Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917

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Journal of Photochemistry and Photobiology A:

Chemistry
journal homepage: www.elsevier.com/locate/jphotochem

Photocatalytic activity of TiO2, ZnO and Nb2O5 applied to degradation

of textile wastewater
Renata P. Souzaa,b , Thbata K.F.S. Freitasa , Fernando S. Dominguesa , Osvaldo Pezotia ,
Elizangela Ambrosioa , Ana M. Ferrari-Limac , Juliana C. Garciaa,*
a
Departamento de Qumica, Universidade Estadual de Maring, Avenida Colombo 5790, 87020-900, Maring, PR, Brazil
b
Coordenao de Engenharia de Bioprocessos e Biotecnologia, Universidade Tecnolgica Federal do Paran, Estrada para Boa Esperana Km 04, 85660-000,
Dois Vizinhos, PR, Brazil
c
Coordenao de Tecnologia em Processos Qumicos, Universidade Tecnolgica Federal do Paran, Rua Marclio Dias 635, 86812-460, Apucarana, PR, Brazil

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

Article history:
Received 7 December 2015 In this work, photocatalysis was employed in the treatment of textile efuent from industrial laundry
Received in revised form 13 June 2016 jeans using the catalysts TiO2 P25 (commercial), TiO2, ZnO and Nb2O5, under articial UV irradiation. The
Accepted 16 June 2016 parameters investigated were: pH of the solution and catalyst concentration. The photocatalytic activity
Available online 18 June 2016 was evaluated by means of kinetic efciency (rate constant and half life time), thermodynamic
(absorbance reduction at 228, 254, 284, 310, 350, 500 and 660 nm), COD reduction, mineralization in
Keywords: terms of the formation of inorganic ions (NH4+, NO3
, NO2
, SO42
and Cl
) and toxicity reduction
Textile efuent (bioassays using Artemia salina). The photocatalytic degradation of textile efuent at pH 3.0 and catalyst
Photodegradation
concentration of 0.250 g L
1 showed the best results, being found 95.91%; 87.35%; 86.95% and 59.18% of
Toxicity
absorbance reduction at 660 nm (lmax) after 300 min of articial irradiation with TiO2 P25, Nb2O5, TiO2
Mineralization
and ZnO, respectively. TiO2 and Nb2O5 were responsible for the reduction of approximately 70 and 66% of
COD and the photocatalytic activity of TiO2 was very close to TiO2 P25. In this sense, Nb2O5 becomes a
promising alternative to replace the commercial TiO2 P25. Bioassays with Artemia salina conrmed the
efcacy of the treatment, indicating that after photodegradation there was an expressive decrease in
efuent toxicity for up to 3 times.
2016 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, the environmental contamination has been
identied as one of the greatest problems of modern society, being
the contamination of natural water sources the biggest one, mainly
due to unmeasured population growth and increase of industrial
activity [1].
Among the industrial processes that are responsible for
generating large volumes of wastewater stand out the textile
sector. The textile industry consumes a considerable amount of
water during the processes of dyeing and nishing [2,3], as well as
a great variety and quantity of chemicals, among them the dyes.
Textile industries usually generate between 200 and 350 m3 of
wastewater per ton of nished product [3]. Due to those factors, it
is classied as one of the most polluting efuents from all
industries [3]. The textile efuents are characterized by being
* Corresponding author.
E-mail address: jucgarcia@ibest.com.br (J.C. Garcia).
highly colored due to the presence of dyes that are not xed to the
ber during the dyeing process. These efuents usually have high
pH values, biochemical oxygen demand (BOD), chemical oxygen
demand (COD), turbidity and other toxic chemical compounds.
Furthermore, many textile dyes or by-products present themselves
carcinogenic and/or mutagenic effects [3,4].
The conventional technologies currently used to degrade textile
efuent are based in the processes of coagulation/occulation
[5,6], electrocoagulation [7], adsorption on activated carbon [8,9]
and reverse osmosis/membrane ltration [10,11]. However, these
techniques are non-destructive, since they only transfer the
organic contaminant into sludge giving rise to a new type of
pollution, which needs further treatment [2,3,12]. In this
perspective, advanced oxidation processes (AOPs) employing
heterogeneous photocatalysis have emerged as potential destruc-
tive technology leading to the total mineralization of most of
organic pollutants without generating solid wastes [1].
Titanium dioxide (TiO2) is one of the most studied catalysts in
photocatalysis due to the high photocatalytic activity, non toxicity
and photostability [13]. Many studies have been reported using

http://dx.doi.org/10.1016/j.jphotochem.2016.06.013
1010-6030/ 2016 Elsevier B.V. All rights reserved.
10 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917
TiO2 as a catalyst for treating wastewater of textile industry
[4,5,1417]. Zinc oxide (ZnO) is also presented as one of the most
extensively investigated photocatalysts and has relatively high
catalyst efciency, low cost, non toxic and chemical stability.
Studies report that the ZnO degraded efciently textile dyes
[12,1820].
The application of niobium pentoxide (Nb2O5) as catalyst for the
photodegradation of dyes in the textile industry has been few
reported in the literature [2123]. Nb2O5 exhibits a semiconduc-
tivity similar to that of TiO2 and therefore presents itself as a
promising photocatalyst to replace TiO2 and even ZnO, since Brazil
holds 90% of world reserves of niobium. Nb2O5 as well as TiO2,
presents good chemical stability, non toxicity and commercial
availability [24]. However, widespread use of TiO2 has become
uneconomical for water treatment operations on large scale [12]
mainly due to the need of UV radiation, reactor design and
additional separation steps requirement [25]. Thereby interest has
been drawn towards the search for suitable alternatives to TiO2.
The aim of this work was to study the articial photocatalytic
degradation of textile efuent from industrial laundry jeans
through evaluation of the photocatalytic activity of TiO2, ZnO
and Nb2O5 catalysts with favorable particle size for the separation
as an alternative to commercial TiO2 P25, contributing for a
sustainable development and economically viable for industrial
application, keeping the photocatalytic activity similar to com-
mercial TiO2 P25.
2. Materials and methods
2.1. Catalysts
The catalysts used in photocatalytic reactions were: TiO2
(Kronos), TiO2 P25 (commercial, Degussa), ZnO (Dynamic) and
Nb2O5 (BCMM Brazilian Company of Metallurgy and Mining). In
order to facilitate recovery at the end of reaction, the catalysts were
subjected to a particle agglomeration process. An hydraulic press
was used under 3.0  103 kgf cm
2 of pressure to form pellets,
which were crushed and sieved to obtain particles with a particle
size between 0.150 and 0.300 mm (100 and 50 mesh, respectively).
Then, the catalysts were calcined at 500  C for 5 h. The commercial
TiO2 P25 was used in photocatalytic reactions in its original form,
without any previous treatment. The catalysts were named as
follows: Ti-500 = TiO2 calcined at 500  C; Zn-500 = ZnO calcined at
500  C; Nb-500 = Nb2O5 calcined at 500  C and TiO2-P25 = com-
mercial TiO2 P25 without calcination.
2.2. Catalysts characterization
The textural properties of catalysts were investigated by N2
adsorption-desorption isotherms at 77 K, using a QuantaChrome
Nova 1200 surface area analyzer. The surface area was determined
by BET method, total pores volume was calculated in the P/P0 = 0.99
and micropores volume was calculated using the t-method. The
catalyst structure was analyzed with X-ray XRD diffractometer
(Shimadzu model D6000, mode 2u with a Cu Ka source, 40 KV,
30 mA, rate 0.2 min
1) using the JCPDS database [26].
The zero point of charge (pHzpc) of the catalysts were
determined using 0.5 g of catalyst added to 25 mL of NaCl
(0.1 mol L
1). The initial pH was adjusted to 2, 4, 6, 8, 10 and 12
by the addition of HCl (0.1 mol L
1) or NaOH (0.1 mol L
1). The
suspension was stirred for 24 h, and the nal pH measured. After
that, the change of pH as function of initial pH curves were plotted,
and the value of the pHzpc corresponding to the value in which the
change in pH is zero [27].
Photoacoustic spectroscopy (PAS) was performed with mono-
chromatic light provided by a xenon lamp of 1000 W (Oriel
Corporation 68820) in an apparatus containing a monochromator
(Oriel Instruments 77250), a high sensitivity capacitive micro-
phone (Bruel and Kjaer) and a lock-in amplier (EG and G5110). The
light beam was modulated with a mechanical modulator (Stanford
Research Systems SR540). The photoacoustic spectrum was
obtained on modulation frequency of 21 Hz at wavelength from
200 to 800 nm. The band gap energies were determined by using
Eq. (1):
hC 1240
Eg 1
l l
Where Eg is the band gap energy (eV), which was obtained by
plotting (Abs  E (eV))m vs E (eV) using the direct method, i.e., m = 2
[1,28].
2.3. Textile efuent and characterization
Samples of textile efuent were collected in an industrial
laundry, located in the northwest of Parana State, Brazil, directly
from the stabilization/equalization pond. The physicochemical
characterization of textile efuent was performed according to the
following parameters: biochemical oxygen demand (BOD), chem-
ical oxygen demand (COD), chloride, ammonia, nitrite, nitrate,
sulfate, pH, temperature, turbidity and UVVis spectrophotometry.
The analytical determinations were performed in accordance with
standard methods [29].
2.4. Photocatalytic degradation
2.4.1. Articial photoreactor
The articial irradiation unit used for the photodegradation
reactions consisted of two batch reactors of borosilicate glass
(capacity of 600 mL each) in a wooden box of 80  80  50 cm
(width, height and depth). At the top of the reactors, a 250 W
(PHILIPS HPL-N) mercury vapor lamp without bulb was set
remaining 15 cm above the samples. Four fans were placed in
the side walls to minimize the effect of heat generated by the lamp
during irradiation (Fig. 1). The reaction unit was characterized by
the emission spectrum of the mercury lamp (without bulb),
obtained in VS140 Linear Array UVvis Spectrometer (HORIBA),
and by the borosilicate glass (reaction vessel) absorption spectrum,
obtained in a Cary 50 spectrophotometer.
2.4.2. Photocatalytic reactions
The reactions of articial photodegradation consisted of
using 350.0 mL of in natura textile efuent and evaluating the
Fig. 1. Articial photoreactor: (1) articial UV light; (2) photochemical reactor
containing the textile efuent; (3) Magnetic stirrer and (4) cooler.
 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917 11

Table 1
Characterization of the catalysts.

Catalyst SBETa (m2 g
1) Vpb (10
2 cm3 g
1) Vmc (10
2 cm3 g
1) dpd (nm) Ege (eV) l (nm) pHzpc
Ti-500 11.40 5.95 0.29 10.44 3.30 376 6.93
TiO2-P25 60.55 8.07 1.77 5.97 3.12 397 6.12
Zn-500 7.42 1.61 0.14 4.33 3.24 383 8.30
Nb-500 134.30 12.40 3.28 1.85 3.27 379 4.79
a
BET surface area calculated from the linear part of the BET plot (P/P0 = 0.050.35).
b
Total pore volume, taken from the volume of N2 adsorbed at P/P0 = 0.99.
c
Micropore volume, calculated by t-method.
d
Average pore diameter.
e
Band gap energy obtained by photoacoustic spectroscopy.

following parameters: pH of solution, catalyst concentration and
photocatalytic activity among the oxides. The catalysts investigat-
ed were: Ti-500; Zn-500; Nb-500 and TiO2-P25. The photolysis
(no catalyst) was also evaluated. All suspensions were kept
under magnetic stirring for 30 min in the dark in order to obtain
the adsorption-desorption equilibrium, and then subjected to
irradiation. The temperature was maintained around 25  C and the
pH of the samples monitored at the end of the reaction. The
duration of photoreactions were 300 min with 5.0 mL aliquots
withdrawing in intervals of 50 min. The solutions were ltered in
vacuum qualitative lter paper to separate the catalyst, and then
analyzed.
2.4.2.1. Effect of pH. The evaluation of the pH effect was performed
using 350.0 mL of textile efuent, starting with catalyst
concentration of 0.250 g L
1 and irradiation time of 300 min,
based on studies reported by Garcia et al. [30]. The pH was adjusted
to 2.0; 3.0; 4.0; 5.0 and 6.0 by the addition of HCl and NaOH
0.10 mol L
1. The natural pH of textile efuent was also studied.
2.4.2.2. Effect of catalyst concentration. Once the ideal pH have
been found, the following catalyst concentrations were evaluated:
0.175; 0.250; 0.500 and 0.750 g L
1. The catalyst was dispersed by
magnetic stirring in 350 mL of textile efuent and irradiated for
300 min.
2.4.3. Photocatalytic activity
The photocatalytic activity of the oxides was evaluated in terms
of thermodynamic efciency by absorbance decrease at wave-
length associated with simple aromatic compounds (228, 254 and
284 nm), conjugated aromatic compounds (310 and 350 nm), and
compounds that absorb in visible region (500 nm) [30]. The
percentage of absorbance reduction was calculated by means of
Eq. (2):
Abso
Abs
%Abs Reduction x100
Abso
Where: Abso = initial absorbance and Abs = nal absorbance (after
photocatalysis).
The kinetic efciency was evaluated by determining the rate
constant and half life time. The data obtained for the photo-
degradation of textile efuent were adjusted to rst order kinetics
Langmuir-Hinshelwood. The efciency of photodegradation was
also evaluated in terms of mineralization (formation of inorganic
ions: NH4+, NO3
, NO2
, SO42
and Cl
) and COD reduction
percentage from Eq. (3):
COD0
CODf
%COD reduction x100
COD0
Where: CODo = concentration (mgO2 L
1) of in natura sample
(untreated) and CODf = concentration (mgO2 L
1) of sample treated
by photocatalysis.
2.4.4. Ecotoxicity Artemia salina
Ecotoxicity bioassays with Artemia salina were performed based
on the methodology proposed by Garcia et al. [31]. Cysts of Artemia
salina were incubated in synthetic seawater (23 g L
1 NaCl in
water) for about 24 h at 25  C with continuous illumination and
aeration. After the cysts had hatched, 611units of alive
crustaceans were selected and added to 1 mL of 23 g L
1 NaCl
mixed with 0, 0.3, 0.7, 1.0, 1.5 and 2.0 mL of samples. For each
dilution of tested efuent, the mortality average value was
calculated and toxicity curves were constructed (mortality vs.
efuent dilution), wherein the lethal concentration (LC50) was
calculated by linear t of toxicity curves using the Origin 8.0
program.
3. Results and discussion
3.1. Catalysts characterization
Textural analysis results are shown in Table 1. Ti-500 showed
higher specic surface area than Zn-500, whose specic surface
area was 7.42 m2 g
1, close to reported by Velmurugan et al. [32].
The specic area obtained for TiO2-P25 was 60.55 m2 g
1 close to
found by other authors [25,33,34]. Nb-500 showed high specic
area, total pore and micropore volume. Garca-Sancho et al. [35]
synthesized Nb2O5 obtaining similar specic area and pore volume
values. Assessing the average pore diameter, it was observed that
all catalysts presented mesoporosity (250 nm), except Nb-500
that presented micropores (<2 nm).
Fig. 2 shows the XRD patterns of the catalysts using the JCPDS
database [26]. For Ti-500 catalyst just anatase phase was identied
and the peaks are in agreement with the literature results [28,36].
TiO2-P25 showed peaks corresponding to anatase and rutile
phases. The peak of the crystal plane (101) for the anatase phase
appeared at 2u equal to 25.37 and the crystal plane (110) for the
2
3
Fig. 2. XRD patterns of the catalysts: (a) Ti-500; (b) TiO2-P25; (c) Zn-500 e (d) Nb-
500. Peaks: (A) anatase e (R) rutile.
12 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917

rutile phase at 27.55, close to the value found by Sakthivel et al.

[19]. Zn-500 showed the crystalline phase of the hexagonal
wurtzite type structure. Characteristic peaks of ZnO were observed
for 2u at 31.73, 34.42, 36.25, 47.48 and 56.53, corresponding to the
planes (100), (002), (101), (102) and (110), respectively. The
relatively high intensity of the peak (101) is indicative of
anisotropic growth and constitutes a preferred orientation of
the crystallites [32]. Nb-500 catalyst showed well dened peaks,
indicating the presence of crystalline phase TT-Nb2O5, showing
hexagonal structure, as reported by other authors [28,37].
Fig. 3 shows the pHzpc values in terms of difference of pH in
solution before and after soaking with sodium chloride. The results
are summarized in Table 1.
The pH at which the oxide surface is neutralized is dened as
the zero point of charge (pHzpc). If the solution in contact with the
catalyst has pH > pHzpc, the surface will be negatively charged and
at pH < pHpcz, the surface is positively charged. This characteristic
Fig. 4. Band gap energies of the catalysts. In sert: UVvis photoacoustic spectra.
affects the photocatalytic process because it determines the
adsorption of species on the catalyst surface. Ti-500 showed pHzpc
close to 7.0, in accordance with literature values [38], indicating wavelengths of the catalysts are in the UV region of the
that the TiO2 surface is positively charged in acidic media (pH electromagnetic spectrum (l < 400 nm). Thus, the catalyst can
<6.93) with predominant species Ti-OH2+, or Ti-O
negatively absorb UV radiation from an articial or solar source and be
charged under alkaline conditions (pH >6.93). Once the textile activated, having the electron-hole pair generated, taking direct
efuent has negatively charged compounds, an acidic solution part in photocatalytic reactions.
favors the adsorption on the surface of photocatalyst and thereby,
the efciency of photodegradation increases [12]. The pHzpc value 3.2. Textile efuent characterization
obtained for TiO2-P25 (6.12) is close to that reported in the
literature [19]. pHzpc of Zn-500 was found to be equal to 8.30, this Table 2 presents the results of physicochemical characterization
value was also obtained by Sakthivel et al. [19]. Nb-500 presented a of in natura textile efuent, immediately after its collection. The
pHzpc (4.79) very close to the value found by Bolzon and Prado [39]. textile efuent showed neutral pH, moderate turbidity and high
According to the literature, the value of pHzpc for commercial levels of organic matter expressed by high concentrations of COD,
CBMM Nb2O5 ranges between 2.0 and 6.0 depending on the presenting low ratio DBO/COD indicating that this efuent is not
calcination temperature [21]. biodegradable. High amounts of organic matter are a result of the
The principle of heterogeneous photocatalysis involves the chemicals used in the nishing process and washing of denim
activation of a catalyst by absorption of radiation with energy equal (detergents, softeners, oxidants acids, bases etc.) as well as the high
to or larger than the band gap energy, allowing the generation of dye content, not xed on the ber, released in the efuent. From
electron-hole pairs that will lead to the formation of oxidant the UVvis absorption spectrum obtained for the in natura textile
radicals. By knowing this value, it is possible to measure the energy efuent (Fig. 5a), it was found a maximum absorbance band at
for its activation and in which region of the electromagnetic about 660 nm, visible region of the electromagnetic spectrum.
spectrum it can be found. Fig. 4 shows the UVvis absorption
spectrum obtained for the catalysts and the obtained band gap 3.3. Photocatalytic degradation
energies. The band gap energy values were determined and the
respective wavelengths are shown in Table 1. 3.3.1. Articial photoreactor
It was observed that the catalysts showed band gap energy The lamp emission spectrum can be seen in Fig. 5 (b). There
values (Eg) close to each other, with the lowest value being found were maximum emission peaks at 365; 438 and 548 nm. It can be
for TiO2-P25 (Eg = 3.12) with absorbing energy close to the visible considered that the rst peak will be responsible for activation of
region (397 nm). Note that all of maximum absorption catalysts, whose lmax showed to be lower than 400 nm (Table 1).
By means of the glass reactor absorption spectrum (Fig. 5c), it was
conrmed that the radiation emitted by the lamp is not absorbed
by the efuent.

Table 2
Physico-chemical characterization of textile efuent from jeans industrial laundry.

Parameter in natura efuent

pH 7.03  0.37
Temperature ( C) 35  2
Turbidity (NTU) 113.0  2.7
COD (mgO2 L
1) 558.50  5.05
BOD5,20  C (mgO2 L
1) 170.0
SO4 2
(mg L
1) 42.07  0.07
NH4+ (mg L
1) 2.39  0.07
NO3
(mg L
1) 1.46  0.13
NO2
(mg L
1) 0.066  0.003
Cl
(mg L
1) 287.5  37.5
maximum absorption l (nm) 660
Fig. 3. Zero point of charge of the catalysts (pHzpc): (&) Ti-500; () TiO2-P25; (D)
Zn-500 and (^) Nb-500.
 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917 13

2.0 548
100 (b)
(a)
438

Normalized intensity (u.a.)

1.5 80 365

Absorbance (u.a.)
60
1.0
580
40 406

312
0.5
20
300

0.0 0
250 300 350 400 450 500 550 600 650 700 750 800 200 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)

10
(c)

Absorbance (u.a.) 6

0
300 400 500 600 700 800
Wavelength (nm)

Fig. 5. (a) UVvis absorption spectrum of the in natura textile efuent (b) Emission spectrum of the mercury lamp (without bulb); (c) absorption spectrum of the
photochemical reactor (borosilicate glass).

3.3.2. Effect of pH The degradation efciency at pH 3.0 can be conrmed by Fig. 7,

The pH of solution is an important parameter for metallic which shows the percentage of COD reduction as a function of pH
oxides acting as photocatalyst since it inuences in the surface after photocatalysis. By increasing the solution pH from 3.0 to 7.0,
charge properties [15]. Fig. 6 shows the percentage of absorbance there is a decrease on the degradation efciency from 70.46% to
reduction (at different wavelengths) versus pH for the textile 11.03% in the presence of Ti-500; from 50.28% to 15.27% in the
efuent treated by photocatalysis. presence of Zn-500; from 65.83% to 16.86% for Nb-500 and from
The best degradation results were obtained at pH 3.0 for all 69.73% to 33.80% using TiO2-P25, yielding an average reduction of
catalysts. The absorbance reduction values monitored at 600 nm 70% on degradation efciency. Therefore, changes in pH can
(lmax) was of 95.91%; 87.35%; 86.95% and 59.18% for TiO2-P25, Nb- inuence the adsorption of dye molecules on the surface of the
500, Ti-500 and Zn-500, respectively, after 300 min of irradiation.

Fig. 6. Absorbance reduction (%) as a function of pH for the textile efuent treated by photocatalysis with: (a) Ti-500; (b) TiO2-P25; (c) Zn-500; (d) Nb-500, and xed
concentration 0.250 g L
1. Wavelengths studied: (&) 228 nm; (&) 254 nm; (*) 284 nm; () 310 nm; (~) 350 nm; (D) 500 nm and (^) 660 nm.
14 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917

0.250 g L
1 of catalyst, above this concentration the photodegra-

dation began to be damaged.
When the catalyst concentration increases, excessive turbidity
of the suspension prevents the light penetration into the reactor
and this deciency will hinder the system. There is also the
possibility of increased particleparticle interactions become
signicant by a large number of particles in suspension, reducing
the density of available reactive sites and electrons on the catalyst
surface [43].

3.4. Photocatalytic activity

The photocatalytic activity between the catalysts was evaluated

under optimal conditions of pH and catalyst concentration. Fig. 9
(a) shows the absorbance reduction percentages at 660 nm (lmax)
as a function of irradiation time and Fig. 9 (b) provides the COD
Fig. 7. COD reduction (%) as a function of pH for the textile efuent treated by reduction percentages for the textile efuent treated by photo-
photocatalysis with: ( ) Ti-500; ( ) Zn-500; ( ) Nb-500 e ( ) TiO2-P25,
catalysis using different catalysts.
and xed concentration in 0.250 g L
1.
It was observed that the photolysis was inefcient in reducing
the absorbance and COD, showing the need of the catalyst. The
catalysts, which is important step for catalytic photo-oxidation
efciency in absorbance reduction (lmax) increased about 85% in
occurrence [3,17].
the presence of Ti-500 and 86% in the presence of Nb-500 and
Taking into account the zero point of charge (pHzpc) of catalyst
degraded the organic material by approximately 71 and 66%,
(Table 1), in an acid medium (pH < pHzpc) the surfaces are
respectively, whereas 97% of absorbance reduction and 70% of COD
positively charged, favoring the electrostatic interaction between
reduction was obtained in the presence of TiO2-P25. Otherwise, for
the anions of the dye molecules and the photocatalyst surface,
Zn-500 the degradation was not very effective, achieving maxi-
thereby increasing the efciency of the photodegradation [3].
mum values of degradation (lmax) and COD reduction around 68
While that under alkaline conditions (pH > pHzpc), the surfaces are
and 50%, respectively. Nb-500 showed different characteristics and
negatively charged, which does not favor adsorption of efuent
textural properties in comparison with the other catalysts, having
components and, consequently, the efciency of the photo-
the smallest value for pHzpc (4.79) and greater surface area, and
degradation is hampered [15,40]. Other authors have reported
provide micropores (Dp = 1.85 nm). These differences contributed
that the efciency of both the absorbance reduction and the COD
to its higher photocatalytic activity, since the adsorption capacity
reduction of textile efuent was higher at acidic conditions [3,41].
of negatively charged compounds present in the textile efuent is
strongly affected by these properties.
3.3.3. Effect of catalyst concentration
Table 3 shows the absorbance reduction percentage, rate
In order to verify the behavior of textile efuent degradation,
constants (k) half-life time (t1/2) and the linear regression
the inuence of the catalyst concentration on the increasing of the
coefcient (R) for the textile efuent treated by photocatalysis
degradation rate was studied (Fig. 8a). Assuming that the catalyst
under articial irradiation.
surface and the light absorption are limiting factors on the
The absorbance reduction values were statistically equal
photodegradation process, it was observed that the increase on
between Ti-500 and Nb-500 catalysts. The greatest percentage
catalyst concentration was not proportional to the increase on
of absorbance reduction occurred at 500 and 660 nm, correspond-
degradation rate. The excessive addition of catalyst caused a
ing to the visible region absorbing compounds. Furthermore, it was
negative effect on degradation, since the speed becomes indepen-
found that the speed of absorbance reduction occurred in the
dent of the catalyst mass, and not all the particles can be irradiated
following order: 660 nm > 500 nm > 350 nm > 310 nm > 284 nm >
[42] due to increased light scattering, that can suppress or inhibit
254 nm > 228 nm. This occurs because, as the aromatic hydro-
photocatalysis mechanism [33]. This effect is evident in the results
carbons are degraded, the aromatic rings are broken into smaller
of COD reduction (%) as a function of catalyst concentration
compounds (simple rings or aliphatic groups), increasing the
(Fig. 8b). The best results were found at a concentration of
absorbance at wavelengths referring to these compounds, which

Fig. 8. (a) Effect of catalyst concentration on the degradation rate constant (k) of the textile efuent at 660 nm: (&) Ti-500; (*) Zn-500; (~) Nb-500 and (!) TiO2-P25 and (b)
percentages of COD reduction as a function of catalyst concentration: ( ) Ti-500; ( ) Zn-500; ( ) Nb-500 and ( )TiO2-P25, with xed pH 3.0.
 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917 15

Fig. 9. (a) Percentages of absorbance reduction at 660 nm (lmax) as a function of irradiation time and (b) percentages of COD reduction of catalysts: (&) Ti-500; (&) Zn-500;
(*) Nb-500; () TiO2-P25 and (~) Photolysis, at pH 3.0 and catalyst concentration of 0.250 g L
1 after 300 min of irradiation.

Table 3
Percentages of absorbance reduction, rate constants of pseudo rst order (k), half life time (t1/2) and linear regressions (R) for the textile efuent treated by photocatalysis
under articial irradiation.

l (nm)
Catalyst 228 254 284 310 350 500 660
Ti-500 % 60.31  2.48a 62.42  2.77a 68.63  3.24a 71.59  2.27a 74.57  1.54a 77.47  2.11a 84.50  2.46a
k (min
1) 0.0029 0.0035 0.0042 0.0044 0.0048 0.0053 0.0066
t1/2 (min) 239 198 165 157 144 130 105
R 0.9150 0.9502 0.9567 0.9626 0.9937 0.9883 0.9908

Zn-500 % 43.19  3.73b 45.46  3.91b 46.32  2.84b 47.75  2.84b 51.69  4.45b 64.61  5.30b 67.82  5.64b
k (min
1) 0.0014 0.0016 0.0017 0.0018 0.0019 0.0023 0.0024
t1/2 (min) 495 433 407 385 364 301 288
R 0.9028 0.9345 0.9717 0.9616 0.9634 0.9224 0.9375

Nb-500 % 62.17  3.82a 66.20  3.75a 70.79  2.56a 75.57  3.40a 78.56  2.13a 81.80  2.44a 86.02  1.33a
k (min
1) 0.0033 0.0035 0.0037 0.0045 0.0049 0.0052 0.0059
t1/2 (min) 210 198 187 154 141 133 117
R 0.9158 0.8973 0.9001 0.9145 0.9548 0.9698 0.9687

TiO2-P25 % 76.58  3.72c 80.40  3.79c 83.76  3.96c 85.26  3.02c 88.70  1.84c 93.54  2.44c 96.78  0.87c
k (min
1) 0.0031 0.0048 0.0050 0.0059 0.0064 0.0074 0.0079
t1/2 (min) 223 144 138 117 108 93 87
R 0.9724 0.9490 0.9499 0.9340 0.9506 0.9326 0.9548

Photolysis % 8.03  3.87d 8.35  4.03d 9.25  3.89d 10.16  2.88d 11.18  3.45d 12.83  2.78d 13.63  3.65d
k (min
1) 0.00070 0.00072 0.00075 0.00077 0.00080 0.00085 0.00090
t1/2 (min) 990 963 924 900 866 815 770
R 0.9532 0.9678 0.9688 0.9702 0.9768 0.9789 0.9812

% = (abso
abs/abso)  100

k = plotting (ln Abs  100/Abso) vs irradiation time; t1/2 = ln2/k;
Catalyst concentration: 0.250 g L and pH 3.0;
Results expressed as means  standard deviations of the triplicate. Different letters in the same column imply values statistically different (P < 0.05) by Tukey test (ACTION,
2013).

are more difcult to be broken. Rodrigues et al. [42] reported that
the compounds with high electron density, which absorb at higher
wavelengths, are more susceptible to rapid attack by photo-
generated radicals, therefore are degraded at a higher speed.
The greater thermodynamic and kinetic efciency was found
for TiO2-P25, because of their relatively high surface area and the
thinner particle size of its particles. In addition, TiO2-P25 showed
lower bang gap energy, absorbing more effectively the energy
supplied by the lamp. However, the Ti-500 and Nb-500 catalysts
also proved to be efcient, which showed absorbance and COD
reductions close to that obtained for TiO2-P25.
TiO2-P25 is largely used commercially and was used as a
positive control in this work, because it is known that it shows high
photocatalytic activity. However, commercial TiO2 P25 is presented
as nanoparticles, making it difcult to industrial use, since
separation and reuse becomes impractical for large-scale appli-
cations, requiring additional investment with separation steps or
devising an appropriate photocatalyst immobilization strategy to
provide a cost-effective solidliquid separation [44]. The differen-
tial of this work is the particle size presented by Ti-500 and Nb-
500, which can be easily separated from the solution using a simple
ltration system with common lter paper, thus contributing to
sustainable development and economically viable for industrial
application, maintaining the photocatalytic activity similar to TiO2-
P25. There was a lower efciency both thermodynamic and
kinetics for Zn-500 (Table 3), indicating low photocatalytic activity,
which can be associated with the low surface area and the greater
pore diameter. Moreover, ZnO can often suffer photocorrosion
when subjected to UV radiation, reducing its photocatalytic
activity [32,45].
3.4.1. Mineralization
The results demonstrated that the textile efuent was
successfully degraded in 300 min of articial irradiation, proven
16 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917

Table 4
Final concentration of mineralized ions at the end of 300 min of articial irradiation of the textile efuent at pH 3.0 and catalyst concentration of 0.250 g L
1.*

Catalyst NH4+ (mg L
1) NO2
(mg L
1) NO3
(mg L
1) SO42
(mg L
1) Cl
(mg L
1)
in natura 2.39  0.07 0.066  0.003 1.46  0.13 42.07  0.07 287.5  27.5
Ti-500 5.98  0.27a 0.164  0.016a 3.99  0.44a 85.87  0.37a 687.5  12.5a
TiO2-P25 6.88  1.00a,c 0.205  0.008b 4.43  0.44a,c 139.62  0.15b 825.0  25.0b
Zn-500 6.56  0.18b 0.156  0.008a 3.76  0.66b 132.76  0.07c 712.5  12.5a
Nb-500 7.78  0.09a,c 0.173  0.008a,b 3.88  0.11a,c 103.34  0.59d 837.5  12.5b
*
Results expressed as means  standard deviations of the triplicate. Different letters in the same column imply values statistically different (P < 0.05) by Tukey test
(ACTION, 2013).

by the COD reduction and absorbance reduction. However, Table 5

mineralization itself can only be conrmed by the formation of
ions such as ammonium, nitrate, nitrite, sulfate and chloride,
which are the likely products of mineralization of the textile dyes,
since they are the most common heteroatoms in the structures of
them. The Table 4 shows the values of the inorganic ions
concentration formed after 300 min of articial irradiation.
It can be noted that the mineralization of textile efuents, based
on the initial values for the in natura textile efuent was efcient
for all catalysts. However, Ti-500 and Nb-500 had the highest
mineralization values, which are statistically equal and close to the
values obtained for TiO2-P25.
3.4.2. Ecotoxicity Artemia salina
The results of ecotoxicity tests, obtained by bioassays with
Artemia salina for textile treated wastewater samples are shown in
Fig. 10. From the linear regression it was possible to calculate the
lethal concentration (LC50) of the in natura textile efuents
(without treatment) and after the photocatalytic treatment, whose
values are shown in Table 5.
The Artemia salina mortality percentage varied with the
concentration of textile efuents. The highest mortality rate was
obtained for the in natura efuent, regardless of concentration. It
was found that the death rate was signicantly decreased after the
application of heterogeneous photocatalysis for all catalysts.
It was found that after the photodegradation of textile efuent
in the presence of TiO2-P25 the lethal concentration (LC50)
increased from 27.59% (in natura) to 90.86%. That is the highest
lethal concentration found, meaning that an efuent concentration
of approximately 3 times the in natura efuent is required for the
occurrence of 50% nauplii mortality, indicating that there was a
signicant decrease of toxic compounds after photodegradation.
The Nb-500 catalyst showed higher LC50 compared to Ti-500 after
Lethal concentration (LC50) for the in natura textile efuent and after 300 min of
photodegradation under articial irradiation at pH 3.0 and catalyst concentration of
0.250 g L
1.
Catalyst LC50 (%)
in natura 27.59
Ti-500 61.62
Zn-500 66.56
Nb-500 77.52
TiO2-P25 90.86
photodegradation of textile efuent, leading to a lethal concentra-
tion increase from 27.59% (in natura) to 77.52% for Nb-500 and
61.62% for Ti-500. Zn-500 also showed LC50 greater than the Ti-
500, reaching 66.56% of toxicity reduction, differently from the
results found for absorbance and COD reduction, which were lower
than the results achieved for Ti-500. The photocatalysis reduced
the textile efuent toxicity by up to 3 times in the presence of Nb-
500, indicating that there was no formation of intermediates and
toxic byproducts during the photodegradation process, showing
the efciency in reducing the toxic compounds and mineralizing
contaminants.
4. Conclusion
The results of the photodegradation of textile efuent under
articial light indicated that both kinetic and thermodynamic
efciency are affected by solution pH and catalyst concentration.
Under optimal conditions, pH 3.0 and catalyst concentration of
0.250 g L
1, Zn-500 had the lowest photocatalytic activity, while
higher values were obtained for Ti-500 and Nb-500. Bioassays with
Artemia salina conrmed the effectiveness of the treatment,
indicating that after photodegradation there was a signicant
decrease in efuent toxicity for up to 3 times. Therefore, the
photocatalysis efciently decreased the toxic organic load of the
efuent, with the best degradation results obtained for TiO2-P25.
However, the photocatalytic activity of Ti-500 and Nb-500
catalysts showed similar values to those found for TiO2-P25. The
use of TiO2-P25 is becoming impractical for industrial applications
on large scale due to nanometric particle size of its particles, which
complicates the process of separation and its possible reuse. Thus,
in view of the high photoactivity presented by Nb-500 under
favorable grain size, this can be an alternative to replace the
commercial TiO2-P25. Considering the applicability of TiO2 in the
industry as raw material and that Brazil is the largest Nb2O5
producer in the world, is possible to replace the TiO2 by the Nb2O5
in photocatalytic processes, maintaining the process efciency and
ensuring a more sustainable cycle.

Acknowledgements

Fig. 10. Percentages of Artemia salina mortality as a function of efuent

Authors thank CAPES, CNPq and Fundao Araucria for
concentration (&) in natura and after photodegradation with: (&) Ti-500; (*)
Zn-500; () Nb-500 and (~) TiO2-P25 at pH 3.0 and catalyst concentration of providing the nancial support to carry out this research work.
0.250 g L
1.
 R.P. Souza et al. / Journal of Photochemistry and Photobiology A: Chemistry 329 (2016) 917
References
[1] L.M.S. Colpini, G.G. Lenzi, M.B. Urio, D.M. Kochepka, H.J. Alves,
Photodiscoloration of textile reactive dyes on Ni/TiO2 prepared by the
impregnation method: effect of calcination temperature, J. Environ. Chem.
Eng. (2014), doi:http://dx.doi.org/10.1016/j.jece.2014.01.007.
[2] M.J. Hernndez-Rodrguez, C. Fernndez-Rodrguez, J.M. Don-Rodrguez, O.
M. Gonzlez-Daz, D. Zerbani, J. Prez Pen, Treatment of efuents from wool
dyeing process by photo-Fenton at solar pilot plant, J. Environ. Chem. Eng. 2
(2014) 163171, doi:http://dx.doi.org/10.1016/j.jece.2013.12.007.
[3] D. Gm, F. Akbal, Photocatalytic degradation of textile dye and wastewater,
Water Air Soil Pollut. 216 (2011) 117124, doi:http://dx.doi.org/10.1007/
s11270-010-0520-zl.
[4] N. Mathur, P. Bhatnagar, P. Nagar, M.K. Bijarnia, Mutagenicity assessment of
efuents from textile/dye industries of Sanganer, Jaipur (India): a case study,
Ecotoxicol. Environ. Saf. 61 (2005) 105113, doi:http://dx.doi.org/10.1016/j.
ecoenv.2004.08.003.
[5] A.K. Verma, R.R. Dash, P. Bhunia, A review on chemical coagulation/occulation
technologies for removal of colour from textile wastewaters, J. Environ. Manage.
93 (2012) 154168, doi:http://dx.doi.org/10.1016/j.jenvman.2011.09.012.
[6] M.T.F. de Souza, E. Ambrosio, C.A. Almeida, T.K.F.S. Freitas, L.B. Santos, V.C.
Almeida, J.C. Garcia, The use of a natural coagulant (Opuntia cus-indica) in
the removal for organic materials of textile efuents, Environ. Monit. Assess.
186 (2014) 52615271, doi:http://dx.doi.org/10.1007/s10661-014-3775-9.
[7] V. Khandegar, A.K. Saroha, Electrocoagulation for the treatment of textile
industry efuent: a review, J. Environ. Manage. 128 (2013) 949963, doi:http://
dx.doi.org/10.1016/j.jenvman.2013.06.043.
[8] A.M. Aljeboree, A.N. Alshiri, A.F. Alkaim, Kinetics and equilibrium study for
the adsorption of textile dyes on coconut shell activated carbon, J. Chem.
(2014), doi:http://dx.doi.org/10.1016/j.arabjc.2014.01.020.
[9] O. Pezoti Junior, A.L. Cazetta, I.P.A.F. Souza, K.C. Bedin, A.C. Martins, T.L. Silva, V.
C. Almeida, Adsorption studies of Methylene Blue onto ZnCl2-activated carbon
produced from Buriti shells (Mauritia exuosa L.), J. Ind. Eng. Chem. Korean
Soc. Ind. Eng. Chem. 20 (2014) 44014407, doi:http://dx.doi.org/10.1016/j.
jiec.2014.02.007.
[10] M. Liu, Z. L, Z. Chen, S. Yu, C. Gao, Comparison of reverse osmosis and
nanoltration membranes in the treatment of biologically treated textile
efuent for water reuse, Desalination 281 (2011) 372378. dx.doi.org/10.1016/
j.desal.2011.08.023.
[11] E. Forgacs, T. Cserhti, G. Oros, Removal of synthetic dyes from wastewaters: a
review, Environ. Int. 30 (2004) 953971, doi:http://dx.doi.org/10.1016/j.
envint.2004.02.001.
[12] N. Daneshvar, D. Salari, A.R. Khataee, Photocatalytic degradation of azo dye
acid red 14 in water on ZnO as an alternative catalyst to TiO2, J. Photochem.
Photobiol. A 162 (2004) 317322, doi:http://dx.doi.org/10.1016/S1010-6030
(03)00378-2.
[13] S.N.R. Inturi, M. Suidan, P.G. Smirniotis, Inuence of synthesis method on
leaching of the Cr-TiO2 catalyst for visible light liquid phase photocatalysis and
their stability, Appl. Catal. B: Environ. 180 (2016) 351361, doi:http://dx.doi.
org/10.1016/j.apcatb.2015.05.046.
[14] L.M.S. Colpini, H.J. Alves, O.A.A. Santos, C.M.M. Costa, Discoloration and
degradation of textile dye aqueous solutions with titanium oxide catalysts
obtained by the sol-gel method, Dyes Pigm. 76 (2008) 525529, doi:http://dx.
doi.org/10.1016/j.dyepig.2006.10.014.
[15] M.H. Habibi, A. Hassanzadeh, S. Mahdavi, The effect of operational parameters
on the photocatalytic degradation of three textile azo dyes in aqueous TiO2
suspensions, J. Photochem. Photobiol. A 172 (2005) 8996, doi:http://dx.doi.
org/10.1016/j.jphotochem.2004.11.009.
[16] O. Prieto, J. Fermoso, Y. Nuez, J.L. del Valle, R. Irusta, Decolouration of textile
dyes in wastewaters by photocatalysis with TiO2, Sol. Energy 79 (2005) 376
383, doi:http://dx.doi.org/10.1016/j.solener.2005.02.023.
[17] I.K. Konstantinous, T.A. Albanis, TiO2-assisted photocatalytic degradation of
azo dyes in aqueous solution: kinetic and mechanistic investigations: a review,
Appl. Catal. B-Environ. 49 (2004) 114, doi:http://dx.doi.org/10.1016/j.
apcatb.2003.11.010.
[18] A. Akyol, M. Bayramoglu, Photocatalytic degradation of remazol red F3 B using
ZnO catalyst, J. Hazard. Mater. B124 (2005) 241246, doi:http://dx.doi.org/
10.1016/j.jhazmat.2005.05.006.
[19] S. Sakthivel, B. Neppolian, M.V. Shankar, B. Arabindoo, M. Palanichamy, V.
Murugesan, Solar photocatalytic degradation of azo dye: comparison of
photocatalytic efciency of ZnO and TiO2, Sol. Energy Mater. Sol. C. 77 (2003)
6582, doi:http://dx.doi.org/10.1016/S0927-0248(02)00255-6.
[20] P. Peralta-Zamora, S.G. de Moraes, R. Pelegrini, M. Freire Jr., J. Reyes, H.
Mansilla, N. Duran, Evaluation of ZnO, TiO2 and supported ZnO on the
photoassisted remediation of black liquor, cellulose and textile mill efuents,
Chemosphere 36 (1998) 21192133, doi:http://dx.doi.org/10.1016/S0045-6535
(97)10074-1.
[21] A.G.S. Prado, L.B. Bolzon, C.P. Pedroso, A.O. Moura, L.L. Costa, Nb2O5 as efcient
and recyclable photocatalyst for indigo carmine degradation, Appl. Catal. B-
Environ. 82 (2008) 219224, doi:http://dx.doi.org/10.1016/j.
apcatb.2008.01.024.
[22] G. Huang, J. Chen, D. Wang, Y. Sun, L. Jiang, Y. Yu, J. Zhou, S. Ma, Y. Kang, Nb2O5/
ZnAl-LDH composites and its calcined products for photocatalytic degradation
of congo red under visible light irradiation, Mater. Lett. 173 (2016) 227230,
doi:http://dx.doi.org/10.1016/j.matlet.2016.03.073.
17
[23] M.K. Silva, R.G. Marques, N.R.C. Fernandes-Machado, O.A.A. Santos, Evaluation
of Nb2O5 and Ag/Nb2O5 in the photocatalytic degradation of dyes from textile
industries, Braz. J. Chem. Eng. 19 (2002) 359363, doi:http://dx.doi.org/
10.1590/S0104-66322002000400001.
[24] J. Yan, G. Wu, N. Guan, L. Li, Nb2O5/TiO2 heterojunctions: synthesis strategy and
photocatalytic activity, Appl. Catal. B-Environ. 152153 (2016) 280288, doi:
http://dx.doi.org/10.1016/j.apcatb.2014.01.049.
[25] R.E. Kalan, S. Yaparatne, A. Amirbahman, C.P. Tripp, P25 titanium dioxide
coated magnetic particles: preparation, characterization and photocatalytic
activity, Appl. Catal. B: Environ. 187 (2016) 249258, doi:http://dx.doi.org/
10.1016/j.apcatb.2016.01.008.
[26] JCPDS Joint Commite on Powder Diffraction Standars, International Center of
Diffraction Data, Pensilvnia, USA, (CDROM) (1995).
[27] D. Prahas, Y. Kartika, N. Indraswati, S. Ismadji, Activated carbon from jackfruit
peel waste by H3PO4 chemical activation: pore structure and surface chemistry
characterization, Chem. Eng. J. 140 (2008) 3242, doi:http://dx.doi.org/
10.1016/j.cej.2007.08.032.
[28] A.M. Ferrari-Lima, R.G. Marques, N.R.C. Fernandes-Machado, M.L. Gimenes,
Photodegradation of petrol station wastewater after coagulation/occulation
with tannin-based coagulant, Catal. Today 209 (2013) (2013) 7983, doi:
http://dx.doi.org/10.1016/j.cattod.2012.10.022.
[29] APHA American Public Health Association, Standard Methods for the
Examination for Water and Wastewater, 20th ed., AWWA, WPCF, Washington,
D. C, 1999.
[30] J.C. Garcia, J.A. Simionato, A.E.C. Silva, J. Nozaki, N.E. Souza, Solar photocatalytic
degradation of real textile efuents by associated titanium dioxide and
hydrogen peroxide, Sol. Energy 83 (2009) 316322, doi:http://dx.doi.org/
10.1016/j.solener.2008.08.004.
[31] J.C. Garcia, T.K.F.S. Freitas, S.M. Palcio, E. Ambrsio, M.T.F. Souza, L.B. Santos, V.
C. Almeida, N.E. Souza, Toxicity assessment of textile efuents treated by
advanced oxidative process (UV/TiO2 and UV/TiO2/H2O2) in the species
Artemia salina L, Environ. Monit. Assess. 185 (2013) 21792187, doi:http://dx.
doi.org/10.1007/s10661-012-2698-6.
[32] R. Velmurugan, K. Selvam, B. Krishnakumar, M. Swaminathan, An efcient
reusable and antiphotocorrosive nano ZnO for the mineralization of Reactive
Orange 4 under UV-A light, Sep. Purif. Technol. 80 (2011) 119124, doi:http://
dx.doi.org/10.1016/j.seppur.2011.04.018.
[33] J. Han, Y. Liu, N. Singhal, L. Wang, W. Gao, Comparative photocatalytic
degradation of estrone in water by ZnO and TiO2 under articial UVA and solar
irradiation, Chem. Eng. J. 213 (2012) 150162, doi:http://dx.doi.org/10.1016/j.
cej.2012.09.066.
[34] G. Wang, L. Xu, J. Zhang, T. Yin, D. Han, Enhanced photocatalytic activity of TiO2
Powders (P25) via calcination treatment, Int. J. Photoenergy 2012 (2012) 19,
doi:http://dx.doi.org/10.1155/2012/265760.
[35] C. Garca-Sancho, J.M. Rubio-Caballero, J.M. Mrida-Robles, R. Moreno-Tost, J.
Santamara-Gonzlez, P. Maireles-Torres, Mesoporous Nb2O5 as solid acid
catalyst for dehydration of d-xylose into furfural, Catal. Today (2014), doi:
http://dx.doi.org/10.1016/j.cattod.2014.02.012.
[36] C. Su, B.Y. Hong, C.M. Tseng, Solgel preparation and photocatalysis of titanium
dioxide, Catal. Today 96 (2004) 119126, doi:http://dx.doi.org/10.1016/j.
cattod.2004.06.132.
[37] J.M. Jehng, I.E. Wachs, Structural chemistry and raman spectra of niobium
oxides, Chem. Mater. 3 (1991) 100107, doi:http://dx.doi.org/10.1021/
cm00013a025.
[38] S. Malato, P. Fernndez-Ibez, M.I. Maldonado, J. Blanco, W. Gernjak,
Decontamination and disinfection of water by solar photocatalysis: recent
overview and trends, Catal. Today 147 (2009) 159, doi:http://dx.doi.org/
10.1016/j.cattod.2009.06.018.
[39] L.B. Bolzon, A.G.S. Prado, Effect of protonation and deprotonation on surface
charge density of Nb2O5, J. Therm. Anal. Calorim. 106 (2011) 427430, doi:
http://dx.doi.org/10.1007/s10973-011-1316-0.
[40] U.G. Akpan, B.H. Hameed, Parameters affecting the photocatalytic degradation
of dyes using TiO2-based photocatalysts: a review, J. Hazard. Mater. 170 (2009)
520529, doi:http://dx.doi.org/10.1016/j.jhazmat.2009.05.039.
[41] P.A. Pekakis, N.P. Xekoukoulotakis, D. Mantzavinos, Treatment of textile dye
house wastewater by TiO2 photocatalysis, Water Res. 40 (2006) 12761286,
doi:http://dx.doi.org/10.1016/j.watres.2006.01.019.
[42] A.C. Rodrigues, M. Boroski, N.S. Shimada, J.C. Garcia, J. Nozaki, N. Hioka,
Treatment of paper pulp and paper mill wastewater by coagulation?
occulation followed by heterogeneous photocatalysis, J. Photochem.
Photobiol. A 194 (2008) 110, doi:http://dx.doi.org/10.1016/j.
jphotochem.2007.07.007.
[43] B. Neppolian, H.C. Choi, S. Sakthivel, B. Arabindoo, V. Murugesan, Solar light
induced and TiO2 assisted degradation of textile dye reactive blue 4,
Chemosphere 46 (2002) 11731181, doi:http://dx.doi.org/10.1016/S0045-6535
(01)00284-3.
[44] S. Dong, J. Feng, M. Fan, Y. Pi, L. Hu, X. Han, M. Liu, J. Sun, J. Sun, Recent
developments in heterogeneous photocatalytic water treatment using visible
light-responsive photocatalysts: a review, RSC Adv. 5 (2015) 1461014630, doi:
http://dx.doi.org/10.1039/c4ra13734e.
[45] X. Wu, L. Wen, K. Lv, K. Deng, D. Tang, H. Ye, D. Du, S. Liu, M. Li, Fabrication of
ZnO/graphene ake-like photocatalyst with enhanced photoreactivity, Appl.
Surf. Sci. 358 (2015) 130136, doi:http://dx.doi.org/10.1016/j.
apsusc.2015.08.061.