Materials Chemistry and Physics 179 (2016) 232e241

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Materials Chemistry and Physics

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

Photocatalytic performance of graphene/TiO2-Ag composites on

amaranth dye degradation
Marcela-Corina Roşu*, Crina Socaci, Veronica Floare-Avram, Gheorghe Borodi,
cean, Maria Coroş, Lidia Ma
Florina Poga geruşan, Stela Pruneanu
National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat Street, 400293 Cluj-Napoca, Romania

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Graphene/TiO2-Ag composites were

prepared by a combined chemical-
thermal method.

The composites showed improved
light-absorption characteristics.

A significant degradation perfor-
mance of amaranth was obtained
with these composites under UV and
natural light exposure.

Graphene/TiO2-Ag composites offer a
high potential for various photo-
catalytic applications in pollutant
removal processes.

a r t i c l e i n f o a b s t r a c t

Article history: Ternary nanocomposites containing TiO2, silver and graphene with different reduction levels were
Received 14 October 2015 prepared and used as photocatalysts for amaranth azo dye degradation, under UV and natural light
Received in revised form exposure. The obtained materials were characterized by TEM, XRD, FTIR and UV-Vis spectroscopy,
12 May 2016
confirming the successful formation of the nanocomposites. HPLC analysis along with UV-Vis spec-
Accepted 14 May 2016
Available online 21 May 2016
troscopy were employed to quantify the concentration of non-degraded dye in solution. The graphene/
TiO2-Ag nanocomposites proved to have remarkable photocatalytic activities for amaranth degradation
under UV and solar irradiation (85.3e98% of dye has disappeared in the first 2 h). Also, significant
Keywords:
Composite materials
removal efficiencies (between 40.5 and 71.8%) of photocatalysts, in day light conditions, were demon-
Optical properties strated. The best result for amaranth dye degradation was obtained with the reduced graphene/TiO2-Ag
Nanostructures catalyst (up to 99.9%). Based on the degradation products analysis, a photodegradation pathway of
Irradiation effects amaranth dye was also proposed.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Azo dyes represent a large class of synthetic colorants with a
wide range of applicability in the textile, paper, wood, leather,
* Corresponding author.
E-mail address: marcela.rosu@itim-cj.ro (M.-C. Roşu).
cosmetic and food industries. These pollutants are considered toxic
and carcinogenic, with negative impact on the aquatic ecosystem,
environment and human health [1e4], and their release into the
environment is undesirable, due to their toxic breakdown products
that can be mutagenic. On these grounds, the pollutants removal
from wastewaters has generated a great interest in the scientific
community. Various physical (coagulation, flocculation, sedimen-
tation, adsorption on activated carbon, nano-filtration, reverse

http://dx.doi.org/10.1016/j.matchemphys.2016.05.035
0254-0584/© 2016 Elsevier B.V. All rights reserved.
 M.-C. Roşu et al. / Materials Chemistry and Physics 179 (2016) 232e241
osmosis etc.), chemical (chlorination, ozonation, chemical precipi-
tation, ion-exchange), and biological (aerobic or anaerobic pro-
cesses) methods were developed in order to remove these
contaminants [5e7]. The removal of synthetic azo dyes raised
particular interest because they are considered aromatic com-
pounds recalcitrant to degradation processes [7,8]. Photocatalysis
represents a cheap, eco-friendly and effective method to destroy
the chromophoric structures of dyes, leading to discoloration that
occurs at initial stage of the azo dyes degradation. Heterogeneous
photocatalysis is generally based on Advanced Oxidation Processes
(AOPs) that are characterized by the generation of highly reactive
oxygen species, such as hydroxyl radicals (
OH), with strong
oxidation potential towards various organic pollutants [7,9].
TiO2 is a semiconductor with a relatively large band gap energy
(3.0e3.2 eV) that limits its spectral response to the UV region (~5%
of the solar spectrum) [11,12]. It is also known as a commonly used
photocatalyst and numerous studies showed its photocatalytic
performance in different practical applications, including degra-
dation of organic pollutants [10]. Beside photocatalytic potential,
TiO2 shows chemical stability and non-toxicity. By combining TiO2
with Ag and graphene, the obtained multiphase nanocomposites
exhibit extended light absorption range and excellent photo-
catalytic properties [13e15].
The aim of this work was to evaluate the photocatalytic per-
formance of TiO2/Ag nanocomposites supported on graphene with
different reduction levels (from graphene oxide to hydrogen
assisted reduced graphene). In order to test the photodegradation
ability of these composites, under various exposure conditions (UV
and natural light irradiation), amaranth, trisodium 2-hydroxy-1-(4-
sulfonato-1-naphthylazo) naphthalene-3,6-disulfonate, an anionic
azo dye, was selected as pollutant model (Fig. 1).
2. Experimental details
2.1. Materials
TiO2-P25 was supplied from Degussa (Germany). Triton X-100
(Fluka, Switzerland) and acetylacetone (Merck, Germany) were
used as organic additives. Silver nitrate (AgNO3) was purchased
from Alfa-Aesar (Germany). Ascorbic acid, methanol (HPLC grade)
and acetic acid were purchased from Merck (Darmstadt, Germany).
Amaranth (AM) was acquired from Sigma Aldrich (Germany).
Ethanol was obtained from Fluka (Germany). All reagents were
used without further purification. The ultrapure water was pro-
duced by a Milli-Q system (Millipore, USA).
2.2. Photocatalysts preparation
2.2.1. TiO2-Ag nanocomposite (TA) preparation
The TiO2-Ag nanocomposite was prepared by liquid impregna-
tion method. 3 g of TiO2 were dispersed in 20 ml double-distilled
water. In order to increase the dispersion of TiO2 nanoparticles, a
mixture of Triton X-100 and acetylacetone (3:2 vol) was poured in
Fig. 1. Structural formula of amaranth dye.
233
the suspension. In the next step, the same amount (96 mg) of
AgNO3 and ascorbic acid were added to the solution. The mixture
was magnetically stirred until a homogenous suspension was ob-
tained. Then, the suspension was dried at 150  C for 2 h. In order to
achieve the crystallization of TiO2-Ag material and remove the
organic additives, an annealing treatment was applied to them, in
the air, at 450  C, for 2 h.
2.2.2. Graphene/TiO2-Ag nanocomposites preparation
A modified Hummer’s method [16] was used for the preparation
of graphene oxide (GO) from natural graphite. GO (75 mg) and
TiO2-Ag (750 mg) were dispersed in 35 ml water:ethanol solution
(3:2 vol), then the suspension was sonicated for 45 min and in the
end, the mixture was dried at 50  C under continuous stirring,
obtaining the sample that was following denoted as TA-GO. TA-GO
was annealed at 300  C for 15 min, under argon atmosphere, giving
the reduced graphene oxide/TiO2-Ag sample (TA-GR). Then, a
certain amount of TA-GR sample was thermally treated at 550  C
for 1 h in H2/Ar atmosphere, leading to TA-GT sample. The photo-
catalytic activity of TA-GO, TA-GR and TA-GT was investigated and
compared with that of TA sample.
2.3. Nanocomposites characterization
Transmission Electron Microscopy (TEM) images were obtained
with an H-7650 120 kV Automatic Microscope (Hitachi, Japan). X-
ray diffraction (XRD) measurements were collected in the
2q ¼ 5e85 angular domain with a BRUKER D8 Advance X-ray
diffractometer using CuKa radiation (l ¼ 1.54056 Å). The FTIR
spectra were recorded with a JASCO FTIR-6100 Instrument, in the
4000e400 cm1 range, using KBr pellet technique. The UV-Vis
absorption spectra were registered with a JASCO V-550 Spectrom-
eter. The photocatalytic degradation measurements were per-
formed with three different experimental set-up: (i) under UV light
from a CN-15.LC darkroom (France) that provided UV radiation
(4  15 W) simultaneously at 264 and 365 nm; (ii) under intense
sun light, or (iii) day light (no direct sun light). The two last ex-
periments were carried outside the laboratory.
2.4. Photocatalytic activity evaluation
The photocatalytic performance of all composites was evaluated
by amaranth azo dye degradation. 4 mg of each catalyst (TA, TA-GO,
TA-GR and TA-GT) were dispersed in 20 ml of amaranth solution
(2  105 M in ultrapure water). In order to reach the adsorption-
desorption equilibrium, the suspensions were magnetically stir-
red, at room temperature, for 1 h. A control experiment was also
conducted by irradiating the amaranth solution, without catalyst.
All samples were exposed to UV light, intense sun light and day
light, for 4 h. The experiments were performed in June, Cluj-
Napoca, Romania (latitude: 47 N; longitude: 24 E; altitude:
354 m), where the total solar radiation on horizontal surface from
June to August is 537 kW h m2 and the total annual solar radiation
on horizontal surface is 1307 kW h m2 [17].
At given time intervals, sample aliquots were collected and the
amaranth degradation was monitored by UV-VIS spectroscopy at
520 nm and by HPLC analysis. Possible intermediate/final products
of the degradation reaction were identified by HPLC-MS analysis.
2.5. Analytical methods
Chromatographic analysis was performed using an ultra-high-
performance liquid chromatography system (Accela UHPLC sys-
tem, Thermo Scientific, USA) equipped with quaternary pump,
autosampler and photodiode array (PDA) detector. The analytical
234 M.-C. Roşu et al. / Materials Chemistry and Physics 179 (2016) 232e241

column was a reversed phase Hypersil BDS C18 (150  4.6 mm, 5 m
particle size). The mobile phase system consisted of 3 mM trie-
thylammonium formate, pH 5.9, adjusted by acetic acid (A) and
methanol (B). The flow rate was 0.3 ml/min and the injection vol-
ume was 10 mL. The gradient elution was programmed as follows:
0e1 min isocratic elution, 85% A: 15% B; 1e10 min, 65% A: 35% B;
10e11 return to initial conditions at 85% A: 15% B; 11e14, equili-
bration of the column. The UHPLC instrument was coupled to a
mass spectrometer (LCQ Fleet, Thermo Scientific, USA) equipped
with an electrospray ionization (ESI) source, using an ion trap mass
analyzer. The electrospray ionization was run in the negative ion
mode, and the best conditions were set as follows: spray voltage of
5.0 kV, capillary voltage of 40 V, sheath gas flow rate 35 units, aux
gas flow rate 30 units and capillary temperature of 355  C.

3. Results and discussion

3.1. Morphological and structural characterization of the

nanocomposites Fig. 3. XRD patterns of GO, TiO2-Ag and graphene/TiO2-Ag based nanocomposites.

The morphology of graphene/TiO2-Ag nanocomposites was

investigated by TEM analysis. In Fig. 2a, one can see that the TiO2-
Ag nanoparticles have irregular shape and tend to agglomerate into
large assemblies. They exhibit similar morphological characteristics
also in the case of graphene-based composites (Fig. 2bed). The
graphene sheets appear thin and scrambled, and are densely
covered by TiO2-Ag nanoparticles.
XRD was used to further characterize the structure of the pre-
pared samples. The XRD diffraction pattern of TA shows that it has a
multiphase composition, containing both anatase (PDF card no. 21-
1272) and rutile (PDF card no. 21-1276) crystalline phases (Fig. 3).
The characteristic silver peaks (2q ¼ 38.21, 44.3, 64.4 and 77.4 )
corresponding to Ag nanoparticles (PDF card no. 04-0783) are not
visible, probably due to its low amount in the nanocomposites. The
diffraction pattern of GO shows a strong peak at 2q ¼ 11. Due to the
presence of various oxygen containing functionalities and interca-
lated water molecules, the corresponding d spacing value was
found out to be 0.77 nm. In the nanocomposites (TA-GO; TA-GR;
TA-GT) patterns, this peak is no longer present, indicating the
successful reduction and the formation of graphene-based nano-
composites. The (002) reflections from 2q ¼ 24.04 corresponding
to reduced GO is overlapped with that of (101) crystalline plane of
TiO2 anatase.
The FTIR spectra of GO and those corresponding to nano-
composite samples are shown in Fig. 4. The presence of different
type of oxygen-containing functional groups, in graphene oxide,
was confirmed. Absorption feature at ~3400 cm1 has been
assigned to the O-H stretching vibrations of hydroxyls groups and
physisorbed water molecules. Carbonyl and carboxyl group vibra-
tions are overlapped within the 1700e1900 cm1 range. The
1630 cm1 absorption band contains contributions involving the
skeletal sp2-hybridized C]C in-plane, C]O stretching vibrations
and H2O scissor modes. The vibration modes at 1390 and

Fig. 2. Representative TEM images of: TA (a); TA-GO (b); TA-GR (c); TA-GT (d); scale bar 200 nm (aed).
 M.-C. Roşu et al. / Materials Chemistry and Physics 179 (2016) 232e241
Fig. 4. FTIR spectra of GO, TiO2-Ag and graphene/TiO2-Ag based nanocomposites.
Fig. 5. UV-Vis absorbance spectra of GO, TiO2-Ag and graphene/TiO2-Ag based
nanocomposites.
1050 cm1 were attributed to C-O bonds. The 400 to 800 cm1
region is dominated by a broad peak corresponding to bulk titania
Scheme 1. Schematic representation of the charge transfer in the graphene/TiO2-Ag nanocomposites under UV-visible irradiation.
235
skeletal (stretching vibration of Ti-O-Ti bonds from crystalline
TiO2). These results are in good agreement with those reported in
the literature [14,18,19]. In the FTIR spectrum of TA-GR and TA-GT
nanocomposites, one can see that the intensities of the absorp-
tion bands of oxygen-containing functional groups are reduced
(1630 cm1) or completely disappear (1725, 1390 and 1050 cm1).
These spectral changes were associated with the decomposition of
some oxygen functional groups from GO, during thermal treatment.
However, interactions between TiO2 and the remaining oxygen-
containing functional groups could occur, and Ti-O-C bonds for-
mation could be established.
The optical absorption properties of the prepared nano-
composites were also examined (Fig. 5). TiO2 is a semiconductor
with strong absorption in the ultraviolet region, corresponding to
the electron transitions from the valence band (VB) to the con-
duction band (CB) (O2p / Ti3d) [20,21]. All as-prepared nano-
composites display an intense UV absorption band, with the main
contribution from TiO2. The characteristic peak at about 250 nm,
corresponding to the p-p* transitions of electrons from aromatic
C]C bonds of graphene [22], was overlapped with that of TiO2.
In addition, one can see that the absorption edge of graphene/
TiO2-Ag nanocomposites was shifted towards visible region. The
largest shift took place in case of TA-GT sample. An improvement of
the light-absorption capability of TiO2 occurred by introducing the
Ag nanoparticles and reduced graphene. Ag particles acted as
electron traps and reduced the possibility of electron-hole recom-
bination. The reduced graphene sheets served as acceptors and
transporters of the photogenerated electrons through their
extended p-conjugation structure. During light irradiation, silver
and graphene concurrently improved the separation of photo-
generated charges and facilitated the interfacial electron transfer
between TiO2 nanoparticles and the multilayer graphene [23e25].
Under UV-visible irradiation a possible photocatalytic mechanism
of the charge transfer in graphene/TiO2-Ag nanocomposites, was
proposed and illustrated in Scheme 1.
The calculated band gap energies of nanocomposite samples
were lower than that of commercial TiO2 (3.27 eV). Thus, the direct
band gaps of TA, TA-GO, TA-GR and TA-GT composites were found
to be 3.09, 3.06, 3.04, and 3.05 eV, respectively. The slight decrease
suggests the Ti-O-C bonds formation, within the nanocomposite
materials. During the TA-GO thermal treatment, the oxygen func-
tional groups at the GO surface were gradually reduced and some
unpaired p electrons of the carbon atom could bind the free TiO2
electrons [26]. All graphene-based nanocomposites showed a
higher absorbance in the 400e800 nm range, compared to TA, due
Fig. 6. Absorption spectral changes of AM stock solution (pink curve) after 2 h of: UV light (a); sun light (b); day light (c); in the absence (light pink curve) and presence of
photocatalysts (TA-orange; TA-GO blue; TA-GR red; TA-GT green curve). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

Fig. 7. Variation of the relative concentration of AM, under: UV (a); sun light (b); day light (c); in the absence and presence of catalysts.
 M.-C. Roşu et al. / Materials Chemistry and Physics 179 (2016) 232e241 237

Fig. 8. Variation of relative AM concentration, under: UV (a), sun light (b), day light (c), in the absence and presence of photocatalysts.

to the well-known absorbance of graphene material in the visible
region [27].
3.2. Photocatalytic performance
Fig. 6aec shows the catalytic performance of the nano-
composites towards amaranth degradation, after 2 h of irradiations
under UV (a), direct sun light (b) and day light (c). The two main
absorption peaks of AM (at 215 and 520 nm) progressively decrease
under UV and natural light irradiation. It can be observed the
flattening trend of amaranth spectral profile that indicates its
decomposition in time, being clearly influenced by the presence of
catalysts. The efficiency of AM photodegradation was enhanced by
addition of graphene oxide to TiO2-Ag nanocomposite, and the
maximum photodegradation rate was observed in the case of TA-
GR sample, for all light irradiation conditions. UV light caused a
significant degradation of dye in the presence of TiO2 that is known
as an effective ultraviolet light absorber (Fig. 6a). The changes in the
absorption spectra of AM are more pronounced under sun light
irradiation (Fig. 6b) indicating that the entire multispectral sun is
involved in dye decomposition processes. Day light e a diffuse light
from the whole sky e produces uniform luminance and illumi-
nance distributions, but carries less energy than the direct solar
beam. Consequently, TiO2-Ag based samples exposed to day light
conditions showed a lower photocatalytic activity (Fig. 6c).
The catalysts efficiency on amaranth photodegradation varies as
follows: TA < TA-GO < TA-GT < TA-GR, under UV and natural light
irradiation. The TA-GR and TA-GT nanocomposites showed supe-
rior photocatalytic activity. The mechanical mixing method used to
obtain TA-GO nanocomposite could not induce strong interactions
between the two components. On the other side, the thermal
methods used to obtain TA-GR and TA-GT samples may improve the
crystallization of TiO2, and determine interactions between TiO2
and graphene sheets that promote the formation of TiO2-nano-
composite. Also, the thermal treatment at 550  C (for TA-GT sam-
ple) may reduce the number of catalytic active centers and shrink
the graphene sheets lattice. These findings are in good agreement
with other studies [28e30] that evidence the influence of thermal
treatment on the catalytic performance of graphene oxide/TiO2
photocatalysts.
The amaranth concentration decreased with the reaction time
due to its photodegradation, as shown in Fig. 7aec. It can be noted
that the AM degradation is very slow in the absence of the catalyst.
As expected, TA had a good photocatalytic activity. However, the
Table 1
Rate constant (k) and linear correlation coefficient (R2) of the first-order kinetic
reaction for AM degradation.
Samples UV light Sun light Day light

The photodegradation process of AM in the presence of catalysts k (min1) R2 k (min1) R2 k (min1) R2

led to a visible color change that demonstrates the rapid breaking of AM 0.0010 0.9565 0.0052 0.9591 0.0006 0.9756
the chromophore groups. In case of TA and TA-GO samples the color TA 0.0168 0.9383 0.0347 0.9044 0.0050 0.9669
shifted in time, from dark pink to light pink; it became colorless for TA-GO 0.0191 0.9853 0.0552 0.9222 0.0063 0.9783
TA-GR and TA-GT materials, while in the blank sample, it remained TA-GR 0.0197 0.9954 0.0583 0.9432 0.0122 0.9738
TA-GT 0.0173 0.9603 0.0505 0.9758 0.0070 0.9803
unchanged.
238 M.-C. Roşu et al. / Materials Chemistry and Physics 179 (2016) 232e241

Fig. 9. Photocatalytic degradation of amaranth under: UV (a), sun light (b), day light (c), in the absence and presence of photocatalysts.

presence of graphene in the nanocomposite samples significantly
improved the degradation activity. Moreover, the thermal treated
nanocomposites (TA-GR and TA-GT) are more efficient than TA or
TA-GO samples.
The different absorbance rates of the nanocomposites in the UV-
Vis region leads to different amaranth degradation degrees. For all
samples, a linear fit of ln (C/C0) vs irradiation time (Fig. 8aec) was
obtained, suggesting that the dye decomposition followed a first-
order kinetic reaction (Eq. (1)):
Ct ¼ C0 ekt
where: C0 (mol$L1) was the initial amaranth concentration and Ct
(mol$L1) was the amaranth concentration at the reaction time t
(min); k (min1) was the constant rate.
In Table 1 one can see that the best photocatalytic activity under
UV and natural light irradiation was obtained for TA-GR and TA-GO
nanocomposites, followed by TA-GT and TA materials. The values
which are close to unit, for coefficients of determination (R2),
indicate a good fit of the experimental data. In the absence of cat-
alysts the amaranth degradation rate constant, is notable low, since
most of synthetic dyes are intentionally designed to be relatively
stable under visible light or other environmental conditions.
The amaranth photodegradation efficiency (DEF) was calculated
according to Eq. (2):
the calibration curve (data not shown).
The above results clearly indicate that amaranth was signifi-
cantly decomposed in the presence of graphene/TiO2-Ag nano-
composites under UV and natural light (Fig. 9aec). The best
catalytic ability of the nanocomposites was observed under sun
light irradiation. However, the experimental results demonstrate a
remarkable photoactivity of the obtained nanocomposites under
day light exposure. Moreover, the day light is a safe and cost
effective source which can be easily exploited for pollutants
degradation. By comparison, the intense sun light is not constant
during the year seasons, while the UV sources could be expensive
(1)
and hazardous.
3.3. Chromatographic (intermediates) analysis
The HPLC-MS analysis was performed in order to analyze the
amaranth and to identify the photodegradation products. The
amaranth peak shape and retention time are very sensitive to the
elution system, due to the three sulfonate functional groups that
can be differently ionized. Non-buffered binary systems formed
Table 2
Amount of non-degraded amaranth (%).
Samples UV light Sun light Day light
30 min 2 h 4h 30 min 2 h 4h 30 min 2 h 4h

C0  Ct AM 100 100 85.4 100 84.6 35.3 100 100 100

DEFð%Þ ¼  100 (2) TA 77.4 22.9 0.8 77.0 12.8 0.04 95.1 57.0 22.5
C0
TA-GO 70.7 11.5 0.2 69.0 7.3 0 92.8 59.5 28.7
The dye concentration was determined from the absorption TA-GR 67.0 9.2 0 55.0 2.0 0 74.3 28.2 3.1
TA-GT 67.2 14.7 0.3 59.2 3.2 0 100 100 100
spectra of amaranth solution, at the 520 nm wavelength, based on
 M.-C. Roşu et al. / Materials Chemistry and Physics 179 (2016) 232e241 239

Fig. 10. HPLC chromatogram of the amaranth intermediates after 30 min (a) and 4 h (b) of sun light irradiation using TA-GR nanocomposite.

Scheme 2. Proposed amaranth photodegradation pathways based on the identification of intermediates, by HPLC-MS technique.

from methanol/water or acetonitrile/water splitted the amaranth performed on all photocatalytic degradation experiments (UV, sun
peak and made impossible its quantification. The multiple peak and day light), the reaction being monitored at 30 min, 2 and 4 h,
problem was solved using a mixture of methanol with triethy- respectively. It was observed the formation of similar products in all
lammonium formate (3 mM, pH ¼ 5.9). HPLC analysis was samples, but the degradation rate of amaranth was different, being
240 M.-C. Roşu et al. / Materials Chemistry and Physics 179 (2016) 232e241
related to the structure of the nanocomposite (Table 2).
Overall, HPLC experiments showed that TA-GR was the most
efficient photocatalyst for the rapid and complete removal of the
amaranth. The HPLC chromatogram of the TA-GR sample after half
an hour sun light exposure (Fig. 10a), showed the presence of only
half of the starting amaranth (5.41 min) and indicate the formation
of two main peaks: one at 4.17 min (with an UV maximum of
240e244 nm) and another one at 4.45 min (with an UV maximum
of 258e260 nm). At 2 h time (data not presented), approximately
82% of the azo dye was consumed and no more non-aromatic
products were formed. After 4 h of photodegradation (Fig. 10b),
all the amaranth and aromatic intermediate products disappeared
(no peaks detected at 254 nm). The chromatogram exhibited one
major peak in the reaction mixture, detectable at 215 nm, retention
time 5.44 min.
In order to obtain further data and identify the possible degra-
dation pathways, an ion trap mass spectrometer was coupled with
the HPLC. The three sulfonate groups of the dye rendered the
ionization only in the negative mode ([M-H] ¼ 537.2) and this
method was kept through all the experiments. Even though not all
separated peaks are ionizing at the same experimental conditions,
some intermediates could be identified (Scheme 2). Corroborating
these products with the literature data on other azo dye com-
pounds [31e33], a possible amaranth degradation scheme was
proposed.
The identified intermediates showed that the generated hy-
droxyl first attacks the C-N bonds attached to the aromatic rings,
thus breaking the chromophore (aromatic-N]N-aromatic) and
causing the observed discoloration. The initially formed phenols
were further degraded, probably leading to short-chain carboxylic
acids as a previous stage of the mineral end-products.
4.. Conclusions
TiO2-Ag nanocomposites supported on graphene were suc-
cessfully prepared through a facile combined chemical-thermal
method. The photocatalytic activity of all nanocomposites to-
wards the amaranth degradation was evaluated under UV and
natural light exposure. Experimental results clearly indicate that
the amaranth decomposition was accelerated in the catalysts
presence. All graphene/TiO2-Ag nanocomposites were found to be
more active than TiO2-Ag. Among them, TA-GR acted as the best
photocatalyst. Amaranth decomposition was slightly slower under
day light irradiation so it may require a longer exposure time for
complete degradation. However, day light is a user-friendly and
cost-effective source for pollutants removal. In addition, the usage
of the synthesized nanocomposites may be extended to other azo
dyes and applied in different photocatalytic processes.
Acknowledgments
This paper was supported by a grant of MEN-UEFISCDI, Project
No. PN-II-PT-PCCA-2013-4-1282 (230/2014), (PN-II-Program 4,
partnership in priority areas, PCCA-type 2).
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