Chemical Engineering Journal 359 (2019) 963–975

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Chemical Engineering Journal

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Synthesis and application of stable, reusable TiO2 polymeric composites for T

photocatalytic removal of metronidazole: Removal kinetics and density
functional analysis
⁎
N. Neghia, Mathava Kumara, , Danil Burkhalovb
a
Environmental and Water Resources Engineering Division, Department of Civil Engineering, IIT Madras, Chennai 600 036, India
b
Department of Chemistry, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea

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

• Polymeric composites were synthe-

sized and applied for metronidazole
removal.
• cles
PVA-CS-TiO was stable after 15 cy-
2
of UV experiments.
• multi-cycle
No loss of TiO from PVA-CS-TiO in
2
photocatalytic experi-
2

ments.
• Density functional analysis was used
to find metronidazole removal by ad-
sorption.
• Modified Langmuir-Hinshelwood
model was used to estimate rate of
photocatalysis.

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

Keywords: TiO2-polymeric composites, i.e. chitosan supported TiO2 (CS-TiO2) and polyvinyl alcohol/chitosan blend sup-
Chitosan-based TiO2 composites ported TiO2 (PVA-CS-TiO2), were synthesized via precipitation in an alkali/solvent medium and applied for
UV/TiO2 photocatalysis photocatalytic removal of metronidazole (MNZ) in a batch reactor. The composites have produced 100% MNZ
Adsorption removal (10 mg L−1) within 120 min at a catalyst loading of 0.3 g L−1. However, a maximum TOC removal of
Reusability studies
76.1% and 63.7% was observed in PVA-CS-TiO2 and CS-TiO2 systems, respectively. In comparison, complete
DFT modelling
MNZ removal in suspended TiO2 system was observed at 8.3 times higher dosage under similar conditions. The
stability of the composites in water and adsorption mechanism was modelled through density functional theory
(DFT). The energy of formation for CS-TiO2, PVA-TiO2 and PVA-CS in water were found to be −0.144, −0.153
and −0.220 eV, respectively. It was inferred that the presence of CS significantly enhanced MNZ adsorption and
moreover, the removal was due to synergetic removal by adsorption (pseudo-second-order) and photocatalysis
(pseudo-first-order) as evidenced via kinetic models. The hierarchy of adsorption capability of different ad-
sorbents towards MNZ is as follows: PVA-CS-TiO2 > CS-TiO2 > CS > TiO2 > PVA. The prepared composites
showed consistent MNZ removal rates and structural integrity over 15 photocatalytic treatment cycles.
Moreover, a kinetic model was developed to identify a best combination of retention time and TiO2 content in
PVA-CS-TiO2 to predict 100% MNZ. Overall, MNZ removal along with enthalpy values indicated that the pre-
pared composites could be applied for pharmaceutical removal on a long-term basis.

⁎
Corresponding author.
E-mail address: mathav@iitm.ac.in (M. Kumar).

https://doi.org/10.1016/j.cej.2018.11.090
Received 27 August 2018; Received in revised form 3 November 2018; Accepted 11 November 2018
Available online 12 November 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
N. Neghi et al.
1. Introduction
The trace organics removal from secondary effluents has become a
difficult task due to the penetration of many emerging contaminants
including pharmaceuticals, personal care products, pesticides, herbi-
cides, etc. to wastewater. Antibiotics usage in human and veterinary
medications has increased several folds, which has indirectly in-
troduced their traces in aqueous and soil environments [1,2]. These
compounds can generate antimicrobial resistance (AMR) and eco-toxi-
city [3]. Metronidazole (MNZ, C6H9N3O3) is an imidazole antibiotic,
used to treat anaerobic bacteria, bacteroides and protozoal infections in
humans and also been used as feed additives in poultry and aquaculture
farms. The presence of MNZ was detected in drinking water, ground/
surface water, soil sediments and wastewater from one to several
ng L−1, globally [4–7]. Moreover, it has been reported that imidazole-
resistant genes occur very commonly in Clostridium difficile-positive
patients indicating that MNZ has a very high resistance rate [8].
Therefore, removal of MNZ and similar other trace organics from water
systems is necessary considering its carcinogenicity and the increasing
AMR.
In this context, advanced oxidation systems such as chemical/elec-
trochemical oxidation [9], Fenton-based [10], ozone-based [11], ra-
diation-based such as UV light [12], visible light [13], E-beam [14],
gamma [15] and sonolysis [16] processes have been developed and
investigated for the complete removal of antibiotics. Photocatalysis
employing titanium dioxide nanoparticles (TiO2 NPs) possess the a)
efficiency of mineralization of trace organics [17] by the production of
hydroxyl radicals (OH.; E0=+2.8V ) and other reactive species as shown
in Eq. (1), b) possibility of catalyst reuse and c) applicability in wide pH
range. Anatase TiO2 NPs (101 facet) in water has proven to be an ideal
photocatalyst owing to its crystallinity, surface area for reaction, high
photocatalytic activity, chemical inertness, adsorption of OH/(OH.) and
cost effectiveness [18].
Trace Organics (R) + hv (UV254 − TiO2) → OH./O2− ./R. → Oxidation
→ CO2 + H2 O + Intermediates (1)
Intense research on TiO2 has been carried out in two major di-
mensions. One aspect is to shift its applicability from UV light to visible
light region by reduction in the band gap of TiO2 [19,20] and the other
is development of recoverable TiO2 composites [21] which can facil-
itate construction of large-scale photochemical reactors for air and
water purification [22]. In the context of developing recoverable pho-
tocatalyst, several investigations have focussed on TiO2 coating on
different substrates such as glass sphere [23], quartz tube [24], natural
zeolite [25], activated carbon [26], concrete surface and also on
membrane surface [27,28] for addressing the recovery issues. It was
observed that coating TiO2 on different surfaces could reduce the
available surface area of TiO2, difficulty in maintaining TiO2 loading
and detachment of TiO2 from substrates. Therefore, embedding TiO2 in
the support could address the issues of the coating process. Based on the
support chosen, the synergy of adsorption and photocatalysis greatly
improves the performance of such photocatalytic composites [29–31].
Recently, investigations were carried out to embed TiO2 in polymer
matrices such as polyaniline [32], polyvinyl alcohol [33], chitosan
[34], cellulose [35], polyethylene [36] in order to retain NPs in the
matrix and reuse it for multiple photocatalytic treatment cycles. Cor-
respondingly, the present study aims to prepare a hybrid photocatalytic
material that (a) performs better or equal efficiency as that of TiO2
suspended systems in short as well as long term operation in water and
UV environment, (b) easily recoverable, (c) possess better retention of
TiO2 within the support and (d) biodegradable/non-toxic in the ex-
posed environment [37]. In this context, two photocatalytic TiO2
composites were developed using chitosan (CS) and polyvinyl alcohol-
chitosan (PVA-CS) polymer blend matrices. CS, the most abundant
natural biopolymer after cellulose, is used in the form of hydrogel beads
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Chemical Engineering Journal 359 (2019) 963–975
to adsorb metal ions [38,39], dyes [40], inorganic ions [41], organic
compounds such as caffeine, phenols, pharmaceuticals [42–44]. How-
ever, instability due to the poor mechanical resistance was observed to
be the major setback in the application of adsorption. In order to
overcome this limitation, a variety of polymer blends (a mix of two or
more polymers) have been developed which complement each other
rather than as individuals. PVA-CS blend is one such combination
which is found to have better hydrophilicity, mechanical properties and
biocompatibility, and it has been applied as (a) an adsorbent for metal
removal [45], (b) food packaging material [46], and (c) biomedical and
tissue replacement material [47]. It is also known that PVA is bio-
compatible and non-toxic when administered orally [48]. Therefore,
such polymeric blends are potential candidates for producing highly
functional materials and interfaces. On the other hand, the information
regarding the application of TiO2 polymeric composites in tertiary
wastewater treatment is less [19]. Moreover, the characteristics and
trace organics removal mechanisms (i.e. both adsorption and photo-
catalysis) in such composites has not been discussed in detail.
Therefore, the major aim of this investigation is the application of
CS and PVA-CS blend as support for the preparation of supported
photocatalysts, i.e. CS-TiO2 and PVA-CS-TiO2 on the light of following
parameters: (i) aqueous and photo stability of the composites using
different characterization techniques, (ii) efficiency of the hybrid pho-
tocatalyst in MNZ removal and its recoverability/reusability, (iii) cal-
culate MNZ removal in composite and suspended TiO2 systems using
modified Langmuir-Hinshelwood kinetic model developed, and (iv)
calculate interaction energies between MNZ and different components
of the composites, bonding energies of the composites in water using
density functional theory.
2. Materials and methods
Chitosan (CS, deacetylation: ≥95%, viscosity 200–600 mPa·s), poly
(vinyl alcohol) (PVA, alcoholysis degree: 86–89%,
Mw ∼ 124,000 g mol−1), methanol and TiO2 (Mean particle size
∼25 nm) were procured from Tokyo chemical industries ltd, Japan, SD
fine chemicals ltd, India and Avra synthesis, India, respectively. All
other chemicals used were of analytical grade and used as received.
2.1. Synthesis of CS-TiO2 and PVA-CS-TiO2 composites
The CS solution (2%) was obtained by dissolving 2 g of CS powder in
100 mL of dilute acetic acid (2.58% v/v) at 60 °C for 3 h under stirring
conditions. The obtained CS and TiO2 solutions (1% w/v) were
homogenized by ultrasonication for 20 min. Subsequently, the gel blend
was cross linked in NaOH (0.5 M) to obtain CS-TiO2 beads. The syn-
thesized beads were thoroughly washed twice with DI water in 6 h
cycles, oven-dried at 100 °C for 2 h and used for the degradation stu-
dies.
For the synthesis of PVA-CS-TiO2 composite, CS solution (2%) and
PVA solution (8%, stirred at 80 °C for 5 h) were prepared separately as
reported earlier [49]. The two solutions were blended for 12 h at 80 °C
and at room temperature for another 12 h. Further, the obtained PVA-
CS blend was mixed with TiO2 solution (2%) by ultrasonication for
30 min and the gel blend was introduced as droplets in NaOH-methanol
solution (0.25 M) under slow stirring conditions. The synthesized beads
were washed with DI water, oven-dried for 2 h, stored in sealed con-
tainers and used for the degradation studies.
2.2. Characterization of photocatalytic composites
The functionalization of the composites, TiO2, chitosan and PVA
were examined by attenuated total reflectance Fourier-transform in-
frared spectroscopy (ATR-FTIR). The FTIR spectra were collected in
4000–550 cm−1 range, with a resolution of 4 cm−1 at room tempera-
ture by using a Perkin Elmer spectrometer. Raman spectroscopy was
N. Neghi et al. Chemical Engineering Journal 359 (2019) 963–975

Fig. 1. FTIR spectra of (a) CS, (b) TiO2, (c) CS-TiO2 before treatment (P0), and (d) CS- TiO2 after 15 cycles of photocatalytic treatment (P15).

Fig. 2. FTIR spectra of (a) CS, (b) PVA, (c) TiO2, (d) PVA-CS-TiO2 before treatment (P0), and (e) PVA-CS- TiO2 after 15 cycles of photocatalytic treatment (P15).

performed by Bruker RFS 27 spectrometer provided with Nd:YAG laser
(1064 nm) as the excitation source. The Raman spectrum was collected
in the spectral range of 4000–50 cm−1, with the resolution of 4 cm−1.
The powder X-ray diffraction (XRD) patterns were done with Cu Kα
radiation (λ = 1.5418 Å) at a scan rate of 0.1° min−1 from 10° to 80°
following 40 kV of accelerating voltage and 30 mA of applied current.
Prior to the measurement, the dried composite flakes were crushed into
powder form. The morphology of samples was observed by field
emission gun based scanning electron microscopy (FEG SEM, Quanta
400) at an accelerating voltage of 15 kV. Moreover, the elemental
composition of the samples was quantitatively determined using energy
dispersive spectroscopy (EDX, Bruker X Flash 6I 10). To further analyse
the morphological characteristics, high resolution transmission electron
microscopy (HRTEM with EDX) was performed using JEOL 3010 at an
accelerating voltage of 200 kV. Surface analysis by XPS was accom-
plished by irradiating the sample with monoenergetic soft X-rays, Mg

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N. Neghi et al.
Fig. 3. XRD spectra of CS-TiO2 before and after 15 cycles of photocatalytic
treatment.
Fig. 4. XRD pattern of PVA-CS-TiO2 before and after 15 cycles of photocatalytic
treatment.
Kα (1253.6 eV) using ESCA probe TPD system in an ultra-high vacuum
system. Thermogravimetric analyses (TGA) of the synthesized compo-
sites, chitosan and PVA were performed in SDT Q 600 TGA (T.A) in-
struments under nitrogen atmosphere (100 mL/min) from 25 °C to
700 °C at a heating rate of 10 °C min−1. A LAMBDA950 UV–vis diffuse
reflectance spectrometer was used to measure the light absorption
properties of TiO2 and composite materials. BaSO4 was used as the
reference material, and the wavelength range was 250–800 nm. The
specific surface area of the composites was obtained by nitrogen ad-
sorption–desorption isotherm at 77 K using Micromeritics ASAP 2020
porosimeter. Specific surface area of the composites was evaluated
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Chemical Engineering Journal 359 (2019) 963–975
using Brunauer–Emmett–Teller (BET) method. Prior to the measure-
ment, both the composites were degassed at 150 °C overnight.
2.3. Photocatalysis using composites
Photocatalytic experiments were conducted using CS-TiO2 and PVA-
CS-TiO2 composite flakes (size range of 1.5–3 mm) in a batch reactor as
designed in our previous work [50]. MNZ solution (2L) having the re-
quired concentration (10, 1 and 0.1 mg L−1) was added with 0.3 g L−1
of photocatalyst (CS-TiO2 or PVA-CS-TiO2). The reactor was provided
with 32 W UV power (λmax = 254 nm), continuous stirring (200 rpm)
and operated for 120 min without pH and temperature controls. At
regular intervals of 30 min, samples were collected from the reactor and
analyzed for MNZ concentration. In addition, control experiments were
conducted without the catalyst but with UV (32 W) for 120 min.
2.4. Reusability studies
In order to find the reusability of the composites, photocatalytic
experiments (120 min) were repeated 15 times (P1 to P15) with the
same composite retained (using a metallic tea strainer mesh) after each
cycle. At the end of each cycle, the samples were collected and analyzed
for MNZ concentration. Additionally, blank runs were performed with
and without UV illumination at similar catalyst loadings, but in the
absence of MNZ, to evaluate the stability of the composites in the
photocatalytic reactor.
2.5. Adsorption studies
Adsorption experiments were conducted in a round bottom flask
with 100 mL MNZ solution (10, 1 and 0.1 mg L−1 concentration) and
0.03 g of photocatalyst as adsorbent. The sorbed amount of MNZ per
unit weight of adsorbent (qe, mg g−1) at equilibrium time (t) was cal-
culated using Eq. (2).
V
qe = (C0 − Ce )
W (2)
where C0, Ce, V and W represent initial MNZ concentration (mg L−1),
MNZ concentration at equilibrium (mg L−1), reaction volume (L) and
weight of the adsorbent (g), respectively. Moreover, the data was used
to estimate maximum MNZ adsorption capacity of CS-TiO2 and PVA-CS-
TiO2 using linearized expressions of Langmuir (Eq. (3)), Freundlich (Eq.
(4)), Temkin (Eq. (5)) and Dubinin-Radushkevich (Eq. (6)) isotherms.
1 1 1
+
qe = qmL qmL KL Ce (3)
1
logqe=logKF + logCe
n (4)
RT
qe =Bln (AT ) + Bln (Ce ); B =
bT (5)
lnqe = lnqm − (KDR ε 2) (6)
In Eq. (3), qmL is the amount of adsorption corresponding to the com-
plete monolayer coverage and KL is the Langmuir isotherm constant. In
Freundlich isotherm equation, 1/n and KF are the adsorption intensity
and Freundlich isotherm constant, respectively. In Eq. (5), AT is the
Temkin isotherm equilibrium binding constant (L mg−1), bT is the
Temkin isotherm constant, R is the universal gas constant
(8.314 J mol−1 K−1), T is the temperature at 298 K and B is the constant
related to heat of sorption (J mol−1). KDR refers to mean free energy of
adsorption (mol2 kJ−2) and ε = RT ln ⎡1 + C ⎤ is Polyani potential (Eq.
1
⎣ e⎦
(6)). MNZ adsorption kinetics on the composites were analyzed by
plotting Lagergren’s pseudo-first order (Eq. (7)), pseudo-second order
(Eq. (8)) and intraparticle diffusion (Eq. (9)) models.
N. Neghi et al.
Fig. 5. TEM images of CS-TiO2 (a) before, and (c) after 15 photocatalytic treatment cycles and PVA-CS-TiO2 (b) before, and (d) after 15 photocatalytic treatment
cycles (Inset shows the lattice spacing (d = 0.36 nm) corresponding to (1 0 1) anatase TiO2).
k1
log (qe − qt ) = logqe − t
2.303
t 1 1
= + t
qt K2 qe2 qe
qt = Kid t 1/2 + c
where qe and qt are the adsorption capacities at equilibrium and at time
(t) (mg g−1). k1 is the pseudo-first order rate constant (min−1), k2 is the
pseudo-second order rate constant (g mg−1 min−1), kid is the intra-
particle diffusion constant (g mg−1 min−0.5) and C is the intercept that
were obtained by plotting Eqs. (7)–(9), respectively.
2.6. Analytical techniques
MNZ concentration was analyzed using high performance liquid
chromatography (HPLC, Dionex, USA) fitted with C18 column and
UV–Visible detector. Acetonitrile and deionized water (60:40) was used
as the mobile phase. The column flow-rate was maintained at
1 mL min−1 and wavelength of UV detector was set at 254 nm. The
reaction mixture pH and temperature were measured using a multi-
parameter analyzer (OAKTON, India) connected to the probes of the
batch reactor. The total organic carbon remaining in the samples was
analyzed by total organic carbon analyzer equipped with non-destruc-
tive infrared analyzer (Shimadzu, Japan).
2.7. Modelling using DFT
Modeling was performed using density functional theory (DFT) and
carried out by means of the pseudo potential code SIESTA [51]. All
calculations were performed using the generalized gradient approx-
imation (GGA-PBE) including spin polarization [52] with taking into
account van der Waals correction [53]. Full optimization of the atomic
Chemical Engineering Journal 359 (2019) 963–975
positions was carried out. During this optimization, the ion cores were
(7) described by norm-conserving nonrelativistic pseudo potentials [54]
with cutoff radii 1.14, 1.48, 1.47, 2.42 and 1.25 a.u. for C, N, O, Ti and
H, respectively; the wave functions were expanded with a double-ζ plus
(8) polarization basis of localized orbitals for non-hydrogen atoms and with
a double-ζ basis for H. Optimizations of the force and total energy were
(9)
performed with the accuracies of 0.04 eV/Å and 1 meV, respectively.
For modeling of CS, three members of CS chains were considered
(Fig. S1a). Similarly, for the modeling of anatase TiO2 and PVA, a slab
made from 4 × 2 × 2 TiO2 supercell with surface passivated by hy-
droxyl groups (Fig. S1b) and three members of CH2–CH–OH chain (Fig.
S1c) was considered, respectively.
The first step in the modeling is evaluation of the composite stability
in water. The second step is, taking into account the stability of com-
posites in water environment; the model evaluates the energy of the
adsorption of molecules from water. Usually the enthalpy of formation
and/or adsorption is calculated by Eq. (10).
E form/ads = Ehost + guest − (Ehost + Eguest) (10)
where Eguest is the total energy of compound in empty space. None-
theless, in this case the parts of the composite and the guest molecules
exist before and after reactions in water environment. Thus, Eq. (10)
should be corrected for the case of composites formation as,
E form = Ecomposite − (E1part + E2part + …) − (E1water + E2water + …)/n (11)
where Epart1 is the total energy of the parts of composites in empty
space, Ewater1 is the energy of interaction of selected part of composites
with water, and n is the coefficient which equals 2 when the parts of
composite participate in the bond formation with guest molecules. The
formation of these new bonds generally originated from one side of the
composite (Fig. S1d). It should be also noted that, other part of the
composites generally interacts with water. Thus, n = 1 and the com-
posites form periodic structure with breaking of all previous
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N. Neghi et al.
Fig. 6. XPS spectra of CS-TiO2 (P15) (a) survey scan, (b) Ti 2p, (c) C 1s, (d) O 1s narrow scans (Inset: XPS spectra of CS-TiO2 before photocatalytic treatment).
interactions of the parts of composite with water. In case of adsorption,
Eq. (12) can be applied.
Eads = Ehost + guest − −(Ehost + Eguest) − −E water (guest) (12)
where Ewater (guest) is the energy of interaction of adsorbed molecules
with water. It is necessary to evaluate the energies of interactions with
water. This is because in an aqueous environment multiple configura-
tions of water molecules were possible. Therefore, building of the exact
model for aqueous environment is difficult and expensive process. In
this regard, the energy of water have been estimated by summarizing
the interaction energies of each hydrophilic groups of TiO2 and CS with
water (about 0.1 eV) [55]. For MNZ, a correction value of 0.44 eV was
used for incorporating the energetics of water. Initially, in order to
check the characteristics of the interaction of MNZ with water, total
energy of interaction between MNZ molecules in solid phase was con-
sidered. Therefore, MNZ stack molecules within periodic boundary
conditions were built (Fig. S1e). The value of interaction energy be-
tween MNZ molecules was found to be −0.641 eV. The magnitude of
this energy was about one and half time (1 ½) larger than the estimated
value of the energy of interaction of MNZ with water. These results are
in agreement with experimentally detected strong hydrophobicity of
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Chemical Engineering Journal 359 (2019) 963–975
MNZ within the boundary conditions [56].
3. Results and discussion
3.1. Characterization of photocatalytic composites
The FT-IR spectra of CS-TiO2 and PVA-CS-TiO2 before (P0) and after
15 cycles of photocatalytic treatment (P15) were analyzed including the
pristine materials (CS, PVA, and TiO2) were shown in Figs. 1 and 2. For
CS, PVA and its composites, the presence of broad peak at 3355 cm−1
corresponds to the stretching of OeH and NeH bonds. The peaks at
2877 and 2906 cm−1 are due to CeH stretching of the alkyl groups
(Figs. 1c and 2d). The peaks seen at 1644 and 1565 cm−1 (as in Figs. 1c,
d and 2d) corresponds to CeO stretching in the primary amide group of
chitosan and bending of NeH of secondary amide [57]. The peak lo-
cated at 1374 is ascribed to CeH and OeH in plane bending vibration
[58].
Compared with CS, the IR spectrum of CS-TiO2 showed similar
peaks except the prominent eOeH bond peaks at 3355 and 1374 cm−1.
This indicates that intermolecular hydrogen bonding of TiO2 with CS
has occurred. The signature area of chitosan structure indicating
N. Neghi et al. Chemical Engineering Journal 359 (2019) 963–975

Fig. 7. XPS spectra of PVA-CS-TiO2 (P15) (a) survey scan, (b) Ti 2p, (c) C 1s, (d) O 1s narrow scans (Inset: XPS spectra of PVA-CS-TiO2 before photocatalytic
treatment).

Table 1
Performance of TiO2, CS-TiO2 and PVA-CS-TiO2 system in MNZ removal.
Type of photocatalysts Catalyst MNZ removal (%) at different MNZ MNZ removal rate (×10−2 min−1) at different MNZ removal rate (×10−3 min−1) at different
loading concentration (mg L−1) after 120 min MNZ concentration (mg L−1) after 120 min as MNZ concentration (mg L−1) after 120 min as
(g L−1) per Eq. (13) per Eq. (15)

0.1 1 10 0.1 1 10 0.1 1 10

TiO2 0.3 33.8 37.8 17.8 0.43 0.34 0.16 0.1 0.1 0.05
CS-TiO2 0.3 99.9 99.9 98.2 4.6^ 4.1 3.3 1.4^ 1.4 1.1
PVA-CS-TiO2 0.3 99.9 99.9 99.7 4.2^ 4.6 4.8 1.4^ 1.5 1.6
Earlier TiO2 2.5 99.7 98.2 96.2 4.8 3.2 2.7 0.02 0.01 0.01
investigation*

* Results of our earlier investigation [50].

^
MNZ removal rates calculated for 90 min.

saccharide linkages at 1151, 1022 and 897 cm−1 could be observed in vibrations in the spectra of photocatalytic composites (Figs. 1c and 2d)
Fig. 1 [59]. It is observed that the saccharide structure remains un- [60].
disturbed in the synthesis of CS-TiO2 but not in PVA-CS-TiO2. More- In PVA-CS-TiO2 composite, the intensity at 3357 and 2877 (in CS)
over, the absorption peak located at 571 cm−1 corresponds to Ti-O-Ti has reduced and shifted to lower and higher frequency, i.e. at 3342 and

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Table 2
MNZ adsorption isotherm parameters calculated for CS-TiO2 and PVA-CS-TiO2 and the pristine materials used for the synthesis of photocatalytic composites.
Isotherm models Parameters TiO2 CS PVA CS-TiO2 PVA-CS-TiO2

−1
Langmuir qm (mg g ) 1.33 2.21 2.11 5.9 5.1
KL (L mg−1) 0.19 0.13 0.09 0.03 0.05
r2 0.9796 0.9947 0.99 0.571 0.3981

Freundlich KF (mg g−1) 0.17 0.22 0.15 0.17 0.24

1 0.8 0.87 0.89 0.9 0.96
n
r2 0.9976 0.9975 0.9986 0.9992 0.9794

Temkin AT (L mg−1) 0.67 0.04 0.68 0.57 0.5

B (J mol−1) 5.48 0.62 4.96 3.15 2.91
r2 0.8642 0.8224 0.8496 0.8339 0.9023

Dubinin-Radushkevich qm (mg g−1) 0.394 0.5 0.38 0.48 0.75

KDR (mol2 KJ−2) 6.0E−08 6.0E−08 7.0E−08 8.0E−08 9.0E−08
E(KJ mol−1) 2887 2887 2672 2500 2357
r2 0.8589 0.8625 0.8511 0.7817 0.9006

Table 3
MNZ kinetic parameters calculated for CS-TiO2 and PVA-CS-TiO2 and the pristine materials used for the synthesis of photocatalytic composites.
Type of photocatalysts MNZ conc (mg L−1) Kinetic models

Pseudo-first-order Pseudo-second-order Intraparticle diffusion

−1 −1 −1 −1 −1
qe (mg g ) k1 (min ) r 2
qe (mg g ) k2 (g mg min ) r 2
kid (g mg−1 min−0.5) r2

TiO2 0.1 0.02 0.05 0.874 0.02 1.43 0.359 0.002 0.895
1 0.13 0.05 0.998 0.05 1.78 0.966 0.017 0.996
10 0.79 0.03 0.998 0.87 0.08 0.772 0.099 0.979

CS 0.1 0.02 0.05 0.861 0.02 0.13 0.328 0.002 0.883

1 0.17 0.1 0.894 0.18 0.35 0.647 0.02 0.862
10 1.43 0.1 0.984 1.06 0.2 0.968 0.14 0.955

PVA 0.1 0.05 0.05 0.994 0.02 6.02 0.878 0.002 0.796
1 0.09 0.03 0.873 0.1 1.72 0.946 0.015 0.769
10 0.96 0.09 0.995 0.84 0.22 0.981 0.11 0.946

CS-TiO2 0.1 0.14 0.24 0.855 0.02 6.4 0.889 0.002 0.976
1 0.24 0.1 0.919 0.1 1.85 0.967 0.015 0.769
10 1.87 0.12 0.952 1.28 0.35 0.993 0.17 0.896

PVA-CS-TiO2 0.1 0.32 0.46 0.834 0.03 13.1 0.986 0.004 0.896
1 0.1 0.58 0.866 0.19 1.35 0.991 0.022 0.839
10 3.26 0.16 0.952 1.45 0.25 0.989 0.12 0.919

2906 cm−1, respectively, indicating that crosslinking of PVA with CS

has occurred [61,62]. On the other hand, the intensity of the peak at
1644 cm−1 has decreased in PVA-CS-TiO2 (Fig. 2d and e) which in-
dicates that the amino group of CS was taking part in the formation of
the composites. In addition, Fig. 2e (i.e. PVA-CS-TiO2 after 15 cycles of
treatment) showed new signals at 1318 and 1420 cm−1 which indicates
CeOeNO2 group [63]. This might be due to the bonding of MNZ with
the composite after treatment. Overall, it is inferred that the structural
integrity of the composites is maintained even after 15 cycles of pho-
tocatalytic treatment.
For further validation of FTIR results, Raman spectroscopy was
performed for the composites for P0 and P15. It is evident that TiO2 was
intact in the anatase form embedded/phase separated in the composites
(Figs. S2 and S3). The characteristic Raman bands of anatase TiO2
present in both the composites around 142, 394, 513 and 639 (cm−1),
well matched out of the six Raman active modes of anatase TiO2 [64].
Moreover, a peak with medium signal at 2898 cm−1 is assigned to CH2
stretching modes, which arise from CS and PVA structure.
The XRD analysis helps to identify the crystallinity of TiO2 present
in the composite for P0 and P15. As illustrated in Figs. 3 and 4 diffrac-
tion peaks clearly show anatase phase structure of TiO2, namely, the
Fig. 8. TGA curves of composites.
planes (1 0 1), (0 0 4), (2 0 0), (1 0 5), (2 1 1), (2 0 4), (1 1 6), (2 2 0) and
(2 1 5) at 2θ (°) values of 25.24, 37.84, 48.03, 53.88, 55.08, 62.57,
68.72, 70.4 and 74.9, respectively. This indicates that all 2θ values are

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N. Neghi et al. Chemical Engineering Journal 359 (2019) 963–975

Fig. 9. Removal profiles throughout 15 cycles using CS-TiO2 and PVA-CS-TiO2 to degrade 10 mg L−1 of MNZ.

Table 4
Calculated energies of formation (eV) of the pairs of the various components of
PVA-CS-TiO2 (EComposite), the energy of adsorption of MNZ onto the composite
(EMNZ) and distance (d) of the shortest hydrogen bonds (in Ǻ) between MNZ and
substrate for single adsorbents and the composites.
Substrate EComposite (eV) EMNZ (eV) d

TiO2 – −0.235 2.82

CS – −0.370 2.60
PVA – −0.053 2.88
CS + PVA −0.220 −0.346 2.62
TiO2 + PVA −0.153 0.125 3.31
TiO2 + CS −0.144 −0.013 2.94

in good agreement with (JCPDS-900-8213) [65]. Moreover, XRD pat-

terns obtained for CS-TiO2 and PVA-CS-TiO2 matched with JCPDS-500-
0223 (compared with TiO2 as base). Similarly, XRD patterns of both the
composites retained after 15 cycles of photocatalytic treatment mat-
ched with JCPDS-900-8213. All the standard cards mentioned above
were representing anatase form of TiO2 (Fig. S4) [66]. Therefore, it
proves that TiO2 phase structure is not disturbed in the composites after
treatment.
The SEM images of both the composites show that TiO2 NPs are
distributed on its surface (Figs. S5 and S6). The morphology of PVA-CS-
TiO2 shows smooth surface compared to CS-TiO2. The energy dispersive
X-ray (EDX) spectrum confirms the presence of Ti, O, N and Na in the
synthesized composite apart from C. It is also observed that %Na was
higher in CS-TiO2 (chemically cross linked in alkaline medium) com-
pared to PVA-CS-TiO2 (chemically cross linked in solvent medium (Fig.
S6) and was absent after photocatalytic treatment cycles in both the
composites. Moreover, a slight increase in %N was seen after treatment
indicating that MNZ adsorption onto composites has occurred. On the
other hand, the both flat (spherical shaped) and sharp (hexagonal
shaped) TiO2 NPs can be seen in the TEM images and also it reveals that
the NPs were well dispersed with limited agglomeration in the polymer
matrix and having an average particle size between 50 and 100 nm. The
insets of Fig. 5 illustrates the well-defined fringes with lattice spacing
(d = 0.36 nm) corresponding to the (1 0 1) plane of anatase TiO2. It can
also be noticed that few TiO2 NPs stack over (blue framed portion) in
both the composites. Additionally, EDX analysis reveals that TiO2 (as
%Ti) present on the surface of PVA-CS-TiO2 is higher than on CS-TiO2, Fig. 10. Optimized atomic structures of MNZ adsorbed on CS-TiO2 composite.
which could be attributed to the enhanced binding nature of PVA-CS
blend towards TiO2 [67]. It was also noted that there was loss in TiO2
NPs by 40% in CS-TiO2 but not in PVA-CS-TiO2 after 15 cycles of
treatment (Fig. S7).

971
N. Neghi et al.
Fig. 11. Schematic illustration of the immobilization of TiO2 in CS and PVA-CS matrix by hydrogen bonding.
The valence states of the five elements (C, O, N, Ti, and Na) present
in both composites after 15 cycles of photocatalytic treatment (P15)
were analyzed using X-ray photoelectron spectroscopy (XPS) (Figs. 6
and 7). The XPS spectra of CS-TiO2 and PVA-CS-TiO2 before treatment
(P0) are provided as insets of Figs. 6 and 7. Accordingly, the binding
energies of Ti 2p levels (Figs. 6b and 7b) present in CS-TiO2 and PVA-
CS-TiO2 indicate two distinct peaks of Ti (as in TiO2). The C 1s spectra
of CS-TiO2 indicates the chitosan structure [68]. On comparison of the
insets of Figs. 6(c) and 7(c), the peak corresponds to C]O is absent in C
1s of PVA-CS-TiO2. This indicates that glycosidic bond present in CS has
interacted with the CeH present in PVA during the formation of PVA-
CS blend. The binding energy of O 1s level in both the composites at
530 eV (Figs. 6(d), 7(d) shows the presence of metal oxide (TieO) on
the surface of the composite. It was observed that Na 1s (∼1067 eV)
was absent in both the composites after treatment. The N 1s spectra
before and after treatment were provided in Fig. S8. The XPS spectra of
CS-TiO2 after treatment (P15) has shown the absence of C]O peak in C
1s (Fig. 6(c)) indicating that saccharide structure of chitosan was dis-
turbed in the presence of UV; whereas PVA-CS-TiO2 after 15 cycles of
photocatalytic treatment (Fig. 7) revealed no major structural changes
on the surface of the material.
The band gap of TiO2, CS-TiO2 and PVA-CS-TiO2 was estimated
from UV–vis-diffuse reflectance spectra (Fig. S9(a)) and the corre-
sponding Tauc plot (Fig. S9(b)). Based on Fig. S8, the band gap of TiO2,
CS-TiO2 and PVA-CS-TiO2 was estimated to be 3.16, 3.2 and 3.17 eV,
respectively. Additionally, it was observed that optical absorption of
TiO2, CS-TiO2 and PVA-CS-TiO2 falls within the range of 350–400 nm.
These observations indicate that the polymeric moieties have no sig-
nificant impact on the performance of the photocatalytic oxidation of
MNZ in UV-C range.
On the other hand, it was reported that protonated amino groups
and amide groups of CS can attract electrons from C and Ti atoms when
they are present in close proximity. Moreover, it was reported that the
presence of PVA can increase the conductance of PVA-CS film due to the
intra- and intermolecular hydrogen bonding (eOH) [69]. Therefore, it
is anticipated that the hybrid photocatalyst prepared in this work could
have enhanced the charge separation of TiO2 and also improved the
rate of MNZ degradation.
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Chemical Engineering Journal 359 (2019) 963–975
3.2. Photocatalytic studies
MNZ removal in different photocatalytic treatment systems are
provided in Table 1. At a photocatalytic dosage of 0.3 g L−1 and MNZ
concentration of 10 mg L−1, 37.8%, 98.2% and 99.7% MNZ removal
was observed in TiO2, CS-TiO2 and PVA-CS-TiO2 systems. Similar MNZ
removal pattern was observed at lower MNZ concentrations, i.e. 1 and
0.1 mg L−1. The profile of degradation under different MNZ con-
centrations and photocatalyst loadings are provided in Fig. S10. A
comparison of our earlier photocatalytic degradation experiments with
TiO2 (2.5 g L−1) and the present study revealed that CS-TiO2 and PVA-
CS-TiO2 systems have produced almost complete MNZ removal at 8.3
times lesser catalyst loading. The reason being MNZ adsorbed on pho-
tocatalytic composites embedded with TiO2 has the synergistic action of
both adsorption and photocatalytic degradation by the hydroxyl radi-
cals. The comparison of MNZ removal by adsorption using TiO2, CS-
TiO2 and PVA-CS-TiO2 shows that MNZ adsorption on PVA-CS-TiO2 was
the highest and faster (Fig. S10). This could have facilitated the faster
removal of MNZ in PVA-CS-TiO2. Using the data, MNZ removal rates in
all the systems were calculated based on Langmuir-Hinshelwood (L-H)
kinetic model as shown in Eq. (13).
Ct
ln = −k1t
C0 (13)
where C0, Ct and k1 are initial MNZ concentration (mg L−1), MNZ
concentration at 120 min (mg L−1) and pseudo-first-order-rate constant
(min−1), respectively, at time (t). The slope of the plot between ln (Ct/
C0) and t gives the value of k1. Table 1 shows the MNZ removal rates in
different systems and it can be noticed that MNZ removal rate was
maximum in PVA-CS-TiO2 (0.048 min−1) compared to CS-TiO2
(0.033 min−1). Moreover, PVA-CS-TiO2 system showed almost steady
MNZ removal rates (∼0.046 min−1) at varying concentrations of MNZ.
It can be noticed in Table 1 that complete MNZ removal was
achieved in TiO2 slurry systems and also in photocatalytic composite
containing ‘x’% TiO2, for a fixed UV power and irradiation time. It is
important to understand how the rate differs in both the conditions. In
order to address this, Eq. (13) is modified as shown in Eq. (14) by in-
corporating concentration of the photocatalyst.
N. Neghi et al.
Ct
ln = −kc ·CT ·t
C0 (14)
where kc is the modified-pseudo-first-order rate constant and CT is the
concentration of TiO2 or the composite to achieve 100% MNZ de-
gradation for a fixed UV energy power. It is conceived that ‘kc’ would be
a better parameter than ‘k1′ to compare the performance of TiO2 which
is either used as nanoparticle form or nanoparticle embedded in an
adsorbent matrix. Eq. (14) is similar to the Chick-Watson equation for
disinfection. Further, Eq. (14) was modified by incorporating the TiO2
content in the composite as shown in Eq. (15).
Ct
ln = − kc ·CT (Xa + Xb )·t
C0 (15)
where Xa and Xb are the proportions of adsorbent and the photocatalyst,
respectively. This equation was applied and the MNZ removal rate was
calculated for TiO2, CS-TiO2 (contains ∼35% Ti) and PVA-CS-TiO2
(contains ∼ 45% Ti) systems (Table 1). The comparison of MNZ re-
moval rate as per Eq. (13) for TiO2 slurry system indicate that the value
of rate constant was increased by 1.8 times in PVA-CS-TiO2 system
(from 0.027 min−1 to 0.048 min−1). On the other hand, the MNZ re-
moval rate by PVA-CS-TiO2 (0.0016 min−1) was 160 times faster than
the TiO2 slurry system (0.00001 min−1) as per Eq. (15). These results
indicate that when an adsorbent is chosen as a matrix to embed TiO2,
the photocatalytic rate is tremendously increased as compared to a
slurry system. This is better understood from the modified-pseudo-first-
order rate constant (kc). Conversely, Eq. (15) can be used to calculate
the required amount of TiO2 content in the composite to attain 100%
removal in shorter retention times or vice-versa.
MNZ degradation in TiO2 system follows a series of hydroxylation,
denitration steps from the parent compound. The breaking of imidazole
moiety leads to small molecular weight carboxylic and alcoholic com-
pounds and further mineralized to CO2 and H2O [70]. Similar pattern of
degradation is expected in the composite system when MNZ gets en-
countered with OH.. The sample collected from CS-TiO2 and PVA-CS-
TiO2 photocatalytic systems (32 W, 0.3 g L−1 of photocatalyst) was
analyzed for TOC and the value was compared with CS-TiO2 and PVA-
CS-TiO2 alone systems (without UV). The TOC reduction was 63.7%
and 76.1% in CS-TiO2 and PVA-CS-TiO2 photocatalytic systems, re-
spectively, whereas the reduction was 9.4% and 11.2% in CS-TiO2 and
PVA-CS-TiO2 alone systems.
3.3. Adsorption studies
The maximum MNZ adsorption capacity of composites including
pristine materials was calculated using Eqs. (3)–(6) and the results are
shown in Table 2. BET surface area of CS-TiO2 and PVA-CS-TiO2 was
found to be 0.5309 m2 g−1 and 0.1813 m2 g−1, respectively. It is evi-
dent that the specific surface area of chitosan and its composites is very
low and the porosity is mainly contributed by TiO2 [71]. Moreover, it
was observed that Freundlich isotherm model well represent MNZ ad-
sorption on CS-TiO2 and PVA-CS-TiO2 (r2 > 0.99). The value of
Freundlich constant (1/n) was found to be between 0 and 1, which
indicates that MNZ adsorption on all materials is favourable. On the
other hand, MNZ equilibrium data better fits both Langmuir and
Freundlich adsorption isotherms for pristine materials, i.e. CS, PVA and
TiO2. However, Temkin isotherm gave a reasonable fit of the equili-
brium data obtained in all the systems, which indicate that there exist
an electrostatic interaction between MNZ and hydroxyl groups present
in the adsorbents. The E value calculated using Dubinin-Radushkevich
isotherm (2357–2887 KJ mol−1) reiterates the fact that chemisorption
is responsible for MNZ removal by adsorption. The kinetic study re-
vealed that MNZ adsorption kinetics in pristine materials has followed
pseudo-first-order kinetics whereas it was pseudo-second-order for CS-
TiO2 and PVA-CS-TiO2 (r2 > 0.98). From the values of k2, it can be
inferred that the rate of adsorption was faster in pristine materials when
973
Chemical Engineering Journal 359 (2019) 963–975
compared to composites (Table 3). This might be due to fact that the
extensive functional groups such as amino and hydroxyl groups present
in the pristine materials were utilized in the formation of composites.
3.4. Stability and reusability studies
Thermal decomposition pattern of the synthesized composites are
shown in Fig. 8. In CS-TiO2, the weight loss started at 270 °C and 488 °C;
whereas in PVA-CS-TiO2 it occurred at 270 °C, 489 °C and 538 °C. It can
be observed from Fig. 8, PVA-CS-TiO2 is more thermally stable than CS-
TiO2 due to the chemical crosslinking of CS with PVA. Moreover, it was
also reported that increase in TiO2 NPs concentration plays a significant
role in the enhancement of tensile strength of PVA-CS [67].
Additionally, it was observed that both photocatalytic composites
synthesized in this work were stable in neutral and alkaline conditions
for almost 15 days. In case of acidic medium, PVA-CS-TiO2 was found to
be stable in 0.05 M HCl (pH ∼ 2) for a longer time than CS-TiO2 (Table
S1). Subsequently, FTIR analysis was performed to check the structural
integrity of the composites under the following conditions: (a) com-
posites stored in airtight glass container for 60 d, (b) composites ob-
tained after 15 cycles from the blank runs with UV illumination and
without MNZ, and (c) composites obtained after 15 cycles from the
blank runs without UV illumination and MNZ (Figs. S11 and S12). It
can be observed that both the composites showed slight changes in the
spectra range of 1644 cm−1 which corresponds to the secondary amide
group of the composites.
The photo stability of the composites in the reactor was evaluated
by the characterization techniques such as FTIR, FT-Raman, XRD, TEM
and XPS results. However, the TEM analysis revealed slight loss in TiO2
after 15 cycles of treatment (Fig. S7(c)) in CS-TiO2. This might be the
reason for the decrease in MNZ removal (97.9%) at 13th cycle in CS-
TiO2; whereas PVA-CS-TiO2 showed complete MNZ removal at varying
MNZ concentrations (0.1, 1 and 10 mg L−1) throughout 15 cycles
(Fig. 9). Additionally, XPS analysis revealed no structural changes in
PVA-CS-TiO2 after 30 h of photocatalytic operation.
3.5. Modelling using DFT
The stability of the photocatalytic composites in water was eval-
uated by calculating the formation energy value using Eq. (11) as
shown in Table 4. It should be noted that, the exact combination of the
parts of the composite (PVA-CS-TiO2) is unknown. Therefore, all other
possible combinations of the pairs of components to interact with each
other and with MNZ were considered. From Table 4, the order of sta-
bility of the composites in water is found to be PVA-CS > PVA-
TiO2 > CS-TiO2. This observation is in qualitative agreement with
experimental results that are shown in Table S1. The magnitude of the
formation energies is moderate, which was few times lower than the
energies of coordination bonds ∼ 1 eV. This is because of the number of
groups such as hydroxyl groups on TiO2 surface that participates in the
formation of various weak bonds per unit cell. For example, the ten-
dency to form hydrogen bonds is moderate for CS than TiO2 (Fig. 10).
On the other hand, both hydrophilic and hydrophobic groups partici-
pated in the formation of bonds depends on the nature of the compo-
sites.
Secondly, MNZ adsorption on each single part of the composite and
on the pairs was evaluated using Eq. (12). The difference in the en-
ergetics of MNZ adsorption was derived from the number and flexibility
of functional groups in the composites participating in the formation of
bonds (Fig. 10). It was also observed that the hydrogen bonds between
different functional groups such as TiO2 passivated with hydroxyl
groups (Ti-OH) and eNH2 (from CS) with MNZ were found to be
stronger than the bonds between the same groups and water. In this
context, the calculated distances were in the range of 2.6–2.8 Ǻ in-
dicating stronger adsorption (hydrogen bonds) while the distances
N. Neghi et al.
greater than 2.8 Ǻ indicates weaker adsorption (dispersion forces). It
has also been found that the adsorption of MNZ on the different com-
binations of composites is accompanied by synergetic combination of
weak forces.
From DFT results, it is inferred that stability of the composites in
water is predominantly due to extensive intermolecular hydrogen
bonds in CS-TiO2. This indicates that there is no compromise on the
intrinsic properties of the components caused by cross-linking or re-
inforcements. Moreover, due to the inherent property of anatase TiO2
passivation in water matrix [72] surface functionalization was not ne-
cessary for its assembly in the composite. This has facilitated for limited
agglomeration of TiO2 on the polymer surface as evident from TEM
analysis. On the basis of the results obtained so far, a schematic illus-
tration of attachment of TiO2 with CS and PVA-CS was proposed in
Fig. 11.
4. Conclusion
Two photocatalytic polymer composites, i.e. CS-TiO2 and PVA-CS-
TiO2, have been synthesized and compared with regard to their stabi-
lity, reusability and efficiency towards the removal of MNZ. Complete
MNZ removal was achieved in all systems- TiO2; CS-TiO2 and PVA-CS-
TiO2 however, it was achieved in the composites at a lower catalyst
loading. PVA-CS-TiO2 was found to be stable in UV environment and
showed negligible loss of TiO2 NPs even after 15 treatment cycles. The
modified rate kinetic model equation was used to compare the removal
rates of TiO2 slurry systems and the photocatalytic composites.
Moreover, PVA-CS-TiO2 was comparatively much stable than CS-TiO2
in all types of aqueous environment (pH 4 to 10) which is attributed to
the enhanced binding nature of PVA-CS towards TiO2. Moreover, the
modelling work carried out by density functional theory (DFT) revealed
that TiO2 passivated with hydroxyl groups assembles to CS or PVA-CS
through extensive hydrogen bonding and MNZ adsorption to the com-
posites has occurred through synergistic action of large number of weak
dispersive forces. The photocatalytic ability of the composites was as-
sessed through kinetic models, and the adsorptive ability of the com-
posites was contributed by CS component as evident from the DFT
analysis. Overall, the composites can be used on a long-term basis and
for cost-effective photocatalytic reactor operation for the removal of
pharmaceuticals.
Acknowledgements
The present study is funded by the ICSR, IIT Madras (Grant number:
CIE/14-15/832/NFIG/SMAT) and WTI, DST, India (Grant number:
DST/TM/WTI/2K15/192).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2018.11.090.
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