Journal of Environmental Chemical Engineering 6 (2018) 5212–5220

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Journal of Environmental Chemical Engineering

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

Remarkable Ti-promotion in vanadium doped anatase titania for methylene T

blue adsorption in aqueous medium
⁎
Kamalesh Pala, , Kalyan Ghoraia, Sudiksha Aggrawalb, Tapas Kumar Mandalb, Paritosh Mohantyb,
⁎
Md Motin Seikhc, Arup Gayena,
a
Department of Chemistry, Jadavpur University, Kolkata, 700032, India
b
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
c
Department of Chemistry, Visva-Bharati University, Santiniketan, West Bengal, 731235, India

A R T I C LE I N FO A B S T R A C T

Keywords: We report here the synthesis of vanadium (5–20 at.%) doped titania and the pristine oxides via surfactant as-
V2O5 sisted coprecipitation method using cetyltrimethylammonium bromide as the surfactant and investigated their
TiO2 adsorption behavior towards hazardous methylene blue dye. The formation of anatase phase in all the doped
V-doped TiO2 materials is confirmed by the powder x-ray diffraction (P-XRD) analysis as corroborated by the Fourier trans-
Surfactant assisted coprecipitation
form-infrared (FT-IR) analysis, with particle sizes in the range 8–11 nm. Pure titania doesn’t show any adsorption
Methylene blue adsorption
property, but its presence enhances the adsorption property of vanadia considerably suggesting a promoting role
of titania in the doped materials. The 10 at.% V-doped material, V0.1Ti0.9O2 is found to exhibit the best ad-
sorption behaviour. The low resolution transmission electron microscopy studies reveal homogeneous nature,
while ring type electron diffraction pattern suggests polycrystalline nature of the material. The high resolution
transmission electron microscopy analysis suggests formation of single phase oxide. Kinetic and equilibrium
studies have revealed the pseudo-second-order kinetics and Langmuir isotherm nature for this physisorption
process. The pH dependency and recycling ability of this material have been discussed. Finally, X-ray photo-
electron spectroscopy, FT-IR and P-XRD studies have been applied to understand the mechanism of regeneration
of the material.

1. Introduction sensation of mouth, nausea, vomiting, profuse sweating, mental con-

The presence of dyes in industrial wastewater is a major concern
due to their adverse effects to many forms of life. Industries like textile,
leather, paper, plastics, etc., use dyes in order to introduce colorful
products. They consume a large amount of water during colorization
technique and thus they also generate a considerable amount of colored
wastewater [1]. Thus, dye wastewater needs to be treated for the pro-
tection of human health and environmental safety. The discharge of
dyes in the environment is a dramatic source of aesthetic pollution,
eutrophication and perturbation degradation [2]. It is well-known that
public awareness regarding water quality is greatly influenced by the
color because color is the first contaminant to be identified in waste-
water. Even a very small amount of dyes in water (less than 1 mg L−1
for some dyes) is highly visible and undesirable [3,4].
Methylene blue (MB; C16H18N3SCl), a familiar basic dye is usually
used for dying cotton, wood and silk. It can cause permanent injury to
the eyes of human and animals. Several other injuries like burning
fusion and methemoglobinemia may also be caused by this dye [5–7].
MB remains very stable in the environment due to its synthetic origin
and complex aromatic molecular structure. Therefore, the treatment of
effluent containing such a dye is an important issue for researchers and
environmentalists.
Several treatment processes have been reported for the removal of
these kinds of dyes from wastewater, such as: photocatalytic degrada-
tion [8,9], electrochemical degradation [20], sonochemical degrada-
tion [10], integrated chemical–biological degradation [11], photo-
assisted-biological treatment [12], Fenton-biological treatment scheme
[13], cation exchange membranes [14] and adsorption processes
[15–18]. Among the several separation techniques adsorption is a very
effective process for the removal of such dyes because of its low initial
cost, insensitivity to the toxic substances, flexibility in design and
simplicity in operation [19,20]. Adsorption does not result in the for-
mation of harmful substances and thus it is a well known equilibrium
separation technique and an effective method for water

⁎
Corresponding authors.
E-mail addresses: kamaleshpal4@gmail.com (K. Pal), agayenju@yahoo.com, arup.gayen@jadavpuruniversity.in (A. Gayen).

https://doi.org/10.1016/j.jece.2018.08.015
Received 29 May 2018; Received in revised form 21 July 2018; Accepted 7 August 2018
Available online 08 August 2018
2213-3437/ © 2018 Elsevier Ltd. All rights reserved.
K. Pal et al. Journal of Environmental Chemical Engineering 6 (2018) 5212–5220

decontamination applications [21–23].
TiO2 plays a very important role in the photodegradation of such
dyes due to the narrow band-gap value of 3.2 eV for the anatase form
[24]. Besides photoactivity, TiO2 also shows adsorption behavior due to
its tunable surface properties, i.e., acidity/ basicity or open coordina-
tion sites, of the resultant materials, which is of importance to the ad-
sorption of molecules [24]. Many researchers have also reported the
beneficial effect of vanadium on TiO2 by enhancing its photocatalytic
activity [2,25,26] and enable it in the field of gas sensing ability [27].
With this background, we have prepared pure oxides of titanium
and vanadium, and a number of their mixed oxides by surfactant as-
sisted co-precipitation (SAC) method. We have chosen the cationic dye
MB as the adsorbate because of its known strong adsorption onto solids.
Based on material screening, Ti0.9V0.1O2 is reported to show the best
adsorption property. The equilibrium and adsorption kinetics, materials
reusability and pH dependence of the adsorption property are dis-
cussed.
2. Experimental
2.1. Material preparation
per step and analyzed by the database of ICDD (International Centre for
Diffraction Data) for phase identification. Average particle sizes were
calculated from the line-width broadening of the peaks using Scherrer’s
equation.
Fourier transform-infrared (FT-IR) spectra were recorded on the
powdered materials in transmission emission mode in a Perkin Elmer
RX-1 FTIR spectrometer in the range of 4000–400 cm−1.
The high resolution transmission electron microscopy (HRTEM)
experiment was performed on a JEOL (2000EX II) microscope operated
at 200 kV. The energy-dispersive X-ray spectroscopy (EDX) elemental
mapping analysis were performed on a JEM ARM200 F cold FEG double
aberration corrected electron microscope equipped with a large solid-
angle CENTURIO EDX detector and Quantum GIF. Materials for TEM
were ground powder under ethanol, and the resulting dispersion was
transferred to a holey carbon film deposited on Ni supported grid.
2.2.2. Surface area analysis
The surface area and porosity analysis of the materials were ana-
lyzed from the N2 sorption isotherms using Autosorb iQ (Quantachrome
Inc.) gas sorption instrument. Prior to N2-sorption experiments all the
materials were degassed at 90 °C for 1 h.

2.2.3. XPS analysis

Pure and doped materials of titanium and vanadium with nominal
The XPS analysis was carried out by PHI-5000 VersaProbe III
composition VxTi1-xO2 (x = 0, 0.05, 0.1, 0.15, 0.2 and 1) were prepared
ULVAC-PHI Inc., XPS spectrophotometer. The analysis was performed
by a surfactant assisted coprecipitated technique using cetyl-
by mounting the specimens on the carbon tape and keeping it overnight
trimethylammonium bromide (CTAB). In a typical synthetic process,
in the sample introduction chamber under vacuum. The measurement
3.64 g (0.1 M in the resulting solution) of CTAB (Spectrochem India,
was performed using monochromatic AlKα radiation (1486.6 eV) under
98%) was dissolved in 50 mL of millipore water in a beaker and in
ultra-high vacuum condition. The binding energy for individual ele-
another beaker calculated amount of ammonium metavanadate (VN;
ments are scaled with reference to C1 s at 284.8 eV.
Sigma Aldrich, 97%) was dissolved in 50 mL of millipore water. The
solutions were left for stirring until clear solution appeared. The con-
2.3. Preparation of dye stock solution
tents of the beakers were then mixed and stirred again for 15 min.
Titanium tetraisopropoxide (TTIP; Sigma Aldrich, 97%) was then added
The dye stock solution was prepared by dissolving calculated
drop wise in this mixture under vigorous stirring. After complete ad-
amount of MB (Merck India Ltd. with water solubility of 50 g L–1 at
dition of TTIP, the solution was left for ageing for 1 h. The solution was
20 °C) in millipore water to the concentration of 100 mg L−1. The ex-
then alkalinized with NH4OH (∼pH 10) and the mixture was left for
perimental solutions of different concentrations were obtained by di-
ageing for overnight under constant stirring at 400 rpm. The precipitate
luting the dye stock solution in accurate proportions.
obtained was separated by centrifuging at 10,000 rpm (REMI PR-24).
The crude obtained was washed 3 times with millipore water followed
2.4. Equilibrium studies
by drying in an oven at 110 °C for ∼4 h. The materials of this study are
the ones obtained on calcination of the crushed crude materials at
400 °C for 3 h at a heating rate 10 °C min−1. Table 1 lists all the ma- For equilibrium studies, different initial concentrations of MB
terials studied here with their name and nominal composition. (C0 = 20, 30, 40 and 50 mg L−1) contained in a beaker were treated
with 20 mg of V10TO material (based on screening tests). The pH of the
mixtures was adjusted to 7.0 using buffer solution. The mixtures were
2.2. Material characterization then magnetically stirred (∼350 rpm) to reach the equilibrium. After
3 h, the suspensions were taken, centrifuged at ∼14,000 rpm for 2 min
2.2.1. Structural and microstructural analysis and the residual MB concentrations were analyzed by a Jasco spectro-
The powder XRD data were collected on a Bruker D8 Advance X-ray photometer (Model no. V-630, Japan) at 662 nm using a of 1 cm path
diffractometer using Cu Kα radiation (λ = 1.5418 Å) operating at 40 kV length. The amount of MB adsorbed (qe mg g−1) by the material in each
and 40 mA. The XRD patterns were recorded in the 2θ range between case was calculated using the mass balance equation:
10° and 100° using Lynxeye detector (1D mode) and a scan time of 2 s
qe = (C0 − Ce ) ∗V / M
Table 1 And the MB removal (%) was calculated using the following equa-
List of synthesized materials with name, BET and porosity data and MB ad- tion:
sorption property for the screening of materials.
MB removal(%) = (C0 − Ce ) ∗100/C0
Composition Name Scherrer Surface Half Pore MB
size (nm) area pore volume adsorption, q where, C0 and Ce (mg L−1) are the initial and equilibrium concentra-
(m2 g−1) width (cm3 (mg g−1) at tions of MB. V is the volume of the solution (mL) and M is the mass of
(Å) g−1) 3h
catalyst (mg).
TiO2 TO 11 174 18 0.09 0 To estimate the equilibrium parameters, four models were used:
V0.05Ti0.95O2 V5TO 9.6 166 18.84 0.15 37 Langmuir, Freundlich, Temkin and Dubinin-Radushkevich [22].
V0.1Ti0.9O2 V10TO 8.4 170 18.97 0.17 56
V0.15Ti0.85O2 V15TO 8.8 168 18.97 0.23 52
2.5. Kinetic studies
V0.2Ti0.8O2 V20TO 8.8 168 18.97 0.33 53
V2O5 VO 39 17 8.44 0.018 35
All the kinetic studies were performed using the same initial

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K. Pal et al. Journal of Environmental Chemical Engineering 6 (2018) 5212–5220

Table 2
Review of some adsorption and kinetic models.
Sl. No. Equations Parameters and their
significance

Adsorption isotherm
1 Langmuir adsorption isotherm q0 (mg g−1)= Maximum
Ce 1 Ce adsorption capacity for
= +
qe q0 KL q0
monolayer
1
RL = KL= Langmuir adsorption
1 + KL Ce
constant
RL= Feasibility of the
adsorption process
2 Freundlich adsorption isotherm 1/n = Intensity of adsorption
ln qe = ln KF +
1
ln Ce KF (mg g−1(L
n
mg−1)1/n)=Adsorption
coefficient
3 Temkin adsorption isotherm b = Heat of adsorption
qe =
RT
ln A +
RT
ln Ce A = Binding energy
b b
4 Dubinin-Radushkevich isotherm qD = Theoretical adsorption Fig. 1. P-XRD patterns of pure oxides of titanium and vanadium and the various
lnqe = lnqD − βε 2 capacity vanadium doped titania obtained at 400 °C.
1 β (kJ−2 mol2)= A constant
ε = RT (1 + )
Ce related to the mean free
E= (−2β )−0.5 energy of adsorption per crystallite size calculated from full width at half maxima (FWHM) of
mole of MB (101) diffraction lines lie in the range 8–11 nm for all titania related
ε = Polanyi potential materials.
E = Free energy
Kinetic model
1 Pseudo first order kinetic model k1 (min−1)= Pseudo-first-
ln (qe − qt ) = ln qe − k1 t order rate constant 3.2. BET studies
2 Pseudo second order kinetic model k2 (g mg−1 min−1)= Pseudo-
t
=
1
+
t second-order rate constant The BET specific surface areas (SAs) of the pure and doped titania
qt k 2 qe2 qe

Thermodynamic parameters
materials are found to be high and lay in the range of 166–174 m2 g−1
1 ΔS 0 ΔH 0 ΔG° = Gibbs free energy (see Table 1). Although the SA is considerably low (∼17 m2 g-1) for
ΔG 0 = − RT ln KD ln KD = −
R RT change pure vanadium oxide, its doing in titania doesn’t have such a lowering
qe
KD = ΔH° = Enthalpy change effect. Among the doped materials, 10 at.% vanadium doped material
Ce
ΔS° = Entropy change
that is shown in our studies to have the best adsorption activity pos-
KD= Distribution coefficient
R= Gas constant (8.314 J sesses the highest surface area.
mol−1 K−1)
T = Temperature (K)
3.3. FTIR analysis

concentrations of MB and mass of V10TO material keeping other con-
ditions identical to the equilibrium studies. The mixtures were mag-
netically stirred at ∼350 rpm. At appropriate time intervals, the sus-
pensions were taken, centrifuged and analyzed by the same UV–vis
spectrophotometer. The amounts of MB adsorbed and MB removal (%)
were calculated similarly. The corresponding kinetic parameters were
calculated using two different models namely, pseudo-first-order and
pseudo-second-order kinetic models [16].
Fig. 2 shows the FTIR spectra of pure and doped titania materials.
For all the materials broad bands observed around 3400 and 1634 cm−1
are assigned to the stretching and bending modes of physisorbed water
on titania [28]. The vibrational mode of the Ti-O-Ti stretching is ob-
served at 427 cm−1 [5]. The symmetric stretching mode of V]O of the
terminal oxygen and the asymmetric and symmetric stretching modes
of VeOeV of bridged oxygen are observed at 1007, 819 and 583 cm−1,
respectively [25].

2.6. Thermodynamic studies

To understand the nature of adsorption and the effect of tempera-

ture on the adsorption of MB onto V10TO, the changes in free energy
(ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were determined [17]. The
required equations for the calculation of these thermodynamic para-
meters are listed in Table 2.

3. Results and discussion

3.1. X-ray diffraction analysis

The powder XRD (P-XRD) patterns of pure and doped materials of

titanium and vanadium obtained on calcination at 400 °C are shown in
Fig. 1. The major diffraction peaks for VO belongs to the Pmmn space
group with orthorhombic structure (ICDD PDF # 89-0612). The major
diffraction peaks of the other materials are indexed with a tetragonal
structure belonging to I41/amd space group (ICDD PDF # 89-4921) and
confirms the formation of pure anatase phase of TiO2. The average Fig. 2. FTIR spectra of pure and doped oxides of titanium and vanadium.

5214
K. Pal et al.
Fig. 3. Adsorption behavior of pure titania and its V-doped oxides.
3.4. Screening of materials
For screening stage we used 50 mL of 10 mg L−1 MB dye solution
with 5 mg of each material and the data are plotted in Fig. 3. Pure
titania does not show any adsorption property, while pure vanadium
oxide shows an adsorption of ∼10% (∼8 mg g-1) initially that is in-
creased to ∼33% (∼30 mg g-1) after 3 h. All the vanadium doped ti-
tania oxides show an increase in adsorption behavior suggesting pro-
moting effect of titanium in the doped oxide (see Fig. 3). The 5 at.%
vanadium doped material shows a sharp rise in the activity at the initial
stage (up to 30 min) and the adsorption activity lies always above that
of the pure oxide of vanadium. The adsorption study clearly reveals that
the 10% vanadium doped titania shows the maximum adsorption ac-
tivity. Further loading of vanadium results in a decrease of adsorption
behavior of the material (both V15TO and V20TO shows nearly similar
adsorption behavior). Therefore V10TO is chosen as the best material
for rest of the studies.
3.5. Microstructural analysis
The transmission electron microscopy (TEM) image of V10TO in-
dicates that the material is purely homogeneous and the particle size is
fairly small (see Fig. 4(a)). The average particle size is ∼10 nm, which
is in good agreement with the XRD results. The lattice fringe analysis
(d = 0.35 nm) obtained from the high resolution transmission electron
microscopy (HRTEM) clearly displays the (101) plane of anatase titania
(see Fig. 4(b)). The selected area electron diffraction (SAED) also ex-
hibits diffraction rings corresponding to the (101), (103), (200), (105)
and (213) lattice planes (inside out) signifying the polycrystalline
nature of the anatase titania (see Fig. 4(c)). The EDX spectra with the
material composition (see Fig. 4(d) & (e)) suggest that Ti : V is very
close to the nominal composition.
3.6. Adsorption isotherms
The nature of MB adsorption isotherms of the V-doped titania is
considered using four well-known adsorption isotherms, namely, (a)
Langmuir, (b) Freundlich (c) Temkin and (d) Dubinin-Radushkevich
models. The fitted data are shown in Fig. 5, while the values of the
corresponding parameters are listed in Table 3. It is noted that there is
minimum deviation in the experimental points from the fitted line
when the Langmuir model is considered (see Fig. 5(a)). Whereas, the
deviation is maximum when the experimental data are fitted following
a Dubinin-Radushkevich adsorption isotherm (see Fig. 5(d)). Deviations
are also clearly evident from the fittings based on Freundlich and
Temkin models (see Fig. 5(b) and (c)).
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Journal of Environmental Chemical Engineering 6 (2018) 5212–5220
3.6.1. Applicability of the different isotherm models
It is obvious from the fitted data of Table 3 that the adsorption of
MB can appropriately be described by the monolayer Langmuir iso-
therm with coefficient of determination, R2 value > 0.99. The max-
imum monolayer MB adsorption capacity for V10TO material was
calculated to be 57.47 mg g−1, which agrees quite well with the ex-
perimental value of 56.64 mg g−1. The low value of KL indicates that
the van der Waals type of adsorption is predominant in the MB ad-
sorption process [16].
In this regard the feasibility of the adsorption process (RL) was
found to be in the range 0 < RL < 1, confirming monolayer adsorption
as the favorable process. Specifically, the RL values decrease from
∼0.396 to ∼0.039 with the increase in initial concentration of MB
solution from 20 ppm to 50 ppm indicating the more favorable ad-
sorption at lower MB concentration. The lower value of R2 for
Freundlich isotherm (see Table 3) suggests that multilayer adsorption
was not favored. The applicability of Temkin model is associated with a
decrease of adsorption subsequent to covering of the solid surface,
which gave lower values for both the binding energy (0.72 kJ mol−1)
and R2 (0.75). The adsorption energy (E) was calculated to be 2.15 kJ
mol−1 for the Dubinin–Radushkevich isotherm suggesting physisorp-
tion nature of the MB adsorption onto V10TO.
3.7. Adsorption kinetics
MB adsorption kinetics of V-doped titania is studied using two well
known models, namely, (a) pseudo-first order and (b) pseudo-second
order kinetics and the experimental as well as the fitted data are shown
in Fig. 6. It is observed that there is maximum deviation of the ex-
perimental points from the fitted line in pseudo-first order kinetics (see
Fig. 6). The deviation between the experimental points and the fitted
line is minimum when a pseudo-second order kinetics is being con-
sidered (see Fig. 6). Various parameters like the rate constant (from the
slope) and mass of adsorbed MB at equilibrium (from the intercept
value), calculated from the kinetic analysis are presented in Table 4.
The rate constant values suggest a decrease with an increase in the MB
concentration.
3.7.1. Applicability of pseudo-second-order kinetic model
According to this model, adsorption rate depends on both the ad-
sorption sites of adsorbent and adsorbate/solute molecules, and related
to the numbers of occupied sites and the vacant available sites for the
adsorbent at equilibrium. The formation of a chemical bond between an
adsorption site and a solute molecule is the rate-limiting step. The
calculated parameters of the model confirms much better fitting with R2
value more than 0.999 (≈1.00) when compared with the pseudo-first-
order kinetic model (see Table 4). Specifically, the close agreement
between the experimental qe value of 56.64 mg g−1 and the calculated
value of 54.95 mg g-1 (for the maximum concentrated solution) un-
equivocally suggests the applicable model to be pseudo-second-order
for the adsorption process.
3.8. Thermodynamic parameters
The calculated thermodynamic parameters at various temperatures
are presented in Table 5. The negative ΔG° values confirm the feasibility
and spontaneity of the adsorption process. Also, the ΔG° values increase
with the increase in temperature suggesting better performance of the
V10TO at lower temperature as expected for a physisorption process.
The ΔH° and ΔS° values for the investigated temperature range were
calculated respectively from the slope and intercept of ln KD versus 1/T
plot shown in Fig. 7. The ΔH° value for the MB adsorption onto V10TO
was found to be −18.3 kJ mol−1, which confirms physisorption and
exothermic nature of the adsorption process. The ΔS° value was also
found to be negative that could be due to the restricted movement of
the free MB molecules at the material interface compared to that in the
K. Pal et al.
Fig. 4. (a) Low resolution TEM, (b) HRTEM, (c) SAED, (d) EDX spectra and (e) EDX elemental composition of V10TO.
solution phase.
3.9. pH dependent behavior
Adsorption activity of MB solution at different pH was analyzed by
the Britton–Robinson buffer (BR buffer) when other conditions for the
adsorption process were kept unchanged (see Fig. 8). It is observed that
only 1% adsorption takes place at a lower pH of 4 essentially due to the
acidic nature of MB. So the adsorption behavior is inhibited in the
acidic medium, whereas the catalyst shows much improved adsorption
behavior at higher pH values (neutral to alkaline) as expected.
3.10. Recycling ability
The stability of the synthesized catalyst was evaluated for four
consecutive cycles. For the first run, 20 mg of V10TO was taken in
45 mL of millipore water and 5 mL of MB stock solution was added to it
with constant stirring at ∼350 rpm in a dark place. After each run, the
material was recovered with centrifugation, followed by washing, first
with 1 N HCl solution then with millipore water. The crude was then
dried at 110 °C for 2 h. The dried crude material was subsequently
calcined at 400 °C for 3 h to regenerate the material that was used as the
catalyst for the next run. The results are displayed in Fig. 9 from which
we may conclude that the present vanadium doped titania catalyst
shows nearly similar activity in each cycle of adsorption and experi-
ences only a minor loss. Specifically, the adsorption reached around
86% in just 5 min and 93% in 1 h for the 1st cycle. This is followed by a
little (∼2%) decrease in adsorption in the subsequent cycles. This loss
of activity may be ascribed to be due to the certain loss of the catalyst
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Journal of Environmental Chemical Engineering 6 (2018) 5212–5220
amount in the washing process.
3.11. Material properties subsequent to adsorption and regeneration
mechanism
To understand the recycling behavior and to look into the me-
chanistic aspect of MB adsorption, we have carried out (i) XPS surface
analysis of the as-prepared (V10TO_AP) material, material collected
after an adsorption cycle (V10TO_Aged) and the regenerated material
(V10TO_Regn); (ii) bulk phase analysis of these three samples by along
with the material collected after an adsorption cycle followed by the
washing steps (V10TO_Washed) by P-XRD and (iii) FTIR analysis of
these four samples in comparison to that of MB.
Fig. 10(a) shows the Ti 2p XP spectra of V10TO in their as-prepared,
aged and regenerated forms. The Ti2p3/2,1/2 spin–orbit doublets cen-
tered at binding energies (BEs) around 458.6 and 464.2 eV for AP and
Regn materials can be attributed to Ti4+ species (see Fig. 10(a)). There
is a shift of about 0.3 eV in the BE position on ageing suggesting minor
reduction of the material during MB adsorption possibly due to for-
mation of TiOx kind of species.
Fig. 10(b) shows the V2p and O1 s core level region of the three
materials. Accordingly, the V 2p3/2,1/2 spin–orbit doublets centered at
BE around 516.4 and 524.0 eV for AP and Aged materials correspond to
V4+ species. There occurs an increase in the BE by about 0.5 eV for the
Regn material suggesting little more increase of oxidizing environment
of vanadium on regeneration. Broad nature of the O 1 s region possibly
suggests presence of a different kind of oxide species on the surface.
The powder XRD patterns of the four forms of the materials are
shown in Fig. 11(a). No signature of change in phase composition is
K. Pal et al. Journal of Environmental Chemical Engineering 6 (2018) 5212–5220

Fig. 5. MB adsorption isotherms using V10TO as catalyst and considering (a) Langmuir, (b) Freundlich, (c) Temkin and (d) Dubinin-Radushkevich models.

Table 3 3.12. Adsorption mechanism

Isotherm parameters for the adsorption of MB onto V10TO.
Parameters Three types of interactions play main role in adsorption reaction,
namely electrostatic attraction, physical adsorption and chemical ad-
Langmuir q0 (mg g−1) KL (L mg−1) R2 sorption. Based on the above results, we may confirm the physical
57.47 0.90 0.992 nature of MB adsorption onto V10TO, as reflected by the various
Freundlich KF (mg g−1(L n R2
mg−1)1/n)
parameters of different isotherm models. The monolayer adsorption
43.51 14.75 0.787 type with bond energy below 80 kJ mol−1 highly recommend the
Temkin A (L g−1) b (kJ mol−1) R2 physical nature. The study of kinetics of the process shows that the
3.31 0.72 0.753 correlation coefficients of pseudo-second-order model is about unity,
Dubinin- qD (mg g−1) β (kJ−2 mol2) E (kJ R2
which also supports the physisorption phenomenon. It is to be high-
Radushkevich mol−1)
52.76 0.11 2.15 0.413 lighted that the BET specific surface area of V10TO is ∼ 174 m2 g−1,
which provides sufficiently large area for this physical adsorption
process. Both Kupfer et al. [15] and Siddiqui et al. [22] have confirmed
noted for all the forms, except the occurrence of an undefined impurity the physisorption nature of MB on these kinds of oxide materials. Sid-
peak (at ∼18°) in the aged and washed material. Calcination leads to diqui et al. have derived two models for MB adsorption process, namely
complete regeneration of the material. intra-particle diffusion model and liquid film diffusion model and they
The FTIR analysis (see Fig. 11(b)) of the various forms of the cat- have advocated for the second model that gave well fitted data for the
alyst together with that of MB clearly suggests its adsorption adsorption process. Whereas, Kupfer et al. have suggested the main role
(V10TO_Aged) and almost removal after washing (V10TO_Washed) that to be played by the intra-particle diffusion model. Our present study
is completed after the regeneration treatment (V10TO_Regn). Washing shows that the MB adsorption onto V10TO is a physical adsorption and
in acid and alkali seems not sufficient enough, suggesting possible follows a pseudo-second-order kinetics in parity with the earlier reports
presence of some chemisorbed species. Therefore the doped material of MB adsorption as discussed above. A comparative study on the MB
can only be regenerated completely through introduction of an inter- adsorption capacity is also done (see Table 6), from which one can
mediate oxidation treatment and hence can be used continuously (re- assess the beneficial role of this kind of simple and well-known doped
peated four times) for the removal of MB, which is really attractive. oxide material for use in the removal of hazardous dye like methylene
More importantly, such regenerated phase exhibits the similar activity blue.
as the pristine phase. Thus one can consider such periodic behavior as
on-off-on modes of performance towards MB adsorption activity and can
MB solution
be presented as “VTO ⥫==============⥬ (VTO ) MB”.
washing followed by oxidation

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K. Pal et al. Journal of Environmental Chemical Engineering 6 (2018) 5212–5220

Fig. 6. MB adsorption kinetics evaluated on the basis of (a) pseudo-first order and (b) pseudo-second order models for V10TO material at 298 K.

Table 4
The values of parameters and correlation coefficients of kinetic models at 298 K.
Parameters MB concentration (mg L−1)

C = 20 C = 30 C = 40 C = 50

Experimental value
qe (mg g−1) 45.77 49.10 52.23 56.64
Pseudo-first order model
k1 (min−1) 0.025 0.020 0.019 0.017
qe (mg g−1) 9.37 13.16 13.43 15.47
R2 0.90 0.95 0.94 0.98
Pseudo-second order model
k2 (g mg−1 min−1) 0.015 0.010 0.010 0.008
qe (mg g−1) 45.66 48.31 51.02 54.95
R2 1.00 1.00 1.00 1.00

Table 5
Thermodynamic parameters for methylene blue adsorption on V10TO. Fig. 8. MB adsorption activity of V10TO at different pH.
T (K) KD ΔG° (kJ mol−1 K−1) ΔH° (kJ mol−1 K−1) ΔS° (J mol−1 K−1)

293 3.05 −2.72 −18.3 −53.1

298 2.73 −2.49
303 2.42 −2.23
313 1.89 −1.66

Fig. 9. Recycling ability of V10TO material in MB adsorption.

4. Conclusions

Fig. 7. Plot of ln KD vs. 1/T for methylene blue adsorption.
This study shows that vanadium doped titania exhibits great activity
towards MB dye adsorption. It was found that 10 at.% vanadium doped
titania shows best performance on MB adsorption. The adsorption ki-
netics could be quite successfully fitted by a pseudo-second order ki-
netic equation and the equilibrium adsorption can be explained on the
basis of Langmuir isotherm model. The physisorption of MB onto
V10TO is predominantly driven by weak van der Waals attractive force.
The feasibility of the process is observed by noting the RL value, which

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K. Pal et al. Journal of Environmental Chemical Engineering 6 (2018) 5212–5220

Fig. 10. XPS core level spectra of (a) Ti 2p and (b) V 2p regions of AP (black line), Aged (red line) and Regn (blue line) of V10TO.

Fig. 11. (a) Powder XRD patterns and (b) FT-IR spectra (along with that of MB) for V10TO material in AP, Aged, Washed and Regn forms.

Table 6 polluting world.

Comparative study of methylene blue removal capacity of different adsorbents.
Adsorbent MB removal capacity (mg Ref.
Acknowledgements
g−1)
The authors greatly acknowledge Prof. Pratik Kumar Sen, Jadavpur
Cortaderia selloana flower spikes 40.00 [29] University for invaluable discussion on adsorption isotherm and kinetic
Phragmites australis 22.70 [30]
ZnS:Ni-NP-AC 21.79 [31]
studies. Financial supports from the Science and Engineering Research
Cu(OH)2-NP-AC 32.90 [32] Board (SERB), Government of India, by a grant (EMR/2016/001811) to
Raw Algerian kaolin 52.76 [33] A. Gayen, UGC research fellowship to K. Pal and DST Special Grant to
Spent yerba mate Ilex 52.00 [34] the Department of Chemistry, Jadavpur University in the International
paraguariensis
Year of Chemistry 2011 are gratefully acknowledged.
Kaolin 45.00 [35]
Zeolite 4A 22.00 [35]
Ball Clay 25.10 [36] References
V10TO 56.64 Present study
[1] K. Ravi, B. Deebika, K. Balu, Decolourization of aqueous dye solutions by a novel
adsorbent: application of statistical designs and surface plots for the optimization
decreases with the increase of MB concentration. The spontaneity of the and regression analysis, J. Hazard. Mater. B122 (2005) 75–83.
[2] M.M. Mohamed, M.M. Al-Esaimi, Characterization, adsorption and photocatalytic
adsorption is reflected by the negative value of ΔG°, which increases at activity of vanadium-doped TiO2 and sulfated TiO2 (rutile) catalysts: degradation of
higher temperature. The pH of the reaction mixture also plays a vital methylene blue dye, J. Mol. Catal. A Chem. 255 (2006) 53–61.
role towards adsorption. The reusability of the doped material for the [3] T. Robinson, G. McMullan, R. Marchant, P. Nigam, Remediation of dyes in textiles
effluent: a critical review on current treatment technologies with a proposed al-
removal of MB can be achieved through involvement of a regeneration
ternative, Biresour. Technol. 77 (2001) 247–255.
step. Keeping in mind the role of MB in various injuries, this improved [4] I.M. Banat, P. Nigam, D. Singh, R. Marchant, Microbial decolourization of textile-
MB adsorption activity of anatase TiO2 in the presence of vanadium dye-containing effluents: a review, Bioresour. Technol. 58 (1996) 217–227.
[5] D. Ghosh, K.G. Bhattacharyya, Adsorption of methylene blue on kaolinite, Appl.
ions, the vanadia doped titania oxide, may play a crucial role in the
Clay Sci. 20 (2002) 295–300.
field of adsorption catalysis by changing various operational para- [6] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Adsorption of basic dye on high-surface area
meters and expected to be useful for applications such as the waste activated carbon prepared from coconut husk: equilibrium, kinetic and thermo-
water treatment in hazardous chemical industry making a relatively less dynamic studies, J. Hazard. Mater. 154 (2008) 337–346.

5219
K. Pal et al.
[7] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Adsorption of basic dye using activated
carbon prepared from oil palm shell: batch and fixed bed studies, Desalination 225
(2008) 13–28.
[8] X. Liu, W. Yang, C. Yu, H. Zhang, Influence of TiO2 morphology on adsorption-
photocatalytic efficiency of TiO2-graphene composites for methylene blue de-
gradation, J. Environ. Chem. Eng. 6 (Aug. (4)) (2018) 4899–4907, https://doi.org/
10.1016/j.jece.2018.07.009.
[9] M. Sleiman, D.L. Vildozo, C. Ferronato, J.M. Chovelon, Photocatalytic degradation
of azo dye Metanil Yellow: optimization and kinetic modeling using a chemometric
approach, Appl. Catal. B 77 (2007) 1–11.
[10] M. Abbasi, N.R. Asl, Sonochemical degradation of Basic Blue 41 dye assisted by
nano TiO2 and H2O2, J. Hazard. Mater. 153 (2008) 942–947.
[11] G. Sudarjanto, B. Keller-Lehmann, J. Keller, Optimization of integrated chemi-
cal–biological degradation of a reactive azo dye using response surface metho-
dology, J. Hazard. Mater. 138 (2006) 160–168.
[12] V. Sarria, M. Deront, P. Peringer, C. Pulgarin, Degradation of a biorecalcitrant dye
precursor present in industrial wastewaters by a new integrated iron (III) photo-
assisted-biological treatment, Appl. Catal. B 40 (2003) 231–246.
[13] B. Lodha, S. Chaudhari, Optimization of Fenton-biological treatment scheme for the
treatment of aqueous dye solutions, J. Hazard. Mater. 148 (2007) 459–466.
[14] J.S. Wu, C.H. Liu, K.H. Chu, S.Y. Suen, Removal of cationic dye methyl violet 2B
from water by cation exchange membranes, J. Membr. Sci. 309 (2008) 239–245.
[15] V.L. Kupfer, Rd.S. Maniezzo, H.H.Cd. Lima, M.R. Guilherme, M.P. Moises,
A.W. Rinaldi, Highly ordered SBA-16 with low nickel amount for enhanced ad-
sorption of methylene blue, J. Environ. Chem. Eng. 6 (2018) 3898–3906.
[16] A.A. Narvekar, J.B. Fernandes, S.G. Tilve, Adsorption behavior of methylene blue
on glycerol based carbon materials, J. Environ. Chem. Eng. 6 (2018) 1714–1725.
[17] E.C. Peres, J.C. Slaviero, A.M. Cunha, A.H. Bandegharaei, G.L. Dotto, Microwave
synthesis of silica nanoparticles and its application for methylene blue adsorption,
J. Environ. Chem. Eng. 6 (2018) 649–659.
[18] R. Pandimurugan, S. Thambidurai, Synthesis of seaweed-ZnO-PANI hybrid com-
posite for adsorption of methylene blue dye, J. Environ. Chem. Eng. 4 (2016)
1332–1347.
[19] A.K. Jain, V.K. Gupta, A. Bhatnagar, Suhas, Utilization of industrial waste products
as adsorbents for the removal of dyes, J. Hazard. Mater. B101 (2003) 31–42.
[20] F. Derbyshire, M. Jagtoyen, R. Andrews, A. Rao, I. Martin-Gullon, E. Grulke, Carbon
materials in environmental applications, in: L.R. Radovic (Ed.), Chemistry and
Physics of Carbon, 27 Marcel Dekker, New York, 2001, pp. 1–66.
[21] A. Dabrowski, Adsorption-from theory to practice, Adv. Colloid Interface Sci. 93
(2001) 135–224.
[22] S.I. Siddiqui, G. Rathi, S.A. Chaudhry, Acid washed black cumin seed powder
5220
Journal of Environmental Chemical Engineering 6 (2018) 5212–5220
preparation for adsorption of methylene blue dye from aqueous solution: thermo-
dynamic, kinetic and isotherm studies, J. Mol. Liq. 264 (2018) 275–284.
[23] M. Rafatullah, O. Sulaiman, R. Hashim, A. Ahmad, Adsorption of copper (II),
chromium (III), nickel (II) and lead (II) ions from aqueous solutions by meranti
sawdust, J. Hazard. Mater. 170 (2009) 969–977.
[24] M. Dahl, Y. Liu, Y. Yin, Composite titanium dioxide nanomaterials, Chem. Rev. 114
(2014) 9853–9889.
[25] W. Zhou, Q. Liu, Z. Zhu, J. Zhang, Preparation and properties of vanadium-doped
TiO2 photocatalysts, J. Phys. D Appl. Phys. 43 (2010) 035301.
[26] Y. Wang, J. Zhang, L. Liu, C. Zhu, X. Liu, Q. Su, Visible light photocatalysis of V2O5/
TiO2 nanoheterostructures prepared via electrospinning, Mater. Lett. 75 (2012)
95–98.
[27] E. Tolmachoff, S. Memarzadeh, H. Wang, Nanoporous titania gas sensing films
prepared in a premixed stagnation flame, J. Phys. Chem. C 115 (2011)
21620–21628.
[28] T. Lopez, J.A. Moreno, R. Gomez, X. Bokhimi, J.A. Wang, H. Yee-Madeira,
G. Pecchi, P. Reyes, Characterization of iron-doped titania sol–gel materials, J.
Mater. Chem. 12 (2002) 714–718.
[29] Z. Jia, Z. Li, T. Ni, S. Li, Adsorption of low-cost absorption materials based on
biomass (Cortaderia selloana flower spikes) for dye removal: kinetics, isotherms and
thermodynamic studies, J. Mol. Liq. 229 (2017) 285–292.
[30] G.B. Kankilic, A.U. Metin, I. Tuzun, Phragmites Australis: an alternative biosorbent
for basic dye removal, Ecol. Eng. 86 (2016) 85–94.
[31] H.Z. Khafri, M. Ghaedi, A. Asfaram, M. Safarpoor, Synthesis and characterization of
ZnS:Ni-NPs loaded on AC derived from apple tree wood and their applicability for
the ultrasound assisted comparative adsorption of cationic dyes based on the ex-
perimental design, Ultrason. Sonochem. 38 (2017) 371–380.
[32] S. Dashamiri, M. Ghaedi, A. Asfaram, F. Zare, S. Wang, Multi-response optimization
of ultrasound assisted competitive adsorption of dyes onto Cu(OH)2-nanoparticle
loaded activated carbon: central composite design, Ultrason. Sonochem. 34 (2017)
343–353.
[33] L. Mouni, L. Belkhiri, J.C. Bollinger, A. Bouzaza, H. Remini, Removal ofmethylene
blue from aqueous solutions by adsorption on kaolin: kinetic and equilibrium stu-
dies, Appl. Clay Sci. 153 (2018) 38–45.
[34] A.B. Albadarin, S. Solomon, M.A. Daher, G. Walke, Efficient removal of anionic and
cationic dyes from aqueous systems using spent yerba mate “Ilex paraguariensis”, J.
Taiwan Inst. Chem. Eng. 82 (2018) 144–155.
[35] K. Rida, S. Bouraoui, S. Hadnine, Adsorption of methylene blue from aqueous so-
lution by kaolin and zeolite, Appl. Clay Sci. 83–84 (2013) 99–105.
[36] M. Auta, B.H. Hameed, Modified mesoporous clay adsorbent for adsorption iso-
therm and kinetics of methylene blue, Chem. Eng. J. 198–199 (2012) 219–227.