Article

Photocatalytic Decolorization of Dye with

Self-Dye-Sensitization under Fluorescent
Light Irradiation
Md. Ashraful Islam Molla 1, *, Mai Furukawa 1 , Ikki Tateishi 1 , Hideyuki Katsumata 1 ,
Tohru Suzuki 2 and Satoshi Kaneco 1,2
1 Department of Chemistry for Materials, Graduate School of Engineering, Mie University,
Tsu 514-8507, Japan; maif@chem.mie-u.ac.jp (M.F.); teishi@gmail.com (I.T.); hidek@chem.mie-u.ac.jp (H.K.);
kaneco@chem.mie-u.ac.jp (S.K.)
2 Mie Global Environment Center for Education & Research, Mie University, Tsu 514-8507, Japan;
suzuki@chem.mie-u.ac.jp
* Correspondence: professoraislam@gmail.com; Tel.: +81-59-231-9427

Received: 10 August 2017; Accepted: 30 September 2017; Published: 5 October 2017

Abstract: A dye-sensitization technique was applied to effective catalysts—TiO2 and ZnO—under

fluorescent light irradiation for Orange II (OII) and Methyl Orange (MO) degradations. Treatments
were carried out at different time periods using 20 mg of catalysts and 30 mL of 5 mg/L of OII and
MO. The degradation efficiency of OII and MO increased with increasing irradiation time under
irradiation of fluorescent light. The photocatalytic activity of ZnO nanoparticles was better compared
with that of TiO2 for MO; and the ZnO activity was the same as TiO2 for OII photodegradation.
Kinetic behavior was evaluated in terms of the Langmuir–Hinshelwood model (pseudo-first order
kinetic). The possible mechanism of photodegradation under fluorescent light was discussed.

Keywords: photocatalytic degradation; fluorescent light; self-dye-sensitization; ZnO; TiO2

1. Introduction
Titanium dioxide (TiO2 ) and zinc oxide (ZnO) have drawn great attention, because they have
become one of the most effective photocatalysts in the mineralization of toxic organic substances,
owing their virtues of low cost, highly chemical stability, and nontoxicity [1,2]. However, these catalysts
can only be excited by the irradiation of UV light, due to their wide band gaps. An artificial light
source, for instance an Hg-Xe lamp, is particularly expensive, whereas a fluorescent lamp is cheap, has
a longer life time, and uses less energy. The UV region occupies only a small fraction of a fluorescent
lamp’s spectrum. This problem can be solved only by improving the light absorption capacity of
photocatalysts [3,4]. Photocatalysts can be modified in order to expand their photoresponse to the
visible region for pollutant degradation with several ways, including the doping with cations/anions
or the coupling with another small band gap materials [5]. Most of these methods, however, are
time-consuming and quite expensive. Dye sensitization, on the other hand, is a simpler method that
can extend catalysts activation to longer wavelengths compared with those corresponding to its band
gap. Dye sensitization begins with electron injection into the conduction band (CB) of a photocatalyst
from the excited dye, followed by interfacial electron transfer [6,7].
Recently, the self-sensitized degradation of dye under visible light irradiation has been
investigated. Wu et al. [8] studied self-photosensitized oxidative decolorization of rhodamine B under
visible light irradiation in TiO2 dispersions with a halogen lamp and cutoff filter. The photosensitized
degradation of a textile azo dye with TiO2 using visible light with a fiber optic illuminator was reported
by Vinodgopal and Kamat [9]. Xing et al. [10] studied the enhanced self-sensitized degradation of

ChemEngineering 2017, 1, 8; doi:10.3390/chemengineering1020008 www.mdpi.com/journal/chemengineering

ChemEngineering 2017, 1, 8 2 of 10

colored pollutants under visible light with a mercury lamp and filter. The photocatalytic performance
of ZnO for self-sensitized degradation of malachite green under solar light was investigated by
Saikia et al. [11]. According to our knowledge, there is little information on the photocatalytic
decolorization of dye in water with self-dye-sensitized photocatalysts under room fluorescent light
irradiation with very weak intensity.
The present work deals with photocatalytic decolorization of dye in water with self-dye-sensitized
TiO2 and ZnO under room fluorescent light irradiation.

2. Materials and Methods

2.1. Materials
All reagents were of analytical grade and were used without further treatment. Orange II and
methyl orange used in this study were purchased from Nacalai Tesque Inc., Kyoto, Japan (grade >99%).
TiO2 powder (P25, purity 99.9%) was obtained from Degussa Co., Essen, Germany. ZnO was purchased
from Sigma-Aldrich, St. Louis, MO, USA. Ultrapure water (18 MΩ cm) was prepared by an ultrapure
water system (Advantec MFS Inc., Tokyo, Japan). The detailed experimental conditions were shown in
Table 1.

Table 1. Experimental conditions.

Orange II (5 mg/L,30 mL)

Samples
Methyl orange (5 mg/L, 30 mL)
P25 TiO2 (20 mg)
Photocatalyst
Aldrich ZnO (20 mg)
Temperature Room temperature (25 ◦ C)
pH 6
450 nm LED light (5.14 mW/cm2 )
Light source
Fluorescent light (0.034 mW/cm2 )
λmax Orange II (485 nm), methyl orange (464 nm)
Irradiation time 6h

2.2. Characterization of Photocatalyst

In order to record the diffraction patterns of photocatalysts (TiO2 and ZnO), the powder X-ray
diffractometer (XRD, RIGAKU Ultima IV, sample horizontal type) was used in the condition of Cu
Kα radiation of wavelength 0.15406 nm with tube current of 50 mA at 40 kV in 2θ angle range from
10◦ to 80◦ with a scan speed of 4◦ /min and a step size of 0.02◦ . Figure S1 shows the X-ray diffraction
(XRD) pattern of TiO2 . Because P25 is a mixture of 20% rutile and 80% anatase, XRD pattern shows
both anatase and rutile lines [12]. Figure S2 illustrates the XRD of ZnO. Three main distinct peaks at
31.76◦ , 34.42◦ , and 36.26◦ are observed in the patterns, which are indexed to the (100), (002), and (101)
diffractions of the wurtzite ZnO, respectively [13]. The particle size of the TiO2 and ZnO have been
obtained from the full width at half maximum (FWHM) of the most intense peaks of the respective
crystals using the Scherrer equation, D = 0.9λ/βcosθ, where λ is the X-ray wavelength, D the average
crystallite size, θ the Bragg diffraction angle, and β the full width at half-maximum. The crystal size of
TiO2 and ZnO could be estimated as ~21 and ~38 nm, respectively.
The diffuse reflectance spectra (DRS) of photocatalysts were checked over a range of 200–800 nm
using a Shimadzu UV-2450 UV–vis system equipped with an integrating sphere diffuse reflectance
accessory with the reference material BaSO4 . The diffuse reflectance spectra of the TiO2 and ZnO
samples were studied, as shown in Figures S3 and S4. The reflectance data was converted to
Kubelka–Munk equation which is expressed as F(R) = (1 − R)2 /2R. The optical band gap of TiO2 was
deduced by extrapolating the straight linear portion of the plot of [F(R)hυ]0.5 versus the photon energy
ChemEngineering 2017, 1, 8 3 of 10

(hυ) to the phonon energy axis, which is shown in the interior of Figure S3. The band gap of ZnO was
estimated from the Tauc plot of [F(R)hυ]2 versus photon energy, which is presented in the interior of
FigureChemEngineering
S4. 2017, 1, 8 3 of 10

2.3. Evaluation of Photocatalytic

ZnO was estimated from theActivity
Tauc plot of [F(R)hυ]2 versus photon energy, which is presented in the
interior of Figure S4.
The photodegradation system is illustrated in Figure S5. The photocatalytic activities of TiO2
and ZnO were checked
2.3. Evaluation by the decolorization
of Photocatalytic Activity of two typical azo dyes, orange II (OII) and methyl
orange (MO), under 450 nm LED light and fluorescent light irradiation. The photocatalytic reactions
The photodegradation system is illustrated in Figure S5. The photocatalytic activities of TiO2
were performed in a Pyrex glass reactor. The catalyst powder (20 mg) was suspended in 30 mL
and ZnO were checked by the decolorization of two typical azo dyes, orange II (OII) and methyl
of dyeorange
solutions
(MO),withunder 5 450
mg/L nm without
LED lightadjustment
and fluorescent of pH.
lightThe luminous
irradiation. Theintensities
photocatalyticwere measured
reactions
by a LI-COR light sensor (LI-250A), and were 5.1 mW/cm 2 for LED lamp and 0.034 mW/cm2 for
were performed in a Pyrex glass reactor. The catalyst powder (20 mg) was suspended in 30 mL of
fluorescent light, respectively.
dye solutions with 5 mg/L The adsorption
without adjustmentexperiment
of pH. The was conducted
luminous with aluminum
intensities were measured foil coverage
by a
to block the impact
LI-COR of radiation.
light sensor (LI-250A), Prior
andtowere
light5.1
illumination,
mW/cm2 forthe LED catalyst
lamp suspension
and 0.034 mW/cm was dispersed
2 for

fluorescentstirrer
by a magnetic light, for
respectively.
30 min inThe adsorption
the dark, experiment
to achieve was conducted
adsorption equilibrium.with During
aluminum foil
irradiation,
coverage to block the impact of radiation. Prior to light illumination, the catalyst
the catalyst was kept in suspension state by a magnetic stirrer. After the illumination, the catalyst was suspension was
dispersed
separated throughby athemagnetic
Advantec stirrer for 30 minfilter
membrane in the dark,
0.45 µm. to The
achieve adsorption
catalysts couldequilibrium. During by
be almost removed
irradiation, the catalyst was kept in suspension state by a magnetic stirrer. After the illumination, the
the filtration. The concentration of dye was measured using a UV–visible spectrometry (UV-1650PC,
catalyst was separated through the Advantec membrane filter 0.45 μm. The catalysts could be almost
SHIMADZU Co., Tokyo, Japan). According to Beer–Lambert law, the relative concentration (C/C0 )
removed by the filtration. The concentration of dye was measured using a UV–visible spectrometry
of the(UV-1650PC,
OII solutionSHIMADZU
was calculated Co.,byTokyo,
the relative
Japan).absorbance
According (A/A 0 ) at 485 nm,law,
to Beer–Lambert wheretheArelative
0 and A are
the absorbance
concentration of the
(C/COII
0) ofsolution at the beginning
the OII solution timeby
was calculated (t0the
) ofrelative
photocatalytic treatment
absorbance (A/A0) atand
485 at
nm,time t,
respectively.
where AThe 0 and photodegradation
A are the absorbance of OII under
of the OII fluorescent
solution at the light irradiation
beginning timewas
(t0) similar to that under
of photocatalytic
visibletreatment
light irradiation
and at time except for the light
t, respectively. Thesource. The photodegradation
photodegradation of MO (5 light
of OII under fluorescent mg/L) was similar
irradiation
was similar to that under visible light irradiation
to that of OII except that the detection wavelength was 464 nm. except for the light source. The photodegradation
of MO (5 mg/L) was similar to that of OII except that the detection wavelength was 464 nm.
3. Results and Discussion
3. Results and Discussion
3.1. UV–Visible Analysis
3.1. UV–Visible Analysis
The temporal absorption spectral changes during the photocatalytic decolorization of OII and
The temporal absorption spectral changes during the photocatalytic decolorization of OII and
MO with TiO2 and ZnO under fluorescent and 450 nm light illuminations were investigated, as shown
MO with TiO2 and ZnO under fluorescent and 450 nm light illuminations were investigated, as
in Figures 1 and 2, respectively. As they can be seen, the intensities of the peak at 485 and 464 nm
shown in Figures 1 and 2, respectively. As they can be seen, the intensities of the peak at 485 and 464
progressively decreased
nm progressively with increasing
decreased irradiation
with increasing time uptime
irradiation to 360
upmin. Themin.
to 360 well-defined absorption
The well-defined
bandsabsorption
decreasedbands
afterdecreased
irradiation forirradiation
after 360 min, for
indicating
360 min,that OII and
indicating thatMO
OIIhad
and been decolored
MO had been in
the presence of TiO and ZnO with fluorescent light and 450 nm LED light irradiation.
decolored in the2presence of TiO2 and ZnO with fluorescent light and 450 nm LED light irradiation.Therefore,
the self-dye-sensitization was very effective
Therefore, the self-dye-sensitization foreffective
was very the decolorization of OII and
for the decolorization of MO under
OII and MOfluorescent
under
fluorescent
and 450 nm lightand 450 nm light illuminations.
illuminations.

0.8 0.8
0 min
a) TiO2 0 min b) ZnO fluorescent light
fluorescent light
0.6 450 nm 0.6 450 nm
Absorbance
Absorbance

0.4 0.4

0.2 0.2

0 0
200 400 600 800 200 400 600 800
Wavelenght (nm) Wavelenght (nm)

Figure
Figure 1. UV–visible
1. UV–visible spectra
spectra ofofaqueous
aqueous solutions
solutions ofofOII
OIIforfor
0 min andand
0 min 360 min
360 using (a) TiO(a)
min using 2 and (b)
TiO 2 and
ZnO under fluorescent and 450 nm LED lights.
(b) ZnO under fluorescent and 450 nm LED lights.
ChemEngineering 2017, 1, 8 4 of 10
ChemEngineering 2017, 1, 8 4 of 10

ChemEngineering 2017, 1, 8 4 of 10
0.8 0.8
0 min
0.8 a) TiO2 0 min
0.8 b) ZnO fluorescent light
fluorescent light 0 min
0.6 a) TiO2 0 min
450 nm 0.6
b) ZnO 450 nm
fluorescent light
fluorescent light
450 nm

Absorbance
0.6 450 nm 0.6
Absorbance

Absorbance
0.4 0.4
Absorbance

0.4 0.4
0.2 0.2
0.2 0.2
0 0
0200 400 600 800
0200 400 600 800
Wavelenght (nm) Wavelenght (nm)
200 400 600 800 200 400 600 800
Wavelenght (nm) Wavelenght (nm)
Figure
Figure 2. UV–visible
2. UV–visible spectra
spectra ofofaqueous
aqueous solutions
solutions ofofMO
MOforfor
0 min andand
0 min 360 min
360using (a) TiO(a)
min using 2 and (b)2 and
TiO
ZnO
(b) ZnO under
under
Figure fluorescent
fluorescent
2. UV–visible and
andLED
spectraLED lights.
lights.solutions of MO for 0 min and 360 min using (a) TiO2 and (b)
of aqueous
ZnO under fluorescent and LED lights.
3.2. Photocatalytic Decolorization of OII and MO with TiO2
3.2. Photocatalytic Decolorization of OII and MO with TiO2
3.2. Photocatalytic
The effect ofDecolorization of OIIon
irradiation time andphotocatalytic
MO with TiO2 decolorization of dye (OII and MO) was
The effect of irradiation time on photocatalytic decolorization of dye (OII and MO) was performed
performed by measuring
The effect the percentage
of irradiation of dye removaldecolorization
time on photocatalytic at different periods
of dyeunder
(OIIfluorescent
and MO) and was
by measuring
450 nm LED thelights,
percentageas shown of dye removal
in Figure 3a,b, atrespectively.
different periods under fluorescent and
MO 450 nm LED
performed by measuring the percentage of dye removal atThe percentage
different periodsof under
OII and removal
fluorescent and
lights,increased
as shown within an
Figure
increase3a,b,in respectively.
irradiation The percentage of OII and MO removal increased with
450 nm LED lights, as shown in Figure time,
3a,b, and reached up
respectively. Thetopercentage
about 61% and
of 24%
OII andforMO
fluorescent
removal
an increase
light in irradiation
and
increased aboutan88%
with time,
and in
increase and
41% reached
for up to
LEDtime,
irradiation light about
after
and 6 61%
reached upand 24% for
h, respectively.
to about fluorescent
The
61% 24% forlight
adsorption
and and about
(removal)
fluorescent
88% and light41%
andfor
percentage ofLED
aboutOII 88%light
on TiO after
and 6 h,for
2 particles
41% respectively.
was
LEDlarge up The
light to 30adsorption
after 6min, whereas(removal) Thepercentage
MO adsorption
h, respectively. of
was very
adsorption OII on TiO2
little.
(removal)
There
particles waswas
percentagelargelittle
of up change
OII to
on30TiO 2 in
min, the OII
whereas
particles wasand
MOlarge MOup solutions
adsorption wasduring
to 30 min, photolysis.
very little.
whereas MO There The little
was
adsorption photocatalytic
was change
very in the
little.
decolorization
OII and MOwas
There solutions processes of both
duringinphotolysis.
little change dyes
the OII andunder
TheMO LED light
photocatalytic were
solutions during more effective
decolorization compared
photolysis. processes with those
of both dyes
The photocatalytic
underobtained
LED lightunder
decolorization were fluorescent
processes oflight
more effective bothradiation.
dyes under
compared TheseLEDfacts
with may
light
those be due
were more
obtained to under
the light
effective intensity,
comparedbecause
fluorescent with those
light the
radiation.
amounts of electron–hole pairs are dependent on them [14].
Theseobtained
facts may under
be due fluorescent
to the lightlightintensity,
radiation.because
These facts
themay be dueoftoelectron–hole
amounts the light intensity,
pairsbecause the
are dependent
amounts
on them [14]. of electron–hole pairs are dependent on them [14].
a) b)
a) 1 1
photolysis b)
1 dark
1
0.8 photolysis 0.8
fluorescent light
dark
0.8 LED (450 nm) 0.8
fluorescent light
0.6
0

LED (450 nm) 0.6

0
C/CC/C

C/CC/C

photolysis
0.6
0

0.6
0

dark
photolysis
0.4 0.4 fluorescent
dark light
0.4 0.4 LED (450 nm)light
fluorescent
0.2 0.2
Dark Irradiation Dark IrradiationLED (450 nm)
0.2 0.2
Dark Irradiation Dark Irradiation
0 0
0 -60 0 60 120 180 240 300 360
0 -60 0 60 120 180 240 300 360
-60 0 60 Time (min)240 300 360
120 180 -60 0 Time
60 120 (min)
180 240 300 360
Time (min) Time (min)
Figure 3. Time courses of concentration of orange II (a) and methyl orange (b). Photolysis: ♦, TiO2
dispersions: under
Figure 3. Time dark ■,
courses of under fluorescent
concentration of orange II (a) and▲
light irradiation and under
methyl LED
orange (b).light irradiation
Photolysis: ●. 2
♦, TiO
Figure 3. Time courses of concentration of orange II (a) and methyl orange (b). Photolysis: , TiO2
dispersions:
dispersions: underunder
darkdark ■, under
, under fluorescentlight
fluorescent irradiation ▲
light irradiation N and
andunder
underLED
LEDlight irradiation
light ●. •.
irradiation
3.3. Photocatalytic Decolorization of OII and MO with ZnO
3.3. Photocatalytic
Figure 4a,b Decolorization
shows of OII and MO
the percentage with ZnO
3.3. Photocatalytic Decolorization of OII and of
MOdyewith
(OIIZnO
and MO) in the presence of ZnO nanopowders
underFigure
fluorescent light and
4a,b shows the 450 nm LEDof
percentage light.
dyeAbout 57%MO)
(OII and and in
28%thedegradation
presence ofofZnO
OII and MO took
nanopowders
Figure
place 4a,b showsfluorescent
underatfluorescent
6 h under the percentage
light and 450 nm of
light, LEDdye
whereas(OII and43%
about
light. About MO) in
and
57% the
10%
and presence
was
28% of ZnO
eliminated
degradation nanopowders
under
of OII 450 MO
and nm LEDunder
took
fluorescent
place atlight and 450
6 h under nm LEDlight,
fluorescent light. Aboutabout
whereas 57% 43%
andand
28%10%
degradation of OII
was eliminated and450
under MOnm
took
LEDplace
at 6 h under fluorescent light, whereas about 43% and 10% was eliminated under 450 nm LED light.
Negligible decolorization occurred in the presence of fluorescent light and 450 nm LED light without
any catalyst, as shown in Figure S6a,b. Without the presence of either photocatalysts (TiO2 and ZnO)
 ChemEngineering 2017, 1, 8 5 of 10

light. Negligible decolorization occurred in the presence of fluorescent light and 450 nm LED light
ChemEngineering 2017, 1, 8 5 of 10
without any catalyst, as shown in Figure S6a,b. Without the presence of either photocatalysts (TiO2
and ZnO) or the light (fluorescent and 450 nm) radiation, little change in the absorbance values was
or theobserved. The adsorption
light (fluorescent and (removal) percentage little
450 nm) radiation, of OIIchange
on TiO2in
and ZnO
the particles was
absorbance large,was
values whereas
observed.
adsorption of MO on the same photocatalyst was very little in the time range. This weaker
The adsorption (removal) percentage of OII on TiO2 and ZnO particles was large, whereas adsorption
adsorption process of methyl orange compared to the OII dye could be due to the MO molecule
of MO on the same photocatalyst was very little in the time range. This weaker adsorption process
having only one SO3− group while the OII molecule has one SO3− and one OH group. These
of methyl orange compared to the OII dye could be due to the MO molecule having only one SO −
observations reveal that visible light and a photocatalyst are needed for effective decolorization of 3
while the OII molecule has one SO3 − and one OH group. These observations reveal that visible
groupdye.
light and a photocatalyst are needed for effective decolorization of dye.

a) b)
1 1

0.8 0.8
photolysis
0.6 0.6 dark
C/C0

photolysis

C/C0
fluorescent light
dark
0.4 fluorescent light 0.4 LED (450 nm)

LED (450 nm)

0.2 0.2 Dark Irradiation
Dark Irradiation

0 0
-60 0 60 120 180 240 300 360 -60 0 60 120 180 240 300 360
Time (min) Time (min)

Figure 4. Time
Figure courses
4. Time of concentration
courses of concentrationofoforange
orange IIII (a) and methyl
(a) and methylorange
orange (b).
(b). Photolysis:
Photolysis: , ZnO
♦, ZnO
dispersions: under
dispersions: dark
under , ■,
dark under
underfluorescent
fluorescent light irradiation▲Nand
light irradiation andunder
under LED
LED light
light ●. •.
irradiation
irradiation

3.4. Kinetic
3.4. Kinetic Analysis
Analysis
The The photocatalytic oxidation process for many organic contaminants has often been modeled
photocatalytic oxidation process for many organic contaminants has often been modeled
with the Langmuir–Hinshelwood (L–H) equation, which also covers the adsorption properties of the
with the Langmuir–Hinshelwood (L–H) equation, which also covers the adsorption properties of
substrate on the photocatalyst surface. This model was developed by Turchi and Ollis [15] and
the substrate on the photocatalyst surface. This model was developed by Turchi and Ollis [15] and
expressed as Equation (1)
expressed as Equation (1):
d𝐶 𝑘𝐾𝐶
r0 𝑟=
0 =
dC
−− d𝑡 == kKC (1)
(1)
1 + 𝐾𝐶
dt 1 + KC
where r0 is the degradation rate of the reactant, k is the reaction rate constant, and K and C are the
where r0 is the degradation rate of the reactant, k is the reaction rate constant, and K and C are the
adsorption equilibrium constant and concentration for the reactant, respectively. If the concentration
adsorption equilibrium constant and concentration for the reactant, respectively. If the concentration
of reactant is very low, i.e., KC << 1, the L–H equation (Equation (1)) simplifies to a
of reactant
pseudo-first-order i.e., KClaw
is very low,kinetic <<(Equation
1, the L–H
(2))equation
where kobs(Equation (1))
is being the simplifies
apparent to a pseudo-first-order
pseudo-first-order rate
kinetic law (Equation (2)) where kobs is being the apparent pseudo-first-order rate constant.
constant.
d𝐶
dC (2)
−− d𝑡 =
= 𝑘𝐾C
kKC==𝑘obs
kobs𝐶C (2)
dt
Integration of the above equation with the limit of C = C0 at t = 0 with C0 gives the equation
Integration of the above equation with the limit of C = C0 at t = 0 with C0 gives the equation:
𝐶
−Ln = 𝑘obs 𝑡 (3)
𝐶C0
− Ln = kobs t (3)
C0
The primary degradation reaction is estimated to follow a pseudo first-order kinetic law,
according to Equation (3). In order to confirm the speculation, Ln(C/C0) was replotted as a function
The primary degradation
of illumination time for OII reaction is estimated
and MO shown to follow
in Figures 5 anda6,pseudo first-order
respectively. kinetic
Because law, according
the linear plots
to Equation (3). In
were observed order to the
as expected, confirm
kineticsthe speculation,
of OII Ln(C/C
and MO in the ) was
TiO 2 suspension
0 replotted
solution as a function
followed the of
illumination time for OII and MO shown in Figures 5 and 6, respectively. Because the linear plots
were observed as expected, the kinetics of OII and MO in the TiO2 suspension solution followed the
first-order degradation curve, which agreed with the L–H model resulting from the low coverage in
the experimental concentration range (5 mg/L).
 ChemEngineering
ChemEngineering 2017,
2017, 1,
1, 88 66 of
of 10
10

first-order
first-order degradation
degradation curve,
curve, which
which agreed
agreed with
with the
the L–H
L–H model
model resulting
resulting from
from the
the low
low coverage
coverage in
in
ChemEngineering 2017, 1, 8 concentration range (5 mg/L).
the experimental 6 of 10
the experimental concentration range (5 mg/L).

a) b)
b)
a) 0
0
0
0

-0.4 -0.4
-0.4
-0.4

Ln(C/C00))
Ln(C/C
Ln(C/C00))

-0.8
-0.8 -0.8
-0.8
Ln(C/C

photolysis photolysis
photolysis
-1.2 photolysis -1.2
-1.2 dark
-1.2 dark
dark dark
fluorescent fluorescent
fluorescent light
-1.6
-1.6 fluorescent light
light -1.6
-1.6
light
LED LED (450 nm)
LED (450
(450 nm)
nm) LED (450 nm)
-2
-2 -2
-2
0
0 60
60 120
120 180
180 240
240 300
300 360
360 0
0 60
60 120
120 180
180 240
240 300
300 360
360
Time
Time (min) Time
(min) Time (min)
(min)
Figure
Figure 5.
5. Kinetic
5. Kinetic plotplot
Kinetic plot of
of Ln(C/C
Ln(C/C
of Ln(C/C 0) versus irradiation time for the photocatalytic degradation of orange
) versusirradiation
irradiation time
timefor
forthe
thephotocatalytic degradation of orange
Figure 0 ) 0versus photocatalytic degradation of orange
II.
II. (a)
(a) TiO
TiO 2, (b) ZnO.
, (b) ZnO.
II. (a) TiO2 , (b) ZnO.
2

a)
a) b)
b)
0
0 0
0

-0.1
-0.1 -0.1
-0.1
Ln(C/C00))

-0.2
-0.2 -0.2
Ln(C/C00))

-0.2
Ln(C/C
Ln(C/C

photolysis
photolysis
photolysis
photolysis
-0.3
-0.3 -0.3 dark
dark
dark -0.3 dark
fluorescent fluorescent
fluorescent light
light
fluorescent light
light
-0.4
-0.4 -0.4 LED
LED (450
(450 nm)
nm)
LED
LED (450
(450 nm)
nm) -0.4
-0.5
-0.5 -0.5
-0.5
0
0 60
60 120
120 180
180 240
240 300
300 360
360 0
0 60
60 120
120 180
180 240
240 300
300 360
360
Time
Time (min)
(min) Time
Time (min)
(min)
Figure 6. Kinetic
Figure
Figure 6. plotplot
6. Kinetic
Kinetic of Ln(C/C
plot of 0 ) 00versus
of Ln(C/C
Ln(C/C versusirradiation
)) versus irradiation timefor
irradiation time
time forthe
for thephotocatalytic
the photocatalytic
photocatalytic degradation
degradation
degradation of of methyl
of methyl
methyl
orange. (a)
orange.TiO
(a) , (b)
TiO 2, ZnO.
(b) ZnO.
orange. (a) 2TiO2, (b) ZnO.

The photocatalytic decolorization kinetic parameters such as pseudo-first-order rate constant,

The photocatalytic decolorizationkinetic
kinetic parameters
parameters such
The photocatalytic decolorization suchasaspseudo-first-order
pseudo-first-order rate rate
constant,
constant,
correlation
correlation coefficient,
coefficient, and
and substrate
substrate half-life
half-life are
are shown
shown inin Table
Table 2.
2. The
The values
values of
of rate
rate constants
constants have
have
correlation
been coefficient, and substrate half-life are shown in Table 2. The values of rate constants have
been determined
determined from
from the
the slope
slope of
of these
these plots.
plots. As
As shown
shown in in Table
Table 2,
2, the
the rate
rate constant
constant values
values kkobs
obs
been (min
determined from the slope of these plots. As shown in Table 2, the rate constant values kobs
(min−1) were lower in
−1) were lower
in fluorescent
fluorescent light
light compared
compared withwith that
that under
under LED
LED light
light for
for both
both dyes.
dyes.
− 1
(min ) were lower in fluorescent light compared with that under LED light for both dyes.
Table
Table 2.
2. Rate
Rate constants,
constants, R
R2,, and
2
and half-life
half-life values
values of
of OII
OII and
and MO
MO dyes
dyes using
using TiO
TiO22 and
and ZnO.
ZnO.
Table 2. Rate constants, R2 , and half-life values of OII and MO dyes using TiO2 and ZnO.
k
kobs (min−1)
obs (min−1)
R2
R2 tt1/2 (min)
1/2 (min)
Light Source
Light Source Catalysts
Catalysts OII
OII
−1 ) MO
MO OII
OII RMO MO
2 OII
OII MO MO t (min)
kobs (min 1/2
Light Source Catalysts TiO
TiO22 0.0019 0.00067 0.80 0.97
0.0019 0.00067 0.80 0.97 367 1029 367 1029
Fluorescent
Fluorescent light
light OII MO OII MO OII MO
ZnO
ZnO 0.0019
0.0019 0.00083
0.00083 0.93
0.93 0.96
0.96 346
346 866 866
TiO2 TiO
0.0019
TiO22 0.0055
0.000670.0013
0.0055 0.97
0.97 0.98
0.0013 0.80 125
125 525
0.98 0.97 525367 1029
Fluorescent light LED light
LED ZnO
light 0.0019
ZnO
ZnO 0.00083
0.0013 0.00023 0.93
0.88 0.88
0.0013 0.00023 0.88 0.88 533 34650.96
533 346
3465 866
TiO2 0.0055 0.0013 0.97 0.98 125 525
LED light
ZnO 0.0013 0.00023 0.88 0.88 533 3465

3.5. Proposed Degradation Mechanisms

TiO2 and ZnO cannot absorb visible light energy directly due to the band gap 3.2 eV
(Supplementary Data Figures S3 and S4) [16]. On the contrary, when a colored organic compound
ChemEngineering 2017, 1, 8 7 of 10

3.5. Proposed Degradation Mechanisms

TiO2 and2017,
ChemEngineering ZnO1, 8 cannot absorb visible light energy directly due to the band gap 3.2 7 ofeV
10
(Supplementary Data Figures S3 and S4) [16]. On the contrary, when a colored organic compound is
present, a sensitized photocatalytic process is possible. Huang et al. investigated dye sensitized
is present, a sensitized
photodegradation whichphotocatalytic
follows the process is possible. Huang
radical mechanism et al.etinvestigated
[17]. Molla al. recently dye sensitized
evaluated the
photodegradation which follows the radical mechanism [17]. Molla et al. recently
reaction mechanism of photocatalytic degradation of dye with self-sensitized TiO2 under visible evaluated the
reaction mechanism
light [18]. Park et ofal.photocatalytic
also mentioneddegradation
that theof dye-sensitization
dye with self-sensitized
can beTiO 2 underfor
applied visible
the
light [18]. Park et al. also mentioned that the dye-sensitization can be applied for the self-degradation
self-degradation of dyes. In dye-sensitization, a dye absorbing visible light excites an electron from
of
thedyes.
HOMO In dye-sensitization,
(highest occupieda molecular
dye absorbing visible
orbital) of alight
dyeexcites
to thean electron
LUMO from the
(lowest HOMO
unoccupied
(highest
molecularoccupied
orbital)molecular
[19]. The orbital)
HOMOofand a dye to thelevels
LUMO LUMO (lowest
and band unoccupied
gap energymolecular
of OII and orbital)
MO were[19].
The HOMO and LUMO levels and band gap energy of OII
obtained from literature and the values are presented in Table 3. and MO were obtained from literature and
the values are presented in Table 3.
Table 3. HOMO and LUMO levels and energy gaps (eV) of dye molecules and λmax (nm).
Table 3. HOMO and LUMO levels and energy gaps (eV) of dye molecules and λmax (nm).
Molecules HOMO LUMO Energy Gaps λmax Reference
Molecules OIIHOMO 0.17 LUMO −1.86 2.03Gaps
Energy 485 λmax [20] Reference
OII MO 0.17 0.84 −2.43
−1.86 3.27
2.03 464 485 [21] [20]
MO 0.84 −2.43 3.27 464 [21]
Figure 7 demonstrates the valence band (VB) and conduction band (CB) levels and the energy
gapsFigure
of catalyst vs. NHE reference
7 demonstrates electrodes.
the valence It isand
band (VB) observed that the
conduction band LUMO levels and
(CB) levels of OII
theand MO
energy
are more negative relative to the conduction band edge potential of TiO 2 and ZnO. Otherwise, due
gaps of catalyst vs. NHE reference electrodes. It is observed that the LUMO levels of OII and MO are
to thenegative
more more negative
relative potential of the lowest
to the conduction unoccupied
band edge potentialmolecular
of TiO2 and orbital
ZnO.(LUMO)
Otherwise,level
duefor
to dye
the
relative to the conduction band (CB) of the catalyst [22], the electron transfer from
more negative potential of the lowest unoccupied molecular orbital (LUMO) level for dye relative the LUMO of dyes
to
to the CB of the catalyst is feasible. It is reported that the redox potential of O
the conduction band (CB) of the catalyst [22], the electron transfer from the LUMO of dyes to the CB2/•O2− is −0.33 V vs.

NHEthe [23], which is more Itpositive than that

conduction band potential
of Oof2 /TiO
• O 2 −and ZnO (−0.5 V vs NHE)
of catalyst is feasible. is reported the redox potential 2 is −0.33 V vs. NHE [23],
[24,25].
which is more positive than conduction band potential of TiO and ZnO (−0.5 V vs. NHE) [24,25].
2

Figure 7. Schematic
Figure 7. Schematicenergy
energylevel
leveldiagram
diagramofofTiO2 2and
TiO andZnO
ZnOwith
withrespect toto
respect potential of of
potential O2O/•2/O −
2 2− and
•O and
• OH/OH− and the HOMO–LUMO levels of dye.
•OH/OH− and the HOMO–LUMO levels of dye.

The surface
surface adsorbed
adsorbed dyes were excited
excited by
by absorbing
absorbing visible
visible light (fluorescent)
(fluorescent) and donated
donated
their
their electrons
electrons to to the
the conduction
conduction band
band of
of the
the catalyst.
catalyst. As a result, the dyes are converted to a cationic
radical +•+•), and • O• − −radical specie were easily formed by the adsorbed oxygen through capturing
radical (dye
(dye ), and 2O2 radical specie were easily formed by the adsorbed oxygen through
electrons • O − can react with
capturingfrom the conduction
electrons from theband of the catalyst.
conduction band of Thethe catalyst.
2 The •O2−surface adsorbed
can react with H 2 O to
surface
•
form H2 O2 which is ultimately converted to OH [26,27]. The surface adsorbed OII and MO radical
cation or surface adsorbed dyes can undergo degradation by • O2 − and • OH. As soon as a dye molecule
degrades, another dye molecule will be adsorbed on TiO2 and ZnO surface and the photocatalytic
 ChemEngineering 2017, 1, 8 8 of 10

adsorbed H2O to form H2O2 which is ultimately converted to •OH [26,27]. The surface adsorbed OII
and MO radical
ChemEngineering 2017, 1, cation
8 or surface adsorbed dyes can undergo degradation by •O2− and •OH. As soon8 of 10
as a dye molecule degrades, another dye molecule will be adsorbed on TiO2 and ZnO surface and the
photocatalytic cycle continues. The peak corresponding to the azo group of dye (OII and MO)
cycledecreased
continues.after
The360 mincorresponding
peak of irradiation (Figures 1a,bgroup
to the azo and 2a,b). This
of dye may
(OII be MO)
and attributed to the after
decreased fact that
360 min
azo bonds are more reactive than the aromatic part of the molecule. They are easily
of irradiation (Figure 1a,b and Figure 2a,b). This may be attributed to the fact that azo bonds oxidized byare
themore
photogenerated •OH radicals. The cleavage of the azo (–N=N–) bond leads to decolorization of dyes •
reactive than the aromatic part of the molecule. They are easily oxidized by the photogenerated OH
[28]. According to the previous studies, a possible decolorization pathway of OII [29] and MO [30] was
radicals. The cleavage of the azo (–N=N–) bond leads to decolorization of dyes [28]. According to the
proposed in Figure 8.
previous studies, a possible decolorization pathway of OII [29] and MO [30] was proposed in Figure 8.

Figure 8. Proposed
Figure decolorization
8. Proposed decolorizationmechanism ofOII
mechanism of OII(a)
(a)and
and MO
MO (b)(b) under
under visible
visible light.light.

4. Conclusions
4. Conclusions
Consequently, the photocatalytic activity of self-dye-sensitized TiO2 and ZnO in the
Consequently, the photocatalytic activity of self-dye-sensitized TiO2 and ZnO in the degradation
degradation of OII and MO was studied under fluorescent light irradiation. The percentage of
of OII and MO was studied under fluorescent light irradiation. The percentage of degradation of
degradation of OII and MO increased with an increase in irradiation time under fluorescent light for
OII and MO increased with an increase in irradiation time under fluorescent light for TiO and
TiO2 and ZnO catalyst. The photocatalytic activity of ZnO nanoparticles was better than that of TiO22
ZnO for
catalyst.
MO, and The
of photocatalytic activity
ZnO and TiO2 showed theofsame
ZnOactivity
nanoparticles was better thanunder
for OII photodegradation that of TiO2 for MO,
fluorescent
and of ZnO
light. Theand TiO2ofshowed
kinetics OII andtheMOsame activity for OII
photodegradation photodegradation
followed the pseudo-firstunder fluorescent
order rate law, and light.
The kinetics
could beof OII andin
described MO photodegradation
terms followed the pseudo-first
of the Langmuir–Hinshelwood order rate law,
model. The photocatalytic and could be
degradation
of waste
described in dye
termsin water
of thewith self-dye-sensitized TiO2 model.
Langmuir–Hinshelwood and ZnOTheunder fluorescent light
photocatalytic irradiation will
degradation of waste
become a promising technique.
dye in water with self-dye-sensitized TiO2 and ZnO under fluorescent light irradiation will become a
promising technique.
Supplementary Materials: The following are available online at www.mdpi.com/2305-7084/1/2/8/s1. Figure S1:
XRD patterns of P25 TiO2; Figure S2: XRD patterns of ZnO; Figure S3: UV-Vis DRS patterns of TiO2. Inset figure:
Supplementary
Tauc plot of Materials: The following
[F(R)hυ]0.5 versus are available
photon energy; online
Figure S4: at www.mdpi.com/2305-7084/1/2/8/s1.
UV-Vis Figure
DRS patterns of ZnO. Inset figure: Tauc plot of S1:
XRD patterns of P25 TiO2 ; Figure
[F(R)hυ] versus photon
2 energy;S2: XRDS5:
Figure patterns
Reactorof
forZnO; Figure S3:degradation
photocatalytic UV-Vis DRS patterns
of dye; ofS6:
Figure TiO 2 . Inset figure:
UV-visible
Tauc plot of [F(R)hυ] 0.5 versus photon energy; Figure S4: UV-Vis DRS patterns of ZnO. Inset figure: Tauc plot of
spectra of aqueous solutions of (a) OII and (b) MO before and after treatment under fluorescent light and 450
[F(R)hυ] 2
nm LEDversus photon energy; Figure S5: Reactor for photocatalytic degradation of dye; Figure S6: UV-visible
light.
spectra of aqueous solutions of (a) OII and (b) MO before and after treatment under fluorescent light and 450 nm
Acknowledgments: The present research was partly supported by Grant-in-Aid for Scientific Research (C)
LED light.
15K00602 from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. All experiments
Acknowledgments:
were conducted atTheMiepresent research
University. was partly
Any opinions, supported
findings, by Grant-in-Aid
conclusions, for Scientific
or recommendations Research
expressed in this (C)
15K00602
paperfrom the Ministry
are those of Education,
of the authors and do not Culture, Sports,
necessarily reflect Science, and
the view of theTechnology of Japan. All experiments
supporting organizations.
were conducted at Mie University. Any opinions, findings, conclusions, or recommendations expressed in this
paperAuthor Contributions:
are those Md.and
of the authors Ashraful Islam
do not Molla andreflect
necessarily Satoshi Kaneco
the view conceived and designed
of the supporting the experiments.
organizations.
Md. Ashraful Islam Molla performed the experiments and wrote the paper. Ikki Tateishi, Mai Furukawa,
Author Contributions: Md. Ashraful Islam Molla and Satoshi Kaneco conceived and designed the experiments.
Hideyuki Katsumata, and Tohru Suzuki analyzed the results and advised the project.
Md. Ashraful Islam Molla performed the experiments and wrote the paper. Ikki Tateishi, Mai Furukawa,
Hideyuki Katsumata,
Conflicts andThe
of Interest: Tohru Suzuki
authors analyzed
declare the of
no conflict results and advised the project.
interest.
Conflicts of Interest: The authors declare no conflict of interest.

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