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Cite This: ACS Omega 2017, 2, 8354−8365

Highly Efficient Photocatalytic Degradation of Amido Black 10B Dye

Using Polycarbazole-Decorated TiO2 Nanohybrids
Jyoti Kashyap, Syed Marghoob Ashraf,† and Ufana Riaz*
Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025, India
*
S Supporting Information

ABSTRACT: The present study reports the synthesis of poly-

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carbazole (PCz)-decorated TiO2 nanohybrids via in situ chemical

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polymerization of carbazole monomers in TiO2 dispersions. The

ratio of the polymer in the nanohybrid varied between 0.5 and 2 wt
%. The synthesized nanohybrids were characterized using infrared
and diffuse reflectance spectroscopies, whereas the morphology was
analyzed using X-ray diffraction (XRD) and transmission electron
microscopy (TEM) techniques. XRD revealed changes in the peak
corresponding to the d(001) plane of TiO2 owing to the interaction
between the two components. TEM confirmed the formation of
PCz-decorated nanohybrids. Amido Black 10B (AB-10B) was chosen
as a model dye for the degradation studies. Sonophotocatalytic
degradation of the dye was studied by varying the catalyst and dye
concentrations. Results showed that PCz/TiO2 nanohybrids
exhibited a complete degradation of AB-10B dye within a short span of 60−90 min, which was faster than pure TiO2 and
the reported decorated TiO2 nanohybrids synthesized by other authors. The degraded dye fragments were identified using liquid
chromatography−mass spectrometry (LCMS). By varying the loading of PCz in TiO2, the nanohybrids could be tuned to achieve
visible light-driven degradation.

1. INTRODUCTION also known to act as sensitizers when combined with

Semiconductor-mediated photocatalysis is one of the widely
adopted techniques for the degradation of dyes and organic
pollutants in water.1−5 The key function of this method is to
generate species such as hydroxyl radicals (•OH) and
superoxide radicals (O2•−) that can degrade the organic
compounds in the dye waste water into harmless by-
products.6−10 One of the major limitations of utilizing TiO2
as a photocatalyst is its high rate of recombination of holes and
electrons owing to its wide band gap of ∼3.2 eV.11,12 As this
band gap corresponds to the wavelength of 387 nm, hardly 4%
of the solar energy is utilized for the degradation of organic
pollutants. Therefore, pristine TiO2 is economically unattractive
as a photocatalyst for waste water remediation.13,14 Several
strategies have been employed to increase the photocatalytic
activity of TiO2 such as increasing the catalyst surface to
volume ratio, sensitization of the catalyst using polymers,
doping of the catalyst with nonmetals such as nitrogen and
carbon, and impregnation of metal ions/transition metals.15−20
Lately, researchers have focused on combining semiconductor
oxide nanoparticles with conducting polymers to achieve
synergetic properties.21−24 Conducting polymers, such as
polyaniline,6 poly(1-naphthylamine),21 and so forth, provide
moderate to high mobility of charge carriers via the extended π-
conjugated electron system that can be electronically coupled
to TiO2, so as to facilitate a better separation of photoinduced
charges in the semiconductor oxide. Conducting polymers are
semiconductor nanoparticles to prevent the electron−hole
recombination.25 Among the several conducting polymers,
polycarbazole (PCz) has been proved to be an exceptionally
efficient polymer owing to its high electrical conductivity,
thermal stability, low band gap, and low toxicity.26−30 It has
been widely used in designing solar devices and organic light-
emitting diodes.31−35
With a view to explore the photocatalytic efficiency of PCz,
the present study reports the sonolytic synthesis of PCz/TiO2
nanohybrids using different weight ratios of the conducting
polymer. The nanohybrids were characterized by FTIR, diffuse
reflectance spectroscopy (DRS), X-ray diffraction (XRD), and
transmission electron microscopy (TEM) techniques. To the
best of our knowledge, the photocatalytic performance of PCz/
TiO2 nanohybrids is reported for the first time. Amido Black
10B (AB-10B) was chosen as a model dye because it is widely
used in staining proteins and is reported to be highly toxic.36
The photocatalytic activity of the nanohybrids was evaluated by
varying the catalyst and dye concentration upon exposure to
UV irradiation for a period of 60 min. The degraded fragments
were identified using the liquid chromatography−mass
Received: August 8, 2017
Accepted: October 16, 2017
Published: November 28, 2017

© 2017 American Chemical Society 8354 DOI: 10.1021/acsomega.7b01154

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spectrometry (LCMS) technique, and a plausible mechanism
for the efficient photocatalytic performance was proposed.
2. RESULTS AND DISCUSSION
2.1. Confirmation of Nanohybrid Formation by IR
Studies. Fourier transform infrared (FT-IR) spectra of pristine
PCz and PCz/TiO2 nanohybrids are shown in Figure 1. The IR
Figure 1. FTIR spectra of pure PCz and PCz/TiO2 nanohybrids.
spectrum of pure PCz revealed two NH stretching vibration
peaks at 3416 and 3045 cm−1. The imine stretching peak was
observed at 1780 cm−1. The peaks corresponding to quinonoid
and benzenoid units were noticed at 1597 and 1491 cm−1,
Figure 2. (a) UV−vis diffuse reflectance spectra (DRS) of TiO2, PCz, and PCz/TiO2 nanohybrids and Kubelka−Munk plot of (b) PCz and (c)
TiO2.
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respectively.29,37−39 The benzenoid to quinonoid (B/Q) ratio
in this case was observed to be 0.91, indicating the formation of
equal number of benzenoid and quinonoid units. The CN
stretching peak was observed at 1232 cm−1, whereas the peaks
at 921, 850, and 752 cm−1 were correlated with the presence of
unsubstituted carbazole, confirming that polymerization took
place from 3 to 6 positions.40 The IR spectrum of PCz/TiO2
(0.5:1) showed a broad NH stretching vibration peak around
3309 cm−1. The broadness of the peak was correlated with the
interaction of NH of PCz with oxygen of TiO2.37−39 The peak
at 667 cm−1 was correlated with the presence of TiO2 and
appeared to be broad, whereas the peaks corresponding to PCz
appeared to be diminished owing to the lower loading of the
polymer in this nanohybrid.
In the case of PCz/TiO2 (1:1), NH stretching vibration
peaks were noticed at 3416 and 3045 cm−1, whereas the imine
stretching peak was observed around 1780 cm−1. The
quinonoid and benzenoid units were observed at 1597 and
1491 cm−1, respectively. The peak associated with TiO2
appeared at 675 cm−1. The NH stretching vibration peaks for
PCz/TiO2 (2:1) were noticed at 3416 and 3047 cm−1, whereas
the imine stretching peak was observed at 1780 cm−1. The
peaks corresponding to quinonoid and benzenoid units were
noticed at 1599, 1448, and 1394 cm−1. The B/Q ratio was
calculated to be 1.04. It can therefore be concluded that with
the increase in the loading of PCz, slight changes were noticed
in the IR spectra of the nanohybrids. Similar observations have
also been reported by other authors.29 However, the NH
stretching vibration peak revealed a significant shift in the case
of PCz/TiO2 (0.5:1). With the increase in the loading of PCz
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in TiO2, the shift was observed to decrease owing to the

encapsulation of TiO2 by PCz. The % transmittance was also
found to decrease with the increase in the loading of PCz. The
lowest intensity was noticed for PCz/TiO2 (2:1), whereas the
highest intensity was observed for PCz/TiO2 (0.5:1). The
weight average molecular weight (M̅ w) of pure PCz was
calculated to be 3582 Da, which confirmed the polymerization
of carbazole.41 Conductivity was found to be 2.65 × 10−4 S/cm.
The conductivities of PCz/TiO2 (0.5:1), PCz/TiO2 (1:1), and
PCz/TiO2 (2:1) were obtained as 1.13 × 10−4, 1.75 × 10−4,
and 2.12 × 10−4 S/cm, respectively.
2.2. Analysis of Electronic Transitions and Band Gap
Energy PCz and PCz/TiO2 Nanohybrids via DRS. The
diffuse reflectance spectrum of pure TiO2 (Figure 2a) revealed
a sharp absorption edge around 390 nm, which could be well-
correlated with the anatase form of TiO2. The diffuse
reflectance spectrum of pure PCz and PCz/TiO2 nanohybrids
showed absorption edge around 410 nm. The peak intensity Figure 3. XRD of PCz and PCz/TiO2 nanohybrids.
was observed to be the lowest for PCz/TiO2 (2:1) but was
found to be higher for PCz/TiO2 (1:1) and matched with that correlated with the d(101) plane of TiO2. Upon further
of pure PCz. increasing the loading of PCz to 1 wt % (Figure 3), the
The Kubelka−Munk42 equation is generally applied to intensity of the peaks appeared to increase. For PCz/TiO2
calculate the band gap of semiconductors which is given by (2:1), the peaks corresponding to PCz showed the highest
intensity. However, the peak correlated to TiO2 revealed the
1 − R2 α highest intensity for PCz/TiO2 (1:1). The presence of the
F (R ) = =
2R s peaks corresponding to both PCz and TiO2 confirmed the
formation of the nanohybrid. The variation in the intensity of
where F(R) is the Kubelka−Munk function, “R” is reflectance the peak corresponding to d(101) plane of TiO2 confirmed its
of the sample, “α” is the absorption coefficient, and “s” is the encapsulation by PCz (Table 1). The area under the peak
scattering coefficient. The scattering coefficient, s, is ignored on
the basis of wavelength dependence, thereby making F(R)
Table 1. XRD Data of PCz and PCz/TiO2 Nanohybrids
proportional to α. Tauc, Davis, and Mott proposed an equation
to calculate the band gap of semiconductors using the peak area height fwhm crystallite size
absorption coefficient given by the expression43,44 nanohybrids (2θ) peak (au) (2θ) (Å)
pure TiO2 25.5 947 741 0.220 6.97
(hνα)1/ n = A(hν − Eg ) PCz/TiO2 25.3 1659 1205 0.194 7.90
(0.5:1)
where α is the adsorption coefficient, h is the Planck’s constant, PCz/TiO2 25.2 1659 1401 0.191 8.02
ν is the vibrational frequency, and Eg is the band gap. The value (1:1)
of n is taken to be 2 for indirect band semiconductors. By PCz/TiO2 25.2 2118 1031 0.190 8.06
(2:1)
substituting the value of n and α = F(R) in the above equation,
the band gap was calculated, as shown in Figure 2b. The band
gap energy of pristine TiO2 was calculated to be 3.2 eV, corresponding to the d(101) plane of TiO2 was found to
whereas that of pure PCz was calculated as 2.95 eV (Figure 2b). increase with the increase in the loading of PCz while the
2.3. Morphological Analysis of TiO2, PCz, and PCz/ crystallite size also showed a slight variation. Hence, it can be
TiO2 Nanohybrids via XRD and TEM Studies. The XRD concluded that an intense synergistic interaction was found to
profiles of PCz and PCz/TiO2 nanohybrids are depicted in exist between PCz and TiO2 because the peak corresponding to
Figure 3. The XRD patterns of anatase TiO2 (inset) revealed TiO2 revealed variations in the area as well as intensity upon
peaks at 2θ = 25.5°, 38.2°, 48.3°, 54.2°, 55.4°, 62.5°, 68.2°, loading of PCz.
70.7°, and 75.5° corresponding to d(101), d(004), d(200), The morphology of pure PCz and PCz/TiO2 nanohybrids is
d(105), d(211), d(204), d(116), d(220), and d(215) planes, shown in Figure 4a−d. The TEM of pure PCz revealed a mixed
respectively. The peaks were found to match with the morphology of cubes as well as hexagonal particles (Figure 4a).
tetragonal anatase form of TiO2 showing cell constants as a The TEM of the PCz/TiO2 (0.5:1) nanohybrid (Figure 4b)
= b = 0.37710 nm, c = 0.9430 nm, and α = β = γ = 90°, which revealed a fused distorted morphology in which the dense TiO2
was found to be in agreement with the standard diffraction data particles were noticed to be surrounded by the PCz
(JCPDS 21-1272).45 The XRD profile of pure PCz revealed nanoparticles. The TEM of the PCz/TiO2 (1:1) nanohybrid
peaks at 2θ = 18.50°, 19°, 19.5°, 22.5°, 23°, and 28° exhibiting (Figure 4c) exhibited huge clusters of distorted core−shell-like
high crystallinity as found in our previous studies.46 The morphology, whereas the PCz/TiO2 (2:1) nanohybrid (Figure
nanohybrids revealed a slight shift in the crystalline peaks as 4d) showed the formation of flowerlike clusters containing
well as variation in their intensities upon nanohybrid formation. dense TiO2 particles surrounded by PCz petals. The TiO2
The PCz/TiO2 (0.5:1) nanohybrid revealed peaks at 2θ = 19°, particles appeared to be decorated with PCz in the case of PCz/
19.5°, 22.5°, 23.2°, and 28°. The intensity of the peaks TiO 2 (1:1) and PCz/TiO 2 (2:1) 47 nanohybrids. The
corresponding to PCz appeared to be highly reduced upon the morphology clearly revealed the synergistic interaction of
addition of TiO2. The peak observed around 2θ = 25.3° was PCz with TiO2. The results were in agreement with the XRD
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Figure 4. TEM of (a) PCz, (b) PCz/TiO2 (0.5:1), (c) PCz/TiO2
(1:1), and (d) PCz/TiO2 (2:1).
studies that showed intact crystalline morphology of the two
components. Hence, it can be confirmed that TiO2 particles are
encapsulated with the PCz chain, leading to the formation of
self-assembled structures.
2.4. Variation of Thermal Stability of PCz and Its
Nanohybrids. The thermal stabilities of PCz and PCz/TiO2
nanohybrids were analyzed by TGA studies. The thermogram
of pure PCz (Figure 5) revealed 10 wt % loss at 200 °C,
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Figure 5. TGA thermograms of PCz and PCz/TiO2 nanohybrids.
whereas 20 wt % loss occurred at 310 °C. The initial weight
loss of around 10 wt % was attributed to the presence of
unreacted monomers. Almost 60 wt % loss was noticed at 480
°C, whereas 95 wt % loss took place at 830 °C. The PCz/TiO2
(0.5:1) nanohybrid revealed 10 wt % loss around 250 °C,
whereas 62 wt % loss was noticed at 830 °C. The thermal
stability was found to be slightly enhanced. The thermogram of
the PCz/TiO2 (1:1) nanohybrid revealed 10 wt % loss at 260
°C, whereas 50 wt % loss took place around 830 °C. Similarly,
the PCz/TiO2 (2:1) nanohybrid showed 10 wt % loss at 260
°C, whereas 30 wt % loss occurred at 830 °C. With the increase
in the loading of PCz in TiO2, the thermal stability was found
to remarkably improve. The thermal stability of PCz/TiO2 was
noticed to be far superior to that of pure PCz and was found to
be in the order PCz/TiO2 (2:1) > PCz/TiO2 (1:1) > PCz/
TiO2 (0.5:1) > PCz.
2.5. Evaluation of Photocatalytic Properties of PCz
and PCz/TiO2 Nanohybrids. The specific surface area plays a
major role in photocatalysis as it leads to an increased catalytic
activity. In our case, the specific surface area of pure PCz and
PCz/TiO2 (2:1) nanohybrids was found to be 236.226 and
281.321 m2/g, respectively. The measured pore volume for PCz
and PCz/TiO2 (2:1) nanohybrids was calculated to be 0.190
and 0.213 cc/g, respectively (given in the Supporting
Information, Figure S1). The photocatalytic activity of the
nanohybrids was evaluated using AB-10B dye. The UV−visible
spectrum of AB-10B revealed a prominent peak at 618 nm and
two small peaks at 226 and 318 nm (Figure 6a).
A prominent peak at 618 nm in the visible region was
observed owing to the presence of an azo group, whereas the
peaks in the ultraviolet region were assigned to π−π* transition
of the aromatic benzene group.48,49 The degradation profile of
pristine PCz (Figure 6b) revealed negligible change during 60
min exposure time. However, in the presence of the PCz/TiO2
nanohybrid, the peaks at 617 and 330 nm revealed a large
decrease in the absorption intensity, indicating a complete
degradation of AB-10B under similar experimental conditions
(Figure 6c−e). Among the three nanohybrids, PCz/TiO2 (1:1)
and PCz/TiO2 (2:1) revealed the complete degradation of AB-
10B dye within a short span of 90 min. To study the effect of
catalyst concentration, degradation of 90 ppm AB-10B dye
solution was carried out using 50, 100, 200, and 300 mg of the
nanohybrid as catalyst for a period of 60 min (Figure 7a,b). The
PCz/TiO2 (1:0.5) nanohybrid revealed 100 wt % degradation
of 50 ppm dye solution when the catalyst concentration was
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Figure 6. UV−visible spectra of (a) AB-10B dye (b) in the presence of PCz as a catalyst, (c) in the presence of PCz/TiO2 (0.5:1) as a catalyst, (d) in
the presence of PCz/TiO2 (1:1) as a catalyst, and (e) in the presence PCz/TiO2 (2:1) as a catalyst.

300 mg, whereas 75 wt % degradation was achieved when the
catalyst concentration was 100 mg (Figure 7a,b). Similarly,
PCz/TiO2 (1:1) and PCz/TiO2 (2:1) nanohybrids revealed
almost 96 wt % degradation in the case of 50 ppm of AB-10B
dye solution, when the catalyst amount was 50 mg (Figure 7b).
It can thus be concluded that the degradation efficiency was
found to be high even at lower loading of the catalyst.
The C/Co plots of the nanohybrids were studied using
different catalyst concentrations in 90 ppm AB-10B dye
solution (Figure 8a−c). When 300 and 200 mg of PCz/TiO2
(0.5:1) nanohybrid was used as the catalyst, almost 75 and 70
wt % degradation was achieved in 60 min, whereas 65 wt %
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degradation was achieved when 100 mg catalyst was used
(Figure 8a). Similarly, the PCz/TiO2 (1:1) nanohybrid (Figure
8b) showed 65−75 wt % degradation when the catalyst amount
was increased from 50 to 300 mg, whereas the degradation
increased from 65 to 90 wt % for the PCz/TiO2 (2:1)
nanohybrid using the same amount of catalyst (Figure 8c). The
plots confirmed that the nanohybrids containing higher PCz
loading exhibited higher degradation efficiency even when used
in small amounts. Upon increasing the concentration of the AB-
10B dye solution from 30 to 120 ppm using a fixed catalyst
amount of 150 mg, it was observed that 87 and 85 wt %
degradation was achieved for 30 and 70 ppm dye solutions,
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Figure 7. Effect of catalyst concentration on the percent degradation
for (a) 50 ppm dye solution and (b) 90 ppm dye solution.
respectively, using the PCz/TiO2 (0.5:1) nanohybrid as the
catalyst (Figure 9a−c). The PCz/TiO2 (1:1) nanohybrid
showed 90 and 80 wt % degradation in 60 min for 30 ppm
and 70 ppm dye solutions, respectively, whereas 120 ppm dye
solution showed 60 wt % degradation in 60 min (Figure 9b).
Around 90 wt % degradation occurred when the PCz/TiO2
(2:1) nanohybrid was used as the catalyst for 120 ppm AB-10B
dye solution (Figure 9c). It can thus be concluded that the
nanohybrid containing 2 wt % PCz revealed degradation
efficiency (as high as 80 wt %) for the degradation of 120 ppm
AB-10B dye solution.
The plots of ln C/Co versus time (Figure 9a−c, insets)
showed that degradation kinetics followed the pseudo first-
order kinetics in all cases. When PCz/TiO2 (0.5:1) was used as
the catalyst, the rate constant (k) was observed to be 0.027
min−1 for 30 ppm dye solution, whereas for 120 ppm dye
solution, it was noticed to be 0.010 min−1. Similarly for the
catalyst, PCz/TiO2 (1:1), the rate constant (k) decreased from
0.057 min−1 for 30 ppm dye solution to 0.015 min−1 for 120
ppm, whereas for PCz/TiO2 (2:1), the rate constant decreased
from 0.090 to 0.038 min−1. Sivakumar et al.48 carried out the
degradation of AB-10B dye using metal-decorated TiO2
nanohybrids, and the rate constant values reported by them
are shown in Table 2. The degradation time in our case was
observed to be 60 min, whereas the authors have carried out
the degradation for a period of 7 h. These observations clearly
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highlight the photocatalytic efficiency of PCz-decorated TiO2
nanohybrids.
2.6. Proposed Degradation Pathway and Analysis of
Degraded Dye Fragments by the LCMS Technique.
Although PCz failed to degrade the dye under UV−visible
irradiation, the PCz/TiO2 nanohybrid was noticed to rapidly
degrade the dye molecules under similar conditions. A plausible
explanation for this behavior is depicted in Scheme 1. Low
band gap of PCz facilitates high electron-hole recombination in
the absence of metal oxide. When PCz/TiO2 is illuminated
under UV light, it promotes the transfer of electrons from the
lowest unoccupied molecular orbital of PCz molecules into the
conduction band (CB) of TiO2 which reacts with oxygen and
hydroxyl radicals present at the surface. The CB of PCz is lower
than that of TiO2, and hence it acts like a sink for the
photogenerated electrons. The holes move in the opposite
direction from the electrons, and the photogenerated holes in
PCz get trapped within the TiO2 particles. In this way, the
charge carrier recombination is reduced, and more charge
carriers are available for the production of free radicals through
interfacial charge transfer (Scheme 1). Radical-trapping experi-
ments were conducted using benzoquinone as a superoxide
anion radical scavenger and tert-butanol as a hydroxyl radical
(given in the Supporting Information, Figure S2). The
concentration of AB-10B dye solution was found to decrease
drastically in the presence of 2 mM t-BuOH and pure TiO2,
whereas the concentration decreased slightly using 2 mM
benzoquinone.15,16 However, when the PCz/TiO2 nanohybrid
was used with the radical scavengers, the concentration of the
AB-10B dye solution decreased drastically in the presence of
benzoquinone, whereas the concentration changed slightly in
the presence of t-BuOH. This behavior confirmed that •OH
radicals were the active species that participated in the
degradation of AB-10B dye solution when PCz/TiO2 nano-
hybrid was used as the catalyst.
Degradation of Amido Black was confirmed by LCMS
studies which revealed a variety of intermediate compounds
formed during the course of the reaction (Scheme 2a). The
intermediates with their increasing m/z values are shown in
Scheme 2b. Around 100% abundance was assigned to the first
intermediate that was taken as the main degradation product.
Intermediates of 100% abundance with low m/z values ranging
from 100 to 70 were obtained. They were labeled as G-1, G-2,
G-3, G-4, and G-5. The first intermediate G-1 (m/z 540)
showed 100% abundance and was taken as the main
degradation product. Intermediates with m/z values 393
(80%), 291 (70%), 269 (83%), and 189 (100%) were obtained.
These intermediates revealed that the degradation proceeded
via elimination of azo and sulphonate groups, attacked by •OH
free radicals. Interestingly, the dye degradation proceeded by
the cleavage of the −NN− group, owing to easy breakdown
of π bond, bearing the unsubstituted phenyl ring. The •OH
radicals preferentially attacked the electron-rich diazo function-
ality of the molecule to form sodium 4-amino-6-diazenyl-5-
hydroxy-3-((4-nitrophenyl)diazenyl)naphthalene-2,7-disulfo-
nate (G-1, m/z 540). The attack of •OH radicals produced
sodium 3,4,6-triamino-5-hydroxynaphthalene-2,7-disulfonate
(G-2, m/z 393). This fragment then degraded into sodium
3,4,6-triamino-5-hydroxynaphthalene-2-sulfonate (G-3, m/z
291). Accordingly, 3,4,6-triamino-5-hydroxynaphthalene-2-sul-
fonic acid (G-4, m/z 269) was obtained from the G-3 fragment.
The degradation product G-5 was formed by the cleavage of
the sulphonate group from the G-4 fragment (Scheme 2(a)).
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Figure 8. C/Co plots for (a) PCz/TiO2 (0.5:1) (inset ln C/Co), (b) PCz/TiO2 (1:11) (inset ln C/Co), and (c) PCz/TiO2 (2:11) (inset ln C/Co).
3. CONCLUSIONS
PCz/TiO2 nanohybrids were successfully prepared via in situ
chemical polymerization using the ultrasonic technique. XRD
and TEM analyses confirmed the interaction between PCz
chains and TiO2 nanoparticles. The thermal stability of PCz/
TiO2 was noticed to be far superior than that of pure PCz and
was found to be in the order PCz/TiO2 (2:1) > PCz/TiO2
(1:1) > PCz/TiO2 (0.5:1) > PCz. PCz/TiO2 nanohybrids
exhibited good photocatalytic activity as compared to pristine
TiO2, whereas PCz revealed no activity. Almost 100%
degradation of AB-10B dye was achieved in the presence of
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PCz/TiO2 nanohybrid. LCMS studies confirmed the degrada-
tion of dye into fragments of low-molecular-weight compounds.
Thus, by varying the loading of PCz in TiO2, the band gap of
the nanohybrid could be modified and tuned to achieve visible
light-driven photocatalysis. Overall, the nanohybrid was found
to hold immense potential to be used as an efficient
photocatalyst for waste water remediation. Studies on the
degradation of other organic pollutants using this nanohybrid
are under progress and will be published soon.
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Figure 9. C/Co plots for (a) PCz/TiO2 (1:0.5) (inset ln C/Co), (b) PCz/TiO2 (1:1) (inset ln C/Co), and (c) PCz/TiO2 (2:1) (inset ln C/Co).
4. MATERIALS AND METHODS
Amido Black-10B (AB-10B) dye was procured from S.D. Fine
Chem. Pvt. Ltd., India and used without further purification.
Carbazole (Sigma-Aldrich, USA), ferric chloride (Sigma-
Aldrich, USA), titanium(IV) oxide (anatase ≥99%, Sigma-
Aldrich, USA), and N-methyl-2-pyrrolidone (Merck, India)
were also used without further purification.
4.1. Synthesis of PCz. Carbazole monomer (2.5 g, 0.014
mol) was added to a 250 mL conical flask containing methanol
and water 1:1 v/v (50 mL each). Ferric chloride (2.7 g, 0.016
mol) was added as the initiator to the reaction mixture kept in
an ultrasonicator maintained at 30 °C. The color of the solution
changed from dusty gray to light yellow, indicating rapid
polymerization of the monomer.37 The reaction was carried out
for 2 h. The synthesized PCz was then taken out and washed
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several times with distilled water/methanol on a Buchner
funnel. PCz was then dried in a vacuum oven for 72 h at 70 °C
for the complete removal of water and impurities.
4.2. Synthesis of PCz/TiO2 Nanohybrids. For the
synthesis of 2:1 TiO2/PCz nanohybrid, carbazole monomer
(3 g, 0.017 mol) and TiO2 (1.6 g, 0.020 mol) were added
together in a 250 mL conical flask containing methanol and
water (1:1 v/v; 50 mL each). Ferric chloride (3.2 g, 0.019 mol)
was added to the reaction mixture keeping the monomer/
initiator ratio to be 1:1. The flask was kept on an ultrasonicator
maintained at 30 °C, and the reaction was carried out for 6 h.
The synthesized PCz nanohybrid was then washed several
times with distilled water and ethanol and dried in vacuum for
72 h at 80 °C to ensure the complete removal of water. A
similar procedure was adopted for the synthesis of 1:1 and 0.5:1
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ACS Omega Article

Table 2. Comparison of the Rate Constant Values of Metal- trations of the nanohybrid (50, 100, 200, and 300 mg) were
Decorated and PCz-Decorated TiO2 Nanohybrids used for degrading 90 ppm AB-10B dye solution. A calibration
plot based on Beer−Lambert’s law was obtained by plotting the
rate constant
surface (min−1) using absorbance against the concentration of dye in solution to
area crystallite degradation catalyst determine the quantity of the dye degraded after different
catalysts (m2/g) size (nm) time 150 mg intervals of time. Each experiment was done in triplicate, and
TiO2 93 21.37 7h 6.52 × 10−3 the deviation from the mean value of the concentration of the
Ni/TiO2 (0.5%)48 47 22.29 7h 8.14 × 10−3 dye at any time was shown by error bars. For kinetics analysis,
Ru/TiO2 (0.5%)48 72 22.40 7h 1.9 × 10−2 the degradation data were plotted in Origin 8.0 software. Out of
PCz/TiO2 (0.5:1) 43.43 60 min 1.1 × 10−2 the graphs plotted for different rate laws, ln C/Co, versus time
Ni/TiO2 (1%)48 62 22.44 7h 9.39 × 10−3 gave the best fit data as the R2 value was observed to be higher
Ru/TiO2 (1%)48 81 22.49 7h 2.3 × 10−2 than 0.995. The slope showed the rate constant value obtained
PCz/TiO2 (1:1) 44.39 60 min 1.5 × 10−2 using different nanohybrids as catalysts. Radical-trapping
Ni/TiO2 (3%)48 41 22.46 7h 8.05 × 10−3 experiments were conducted to identify the radicals involved
Ru/TiO2 (3%)48 60 22.53 7h 1.55 × 10−2 in the degradation of AB-10B dye solution using benzoquinone
PCz/TiO2 (2:1) 281 66.34 60 min 3.8 × 10−2 (O2•− radical scavenger) and tert-butanol (•OH radical
scavenger). The nanohybrid (2 mg) along with the scavenger
nanohybrids, and they were designated as PCz/TiO2 (0.5:1), (5 mL, 2 mM) was added to 50 mL of AB-10B dye solution (50
PCz/TiO2 (1:1), and PCz/TiO2 (2:1) based on the wt % mg L−1) and was sonicated together for 3 h in the dark to reach
loading of PCz in TiO2. adsorption equilibrium. The samples were sonolytically
4.3. Photocatalytic Activity. A stock solution of 500 ppm irradiated under UV light. The suspensions were separated at
AB-10B dye solution was prepared by dissolving 500 mg of AB- fixed time intervals by centrifugation, and the decrease in the
10B dye in 1 L of deionized water. To study the effect of dye concentration of AB-10B dye solution was measured by taking
concentration, solutions of AB-10B dye of 120 mg/L, 90 mg/L, the UV−vis spectra.
70 mg/L (mg), and 50 mg/L were prepared by the dilution of 4.4. Instrumentation and Characterization. Molecular
500 mg/L stock solution and were designated as AB-10B-120, weight mass determination was done using the Viscotek
AB-10B-90, AB-10B-70, and AB-10B-50, respectively. Fixed GPCmax autosampler system consisting of a pump, a Viscotek
catalyst amount (150 mg) was taken with 200 mL of dye UV detector, and a Viscotek differential refractive index
solution prior to UV irradiation, and the suspension was stirred detector. A ViscoGEL GPC column 151 (G2000HHR) (7.8
for 30 min and kept under dark conditions (for 24 h) to mm internal diameter, 300 mm length) was used. The effective
establish the equilibrium. Photocatalytic experiments were molecular weight range of the column used was 456−42 800,
performed under UV irradiation in a photochemical reactor and tetrahydrofuran was used as an eluant at a flow rate of 1.0
(model LELESIL), fitted with a UV lamp of LP 400 W, lamp mL/min at 30 °C. Analysis of the data was done using Viscotek
arc: 125 mm with built in resistor, and wavelength spectrum: OmniSEC Omni-01 software. Conductivity was measured in a
200−1100 nm. The lamp was switched on to initiate the pellet form on a Keithley multimeter model DMM 2001 via
photocatalytic degradation reaction. The dye solutions were four probe method. FT-IR spectra of the nanohybrid were
exposed to UV irradiation, and aliquots (2 mL) of the dye taken in the form of KBR pellets on an FT-IR spectropho-
solution were taken out at regular intervals of 15, 30, 45, and 60 tometer model Shimadzu IRA Affinity-1. Diffuse reflectance
min and centrifuged for 10 min at a speed of 5000 rpm and spectra were taken on a UV−vis−NIR spectrophotometer with
analyzed using a UV−visible spectrophotometer model an integrated spherical detector (UV-2501PC, Shimadzu,
Shimadzu UV 1800 at λmax of AB-10B dye (618 nm). To Japan) in the range of 200−800 nm. XRD profiles of the
study the effect of catalyst concentration, different concen- nanohybrid were recorded on a Philips PW 3710 powder

Scheme 1. Mechanism of Radical Generation in (a) PCz and (b) PCz/TiO2 Nanohybrids

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Scheme 2. (a) Proposed Degradation Pathway of AB-10B Dye (Inset: LCMS Spectrum) and (b) LCMS Spectrum of
Intermediates of AB-10B Dye Using PCz/TiO2 (2:1) as a Catalyst
diffractometer (nickel-filtered Cu Kα radiations). Peak
parameters were analyzed using Origin 8.0 software. Trans-
mission electron micrographs were taken on Morgagni 268-D
TEM, FEI, USA, operated at an accelerated voltage of 120 kV.
The thermal stability of PCz and PCz/TiO2 nanohybrids was
investigated by TGA using a thermal analyzer STA 6000,
PerkinElmer. The samples were heated from 30 to 850 °C at a
heating rate of 10 °C/min in N2 atmosphere at a flow rate of 20
mL/min. The specific surface area of PCz and PCz/TiO2
8363
Article
nanohybrids was analyzed via nitrogen adsorption isotherms
(78 K) using the Brunauer−Emmett−Teller (BET) method.
The pore size distributions of PCz and PCz/TiO2 (2:1)
nanohybrids were derived from the absorption isotherms by
using the BET surface area analyzer, Nova Station 2000e,
Quantachrome Instruments Limited, USA, using the multiple-
point BET method. For the detection and identification of
degradation products, LCMS was conducted using a Waters
Xevo G2-S TOF, USA, mass spectrometer equipped with an
DOI: 10.1021/acsomega.7b01154
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ACS Omega
electrospray ionization interface source and operated in the
negative polarity mode fitted with BEH C18 (1.7 × 50 mm)
containing 2.1 packed particles. Acetonitrile and Milli-Q water
containing 0.1% formic acid, pH 2.7, were used as eluants. The
experiments were carried out in triplicate for evaluating the
effect of nanohybrid catalyst dosage and AB-10B dye
concentration.
■
ASSOCIATED CONTENT
* Supporting Information
S Tungsten Oxides for Photocatalysis, Electrochemistry, and Photo-
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsomega.7b01154.
Nitrogen adsorption isotherms and photocatalytic
degradation of AB-10B dye using radical scavengers
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: ufana2002@yahoo.co.in. Phone: +91-9810776242
(U.R.).
ORCID
Ufana Riaz: 0000-0001-7485-4103
Notes
The authors declare no competing financial interest.
† (17) Li, J.; Xie, Y.; Zhong, Y.; Hu, Y. Facile synthesis of Z-scheme
Now retired (S.M.A.).
■
ACKNOWLEDGMENTS
J.K. wishes to acknowledge the University Grants Commission
(UGC) of Basic Science fellowship (BSR-2015) for the
financial support. The author also wishes to thank the
sophisticated analytical instrumentation facility (SAIF) at All
India Institute of Medical Sciences (AIIMS) for granting the
TEM facility.
■
REFERENCES
(1) Riaz, U.; Ashraf, S. M.; Kashyap, J. Enhancement of photo-
catalytic properties of transitional metal oxides using conducting
polymers: A mini review. Mater. Res. Bull. 2015, 71, 75−90.
(2) Riaz, U.; Ashraf, S. M.; Kashyap, J. Role of Conducting Polymers
in Enhancing TiO2-based Photocatalytic Dye Degradation: A Short
Review. Polym.-Plast. Technol. Eng. 2015, 54, 1850−1870.
(3) Chen, C.; Ma, W.; Zhao, J. Semiconductor-mediated photo-
degradation of pollutants under visible-light irradiation. Chem. Soc. Rev.
2010, 39, 4206−4219.
(4) Hoffmann, M. R.; Martin, S. T.; Choi, W.; Bahnemann, D. W.
Environmental applications of semiconductor photocatalysis. Chem.
Rev. 1995, 95, 69−96.
(5) Pekakis, P. A.; Xekoukoulotakis, N. P.; Mantzavinos, D.
Treatment of textile dyehouse wastewater by TiO2 photocatalysis.
Water Res. 2006, 40, 1276−1286.
(6) Riaz, U.; Ashraf, S. M.; Farooq, M. Effect of pH on the
microwave-assisted degradation of methyl orange using poly(1-
naphthylamine) nanotubes in the absence of UV−visible radiation.
Colloid Polym. Sci. 2015, 293, 1035−1042.
(7) Vinodgopal, K.; Wynkoop, D. E.; Kamat, P. V. Environmental
photochemistry on semiconductor surfaces: photosensitized degrada-
tion of a textile azo dye, acid orange 7, on TiO2 particles using visible
light. Environ. Sci. Technol. 1996, 30, 1660−1666.
(8) Gao, L.; Li, Y.; Ren, J.; Wang, S.; Wang, R.; Fu, G.; Hu, Y.
Passivation of defect states in anatase TiO2 hollow spheres with Mg
doping: Realizing efficient photocatalytic overall water splitting. Appl.
Catal., B 2017, 202, 127−133.
(9) Hu, J.-L.; Qian, H.-S.; Li, J.-J.; Hu, Y.; Li, Z.-Q.; Yu, S.-H.
Synthesis of Mesoporous SiO2@TiO2 Core/Shell Nanospheres with
8364
Article
Enhanced Photocatalytic Properties. Part. Part. Syst. Charact. 2013, 30,
306−310.
(10) An, X.; Yu, J. C.; Wang, F.; Li, C.; Li, Y. One-pot synthesis of
In2S3 nanosheets/graphene composites with enhanced visible-light
photocatalytic activity. Appl. Catal., B 2013, 129, 80−88.
(11) Kumar, S. G.; Rao, K. S. R. K. Tungsten-based nanomaterials
(WO3 & Bi2WO6): Modifications related to charge carrier transfer
mechanisms and photocatalytic applications. Appl. Surf. Sci. 2015, 355,
939−958.
(12) Huang, Z.-F.; Song, J.; Pan, L.; Zhang, X.; Wang, L.; Zou, J.-J.
therapy. Adv. Mater. 2015, 27, 5309−5327.
(13) Kumar, S. G.; Rao, K. S. R. K. Zinc oxide based photocatalysis:
tailoring surface-bulk structure and related interfacial charge carrier
dynamics for better environmental applications. RSC Adv. 2015, 5,
3306−3351.
(14) Riaz, U.; Ashraf, S. M. Microwave-induced catalytic degradation
of a textile dye using bentonite−poly(o-toluidine) nanohybrid. RSC
Adv. 2015, 5, 3276−3285.
(15) Etogo, A.; Liu, R.; Ren, J.; Qi, L.; Zheng, C.; Ning, J.; Zhong, Y.;
Hu, Y. Facile one-pot solvothermal preparation of Mo-doped Bi2WO6
biscuit-like microstructures for visible-light-driven photocatalytic water
oxidation. J. Mater. Chem. A 2016, 4, 13242−13250.
(16) Qiao, R.; Mao, M.; Hu, E.; Zhong, Y.; Ning, J.; Hu, Y. Facile
Formation of Mesoporous BiVO4/Ag/AgCl Heterostructured Micro-
spheres with Enhanced Visible-Light Photoactivity. Inorg. Chem. 2015,
54, 9033−9039.
Ag2CO3/Ag/AgBr ternary heterostructured nanorods with improved
photostability and photoactivity. J. Mater. Chem. A 2015, 3, 5474−
5481.
(18) Rosseler, O.; Shankar, M. V.; Du, M. K.-L.; Schmidlin, L.; Keller,
N.; Keller, V. Solar light photocatalytic hydrogen production from
water over Pt and Au/TiO2(anatase/rutile) photocatalysts: Influence
of noble metal and porogen promotion. J. Catal. 2010, 269, 179−190.
(19) Li, Q.; Li, Y. W.; Wu, P.; Xie, R.; Shang, J. K. Palladium oxide
nanoparticles on nitrogen-doped titanium oxide: Accelerated photo-
catalytic disinfection and post-illumination catalytic “memory”. Adv.
Mater. 2008, 20, 3717−3723.
(20) Woan, K.; Pyrgiotakis, G.; Sigmund, W. Photocatalytic carbon-
nano tube-TiO2 composites. Adv. Mater. 2009, 21, 2233−2239.
(21) Riaz, U.; Ashraf, S. M.; Aqib, M. Microwave-assisted degradation
of acid orange using a conjugated polymer, polyaniline, as catalyst.
Arabian J. Chem. 2014, 7, 79−86.
(22) Riaz, U.; Ashraf, S. M. Synergistic effect of microwave irradiation
and conjugated polymeric catalyst in the facile degradation of dyes.
RSC Adv. 2014, 4, 47153−47162.
(23) Riaz, U.; Ashraf, S. M.; Raza, R.; Kohli, K.; Kashyap, J.
Sonochemical Facile Synthesis of Self-assembled Poly(o-phenylenedi-
amine)/Cobalt ferrite Nanohybrid With Enhanced Photocatalytic
Activity. Ind. Eng. Chem. Res. 2016, 55, 6300−6309.
(24) Riaz, U.; Ashraf, S. M.; Budhiraja, V.; Aleem, S.; Kashyap, J.
Comparative studies of the photocatalytic and microwave-assisted
degradation of alizarin red using ZnO/poly(1-naphthylamine) nano-
hybrids. J. Mol. Liq. 2016, 216, 259−267.
(25) Riaz, U.; Ashraf, S. M. Latent photocatalytic behavior of semi-
conducting poly(1-naphthylamine) nanotubes in the degradation of
Comassie Brilliant Blue RG-250. Sep. Purif. Technol. 2012, 95, 97−102.
(26) Riaz, U.; Ashraf, S. M. Microwave-Assisted Solid State in Situ
Polymerization and Intercalation of Poly(carbazole) between
Bentonite Layers: Effect of Microwave Irradiation and Gallery
Confinement on the Spectral, Fluorescent, and Morphological
Properties. J. Phys. Chem. C 2012, 116, 12366−12374.
(27) Morin, J.-F.; Leclerc, M.; Adès, D.; Siove, A. Polycarbazoles: 25
Years of Progress. Macromol. Rapid Commun. 2005, 26, 761−778.
(28) Raj, V.; Madheswari, D.; Ali, M. M. Chemical Formation,
Characterization and Properties of Polycarbazole. J. Appl. Polym. Sci.
2010, 116, 147−154.
DOI: 10.1021/acsomega.7b01154
ACS Omega 2017, 2, 8354−8365
ACS Omega Article

(29) Shakir, M.; Noor-e-Iram; Khan, M. S.; Al-Resayes, S. I.; Khan, A. catalysts for the photocatalytic degradation of Amidoblack-10B. Chem.
A.; Baig, U. Electrical Conductivity, Isothermal Stability, and Eng. J. 2012, 210, 385−397.
Ammonia-Sensing Performance of Newly Synthesized and Charac- (49) Qamar, M.; Saquib, M.; Muneer, M. Photocatalytic degradation
terized Organic−Inorganic Polycarbazole−Titanium Dioxide Nano- of two selected dye derivatives, chromotrope 2B and amido black 10B,
composite. Ind. Eng. Chem. Res. 2014, 53, 8035−8044. in aqueous suspensions of titanium dioxide. Dyes Pigm. 2005, 65, 1−9.
(30) Pandey, P. C.; Prakash, R.; Singh, G.; Tiwari, L.; Tripathi, V. S.
Studies on Polycarbazole-Modified Electrode and Its Applications in
the Development of Solid-State Potassium and Copper(II) Ion
Sensors. J. Appl. Polym. Sci. 2000, 75, 1749−1759.
(31) Guo, E.; Yin, L.; Zhang, L. CdS quantum dot sensitized anatase
TiO2 hierarchical nanostructures for photovoltaic application.
CrystEngComm 2014, 16, 3403−3413.
(32) Li, J.; Grimsdale, A. C. Carbazole-based polymers for organic
photovoltaic devices. Chem. Soc. Rev. 2010, 39, 2399−2410.
(33) Sun, J.; Zhu, Y.; Xu, X.; Lan, L.; Zhang, L.; Cai, P.; Chen, J.;
Peng, J.; Cao, Y. High Efficiency and High Voc Inverted Polymer Solar
Cells Based on a Low-Lying HOMO Polycarbazole Donor and a
Hydrophilic Polycarbazole Interlayer on ITO Cathode. J. Phys. Chem.
C 2012, 116, 14188−14198.
(34) Cheng, Y.-J.; Wu, J.-S.; Shih, P.-I.; Chang, C.-Y.; Jwo, P.-C.; Kao,
W.-S.; Hsu, C.-S. Carbazole-based ladder-type heptacylic arene with
aliphatic side chains leading to enhanced efficiency of organic
photovoltaics. Chem. Mater. 2011, 23, 2361−2369.
(35) Zhang, B.; Hu, X.; Wang, M.; Xiao, H.; Gong, X.; Yang, W.;
Cao, Y. Highly efficient polymer solar cells based on poly(carbazole-
alt-thiophene-benzofurazan). New J. Chem. 2012, 36, 2042−2047.
(36) Pagga, U.; Brown, D. The degradation of dyestuffs: Part II
Behaviour of dyestuffs in aerobic biodegradation tests. Chemosphere
1986, 15, 479−491.
(37) Riaz, U.; Ashraf, S. M.; Khan, N. Effects of surfactants on
microwave-assisted solid-state intercalation of poly(carbazole) in
Bentonite. J. Nanopart. Res. 2011, 13, 6321−6331.
(38) Tao, Y.; Zhang, K.; Zhang, Z.; Cheng, H.; Jiao, C.; Zhao, Y.; Xu,
W. Enhanced electrochromic properties of donor−acceptor polymers
via TiO2 composite. Polymer 2016, 91, 98−105.
(39) Iram, N. e.; Khan, M. S.; Jolly, R.; Arshad, M.; Alam, M.; Alam,
P.; Khan, R. H.; Firdaus, F. Interaction mode of polycarbazole−
titanium dioxide nanocomposite with DNA: Molecular docking
simulation and in-vitro antimicrobial study. J. Photochem. Photobiol.,
B 2015, 153, 20−32.
(40) Macit, H.; Sen, S.; Saçak, M. Electrochemical synthesis and
characterization of polycarbazole. J. Appl. Polym. Sci. 2005, 96, 894−
898.
(41) Gupta, B.; Prakash, R. Interfacial polymerization of carbazole:
Morphology controlled synthesis. Synth. Met. 2010, 160, 523−528.
(42) Chaudhary, D.; Khare, N.; Vankar, V. D. Ag nanoparticles
loaded TiO2/MWCNT ternary nanocomposite: A visible-light-driven
photocatalyst with enhanced photocatalytic performance and stability.
Ceram. Int. 2016, 42, 15861−15867.
(43) Tachikawa, T.; Tojo, S.; Kawai, K.; Endo, M.; Fujitsuka, M.;
Ohno, T.; Nishijima, K.; Miyamoto, Z.; Majima, T. Photocatalytic
Oxidation Reactivity of Holes in the Sulfur- and Carbon-Doped TiO2
Powders Studied by Time-Resolved Diffuse Reflectance Spectroscopy.
J. Phys. Chem. B 2004, 108, 19299−19306.
(44) Tauc, J. Optical properties and electronic structure of
amorphous Ge and Si. Mater. Res. Bull. 1968, 3, 37−46.
(45) Davis, E. A.; Mott, N. F. Conduction in non-crystalline systems
V. Conductivity, optical absorption and photoconductivity in
amorphous semiconductors. Philos. Mag. 1970, 22, 0903−0922.
(46) Jadoun, S.; Ashraf, S. M.; Riaz, U. Tuning the spectral, thermal
and fluorescent properties of conjugated polymers via random
copolymerization of hole transporting monomers. RSC Adv. 2017, 7,
32757−32768.
(47) Zhang, Q.; Lima, D. Q.; Lee, I.; Zaera, F.; Chi, M.; Yin, Y. A
Highly Active Titanium Dioxide Based Visible-Light Photocatalyst
with Nonmetal Doping and Plasmonic Metal Decoration. Angew.
Chem., Int. Ed. 2011, 50, 7088−7092.
(48) Joice, J. A. I.; Sivakumar, T.; Ramakrishnan, R.; Ramya, G.;
Prasad, K. P. S.; Selvan, D. A. Visible active metal decorated titania

8365 DOI: 10.1021/acsomega.7b01154

ACS Omega 2017, 2, 8354−8365