaccha-
ride solution is 2 wt%. To obtain jellified hybrid beads, the mixed
polysaccharide solutions were manually dropped into aqueous
Ca2+ baths of known concentrations (0.13–0.34 M) through 1.2 mm
diameter nozzle. The average size of the synthesized beads was
1.2 mm. The beads were kept in their respective calcium chloride
baths for 3 h, and were subsequently washed with water to remove
any excess Ca2+.
2.3. Synthesis of composite titania beads
The polysaccharide beads were dehydrated by equilibration in a
series of solvents ranging from water to ethanol and finally in
isopropanol (for 3 h in each solvent). The beads were soaked in the
3 ml mixture of titanium (IV) isopropoxide precursor sol (TIP) and
isopropanol (IP) of different ratio (v/v) (Table 1) for 16 h at room
temperature during which porous polysaccharide beads were
impregnated with titanium isopropoxide precursor sol. The
hydrolysis and polycondensation of the precursor in presence of
isopropanol resulted into composite titania beads, which were
dried in an oven at 35–40  C for 8 h after equilibration in a 1:1 (v/v)
water/isopropanol solution.
2.4. Synthesis of porous titania spheres (TS)
The dried composite titania beads were calcined in air to
different temperatures ranging from 300 to 750  C for 2 h at each

Table 1
Design of TS by varying different synthetic parameters at fixed polysaccharide concentration (2% w/v; mixed or neat), Dye adsorption was monitored at pH 2, contact volume
20 ml, contact time 8 h, rpm 150, TS dose 50 mg, temperature 30  C.

Alginate (g) Gum acacia (g) [CaCl2] (M) TIP (ml) IP (ml) Composite TiO2 beads Calcination ( C) TS Yield (g)
0.1 0.4 0.2 2.1 0.9 BAA1 450 TSAA1 0.206
0.3 0.2 0.2 2.1 0.9 BAA2 450 TSAA2 0.208
0.4 0.1 0.2 2.1 0.9 BSAA3 450 TSAA3 0.212
0.5 – 0.2 2.1 0.9 BSA 450 TSA 0.210
0.4 0.1 0.13 2.1 0.9 BSAA4 450 TSAA4 0.209
0.4 0.1 0.27 2.1 0.9 BAA5 450 TSAA5 0.211
0.4 0.1 0.34 2.1 0.9 BAA6 450 TSAA6 0.212
0.4 0.1 0.20 0.7 2.3 BAA7 450 TSAA7 0.210
0.4 0.1 0.20 1.4 1.6 BAA8 450 TSAA8 0.209
0.4 0.1 0.20 2.8 0.2 BAA9 450 TSAA9 0.212
0.4 0.1 0.20 2.1 0.9 BAA10 300 TSAA10 0.220
0.4 0.1 0.20 2.1 0.9 BAA11 550 TSAA11 0.196
0.4 0.1 0.20 2.1 0.9 BAA12 650 TSAA12 0.186
0.4 0.1 0.20 2.1 0.9 BAA13 750 TSAA13 0.172
0.5 – 0.20 2.1 0.9 BA1 550 TSA1 0.250
 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737
temperature. Titania spheres (TS) were obtained when the
templating polysaccharide beads burnt out during the calcination
of the composite titania beads.
2.5. Moisture retention by TS
All the synthesized dried and desiccated TS samples (0.1 g each)
were left overnight at room temperature in a watch glass and after
24 h gravimetric increase in the weight of the samples was
monitored to study the moisture retention ability of the samples.
2.6. Ash content of TS
To find out the ash content, 0.5 g TS was heated for 8 h on
Bunsen burner flame in a silica crucible and the remaining ash was
weighed to find out the ash content.% ash was calculated as under.
wt of the the crucible and ash  wt of the crucible
%Ash ¼
wt of the crucible þ sample  wt of the crucible

100
2.7. Dye removal using TS
Batch adsorption study was performed to study the effect of
experimental parameters such as pH, initial dye concentration,
adsorbent dose, and contact time. Standard stock solution of
reactive blue H5G dye was prepared by dissolving 5 g dye in 1 l
deionized double-distilled water which was subsequently diluted
with deionized water to the required initial concentrations
(50–300 mg/l). The dye solutions were adjusted to different pH
values by adding either 0.1 N HCl or 0.1 N NaOH.
The dye removal was optimized by varying one process
parameter while keeping the other parameters fixed. All batch
adsorption experiments were performed by adding 50 mg TS to
20 ml of dye solution (of appropriate concentration and pH) in a
50 ml flask thermostated at 30  2  C. The flasks were agitated on
an orbital shaker at 150 rpm for 8 h throughout the study. All
adsorption experiments were conducted in duplicate to check the
reproducibility of results. After shaking, the reaction mixture was
filtered by Whatman filter paper and the residual dye concentra-
tion in the solution was analyzed by visible spectrophotometer at
619 nm wavelength. The percentage removal of dye from the
solution was calculated based on the difference between the initial
Table 2
Details of the studied dye.
Dye C.I. Name Type
Reactive Blue H5G (blue) C.I. Reactive Blue 81 5-Amino-2-anilinobenzene-sulfonic acid
2729
and the final readings of dye concentration as given below:
ðC 0  C e ÞV
qe ðmg=gÞ ¼
W
where qe (mg/g) is the adsorption capacity after reaching the
equilibrium, C0 is the initial dye concentration (mg/l), Ce is the
equilibrium concentration of the dye in solution (mg/l), V is the
volume of dye solution (ml), and W(g) is the weight of the TS.
The adsorption isotherms were studied at temperatures
ranging from 30 to 50  C using 50 mg TS dose, 20 ml contact
volume, pH 2, rpm 150, and contact time 8 h. The kinetic study was
performed under the same conditions at three different initial dye
concentrations (100, 150 and 200 mg/l). Dye loaded TS were
desorbed by stirring with 1 M NaOH for 2 h at 60 rpm and were
reused in the next cycle.
3. Results and discussion
Alginate is constituted of homopolymeric blocks of (1 ! 4)-
ð1Þ
linked b-D-mannuronate (M) and a-L-guluronate (G) residues. It
has zig-zag conformation with “egg box” cavities framed at G
blocks. The polysaccharide can easily be shaped into spherical
beads by interacting with calcium ions and the size of the beads
can be controlled by using an appropriate nozzle sized dropping
device. Gum acacia on the other hand is a polyanionic polysaccha-
ride which is composed of D-galactose, L-arabinose, L-rhamnose, D-
glucuronic acid, and 4-O-methyl-D-glucuronic acid [26]. Composite
beads of unique microstructure and characteristics, different from
pure alginate beads were obtained using the mixed polysaccharide
solution. The composite bead templation furnished composite
titania spheres on calcination. The characteristics and texture of
the composite beads were changed by changing the ratio of the two
polysaccharides in the beads and also on the concentration of
calcium chloride in the Ca2+ bath. Titania spheres of different
performances in terms of dye adsorption were obtained by
changing the titania precursor to isopropanol ratio and calcination
temperature of the composite titania beads (Table 1). The most
suitable beads for templation (BAA11) were obtained when the ratio
of alginate to gum acacia was 4:1 while no bead was formed when
the ratio was just reverse. Appropriate CaCl2 concentration was
0.2 M and TIP and IP ratio was 2.1–0.9 (2.33:1), while 550  C was
the optimum calcination temperature for obtaining titania spheres
of optimum performance (TSAA11) in terms of reactive blue dye
uptake (92%), which is a toxic vinyl sulfone azo dye (Table 2). TS
obtained in different sets of experiments have been compared in
l (nm) Absorbance Solution pH
(50 mg/L)
660, 619.5 1.1, 1.0 4
2730 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737

Table 3
Dye removal and some characteristics of the synthesized TS.

Sample Moisture retention (%) Surface area (m2/g) Ash content (%) Dye adsorption (%)
TSAA1 3.1 19 61 68
TSAA2 3.3 19 61 69
TSAA3 3.0 26 64 84
TSA 3.3 20 67 68
TSAA4 6.7 23 65 78
TSAA5 5.1 25 65 83
TSAA6 3.3 23 66 74
TSAA7 5.1 23 64 78
TSAA8 3.0 24 65 80
TSAA9 3.3 23 66 75
TSAA10 5.1 18 51 69
TSAA11 0.0 32 84 92
TSAA12 0.0 27 88 89
TSAA13 0.0 19 100 69
TSA1 1.7 22 86 79

terms of surface area, moisture retention capacity, ash content and
their capacity to uptake dye from 100 mg/l dye solution (Table 3). It
is observed that the dye removal by the TS samples can be
correlated with their surface areas; the highest removal was
witness TSAA11, which also had the highest surface area. The
moisture retention capacity of the synthesized TS was dependent
on the calcination temperature of the titania composite beads and
also on the polysaccharide content in them. For the TS samples
which were obtained after calcination >500  C, the moisture
retention was zero as they do not have any surface hydroxyls left
for moisture retention, while the sample TSAA4 which had less
calcium content in the templating beads, moisture retention was
high. The sample TSAA10 also showed appreciable moisture
retention as the sample was obtained by calcination at 300  C
and the hybrid spheres are not fully devoid of surface hydroxyls as
that of TSAA11, where the calcination temperature was high by
which all surface groups get condensed during the calcination. The
ash content of the spheres was in conformity with the inorganic
content in the TS.
3.1. Characterization of TS
3.1.1. Fourier transform infra red Spectroscopy
Titania spheres (TSA1) obtained by calcination of sodium
alginate templated composite titania beads (BA1) showed peaks
at 3398 cm1 (O H stretching), 3019 cm1 (C H stretching),
1
1384 cm (COO symmetrical stretching), and 1637 cm1 (COO 
asymmetrical stretching). The peaks at 759, and 669 cm1 can be
ascribed to the absorption bands of Ti O and O TiO flexion
vibration (Fig. 1a).
In TS (TSAA11) obtained by calcination of sodium alginate-gum
acacia templated composite titania beads (BAA11), C O stretching
peak is seen at 1068 cm1. A strong peak at 872 cm1 is
characteristic absorbance of TiO2 due to the formation of an
O Ti O network (Fig. 1b). Peaks due to O H stretching, C
H
stretching (merged with OH stretching at uronic acid groups),
COO  symmetrical stretching, COO asymmetrical stretching,
CO stretching, Ti OTi stretching, and TiO stretching are
observed at 3398, 3019, 1637, 1384, 1068, 872, 669, and 770 cm1,

Fig. 1. FTIR spectra of (a) TSA1, (b) TSAA11, (c) BAA11, (d) TSAA11-dye.
 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737
respectively. Thus it appears that polysaccharides did not fully
escape during the calcination.
The FT-IR spectrum of BAA11 showed peaks at 3387 and
1599 cm1 (Fig. 1c) which can be ascribed to O H stretching
and bending vibrations of surface-adsorbed water and hydroxyl
groups, respectively [27]. Peaks due to symmetrical COO stretch-
ing’s is observed at 1419 cm,1 while the peak due to asymmetrical
COO stretching is seen blended with OH bending, which is due to
uronic acid components of the polysaccharides. C O stretching
[28] is seen at 1215 cm1 and 1025 cm1. Several peaks below
1000 cm1 can be assigned to absorption bands of Ti O and
O Ti O flexion vibration. Peak observed at 3019 cm1 can be
assigned to OH stretching of uronic acid groups at the
polysaccharides. The absorbance peaks at 669 and 760 cm1
originated from Ti O and OTi O network in titanium dioxide
[29].
The most of characteristic peaks remains unchanged after
RBH5G dye loading (Fig. 1). However, some peaks have changed
their positions and intensity. The peak due to azo group of the dye
is not separately seen rather it appears as broad peak merged with
COO asymmetrical stretching at 1384 cm1. It also exhibited a
relatively sharp peak at 3389 cm1 which is representing  NH 
and hydroxyl (OH) extensions. The peaks due the aromatic ring
(C¼C), C N extension, and C Cl of the loaded dye are seen
between 700 cm1 and 1500 cm1. The sulfonic groups (S¼O) and
the C S vibration are seen below 700 cm1 [30].
3.1.2. Scanning electron microscopy
A scanning electron microscope was used to examine the
surface morphology of the porous titania spheres. SEM pictures
revealed that plain alginate bead templated TS (TSA1) have fairly
different morphology and much less porosity as compared to
spheres derived from mixed beads (TSAA11). Porous internal surface
Fig. 2. SEM picture of (a) TSA1, (b) TSAA11, (c) BAA11, (d) TSAA11.
2731
indicates that they should behave as proficient adsorbent. The as-
prepared composite bead exhibited complex porous external
surface texture constituted of agglomerated small spherical
particles, which acquires better porosity after calcination
(Fig. 2c and d) as the templating polysaccharide beads are lost.
Inclusion of gum acacia during alginate bead formation enhanced
the overall porosity of TS. After dye loading surface topology of TS
has changed (Fig. 3b) where more or less spherical particles show
flattened interconnected morphology.
3.1.3. X-ray diffraction
X-ray diffraction revealed that both TSA1 and TSAA11 are
crystalline and have almost identical X-ray diffraction patterns
(Fig. 4). The dye adsorption did not alter the diffraction pattern of
TSAA11, which indicated that the dye was only physically adsorbed.
The Debye–Scherrer formula has been used to calculate the
average crystallite sizes (d) which have been tabulated as (Table 4).
The average crystallite size of TSA1 and TSAA11 is 12 nm, while dye
loaded TSAA11 show slightly higher crystallite size (14 nm) as also
seen in SEM image.
3.1.4. BET surface area
Nitrogen adsorption–desorption isotherms and pore size
distribution plots for TSA1 and TSAA11 are shown in Fig. 5. BET
study indicated mesoporous nature of the isotherm for both types
of spheres, TSA1 and TSAA11. Both types of TS (TSA1 and TSAA11)
showed type-IV isotherms [31] with an H2 type hysteresis loop at
relative pressure of P/P0 0.67–0.99 and 0.85–0.99, respectively
which indicated the presence of interconnected mesopores. Both
TSA1 and TSAA11 showed wide pore distribution ranging from of
2.5–15 nm, and pore volume 0.02 cc/g. Brunauer–Emmett–Teller
(BET) study indicated that the surface areas of TSA1 and TSAA11 are
22 and 32 m2/g respectively while the other samples had the
2732 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737

Fig. 3. SEM picture of (a) TSAA11 (b) TSAA11 dye.

surface areas ranging from 18 to 27 m2/g. The type of templating
beads exhibited tremendous effect on the surface areas of the
porous TS synthesized thereof. In the present study it has been
revealed that incorporation of gum acacia in small amount has
significant effect on the surface area of the final titania spheres. The
surface area of TS (TSAA11) derived from composite beads is 1.4
times to the surface area of TS derived from pure alginate beads
(TSA1). The mesoporous structure of the titania spheres might have
originated through the burning of the alginate-gum acacia
biopolymeric beads, and due to agglomeration of titania nano-
crystals during calcination [32].
3.2. Adsorption kinetics
The kinetic data were recorded for 100, 150 and 200 mg/l initial
dye concentrations at 30  C using 50 mg TSAA11 as adsorbent, pH 2,
rpm 150, contact time 8 h.
To understand the mechanism of the adsorption, the adsorption
kinetic data were modeled [16] using first order Lagergren
equation, the pseudo-second order equation and the second-order
rate equation shown below in Eqs. (2)–(4) respectively.
kL t
Logðqe  qt Þ ¼ Logqe 
2:303
concentration, pH 2, 150 rpm, at 30  C. The amount of the
adsorbed dye onto TSAA11 increased with time and, reached to
equilibrium in 8 h beyond which no more dye adsorption was
possible (Fig. 7(a)). At this point, the amount of dye being adsorbed
onto TSAA11 was in a state of dynamic equilibrium with the amount
of the dye desorbing from the adsorbent. It was observed that the%
adsorption increased from 79 to 92% with increase in contact time
from 1 to 8 h [16]. No change in dye uptake was observed with
further increase in the equilibration time up to 12 h. Initially all
adsorbent sites of the adsorbent were unoccupied due to which a
concentration gradient between adsorbate in solution and adsor-
bate in the adsorbent was established. As the availability of the
adsorption sites decreased gradually an equilibrium state was
achieved in 8 h. Other authors have also reported similar results
have [33,34].
3.3.2. Effect of synthetic conditions of TS
The dye adsorption capacities of TS fabricated under different
conditions were different. Two factors are most evident (i) ratio of
alginate to gum acacia in the templating beads, (ii) calcination
temperature of composite titania beads (Tables 1 and 3). The
synthetic conditions for obtaining optimum performance TS
ð2Þ (TSAA11) in terms of dye removal are: 0.4 g alginate, 0.1 g gum

1200
t 1 t
¼ 0 þ ð3Þ
qt k qe 2 qe 800 TSAA11-Dye

400

1 1 0
¼ þ k2 t ð4Þ
ðqe  qt Þ qe 20 30 40 50 60 70 80 90 100
Intensity (a.u)

The kinetic data best fitted to pseudo second order kinetic 1200
model with correlation coefficient nearing to unity. The pseudo TSAA11
800
second order rate constant and qe has been computed at three
400
different initial dye concentrations 100, 150 and 200 mg/l from
(Fig. 6) and has been compared with other kinetic models in 0
(Table 5). 20 30 40 50 60 70 80 90 100
The temperature dependence of the dye uptake and pseudo 1600
second order kinetics of adsorption indicated that chemisorption 1200 TSA1
take place in the rate determining step which controlled the rate.
800
400
3.3. Optimization of the adsorption
0

3.3.1. Effect of contact time 20 30 40 50 60 70 80 90 100

Percentage removal of the dye was monitored with contact time 2-Theta
at fixed adsorbent dose (50 mg) for 100 mg/l initial dye
Fig. 4. XRD patterns of TSA1, TSAA11 and TSAA11 dye.
 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737 2733

Table 4
Average crystallite size for the adsorbents and dye loaded HTSAA11 calculated through XRD data.

TSA1 2-theta Crystallite size (d) (nm) HTSAA11 Crystallite size (d) HTSAA11-dye Crystallite size (d)
24.9 9.9 24.9 9.6 24.9 9.9
28.9 16.5 28.9 15.3 29.2 19.3
35.8 18.2 35.5 18.5 35.5 20.3
39.0 18.1 39.0 23.4 37.6 11.3
42.8 18.1 42.8 10.9 39.3 31.1
47.6 5.4 47.1 8.9 43.0 17.5
54.5 4.8 54.3 5.8 47.5 6.4
56.9 9.7 57.1 9.2 54.3 5.3
60.6 11.2 60.6 10.9 56.8 5.5
62.5 7.2 62.5 15.9 60.6 11.2
64.6 8.3 64.4 9.2 62.4 12.9
24.9 9.9 24.9 9.6 64.5 10.1
28.9 16.5 28.9 15.3 69.3 4.7
35.8 18.2 35.5 18.5 24.9 9.98
39.0 18.2 39.0 23.3 29.2 19.3
42.8 18.1 42.8 10.9 35.4 20.3
47.6 5.4 47.1 8.9 37.6 11.34
54.5 4.8 54.3 5.8 39.3 31.1
56.8 9.7 57.1 9.2 43.0 17.5

acacia (for making mixed polysaccharide solution of 2% w/v), 3.3.4. Effect of TSAA11 dose
0.20 M CaCl2, 2.1 ml TIP, and 0.9 ml IP, and 550  C calcination To study the effect of adsorbent dose on the dye adsorption,
temperature. TSAA11 could adsorb 92% RBH5G dye from 100 mg/l dye TSAA11 doses ranging from 30 to 100 mg were used for 20 ml of
solution. While identically synthesized TS from pure alginate 100 mg/l reactive blue H5G dye solutions at pH 2 and rpm 150
beads (TSA1) could exhibit only 79% dye uptake under identical (Fig. 7(c)). It was observed that increase in the adsorbent dose from
experimental conditions. Thus bead composition played an 30 to 100 mg increased the dye removal from 72 to 95% as now
important role in finalizing the overall texture and performance extra adsorbent sites become available for the sorption. Also with
of the TS, the TSAA11 being the optimum sample in terms of dye the increase of adsorbent dose, the quantity of adsorbed dye per
uptake. unit volume decreased, thus a decrease qe has been observed with
increase in adsorbent dose [16].
3.3.3. Effect of pH
The pH of dye solution affects the surface charge of the 3.3.5. Effect of initial dye concentration
adsorbent and therefore decides the overall adsorption of the With the increase in the initial dye concentration from 50 to
charged dyes. In the present study, the adsorption of the dye is 300 mg/l, there was an increase in the sorption (from 18 to 86 mg/
highest at pH 2 and in the pH range of 1–3 it varied from 91 to 92%. g) due to the availability of extra dye for binding (Fig. 7(d)). On
It is reported that adsorption of negatively charged anionic reactive increasing the initial dye concentration from 50 to 300 mg/l, the
dyes is favorable at low pH values [35,36]. It decreased to 69% as sorption increased from 18.8 to 86.7 mg/g. However with increase
the pH was increased to pH 4, and only 59% adsorption was noticed in dye concentration, % adsorption decreased from 94.4 to 72.2%
when pH was increased to pH 8 (Fig. 7(b)). The zero point charge of due to decreased adsorbent to adsorbate ratio [39].
TSAA11 (as been determined by pH drift method) is 7.3 (Fig. 8). Thus
at pH < 7.3, the surface charge at TSAA11 is positive, >7.3, the surface 3.3.6. Effect of temperature
of the adsorbent is negative, and at pH 7.3 the adsorbent surface The effect of temperature on the sorption was studied in the
has no charge. Since the study has been performed at pH 2, the temperature range of 30–50  C at 100 mg/l initial dye concentra-
surface of the hybrid titania will be positively charged which tion, 50 mg adsorbent dose, and pH 2. It was observed that with
electrostatically attracts the anionic azo dye molecules [37,38] increase in temperature from 30  to 50  C, the adsorption
(Fig. 9). increased from 36.94 to 40.12 mg/g, (Fig. 7(e)) indicating

28
Volume of N2 uptake (cc/g) at STP

Ad
Ds 2 Pore Volume 0.0216 cc/g
Surface area 31 m /g TSA
24 Ad 0.0012
TSAA
Ds (B) Pore Volume 0.021 cc/g
dV(w)[ccÅ g ]

20
-1 -1

0.0008
16
12
0.0004
8 (A)
2
Surface area 22 m /g
4 0.0000

0.0 0.2 0.4 0.6 0.8 1.0 0 5 10 15 20 25 30 35 40

Relative pressure (p/p0) Pore width (nm)

Fig. 5. BET (a) surface area (b) and pore volumes of TSA1 and TSAA11.
2734 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737

due to the creation of new active sites at higher temperature. The

14
t / qt (m in. g/ m g) 12 (a) y = 0.026x + 0.455 formation of more than one molecular layer on the surface of the
10 R² = 0.998 adsorbent is also indicated by the isotherm study where Freundlich
8 (b) y = 0.019x + 0.136 isotherm better conformed to the results.
6 R² = 0.999
4 (c) y = 0.016x + 0.024 3.4. Adsorption isotherm
2 R² = 1
0 The equilibrium between adsorbent and adsorbate is correlated
through adsorption isotherms [16]. In the present study, two
0 200 400 600
adsorption isotherm models, namely, Langmuir and Freundlich
t (min) have been considered to describe the adsorption equilibrium. The
applicability of the isotherm was judged by the correlation
Fig. 6. Pseudo second order kinetic model for the adsorption of RB H5G dye at
coefficients values.
HTSAA11.
The Langmuir isotherm is valid for monolayer sorption due to a
surface of a finite number of identical sites and expressed as Eq. (5).
endothermic nature of the adsorption. Similar behavior has been
previously reported for other reactive dyes [40]. The surface Ce 1 Ce
¼ þ ð5Þ
coverage increased at higher temperatures due to the better qe Q 0 b Q 0
penetration of the dye within the mesopores of the adsorbent or

Table 5
Comparison of Lagergren first order; pseudo second order and second order kinetic parameters at pH 2, rpm 150, adsorbent dose 50 mg, contact volume 20 ml, contact time
8 h at 30  C.

Dye initial concentration Lagergren first order Pseudo second order Second order equation
2 0 2
kL R k qe R k2 R2
4 3 3
100 1.15
10 0.678 1.48
10 38.4 0.998 2.0
10 0.688
150 2.07
10 4 0.887 2.65
103 52.6 0.999 2.7
102 0.812
200 1.15
10 4 0.826 10.6
103 62.5 1.000 2.1
102 0.904

Fig. 7. Effect of (a) pH, (b) adsorbent dose, (c) concentration on the dye uptake by TSAA11.
 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737 2735

calculated using the following equation.

10
9 1
RL ¼ ð6Þ
8 ð1 þ bC 0 Þ
7
where C0 is the initial dye concentration (mg/l). If RL values lies
6
Fin al p H

between 0 and 1, the adsorption is favorable.

5
The Freundlich isotherm model is an empirical model which
4
expresses the multilayer sorption and estimate the adsorption
3
intensity of adsorbate onto adsorbent.
2 The linear form of Freundlich isotherm model is expressed by
1 Eq. (7):
0
1
0 1 2 3 4 5 6 7 8 9 10 logqe ¼ logK f þ
log C e ð7Þ
n
Inial pH qe = the adsorbed amount (mg/g) at equilibrium, Ce = concentration
Fig. 8. Determination of pHzpc of HTSAA11. of the dye at equilibrium (g/l), Kf is the Freundlich constant which
indicates the adsorption capacity (mg/g), and “n” is an empirical
where qe the amount of dye sorbed (mg/g) at equilibrium, Ce is the parameter related to adsorption efficiency which varies with the
equilibrium concentration in mg/l. The Langmuir constant Q0 (mg/ heterogeneity of the adsorbent. The Freundlich exponent 1/n
g) represents monolayer adsorption capacity where as b (l/mg) indicates favorable condition of adsorption if 0 < 1/n < 1 [41,42].
relates the heat of adsorption. RL, a dimensionless constant is The adsorption equilibrium data of the adsorption of RBH5G dye
known as separation factor or equilibrium parameter for predict- at TSAA11 better conformed to Freundlich adsorption at all the three
ing whether an adsorption system is favorable or unfavorable. RL is studied temperatures indicating surface heterogeneity [43] of the
adsorbent. It also indicated that the adsorbent has adsorption sites
of variable energies which results into multilayer adsorption of the
dye. Since value of the 1/n is 0 < 1/n < 1, the adsorption of the dye at

H2O
Dye-SO3Na Dye-SO3 + Na
Dissociation

pH 2 Positive surface sites of titania

TS (pHzpc = 7.3)
Dye-SO3 SO3-Dye
Dye-SO3 SO3-Dye

Dye-SO3 SO3-Dye
SO3-Dye
Fig. 9. Schematic diagram showing electrostatic interaction between dye and TS.

Fig. 10. Langmuir and Freundlich adsorption isotherms at (a) 30, 40 and 50  C at initial 100 mg/l dye concentration, pH 2, rpm 150, contact volume 20 ml, adsorbent dose
50 mg and contact time 8 h.
2736 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737

Table 6
10.88
Langmuir and Freundlich constants at pH 2 for RB dye.
y = -750x + 13.15
Temperature ( C) Langmuir isotherm Freundlich isotherm 10.84
R² = 0.8929
Q0 (mg/g) b (L/mg) R2 Kf (mg/g) 1/n R2
10.8
30 100 0.0595 0.952 13.86 0.3984 0.964

lnb
40 100 0.0617 0.972 15.92 0.3690 0.980
10.76
50 77 0.0694 0.975 13.15 0.3610 0.983

10.72

the TSAA11 is favorable. The monolayer adsorption capacity (Q0) for
TS AA11 as calculated by Langmuir isotherm (at 30  C) is pretty high
(100 mg/g).
Langmuir and Freundlich adsorption isotherms at three
different temperatures are shown in (Fig. 10) and the data derived
thereof have been summarized in (Table 6). Though Langmuir
constant increase with the increase in temperature, indicating the
nature of the adsorption to be endothermic (cf effect of
temperature), the Q0, the monolayer adsorption capacity of the
adsorbent did not show a definite trend on increasing the
temperature. This may be attributed to availability of heteroga-
mous adsorption surface sites at the adsorbent which is
established by the better conformity of the adsorption equilibrium
data with Freundlich isotherm. It is known that the Langmuir
model fails to account for the surface roughness of the adsorbent
and also any possible adsorbate/adsorbate interactions. It appears
that the change in temperature affected the dye–dye interaction at
the adsorbate surface [44].
The RL value at 100 mg/l dye concentration and 30  C tempera-
ture was calculated to be 0.1633, indicating favorable nature of the
adsorption. The high KF value indicated the good intensity of
adsorption.
3.5. Adsorption thermodynamics
10.68
10.64
0.003 0.0031 0.0032 0.0033
1/T
Fig. 11. Van’t Hoff plot of the reactive blue H5G adsorption over HTSAA11.
reflects the decrease in the disorder of the system at the solid-
solution interface. It also indicated that the dye adsorption did not
alter the internal structure of the adsorbent.
3.6. Desorption
The preliminary desorption experiments were performed with
1 M HCl and 1 M NaOH where 1 M NaOH was found useful in the
dye desorption. 90% of the adsorbed dye could be successfully
desorbed when the dye loaded TSAA11 was stirred in 1 M NaOH for
2 h at 30  C, and 120 rpm. The adsorption–desorption was repeated
for three consecutive cycles at 100 mg/l initial dye concentration,
pH 2, rpm 150, contact volume 20 ml, adsorbent dose 50 mg, and,
contact time 8 h. The desorption experiments indicated high
reusability of the adsorbent as even in the third cycle, 87% dye
could be adsorbed. There was only 5% decline in the adsorption
efficiency of TSAA11 during the three cycles.

The thermodynamic parameters such as Gibbs free energy
change (DG ), enthalpy of adsorption (DH ) and entropy change
(DS ) were calculated using Vant Hoff’s equation which is given
below.
DG ¼ RTlnb
 
DS DH
lnb ¼  ð9Þ
R R
where R is the ideal gas constant (8.314 J/mol K), b the Langmuir
isotherm constant (l/mol), DG the change in Gibbs free energy (J/
mol), DH the enthalpy of adsorption (J/mol) and DS the entropy
of adsorption (J/mol K). The results of the thermodynamic
calculations are shown in Table 7. The negative values of change
in Gibbs free energy (DG ) indicated the feasibility of the process
and the spontaneous nature of the adsorption under the
experimental conditions used. DH and DS was determined from
the slope and the intercept of the linear plot of ln b vs. 1/T, as shown
in Fig. 11. The positive value for enthalpy change DH (6.23 kJ/mol),
confirmed that the adsorption of Reactive blue H5G over HTSAA11 is
an endothermic process. The negative value of DS (0.10 K J/mol K)
Table 7
Thermodynamic parameters of reactive blue H5G adsorption over at different
HTSAA11.
3.7. Photocatalytic activity
Photo catalytic activity of TSAA11 was studied for degradation of
the RBH5G dye. When exposed to 5 h in sunlight, the material could
degrade 76% of dye from 100 mg/l synthetic dye solution. Thus
ð8Þ
potentially dye desorption from the dye loaded spheres is possible
by simple exposing to sunlight [45], however this aspect needs a
detailed investigation. The photocatalytic degradation of the dye
using TSAA11 can be explained by the porous structure of TSAA11
which allowed absorption of light by light reflections and multiple-
scattering within it [46].
4. Conclusions
Mesoporous titania spheres have been fabricated in a greener
way without using any polymeric template or surfactants. The
spheres performed as efficient adsorbent for anionic azo reactive
blue dye “RBH5G”. The adsorbent performed well in the pH range of
pH 1–3, the optimum pH being pH 2 where 92% dye was adsorbed
from 100 mg/l dye solution. Titania spheres could be successfully
recycled for three consecutive cycles where 87% dye was captured
in the third cycle. The adsorption had a high Qmax (100 mg/g) and
adsorption equilibrium was established in 8 h. The adsorption
followed a pseudo second order kinetic model that suggested
chemisorption is taking place. The titania spheres also showed
photocatalytic activity in degrading the dye.

Temperature (K) ln b DG (KJ/mol) DH (KJ/mol) DS (KJ/mol) Acknowledgements

303 10.69 26.19 +6.23 kJ/mol 0.11 K
313 10.72 27.27 Council of Scientific and Industrial Research is acknowledged
323 10.84 28.22
for the financial support to carry out this work. Authors
 V. Singh, Preeti / Journal of Environmental Chemical Engineering 3 (2015) 2727–2737
acknowledge Prof. Asim Bhaumik, Indian Cultivation of Sciences,
Kolkata, India for BET facility, IIT Bombay for SEM, Nanoposphor
center, Allahabad University for XRD, and Central Drug Research
Institute, Lucknow for FTIR facility.
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